WO2004053033A1 - Molybdenum-containing lubricant for improved power or fuel economy - Google Patents
Molybdenum-containing lubricant for improved power or fuel economy Download PDFInfo
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- WO2004053033A1 WO2004053033A1 PCT/US2003/038385 US0338385W WO2004053033A1 WO 2004053033 A1 WO2004053033 A1 WO 2004053033A1 US 0338385 W US0338385 W US 0338385W WO 2004053033 A1 WO2004053033 A1 WO 2004053033A1
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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
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/045—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and non-macromolecular compounds
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
- C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/26—Overbased carboxylic acid salts
- C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/2805—Esters used as base material
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/40—Fatty vegetable or animal oils
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
- C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
- C10M2215/30—Heterocyclic compounds
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- 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
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- 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
- C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2221/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2221/041—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds involving sulfurisation of macromolecular compounds, e.g. polyolefins
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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
- 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
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/061—Esters derived from boron
- C10M2227/062—Cyclic esters
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/12—Groups 6 or 16
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
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- 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
- C10N2030/02—Pour-point; Viscosity index
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- 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
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- 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
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- 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
Definitions
- the present invention relates to a lubricant composition for use in internal combustion engines.
- the lubricants in particular include a molybdenum salt and certain esters and borated esters.
- the present invention relates to a lubricant composition
- a lubricant composition comprising:
- the invention further provided a method for lubricating an internal combustion engine, comprising supplying thereto the above lubricant composition.
- One component of the present invention is an oil of lubricating viscosity.
- Oils of lubricating viscosity include natural and synthetic lubricating oils and mixtures thereof.
- Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil-) as well as liquid petroleum oils and- solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic- naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.
- Synthetic lubricating oils include hydrocarbon oils such as polymer- ized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propyl- ene-isobutylene copolymers, poly(l-hexenes, poly(l-octenes), poly(l-decenes), and mixtures thereof); alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, and di(2-ethylhexyl)-benzenes); polyphenyls (e.g., biphenyls, terphenyls, and alkylated polyphenyls), alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs, and homologs thereof.
- hydrocarbon oils such as polymer- ized and interpolymerized o
- Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etheri- fication, or similar reaction constitute another class of known synthetic lubricating oils. These are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyal- kylene polymers (e.g., methylpolyisopropylene glycol ether having an average molecular weight of 1,000, diphenyl ether of polyethylene glycol having a molecular weight of 500-1,000, diethyl ether of polypropylene glycol having a molecular weight of 1,000-1,500) or mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3-C8 fatty acid esters, or the C13 Oxo acid diester of tetraethylene glycol.
- the oils prepared through polymerization of ethylene oxide or propylene oxide the alkyl
- Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, and alkenyl malonic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, and propylene glycol).
- dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, lin
- esters include dibutyl adipate, di (2-ethylhexyl sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phtha- late, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.
- Esters useful as synthetic oils also include those made from C5 to C12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol.
- Other oils of lubricating viscosity which may be classified as synthetic oils, are those derived from a gas-to-liquid conversion process, or a Fischer-Tropsch process. Such liquids are made from synthesis gas containing H 2 and CO using a Fischer-Tropsch catalyst. The resulting hydrocarbons typi- cally are subjected to further processing, such as hydroisomerization, hydro- cracking, or dewaxing.
- Unrefined, refined and rerefined oils (and mixtures of each with each other) of the type disclosed hereinabove can be used in the lubricant compositions of the present invention.
- Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment.
- a shale oil obtained directly from retorting operations a petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil.
- Refined oils are similar to the unrefined oils except that they have been further treated in one or more purification steps to improve one or more properties.
- Rerefined oils are obtained by processes similar to those used to obtain refined oils which have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products.
- Oils of lubricating viscosity have also been characterized by the API as Groups I, II, III, IV, and V, on the basis of sulfur content, amount of saturates, and viscosity index (for Groups I - III), with all polyalphaolefins referred to as Group IV and all others not in Groups I - IV as Group V.
- Group III oils are often blended with synthetic oils.
- the present invention can be used in any of these API Groups or blends thereof.
- Viscosity modifiers are commonly used in natural lubricating formulations, and are sometimes unnecessary in high grade synthetic formulations. Viscosity modifiers are generally polymeric materials which are well known to those skilled in the art of lubricant formulation, and include polyisobutenes, polyme- thacrylate acid esters, polyacrylate acid esters, diene polymers, polyalkyl styre- nes, alkenyl aryl conjugated diene copolymers, polyolefins and multifunctional viscosity improvers, including dispersant viscosity modifiers (which impart both dispersancy and viscosity improvement).
- the formulations of the present invention can be used in lubricating oils without particular restriction as to viscosity grade.
- they can be used in oils, optionally including a viscosity modifier, having an SAE multigrade viscosity rating of OW-10, 0W-20, OW-30, 5W-20, or 5W-30, or in monograde oils having SAE viscosity ratings of 20 or 30.
- the oil when used in a synthetic oil base stock, the oil can advantageously be a blend of a polyalphaolefin and a synthetic ester.
- the polyalphaolefin and the synthetic ester can be present, for example, in weight ratios of 95:5 to 80:20 or about 90:10.
- These oils can be selected from materials having suitable viscosity to provide to the composition a viscosity grade of OW-10, with or without the presence of a viscosity modifier. Such a formulation may be desirable for very high performance or racing applications.
- the oil of lubricating viscosity is typically the major component of the lubricant, comprising the balance of the composition after the additives are accounted for.
- the oil will comprise 50-99 percent by weight of the composition, or 80 to 97 percent, or 85 to 95 percent.
- the concentration of the additive or additives is increased by about an order of magnitude, the amount of oil will be correspondingly decreased.
- molybdenum salts include molybdenum dithiocarbamates (or, commonly, molybdenum dihydrocarbyldithiocarbamates, "MoDTC”), which are generally represented by the formula
- Ri and R are the same or different groups, including hydrocarbyl groups such as alkyl groups, or hydrogen; typically Ri and R 2 are C 8 to C ⁇ 8 hydrocarbyl groups; m and n are positive integers whose total is 4. Typically m is 1-4 and n is 0-3; preferably m is 2-4 or 2-3 and n is 0-2 or 1-2, respectively. In a particularly preferred material m is 2 and n is 2.
- MoDTCs include commercial materials such as VanlubeTM 822 and MolyvanTM A from R.T. Nanderbilt Co., Ltd., and Adeka Sakura-LubeTM S-100, S-165 and S-600 from Asahi Denka Kogyo K.K.
- Other molybdenum dithiocarbamates are described by Tomizawa in U.S. Patent 5,688,748; by Ward in U.S. Patent 4,846,983; by deNries et al. in U.S. Patent ⁇ 4,265,773; and by Tnoue et al. in U.S. Patent 47529,536.
- Common groups for R x and R 2 are 2-ethylhexyl groups and alkyl groups generally containing 6 to 18 carbon atoms, including, in one example, mixtures of alkyl groups containing 6 and 13 carbon atoms.
- Ri and R 2 can each be independently not only hydrocarbyl groups, but also aminoalkyl groups or acylated aminoalkyl groups. More generally, any such R groups are derived from a basic nitrogen compound (comprising the structure R ⁇ -N-R ) as described in detail in U.S. Patent 4,265,773. If they are hydrocarbyl groups, they can be alkyl groups of 4 to 24 carbons, typically 6 to 18 carbons, or 8 to 12 carbons.
- a useful C-8 group is the 2-ethylhexyl group; thus, the di-2-ethylhexyl dithiocarbamate is a preferred group.
- the aminoalkyl groups which can serve as Ri or R 2 typically arise from the use of a polyalkylenepolyamine in the synthesis of the dithiocarbamate moiety.
- Typical polyalkenepolyamines include ethylenediamine, diethylenetria- mine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and corresponding higher homologues, and mixtures thereof Such polyamines are described in detail under the heading Ethylene Amines in Kirk Othmer's "Encyclopedia of Chemical Technology", 2d Edition, Vol. 7, pages 22-37, Interscience Publishers, New York (1965).
- Such polyamines can be prepared by the reaction of ethylene dichloride with ammonia or by reaction of an ethylene imine with a ring opening reagent such as water or ammonia. These reactions result in the production of a complex mixture of polyalkylenepolyamines including cyclic condensation products such as piperazines, which mixtures are also useful.
- Other useful types of polyamine mixtures are those resulting from stripping of the above-described polyamine mixtures to leave as residue what is often termed "polyamine bottoms.”
- Ri and R 2 can be acylated aminoalkane groups, particularly arising from the use of an acylated polyalkylenepolyamine in the synthesis of the dithiocarbamate moiety.
- Acylated polyalkylenepolyamines typically find use as dispersants for lubricating applications. If a hydrocarbyl diacid such as hydro- carbyl-substituted succinic acid or anhydride is reacted, as the acylating agent, with a polyalkylenepolyamine, the product is typically known as a succinimide dispersant.
- the acylating agent If a monocarboxylic acid, such as isostearic acid, is used as the acylating agent, the resulting product will typically be an amide, although cyclization to form an imidazoline structure can also occur.
- the molybdenum salt can be described as the product of (a) reacting a carboxylic acid or reactive equivalent thereof having, for exam-
- pie, 8 to 34 carbon atoms with ah alkylene polyamine and (b) reacting the product of (a) with, in any order, (i) a molybdenum compound such as MoO , H 2 MoO , Mo (CO) 6 , Mo(OH) 3 , MoS 2 , or phosphomolybdic acid, and (ii) carbon disulfide, thereby forming a molybdenum dithiocarbamate.
- a molybdenum compound such as MoO , H 2 MoO , Mo (CO) 6 , Mo(OH) 3 , MoS 2 , or phosphomolybdic acid
- Example A Polyethyleneamine bottoms (1.31 kg, 31.7 equivalents) are charged to a 12 L flask equipped with a Dean-Stark distillate trap, stirrer, thermal probe, and subsurface N 2 sparge set to 8.5 L/hr (0.3 std. cubic feet per hour) and heated to 75-85°C. Isostearic acid (5.92 kg, 19.4 equivalents) is added over a 5 minute period. The mixture is heated to 220°C over 1.5 hours and maintained at temperature for 6.5 hours while distillates are removed. The mixture is allowed to cool to 150°C and filtered using 120 g filter aid to provide 6.56 g of intermediate material.
- the intermediate material, 830 g, 1.18 equivalents, in 400 g toluene, is charged to a 3 L flask, equipped as above, including a caustic trap for H S removal.
- the mixture is heated to 40°C over 30 minutes, then MoO 3 (68.2 g, 0.47 equivalents) and water (30 g) are added with stirring.
- the reaction mixture is heated to 65°C. Heating is discontinued and carbon disulfide (99.2 g, 1.3 equivalents) is added drop wise to the mixture over 15 minutes.
- the mixture is then stirred and slowly heated to 85°C and maintained at this temperature for 24 hours.
- the reaction mixture is vacuum stripped to 145°C / 1.3 kPa (10 mm Hg) over 1 hour.
- the residue is allowed to cool to 100°C.
- To the residue is added 111.3 g of a Ci 6 — C ⁇ alpha olefin while stirring.
- the reaction mixture is heated to 125°C and stirred for 6 hours, then vacuum stripped to 125°C / 53 kPa (400 mm Hg) over 1 hour.
- the residue, filtered through a filter aid, is the product.
- Example B [0030] Example A is substantially repeated except that the polyethyleneamine bottoms are replaced by an equivalent amount of tetraethylene pentamine.
- the amount of the molybdenum salt in the final lubricant composition is an amount suitable to provide 50 to 4000 or 50 to 3000 or 50 to 2000 parts per million by weight Mo to the composition. Other amounts will provide 100 to 1500 parts, 125 to 1300 parts, 140 to 500 parts, or 150 to 350 parts per million by weight.
- the amount of the molybdenum compound to provide these levels of Mo will, of course, depend on the specific identity of the compound.
- the amount of the salt can be 0.025 to 1 parts by weight per 100 parts of the base oil, or more specifically 0.05 to 0.75 parts, 0.062 to 0.65 parts, 0.07 to 0.25 parts, or 0.75 to 0.38 parts. Its amount in a concentrate will be increased, for instance, to 0.5 to 10 parts.
- Another component of the present invention is a monoester (or partial ester) of a polyol and an aliphatic carboxylic acid, typically an acid containing 12 to 24 carbon atoms.
- Polyols include diols, triols, and alcohols with higher numbers of alcoholic OH groups.
- Polyhydric alcohols include ethylene glycols, including di-, tri- and tetraethylene glycols; propylene glycols, including di-, tri- and tetrapropylene glycols; glycerol; butane diol; hexane diol; sorbitol; arabitol; mannitol; sucrose; fructose; glucose; cyclohexane diol; erythritol; and penta- erythritols, including di- and tripentaerythritol; preferably, diethylene glycol, triethylene glycol, glycerol, sorbitol, pentaerythritol and dipentaerythritol.
- the aliphatic carboxylic acids which form the esters are those acids containing 12 to 24 carbon atoms.
- Such acid can be characterized by the following general formula: Ri-COOH wherein Ri is a hydrocarbyl group, which can be a straight chain hydrocarbyl group, a branched chain or cyclic-containing hydrocarbyl group, or mixtures thereof.
- Ri is a hydrocarbyl group, which can be a straight chain hydrocarbyl group, a branched chain or cyclic-containing hydrocarbyl group, or mixtures thereof.
- Straight chain hydrocarbyl group containing 12 to 24 carbon atoms are preferred, for instance, 14 to 20 or 16 to 18 carbon atoms.
- Such acids can be used in combination with acids with more or fewer carbon atoms as well.
- the acid Ri-COOH is a monocarboxylic acid since polycarboxylic acids tend to form polymeric products if the reaction conditions and amounts of reactants are not carefully regulated. Mixtures of monocarboxylic acids and minor amounts of dicarboxylic acids or anhydrides, however, can be used in preparing the esters.
- Examples of carboxylic acids include dode- canoic acid, stearic acid, lauric acid, behenic acid, and oleic acid.
- the carboxylic esters are prepared by the very well-known reaction of at least one carboxylic acid (or reactive equivalent thereof, such as ester, halide, or anhydride) with at least one of the above-described ' polyhyd ⁇ oxy compounds.
- esters used in the present invention are in particular the mono- esters of such polyols and such carboxylic acids.
- a preferred ester is glycerol monooleate.
- glycerol monooleate is a mixture which includes such materials as glycerol, oleic acid, other long chain acids, glycerol dioleate, and glycerol trioleate.
- the commercial material is believed to include about 60 + 5 percent by weight of the chemical species "glycerol monooleate,” along with 35 + 5 percent glycerol dioleate, and less than about 5 percent trioleate and oleic acid.
- the amounts of the monoesters, described below, are calculated based on the actual, corrected, amount of polyol monoester present in any such mixture. Similar materials are available under the name UNIFLEX 1803 TM from Arizona Chemical.
- the amount of the polyol ester in the compositions of the present invention is typically 0.03 to 0.2 parts per 100 parts of the oil of lubricating viscosity. Alternative amounts are 0.05 to 1.0, or 0.7 to 0.75, or 0.1 to 0.3, or about 0.15 parts per 100 parts of the oil. Its amount in a concentrate will be correspondingly increase, for instance, to 0.3 to 10 parts
- Another component of the present invention is a borated epoxide containing 12-24 carbon atoms.
- This material can alternatively described as a borate ester of a vicinal diol containing 12 to 24 carbon atoms. Such a material may be re
- each of R 1 , R 2 , R 3 , and R 4 are independently hydrogen or an aliphatic radical, or any two thereof together with the carbon atom or atoms to which they are attached form a cyclic radical.
- at least one of the R groups is an alkyl group containing at least 8 or at least 10 carbon atoms.
- one of the R groups is such an alkyl group and the remaining R groups are hydrogen.
- Borated epoxides are described in detail in U.S. Pat. No. 4,584,115. Borated epoxides are generally prepared by reacting an epoxide with a boron source such as boric acid or boron trioxide.
- Borated epoxides are not themselves epoxides, but are the ring-opened boron-containing reaction .products of_epox-r . ides. Suitable epoxides include commercial mixtures of C ⁇ 4 - ⁇ 6 or C 1 - ⁇ 8 or C ⁇ 6 - ⁇ 8 epoxides, which can be purchased from Elf-Atochem or Union Carbide and which can be prepared from the corresponding olefins by known methods. Purified epoxy compounds such as 1,2-epoxyhexadecane can be purchased from Aldrich Chemicals.
- the borated compounds are prepared by blending the boron compound and the epoxide and heating them at a suitable temperature, typically 80° to 250°C, until the desired reaction has occurred.
- An inert liquid such as toluene, xylene, or dimethylformamide can be used as a reaction medium. Water is formed and is typically distilled off during the reaction. Alkaline reagents can be used to catalyze the reaction.
- a preferred borated epoxide is the borated epoxide of a predominantly 16 carbon olefin.
- the amount of the borate ester is typically an amount which will provide 30 to 2000 parts per million by weight boron to the composition, alternatively 40 to 1500 ppm, 50 to 1200 ppm, or 60 to 800 ppm. Alternatively ex-pressed, the amount can be 0.05 to 2.0 parts by weight of the composition, alternatively 0.1 to 1.75 percent, 0.2 to 1.5 percent, 0.1 to 1.2 percent, or about 1 percent. Its amount in a concentrate will be correspondingly increased to, for instance, 0.5 to 20 parts.
- Additional materials which may individually also be present (or which may be absent) include those typically found in lubricant formulations, such as dispersants, overbased detergents, metal salts of dialkyldithiophosphates, sul- furized oils, and other boron compounds (other than a borate ester of a vicinal diol containing 12 to 24 carbon atoms described above).
- Dispersants are well known in the field of lubricants and include primarily what are sometimes referred to as "ashless" dispersants because (prior to mixing in a lubricating composition) they do not contain ash-forming metals and they do not normally contribute any ash forming metals when added to a lubricant.
- Dispersants are characterized by a polar group attached to a relatively high molecular weight hydrocarbon chain.
- One class of dispersant is Mannich bases. These are materials which are formed by the condensation of a higher molecular weight, alkyl substituted phenol, an alkylene polyamine, and an aldehyde such as formaldehyde.
- Another class of dispersant is high molecular weight esters.
- dispersants include polymeric dispersant additives, which are generally hydrocarbon-based polymers which contain polar functionality to impart dispersancy characteristics to the polymer.
- a preferred class of dispersants is the carboxylic dispersants.
- Car- boxylic dispersants include succinic-based dispersants, which are the reaction product of a hydrocarbyl substituted succinic acylating agent with an organic hydroxy compound or, preferably, an amine containing at least one hydrogen attached to a nitrogen atom, or a mixture of said hydroxy compound and amine.
- succinic acylating agent refers to a hydrocarbon-substituted succinic acid or succinic acid-producing compound (which term also encompasses the acid itself). Such materials typically include hydrocarbyl-substituted succinic acids, anhydrides, esters (including half esters) and halides.
- Succinic based dispersants typically known as succinimide dispersants, have a wide variety of chemical structures including typically structures such as
- each RI is independently a hydrocarbyl group, preferably a polyolefin-derived group having an Mn of 500 or 700 to 10,000.
- the hydrocarbyl group is an alkyl group, frequently a polyisobutyl group with a molecular weight of 500 or 700 to 5000, preferably 1500 or 2000 to 5000.
- the R 2 are alkenyl groups, commonly ethylenyl (C 2 H 4 ) groups. Such molecules are commonly derived from reaction of an alkenyl acylating agent with a polyamine, and a wide variety of linkages between the two moieties is possible.
- the amines which are reacted with the succinic acylating agents to form the carboxylic dispersant composition can be monoamines or polyamines and will normally be characterized by the presence within their structure of at least one H-N ⁇ group, that is at least one primary (i.e., H 2 N-) or secondary amino (i.e., H-N ⁇ ) group.
- Examples of monoamines include ethylamine, di- ethylamine, n-butylamine, di-n-butylamine, allylamine, isobutylamine, co- coamine, stearylamine, laurylamine, methyllaurylamine, oleyl-amine, N-methyl- octylamine, dodecylamine, and octadecylamine.
- polyamines examples include alkylene polyamines such as ethylene diamine, triethylene tetramine, propylene diamine, decamethylehe diamine, octamethylene diamine7 ⁇ ⁇ i(heptamethylene) " triamine, tripropylene tetramine, tetraethylene pentamine, trimethylene diamine, pentaethylene hexamine, di(-trimethylene) triamine. Higher homologues such as are obtained by condensing two or more of the above-illustrated alkylene amines likewise are useful. Tetraethylene pentamine is particularly useful.
- the dispersants may be borated materials. Borated dispersants are well-known materials and can be prepared by treatment with a borating agent such as boric acid. Typical conditions include heating the dispersant with boric acid at 100 to 150°C. The dispersants may also be treated by reaction with maleic anhydride.
- the amount of the dispersant in a completely formulated lubricant will typically be 0.5 to 10 percent by weight, preferably 1 to 8 percent by weight, and more preferably 3 to 7 percent by weight. Its concentration in a concentrate will be correspondingly increased, to, e.g., 5 to 80 weight percent.
- Detergents are generally salts of organic acids, which are often over- based. Metal overbased salts of organic acids are widely known to those of skill in the art and generally include metal salts wherein the amount of metal present exceeds the stoichiometric amount.
- Such salts are said to have conversion levels in excess of 100% (i.e., they comprise more than 100% of the theoretical amount of metal needed to convert the acid to its "normal” or “neutral” salt). They are commonly referred to as overbased, hyperbased or superbased salts and are usually salts of organic sulfur acids, organic phosphorus acids, carboxylic acids, phenols or mixtures of two or more of any of these. As a skilled worker would realize, mixtures of such overbased salts can also be used.
- metal ratio designates the ratio of the total chemical equivalents of the metal in the overbased salt to the chemical equivalents of the metal in the salt which would be expected to result in the reaction between the organic acid to be overbased and the basic reacting metal compound according to the known chemical reactivity and stoichiometry of the two reactants.
- the metal ratio in a normal or neutral salt the metal ratio is one and, in an overbased salt, the metal ratio is greater than one.
- the overbased salts used as component (A) in this invention usually have metal ratios of at least 3:1. Typically, they have ratios of at least 12:1. Usually they have metal ratios not exceeding 40:1. " Typically, salts having ratios of 12: 1 to ' 2011 are used.
- Overbased compositions are well known and can be prepared based on a variety of well known organic acidic materials including sulfonic acids, carboxylic acids (including substituted salicylic acids), phenols, phosphonic acids, and mixtures of any two or more of these.
- organic acidic materials including sulfonic acids, carboxylic acids (including substituted salicylic acids), phenols, phosphonic acids, and mixtures of any two or more of these.
- These materials and methods for overbasing of them are well known from numerous U.S. Patents including 2,501,731; 2,616,905; 2,616,911; 2,616,925; 2,777,874; 3,256,186; 3,384,585; 3,365,396; 3,320,162; 3,318,809; 3,488,284; and 3,629,109 and need not be further described in detail.
- Preferred overbased materials include overbased phenates derived from the reaction of an alkylated phenol; overbased sulfonates derived from an alkylated aryl sulfonic acids; also overbased carboxylates derived from fatty acids; overbased alkyl-substituted salicylates; overbased saligenin derivatives as described in U.S. patent 6,310,009; and overbased salixarates as described in U.S. Patent 6,200,936 and PCT Publication WO 01/56968.
- the amount of the detergent component in a completely formulated lubricant will typically be 0.5 to 10 percent by weight, preferably 1 to 7 percent by weight, and more preferably 1.2 to 4 percent by weight. Its concentration in a concentrate will be correspondingly increased, to, e.g., 5 to 65 weight percent.
- Metal salts of dialkyldithiophosphates are typically materials of the formula
- R8 and R9 are independently hydrocarbyl groups containing 3 to 30 carbon atoms. They are well known materials which are readily obtainable by the reaction of phosphorus pentasulfide and an alcohol or phenol to form an O,O- dihydrocarbyl phosphorodithioic acid corresponding to the formula
- the metal M having a valence n, is generally aluminum, lead, tin, manganese, cobaLt, nickel, zinc, or copper, .and most preferably zinc.
- the basic metal compound is thus preferably zinc oxide, and the resulting metal compound is represented by the formula
- the R 8 and R 9 groups are independently hydrocarbyl groups that are preferably free from acetylenic and usually also from ethylenic unsaturation. They are typically alkyl, cycloalkyl, aralkyl or alkaryl group and have 3 to 20 carbon atoms, preferably 3 to 16 carbon atoms and most preferably up to 13 carbon atoms, e.g., 3 to 12 carbon atoms.
- the alcohols which react to provide the R 8 and R 9 groups can be one or more primary alcohols, one or more secon- dary alcohols, a mixture of secondary alcohol and primary alcohol. A mixture of two secondary alcohols such as isopropanol and 4-methyl-2-pentanol is often desirable.
- the amount of the metal dialkyldithiophosphate in a completely formulated lubricant will typically be 0.1 to 5 percent by weight, preferably 0.3 to 2 percent by weight, and more preferably 0.5 to 1.5 percent by weight. Its concentration in a concentrate will be correspondingly increased, to, e.g., 5 to 60 weight percent.
- Sulfurized oils include sulfurized vegetable oils, sulfurized animal oils such as sulfurized lard oil, and sulfurized olefins such as sulfurized C ⁇ 6 - ⁇ 8 ole- fins, and mixtures of such materials. Sulfurized oils are useful for their antioxi- dant, antiwear, friction modifying, and extreme pressure protective properties. They can be prepared by well-known methods, such as by treating the appropriate oils, fatty acids, olefins, or mixtures thereof, with sulfur and/or sodium sulfide or hydrosulfide, in the presence of such materials as sodium hydroxide and phosphoric acid.
- the other optional boron compounds include those disclosed in PCT publication WO02/062930, including borate esters of any of the general formulae where each R is independently hydrogen or, preferably, an organic group, e.g., a hydrocarbyl or an alkyl group, or where any two adjacent R groups may together form a cyclic ring
- An example of such a boron compound is 2-ethylhexyl borate.
- Others include materials represented by the formulas B(OC 5 H ⁇ ) 3 or B(OC 4 H ) .
- Another example is a phenolic borate available from Crompton Corporation under the trade designation LA-2607.
- antioxidants e.g., hindered phenols, alkylated diphenylamines
- Anti-wear agents include hindered phenols, ester-containing hindered phenols as disclosed in U.S. Patent 6,559,105, alkylated diphenylamines, and reaction products of a sulfur source and a Diels-Alder adduct, which in turn can be prepared from a dienophile having a carboxylic ester group.
- antioxidants e.g., hindered phenols, alkylated diphenylamines
- Anti-wear agents include hindered phenols, ester-containing hindered phenols as disclosed in U.S. Patent 6,559,105, alkylated diphenylamines, and reaction products of a sulfur source and a Diels-Alder adduct, which in turn can be prepared from a dienophile having a carboxylic ester group.
- hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include:
- hydrocarbon substituents that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic-substituted aromatic substituents, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring);
- aliphatic e.g., alkyl or alkenyl
- alicyclic e.g., cycloalkyl, cycloalkenyl
- aromatic-, aliphatic-, and alicyclic-substituted aromatic substituents as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring);
- substituted hydrocarbon substituents that is, substituents containing non- hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent (e.g., halo (especially chloro and fluoro) hydroxyr alkoxy, mercapto; alkylmercapto; nitro, nitrosorand sulfoxy);
- hetero substituents that is, substituents which, while having a predominantly hydrocarbon character, in the context of this invention, contain other than carbon in a ring or chain otherwise composed of carbon atoms.
- Heteroa- toms include sulfur, oxygen, nitrogen, and encompass substituents as pyridyl, furyl, thienyl and imidazolyl.
- substituents as pyridyl, furyl, thienyl and imidazolyl.
- no more than two, preferably no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; typically, there will be no non-hydrocarbon substituents in the hydrocarbyl group.
- Example 1 A racing oil formulation is prepared by mixing the fol- lowing components:
- Lubricating formulations for highway vehicles are prepared by mixing the following components:
- Example 3 Alternative formulations for highway vehicles are prepared as in Example 2, except using: 0.25 parts by weight of the molybdenum dithiocarbamate
- Examples 4 - 7 Three' reference lubricants (comparative) and one lubricant of the present invention are prepared, having the composition shown in the table below, and are subjected to various performance tests as reported in the table and further described below. Amounts are reported in parts per 100 parts base oil and are expressed on an active ingredient (oil-free) basis.
- the Sequence IVA engine valve train wear tests is a fired engine- dynamometer lubricant test which evaluates the ability of a lubricant to reduce camshaft lobe wear in a 1994 Nissan model DA24E engine. After 100 cycles of two stages (a 50 minute idle speed stage and a 10 minute 1500 r.p.m. stage) the wear at 7 locations on the cam lobes is measured and averaged. The results in the above table, expressed as % wear of the baseline fluid, show that the lubricant of inventive example 7 exhibits a strong pass.
- the Sequence VIB fuel test (ASTM D 6837) measures the effect of engine oil on fuel economy of passenger cars.
- the test is conducted using a 4.6 L spark-ignited engine on a dynamometer test stand.
- the test includes measuring the laboratory engine brake specific fuel consumption under 5 speed/ load/ temperature conditions.
- Test results are expressed as percent change in weighted fuel consumption relative to the baseline calibration. The results show excellent fuel economy for the lubricant of inventive example 7.
- the SRV test is a reciprocating cylinder-on-disk test that measures and reports the friction coefficient of a lubricant between 100°C and 120°C. The lubricant is heated for minutes while applying a 400 N load with a 1 mm reciprocating stroke.
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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AU2003293266A AU2003293266B2 (en) | 2002-12-06 | 2003-12-02 | Molybdenum-containing lubricant for improved power or fuel economy |
CA2508802A CA2508802C (en) | 2002-12-06 | 2003-12-02 | Molybdenum-containing lubricant |
JP2004559243A JP2006524263A (en) | 2002-12-06 | 2003-12-02 | Molybdenum-containing lubricants for improved power or fuel savings |
EP03790265.7A EP1567624B1 (en) | 2002-12-06 | 2003-12-02 | Molybdenum-containing lubricant for improved power or fuel economy |
Applications Claiming Priority (2)
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US43130602P | 2002-12-06 | 2002-12-06 | |
US60/431,306 | 2002-12-06 |
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WO2004053033A1 true WO2004053033A1 (en) | 2004-06-24 |
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PCT/US2003/038385 WO2004053033A1 (en) | 2002-12-06 | 2003-12-02 | Molybdenum-containing lubricant for improved power or fuel economy |
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EP (1) | EP1567624B1 (en) |
JP (1) | JP2006524263A (en) |
AU (1) | AU2003293266B2 (en) |
CA (1) | CA2508802C (en) |
WO (1) | WO2004053033A1 (en) |
Cited By (2)
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JP2009527613A (en) * | 2006-02-21 | 2009-07-30 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | Lubricating oil composition |
WO2012025901A1 (en) | 2010-08-27 | 2012-03-01 | Total Raffinage Marketing | Engine lubricant |
Families Citing this family (1)
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JP2020037647A (en) * | 2018-09-04 | 2020-03-12 | 東ソー株式会社 | Lubricant composition |
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EP0987311A2 (en) * | 1998-09-14 | 2000-03-22 | The Lubrizol Corporation | Transmission fluid compositions |
WO2002016533A2 (en) * | 2000-08-22 | 2002-02-28 | The Lubrizol Corporation | Extended drain manual transmission lubricants and concentrates |
US20020119895A1 (en) * | 1995-05-26 | 2002-08-29 | Susan P. Cook | Lubricants with molybdenum containing compositions and methods of using the same |
EP1318189A1 (en) * | 2001-12-06 | 2003-06-11 | Infineum International Limited | Dispersants and lubricating oil compositions containing same |
WO2003070863A2 (en) * | 2002-02-15 | 2003-08-28 | The Lubrizol Corporation | Molybdenum, sulfur and boron containing lubricating oil compositions |
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CA1164008A (en) * | 1980-03-24 | 1984-03-20 | Andrew G. Horodysky | Borated glycerol and thioglycerol hydroxyester friction reducing additives and lubricant compositions containing same |
JPS57200496A (en) * | 1981-05-26 | 1982-12-08 | Lubrizol Corp | Manufacture of boron-containing composition and boron-containing composition, additive condensate and lubricant composition |
NZ201613A (en) * | 1981-09-22 | 1985-09-13 | Mobil Oil Corp | Lubricant compositions containing borated diols |
JPS59190996A (en) * | 1983-04-14 | 1984-10-29 | モ−ビル オイル コ−ポレ−ション | Boronated epoxides, lubricating agent and fuel containing same |
JPH05279686A (en) * | 1992-03-31 | 1993-10-26 | Tonen Corp | Lubricant oil composition for internal-combustion engine |
US5641731A (en) * | 1994-11-04 | 1997-06-24 | Ashland, Inc. | Motor oil performance-enhancing formulation |
JPH08209178A (en) * | 1995-02-02 | 1996-08-13 | Tonen Corp | Lubricating oil composition |
JPH11508288A (en) * | 1995-05-26 | 1999-07-21 | ザ ルブリゾル コーポレイション | Lubricants using molybdenum-containing compositions and methods of using them |
JP3985330B2 (en) * | 1998-03-20 | 2007-10-03 | 株式会社コスモ総合研究所 | Diesel engine oil composition |
-
2003
- 2003-12-02 AU AU2003293266A patent/AU2003293266B2/en not_active Ceased
- 2003-12-02 CA CA2508802A patent/CA2508802C/en not_active Expired - Lifetime
- 2003-12-02 WO PCT/US2003/038385 patent/WO2004053033A1/en active Application Filing
- 2003-12-02 JP JP2004559243A patent/JP2006524263A/en active Pending
- 2003-12-02 EP EP03790265.7A patent/EP1567624B1/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US20020119895A1 (en) * | 1995-05-26 | 2002-08-29 | Susan P. Cook | Lubricants with molybdenum containing compositions and methods of using the same |
EP0987311A2 (en) * | 1998-09-14 | 2000-03-22 | The Lubrizol Corporation | Transmission fluid compositions |
WO2002016533A2 (en) * | 2000-08-22 | 2002-02-28 | The Lubrizol Corporation | Extended drain manual transmission lubricants and concentrates |
EP1318189A1 (en) * | 2001-12-06 | 2003-06-11 | Infineum International Limited | Dispersants and lubricating oil compositions containing same |
WO2003070863A2 (en) * | 2002-02-15 | 2003-08-28 | The Lubrizol Corporation | Molybdenum, sulfur and boron containing lubricating oil compositions |
Cited By (2)
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JP2009527613A (en) * | 2006-02-21 | 2009-07-30 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | Lubricating oil composition |
WO2012025901A1 (en) | 2010-08-27 | 2012-03-01 | Total Raffinage Marketing | Engine lubricant |
Also Published As
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JP2006524263A (en) | 2006-10-26 |
EP1567624A1 (en) | 2005-08-31 |
CA2508802A1 (en) | 2004-06-24 |
CA2508802C (en) | 2013-10-01 |
EP1567624B1 (en) | 2016-03-09 |
AU2003293266B2 (en) | 2009-07-02 |
AU2003293266A1 (en) | 2004-06-30 |
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