EP0684978B1 - Schmierstoffzusammensetzung die alkoxylierten aminsalze aus säuren enthält - Google Patents

Schmierstoffzusammensetzung die alkoxylierten aminsalze aus säuren enthält Download PDF

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Publication number
EP0684978B1
EP0684978B1 EP94909034A EP94909034A EP0684978B1 EP 0684978 B1 EP0684978 B1 EP 0684978B1 EP 94909034 A EP94909034 A EP 94909034A EP 94909034 A EP94909034 A EP 94909034A EP 0684978 B1 EP0684978 B1 EP 0684978B1
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Prior art keywords
acid
composition
carbon atoms
derived
salt
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EP94909034A
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English (en)
French (fr)
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EP0684978A1 (de
Inventor
Jacob Joseph Habeeb
Morton Beltzer
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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Priority claimed from US08/021,294 external-priority patent/US5330666A/en
Priority claimed from US08/021,292 external-priority patent/US5320766A/en
Priority claimed from US08/021,509 external-priority patent/US5308518A/en
Priority claimed from US08/021,295 external-priority patent/US5320767A/en
Priority claimed from US08/021,505 external-priority patent/US5275745A/en
Application filed by Exxon Research and Engineering Co filed Critical Exxon Research and Engineering Co
Publication of EP0684978A1 publication Critical patent/EP0684978A1/de
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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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
    • C10M129/54—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M133/08—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
    • C10M135/10—Sulfonic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/16—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiourea type, i.e. containing the group
    • 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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
    • C10M137/105—Thio derivatives not containing metal
    • C—CHEMISTRY; METALLURGY
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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
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/146—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings having carboxyl groups bound to carbon atoms of six-membeered aromatic rings having a hydrocarbon substituent of thirty or more 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C10M2219/064—Thiourea type compounds
    • 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
    • C10M2219/09—Heterocyclic compounds containing no sulfur, selenium or tellurium compounds in the ring
    • 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
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • 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
    • 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
    • C10M2223/047—Thioderivatives not containing metallic elements
    • 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
    • C10N2030/08—Resistance to extreme temperature
    • 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
    • C10N2040/12—Gas-turbines
    • 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
    • C10N2040/12—Gas-turbines
    • C10N2040/13—Aircraft turbines
    • 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
    • C10N2040/135—Steam engines or turbines
    • 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
    • C10N2040/251—Alcohol fueled 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
    • 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
    • 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
    • C10N2040/26—Two-strokes or two-cycle 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
    • C10N2040/28—Rotary engines

Definitions

  • This invention relates to lubricant compositions containing alkoxylated amine salts of hydrocarbylsalicylic acids, trithiocyanuric acid, hydrocarbylsulfonic acids, dihydrocarbyldithiophosphoric acids or dihydrocarbyldithiobenzoic acids and to the use of such salts to reduce friction and/or improve fuel economy in an internal combustion engine.
  • ZDDP zinc dialkyldithiophosphate
  • U.S. Patent 4,575,431 discloses a lubricating oil additive composition containing dihydrocarbyl hydrogen dithiophosphates and sulfur-free hydrocarbyl dihydrogen phosphates and dihydrocarbyl hydrogen phosphates, said composition being at least 50% neutralized by a hydrocarbyl amine having 10 to 30 carbons in said hydrocarbyl group.
  • Patent 4, 089,790 discloses an extreme-pressure lubricating oil containing (1) hydrated potassium borate, (2) an antiwear agent selected from (a) ZDDP, (b) an ester, an amide or an amine salt of a dihydrocarbyl dithiophosphoric acid or (c) a zinc alky aryl sulfonate and (3) an oil-soluble organic sulfur compound.
  • U.S. Patent No. 5,076,945 discloses a lubricating oil composition containing an amine salt of a dithiobenzoic acid.
  • the amines used to prepare the salts are long chain hydrocarbyl amines.
  • U.S. Patents 3,849,319 and 3,951,973 describe lubricant compositions containing di- and tri(hydrocarbylammonium)trithio-cyanurates.
  • the hydrocarbyl radicals include alkyl, aralkyl, aryl, alkaryl and cycloalkyl and the examples are directed to alkylamines. These lubricant compositions were stated to have improved load-carrying properties.
  • WO 91/14756 describes additive compositions having utility in metal working lubrication comprising alkoxylated amine salts of dihydrocarbyldithiophosphoric acid which may be diluted with oil to form concentrates which contain from 5 to 90% by weight of the additive compositions.
  • compositions which contain less phosphorous.
  • This invention relates to lubricant compositions containing alkoxylated amine salts of hydrocarbylsalicylic acids, trithiocyanuric acid, hydrocarbylsulfonic acids, dihydrocarbyldithiophosphoric acids or dihydrocarbyldithiobenzoic acids having improved friction reducing properties which results in improved fuel economy In an internal combustion engines.
  • salts other than those derived from dihydrocarbyldithiophosphoric acids there is the added advantage of the salts being substantially free of phosphorous which can poison the catalytic converters of cars.
  • some of the salts e.g. dihydrocarbyldithiobenzoic acid derived salts have antiwear and antioxidant activity.
  • the present invention therefore provides a lubricating oil composition for internal combustion engines which comprises (a) a major amount of a lubricating oil basestock and (b) a minor amount of an alkoxylated amine salt of an acid said salt having the general formula 1-.
  • Z is derived from either a hydrocarbylsalicylic acid, trithiocyanuric acid, a hydrocarbylsulfonic acid, a dihydrocarbyldithiophosphoric acid or a dihydrocarbyldithiobenzoic acid and wherein R is a hydrocarbyl group having from 2 to 22 carbon atoms with the proviso that when Z is derived from a hydrocarbylsalicylic acid R is an alkyl or alkenyl group of from 6 to 18 carbon atoms and when Z is derived from a hydrocarbylsulfonic acid that R is a hydrocarbyl group of from 6 to 18 carbon atoms, x and y are each independently integers of from 1 to 15 with the proviso that the sum of x + y is from 2 to 20 and n is 1 or from 1 to 3 preferably 3 when the acid is trithiocyanuric acid and that when Z in formula I is derived from a dihydrocarbyldithi
  • the invention further provides a lubricating oil composition for internal combustion engines which comprises
  • the present invention provides for the use, for reducing friction and/or improving fuel economy in an internal combustion engine, of an alkoxylated amine salt having the formula (1) set forth.
  • the lubricating oil will contain a major amount of a lubricating oil basestock.
  • the lubricating oil basestocks are well known in the art and can be derived from natural lubricating oils, synthetic lubricating oils, or mixtures thereof.
  • the lubricating oil basestock will have a kinematic viscosity ranging from 5 to 10,000 cSt at 40°C, although typical applications will require an oil having a viscosity ranging from about 10 to 1,000 cSt at 40°C.
  • Natural lubricating oils include animal oils, vegetable oils (e.g., castor oil and lard oil), petroleum oils, mineral oils, and oils derived from coal and shale.
  • Synthetic oils include hydrocarbon oils and halo-substituted, hydrocarbon oils such as polymerized and interpolymerized olefins, alkylbenzenes, polyphenyls, alkylated diphenyl ethers, alkylated diphenyl sulfides, as well as their derivatives, analogs, and homologs thereof, and the like.
  • Synthetic lubricating oils also include alkylene oxide polymers, interpolymers, copolymers and derivatives thereof wherein the terminal hydroxyl groups have been modified by esterification, etherification, etc.
  • Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids with a variety of alcohols. Esters useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol ethers.
  • Silicon-based oils (such as the polyakyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils) comprise another useful class of synthetic lubricating oils.
  • Other synthetic lubricating oils include liquid esters of phosphorous-containing acids, polymeric tetrahydrofurans, polyalphaolefins, and the like.
  • the lubricating oil may be derived from unrefined, refined, rerefined oils, or mixtures thereof.
  • Unrefined oils are obtained directly from a natural source or synthetic source (e.g., coal, shale, or tar sands bitumen) without further purification or treatment.
  • Examples of unrefined oils include a shale oil obtained directly from a retorting operation, a petroleum oil obtained directly from distillation, or an ester oil obtained directly from an esterification process, each of which is then used without further treatment.
  • Refined oils are similar to the unrefined oils except that refined oils have been treated in one or more purification steps to improve one or more properties.
  • Suitable purification techniques include distillation, hydrotreating, dewaxing, solvent extraction, acid or base extraction, filtration, and percolation, all of which are known to those skilled in the art.
  • Rerefined oils are obtained by treating refined oils in processes similar to those used to obtain the refined oils. These rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.
  • the amine salts of the acids are prepared from the reaction of alkoxylated, preferably propoxylated or ethoxylated, most preferably ethoxylated amines with the acid.
  • Preferred ethoxylated amines used to prepare amine salts have the formula where R is hydrocarbyl group of from 2 to 22 carbon atoms, preferably 6 to 18 carbon atoms.
  • the hydrocarbyl groups include aliphatic (alky or alkenyl) groups which may be substituted with hydroxy, mercapto, amino and the like and the hydrocarbyl group may be interrupted by oxygen, nitrogen or sulfur.
  • the sum of x + y is preferably 2 to 15.
  • Ethoxylated and/or propoxylated amines are commercially available from Sherex Chemicals under the trade name Varonic and from Akzo Corporation under the trade names Ethomeen®, Ethoduomeen®, and Propomeen®.
  • Examples of preferred amines containing from 2 to 15 ethoxy groups include ethoxylated (5) cocoalkylamine, ethoxylated (2) tallowalkylamine, ethoxylated (15) cocoalkylamine and ethoxylated (5) soyaalkylamine.
  • Prefered hydrocarbylsalicylic acids used to react with alkoxylated amines to form amine salts have the following formula: wherein R 1 is a hydrocarbyl group having from 2 to 30 carbon atoms preferably a hydrocarbyl group of from 2 to 26 carbon atoms.
  • Such hydrocarbyl groups include aliphatic (alkyl or alkenyl) and alicyclic groups.
  • the aliphatic and alicyclic groups may be substituted with hydroxy, alkoxy, cyano, nitro and the like and the alicyclic group may contain O, S or N as hetero atoms.
  • These substituted salicylic acids are commercially available or may be prepared by methods known in the art, e.g. U.S. Patent 5,023,366.
  • Trithiocyanuric acid may exist in different tautomeric forms represented by formulas II, III or mixtures thereof:
  • Trithiocyanuric acid is prepared by methods well known in the art. These methods involve the treatment of cyanuric chloride with sulfur nucleophiles according to the following reaction scheme: Other sulfur nucleophiles which may be employed in the above reaction scheme include sodium sulfide, thiourea and thioacetic acid.
  • Prefered hydrocarbylsulfonic acids used to react with alkoxylated amines to form amine salts have the following formula: wherein R 1 is preferably a hydrocarbyl group having from 2 to 30 and most preferably having from 2 to 26 carbon atoms.
  • Such hydrocarbyl groups include aliphatic (alkyl or alkenyl) and alicyclic groups.
  • the aliphatic and alicyclic groups may be substituted with hydroxy, alkoxy, cyano, nitro and the like and the alicyclic group may contain O, S or N as hetero atoms.
  • These sulfonic acids are commercially available or may be prepared by methods well known in the art.
  • Preferred dihydrocarbyldithiophosphoric acids used to react with alkoxylated amines to form amine salts have the following formula: wherein R 1 and R 2 are independently hydrocarbyl groups having from 3 to 30 carbon atoms, preferably 3-20 carbon atoms.
  • Such hydrocarbyl groups include aliphatic (alkyl or alkenyl) and alicyclic groups.
  • the aliphatic and alicyclic groups may be substituted with hydroxy, alkoxy, cyano, nitro and the like and the alicyclic group may contain O, S or N as hetero atoms.
  • dialkyldithiophosphoric acids made from mixed (85%) 2-butyl alcohol and (15%) isooctylalcohol (mixed primary and secondary alcohols).
  • Dihydrocarbyldithiophosphoric acids are commercially available from Exxon Chemical Company.
  • Preferred dihydrocarbyldithiobenzoic acids used to reacted with alkoxylated amines to form amine salts have the following formula: wherein R 2 to R 6 are each preferably hydrogen; a hydrocarbyl group containing from 1 to 18 carbon atoms or a hydroxy group with the proviso that at least one of R 2 to R 5 is a hydrocarbyl group, preferably an alkyl group containing 1 to 18 carbon atoms, more preferably 1 to 6 carbon atoms. R 3 and R 5 are most preferably t-butyl groups and R 4 is most preferably hydroxy.
  • the hydrocarbyl groups include aliphatic (alky or alkenyl) and alicyclic groups which may be substituted with hydroxy, mercapto, amino and the like and the hydrocarbyl group may be interrupted by oxygen, nitrogen or sulfur.
  • Dithiobenzoic acids may be prepared from a phenol according to the following method.
  • a phenol of the formula: is dissolved in a solvent such as dimethylsulfoxide and treated under nitrogen with potassium hydroxide dissolved in a minimum of water.
  • Carbon disulfide is added under nitrogen to this mixture which is maintained at about room temperature.
  • the resulting reaction mixture is heated at between 25 to 100°C for 1-3 hours and then added to an acidified water solution.
  • the resulting dithiobenzoic acid can be isolated by solvent extraction using, e.g. ether and the solvent evaporated.
  • alkoxylated amine salts according to the present invention are prepared by methods known to those skilled in the art.
  • the preparative reaction scheme is illustrated as follows: wherein R, n, x and y are defined as above.
  • Approximately equimolar amounts of alkoxylated amine and acid are mixed together in an acid/base neutralization reaction.
  • the amounts of acid or base may be varied to achieve the desired acid/base balance of the final amine salt.
  • the lubricant oil compositions according to the present invention comprises a major amount of lubricating oil basestock and a minor amount of the alkoxylated amine salt.
  • the amount of amine salt will be from 0.001 wt% to 5 wt%, based on oil basestock, except where it is derived from a dihydrocarbyldithiophosphoric acid.
  • the amount of amine salt is from 0.05 wt% to 1.0 wt%.
  • the lubricant oil composition comprises a major amount of lubricating basestock and typically from 0.1 to about 5 wt%, except 5.0 wt %, and most preferably from 0.5 to 2 wt% of the salt.
  • the lubricant oil composition comprises a major amount of lubricating basestock and from 0.1 to 5 wt% and most preferably from 0.5 to 2 wt% of the salt.
  • the amount of alkoxylated amine salt present will be an amount effective to provide reduced friction and/or improved fuel economy in internal combustion engines.
  • additives known in the art may be added to the lubricating oil basestock.
  • additives include dispersants, antiwear agents, antioxidants, rust inhibitors, corrosion inhibitors, detergents, pour point depressants, extreme pressure additives, viscosity index improvers, other friction modifiers, hydrolytic stabilizers and the like. These additives are typically disclosed, for example, in "Lubricant Additives” by C. V. Smalhear and R. Kennedy Smith, 1967, pp. 1-11 and in U.S. Patent 4,105,571.
  • the lubricating oil composition of this invention can be used in the lubrication system of essentially any internal combustion engine, including automobile and truck engines, two-cycle engines, aviation piston engines, marine and railroad engines, and the like. Also contemplated are lubricating oils for gas-fired engines, alcohol (e.g., methanol) powered engines, stationery powered engines, turbines, and the like.
  • alcohol e.g., methanol
  • This Example illustrates the preparation of an ethoxylated amine salt of salicylic acid according to the invention.
  • 114 g of ethoxylated(5)cocoalkylamine was heated to 80°C with stirring in a 3-neck round bottom flask fitted with a thermometer and a water cooled condenser.
  • 100 g of salicylic acid having formula was added gradually to the stirred amine solution.
  • the temperature rose to 104°C due to the exothermic reaction between acid and amine.
  • the reaction mixture was maintained at 104°C for 1.5 hours and then cooled to room temperature.
  • the ethoxylated amine salt of alkyl salicylic acid is an effective friction modifier as shown in this example.
  • the Ball on Cylinder (BOC) friction tests were performed using the experimental procedure described by S. Jahanmir and M. Beltzer in ASLE Transactions, Vol. 29, No. 3, p.425 (1985) using a force of 0.8 Newtons (1 Kg) applied to a 12.5 mm steel ball in contact with a rotating steel cylinder that has a 43.9 mm diameter.
  • the cylinder rotates inside a cup containing a sufficient quantity of lubricating oil to cover 2 mm of the bottom of the cylinder.
  • the cylinder was rotated at 0.25 RPM.
  • the friction force was continuously monitored by means of a load transducer.
  • Friction experiments were conducted with an oil temperature of 100°C. Various amounts of ethoxylated(5)cocoalkyl amine salicylate prepared in Example 1 were added to solvent 150 N. The results of BOC friction tests are shown in Table 1.
  • This Example illustrates the preparation of an ethoxylated amine salt of trithiocyanuric acid according to the invention.
  • 100 g of ethoxylated(5)cocoalkylamine was heated to 70°C with stirring in a 3-neck round bottom flask fitted with a thermometer and a water cooled condenser.
  • 14 g of trithiocyanuric acid was added gradually to the stirred amine solution.
  • the temperature rose to 105°C due to the exothermic reaction between acid and amine.
  • the reaction mixture was maintained at 105°C for 2 hours and then cooled to room temperature.
  • the ethoxylated amine salt of trithiocyanuric acid is an effective friction modifier as shown in this example.
  • the Ball on Cylinder (BOC) friction tests were performed using the experimental procedure described in Example 2 Various amounts of ethoxylated(5)cocalkylamine trithiocyanurate prepared in Example 3 were added to solvent 150 N. The results of BOC friction tests are shown in Table 2. TABLE 2 Wt% of Ethoxylated(5)Cocoalkylamine Trithiocyanurate in Solvent 150N Coefficient Of Friction 0.00 0.29 0.05 0.16 0.10 0.076 0.20 0.06 0.30 0.05 0.50 0.05 0.80 0.05 1.00 0.05
  • This Example illustrates the preparation of an ethoxylated amine salt of sulfonic acid according to the invention.
  • 300 g of ethoxylated(5)cocoalkylamine was heated to 60°C with stirring in a 3-neck round bottom flask fitted with a thermometer and a water cooled condenser.
  • An ethoxylated(2)tallowalkylamine sulfonate salt was prepared using the same procedure from 140 g of ethoxylated(2)tallowamine and 198 g of alky sulfonic acid.
  • the ethoxylated amine salt of sulfonic acid is an effective friction modifier as shown in this example.
  • the Ball on Cylinder (BOC) friction tests were performed using the experimental procedure described in Example 2.
  • Various amounts of ethoxylated(5)cocoalkyl amine alkylsulfonate prepared in Example 5 were added to solvent 150 N.
  • the results of BOC friction tests are shown in Table 3.
  • Example 6 The procedure of Example 6 was repeated except that ethoxylated(2)tallowalkylamine was substituted for ethoxylated(5)cocoalkylamine in the sulfonate salt.
  • the results are shown in Table 4.
  • TABLE 4 Wt% of Ethoxylated(5)tallowalkylamine Alkyl Sulfonate in Solvent 150N Coefficient Of Friction 0.0 0.32 0.1 0.20 0.2 0.17 0.3 0.13 0.5 0.10 0.8 0.07 1.0 0.06
  • the Sequence VI High Temperature Rapid Screen Test is a shortened version of the actual ASTM Sequence VI test for fuel economy. Although it uses the same engine as the Sequence VI, only the high temperature phase of the test is run. This emphasizes the boundary lubrication regime which basically determines the fuel economy capability of the additive.
  • the test procedure is outlined below: Step # Test Sequence Time 1 Cool down/warm up 20 min 2 Detergent Flush to Candidate Oil 1 hr, 20 min 3 Stabilize Step 1 - Stage 275°F 2 hr 4 BSFC Measurement Step 1 - Stage 275°F 30 min 5 Stabilize Step 2 - Stage 275°F 2 hr 6 BSFC Measurement Step 2 - Stage 275°F 30 min
  • Each candidate oil run is preceded by a flush oil run to ensure that any "carry-over" effect is eliminated.
  • the fuel economy of the candidate oil as measured by brake specific fuel consumption (BSFC), is measured twice in the experiment. Once after a two hour stabilization, or break-in period, and then again after another two hour stabilization period.
  • a base oil is run periodically throughout the test to determine the test precision. In this particular test the base oil was a commercially available SAE 5W-30 oil. The results are shown in the following table.
  • ethoxylated (5) cocoalkylamine 140 g was placed in a 3-neck round bottom flask fitted with a thermometer and a water cooled condenser. The ethoxylated amine was stirred and heated to 50°C. A stoichiometic amount of 4-hydroxy-3, 5-ditertiary-butyldithiobenzoic acid (100g) was then slowly added into the warm ethoxylated amine solution with stirring. The temperature was raised to 95°C for 2 hours. The neutralization reaction was controlled with a portable pH meter. The addition of the acid was stopped at pH 7. After 2 hours of stirring at 95°C, the reaction product was cooled to room temperature and used without further purification.

Claims (18)

  1. Schmierölzusammensetzung für Verbrennungsmotoren, die
    (a) eine größere Menge Schmieröleinsatzmaterial und
    (b) eine kleinere Menge alkoxyliertes Aminsalz einer Säure umfaßt, wobei das Salz die allgemeine Formel I aufweist:
    Figure imgb0022
     in der Z sich entweder von einer Kohlenwasserstoffsalicylsäure, Trithiocyanursäure, einer Kohlenwasserstoffsulfonsäure, einer Dikohlenwasserstoffdithiophosphorsäure oder einer Dikohlenwasserstoffdithiobenzoesäure ableitet und R eine Kohlenwasserstoffgruppe mit 2 bis 20 Kohlenstoffatomen ist, mit der Maßgabe, daß, wenn Z sich von einer Kohlenwasserstoffsalicylsäure ableitet, R eine Alkyl- oder Alkenylgruppe mit 6 bis 18 Kohlenstoffatomen ist, und wenn sich Z von einer Kohlenwasserstoffsulfonsäure ableitet, R eine Kohlenwasserstoffgruppe mit 6 bis 18 Kohlenstoffatomen ist, x und y jeweils unabhängig voneinander Zahlen von 1 bis 15 mit der Maßgabe sind, daß die Summe von x + y 2 bis 20 beträgt, und n 1 oder 1 bis 3, vorzugsweise 3 ist, wenn die Säure Trithiocyanursäure ist, und daß, wenn Z in Formel I sich von einer Dikohlenwasserstoffdithiophosphorsäure ableitet, die Konzentration des resultierenden Salzes in der Schmierölzusammensetzung 0,001 bis etwa 5,0 Gew.-% beträgt, mit der Maßgabe, daß die Konzentration nicht 5,0 Gew.-% ist.
  2. Schmierölzusammensetzung für Verbrennungsmotoren, die
    (a) eine größere Menge Schmieröleinsatzmaterial und
    (b) eine kleinere Menge alkoxyliertes Aminsalz einer Säure umfaßt, wobei das Salz die allgemeine Formel I aufweist:
    Figure imgb0023
     in der sich Z entweder von einer Kohlenwasserstoffsalicylsäure, Trithiocyanursäure, einer Kohlenwasserstoffsulfonsäure, einer Dikohlenwasserstoffdithiophosphorsäure oder einer Dikohlenwasserstoffdithiobenzoesäure ableitet und R eine Kohlenwasserstoffgruppe mit 2 bis 22 Kohlenstoffatomen ist, mit der Maßgabe, daß, wenn sich Z von einer Kohlenwasserstoffsalicylsäure ableitet, R eine Alkyl- oder Alkenylgruppe mit 6 bis 18 Kohlenstoffatomen ist, und wenn sich Z von einer Kohlenwasserstoffsulfonsäure ableitet, R eine Kohlenwasserstoffgruppe mit 6 bis 18 Kohlenstoffatomen ist, x und y jeweils unabhängig voneinander Zahlen von 1 bis 15 mit der Maßgabe sind, daß die Summe x + y 2 bis 20 ist, und n 1 oder 1 bis 3, vorzugsweise 3 ist, wenn die Säure Trithiocyanursäure ist, und daß, wenn sich Z in Formel I von einer Dikohlenwasserstoffdithiophosphorsäure ableitet, die Konzentration des resultierenden Salzes in der Schmierölzusammensetzung 0,001 bis 2 Gew.-% beträgt.
  3. Zusammensetzung nach Anspruch 1 oder 2, bei der sich Z von einer Kohlenwasserstoffsulfonsäure der folgenden Formel ableitet:
    Figure imgb0024
     in der R1 eine Kohlenwasserstoffgruppe mit 2 bis 30 Kohlenstoffatomen ist.
  4. Zusammensetzung nach Anspruch 1 oder 2, bei der sich Z von einer Kohlenwasserstoffsalicylsäure der folgenden Formel ableitet:
    Figure imgb0025
     in der R1 eine Kohlenwasserstoffgruppe mit 2 bis 30 Kohlenstoffatomen ist.
  5. Zusammensetzung nach Anspruch 3 oder Anspruch 4, bei der R1 eine Kohlenwasserstoffgruppe mit 2 bis 26 Kohlenstoffatomen ist.
  6. Zusammensetzung nach Anspruch 1 oder 2, bei der sich Z von Dikohlenwasserstoffdithiobenzoesäure der folgenden Formel ableitet:
    Figure imgb0026
     in der R2, R3, R4, R5 und R6 jeweils unabhängig Wasserstoff oder eine Kohlenwasserstoffgruppe mit 1 bis 24 Kohlenstoffatomen oder eine Hydroxygruppe sind, mit der Maßgabe, daß mindestens eine der Gruppen R2 bis R6 eine Kohlenwasserstoffgruppe ist.
  7. Zusammensetzung nach Anspruch 6, bei der R4 Hydroxy ist.
  8. Zusammensetzung nach entweder Anspruch 6 oder Anspruch 7, bei dem mindestens eine der Gruppen R2 bis R6 Alkyl mit 1 bis 18 Kohlenstoffatomen ist.
  9. Zusammensetzung nach einem der Ansprüche 6 bis 8, bei der R3 und R5 t-Butyl sind.
  10. Zusammensetzung nach Anspruch 1 oder Anspruch 2, bei der sich Z von einer Dikohlenwasserstoffdithiophosphorsäure mit der folgenden allgemeinen Struktur ableitet:
    Figure imgb0027
     in der R1 und R2 jeweils unabhängig voneinander Kohlenwasserstoffgruppen mit 3 bis 30 Kohlenstoffatomen sind.
  11. Zusammensetzung nach Anspruch 10, bei der R1 und R2 Alkyl oder Alkenyl mit 3 bis 20 Kohlenstoffatomen sind.
  12. Zusammensetzung nach entweder Anspruch 10 oder 11, bei der R in dem Amin mit OH, SH oder NH2 an dem endständigen Kohlenstoffatom der Kohlenwasserstoffgruppe substituiert ist.
  13. Zusammensetzung nach einem der Ansprüche 1 bis 11, bei der R Alkyl oder Alkenyl mit 6 bis 18 Kohlenstoffatomen ist.
  14. Zusammensetzung nach einem der Ansprüche 1 bis 13, bei der die Summe von x + y 2 bis 15 ist.
  15. Zusammensetzung nach einem der Ansprüche 6 bis 9, bei der die Menge an Salz 0,1 bis 5,0 Gew.-%, bezogen auf Öleinsatzmaterial, beträgt.
  16. Zusammensetzung nach einem der Ansprüche 3 bis 5, bei der die Menge an Salz 0,001 bis 5,0 Gew.-%, bezogen auf Öleinsatzmaterial, beträgt.
  17. Verwendung eines alkoxylierten Aminsalzes der Formel (I) gemäß einem der Ansprüche 1 bis 16 zur Verringerung der Reibung und/oder Verbesserung der Brennstoffwirtschaftlichkeit in einem Verbrennungsmotor.
  18. Verfahren zur Verringerung der Reibung und/oder Verbesserung der Brennstoffwirtschaftlichkeit in einem Verbrennungsmotor, das die Verwendung einer Schmierölzusammensetzung in einem solchen Motor umfaßt, die ein alkoxyliertes Aminsalz der Formel (I) gemäß einem der Ansprüche 1 bis 16 umfaßt.
EP94909034A 1993-02-22 1994-02-22 Schmierstoffzusammensetzung die alkoxylierten aminsalze aus säuren enthält Expired - Lifetime EP0684978B1 (de)

Applications Claiming Priority (11)

Application Number Priority Date Filing Date Title
US08/021,294 US5330666A (en) 1993-02-22 1993-02-22 Lubricant composition containing alkoxylated amine salt of hydrocarbylsalicyclic acid
US21295 1993-02-22
US21509 1993-02-22
US21292 1993-02-22
US08/021,292 US5320766A (en) 1993-02-22 1993-02-22 Lubricant composition containing alkoxylated amine salt of a dihydrocarbyldithiophosphoric acid
US21294 1993-02-22
US08/021,509 US5308518A (en) 1993-02-22 1993-02-22 Lubricant composition containing alkoxylated amine salt of a dihydrocarbyldithiobenzoic acid
US08/021,295 US5320767A (en) 1993-02-22 1993-02-22 Lubricant composition containing alkoxylated amine salt of hydrocarbylsulfonic acid
US08/021,505 US5275745A (en) 1993-02-22 1993-02-22 Lubricant composition containing alkoxylated amine salt of trithiocyanuric acid
PCT/EP1994/000521 WO1994019434A1 (en) 1993-02-22 1994-02-22 Lubricant composition containing alkoxylated amine salts of acids
US21505 2001-12-19

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US5352374A (en) * 1993-02-22 1994-10-04 Exxon Research & Engineering Co. Lubricant composition containing alkoxylated amine salt of a dihydrocarbyldithiophosphoric acid (law024)
CN1045103C (zh) * 1994-06-18 1999-09-15 兰州炼油化工总厂三星公司 一种烷基水杨酸盐润滑油添加剂
US8343901B2 (en) * 2010-10-12 2013-01-01 Chevron Oronite Company Llc Lubricating composition containing multifunctional hydroxylated amine salt of a hindered phenolic acid
US8334242B2 (en) 2010-10-12 2012-12-18 Chevron Oronite Company Llc Lubricating composition containing multifunctional borated hydroxylated amine salt of a hindered phenolic acid
SG191243A1 (en) * 2010-12-21 2013-07-31 Lubrizol Corp Lubricating composition containing an antiwear agent
CN107109279B (zh) 2014-10-31 2020-12-25 巴斯夫欧洲公司 润滑剂组合物中的烷氧基化酰胺、酯和抗磨剂

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US4382006A (en) * 1979-11-06 1983-05-03 Mobil Oil Corporation Friction reduction additives and compositions thereof
US5080813A (en) * 1990-03-26 1992-01-14 Ferro Corporation Lubricant composition containing dialkyldithiophosphoric acid neutralized with alkoxylated aliphatic amines
EP0580587B1 (de) * 1990-12-27 1997-05-21 Exxon Research And Engineering Company Rauchverringernde additive für schmier- und kraftstoff- mischungen für zweitaktkraftmaschinen

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CA2156608A1 (en) 1994-09-01

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