WO2008147704A1 - Lubricating composition containing ashfree antiwear agent based on hydroxypolycarboxylic acid derivative and a molybdenum compound - Google Patents

Lubricating composition containing ashfree antiwear agent based on hydroxypolycarboxylic acid derivative and a molybdenum compound Download PDF

Info

Publication number
WO2008147704A1
WO2008147704A1 PCT/US2008/063671 US2008063671W WO2008147704A1 WO 2008147704 A1 WO2008147704 A1 WO 2008147704A1 US 2008063671 W US2008063671 W US 2008063671W WO 2008147704 A1 WO2008147704 A1 WO 2008147704A1
Authority
WO
WIPO (PCT)
Prior art keywords
lubricating composition
molybdenum
oil
group
lubricating
Prior art date
Application number
PCT/US2008/063671
Other languages
French (fr)
Inventor
Patrick E. Mosier
Jody Kocsis
Mark Davies
Original Assignee
The Lubrizol Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Lubrizol Corporation filed Critical The Lubrizol Corporation
Priority to KR1020097027028A priority Critical patent/KR101496484B1/en
Priority to US12/598,104 priority patent/US20100197536A1/en
Priority to CN200880017335A priority patent/CN101679900A/en
Priority to JP2010509454A priority patent/JP2010528156A/en
Priority to EP08755509A priority patent/EP2152838B1/en
Priority to CA2688098A priority patent/CA2688098C/en
Publication of WO2008147704A1 publication Critical patent/WO2008147704A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/12Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/68Esters
    • C10M129/72Esters of polycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/68Esters
    • C10M129/76Esters containing free hydroxy or carboxyl groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028Overbased salts thereof
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/24Epoxidised acids; Ester derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26Overbased carboxylic acid salts
    • C10M2207/262Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/281Esters of (cyclo)aliphatic monocarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/287Partial esters
    • C10M2207/289Partial esters containing free hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08Amides
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08Amides
    • C10M2215/082Amides containing hydroxyl groups; Alkoxylated derivatives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/086Imides
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22Heterocyclic nitrogen compounds
    • C10M2215/223Five-membered rings containing nitrogen and carbon only
    • C10M2215/224Imidazoles
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28Amides; Imides
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046Overbasedsulfonic acid salts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066Thiocarbamic type compounds
    • C10M2219/068Thiocarbamate metal salts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089Overbased salts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • C10M2223/043Ammonium or amine salts thereof
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • C10M2223/045Metal containing thio derivatives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10Inhibition of oxidation, e.g. anti-oxidants
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40Low content or no content compositions
    • C10N2030/42Phosphor free or low phosphor content compositions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40Low content or no content compositions
    • C10N2030/43Sulfur free or low sulfur content compositions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40Low content or no content compositions
    • C10N2030/45Ash-less or low ash content
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/25Internal-combustion engines

Definitions

  • the invention provides a lubricating composition containing an oil of lubricating viscosity, an oil soluble molybdenum compound, and an ashless antiwear agent.
  • the invention further provides for a new antioxidant.
  • the lubricating composition is suitable for lubricating an internal combustion engine.
  • lubricating oils It is well known for lubricating oils to contain a number of additives (including antiwear agents, antioxidants, dispersants, detergents etc.) used to protect the mechanical devices such as internal combustion engines from wear, oxidation, soot deposits and acidity build up.
  • a common antiwear additive for engine lubricating oils is zinc dialkyldithiophosphate (ZDDP). It is believed that ZDDP antiwear additives protect the engine by forming a protective film on metal surfaces. ZDDP is also believed to have a detrimental impact on fuel economy and efficiency. Consequently, engine lubricants also contain friction modifier to obviate the detrimental impact of ZDDP on fuel economy and efficiency.
  • the lubricant composition disclosed may also contain zinc dihydrocarbyldithiophosphates, or other phosphorous-containing additives such as trilauryl phosphate or triphenylphosphorothionate.
  • the lubricant composition has anti-wear or anti-fatigue properties.
  • International Publication WO 2006/04441 1 discloses a low-sulphur, low-phosphorus, low-ash lubricant composition suitable for lubricating an internal combustion engine, containing a tartrate ester, or amide having 1 to 150 carbon atoms per ester of amide group.
  • US Patent 5,338,470 discloses alkylated citric acid derivatives obtained as a reaction product of citric acid and an alkyl alcohol or amine.
  • the alkylated citric acid derivative is effective as an antiwear agent and friction modifier.
  • U.S. Patent 4,237,022 discloses tartrimides useful as additives in lubricants and fuels for effective reduction in squeal and friction as well as improvement in fuel economy.
  • U.S. Patent 4,952,328 discloses lubricating oil compositions for internal combustion engines, comprising (A) oil of lubricating viscosity, (B) a carboxylic derivative produced by reacting a succinic acylating agent with certain amines, and (C) a basic alkali metal salt of sulphonic or carboxylic acid.
  • U.S. Patent 4,326,972 discloses lubricant compositions for improving fuel economy of internal combustion engines. The composition includes a specific sulphurised composition (based on an ester of a carboxylic acid) and a basic alkali metal sulphonate.
  • U.S. Patent Application 60/867534 discloses malonate esters suitable as antiwear agents.
  • Canadian Patent CA 1 183 125 discloses lubricants for gasoline engines containing alkyl-ester tartrates, where the sum of carbon atoms on the alkyl groups is at least 8.
  • a lubricating composition capable of providing at least one of (i) reducing or preventing phosphorus emissions, (ii) reducing or preventing sulphur emissions, (ii) wholly or partially replacing ZDDP in lubricating oils, (iii) improving fuel economy, (iv) fuel economy retention/efficiency, and (v) oxidation control.
  • the present invention provides an antiwear agent capable of achieving at least one of (i), (ii) (iii), (iv), and (v).
  • the antiwear agent may also be desirable for the antiwear agent to not have a detrimental affect on other components of a mechanical device. It may also be desirable for the antiwear agent to have antioxidant performance.
  • the invention provides a lubricating composition
  • a lubricating composition comprising an oil of lubricating viscosity, an oil-soluble molybdenum compound, and an ashless antiwear agent represented by Formula (1):
  • X is independently -Z-O-Z'-, >CH 2 , >CHR 4 , >CR 4 R 5 , >C(OH)(CO 2 R 2 ), >C(CO 2 R 2 ) 2 , >CC1I.;CO 2 R% or >CHOR 6 ;
  • Z and Z' are independently >CH 2 , >CHR 4 , >CR 4 R 5 , >C(OH)(CO 2 R 2 ), or >CHOR 6 ;
  • m is 0 or 1 ;
  • R 1 is independently hydrogen or a hydrocarbyl group, typically containing 1 to 150, 4 to 30, or 6 to 20, or 10 to 20, or 11 to 18, or 8 to 10 carbon atoms, with the proviso that when R 1 is hydrogen, m is 0, and n is more than or equal to l;
  • R 2 is a hydrocarbyl group, typically containing 1 to 150, 4 to 30, or 6 to 20, or 10 to 20, or 1 1 to 18, or 8 to 10 carbon atoms;
  • R 3 , R 4 and R 5 are independently hydrocarbyl groups or hydroxy - containing hydrocarbyl groups or carboxyl-containing hydrocarbyl groups;
  • R 6 is hydrogen or a hydrocarbyl group, typically containing 1 to 150, or 4 to 30 carbon atoms.
  • the lubricating composition is characterised as having at least one of (i) a sulphur content of 0.8 wt % or less, (ii) a phosphorus content of 0.2 wt % or less, or (iii) a sulphated ash content of 2 wt % or less. [0017] In one embodiment the invention the lubricating composition is characterised as having (i) a sulphur content of 0.5 wt % or less, (ii) a phosphorus content of 0.1 wt % or less, and (iii) a sulphated ash content of 1.5 wt % or less.
  • the invention provides a method of lubricating an internal combustion engine comprising, supplying to the internal combustion engine a lubricating compositions as disclosed herein.
  • the invention provides for the use of a lubricating composition as disclosed herein for providing at least one of (i) reducing or preventing phosphorus emissions, (ii) reducing or preventing sulphur emissions, (ii) wholly or partially replacing ZDDP in lubricating oils, (iii) improving fuel economy, and (iv) fuel economy retention/efficiency.
  • the invention provides for the use of a compound of Formula (1) as an antioxidant in a lubricant, wherein the compound of Formula (1) may be represented by: wherein
  • X is independently -Z-O-Z'-, >CH 2 , >CHR 4 , >CR 4 R 5 , >C(OH)(CO 2 R 2 ), >C(CO 2 R 2 ) 2 , or >CH0R 6 ;
  • Z and Z' are independently >CH 2 , >CHR 4 , >CR 4 R 5 , >C(OH)(CO 2 R 2 ), or >CH0R 6 ;
  • m is 0 or 1 ;
  • R 1 is independently hydrogen or a hydrocarbyl group, typically containing 1 to 150, 4 to 30, or 6 to 20, or 10 to 20, or 11 to 18, or 8 to 10 carbon atoms, with the proviso that when R 1 is hydrogen, m is 0, and n is more than or equal to l;
  • R 2 is a hydrocarbyl group, typically containing 1 to 150, 4 to 30, or 6 to 20, or 10 to 20, or 1 1 to 18, or 8 to 10 carbon atoms;
  • R 3 , R 4 and R 5 are independently hydrocarbyl groups
  • R 6 is hydrogen or a hydrocarbyl group, typically containing 1 to 150, or 4 to 30 carbon atoms.
  • the invention provides for the use of the compound of Formula (1) as an antioxidant in a lubricant, wherein the compound of Formula (1) is an ester (such as a monoester, a diester or a triester).
  • an ester such as a monoester, a diester or a triester
  • the invention provides for the use of the compound of Formula (1) as an antioxidant in a lubricant, wherein the compound of Formula (1) is not a citrate.
  • the invention provides for the use of a tartaric acid derivative (typically a tartrate ester) as an antioxidant in a lubricant.
  • a tartaric acid derivative typically a tartrate ester
  • the invention provides for the use of the compound of Formula (1) (typically a tartaric acid derivative) as an antioxidant in an internal combustion engine lubricant.
  • the present invention provides a lubricating composition and a method for lubricating an engine as disclosed above.
  • Oil-Soluble Molybdenum Compound oil-Soluble Molybdenum Compound
  • the oil-soluble molybdenum compound may have the functional performance of an antiwear agent, an antioxidant, a friction modifier, or mixtures thereof.
  • the oil-soluble molybdenum compound includes molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum sulphides, molybdenum carboxylates, molybdenum alkoxides, or mixtures thereof.
  • the molybdenum sulphides include molybdenum disulphide.
  • the molybdenum disulphide may be in the form of stable dispersions.
  • oil-soluble molybdenum compound may be selected from the group consisting of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment the oil-soluble molybdenum compound is a molybdenum dithio carbamate.
  • Suitable examples of molybdenum dithiocarbamates which may be used as an antioxidant include commercial materials sold under the trade names such as MoIy van 822TM and MolyvanTM A from R. T. Vanderbilt Co., Ltd., and Adeka Sakura-LubeTM S-100, S-165, S-515, and S-600 from Asahi Denka Kogyo K. K and mixtures thereof.
  • the oil-soluble molybdenum compound may be present in an amount sufficient to provide 0.5 ppm to 2000 ppm, 1 ppm to 700 ppm, 1 ppm to 550 ppm, 5 ppm to 300 ppm, or 20 ppm to 250 ppm of molybdenum.
  • Ashless Antiwear Agent 0.5 ppm to 2000 ppm, 1 ppm to 700 ppm, 1 ppm to 550 ppm, 5 ppm to 300 ppm, or 20 ppm to 250 ppm of molybdenum.
  • the compound of Formula (1) is an ashless antiwear agent, and it may also act as an antioxidant.
  • the compound of Formula (1) contains an imide group.
  • the compound of Formula (1) has m, n, X, and R 1 , R 2 and R 6 defined as follows: m is 0 or 1 , n is 1 to 2, X is >CHOR 6 , and R 1 , R 2 and R 6 are independently hydrocarbyl groups containing 4 to 30 carbon atoms.
  • Y and Y' are both -O-.
  • the compound of Formula (1) has m, n, X, Y, Y' and R 1 , R 2 and R 6 defined as follows: m is 0 or 1, n is 1 to 2, X is >CHOR 6 ; Y and Y' are both -O-, and R 1 , R 2 and R 6 are independently hydrogen or hydrocarbyl groups containing 4 to 30 carbon atoms.
  • the ashless antiwear agent includes imides, di- esters, di-amides, di-imides, ester-amides, ester-imides, or imide-amides. In one embodiment the antiwear agent includes imides, di-esters, di-amides, or ester- amides.
  • the di-esters, di-amides, ester-amide, ester-imide compounds of Formula (1) may be prepared by reacting a dicarboxylic acid (such as tartaric acid), with an amine or alcohol, optionally in the presence of a known esterification catalyst.
  • a dicarboxylic acid such as tartaric acid
  • an amine or alcohol optionally in the presence of a known esterification catalyst.
  • ester-imide compounds it is necessary to have at least three carboxylic acid groups (such as citric acid). h> tho oa.v. ol a di-imuk, u it- noecsMrv to tour earhowiie acid ⁇ roup;s
  • the amine or alcohol typically has sufficient carbon atoms to fulfill the requirements of R 1 and/or R 2 as defined in Formula (1).
  • R 1 and R 2 are independently linear or branched hydrocarbyl groups. In one embodiment the hydrocarbyl groups are branched. In one embodiment the hydrocarbyl groups are linear.
  • the R 1 and R 2 may be incorporated into Formula (1) by either an amine or an alcohol.
  • the alcohol includes both monohydric alcohol and polyhydric alcohol.
  • the carbon atoms of the alcohol may be linear chains, branched chains, or mixtures thereof.
  • Examples of a suitable branched alcohol include 2-ethylhexanol, isotridecanol, Guerbet alcohols, or mixtures thereof.
  • Examples of a monohydric alcohol include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, or mixtures thereof.
  • the monohydric alcohol contains 5 to 20 carbon atoms.
  • the alcohol includes either a monohydric alcohol or a polyhydric alcohol.
  • suitable polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,5-pentane diol, 1 ,6-hexane diol, glycerol, sorbitol, pentaerythritol, trimethylolpropane, starch, glucose, sucrose, methylglucoside, or mixtures thereof.
  • the polyhydric alcohol is used in a mixture along with a monohydric alcohol. Typically, in such a combination the monohydric alcohol constitutes at least 60 mole percent, or at least 90 mole percent of the mixture.
  • ashless antiwear agent is derived from tartaric acid.
  • the tartaric acid used for preparing the tartrates of the invention can be commercially available, and it is likely to exist in one or more isomeric forms such as d-tartaric acid, 1-tartaric acid or mesotartaric acid, often depending on the source (natural) or method of synthesis (from maleic acid).
  • a racemic mixture of d-tartaric acid and 1-tartaric acid is obtained from a catalysed oxidation of maleic acid with hydrogen peroxide (with tungstic acid catalyst).
  • These derivatives can also be prepared from functional equivalents to the diacid readily apparent to those skilled in the art, such as esters, acid chlorides, or anhydrides.
  • resultant tartrates may be solid, semi-solid, or oil depending on the particular alcohol used in preparing the tartrate.
  • the tartrates are advantageously soluble and/or stably dispersible in such oleaginous compositions.
  • compositions intended for use in oils are typically oil-soluble and/or stably dispersible in an oil in which they are to be used.
  • oil-soluble as used in this specification and appended claims does not necessarily mean that all the compositions in question are miscible or soluble in all proportions in all oils.
  • composition is soluble in an oil (mineral, synthetic, etc.) in which it is intended to function to an extent which permits the solution to exhibit one or more of the desired properties.
  • oil mineral, synthetic, etc.
  • solutions it is not necessary that such "solutions" be true solutions in the strict physical or chemical sense. They may instead be micro-emulsions or colloidal dispersions which, for the purpose of this invention, exhibit properties sufficiently close to those of true solutions to be, for practical purposes, interchangeable with them within the context of this invention.
  • the ashless antiwear agent includes a compound derived from a hydroxycarboxylic acid.
  • the ashless antiwear agent is derived from at least one of hydroxy-polycarboxylic acid di-ester, a hydroxy-polycarboxylic acid di-amide, a hydroxy-polycarboxylic acid di-imide, a hydroxy-polycarboxylic acid ester-amide, a hydroxy-polycarboxylic acid ester- imide, and a hydroxy-polycarboxylic acid imide-amide.
  • the ashless antiwear agent is derived from at least one of the group consisting of a hydroxy-polycarboxylic acid di-ester, a hydroxy-polycarboxylic acid di-amide, and a hydroxy-polycarboxylic acid ester-amide.
  • a suitable a hydroxycarboxylic acid examples include citric acid, tartaric acid, lactic acid, glycolic acid, hydroxy-propionic acid, hydroxyglutaric acid, or mixtures thereof.
  • ashless antiwear agent is derived from tartaric acid, citric acid, hydroxy-succinic acid, dihydroxy mono-acids, mono-hydroxy diacids, or mixtures thereof.
  • the ashless antiwear agent includes a compound derived from tartaric acid or citric acid.
  • the ashless antiwear agent includes a compound derived from tartaric acid.
  • the compound of Formula (1) is not a citrate.
  • US Patent Application 2005/198894 discloses suitable hydroxycarboxylic acid compounds, and methods of preparing the same. [0045] Canadian Patent 1183125; US Patent Publication numbers 2006/0183647 and US-2006-0079413; US Patent Application number 60/867402; and British Patent 2 105 743 A, all disclose examples of suitable tartaric acid derivatives.
  • the di-esters, di-amides, di-imides, ester-amide, ester-imide, imide-amide compounds are derived from a compound of Formula (1). In one embodiment the di-esters, di-amides, ester-amide, compounds are derived from a compound of Formula (1). [0047] A detailed description of methods for preparing suitable tartrimides (by reacting tartaric acid with a primary amine) is disclosed in US Patent 4,237,022.
  • the ashless antiwear agent includes imide, di- esters, di-amides, ester-amide derivatives of tartaric acid.
  • Examples of a suitable citric acid derivative include trialkyl citrates or borated trialkyl citrates. Suitable examples include triethyl citrate, tripentyl citrate with ethyl dipentyl citrate, borated triethyl citrate, tributyl citrate, triethyl citrate transesterified with 1 ,2-propandiol, triethyl O-acetyl citrate, triethyl citrate octadecyl succinate, or mixtures thereof.
  • suitable citrates include 2-ethylhexyl citrate, dodecyl citrate, or mixtures thereof.
  • the ashless antiwear agent of the invention may also function as rust and corrosion inhibitors, friction modifiers, antiwear agents and demulsifiers.
  • the ashless antiwear agent is not borated.
  • the ashless antiwear agent of the may be present at 0.01 wt % to 20 wt %, or 0.05 to 10 wt %, or 0.1 to 5 wt % of the lubricating composition. Oils of Lubricating Viscosity
  • the lubricating composition comprises an oil of lubricating viscosity.
  • oils include natural and synthetic oils, oil derived from hydrocracking, hydrogenation, and hydro finishing, unrefined, refined and re-refined oils and mixtures thereof.
  • Unrefined oils are those obtained directly from a natural or synthetic source generally without (or with little) further purification treatment.
  • Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Purification techniques are known in the art and include solvent extraction, secondary distillation, acid or base extraction, filtration, percolation and the like.
  • Re-refined oils are also known as reclaimed or reprocessed oils, and are obtained by processes similar to those used to obtain refined oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products.
  • Natural oils useful in making the inventive lubricants include animal oils, vegetable oils (e.g., castor oil,), mineral lubricating oils such as liquid petroleum oils and solvent -treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types and oils derived from coal or shale or mixtures thereof.
  • animal oils e.g., castor oil,
  • mineral lubricating oils such as liquid petroleum oils and solvent -treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types and oils derived from coal or shale or mixtures thereof.
  • Synthetic lubricating oils are useful and include hydrocarbon oils such as polymerized, oligomemed, or interpolymerised olefins (e.g., polybutylenes, polypropylenes, propyleneisobutylene copolymers); poly(l-hexenes), poly(l- octenes), rrimcrs or oligomers of 1-decenc e.g., poly(l-decenes), such materials being often referred to as poly ⁇ /-olefins, and mixtures thereof; alkyl-benzenes (e.g.
  • dodecylbenzenes dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)- benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls); diphenyl alkanes, alkylated diphenyl alkanes, alkylated diphenyl ethers and alkylated diphenyl sulphides and the derivatives, analogs and homologs thereof or mixtures thereof.
  • polyphenyls e.g., biphenyls, terphenyls, alkylated polyphenyls
  • diphenyl alkanes alkylated diphenyl alkanes, alkylated diphenyl ethers and alkylated diphenyl sulphides and the derivatives, analogs and homologs thereof or mixtures
  • Other synthetic lubricating oils include polyol esters (such as Prolube®3970), diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and the diethyl ester of decane phosphonic acid), or polymeric tetrahydrofurans.
  • Synthetic oils may be produced by Fischer-Tropsch reactions and typically may be hydroisomerised Fischer-Tropsch hydrocarbons or waxes. In one embodiment oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure as well as other gas-to-liquid oils.
  • Oils of lubricating viscosity may also be defined as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines.
  • the five base oil groups are as follows: Group I (sulphur content >0.03 wt %, and/or ⁇ 90 wt % saturates, viscosity index 80-120); Group II (sulphur content ⁇ 0.03 wt %, and >90 wt % saturates, viscosity index 80-120); Group III (sulphur content ⁇ 0.03 wt %, and >90 wt % saturates, viscosity index >120); Group IV (all polyalphaolefins (PAOs)); and Group V (all others not included in Groups I, II, III, or IV).
  • PAOs polyalphaolefins
  • the oil of lubricating viscosity comprises an API Group I, Group II, Group III, Group IV, Group V oil or mixtures thereof. Often the oil of lubricating viscosity is an API Group I, Group II, Group III, Group IV oil or mixtures thereof. Alternatively the oil of lubricating viscosity is often an API Group II, Group III or Group IV oil or mixtures thereof.
  • the amount of the oil of lubricating viscosity present is typically the balance remaining after subtracting from 100 wt % the sum of the amount of the ashless antiwear agent, the oil-soluble molybdenum compound and the other performance additives.
  • the lubricating composition may be in the form of a concentrate and/or a fully formulated lubricant. If the lubricating composition of the invention (comprising (i) the ashless antiwear agent and (ii) the oil-soluble molybdenum compound) is in the form of a concentrate (which may be combined with additional oil to form, in whole or in part, a finished lubricant), the ratio of the of components of the invention to the oil of lubricating viscosity and/or to diluent oil include the ranges of 1 :99 to 99: 1 by weight, or 80:20 to 10:90 by weight.
  • the composition optionally comprises other performance additives.
  • the other performance additives comprise at least one of metal deactivators, viscosity modifiers, detergents, friction modifiers (other than an oil-soluble molybdenum compound or a compound of Formula (I)), antiwear agents (other than the ashless antiwear agent of the invention), corrosion inhibitors, dispersants, dispersant viscosity modifiers, extreme pressure agents, antioxidants (other than an oil-soluble molybdenum compound of the invention), foam inhibitors, demulsifiers, pour point depressants, seal swelling agents and mixtures thereof.
  • fully-formulated lubricating oil will contain one or more of these performance additives.
  • the lubricating composition comprises the ashless antiwear agent and further comprises at least one of a viscosity modifier, an antioxidant, an overbased detergent, a succinimide dispersant, or mixtures thereof.
  • the lubricating composition comprising the ashless antiwear agent further comprises a phosphorus-containing antiwear agent.
  • the lubricant composition optionally further comprises other known neutral or overbased detergents.
  • Suitable detergent substrates include phenates, sulphur containing phenates, sulphonates, salixarates, salicylates, carboxylic acid, phosphorus acid, mono- and/or di- thiophosphoric acid, alkyl phenol, sulphur coupled alkyl phenol compounds, or saligenins.
  • the detergent substrate is typically salted with a metal such as calcium, magnesium, potassium, sodium, or mixtures thereof.
  • the lubricating composition further includes an overbased detergent.
  • the overbased detergent includes phenates, sulphur containing phenates, sulphonates, salixarates, salicylates, or mixtures thereof.
  • the detergent may be present at 0 wt % to 10 wt %, or 0.1 wt % to 8 wt %, or 1 wt % to 4 wt %, or greater than 4 to 8 wt %.
  • Dispersants may be present at 0 wt % to 10 wt %, or 0.1 wt % to 8 wt %, or 1 wt % to 4 wt %, or greater than 4 to 8 wt %.
  • Dispersants are often known as ashless-type dispersants because, prior to mixing in a lubricating oil composition, they do not contain ash-forming metals and they do not normally contribute any ash forming metals when added to a lubricant and polymeric dispersants.
  • Ashless type dispersants are characterised by a polar group attached to a relatively high molecular weight hydrocarbon chain.
  • Typical ashless dispersants include N-substituted long chain alkenyl succinimides. Examples of N-substituted long chain alkenyl succinimides include polyisobutylene succinimide with number average molecular weight of the polyisobutylene substituent in the range 350 to 5000, or 500 to 3000.
  • Succinimide dispersants and their preparation are disclosed, for instance in US Patent 3,172,892 or US Patent 4,234,435 or in EP 03558 ⁇ 5.
  • Succinimide dispersants are typically the imide formed from a polyamine, typically a poly(ethyleneamine).
  • the invention further comprises at least one poly ⁇ Nobutylcnc sueeimmide di;-pcrs>dnt dom ed from polybobutylcno with number average molecular weight in the range 350 to 5000, or 500 to 3000.
  • the polyisobutylene succinimide may be used alone or in combination with other dispersants.
  • the invention further comprises at least one dispersant derived from polyisobutylene succinic anhydride, an amine and zinc oxide to form a polyisobutylene succinimide complex with zinc.
  • the polyisobutylene succinimide complex with zinc may be used alone or in combination.
  • Mannich bases Another class of ashless dispersant is Mannich bases.
  • Mannich dispersants are the reaction products of alkyl phenols with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines).
  • the alkyl group typically contains at least 30 carbon atoms.
  • the dispersants may also be post-treated by conventional methods by a reaction with any of a variety of agents. Among these are boron, urea, thiourea, dimercaptothiadiazoles, carbon disulphide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, and phosphorus compounds.
  • the dispersant may be present at 0 wt % to 20 wt %, or 0.1 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 1 wt % to 6 wt %, or 7 wt % to 12 wt % of the lubricating composition.
  • Antioxidants may be present at 0 wt % to 20 wt %, or 0.1 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 1 wt % to 6 wt %, or 7 wt % to 12 wt % of the lubricating composition.
  • Antioxidant compounds include for example, sulphurised olefins (typically sulphurised 4-carbobutoxy cyclohexene, or triphenylphosphite equivalents thereof, or olefin sulphide), alkylated diphenylamines (e.g., nonyl diphenyluinioe, typically di-nonyl diphenylamine, octyl diphenylamine, di-octyl diphenylamine), hindered phenols, or mixtures thereof.
  • Antioxidant compounds may be used alone or in combination.
  • the antioxidant may be present in ranges 0 wt % to 20 wt %, or 0.1 wt % to 10 wt %, or 1 wt % to 5 wt %, of the lubricating composition.
  • the hindered phenol antioxidant often contains a secondary butyl and/or a tertiary butyl group as a sterically hindering group.
  • the phenol group is often further substituted with a hydrocarbyl group and/or a bridging group linking to a second aromatic group.
  • Suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4- ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di- tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol.
  • the hindered phenol antioxidant is an ester and may include, e.g., IrganoxTM L-135 from Ciba or an ;:ddiuoo product derived from 2,6-di-tert-butylphenol and an alkyl acrylate, wherein the alkyl group may contain 1 to 18, or 2 to 12, or 2 to 8, or 2 to 6, or 4 carbon atoms.
  • IrganoxTM L-135 from Ciba or an ;:ddiuoo product derived from 2,6-di-tert-butylphenol and an alkyl acrylate, wherein the alkyl group may contain 1 to 18, or 2 to 12, or 2 to 8, or 2 to 6, or 4 carbon atoms.
  • suitable ester- containing hindered phenol antioxidant chemistry is found in US Patent 6,559,105.
  • the lubricant does not contain (or contains reduced amounts of) phenolic antioxidant, when the compound of Formula (1) is employed.
  • This embodiment may be useful because the compound of Formula (1) may be used as a partial or whole replacement for phenolic antioxidants. It is believed that during the preparation of tertiary butyl phenols trace amounts of an impurity tris-tert-butyl phenol are formed and retained in the final product. Tris- tert-butyl phenol is known to bioaccumulate and builds up to high concentrations in sediment. Thus employing the compound of Formula (1) as an antioxidant may allow for reduction of bioaccumulants. Viscosity Modifiers
  • Viscosity modifiers include hydrogenated copolymers of styrene- butadiene, ethylene-propylene copolymers, polyisobutenes, hydrogenated styrene-isoprene polymers, hydrogenated isoprene polymers, polymethacrylates, poly aery lates, polyalkyl styrenes, hydrogenated alkenyl aryl conjugated diene copolymers, polyolefins, esters of maleic anhydride-styrene copolymers, or caters of (alpha-olefin maleic anhydride) copolymers, or mixtures thereof.
  • Dispersant Viscosity Modifiers include hydrogenated copolymers of styrene- butadiene, ethylene-propylene copolymers, polyisobutenes, hydrogenated styrene-isoprene polymers, hydrogenated isoprene polymers, polymethacrylates, poly
  • Dispersant viscosity modifiers include functionalised polyolefins, for example, ethylene-propylene copolymers that have been functionalised with the reaction product of an acylating agent (such as maleic anhydride) and an amine; polymethacrylates functionalised with an amine, or esterified maleic anhydride-styrene copolymers reacted with an amine.
  • an acylating agent such as maleic anhydride
  • the total amount of viscosity modifier and/or dispersant viscosity modifier may be 0 wt % to 20 wt %, 0.1 wt % to 15 wt %, or 0.1 wt % to 10 wt %, of the lubricating composition.
  • Antiwear Agents 0 wt % to 20 wt %, 0.1 wt % to 15 wt %, or 0.1 wt % to 10 wt %, of the lubricating composition.
  • the lubricant composition optionally further comprises at least one other antiwear agent other than the ashless antiwear agent of the invention.
  • suitable antiwear agents include phosphate esters, sulphurised olefins, sulphur-containing anti-wear additives including metal dihydrocarbyldithiophosphates (such as zinc dialkyldithiophosphates), thiocarbamate-containing compounds including, thiocarbamate esters, alkylene- coupled thiocarbamates, and bis(S-alkyldithiocarbamyl) disulphides.
  • the dithiocarbamate-containing compounds may be prepared by reacting a di thiocarbamate acid or salt with an unsaturated compound.
  • the dithio carbamate containing compounds may also be prepared by simultaneously reacting an amine, carbon disulphide and an unsaturated compound. Generally, the reaction occurs at a temperature of 25 0 C to 125 0 C.
  • US Patents 4,758,362 and 4,997,969 describe dithiocarbamate compounds and methods of making them.
  • Suitable olefins that may be sulphurised to form an the sulphurised olefin include propylene, butylene, isobutylene, pentene, hexane, heptene, octane, nonene, decene, undecene, dodecene, undecyl, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, octadecenene, nonodecene, eicosene or mixtures thereof.
  • hexadecene, heptadecene, octadecene, octadecenene, nonodecene, eicosene or mixtures thereof and their dimers, trimers and tetramers are especially useful olefins.
  • the olefin may be a Diels-Alder adduct of a diene such as 1,3-butadiene and an unsaturated ester, such as, butylacrylate.
  • Another class of sulphurised olefin includes fatty acids and their esters. The fatty acids are often obtained from vegetable oil or animal oil and typically contain 4 to 22 carbon atoms.
  • Suitable fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid or mixtures thereof. Often, the fatty acids are obtained from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil or mixtures thereof. In one embodiment fatty acids and/or ester are mixed with olefins, such as « -olefins.
  • the ashless antiwear agent (which may also be described as a friction modifier) may be a monoester of a polyol and an aliphatic carboxylic acid, often an acid containing 12 to 24 carbon atoms.
  • the monoester of a polyol and an aliphatic carboxylic acid is in the form of a mixture with a sunflower oil or the like, which may be present in the ashless antiwear agent mixture include 5 to 95, or in other embodiments 10 to 90, or 20 to 85, or 20 to 80 weight percent of said mixture.
  • the aliphatic carboxylic acids which form the esters are those acids typically containing 12 to 24 or 14 to 20 carbon atoms. Examples of carboxylic acids include dodecanoic acid, stearic acid, lauric acid, behenic acid, and oleic acid.
  • 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; butanediol; hexanediol; sorbitol; arabitol; mannitol; sucrose; fructose; glucose; cyclohexane diol; erythritol; and pentaerythritols, including di- and tripentaerythritol.
  • the polyol is diethyl- ene glycol, triethylene glycol, glycerol, sorbitol, pentaerythritol or dipentaerythritol.
  • the commercial material known as glycerol monooleate 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 the amounts of the commercial grade material.
  • the antiwear agent may be present in ranges including 0 wt % to 15 wt %, or 0 wt % to 10 wt %, or 0.05 wt % to 5 wt %, or 0.1 wt % to 3 wt % of the lubricating composition.
  • the lubricating composition is free of zinc dihydrocarbyl dithiophosphate. In one embodiment the lubricating composition further includes zinc dihydrocarbyl dithiophosphate. Extreme Pressure Agents
  • EP agents that are soluble in the oil include sulphur- and chlorosulphur-containing EP agents, chlorinated hydrocarbon EP agents and phosphorus EP agents.
  • EP agents include chlorinated wax; organic sulphides and polysulphides such as dibenzyldisulphide, bis-(chlorobenzyl) disulphide, dibutyl tetrasulphide, sulphurised methyl ester of oleic acid, sulphurised alkylphenol, sulphurised dipentene, sulphurised terpene, and sulphurised Diels-Alder adducts; phosphosulphurised hydrocarbons such as the reaction product of phosphorus sulphide with turpentine or methyl oleate; phosphorus esters such as the dihydrocarbon and trihydrocarbon phosphites, e.g., dibutyl phosphite, diheptyl phos
  • the friction modifier may be present in ranges including 0 wt % to 10 wt %, or 0.05 wt % to 8 wt %, or 0.1 wt % to 4 wt %.
  • suitable friction modifiers include long chain fatty acid derivatives of long chain fatty acid derivatives of amines, esters, or epoxides; fatty imidazolines (that is, long chain fatty amides, long chain fatly enters, long chairs fatty epoxide derivatives, and long chain fatty imidazolines); and amine salts of alkylphosphoric acids.
  • Friction modifiers may also encompass materials such as sulphurised fatty compounds and olefins, triglycerides (e.g. sunflower oil) or monoester of a polyol and an aliphatic carboxylic acid (all these friction modifiers have been described as antioxidants or antiwear agents).
  • materials such as sulphurised fatty compounds and olefins, triglycerides (e.g. sunflower oil) or monoester of a polyol and an aliphatic carboxylic acid (all these friction modifiers have been described as antioxidants or antiwear agents).
  • the friction modifier is a long chain fatty amide, a long chain farry ester, a long chain fatty epoxide derivatives, or a long chain fatty imidazoline.
  • the friction modifier is a long chain fatty acid ester (previously described above as an ashless antiwear agent).
  • the long chain fatty acid ester is a mono-ester and in another embodiment the long chain fatty acid ester is a (tri)glyceride.
  • corrosion inhibitors include those described in paragraphs 5 to 8 of US Application US05/038319 (filed on October 25, 2004 McAtee and Boyer as named inventors), octylamine octanoate, and condensation products of dodecenyl succinic acid or anhydride and a fatty acid such as oleic acid with a polyamine.
  • the corrosion inhibitors include the Synalox® corrosion inhibitor.
  • the Synalox® corrosion inhibitor is typically a homopolymer or copolymer of propylene oxide.
  • the Synalox® corrosion inhibitor is described in more detail in a product brochure with Form No. 118-01453-0702 AMS, published by The Dow Chemical Company.
  • the product brochure is entitled "SYNALOX Lubricants, High-Performance Polyglycols for Demanding Applications.”
  • Metal deactivators including derivatives of benzotriazoles (typically tolyltriazole), dimercaptothiadiazole derivatives, 1 ,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles, or 2-alkyldithiobenzothiazoles; foam inhibitors including copolymers of ethyl acrylate and 2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylates, polyacrylates or polyacrylamides.
  • the lubricating composition may be utilised in a range of surfaces typically found in mechanical devices, including aluminum- alloy surfaces.
  • the mechanical devices include an internal combustion engine, a gearbox, an automatic transmission, a hydraulic or a turbine.
  • the lubricating composition may be an engine oil, a gear oil, an automatic transmission oil, a hydraulic fluid, a turbine oil, a metal working fluid or a circulating oil.
  • the mechanical device is an internal combustion engine.
  • the internal combustion engine may be a diesel fuelled engine, a gasoline fuelled engine, a natural gas fuelled engine or a mixed gasoline/alcohol fuelled engine.
  • the internal combustion engine may be a diesel fuelled engine and in another embodiment a gasoline fuelled engine.
  • the internal combustion engine may be a 2-stroke or 4-stroke engine. Suitable internal combustion engines include marine diesel engines, aviation piston engines, low-load diesel engines, and automobile and truck engines. [0099] In one embodiment the internal combustion engine contains components of an aluminium-alloy.
  • the aluminium-alloy includes aluminium silicates, aluminium oxides, or other ceramic materials. In one embodiment the aluminium-alloy is an aluminium-silicate surface. As used herein, the term
  • ⁇ aluminum alloy'' is intended to be synonymous with "aluminium composite' 1 and to describe a component or surface comprising aluminium and another component intermixed or reacted on a microscopic or nearly microscopic level, regardless of the detailed structure thereof. This would include any conventional a lloys ⁇ with metals other than aluminium as well as composite or alloy-like structures with non-metallic elements or compounds such as with ceramie-likc materials.
  • the lubricant composition for an internal combustion engine may be suitable for any engine lubricant irrespective of the sulphur, phosphorus or sulphated ash (ASTM D-874) content.
  • the sulphur content of the engine oil lubricant may be 1 wt % or less, or 0.8 wt % or less, or 0.5 wt % or less, or 0.3 wt % or less. In one embodiment the sulphur content may be in the range of 0.001 wt % to 0.5 wt %, or 0.01 wt % to 0.3 wt %.
  • the phosphorus content may be 0.2 wt % or less, or 0.1 wt % or less, or 0.085 wt % or less, or even 0.06 wt % or less, 0.055 wt % or less, or 0.05 wt % or less. In one embodiment the phosphorus content may be 100 ppm to 1000 ppm, or 325 ppm to 700 ppm.
  • the total sulphated ash content may be 2 wt % or less, or 1.5 wt % or less, or 1.1 wt % or less, or 1 wt % or less, or 0.8 wt % or less, or 0.5 wt % or less.
  • the sulphated ash content may be 0.05 wt % to 0.9 wt %, or 0.1 wt % or 0.2 wt % to 0.45 wt %.
  • the sulphur content is 0.4 wt % or less, the phosphorus content is 0-08 wt % or less, and the sulphated ash is I wt % or less.
  • the sulphur content is 0.3 wt% or less, the phosphorus content is 0.05 wt % or less, and the sulphated asb is 0.8 wt % or less.
  • the lubricating composition is an engine oil, wherein the lubricating composition is characterised as having (i) a sulphur content of 0.5 wt % or less, (ii) a phosphorus content of 0.1 wt % or less, and (iii) a sulphated ash content of 1.5 wt % or less.
  • the lubricating composition is suitable for a 2- stroke or a 4-stroke marine diesel internal combustion engine. In one embodiment the marine diesel combustion engine is a 2-stroke engine.
  • the ashless antiwear agent of the invention may be added to a marine diesel lubricating composition at 0.01 to 20 wt %, or 0.05 to 10 wt %, or 0.1 to 5 wt %.
  • diluent oil constitutes 20 wt % to 90 wt % of each component.
  • diluent oil constitutes 20 wt % to 90 wt % of each component.
  • antiwear agents, corrosion inhibitors, antioxidants the amounts shown are on an actives basis i.e. excluding diluent oil because the components are typically not carried in diluent oil.
  • Example 1 A lubricating composition is prepared containing 1 wt % of di-2-ethylhexyl tartrate, 0.6 wt % of other antiwear agents, 7.9 wt % of dispersants, 1.5 wt % of detergents, 3.6 wt % of antioxidants including an effective amount of molybdenum dithiocarbamate, 6.1 wt % of viscosity modifier, 0.1 wt % of corrosion inhibitor, and 0.1 wt % of friction modifier.
  • the lubricating composition has a sulphated ash content of 0.6 wt %, a phosphorus content of about 570 ppm, and a sulphur content of 0.17 wt %.
  • the lubricating composition has a phosphorus content of about 560 ppm.
  • Comparative Example 1 is similar to Example 2 except the composition does not contain 0.7 wt % of molybdenum dithiocarbamate, nor 1 wt % of a Ci 2 -i 4 -alkyl tartrate.
  • Comparative Example 2 (CE2): is similar to Example 2 except the composition does not contain 0.7 wt % of molybdenum dithiocarbamate.
  • Comparative Example 3 (CE3): is similar to Example 2 except the composition does not contain 1 wt % of a Ci 2 -i 4 -alkyl tartrate. [0110] 10 g samples of the examples above are each treated with one volume percent of cumene hydroperoxide.
  • HFRR isothermal temperature high frequency reciprocating rig
  • the lubricating composition of the invention is capable of providing at least one of (i) reducing or preventing phosphorus emissions, (ii) reducing or preventing sulphur emissions, (ii) wholly or partially replacing ZDDP in lubricating oils, (iii) improving fuel economy, and (iv) fuel economy retention/efficiency.
  • Example 3 (EX3): A lubricating composition is designed to meet Euro 4 and Euro 5 emission standards and containing 1 wt % of C 8-10 alkyl tartrate.
  • the lubricating composition has a phosphorus content of 900 ppm or less, 0.3 wt % or less of sulphur, and U ⁇ * wt % or less of sulphated ash.
  • Example 4 A lubricating composition is designed to meet Euro 4 and Euro 5 emission standards and containing 1 wt % of C 8-10 alkyl tartrate.
  • the lubricating composition has a phosphorus content of 500 ppm or less, 0.2 wt % or less of sulphur, and 0.5 wt % or less of sulphated ash.
  • Comparative Examples 4 (CE4) and 5 (CE5) are lubricating composition similar to EX3 and EX4 respectively, except the C 8-10 alkyl tartrate is not included.
  • hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
  • hydrocarbyl groups include:
  • hydrocarbon substituents 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), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulphoxy);
  • 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.
  • Heteroatoms include sulphur, oxygen, nitrogen, and encompass substituents as pyridyl, furyl, thienyl and imidazolyl. In general, 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

The invention provides a lubricating composition containing an oil of lubricating viscosity, an oil soluble molybdenum compound, and an ashless antiwear agent. The invention further provides for a new antioxidant. The lubricating composition is suitable for lubricating an internal combustion engine.

Description

LUBRICATING COMPOSITION CONTAINING ASHFREE ANTIWEAR AGENT
BASED ON HYDROXYPOLYCARBOXYLIC ACID DERIVATIVE AND A
MOLYBDENUM COMPOUND
FIELD OF INVENTION
The invention provides a lubricating composition containing an oil of lubricating viscosity, an oil soluble molybdenum compound, and an ashless antiwear agent. The invention further provides for a new antioxidant. The lubricating composition is suitable for lubricating an internal combustion engine.
BACKGROUND OF THE INVENTION
[0001] Engine manufacturers have focused on improving engine design in order to improve fuel economy and efficiency (typically, based on Federal Corporate Average Fuel Economy (CAFE) standards). Whilst improvements in engine design and operation have contributed, improved formulation of engine oil lubricant may also improve fuel economy and efficiency. Lubricants function to reduce and disperse engine deposits which accumulate when the engines are running. They also serve to reduce the friction between sliding moving parts (typically metallic or ceramic) that are in contact.
[0002] It is well known for lubricating oils to contain a number of additives (including antiwear agents, antioxidants, dispersants, detergents etc.) used to protect the mechanical devices such as internal combustion engines from wear, oxidation, soot deposits and acidity build up. A common antiwear additive for engine lubricating oils is zinc dialkyldithiophosphate (ZDDP). It is believed that ZDDP antiwear additives protect the engine by forming a protective film on metal surfaces. ZDDP is also believed to have a detrimental impact on fuel economy and efficiency. Consequently, engine lubricants also contain friction modifier to obviate the detrimental impact of ZDDP on fuel economy and efficiency. Both ZDDP and friction modifier function by adsorption on sliding surfaces, and each may interfere with each other's respective functions. [0003] Further, engine lubricants containing phosphorus compounds and sulphur have been shown to contribute in part to particulate emissions, and emissions of other pollutants. In addition, sulphur and phosphorus tend to poison the catalysts used in catalytic converters, resulting in a reduction in performance of said catalysts. [0004] With increasing control of emissions (often associated with contributing to NOx formation, SOx formation, formation of sulphated ash and reducing the efficiency of after-treatment catalytic converters) there is a desire towards reduced amounts of sulphur, phosphorus and sulphated ash in engine oils. However, reducing the levels of antiwear additives such as ZDDP, is likely to increase wear and result in other detrimental performance of an engine. [0005] In addition, as technology develops, components of an engine are exposed to more severe operating conditions. Operating conditions may include higher power density engines, use of turbo chargers, use of alternative fuels and the like. Under many severe operating conditions, oxidation of lubricant and components occurs more readily. Thus there is a need to reduce oxidation, that in turn may also increase equipment longevity, or reliability. [0006] International Publication WO 2005/087904 discloses a lubricant composition containing at least one hydroxycarboxylic acid ester or hydroxy polycarboxylic acid. The lubricant composition disclosed may also contain zinc dihydrocarbyldithiophosphates, or other phosphorous-containing additives such as trilauryl phosphate or triphenylphosphorothionate. The lubricant composition has anti-wear or anti-fatigue properties.
[0007] International Publication WO 2006/04441 1 discloses a low-sulphur, low-phosphorus, low-ash lubricant composition suitable for lubricating an internal combustion engine, containing a tartrate ester, or amide having 1 to 150 carbon atoms per ester of amide group.
[0008] US Patent 5,338,470 discloses alkylated citric acid derivatives obtained as a reaction product of citric acid and an alkyl alcohol or amine. The alkylated citric acid derivative is effective as an antiwear agent and friction modifier.
[0009] U.S. Patent 4,237,022 discloses tartrimides useful as additives in lubricants and fuels for effective reduction in squeal and friction as well as improvement in fuel economy.
[0010] U.S. Patent 4,952,328 discloses lubricating oil compositions for internal combustion engines, comprising (A) oil of lubricating viscosity, (B) a carboxylic derivative produced by reacting a succinic acylating agent with certain amines, and (C) a basic alkali metal salt of sulphonic or carboxylic acid. [0011] U.S. Patent 4,326,972 discloses lubricant compositions for improving fuel economy of internal combustion engines. The composition includes a specific sulphurised composition (based on an ester of a carboxylic acid) and a basic alkali metal sulphonate.
[0012] U.S. Patent Application 60/867534 discloses malonate esters suitable as antiwear agents.
[0013] Canadian Patent CA 1 183 125 discloses lubricants for gasoline engines containing alkyl-ester tartrates, where the sum of carbon atoms on the alkyl groups is at least 8.
[0014] Consequently, it would be desirable to provide a lubricating composition capable of providing at least one of (i) reducing or preventing phosphorus emissions, (ii) reducing or preventing sulphur emissions, (ii) wholly or partially replacing ZDDP in lubricating oils, (iii) improving fuel economy, (iv) fuel economy retention/efficiency, and (v) oxidation control. The present invention provides an antiwear agent capable of achieving at least one of (i), (ii) (iii), (iv), and (v). In addition it may also be desirable for the antiwear agent to not have a detrimental affect on other components of a mechanical device. It may also be desirable for the antiwear agent to have antioxidant performance.
SUMMARY OF THE INVENTION
[0015] In one embodiment the invention provides a lubricating composition comprising an oil of lubricating viscosity, an oil-soluble molybdenum compound, and an ashless antiwear agent represented by Formula (1):
Figure imgf000004_0001
Formula (1) wherein
Y and Y' are independently -O-, >NH, >NR3, or an imide group formed by taking together both Y and Y' groups and forming a R*-N< group between two >C=O groups;
X is independently -Z-O-Z'-, >CH2, >CHR4, >CR4R5, >C(OH)(CO2R2), >C(CO2R2)2, >CC1I.;CO2R% or >CHOR6; Z and Z' are independently >CH2, >CHR4, >CR4R5, >C(OH)(CO2R2), or >CHOR6; n is 0 to 10, or 1 to 8, or 1 to 6, or 2 to 6, or 2 to 4, with the proviso that when n=l, X is not >CH2, and when n=2, both X's are not Mmulianeously >CH2; m is 0 or 1 ;
R1 is independently hydrogen or a hydrocarbyl group, typically containing 1 to 150, 4 to 30, or 6 to 20, or 10 to 20, or 11 to 18, or 8 to 10 carbon atoms, with the proviso that when R1 is hydrogen, m is 0, and n is more than or equal to l;
R2 is a hydrocarbyl group, typically containing 1 to 150, 4 to 30, or 6 to 20, or 10 to 20, or 1 1 to 18, or 8 to 10 carbon atoms;
R3, R4 and R5 are independently hydrocarbyl groups or hydroxy - containing hydrocarbyl groups or carboxyl-containing hydrocarbyl groups; and
R6 is hydrogen or a hydrocarbyl group, typically containing 1 to 150, or 4 to 30 carbon atoms.
[0016] In one embodiment the lubricating composition is characterised as having at least one of (i) a sulphur content of 0.8 wt % or less, (ii) a phosphorus content of 0.2 wt % or less, or (iii) a sulphated ash content of 2 wt % or less. [0017] In one embodiment the invention the lubricating composition is characterised as having (i) a sulphur content of 0.5 wt % or less, (ii) a phosphorus content of 0.1 wt % or less, and (iii) a sulphated ash content of 1.5 wt % or less.
[0018] In one embodiment the invention provides a method of lubricating an internal combustion engine comprising, supplying to the internal combustion engine a lubricating compositions as disclosed herein.
[0019] In one embodiment the invention provides for the use of a lubricating composition as disclosed herein for providing at least one of (i) reducing or preventing phosphorus emissions, (ii) reducing or preventing sulphur emissions, (ii) wholly or partially replacing ZDDP in lubricating oils, (iii) improving fuel economy, and (iv) fuel economy retention/efficiency.
[0020] In one embodiment the invention provides for the use of a compound of Formula (1) as an antioxidant in a lubricant, wherein the compound of Formula (1) may be represented by:
Figure imgf000006_0001
wherein
Y and Y' are independently -O-, >NH, >NR3, or an imide group formed by taking together both Y and Y' groups and forming a Rx-N< group between two >C=O groups;
X is independently -Z-O-Z'-, >CH2, >CHR4, >CR4R5, >C(OH)(CO2R2), >C(CO2R2)2, or >CH0R6;
Z and Z' are independently >CH2, >CHR4, >CR4R5, >C(OH)(CO2R2), or >CH0R6; n is 0 to 10, or 1 to 8, or 1 to 6, or 2 to 6, or 2 to 4, with the proviso that when n=l, X is not >CH2, and when n=2, both X's are not >CH2; m is 0 or 1 ;
R1 is independently hydrogen or a hydrocarbyl group, typically containing 1 to 150, 4 to 30, or 6 to 20, or 10 to 20, or 11 to 18, or 8 to 10 carbon atoms, with the proviso that when R1 is hydrogen, m is 0, and n is more than or equal to l;
R2 is a hydrocarbyl group, typically containing 1 to 150, 4 to 30, or 6 to 20, or 10 to 20, or 1 1 to 18, or 8 to 10 carbon atoms;
R3, R4 and R5 are independently hydrocarbyl groups; and
R6 is hydrogen or a hydrocarbyl group, typically containing 1 to 150, or 4 to 30 carbon atoms.
[0021] In one embodiment the invention provides for the use of the compound of Formula (1) as an antioxidant in a lubricant, wherein the compound of Formula (1) is an ester (such as a monoester, a diester or a triester).
[0022] In one embodiment the invention provides for the use of the compound of Formula (1) as an antioxidant in a lubricant, wherein the compound of Formula (1) is not a citrate.
[0023] In one embodiment the invention provides for the use of a tartaric acid derivative (typically a tartrate ester) as an antioxidant in a lubricant. [0024] In one embodiment the invention provides for the use of the compound of Formula (1) (typically a tartaric acid derivative) as an antioxidant in an internal combustion engine lubricant.
DETAILED DESCRIPTION OF THE INVENTION
[0025] The present invention provides a lubricating composition and a method for lubricating an engine as disclosed above. Oil-Soluble Molybdenum Compound)
[0026] The oil-soluble molybdenum compound may have the functional performance of an antiwear agent, an antioxidant, a friction modifier, or mixtures thereof. Typically, the oil-soluble molybdenum compound includes molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum sulphides, molybdenum carboxylates, molybdenum alkoxides, or mixtures thereof. The molybdenum sulphides include molybdenum disulphide. The molybdenum disulphide may be in the form of stable dispersions. In one embodiment the oil-soluble molybdenum compound may be selected from the group consisting of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment the oil-soluble molybdenum compound is a molybdenum dithio carbamate.
[0027] Suitable examples of molybdenum dithiocarbamates which may be used as an antioxidant include commercial materials sold under the trade names such as MoIy van 822™ and Molyvan™ A from R. T. Vanderbilt Co., Ltd., and Adeka Sakura-Lube™ S-100, S-165, S-515, and S-600 from Asahi Denka Kogyo K. K and mixtures thereof.
[0028] The oil-soluble molybdenum compound may be present in an amount sufficient to provide 0.5 ppm to 2000 ppm, 1 ppm to 700 ppm, 1 ppm to 550 ppm, 5 ppm to 300 ppm, or 20 ppm to 250 ppm of molybdenum. Ashless Antiwear Agent
[0029] In one embodiment the compound of Formula (1) is an ashless antiwear agent, and it may also act as an antioxidant. [0030] In one embodiment the compound of Formula (1) contains an imide group. The imide group is typically formed by taking together the Y and Y' groups and forming a R*-N< group between two >C=O groups. [0031] In one embodiment the compound of Formula (1) has m, n, X, and R1, R2 and R6 defined as follows: m is 0 or 1 , n is 1 to 2, X is >CHOR6, and R1, R2 and R6 are independently hydrocarbyl groups containing 4 to 30 carbon atoms. [0032] In one embodiment Y and Y' are both -O-.
[0033] In one embodiment the compound of Formula (1) has m, n, X, Y, Y' and R1, R2 and R6 defined as follows: m is 0 or 1, n is 1 to 2, X is >CHOR6; Y and Y' are both -O-, and R1, R2 and R6 are independently hydrogen or hydrocarbyl groups containing 4 to 30 carbon atoms.
[0034] In one embodiment the ashless antiwear agent includes imides, di- esters, di-amides, di-imides, ester-amides, ester-imides, or imide-amides. In one embodiment the antiwear agent includes imides, di-esters, di-amides, or ester- amides.
[0035] The di-esters, di-amides, ester-amide, ester-imide compounds of Formula (1) may be prepared by reacting a dicarboxylic acid (such as tartaric acid), with an amine or alcohol, optionally in the presence of a known esterification catalyst. In the case of ester-imide compounds it is necessary to have at least three carboxylic acid groups (such as citric acid). h> tho oa.v. ol a di-imuk, u it- noecsMrv to
Figure imgf000008_0001
tour earhowiie acid ήroup;s The amine or alcohol typically has sufficient carbon atoms to fulfill the requirements of R1 and/or R2 as defined in Formula (1).
[0036] In one embodiment R1 and R2 are independently linear or branched hydrocarbyl groups. In one embodiment the hydrocarbyl groups are branched. In one embodiment the hydrocarbyl groups are linear. The R1 and R2 may be incorporated into Formula (1) by either an amine or an alcohol. The alcohol includes both monohydric alcohol and polyhydric alcohol. The carbon atoms of the alcohol may be linear chains, branched chains, or mixtures thereof. [0037] Examples of a suitable branched alcohol include 2-ethylhexanol, isotridecanol, Guerbet alcohols, or mixtures thereof.
[0038] Examples of a monohydric alcohol include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, or mixtures thereof. In one embodiment the monohydric alcohol contains 5 to 20 carbon atoms.
[0039] The alcohol includes either a monohydric alcohol or a polyhydric alcohol. Examples of a suitable polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,5-pentane diol, 1 ,6-hexane diol, glycerol, sorbitol, pentaerythritol, trimethylolpropane, starch, glucose, sucrose, methylglucoside, or mixtures thereof. In one embodiment the polyhydric alcohol is used in a mixture along with a monohydric alcohol. Typically, in such a combination the monohydric alcohol constitutes at least 60 mole percent, or at least 90 mole percent of the mixture.
[0040] In one embodiment ashless antiwear agent is derived from tartaric acid. The tartaric acid used for preparing the tartrates of the invention can be commercially available, and it is likely to exist in one or more isomeric forms such as d-tartaric acid, 1-tartaric acid or mesotartaric acid, often depending on the source (natural) or method of synthesis (from maleic acid). For example a racemic mixture of d-tartaric acid and 1-tartaric acid is obtained from a catalysed oxidation of maleic acid with hydrogen peroxide (with tungstic acid catalyst). These derivatives can also be prepared from functional equivalents to the diacid readily apparent to those skilled in the art, such as esters, acid chlorides, or anhydrides.
[0041] When the compound of Formula (1) is derived from tartaric acid, resultant tartrates may be solid, semi-solid, or oil depending on the particular alcohol used in preparing the tartrate. For use as additives in a lubricating composition the tartrates are advantageously soluble and/or stably dispersible in such oleaginous compositions. For example, compositions intended for use in oils are typically oil-soluble and/or stably dispersible in an oil in which they are to be used. The term "oil-soluble" as used in this specification and appended claims does not necessarily mean that all the compositions in question are miscible or soluble in all proportions in all oils. Rather, it is intended to mean that the composition is soluble in an oil (mineral, synthetic, etc.) in which it is intended to function to an extent which permits the solution to exhibit one or more of the desired properties. Similarly, it is not necessary that such "solutions" be true solutions in the strict physical or chemical sense. They may instead be micro-emulsions or colloidal dispersions which, for the purpose of this invention, exhibit properties sufficiently close to those of true solutions to be, for practical purposes, interchangeable with them within the context of this invention.
[0042] In one embodiment the ashless antiwear agent includes a compound derived from a hydroxycarboxylic acid. In one embodiment the ashless antiwear agent is derived from at least one of hydroxy-polycarboxylic acid di-ester, a hydroxy-polycarboxylic acid di-amide, a hydroxy-polycarboxylic acid di-imide, a hydroxy-polycarboxylic acid ester-amide, a hydroxy-polycarboxylic acid ester- imide, and a hydroxy-polycarboxylic acid imide-amide. In one embodiment the ashless antiwear agent is derived from at least one of the group consisting of a hydroxy-polycarboxylic acid di-ester, a hydroxy-polycarboxylic acid di-amide, and a hydroxy-polycarboxylic acid ester-amide.
[0043] Examples of a suitable a hydroxycarboxylic acid include citric acid, tartaric acid, lactic acid, glycolic acid, hydroxy-propionic acid, hydroxyglutaric acid, or mixtures thereof. In one embodiment ashless antiwear agent is derived from tartaric acid, citric acid, hydroxy-succinic acid, dihydroxy mono-acids, mono-hydroxy diacids, or mixtures thereof. In one embodiment the ashless antiwear agent includes a compound derived from tartaric acid or citric acid. In one embodiment the ashless antiwear agent includes a compound derived from tartaric acid. In one embodiment the compound of Formula (1) is not a citrate. [0044] US Patent Application 2005/198894 discloses suitable hydroxycarboxylic acid compounds, and methods of preparing the same. [0045] Canadian Patent 1183125; US Patent Publication numbers 2006/0183647 and US-2006-0079413; US Patent Application number 60/867402; and British Patent 2 105 743 A, all disclose examples of suitable tartaric acid derivatives.
[0046] In one embodiment the di-esters, di-amides, di-imides, ester-amide, ester-imide, imide-amide compounds are derived from a compound of Formula (1). In one embodiment the di-esters, di-amides, ester-amide, compounds are derived from a compound of Formula (1). [0047] A detailed description of methods for preparing suitable tartrimides (by reacting tartaric acid with a primary amine) is disclosed in US Patent 4,237,022.
[0048] In one embodiment the ashless antiwear agent includes imide, di- esters, di-amides, ester-amide derivatives of tartaric acid.
[0049] Examples of a suitable citric acid derivative include trialkyl citrates or borated trialkyl citrates. Suitable examples include triethyl citrate, tripentyl citrate with ethyl dipentyl citrate, borated triethyl citrate, tributyl citrate, triethyl citrate transesterified with 1 ,2-propandiol, triethyl O-acetyl citrate, triethyl citrate octadecyl succinate, or mixtures thereof. A more detailed description of suitable citrates is disclosed in WO 2005/087904 and U.S. Patent 5,338,470. Other suitable citrates include 2-ethylhexyl citrate, dodecyl citrate, or mixtures thereof.
[0050] The ashless antiwear agent of the invention, typically a tartrate, may also function as rust and corrosion inhibitors, friction modifiers, antiwear agents and demulsifiers.
[0051] In one embodiment the ashless antiwear agent is not borated. [0052] The ashless antiwear agent of the may be present at 0.01 wt % to 20 wt %, or 0.05 to 10 wt %, or 0.1 to 5 wt % of the lubricating composition. Oils of Lubricating Viscosity
[0053] The lubricating composition comprises an oil of lubricating viscosity. Such oils include natural and synthetic oils, oil derived from hydrocracking, hydrogenation, and hydro finishing, unrefined, refined and re-refined oils and mixtures thereof.
[0054] Unrefined oils are those obtained directly from a natural or synthetic source generally without (or with little) further purification treatment. [0055] Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Purification techniques are known in the art and include solvent extraction, secondary distillation, acid or base extraction, filtration, percolation and the like.
[0056] Re-refined oils are also known as reclaimed or reprocessed oils, and are obtained by processes similar to those used to obtain refined oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products.
[0057] Natural oils useful in making the inventive lubricants include animal oils, vegetable oils (e.g., castor oil,), mineral lubricating oils such as liquid petroleum oils and solvent -treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types and oils derived from coal or shale or mixtures thereof.
[0058] Synthetic lubricating oils are useful and include hydrocarbon oils such as polymerized, oligomemed, or interpolymerised olefins (e.g., polybutylenes, polypropylenes, propyleneisobutylene copolymers); poly(l-hexenes), poly(l- octenes), rrimcrs or oligomers of 1-decenc e.g., poly(l-decenes), such materials being often referred to as poly {/-olefins, and mixtures thereof; alkyl-benzenes (e.g. dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)- benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls); diphenyl alkanes, alkylated diphenyl alkanes, alkylated diphenyl ethers and alkylated diphenyl sulphides and the derivatives, analogs and homologs thereof or mixtures thereof.
[0059] Other synthetic lubricating oils include polyol esters (such as Prolube®3970), diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and the diethyl ester of decane phosphonic acid), or polymeric tetrahydrofurans. Synthetic oils may be produced by Fischer-Tropsch reactions and typically may be hydroisomerised Fischer-Tropsch hydrocarbons or waxes. In one embodiment oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure as well as other gas-to-liquid oils.
[0060] Oils of lubricating viscosity may also be defined as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five base oil groups are as follows: Group I (sulphur content >0.03 wt %, and/or <90 wt % saturates, viscosity index 80-120); Group II (sulphur content <0.03 wt %, and >90 wt % saturates, viscosity index 80-120); Group III (sulphur content <0.03 wt %, and >90 wt % saturates, viscosity index >120); Group IV (all polyalphaolefins (PAOs)); and Group V (all others not included in Groups I, II, III, or IV). The oil of lubricating viscosity comprises an API Group I, Group II, Group III, Group IV, Group V oil or mixtures thereof. Often the oil of lubricating viscosity is an API Group I, Group II, Group III, Group IV oil or mixtures thereof. Alternatively the oil of lubricating viscosity is often an API Group II, Group III or Group IV oil or mixtures thereof.
[0061] The amount of the oil of lubricating viscosity present is typically the balance remaining after subtracting from 100 wt % the sum of the amount of the ashless antiwear agent, the oil-soluble molybdenum compound and the other performance additives.
[0062] The lubricating composition may be in the form of a concentrate and/or a fully formulated lubricant. If the lubricating composition of the invention (comprising (i) the ashless antiwear agent and (ii) the oil-soluble molybdenum compound) is in the form of a concentrate (which may be combined with additional oil to form, in whole or in part, a finished lubricant), the ratio of the of components of the invention to the oil of lubricating viscosity and/or to diluent oil include the ranges of 1 :99 to 99: 1 by weight, or 80:20 to 10:90 by weight.
Other Performance Additives
[0063] The composition optionally comprises other performance additives. The other performance additives comprise at least one of metal deactivators, viscosity modifiers, detergents, friction modifiers (other than an oil-soluble molybdenum compound or a compound of Formula (I)), antiwear agents (other than the ashless antiwear agent of the invention), corrosion inhibitors, dispersants, dispersant viscosity modifiers, extreme pressure agents, antioxidants (other than an oil-soluble molybdenum compound of the invention), foam inhibitors, demulsifiers, pour point depressants, seal swelling agents and mixtures thereof. Typically, fully-formulated lubricating oil will contain one or more of these performance additives.
[0064] In one embodiment the lubricating composition comprises the ashless antiwear agent and further comprises at least one of a viscosity modifier, an antioxidant, an overbased detergent, a succinimide dispersant, or mixtures thereof.
[0065] In one embodiment the lubricating composition comprising the ashless antiwear agent further comprises a phosphorus-containing antiwear agent. Detergents
[0066] The lubricant composition optionally further comprises other known neutral or overbased detergents. Suitable detergent substrates include phenates, sulphur containing phenates, sulphonates, salixarates, salicylates, carboxylic acid, phosphorus acid, mono- and/or di- thiophosphoric acid, alkyl phenol, sulphur coupled alkyl phenol compounds, or saligenins. Various overbased detergents and their methods of preparation are described in greater detail in numerous patent publications, including WO2004/096957 and references cited therein. The detergent substrate is typically salted with a metal such as calcium, magnesium, potassium, sodium, or mixtures thereof. In one embodiment the lubricating composition further includes an overbased detergent. Typically the overbased detergent includes phenates, sulphur containing phenates, sulphonates, salixarates, salicylates, or mixtures thereof.
[0067] The detergent may be present at 0 wt % to 10 wt %, or 0.1 wt % to 8 wt %, or 1 wt % to 4 wt %, or greater than 4 to 8 wt %. Dispersants
[0068] Dispersants are often known as ashless-type dispersants because, prior to mixing in a lubricating oil composition, they do not contain ash-forming metals and they do not normally contribute any ash forming metals when added to a lubricant and polymeric dispersants. Ashless type dispersants are characterised by a polar group attached to a relatively high molecular weight hydrocarbon chain. Typical ashless dispersants include N-substituted long chain alkenyl succinimides. Examples of N-substituted long chain alkenyl succinimides include polyisobutylene succinimide with number average molecular weight of the polyisobutylene substituent in the range 350 to 5000, or 500 to 3000. Succinimide dispersants and their preparation are disclosed, for instance in US Patent 3,172,892 or US Patent 4,234,435 or in EP 03558^5. Succinimide dispersants are typically the imide formed from a polyamine, typically a poly(ethyleneamine).
[0069] In one embodiment the invention further comprises at least one polyΪNobutylcnc sueeimmide di;-pcrs>dnt dom ed from polybobutylcno with number average molecular weight in the range 350 to 5000, or 500 to 3000. The polyisobutylene succinimide may be used alone or in combination with other dispersants.
[0070] In one embodiment the invention further comprises at least one dispersant derived from polyisobutylene succinic anhydride, an amine and zinc oxide to form a polyisobutylene succinimide complex with zinc. The polyisobutylene succinimide complex with zinc may be used alone or in combination.
[0071] Another class of ashless dispersant is Mannich bases. Mannich dispersants are the reaction products of alkyl phenols with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines). The alkyl group typically contains at least 30 carbon atoms.
[0072] The dispersants may also be post-treated by conventional methods by a reaction with any of a variety of agents. Among these are boron, urea, thiourea, dimercaptothiadiazoles, carbon disulphide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, and phosphorus compounds.
[0073] The dispersant may be present at 0 wt % to 20 wt %, or 0.1 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 1 wt % to 6 wt %, or 7 wt % to 12 wt % of the lubricating composition. Antioxidants
[0074] Antioxidant compounds are known and include for example, sulphurised olefins (typically sulphurised 4-carbobutoxy cyclohexene, or triphenylphosphite equivalents thereof, or olefin sulphide), alkylated diphenylamines (e.g., nonyl diphenyluinioe, typically di-nonyl diphenylamine, octyl diphenylamine, di-octyl diphenylamine), hindered phenols, or mixtures thereof. Antioxidant compounds may be used alone or in combination. The antioxidant may be present in ranges 0 wt % to 20 wt %, or 0.1 wt % to 10 wt %, or 1 wt % to 5 wt %, of the lubricating composition.
[0075] The hindered phenol antioxidant often contains a secondary butyl and/or a tertiary butyl group as a sterically hindering group. The phenol group is often further substituted with a hydrocarbyl group and/or a bridging group linking to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4- ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di- tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment the hindered phenol antioxidant is an ester and may include, e.g., Irganox™ L-135 from Ciba or an ;:ddiuoo product derived from 2,6-di-tert-butylphenol and an alkyl acrylate, wherein the alkyl group may contain 1 to 18, or 2 to 12, or 2 to 8, or 2 to 6, or 4 carbon atoms. A more detailed description of suitable ester- containing hindered phenol antioxidant chemistry is found in US Patent 6,559,105.
[0076] In one embodiment the lubricant does not contain (or contains reduced amounts of) phenolic antioxidant, when the compound of Formula (1) is employed. This embodiment may be useful because the compound of Formula (1) may be used as a partial or whole replacement for phenolic antioxidants. It is believed that during the preparation of tertiary butyl phenols trace amounts of an impurity tris-tert-butyl phenol are formed and retained in the final product. Tris- tert-butyl phenol is known to bioaccumulate and builds up to high concentrations in sediment. Thus employing the compound of Formula (1) as an antioxidant may allow for reduction of bioaccumulants. Viscosity Modifiers
[0077] Viscosity modifiers include hydrogenated copolymers of styrene- butadiene, ethylene-propylene copolymers, polyisobutenes, hydrogenated styrene-isoprene polymers, hydrogenated isoprene polymers, polymethacrylates, poly aery lates, polyalkyl styrenes, hydrogenated alkenyl aryl conjugated diene copolymers, polyolefins, esters of maleic anhydride-styrene copolymers, or caters of (alpha-olefin maleic anhydride) copolymers, or mixtures thereof. Dispersant Viscosity Modifiers
[0078] Dispersant viscosity modifiers (often referred to as DVM), include functionalised polyolefins, for example, ethylene-propylene copolymers that have been functionalised with the reaction product of an acylating agent (such as maleic anhydride) and an amine; polymethacrylates functionalised with an amine, or esterified maleic anhydride-styrene copolymers reacted with an amine. [0079] The total amount of viscosity modifier and/or dispersant viscosity modifier may be 0 wt % to 20 wt %, 0.1 wt % to 15 wt %, or 0.1 wt % to 10 wt %, of the lubricating composition. Antiwear Agents
[0080] The lubricant composition optionally further comprises at least one other antiwear agent other than the ashless antiwear agent of the invention. Examples of suitable antiwear agents include phosphate esters, sulphurised olefins, sulphur-containing anti-wear additives including metal dihydrocarbyldithiophosphates (such as zinc dialkyldithiophosphates), thiocarbamate-containing compounds including, thiocarbamate esters, alkylene- coupled thiocarbamates, and bis(S-alkyldithiocarbamyl) disulphides. [0081] The dithiocarbamate-containing compounds may be prepared by reacting a di thiocarbamate acid or salt with an unsaturated compound. The dithio carbamate containing compounds may also be prepared by simultaneously reacting an amine, carbon disulphide and an unsaturated compound. Generally, the reaction occurs at a temperature of 25 0C to 125 0C. US Patents 4,758,362 and 4,997,969 describe dithiocarbamate compounds and methods of making them. [0082] Examples of suitable olefins that may be sulphurised to form an the sulphurised olefin include propylene, butylene, isobutylene, pentene, hexane, heptene, octane, nonene, decene, undecene, dodecene, undecyl, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, octadecenene, nonodecene, eicosene or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecene, octadecenene, nonodecene, eicosene or mixtures thereof and their dimers, trimers and tetramers are especially useful olefins. Alternatively, the olefin may be a Diels-Alder adduct of a diene such as 1,3-butadiene and an unsaturated ester, such as, butylacrylate. [0083] Another class of sulphurised olefin includes fatty acids and their esters. The fatty acids are often obtained from vegetable oil or animal oil and typically contain 4 to 22 carbon atoms. Examples of suitable fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid or mixtures thereof. Often, the fatty acids are obtained from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil or mixtures thereof. In one embodiment fatty acids and/or ester are mixed with olefins, such as « -olefins. [0084] In an alternative embodiment, the ashless antiwear agent (which may also be described as a friction modifier) may be a monoester of a polyol and an aliphatic carboxylic acid, often an acid containing 12 to 24 carbon atoms. Often the monoester of a polyol and an aliphatic carboxylic acid is in the form of a mixture with a sunflower oil or the like, which may be present in the ashless antiwear agent mixture include 5 to 95, or in other embodiments 10 to 90, or 20 to 85, or 20 to 80 weight percent of said mixture. The aliphatic carboxylic acids (especially a monocarboxylic acid) which form the esters are those acids typically containing 12 to 24 or 14 to 20 carbon atoms. Examples of carboxylic acids include dodecanoic acid, stearic acid, lauric acid, behenic acid, and oleic acid.
[0085] 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; butanediol; hexanediol; sorbitol; arabitol; mannitol; sucrose; fructose; glucose; cyclohexane diol; erythritol; and pentaerythritols, including di- and tripentaerythritol. Often the polyol is diethyl- ene glycol, triethylene glycol, glycerol, sorbitol, pentaerythritol or dipentaerythritol. The commercial material known as glycerol monooleate 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 the amounts of the commercial grade material. [0086] The antiwear agent may be present in ranges including 0 wt % to 15 wt %, or 0 wt % to 10 wt %, or 0.05 wt % to 5 wt %, or 0.1 wt % to 3 wt % of the lubricating composition.
[0087] In one embodiment the lubricating composition is free of zinc dihydrocarbyl dithiophosphate. In one embodiment the lubricating composition further includes zinc dihydrocarbyl dithiophosphate. Extreme Pressure Agents
[0088] Extreme Pressure (EP) agents that are soluble in the oil include sulphur- and chlorosulphur-containing EP agents, chlorinated hydrocarbon EP agents and phosphorus EP agents. Examples of such EP agents include chlorinated wax; organic sulphides and polysulphides such as dibenzyldisulphide, bis-(chlorobenzyl) disulphide, dibutyl tetrasulphide, sulphurised methyl ester of oleic acid, sulphurised alkylphenol, sulphurised dipentene, sulphurised terpene, and sulphurised Diels-Alder adducts; phosphosulphurised hydrocarbons such as the reaction product of phosphorus sulphide with turpentine or methyl oleate; phosphorus esters such as the dihydrocarbon and trihydrocarbon phosphites, e.g., dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite; dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite and polypropylene substituted phenyl phosphite; metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptylphenol diacid; amine salts of alkyl and dialkylphosphoric acids, including, for example, the amine salt of the reaction product of a dialkyldithiophosphoric acid with propylene oxide; and mixtures thereof. Friction Modifiers
[0089] In one embodiment the further comprises a friction modifier, or mixtures thereof. Typically the friction modifier may be present in ranges including 0 wt % to 10 wt %, or 0.05 wt % to 8 wt %, or 0.1 wt % to 4 wt %. [0090] Examples of suitable friction modifiers include long chain fatty acid derivatives of long chain fatty acid derivatives of amines, esters, or epoxides; fatty imidazolines (that is, long chain fatty amides, long chain fatly enters, long chairs fatty epoxide derivatives, and long chain fatty imidazolines); and amine salts of alkylphosphoric acids.
[0091] Friction modifiers may also encompass materials such as sulphurised fatty compounds and olefins, triglycerides (e.g. sunflower oil) or monoester of a polyol and an aliphatic carboxylic acid (all these friction modifiers have been described as antioxidants or antiwear agents).
[0092] In one embodiment the friction modifier is a long chain fatty amide, a long chain farry ester, a long chain fatty epoxide derivatives, or a long chain fatty imidazoline.
[0093] In one embodiment the friction modifier is a long chain fatty acid ester (previously described above as an ashless antiwear agent). In another embodiment the long chain fatty acid ester is a mono-ester and in another embodiment the long chain fatty acid ester is a (tri)glyceride. Other Additives
[0094] Other performance additives such as corrosion inhibitors include those described in paragraphs 5 to 8 of US Application US05/038319 (filed on October 25, 2004 McAtee and Boyer as named inventors), octylamine octanoate, and condensation products of dodecenyl succinic acid or anhydride and a fatty acid such as oleic acid with a polyamine. In one embodiment the corrosion inhibitors include the Synalox® corrosion inhibitor. The Synalox® corrosion inhibitor is typically a homopolymer or copolymer of propylene oxide. The Synalox® corrosion inhibitor is described in more detail in a product brochure with Form No. 118-01453-0702 AMS, published by The Dow Chemical Company. The product brochure is entitled "SYNALOX Lubricants, High-Performance Polyglycols for Demanding Applications."
[0095] Metal deactivators including derivatives of benzotriazoles (typically tolyltriazole), dimercaptothiadiazole derivatives, 1 ,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles, or 2-alkyldithiobenzothiazoles; foam inhibitors including copolymers of ethyl acrylate and 2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylates, polyacrylates or polyacrylamides. Industrial Application
[0096] The lubricating composition may be utilised in a range of surfaces typically found in mechanical devices, including aluminum- alloy surfaces. The mechanical devices include an internal combustion engine, a gearbox, an automatic transmission, a hydraulic or a turbine. Typically the lubricating composition may be an engine oil, a gear oil, an automatic transmission oil, a hydraulic fluid, a turbine oil, a metal working fluid or a circulating oil. In one embodiment the mechanical device is an internal combustion engine. [0097] In one embodiment the internal combustion engine may be a diesel fuelled engine, a gasoline fuelled engine, a natural gas fuelled engine or a mixed gasoline/alcohol fuelled engine. In one embodiment the internal combustion engine may be a diesel fuelled engine and in another embodiment a gasoline fuelled engine.
[0098] The internal combustion engine may be a 2-stroke or 4-stroke engine. Suitable internal combustion engines include marine diesel engines, aviation piston engines, low-load diesel engines, and automobile and truck engines. [0099] In one embodiment the internal combustion engine contains components of an aluminium-alloy. The aluminium-alloy includes aluminium silicates, aluminium oxides, or other ceramic materials. In one embodiment the aluminium-alloy is an aluminium-silicate surface. As used herein, the term
"aluminum alloy'' is intended to be synonymous with "aluminium composite'1 and to describe a component or surface comprising aluminium and another component intermixed or reacted on a microscopic or nearly microscopic level, regardless of the detailed structure thereof. This would include any conventional a lloys with metals other than aluminium as well as composite or alloy-like structures with non-metallic elements or compounds such as with ceramie-likc materials.
[01001 The lubricant composition for an internal combustion engine may be suitable for any engine lubricant irrespective of the sulphur, phosphorus or sulphated ash (ASTM D-874) content. The sulphur content of the engine oil lubricant may be 1 wt % or less, or 0.8 wt % or less, or 0.5 wt % or less, or 0.3 wt % or less. In one embodiment the sulphur content may be in the range of 0.001 wt % to 0.5 wt %, or 0.01 wt % to 0.3 wt %. The phosphorus content may be 0.2 wt % or less, or 0.1 wt % or less, or 0.085 wt % or less, or even 0.06 wt % or less, 0.055 wt % or less, or 0.05 wt % or less. In one embodiment the phosphorus content may be 100 ppm to 1000 ppm, or 325 ppm to 700 ppm. The total sulphated ash content may be 2 wt % or less, or 1.5 wt % or less, or 1.1 wt % or less, or 1 wt % or less, or 0.8 wt % or less, or 0.5 wt % or less. In one embodiment the sulphated ash content may be 0.05 wt % to 0.9 wt %, or 0.1 wt % or 0.2 wt % to 0.45 wt %. In another embodiment the sulphur content is 0.4 wt % or less, the phosphorus content is 0-08 wt % or less, and the sulphated ash is I wt % or less. In yet another embodiment the sulphur content is 0.3 wt% or less, the phosphorus content is 0.05 wt % or less, and the sulphated asb is 0.8 wt % or less.
[0101] In one embodiment the lubricating composition is an engine oil, wherein the lubricating composition is characterised as having (i) a sulphur content of 0.5 wt % or less, (ii) a phosphorus content of 0.1 wt % or less, and (iii) a sulphated ash content of 1.5 wt % or less. [0102] In one embodiment the lubricating composition is suitable for a 2- stroke or a 4-stroke marine diesel internal combustion engine. In one embodiment the marine diesel combustion engine is a 2-stroke engine. The ashless antiwear agent of the invention may be added to a marine diesel lubricating composition at 0.01 to 20 wt %, or 0.05 to 10 wt %, or 0.1 to 5 wt %. [0103] The following examples provide illustrations of the invention. These examples are non-exhaustive and are not intended to limit the scope of the invention. EXAMPLES
[0104] As used herein all of the quantities for dispersants, detergents and viscosity modifiers shown below include conventional amount of diluent oil Typically the diluent oil constitutes 20 wt % to 90 wt % of each component. For antiwear agents, corrosion inhibitors, antioxidants the amounts shown are on an actives basis i.e. excluding diluent oil because the components are typically not carried in diluent oil.
[0105] Example 1 (EXl): A lubricating composition is prepared containing 1 wt % of di-2-ethylhexyl tartrate, 0.6 wt % of other antiwear agents, 7.9 wt % of dispersants, 1.5 wt % of detergents, 3.6 wt % of antioxidants including an effective amount of molybdenum dithiocarbamate, 6.1 wt % of viscosity modifier, 0.1 wt % of corrosion inhibitor, and 0.1 wt % of friction modifier. The lubricating composition has a sulphated ash content of 0.6 wt %, a phosphorus content of about 570 ppm, and a sulphur content of 0.17 wt %. [0106] Example 2 (EX2): A lubricating composition is prepared containing 1 wt % of a Ci2-i4-alkyl tartrate, 4.1 wt % of dispersants, 1.4 wt % of detergents, 2.5 wt % of antioxidants including 0.7 wt % of molybdenum dithiocarbamate (commercially available as Sakuralube™515, manufactured by Asahi Denka), 0.56 wt % of antiwear agents, 0.1 wt % of corrosion inhibitor, and 0.1 wt % of friction modifier. The lubricating composition has a phosphorus content of about 560 ppm.
[0107] Comparative Example 1 (CEl): is similar to Example 2 except the composition does not contain 0.7 wt % of molybdenum dithiocarbamate, nor 1 wt % of a Ci2-i4-alkyl tartrate. [0108] Comparative Example 2 (CE2): is similar to Example 2 except the composition does not contain 0.7 wt % of molybdenum dithiocarbamate. [0109] Comparative Example 3 (CE3): is similar to Example 2 except the composition does not contain 1 wt % of a Ci2-i4-alkyl tartrate. [0110] 10 g samples of the examples above are each treated with one volume percent of cumene hydroperoxide. The samples (2 ml portions) are then evaluated for wear performance in an isothermal temperature high frequency reciprocating rig (HFRR) available from PCS Instruments. HFRR conditions for the evaluations are 50Og load, 75 minute duration, 1000 micrometer stroke, 20 hertz frequency, and at 105 0C. Wear scar in micrometers and film formation as percent film thickness are then measured with lower wear scar values and higher film formation values indicating improved wear performance. The results obtained are:
Figure imgf000023_0001
[0111] Overall the results indicate that the lubricating composition of the invention is capable of providing at least one of (i) reducing or preventing phosphorus emissions, (ii) reducing or preventing sulphur emissions, (ii) wholly or partially replacing ZDDP in lubricating oils, (iii) improving fuel economy, and (iv) fuel economy retention/efficiency.
[0112] Example 3 (EX3): A lubricating composition is designed to meet Euro 4 and Euro 5 emission standards and containing 1 wt % of C8-10 alkyl tartrate. The lubricating composition has a phosphorus content of 900 ppm or less, 0.3 wt % or less of sulphur, and UΛ* wt % or less of sulphated ash.
[0113] Example 4 (EX4): A lubricating composition is designed to meet Euro 4 and Euro 5 emission standards and containing 1 wt % of C8-10 alkyl tartrate. The lubricating composition has a phosphorus content of 500 ppm or less, 0.2 wt % or less of sulphur, and 0.5 wt % or less of sulphated ash. [0114] Comparative Examples 4 (CE4) and 5 (CE5): are lubricating composition similar to EX3 and EX4 respectively, except the C8-10 alkyl tartrate is not included.
[0115] An iron-catalysed bulk oxidation test is carried out on EX3, EX4, CE4 and CE5. The test is run at 170 0C, with an air flow of 10 litres per hour, and in the presence of 360 ppm of iron catalyst. Oxidation is measured by the monitoring the peak area increase of the CO stretch from FT-IR. The results obtained for EX4 and CE5 indicate that the relative peak area increases by 383 units for EX4. In contrast, the relative peak area increases by 428 units for CE5. Thus using a compound within the definition of Formula (1) of the present invention reduces oxidation of a lubricant (especially an internal combustion engine).
[0116] It is known that some of the materials described above may interact in the final formulation, so that the components of the final formulation may be different from those that are initially added. The products formed thereby, including the products formed upon employing lubricant composition of the present invention in its intended use, may not be susceptible of easy description. Nevertheless, all such modifications and reaction products are included within the scope of the present invention; the present invention encompasses lubricant composition prepared by admixing the components described above. [0117] Each of the documents referred to above is incorporated herein by reference. Except in the Examples, or where otherwise explicitly indicated, all numerical quantities in this description specifying amounts of materials, reaction conditions, molecular weights, number of carbon atoms, and the like, are to be understood as modified by the word "about." Unless otherwise indicated, each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade. However, the amount of each chemical component is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material, unless otherwise indicated. It is to be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined. Similarly, the ranges and amounts for each element of the invention may be used together with ranges or amounts for any of the other elements.
[0118] As used herein, the term "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:
(i) 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);
(ii) 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), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulphoxy);
(iii) 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. [0119] Heteroatoms include sulphur, oxygen, nitrogen, and encompass substituents as pyridyl, furyl, thienyl and imidazolyl. In general, 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.
[0120] While the invention has been explained in relation to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. Therefore, it is to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims. [0121] The antiwear agent described herein may be an oil-soluble derivative of a molecule containing a first carboxy group and at least one additional -OH, -NHR, or =0 moiety separated from the carbon of said first carboxy group by a chain of 2 or 3 atoms, where R is hydrogen or alkyl, e.g, C 1-6 alkyl.

Claims

What is claimed is:
1. A lubricating composition comprising an oil of lubricating viscosity, an oil-soluble molybdenum compound, and an ashless antiwear agent represented by Formula (1):
Figure imgf000027_0001
Formula (1) wherein
Y and Y' are independently -O-, >NH, >NR3, or an imide group formed by taking together both Y and Y' groups and forming a Rx-N< group between two >C=O groups;
X is independently -Z-O-Z'-, >CH2, >CHR4, >CR4R5, >C(OH)(CO2R2), >C(CO2R2)2, >CCH2CO2R2 or >CHOR6;
Z and Z' are independently >CH2, >CHR4, >CR4R5, >C(OH)(CO2R2), or >CHOR6; n is 0 to 10, with the proviso that when n=l, X is not >CH2, and when n=2, both X's are not simultaneously >CH2; m is 0 or 1 ;
R1 is independently hydrogen or a hydrocarbyl group, typically containing 1 to 150 carbon atoms, with the proviso that when R1 is hydrogen, m is 0, and n is more than or equal to 1 ;
R2 is a hydrocarbyl group, typically containing 1 to 150 carbon atoms;
R3, R4 and R5 are independently hydrocarbyl groups or hydro xy- containing hydrocarbyl groups or carboxyl-containing hydrocarbyl groups; and
R6 is hydrogen or a hydrocarbyl group, typically containing 1 to 150 carbon atoms.
2. The lubricating composition of claim 1, wherein the ashless antiwear agent of Formula (1) is derived from at least one hydro xy- polycarboxylic acid.
3. The lubricating composition of claim 1 wherein the ashless anti- wear agent comprises a hydroxy-polycarboxylic acid di-ester, a hydroxy- polycarboxylic acid di-amide, a hydroxyl-polycarboxylic acid imide, a hydroxy- polycarboxylic acid di-imide, a hydroxy-polycarboxylic acid ester-amide, a hydroxy-polycarboxylic acid ester-imide, and a hydroxy-polycarboxylic acid imide-amide.
4. The lubricating composition of claim 1, wherein the ashless antiwear agent represented by Formula (1) is an imide, a di-ester, or a di-amide..
5. The lubricating composition of claim 1, wherein Y and Y' of Formula (1) are both -O- .
6. The lubricating composition of claim 1, wherein Formula (1) defines m as 0 or 1, n as 1 to 2, X is >CHOR6, and R1, R2 and R6 are independently hydrogen or hydrocarbyl groups containing 4 to 30 carbon atoms.
7. The lubricating composition of claim 1 wherein the ashless antiwear agent is derived from tartaric acid or citric acid.
8. The lubricating composition of claim 1, wherein the ashless antiwear agent is present at 0.05 to 10 wt %, or 0.1 to 5 wt % of the lubricating composition.
9. The lubricating composition of claim 1, wherein the oil-soluble molybdenum compound is selected from at least one member of the group consisitng of molybdenum dithio carbamates, molybdenum dialkyldithiophosphates, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum sulphides, molybdenum carboxylates, and molybdenum alkoxides.
10. The lubricating composition of claim 9, wherein the oil-soluble molybdenum compound is selected from at least one member of the group consisting of molybdenum dithio carbamates, molybdenum dialkyldithiophosphates, and amine salts of molybdenum compounds.
11. The lubricating composition of claim 10, wherein the oil-soluble molybdenum compound is a molybdenum dithiocarbamate.
12. The lubricating composition of claim 1, wherein the oil-soluble molybdenum compound is present in an amount to provide 0.5 ppm to 2000 ppm, 1 ppm to 700 ppm, or 20 ppm to 250 ppm of molybdenum.
13. The lubricating composition of claim 1, wherein the lubricating composition is further characterised as having at least one of (i) a sulphur content of 0.8 wt % or less, (ii) a phosphorus content of 0.2 wt % or less, or (iii) a sulphated ash content of 2 wt % or less.
14. The lubricating composition of claim 1, wherein the lubricating composition is characterised as having (i) a sulphur content of 0.5 wt % or less, (ii) a phosphorus content of 0.1 wt % or less, and (iii) a sulphated ash content of 1.5 wt % or less.
15. The lubricating composition of claim 1 further comprises at least one of a friction modifier (other than an oil-soluble molybdenum compound or a compound of Formula (I)), a viscosity modifier, an antioxidant (other than the oil-soluble molybdenum compound), an overbased detergent, a succinimide dispersant, or mixtures thereof.
16. The lubricating composition of claim 15, wherein the friction modifier is selected from the group consisting of long chain fatty amides, long chain fatty esters, long chain fatty epoxide derivatives, long chain fatty imidazolines, and amine salts of alkylphosphoric acids.
17. The lubricating composition of claim 1 further comprising a phosphorus-containing antiwear agent.
18. The lubricating composition of claim 1 further comprising an overbased detergent.
19. The lubricating composition of claim 18, wherein the overbased detergent is selected from the group consisting of non-sulphur-containing phenates, sulphur-containing phenates, sulphonates, salixarates, salicylates, and mixtures thereof.
20. A method of lubricating an internal combustion engine comprising, supplying to the internal combustion engine the lubricating composition of claim 1.
21. The use of a tartaric acid derivative as an antioxidant in a lubricant.
22. The use of claim 21, wherein the tartaric acid derivative is a tartrate ester.
PCT/US2008/063671 2007-05-24 2008-05-15 Lubricating composition containing ashfree antiwear agent based on hydroxypolycarboxylic acid derivative and a molybdenum compound WO2008147704A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
KR1020097027028A KR101496484B1 (en) 2007-05-24 2008-05-15 Lubricating composition containing ashfree antiwear agent based on hydroxypolycarboxylic acid derivative and a molybdenum compound
US12/598,104 US20100197536A1 (en) 2007-05-24 2008-05-15 Lubricating Composition Containing Ashfree Antiwear Agent Based on Hydroxypolycarboxylic Acid Derivative and a Molybdenum Compound
CN200880017335A CN101679900A (en) 2007-05-24 2008-05-15 Comprise lubricating composition based on the ash-free antiwear agent of hydroxypolycarboxylic acid's derivative and molybdenum compound
JP2010509454A JP2010528156A (en) 2007-05-24 2008-05-15 Lubricating compositions containing ashless antiwear agents and molybdenum compounds based on hydroxypolycarboxylic acid derivatives
EP08755509A EP2152838B1 (en) 2007-05-24 2008-05-15 Lubricating composition containing ashfree antiwear agent based on tartaric acid derivative and a molybdenum compound
CA2688098A CA2688098C (en) 2007-05-24 2008-05-15 Lubricating composition containing ashfree antiwear agent based on hydroxypolycarboxylic acid derivative and a molybdenum compound

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US93994907P 2007-05-24 2007-05-24
US60/939,949 2007-05-24

Publications (1)

Publication Number Publication Date
WO2008147704A1 true WO2008147704A1 (en) 2008-12-04

Family

ID=39591642

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2008/063671 WO2008147704A1 (en) 2007-05-24 2008-05-15 Lubricating composition containing ashfree antiwear agent based on hydroxypolycarboxylic acid derivative and a molybdenum compound

Country Status (7)

Country Link
US (1) US20100197536A1 (en)
EP (2) EP2152838B1 (en)
JP (1) JP2010528156A (en)
KR (1) KR101496484B1 (en)
CN (1) CN101679900A (en)
CA (1) CA2688098C (en)
WO (1) WO2008147704A1 (en)

Cited By (157)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010005921A1 (en) * 2008-07-10 2010-01-14 The Lubrizol Corporation Carboxylic acid derivatives as friction modifiers in fuels
WO2010053893A1 (en) 2008-11-05 2010-05-14 The Lubrizol Corporation Method of lubricating an internal combustion engine
WO2010077630A1 (en) 2008-12-09 2010-07-08 The Lubrizol Corporation Lubricating composition containing a compound derived from a hydroxy-carboxylic acid
WO2010096291A1 (en) 2009-02-18 2010-08-26 The Lubrizol Corporation Compounds and a method of lubricating an internal combustion engine
WO2010099136A1 (en) 2009-02-26 2010-09-02 The Lubrizol Corporation Lubricating compositions containing the reaction product of an aromatic amine and a carboxylic functionalised polymer and dispersant
WO2010132229A1 (en) * 2009-05-13 2010-11-18 The Lubrizol Corporation Internal combustion engine lubricant
WO2010132320A1 (en) 2009-05-13 2010-11-18 The Lubrizol Corporation Lubricating composition containing a malic acid derivative
WO2011005741A1 (en) 2009-07-08 2011-01-13 The Lubrizol Corporation Polymer blends useful as viscosity modifiers
WO2011022263A1 (en) 2009-08-18 2011-02-24 The Lubrizol Corporation Antiwear composition and method of lubricating driveline device
WO2011022317A1 (en) 2009-08-18 2011-02-24 The Lubrizol Corporation Lubricating composition containing an antiwear agent
WO2011022347A1 (en) 2009-08-18 2011-02-24 The Lubrizol Corporation Antiwear composition and method of lubricating an internal combustion engine
WO2011022245A1 (en) 2009-08-18 2011-02-24 The Lubrizol Corporation Lubricating composition containing an antiwear agent
WO2011022266A2 (en) 2009-08-18 2011-02-24 The Lubrizol Corporation Lubricating composition containing an antiwear agent
WO2011031659A1 (en) 2009-09-14 2011-03-17 The Lubrizol Corporation Farm tractor lubricating composition with good water tolerance
WO2011034829A1 (en) 2009-09-16 2011-03-24 The Lubrizol Corporation Lubricating composition containing an ester
WO2011066142A1 (en) * 2009-11-30 2011-06-03 The Lubrizol Corporation Stabilized blends containing friction modifiers
WO2011066242A1 (en) 2009-11-24 2011-06-03 The Lubrizol Corporation Lubricating composition containing viscosity modifier combination
WO2011071756A1 (en) 2009-12-07 2011-06-16 The Lubrizol Corporation Method of lubricating a manual transmission
WO2011075403A1 (en) 2009-12-14 2011-06-23 The Lubrizol Corporation Lubricating composition containing an antiwear agent
WO2011075401A1 (en) 2009-12-14 2011-06-23 The Lubrizol Corporation Lubricating composition containing a nitrile compound
WO2011081835A1 (en) 2009-12-14 2011-07-07 The Lubrizol Corporation Lubricating composition containing an antiwear agent
WO2011085339A1 (en) 2010-01-11 2011-07-14 The Lubrizol Corporation Overbased alkylated arylalkyl sulfonates
WO2011084657A1 (en) 2009-12-17 2011-07-14 The Lubrizol Corporation Lubricating composition containing an aromatic compound
WO2011126736A1 (en) 2010-04-06 2011-10-13 The Lubrizol Corporation Zinc salicylates for rust inhibition in lubricants
WO2011130142A1 (en) 2010-04-15 2011-10-20 The Lubrizol Corporation Low-ash lubricating oils for diesel engines
WO2011146456A1 (en) 2010-05-20 2011-11-24 The Lubrizol Corporation Low ash lubricants with improved seal and corrosion performance
WO2011146692A1 (en) 2010-05-20 2011-11-24 The Lubrizol Corporation Lubricating composition containing a dispersant
WO2011146467A1 (en) 2010-05-20 2011-11-24 The Lubrizol Corporation Lubricating composition containing a dispersant
WO2011149810A1 (en) 2010-05-24 2011-12-01 The Lubrizol Corporation Lubricating composition
WO2011153178A2 (en) 2010-06-02 2011-12-08 The Lubrizol Corporation Lubricating composition containing a carboxylic functionalised polymer
WO2011161406A1 (en) * 2010-06-25 2011-12-29 Castrol Limited Uses and compositions
WO2012025901A1 (en) * 2010-08-27 2012-03-01 Total Raffinage Marketing Engine lubricant
WO2012027254A1 (en) 2010-08-23 2012-03-01 The Lubrizol Corporation Lubricants containing aromatic dispersants and titanium
WO2012030616A1 (en) 2010-08-31 2012-03-08 The Lubrizol Corporation Star polymer and lubricating composition thereof
WO2012030590A1 (en) 2010-08-31 2012-03-08 The Lubrizol Corporation Lubricating composition containing an antiwear agent
WO2012047949A1 (en) 2010-10-06 2012-04-12 The Lubrizol Corporation Lubricating oil composition with anti-mist additive
WO2012056191A1 (en) 2010-10-26 2012-05-03 Castrol Limited Non-aqueous lubricant and fuel compositions comprising fatty acid esters of hydroxy- carboxylic acids, and uses thereof
WO2012087781A1 (en) 2010-12-21 2012-06-28 The Lubrizol Corporation Functionalized copolymers and lubricating compositions thereof
WO2012087773A1 (en) 2010-12-21 2012-06-28 The Lubrizol Corporation Lubricating composition containing an antiwear agent
WO2012087775A1 (en) 2010-12-21 2012-06-28 The Lubrizol Corporation Lubricating composition containing a detergent
WO2012097026A1 (en) 2011-01-12 2012-07-19 The Lubrizol Corporation Engine lubricants containing a polyether
WO2012112648A2 (en) 2011-02-16 2012-08-23 The Lubrizol Corporation Method of lubricating a driveline device
WO2012112635A1 (en) 2011-02-16 2012-08-23 The Lubrizol Corporation Lubricating composition and method of lubricating driveline device
JP2012520350A (en) * 2009-03-10 2012-09-06 ザ ルブリゾル コーポレイション Abrasion resistant composition and method for lubricating power transmission line devices
WO2012122202A1 (en) 2011-03-10 2012-09-13 The Lubrizol Corporation Lubricating composition containing a thiocarbamate compound
US20120283158A1 (en) * 2009-11-30 2012-11-08 The Lubrizol Corporation Stabilized Blends Containing Friction Modifiers
WO2012174075A1 (en) 2011-06-15 2012-12-20 The Lubrizol Corporation Lubricating composition containing an ester of an aromatic carboxylic acid
WO2012174184A1 (en) 2011-06-15 2012-12-20 The Lubrizol Corporation Lubricating composition containing a salt of a carboxylic acid
WO2012177549A1 (en) 2011-06-21 2012-12-27 The Lubrizol Corporation Lubricating composition containing a dispersant
WO2012177537A1 (en) 2011-06-21 2012-12-27 The Lubrizol Corporation Lubricating composition containing a dispersant
WO2013066585A1 (en) 2011-10-31 2013-05-10 The Lubrizol Corporation Ashless friction modifiers for lubricating compositions
EP2610332A1 (en) 2011-12-30 2013-07-03 The Lubrizol Corporation Star polymer and lubricating composition thereof
WO2013101882A1 (en) 2011-12-29 2013-07-04 The Lubrizol Corporation Limited slip friction modifiers for differentials
US20140080743A1 (en) * 2011-05-26 2014-03-20 The Lubrizol Corporation Stabilized Blends Containing Friction Modifiers
WO2014137580A1 (en) 2013-03-07 2014-09-12 The Lubrizol Corporation Limited slip friction modifiers for differentials
WO2014158435A1 (en) 2013-03-13 2014-10-02 The Lubrizol Corporation Engine lubricants containing a polyether
WO2014164087A1 (en) 2013-03-12 2014-10-09 The Lubrizol Corporation Lubricating composition containing lewis acid reaction product
WO2014193543A1 (en) 2013-05-30 2014-12-04 The Lubrizol Corporation Lubricating composition containing an oxyalkylated hydrocarbyl phenol
WO2015094942A1 (en) 2013-12-19 2015-06-25 The Lubrizol Corporation Hydrogenated natural oils in rust preventive coatings
WO2015106090A1 (en) 2014-01-10 2015-07-16 The Lubrizol Corporation Method of lubricating an internal combustion engine
WO2015106083A1 (en) 2014-01-10 2015-07-16 The Lubrizol Corporation Method of lubricating an internal combustion engine
WO2015138109A1 (en) 2014-03-12 2015-09-17 The Lubrizol Corporation Method of lubricating an internal combustion engine
WO2015138108A1 (en) 2014-03-12 2015-09-17 The Lubrizol Corporation Method of lubricating an internal combustion engine
WO2015138088A1 (en) 2014-03-11 2015-09-17 The Lubrizol Corporation Method of lubricating an internal combustion engine
WO2015142482A1 (en) 2014-03-19 2015-09-24 The Lubrizol Corporation Lubricants containing blends of polymers
WO2015171674A1 (en) 2014-05-06 2015-11-12 The Lubrizol Corporation Lubricant composition containing an antiwear agent
WO2015184276A1 (en) 2014-05-30 2015-12-03 The Lubrizol Corporation Epoxide quaternized quaternary ammonium salts
WO2015184247A1 (en) 2014-05-30 2015-12-03 The Lubrizol Corporation High molecular weight imide containing quaternary ammonium salts
WO2015183908A1 (en) 2014-05-30 2015-12-03 The Lubrizol Corporation Low molecular weight imide containing quaternary ammonium salts
WO2015184254A1 (en) 2014-05-30 2015-12-03 The Lubrizol Corporation High molecular weight amide/ester containing quaternary ammonium salts
WO2015184301A2 (en) 2014-05-30 2015-12-03 The Lubrizol Corporation Coupled quaternary ammonium salts
WO2015184251A1 (en) 2014-05-30 2015-12-03 The Lubrizol Corporation Branched amine containing quaternary ammonium salts
WO2015184280A1 (en) 2014-05-30 2015-12-03 The Lubrizol Corporation Imidazole containing quaternary ammonium salts
WO2015183916A1 (en) 2014-05-30 2015-12-03 The Lubrizol Corporation Low molecular weight amide/ester containing quaternary ammonium salts
RU2574580C2 (en) * 2010-08-27 2016-02-10 Тоталь Маркетин Сервис Engine lubricant
WO2016077134A1 (en) 2014-11-12 2016-05-19 The Lubrizol Corporation Mixed phosphorus esters for lubricant applications
WO2016090108A1 (en) 2014-12-03 2016-06-09 The Lubrizol Corporation Lubricating composition containing an oxyalkylated aromatic polyol compound
WO2016090065A1 (en) 2014-12-03 2016-06-09 The Lubrizol Corporation Lubricating composition containing an oxyalkylated hydrocarbyl phenol
WO2016100206A1 (en) 2014-12-15 2016-06-23 The Lubrizol Corporation Oxidized alpha-olefins in rust preventive coatings
WO2016100180A1 (en) 2014-12-15 2016-06-23 The Lubrizol Corporation Catalytic oxidation of hydrocarbons
WO2016099490A1 (en) 2014-12-17 2016-06-23 The Lubrizol Corporation Lubricating composition for lead and copper corrosion inhibition
WO2016109275A1 (en) 2014-12-29 2016-07-07 The Lubrizol Corporation Synergistic rust inhibitor combination for lubricating grease
WO2016138227A1 (en) 2015-02-26 2016-09-01 The Lubrizol Corporation Aromatic detergents and lubricating compositions thereof
WO2016138248A1 (en) 2015-02-26 2016-09-01 The Lubrizol Corporation Aromatic tetrahedral borate compounds for lubricating compositions
WO2016144880A1 (en) 2015-03-09 2016-09-15 The Lubrizol Corporation Method of lubricating an internal combustion engine
WO2016148708A1 (en) 2015-03-18 2016-09-22 The Lubrizol Corporation Lubricant compositions for direct injection engines
WO2017031143A1 (en) 2015-08-20 2017-02-23 The Lubrizol Corporation Azole derivatives as lubricating additives
WO2017039855A2 (en) 2015-07-20 2017-03-09 The Lubrizol Corporation Zinc-free lubricating composition
WO2017079575A1 (en) 2015-11-06 2017-05-11 The Lubrizol Corporation Lubricant composition containing an antiwear agent
WO2017079584A1 (en) 2015-11-06 2017-05-11 The Lubrizol Corporation Lubricant composition containing an antiwear agent
WO2017083243A1 (en) 2015-11-11 2017-05-18 The Lubrizol Corporation Lubricating composition comprising thioether-substituted phenolic compound
WO2017083042A1 (en) 2015-11-09 2017-05-18 The Lubrizol Corporation Using quaternary amine additives to improve water separation
WO2017087384A1 (en) 2015-11-17 2017-05-26 The Lubrizol Corporation Toxicologically acceptable alkylphenol detergents as friction modifiers in automotive lubricating oils
WO2017096175A1 (en) 2015-12-02 2017-06-08 The Lubrizol Corporation Ultra-low molecular weight imide containing quaternary ammonium salts having short hydrocarbon tails
WO2017096159A1 (en) 2015-12-02 2017-06-08 The Lubrizol Corporation Ultra-low molecular weight amide/ester containing quaternary ammonium salts having short hydrocarbon tails
WO2017147380A1 (en) 2016-02-24 2017-08-31 The Lubrizol Corporation Lubricant compositions for direct injection engines
WO2017151334A1 (en) 2016-03-03 2017-09-08 The Lubrizol Corporation Lubricating oil composition having improved air release
WO2017176546A1 (en) 2016-04-07 2017-10-12 The Lubrizol Corporation Mercaptoazole derivatives as lubricating additives
WO2017184688A1 (en) 2016-04-20 2017-10-26 The Lubrizol Corporation Lubricant for two-stroke cycle engines
WO2017200688A1 (en) 2016-05-18 2017-11-23 The Lubrizol Corporation Hydraulic fluid composition
EP3255129A1 (en) 2016-06-06 2017-12-13 The Lubrizol Corporation Thiol-carboxylic adducts as lubricating additives
WO2017218662A1 (en) 2016-06-17 2017-12-21 The Lubrizol Corporation Lubricating compositions
WO2017218657A2 (en) 2016-06-17 2017-12-21 The Lubrizol Corporation Polyisobutylene-substituted phenol, derivatives thereof, and lubricating compositions containing the polyisobutylene-substituted phenol and its derivatives
WO2017218654A1 (en) 2016-06-17 2017-12-21 The Lubrizol Corporation Lubricating compositions
WO2017218664A1 (en) 2016-06-17 2017-12-21 The Lubrizol Corporation Lubricating compositions
EP3263678A1 (en) 2016-06-30 2018-01-03 The Lubrizol Corporation Hydroxyaromatic succinimide detergents for lubricating compositions
WO2018013451A1 (en) 2016-07-15 2018-01-18 The Lubrizol Corporation Engine lubricants for siloxane deposit control
WO2018017913A1 (en) 2016-07-22 2018-01-25 The Lubrizol Corporation Aliphatic tetrahedral borate compounds for fully formulated lubricating compositions
WO2018048781A1 (en) 2016-09-12 2018-03-15 The Lubrizol Corporation Total base number boosters for marine diesel engine lubricating compositions
WO2018052692A1 (en) 2016-09-14 2018-03-22 The Lubrizol Corporation Lubricating composition and method of lubricating an internal combustion engine
WO2018053098A1 (en) 2016-09-14 2018-03-22 The Lubrizol Corporation Lubricating composition comprising sulfonate detergent and ashless hydrocarbyl phenolic compound
WO2018125569A1 (en) 2016-12-27 2018-07-05 The Lubrizol Corporation Lubricating composition including n-alkylated dianiline
WO2018125567A1 (en) 2016-12-27 2018-07-05 The Lubrizol Corporation Lubricating composition with alkylated naphthylamine
WO2019005680A1 (en) 2017-06-27 2019-01-03 The Lubrizol Corporation LUBRICATING COMPOSITION CONTAINING A SELF-ASSEMBLING POLYMETHACRYLATE BLOCK COPOLYMER AND AN ETHYLENE-α-OLEFIN COPOLYMER
WO2019005738A1 (en) 2017-06-27 2019-01-03 The Lubrizol Corporation Lubricating composition for and method of lubricating an internal combustion engine
WO2019018329A1 (en) 2017-07-17 2019-01-24 The Lubrizol Corporation Low dispersant lubricant composition
WO2019018326A1 (en) 2017-07-17 2019-01-24 The Lubrizol Corporation Low zinc lubricant composition
WO2019023219A1 (en) 2017-07-24 2019-01-31 Chemtool Incorporated Extreme pressure metal sulfonate grease
WO2019108588A1 (en) 2017-11-28 2019-06-06 The Lubrizol Corporation Lubricant compositions for high efficiency engines
WO2019112720A1 (en) 2017-12-04 2019-06-13 The Lubrizol Corporation Alkylphenol detergents
WO2019118117A1 (en) 2017-12-15 2019-06-20 The Lubrizol Corporation Alkylphenol detergents
US10407641B2 (en) 2009-03-03 2019-09-10 The Lubrizol Corporation Ashless or reduced ash quaternary detergents
WO2019246192A1 (en) 2018-06-22 2019-12-26 The Lubrizol Corporation Lubricating compositions for heavy duty diesel engines
US10577556B2 (en) 2015-06-12 2020-03-03 The Lubrizol Corporation Michael adduct amino esters as total base number boosters for marine diesel engine lubricating compositions
WO2020102672A1 (en) 2018-11-16 2020-05-22 The Lubrizol Corporation Alkylbenzene sulfonate detergents
US10669505B2 (en) 2015-03-18 2020-06-02 The Lubrizol Corporation Lubricant compositions for direct injection engines
WO2020123438A1 (en) 2018-12-10 2020-06-18 The Lubrizol Corporation Lubricating compositions having a mixed dispersant additive package
WO2020263964A1 (en) 2019-06-24 2020-12-30 The Lubrizol Corporation Continuous acoustic mixing for performance additives and compositions including the same
WO2021061808A1 (en) 2019-09-26 2021-04-01 The Lubrizol Corporation Lubricating compositions and methods of operating an internal combustion engine
WO2021061986A1 (en) 2019-09-26 2021-04-01 The Lubrizol Corporation Lubricating compositions and methods of operating an internal combustion engine
US10975323B2 (en) 2015-12-15 2021-04-13 The Lubrizol Corporation Sulfurized catecholate detergents for lubricating compositions
WO2021076733A1 (en) 2019-10-15 2021-04-22 The Lubrizol Corporation Fuel efficient lubricating composition
WO2021127183A1 (en) 2019-12-18 2021-06-24 The Lubrizol Corporation Polymeric surfactant compound
EP3842508A1 (en) 2013-09-19 2021-06-30 The Lubrizol Corporation Use of lubricant compositions for direct injection engines
WO2021158757A1 (en) 2020-02-04 2021-08-12 The Lubrizol Corporation Lubricating compositions and methods of operating an internal combustion engine
EP3878933A1 (en) 2013-09-19 2021-09-15 The Lubrizol Corporation Lubricant compositions for direct injection engines
WO2021183230A1 (en) 2020-03-12 2021-09-16 The Lubrizol Corporation Oil-based corrosion inhibitors
WO2021231220A1 (en) 2020-05-13 2021-11-18 The Lubrizol Corporation Lubricating composition for and method of lubricating an internal combustion engine
WO2022066721A1 (en) 2020-09-22 2022-03-31 The Lubrizol Corporation Diesel engine lubricating compositions and methods of use thereof
WO2022140496A1 (en) 2020-12-23 2022-06-30 The Lubrizol Corporation Benzazepine compounds as antioxidants for lubricant compositions
WO2022212844A1 (en) 2021-04-01 2022-10-06 The Lubrizol Corporation Zinc free lubricating compositions and methods of using the same
WO2023009774A1 (en) 2021-07-29 2023-02-02 The Lubrizol Corporation 1,4-benzoxazine compounds and lubricant compositions containing the same
WO2023023224A1 (en) 2021-08-19 2023-02-23 The Lubrizol Corporation Friction modifiers with improved frictional properties and lubricating compositions containing the same
IT202100022328A1 (en) 2021-08-25 2023-02-25 Versalis Spa METHOD FOR THE PREPARATION OF Ω-AMINO-CARBOXYLIC ACIDS AND THEIR DERIVATIVES.
US11608478B2 (en) 2015-03-25 2023-03-21 The Lubrizol Corporation Lubricant compositions for direct injection engine
WO2023133090A1 (en) 2022-01-04 2023-07-13 The Lubrizol Corporation Compounds and lubricant compositions containing the same
WO2024006125A1 (en) 2022-06-27 2024-01-04 The Lubrizol Corporation Lubricating composition and method of lubricating an internal combustion engine
WO2024019952A1 (en) 2022-07-18 2024-01-25 The Lubrizol Corporation Deposit control compounds for lubricating compositions
WO2024030591A1 (en) 2022-08-05 2024-02-08 The Lubrizol Corporation Processes for producing reaction products including quaternary ammonium salts
WO2024030592A1 (en) 2022-08-05 2024-02-08 The Lubrizol Corporation Processes for producing radically-functionalized pibsa product derivatives and compositions comprising same
WO2024047447A1 (en) 2022-09-01 2024-03-07 The Lubrizol Corporation Gelling agent for calcium sulfonate greases
WO2024091494A1 (en) 2022-10-25 2024-05-02 The Lubrizol Corporation Lubricant compositions and methods of lubricating internal combustion engines
WO2024091553A1 (en) 2022-10-25 2024-05-02 The Lubrizol Corporation Lubricant compositions and methods of lubricating internal combustion engines
WO2024112665A1 (en) 2022-11-23 2024-05-30 The Lubrizol Corporation Powertrain lubricant containing polyether
WO2024158648A1 (en) 2023-01-24 2024-08-02 The Lubrizol Corporation Lubricating composition with phenolic antioxidant and low active sulfur
WO2024163826A1 (en) 2023-02-03 2024-08-08 The Lubrizol Corporation Processes for producing reaction products including quaternary ammonium salts
WO2024206736A1 (en) 2023-03-31 2024-10-03 The Lubrizol Corporation Process for preparing overbased alkaline earth metal alkylhydroxybenzoate

Families Citing this family (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102165050A (en) * 2008-09-26 2011-08-24 绿金润滑剂有限公司 Lubricant composition and methods of manufacture thereof
EP2438148B1 (en) * 2009-06-04 2015-08-12 The Lubrizol Corporation Lubricating composition containing friction modifier and viscosity modifier
CA2823623A1 (en) 2011-01-04 2012-07-12 The Lubrizol Corporation Continuously variable transmission fluid with extended anti-shudder durability
WO2012112658A1 (en) 2011-02-17 2012-08-23 The Lubrzol Corporation Lubricants with good tbn retention
US20140045734A1 (en) * 2011-05-26 2014-02-13 The Lubrizol Corporation Stabilized Blends Containing Friction Modifiers
EP2729555A1 (en) 2011-07-07 2014-05-14 The Lubrizol Corporation Lubricant providing improved cleanliness for two-stroke cycle engines
WO2013059173A1 (en) 2011-10-20 2013-04-25 The Lubrizol Corporation Bridged alkylphenol compounds
CN104540842B (en) 2012-02-08 2017-09-22 路博润公司 The method for preparing vulcanization alkaline-earth metal dodecylphenol salt
US9321979B2 (en) * 2012-03-13 2016-04-26 Chemtura Corporation Friction modifier composition for lubricants
US20160201004A1 (en) * 2012-03-13 2016-07-14 Chemtura Corporation Friction modifier composition for lubricants
US20150024983A1 (en) * 2012-03-26 2015-01-22 The Lubrizol Corporation Manual transmission lubricants with improved synchromesh performance
WO2013151911A1 (en) 2012-04-04 2013-10-10 The Lubrizol Corporation Bearing lubricants for pulverizing equipment
EP2864458B1 (en) 2012-06-20 2017-05-17 Castrol Limited Friction modifier and their use in lubricants and fuels
PL2864457T3 (en) 2012-06-20 2018-01-31 Castrol Ltd Friction modifier and their use in lubricants and fuels
US9695377B2 (en) 2012-12-07 2017-07-04 The Lubrizol Corporation Pyran dispersants
CN105143160B (en) 2013-02-11 2018-11-20 路博润公司 Bridging alkaline-earth metal alkyl phenate
CN105339476A (en) * 2013-05-30 2016-02-17 路博润公司 Synergistic additive combination for industrial gear oils
EP3039096A1 (en) 2013-09-10 2016-07-06 The Lubrizol Corporation Viscoelastic oil-based fluid and related methods
CN103553907B (en) * 2013-10-18 2015-09-23 湖南省华京粉体材料有限公司 A kind of preparation method of oil-soluble organic molybdenum additive
US9708422B2 (en) 2013-12-10 2017-07-18 The Lubrizol Corporation Method for preparing functionalized graft polymers
US9885004B2 (en) 2013-12-23 2018-02-06 Exxonmobil Research And Engineering Company Method for improving engine fuel efficiency
US10190072B2 (en) 2013-12-23 2019-01-29 Exxonmobil Research And Engineering Company Method for improving engine fuel efficiency
US20170015925A1 (en) 2014-04-04 2017-01-19 The Lubrizol Corporation Method for preparing a sulfurized alkaline earth metal dodecylphenate
KR102425108B1 (en) 2014-06-27 2022-07-26 더루우브리졸코오포레이션 Mixtures of friction modifiers to provide good friction performance to transmission fluids
SG11201700902QA (en) 2014-08-06 2017-03-30 Lubrizol Corp Industrial gear lubricant additive package with biodegradable sulfur component
WO2016164345A1 (en) 2015-04-09 2016-10-13 The Lubrizol Corporation Lubricants containing quaternary ammonium compounds
ES2930218T3 (en) 2015-07-10 2022-12-09 Lubrizol Corp Viscosity Modifiers to Improve Fluoroelastomer Seal Performance
KR102078435B1 (en) 2016-07-14 2020-02-17 주식회사 엘지화학 Organic light emitting diode and manufacturing method of the same
PE20190852A1 (en) 2016-10-17 2019-06-18 Lubrizol Corp ACID EMULSIFIED TECHNOLOGY FOR CONTINUOUS MIXED EMULSIFIED ACID SYSTEMS
WO2021247428A1 (en) 2020-06-01 2021-12-09 The Lubrizol Corporation Surface isolation resistance compatibility test system and method
CN113845946A (en) * 2020-06-28 2021-12-28 中国石油化工股份有限公司 Fuel additive, preparation method thereof and fuel composition
WO2024182476A1 (en) 2023-02-28 2024-09-06 The Lubrizol Corporation Industrial gear lubricant

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4237022A (en) 1979-10-01 1980-12-02 The Lubrizol Corporation Tartarimides and lubricants and fuels containing the same
US4326972A (en) 1978-06-14 1982-04-27 The Lubrizol Corporation Concentrates, lubricant compositions and methods for improving fuel economy of internal combustion engine
GB2105743A (en) 1981-09-10 1983-03-30 Lubrizol Corp Fuel economy additives or lubricants
EP1116783A1 (en) * 1997-09-17 2001-07-18 Infineum International Limited Lubricating composition
US20020042348A1 (en) * 1997-01-03 2002-04-11 Mcneil Hugh A. Engine, fuel, gear, and grease treatment compositions and methods related thereto
US20050198894A1 (en) 2004-03-11 2005-09-15 Crompton Corporation Lubricant and fuel compositions containing hydroxy carboxylic acid and hydroxy polycarboxylic acid esters
US20060079413A1 (en) 2004-10-12 2006-04-13 The Lubrizol Corporation, A Corporation Of The State Of Ohio Tartaric acid derivatives as fuel economy improvers and antiwear agents in crankcase oils and preparation thereof
US20060183647A1 (en) 2004-10-12 2006-08-17 Jody Kocsis Tartaric acid derivatives as fuel economy improvers and antiwear agents in crankcase oils and preparation thereof

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2365291A (en) * 1941-05-26 1944-12-19 Lubri Zol Corp Stabilizing agents for hydrocarbon compositions and the like
US2443578A (en) * 1944-10-13 1948-06-15 Socony Vacuum Oil Co Inc Mineral oil composition
DE1248643B (en) 1959-03-30 1967-08-31 The Lubrizol Corporation, Cleveland, Ohio (V. St. A.) Process for the preparation of oil-soluble aylated amines
US4329449A (en) 1978-09-01 1982-05-11 A. E. Staley Manufacturing Company Method of using recycled mother liquors to produce aldosides
US4234435A (en) 1979-02-23 1980-11-18 The Lubrizol Corporation Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation
US4692257A (en) * 1981-09-22 1987-09-08 Mobil Oil Corporation Borated hydroxy-containing compositions and lubricants containing same
US4478604A (en) * 1982-04-01 1984-10-23 Phillips Petroleum Company Gasoline compositions containing branched chain amines or derivatives thereof
US4640787A (en) * 1982-04-01 1987-02-03 Phillips Petroleum Company Gasoline compositions containing branched chain amines or derivatives thereof
US4741848A (en) * 1986-03-13 1988-05-03 The Lubrizol Corporation Boron-containing compositions, and lubricants and fuels containing same
US4758362A (en) 1986-03-18 1988-07-19 The Lubrizol Corporation Carbamate additives for low phosphorus or phosphorus free lubricating compositions
US4952328A (en) * 1988-05-27 1990-08-28 The Lubrizol Corporation Lubricating oil compositions
US4997969A (en) 1988-12-12 1991-03-05 The Lubrizol Corporation Carbamate additives for lubricating compositions
US5038319A (en) 1989-04-24 1991-08-06 Xerox Corporation System for recording and remotely accessing operating data in a reproduction machine
US5338470A (en) 1992-12-10 1994-08-16 Mobil Oil Corporation Alkylated citric acid adducts as antiwear and friction modifying additives
US5387251A (en) * 1994-05-02 1995-02-07 Rouse; Evan D. Endless belt sanding block
US6559105B2 (en) 2000-04-03 2003-05-06 The Lubrizol Corporation Lubricant compositions containing ester-substituted hindered phenol antioxidants
US7022653B2 (en) * 2003-03-10 2006-04-04 Infineum International Limited Friction modifiers for engine oil composition
WO2004096957A1 (en) 2003-04-24 2004-11-11 The Lubrizol Corporation Diesel lubricant low in sulfur and phosphorus
US7785769B2 (en) * 2003-07-25 2010-08-31 The United States of America as reprsented by the Secretary of the Navy Immobilization of oligonucleotides and proteins in sugar-containing hydrogels

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4326972A (en) 1978-06-14 1982-04-27 The Lubrizol Corporation Concentrates, lubricant compositions and methods for improving fuel economy of internal combustion engine
US4237022A (en) 1979-10-01 1980-12-02 The Lubrizol Corporation Tartarimides and lubricants and fuels containing the same
GB2105743A (en) 1981-09-10 1983-03-30 Lubrizol Corp Fuel economy additives or lubricants
CA1183125A (en) 1981-09-10 1985-02-26 Daniel E. Barrer Compositions, concentrates, lubricant compositions and methods for improving fuel economy of internal combustion engines
US20020042348A1 (en) * 1997-01-03 2002-04-11 Mcneil Hugh A. Engine, fuel, gear, and grease treatment compositions and methods related thereto
EP1116783A1 (en) * 1997-09-17 2001-07-18 Infineum International Limited Lubricating composition
US20050198894A1 (en) 2004-03-11 2005-09-15 Crompton Corporation Lubricant and fuel compositions containing hydroxy carboxylic acid and hydroxy polycarboxylic acid esters
US20060079413A1 (en) 2004-10-12 2006-04-13 The Lubrizol Corporation, A Corporation Of The State Of Ohio Tartaric acid derivatives as fuel economy improvers and antiwear agents in crankcase oils and preparation thereof
WO2006044411A1 (en) * 2004-10-12 2006-04-27 The Lubrizol Corporation Tartaric acid derivatives as fuel economy improvers and antiwear agents in crankcase oils and preparation thereof
US20060183647A1 (en) 2004-10-12 2006-08-17 Jody Kocsis Tartaric acid derivatives as fuel economy improvers and antiwear agents in crankcase oils and preparation thereof

Cited By (224)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010005921A1 (en) * 2008-07-10 2010-01-14 The Lubrizol Corporation Carboxylic acid derivatives as friction modifiers in fuels
WO2010053893A1 (en) 2008-11-05 2010-05-14 The Lubrizol Corporation Method of lubricating an internal combustion engine
US20120172265A1 (en) * 2008-12-09 2012-07-05 The Lubrizol Corporation Lubricating Composition Containing a Compound Derived from a Hydroxy-carboxylic Acid
KR20110106865A (en) * 2008-12-09 2011-09-29 더루우브리졸코오포레이션 Lubricating composition containing a compound derived from a hydroxy-carboxylic acid
JP2012511593A (en) * 2008-12-09 2012-05-24 ザ ルブリゾル コーポレイション Lubricating composition comprising a compound derived from hydroxycarboxylic acid
WO2010077630A1 (en) 2008-12-09 2010-07-08 The Lubrizol Corporation Lubricating composition containing a compound derived from a hydroxy-carboxylic acid
KR101679093B1 (en) * 2008-12-09 2016-11-23 더루우브리졸코오포레이션 Lubricating composition containing a compound derived from a hydroxy-carboxylic acid
CN105602652A (en) * 2008-12-09 2016-05-25 路博润公司 Lubricating composition containing compound derived from hydroxy-carboxylic acid
WO2010096291A1 (en) 2009-02-18 2010-08-26 The Lubrizol Corporation Compounds and a method of lubricating an internal combustion engine
WO2010099136A1 (en) 2009-02-26 2010-09-02 The Lubrizol Corporation Lubricating compositions containing the reaction product of an aromatic amine and a carboxylic functionalised polymer and dispersant
EP2431448A1 (en) 2009-02-26 2012-03-21 The Lubrizol Corporation Lubricating compositions containing the reaction product of an aromatic amine and a carboxylic functionalised polymer and dispersant
EP3572484A1 (en) 2009-03-03 2019-11-27 The Lubrizol Corporation Ashless or reduced ash quaternary detergents
US10407641B2 (en) 2009-03-03 2019-09-10 The Lubrizol Corporation Ashless or reduced ash quaternary detergents
JP2012520350A (en) * 2009-03-10 2012-09-06 ザ ルブリゾル コーポレイション Abrasion resistant composition and method for lubricating power transmission line devices
CN105695040A (en) * 2009-05-13 2016-06-22 路博润公司 Composition containing an oil of lubricating viscosity
AU2010247917B2 (en) * 2009-05-13 2016-07-07 The Lubrizol Corporation Lubricating composition containing a malic acid derivative
WO2010132229A1 (en) * 2009-05-13 2010-11-18 The Lubrizol Corporation Internal combustion engine lubricant
US8901051B2 (en) 2009-05-13 2014-12-02 The Lubrizol Corporation Internal combustion engine lubricant
US8940671B2 (en) 2009-05-13 2015-01-27 The Lubrizol Corporation Lubricating composition containing a malic acid derivative
WO2010132320A1 (en) 2009-05-13 2010-11-18 The Lubrizol Corporation Lubricating composition containing a malic acid derivative
KR20120059454A (en) * 2009-05-13 2012-06-08 더루우브리졸코오포레이션 Lubricating composition containing malic acid derivative
CN102482605A (en) * 2009-05-13 2012-05-30 卢布里佐尔公司 Internal combustion engine lubricant
CN102459535A (en) * 2009-05-13 2012-05-16 卢布里佐尔公司 Lubricating composition containing a malic acid derivative
US9617493B2 (en) 2009-05-13 2017-04-11 The Lubrizol Corporation Internal combustion engine lubricant
KR101674702B1 (en) * 2009-05-13 2016-11-09 더루우브리졸코오포레이션 Lubricating composition containing malic acid derivative
JP2012526896A (en) * 2009-05-13 2012-11-01 ザ ルブリゾル コーポレイション Internal combustion engine lubricant
WO2011005741A1 (en) 2009-07-08 2011-01-13 The Lubrizol Corporation Polymer blends useful as viscosity modifiers
KR101808012B1 (en) * 2009-08-18 2017-12-11 더루우브리졸코오포레이션 Antiwear composition and method of lubricating driveline device
WO2011022266A2 (en) 2009-08-18 2011-02-24 The Lubrizol Corporation Lubricating composition containing an antiwear agent
EP2891700A1 (en) 2009-08-18 2015-07-08 The Lubrizol Corporation Lubricating composition containing an antiwear agent
US9738849B2 (en) 2009-08-18 2017-08-22 The Lubrizol Corporation Lubricating composition containing an antiwear agent
EP2891701A1 (en) 2009-08-18 2015-07-08 The Lubrizol Corporation Lubricating composition containing a corrosion inhibitor
WO2011022266A3 (en) * 2009-08-18 2011-05-19 The Lubrizol Corporation Lubricating composition containing an antiwear agent
WO2011022317A1 (en) 2009-08-18 2011-02-24 The Lubrizol Corporation Lubricating composition containing an antiwear agent
WO2011022263A1 (en) 2009-08-18 2011-02-24 The Lubrizol Corporation Antiwear composition and method of lubricating driveline device
WO2011022245A1 (en) 2009-08-18 2011-02-24 The Lubrizol Corporation Lubricating composition containing an antiwear agent
WO2011022347A1 (en) 2009-08-18 2011-02-24 The Lubrizol Corporation Antiwear composition and method of lubricating an internal combustion engine
WO2011031659A1 (en) 2009-09-14 2011-03-17 The Lubrizol Corporation Farm tractor lubricating composition with good water tolerance
WO2011034829A1 (en) 2009-09-16 2011-03-24 The Lubrizol Corporation Lubricating composition containing an ester
WO2011066242A1 (en) 2009-11-24 2011-06-03 The Lubrizol Corporation Lubricating composition containing viscosity modifier combination
US9193934B2 (en) 2009-11-30 2015-11-24 The Lubrizol Corporation Stabilized blends containing friction modifiers
US20120283158A1 (en) * 2009-11-30 2012-11-08 The Lubrizol Corporation Stabilized Blends Containing Friction Modifiers
US10190071B2 (en) 2009-11-30 2019-01-29 The Lubrizol Corporation Stabilized blends containing friction modifiers
WO2011066142A1 (en) * 2009-11-30 2011-06-03 The Lubrizol Corporation Stabilized blends containing friction modifiers
US20120329691A1 (en) * 2009-11-30 2012-12-27 The Lubrizol Corporation Stabilized Blends Containing Friction Modifiers
US9163196B2 (en) 2009-11-30 2015-10-20 The Lubrizol Corporation Stabilized blends containing friction modifiers
US9175241B2 (en) 2009-11-30 2015-11-03 The Lubrizol Corporation Stabilized blends containing friction modifiers
CN102712866A (en) * 2009-11-30 2012-10-03 卢布里佐尔公司 Stabilized blends containing friction modifiers
US9528067B2 (en) * 2009-11-30 2016-12-27 The Lubrizol Corporation Stabilized blends containing friction modifiers
WO2011071756A1 (en) 2009-12-07 2011-06-16 The Lubrizol Corporation Method of lubricating a manual transmission
WO2011075403A1 (en) 2009-12-14 2011-06-23 The Lubrizol Corporation Lubricating composition containing an antiwear agent
WO2011075401A1 (en) 2009-12-14 2011-06-23 The Lubrizol Corporation Lubricating composition containing a nitrile compound
WO2011081835A1 (en) 2009-12-14 2011-07-07 The Lubrizol Corporation Lubricating composition containing an antiwear agent
WO2011084657A1 (en) 2009-12-17 2011-07-14 The Lubrizol Corporation Lubricating composition containing an aromatic compound
WO2011085339A1 (en) 2010-01-11 2011-07-14 The Lubrizol Corporation Overbased alkylated arylalkyl sulfonates
WO2011126736A1 (en) 2010-04-06 2011-10-13 The Lubrizol Corporation Zinc salicylates for rust inhibition in lubricants
WO2011130142A1 (en) 2010-04-15 2011-10-20 The Lubrizol Corporation Low-ash lubricating oils for diesel engines
WO2011146467A1 (en) 2010-05-20 2011-11-24 The Lubrizol Corporation Lubricating composition containing a dispersant
WO2011146456A1 (en) 2010-05-20 2011-11-24 The Lubrizol Corporation Low ash lubricants with improved seal and corrosion performance
WO2011146692A1 (en) 2010-05-20 2011-11-24 The Lubrizol Corporation Lubricating composition containing a dispersant
WO2011149810A1 (en) 2010-05-24 2011-12-01 The Lubrizol Corporation Lubricating composition
WO2011153178A2 (en) 2010-06-02 2011-12-08 The Lubrizol Corporation Lubricating composition containing a carboxylic functionalised polymer
US9080120B2 (en) 2010-06-25 2015-07-14 Castrol Limited Uses and compositions
RU2597263C2 (en) * 2010-06-25 2016-09-10 Кастрол Лимитед Applications and compositions
AU2011268759B2 (en) * 2010-06-25 2015-07-09 Castrol Limited Uses and compositions
WO2011161406A1 (en) * 2010-06-25 2011-12-29 Castrol Limited Uses and compositions
WO2012027254A1 (en) 2010-08-23 2012-03-01 The Lubrizol Corporation Lubricants containing aromatic dispersants and titanium
RU2574580C2 (en) * 2010-08-27 2016-02-10 Тоталь Маркетин Сервис Engine lubricant
FR2964115A1 (en) * 2010-08-27 2012-03-02 Total Raffinage Marketing ENGINE LUBRICANT
WO2012025901A1 (en) * 2010-08-27 2012-03-01 Total Raffinage Marketing Engine lubricant
EP3184615A1 (en) 2010-08-31 2017-06-28 The Lubrizol Corporation Method of lubricating a driveline device
WO2012030616A1 (en) 2010-08-31 2012-03-08 The Lubrizol Corporation Star polymer and lubricating composition thereof
WO2012030590A1 (en) 2010-08-31 2012-03-08 The Lubrizol Corporation Lubricating composition containing an antiwear agent
EP2623582A1 (en) 2010-08-31 2013-08-07 The Lubrizol Corporation Lubricating composition containing an antiwear agent
WO2012047949A1 (en) 2010-10-06 2012-04-12 The Lubrizol Corporation Lubricating oil composition with anti-mist additive
US9828564B2 (en) 2010-10-26 2017-11-28 Castrol Limited Non-aqueous lubricant and fuel compositions comprising fatty acid esters of hydroxy-carboxylic acids, and uses thereof
US9127232B2 (en) 2010-10-26 2015-09-08 Castrol Limited Non-aqueous lubricant and fuel compositions comprising fatty acid esters of hydroxy-carboxylic acids, and uses thereof
WO2012056191A1 (en) 2010-10-26 2012-05-03 Castrol Limited Non-aqueous lubricant and fuel compositions comprising fatty acid esters of hydroxy- carboxylic acids, and uses thereof
WO2012087781A1 (en) 2010-12-21 2012-06-28 The Lubrizol Corporation Functionalized copolymers and lubricating compositions thereof
WO2012087773A1 (en) 2010-12-21 2012-06-28 The Lubrizol Corporation Lubricating composition containing an antiwear agent
WO2012087775A1 (en) 2010-12-21 2012-06-28 The Lubrizol Corporation Lubricating composition containing a detergent
US10704006B2 (en) 2010-12-21 2020-07-07 The Lubrizol Corporation Lubricating composition containing an antiwear agent
WO2012097026A1 (en) 2011-01-12 2012-07-19 The Lubrizol Corporation Engine lubricants containing a polyether
WO2012112635A1 (en) 2011-02-16 2012-08-23 The Lubrizol Corporation Lubricating composition and method of lubricating driveline device
WO2012112648A2 (en) 2011-02-16 2012-08-23 The Lubrizol Corporation Method of lubricating a driveline device
WO2012122202A1 (en) 2011-03-10 2012-09-13 The Lubrizol Corporation Lubricating composition containing a thiocarbamate compound
US20140080743A1 (en) * 2011-05-26 2014-03-20 The Lubrizol Corporation Stabilized Blends Containing Friction Modifiers
US9631160B2 (en) * 2011-05-26 2017-04-25 The Lubrizol Corporation Stabilized blends containing friction modifiers
WO2012174075A1 (en) 2011-06-15 2012-12-20 The Lubrizol Corporation Lubricating composition containing an ester of an aromatic carboxylic acid
WO2012174184A1 (en) 2011-06-15 2012-12-20 The Lubrizol Corporation Lubricating composition containing a salt of a carboxylic acid
WO2012177537A1 (en) 2011-06-21 2012-12-27 The Lubrizol Corporation Lubricating composition containing a dispersant
WO2012177549A1 (en) 2011-06-21 2012-12-27 The Lubrizol Corporation Lubricating composition containing a dispersant
US10590363B2 (en) 2011-10-31 2020-03-17 Daniel J. Saccomando Ashless-friction modifiers for lubricating compositions
WO2013066585A1 (en) 2011-10-31 2013-05-10 The Lubrizol Corporation Ashless friction modifiers for lubricating compositions
WO2013101882A1 (en) 2011-12-29 2013-07-04 The Lubrizol Corporation Limited slip friction modifiers for differentials
EP2610332A1 (en) 2011-12-30 2013-07-03 The Lubrizol Corporation Star polymer and lubricating composition thereof
EP3088498A1 (en) 2011-12-30 2016-11-02 The Lubrizol Corporation Use of star polymers
WO2014137580A1 (en) 2013-03-07 2014-09-12 The Lubrizol Corporation Limited slip friction modifiers for differentials
WO2014164087A1 (en) 2013-03-12 2014-10-09 The Lubrizol Corporation Lubricating composition containing lewis acid reaction product
WO2014158435A1 (en) 2013-03-13 2014-10-02 The Lubrizol Corporation Engine lubricants containing a polyether
EP3556830A1 (en) 2013-05-30 2019-10-23 The Lubrizol Corporation Lubricating composition containing an oxyalkylated hydrocarbyl phenol
WO2014193543A1 (en) 2013-05-30 2014-12-04 The Lubrizol Corporation Lubricating composition containing an oxyalkylated hydrocarbyl phenol
EP3842508A1 (en) 2013-09-19 2021-06-30 The Lubrizol Corporation Use of lubricant compositions for direct injection engines
EP3878933A1 (en) 2013-09-19 2021-09-15 The Lubrizol Corporation Lubricant compositions for direct injection engines
EP4438702A2 (en) 2013-09-19 2024-10-02 The Lubrizol Corporation Lubricant compositions for direct injection engines
WO2015094942A1 (en) 2013-12-19 2015-06-25 The Lubrizol Corporation Hydrogenated natural oils in rust preventive coatings
WO2015106083A1 (en) 2014-01-10 2015-07-16 The Lubrizol Corporation Method of lubricating an internal combustion engine
WO2015106090A1 (en) 2014-01-10 2015-07-16 The Lubrizol Corporation Method of lubricating an internal combustion engine
WO2015138088A1 (en) 2014-03-11 2015-09-17 The Lubrizol Corporation Method of lubricating an internal combustion engine
WO2015138108A1 (en) 2014-03-12 2015-09-17 The Lubrizol Corporation Method of lubricating an internal combustion engine
WO2015138109A1 (en) 2014-03-12 2015-09-17 The Lubrizol Corporation Method of lubricating an internal combustion engine
WO2015142482A1 (en) 2014-03-19 2015-09-24 The Lubrizol Corporation Lubricants containing blends of polymers
WO2015171674A1 (en) 2014-05-06 2015-11-12 The Lubrizol Corporation Lubricant composition containing an antiwear agent
WO2015184276A1 (en) 2014-05-30 2015-12-03 The Lubrizol Corporation Epoxide quaternized quaternary ammonium salts
WO2015183908A1 (en) 2014-05-30 2015-12-03 The Lubrizol Corporation Low molecular weight imide containing quaternary ammonium salts
WO2015184251A1 (en) 2014-05-30 2015-12-03 The Lubrizol Corporation Branched amine containing quaternary ammonium salts
WO2015184301A2 (en) 2014-05-30 2015-12-03 The Lubrizol Corporation Coupled quaternary ammonium salts
WO2015184254A1 (en) 2014-05-30 2015-12-03 The Lubrizol Corporation High molecular weight amide/ester containing quaternary ammonium salts
WO2015184280A1 (en) 2014-05-30 2015-12-03 The Lubrizol Corporation Imidazole containing quaternary ammonium salts
EP3511396A1 (en) 2014-05-30 2019-07-17 The Lubrizol Corporation Low molecular weight imide containing quaternary ammonium salts
EP3536766A1 (en) 2014-05-30 2019-09-11 The Lubrizol Corporation Epoxide quaternized quaternary ammonium salts
WO2015184247A1 (en) 2014-05-30 2015-12-03 The Lubrizol Corporation High molecular weight imide containing quaternary ammonium salts
EP3514220A1 (en) 2014-05-30 2019-07-24 The Lubrizol Corporation Low molecular weight amide/ester containing quaternary ammonium salts
EP3517593A1 (en) 2014-05-30 2019-07-31 The Lubrizol Corporation Low molecular weight amide/ester containing quaternary ammonium salts
EP3521404A1 (en) 2014-05-30 2019-08-07 The Lubrizol Corporation Low molecular weight imide containing quaternary ammonium salts
EP3524663A1 (en) 2014-05-30 2019-08-14 The Lubrizol Corporation Imidazole containing quaternary ammonium salts
WO2015183916A1 (en) 2014-05-30 2015-12-03 The Lubrizol Corporation Low molecular weight amide/ester containing quaternary ammonium salts
WO2016077134A1 (en) 2014-11-12 2016-05-19 The Lubrizol Corporation Mixed phosphorus esters for lubricant applications
US10611981B2 (en) 2014-11-12 2020-04-07 The Lubrizol Corporation Mixed phosphorus esters for lubricant applications
WO2016090121A1 (en) 2014-12-03 2016-06-09 The Lubrizol Corporation Lubricating composition containing an oxyalkylated aromatic polyol compound
WO2016090108A1 (en) 2014-12-03 2016-06-09 The Lubrizol Corporation Lubricating composition containing an oxyalkylated aromatic polyol compound
WO2016090065A1 (en) 2014-12-03 2016-06-09 The Lubrizol Corporation Lubricating composition containing an oxyalkylated hydrocarbyl phenol
WO2016100206A1 (en) 2014-12-15 2016-06-23 The Lubrizol Corporation Oxidized alpha-olefins in rust preventive coatings
WO2016100180A1 (en) 2014-12-15 2016-06-23 The Lubrizol Corporation Catalytic oxidation of hydrocarbons
WO2016099490A1 (en) 2014-12-17 2016-06-23 The Lubrizol Corporation Lubricating composition for lead and copper corrosion inhibition
WO2016109275A1 (en) 2014-12-29 2016-07-07 The Lubrizol Corporation Synergistic rust inhibitor combination for lubricating grease
WO2016138248A1 (en) 2015-02-26 2016-09-01 The Lubrizol Corporation Aromatic tetrahedral borate compounds for lubricating compositions
WO2016138227A1 (en) 2015-02-26 2016-09-01 The Lubrizol Corporation Aromatic detergents and lubricating compositions thereof
US10336963B2 (en) 2015-02-26 2019-07-02 The Lubrizol Corporation Aromatic tetrahedral borate compounds for lubricating compositions
WO2016144880A1 (en) 2015-03-09 2016-09-15 The Lubrizol Corporation Method of lubricating an internal combustion engine
WO2016148708A1 (en) 2015-03-18 2016-09-22 The Lubrizol Corporation Lubricant compositions for direct injection engines
US10669505B2 (en) 2015-03-18 2020-06-02 The Lubrizol Corporation Lubricant compositions for direct injection engines
US11608478B2 (en) 2015-03-25 2023-03-21 The Lubrizol Corporation Lubricant compositions for direct injection engine
EP4194530A1 (en) 2015-03-25 2023-06-14 The Lubrizol Corporation Use of lubricant compositions for direct injection engines
US10577556B2 (en) 2015-06-12 2020-03-03 The Lubrizol Corporation Michael adduct amino esters as total base number boosters for marine diesel engine lubricating compositions
US10988702B2 (en) 2015-07-20 2021-04-27 The Lubrizol Corporation Zinc-free lubricating composition
US11518954B2 (en) 2015-07-20 2022-12-06 The Lubrizol Corporation Zinc-free lubricating composition
WO2017039855A2 (en) 2015-07-20 2017-03-09 The Lubrizol Corporation Zinc-free lubricating composition
WO2017031143A1 (en) 2015-08-20 2017-02-23 The Lubrizol Corporation Azole derivatives as lubricating additives
WO2017079584A1 (en) 2015-11-06 2017-05-11 The Lubrizol Corporation Lubricant composition containing an antiwear agent
WO2017079575A1 (en) 2015-11-06 2017-05-11 The Lubrizol Corporation Lubricant composition containing an antiwear agent
WO2017083042A1 (en) 2015-11-09 2017-05-18 The Lubrizol Corporation Using quaternary amine additives to improve water separation
WO2017083243A1 (en) 2015-11-11 2017-05-18 The Lubrizol Corporation Lubricating composition comprising thioether-substituted phenolic compound
WO2017087384A1 (en) 2015-11-17 2017-05-26 The Lubrizol Corporation Toxicologically acceptable alkylphenol detergents as friction modifiers in automotive lubricating oils
WO2017096175A1 (en) 2015-12-02 2017-06-08 The Lubrizol Corporation Ultra-low molecular weight imide containing quaternary ammonium salts having short hydrocarbon tails
WO2017096159A1 (en) 2015-12-02 2017-06-08 The Lubrizol Corporation Ultra-low molecular weight amide/ester containing quaternary ammonium salts having short hydrocarbon tails
US10975323B2 (en) 2015-12-15 2021-04-13 The Lubrizol Corporation Sulfurized catecholate detergents for lubricating compositions
WO2017147380A1 (en) 2016-02-24 2017-08-31 The Lubrizol Corporation Lubricant compositions for direct injection engines
EP3778837A1 (en) 2016-02-24 2021-02-17 The Lubrizol Corporation Lubricant compositions for direct injection engines
WO2017151334A1 (en) 2016-03-03 2017-09-08 The Lubrizol Corporation Lubricating oil composition having improved air release
WO2017176546A1 (en) 2016-04-07 2017-10-12 The Lubrizol Corporation Mercaptoazole derivatives as lubricating additives
WO2017184688A1 (en) 2016-04-20 2017-10-26 The Lubrizol Corporation Lubricant for two-stroke cycle engines
WO2017200688A1 (en) 2016-05-18 2017-11-23 The Lubrizol Corporation Hydraulic fluid composition
US11261398B2 (en) 2016-05-18 2022-03-01 The Lubrizol Corporation Hydraulic fluid composition
EP3255129A1 (en) 2016-06-06 2017-12-13 The Lubrizol Corporation Thiol-carboxylic adducts as lubricating additives
WO2017218662A1 (en) 2016-06-17 2017-12-21 The Lubrizol Corporation Lubricating compositions
WO2017218657A2 (en) 2016-06-17 2017-12-21 The Lubrizol Corporation Polyisobutylene-substituted phenol, derivatives thereof, and lubricating compositions containing the polyisobutylene-substituted phenol and its derivatives
WO2017218654A1 (en) 2016-06-17 2017-12-21 The Lubrizol Corporation Lubricating compositions
WO2017218664A1 (en) 2016-06-17 2017-12-21 The Lubrizol Corporation Lubricating compositions
EP3263678A1 (en) 2016-06-30 2018-01-03 The Lubrizol Corporation Hydroxyaromatic succinimide detergents for lubricating compositions
WO2018013451A1 (en) 2016-07-15 2018-01-18 The Lubrizol Corporation Engine lubricants for siloxane deposit control
WO2018017913A1 (en) 2016-07-22 2018-01-25 The Lubrizol Corporation Aliphatic tetrahedral borate compounds for fully formulated lubricating compositions
WO2018017911A1 (en) 2016-07-22 2018-01-25 The Lubrizol Corporation Aliphatic tetrahedral borate compounds for lubricating compositions
WO2018048781A1 (en) 2016-09-12 2018-03-15 The Lubrizol Corporation Total base number boosters for marine diesel engine lubricating compositions
US11427780B2 (en) 2016-09-12 2022-08-30 The Lubrizol Corporation Total base number boosters for marine diesel engine lubricating compositions
EP3851508A1 (en) 2016-09-14 2021-07-21 The Lubrizol Corporation Method of lubricating an internal combustion engine
WO2018052692A1 (en) 2016-09-14 2018-03-22 The Lubrizol Corporation Lubricating composition and method of lubricating an internal combustion engine
WO2018053098A1 (en) 2016-09-14 2018-03-22 The Lubrizol Corporation Lubricating composition comprising sulfonate detergent and ashless hydrocarbyl phenolic compound
US11162048B2 (en) 2016-12-27 2021-11-02 The Lubrizol Corporation Lubricating composition with alkylated naphthylamine
WO2018125569A1 (en) 2016-12-27 2018-07-05 The Lubrizol Corporation Lubricating composition including n-alkylated dianiline
WO2018125567A1 (en) 2016-12-27 2018-07-05 The Lubrizol Corporation Lubricating composition with alkylated naphthylamine
WO2019005680A1 (en) 2017-06-27 2019-01-03 The Lubrizol Corporation LUBRICATING COMPOSITION CONTAINING A SELF-ASSEMBLING POLYMETHACRYLATE BLOCK COPOLYMER AND AN ETHYLENE-α-OLEFIN COPOLYMER
WO2019005738A1 (en) 2017-06-27 2019-01-03 The Lubrizol Corporation Lubricating composition for and method of lubricating an internal combustion engine
EP3896142A1 (en) 2017-06-27 2021-10-20 The Lubrizol Corporation Lubricating composition for and method of lubricating an internal combustion engine
WO2019018326A1 (en) 2017-07-17 2019-01-24 The Lubrizol Corporation Low zinc lubricant composition
WO2019018329A1 (en) 2017-07-17 2019-01-24 The Lubrizol Corporation Low dispersant lubricant composition
US11674106B2 (en) 2017-07-17 2023-06-13 The Lubrizol Corporation Low zinc lubricant composition
WO2019023219A1 (en) 2017-07-24 2019-01-31 Chemtool Incorporated Extreme pressure metal sulfonate grease
WO2019108588A1 (en) 2017-11-28 2019-06-06 The Lubrizol Corporation Lubricant compositions for high efficiency engines
WO2019112720A1 (en) 2017-12-04 2019-06-13 The Lubrizol Corporation Alkylphenol detergents
WO2019118117A1 (en) 2017-12-15 2019-06-20 The Lubrizol Corporation Alkylphenol detergents
US11702610B2 (en) 2018-06-22 2023-07-18 The Lubrizol Corporation Lubricating compositions
WO2019246192A1 (en) 2018-06-22 2019-12-26 The Lubrizol Corporation Lubricating compositions for heavy duty diesel engines
WO2020102672A1 (en) 2018-11-16 2020-05-22 The Lubrizol Corporation Alkylbenzene sulfonate detergents
WO2020123438A1 (en) 2018-12-10 2020-06-18 The Lubrizol Corporation Lubricating compositions having a mixed dispersant additive package
WO2020263964A1 (en) 2019-06-24 2020-12-30 The Lubrizol Corporation Continuous acoustic mixing for performance additives and compositions including the same
WO2021061986A1 (en) 2019-09-26 2021-04-01 The Lubrizol Corporation Lubricating compositions and methods of operating an internal combustion engine
US11932825B2 (en) 2019-09-26 2024-03-19 The Lubrizol Corporation Lubricating compositions and methods of operating an internal combustion engine
WO2021061808A1 (en) 2019-09-26 2021-04-01 The Lubrizol Corporation Lubricating compositions and methods of operating an internal combustion engine
WO2021076733A1 (en) 2019-10-15 2021-04-22 The Lubrizol Corporation Fuel efficient lubricating composition
US12098345B2 (en) 2019-12-18 2024-09-24 The Lubrizol Corporation Polymeric surfactant compound
WO2021127183A1 (en) 2019-12-18 2021-06-24 The Lubrizol Corporation Polymeric surfactant compound
WO2021158757A1 (en) 2020-02-04 2021-08-12 The Lubrizol Corporation Lubricating compositions and methods of operating an internal combustion engine
WO2021183230A1 (en) 2020-03-12 2021-09-16 The Lubrizol Corporation Oil-based corrosion inhibitors
WO2021231220A1 (en) 2020-05-13 2021-11-18 The Lubrizol Corporation Lubricating composition for and method of lubricating an internal combustion engine
WO2022066721A1 (en) 2020-09-22 2022-03-31 The Lubrizol Corporation Diesel engine lubricating compositions and methods of use thereof
WO2022140496A1 (en) 2020-12-23 2022-06-30 The Lubrizol Corporation Benzazepine compounds as antioxidants for lubricant compositions
WO2022212844A1 (en) 2021-04-01 2022-10-06 The Lubrizol Corporation Zinc free lubricating compositions and methods of using the same
WO2023009774A1 (en) 2021-07-29 2023-02-02 The Lubrizol Corporation 1,4-benzoxazine compounds and lubricant compositions containing the same
WO2023023224A1 (en) 2021-08-19 2023-02-23 The Lubrizol Corporation Friction modifiers with improved frictional properties and lubricating compositions containing the same
IT202100022328A1 (en) 2021-08-25 2023-02-25 Versalis Spa METHOD FOR THE PREPARATION OF Ω-AMINO-CARBOXYLIC ACIDS AND THEIR DERIVATIVES.
WO2023026127A1 (en) 2021-08-25 2023-03-02 Versalis S.P.A. Method for the preparation of ω-amino-carboxylic acids and derivatives thereof
WO2023133090A1 (en) 2022-01-04 2023-07-13 The Lubrizol Corporation Compounds and lubricant compositions containing the same
WO2024006125A1 (en) 2022-06-27 2024-01-04 The Lubrizol Corporation Lubricating composition and method of lubricating an internal combustion engine
WO2024019952A1 (en) 2022-07-18 2024-01-25 The Lubrizol Corporation Deposit control compounds for lubricating compositions
WO2024030592A1 (en) 2022-08-05 2024-02-08 The Lubrizol Corporation Processes for producing radically-functionalized pibsa product derivatives and compositions comprising same
WO2024030591A1 (en) 2022-08-05 2024-02-08 The Lubrizol Corporation Processes for producing reaction products including quaternary ammonium salts
WO2024047447A1 (en) 2022-09-01 2024-03-07 The Lubrizol Corporation Gelling agent for calcium sulfonate greases
WO2024091494A1 (en) 2022-10-25 2024-05-02 The Lubrizol Corporation Lubricant compositions and methods of lubricating internal combustion engines
WO2024091553A1 (en) 2022-10-25 2024-05-02 The Lubrizol Corporation Lubricant compositions and methods of lubricating internal combustion engines
WO2024112665A1 (en) 2022-11-23 2024-05-30 The Lubrizol Corporation Powertrain lubricant containing polyether
WO2024158648A1 (en) 2023-01-24 2024-08-02 The Lubrizol Corporation Lubricating composition with phenolic antioxidant and low active sulfur
WO2024163826A1 (en) 2023-02-03 2024-08-08 The Lubrizol Corporation Processes for producing reaction products including quaternary ammonium salts
WO2024206736A1 (en) 2023-03-31 2024-10-03 The Lubrizol Corporation Process for preparing overbased alkaline earth metal alkylhydroxybenzoate

Also Published As

Publication number Publication date
KR20100019539A (en) 2010-02-18
EP2463358A1 (en) 2012-06-13
EP2152838B1 (en) 2012-10-17
CA2688098C (en) 2016-04-19
CN101679900A (en) 2010-03-24
EP2152838A1 (en) 2010-02-17
CA2688098A1 (en) 2008-12-04
KR101496484B1 (en) 2015-03-09
EP2463358B1 (en) 2015-07-15
US20100197536A1 (en) 2010-08-05
JP2010528156A (en) 2010-08-19

Similar Documents

Publication Publication Date Title
EP2463358B1 (en) Lubricating composition containing ashfree antiwear agent based on hydroxypolycarboxylic acid derivative and a molybdenum compound
CA2688091C (en) Lubricating composition containing sulphur, phosphorous and ashfree antiwear agent and amine containing friction modifier
CA2688094C (en) Method of lubricating an aluminium silicate composite surface with a lubricant comprising ashless, sulphur, phosphorus free antiwear agent
EP2540811B1 (en) Use of heterocyclic compounds for lubricating an internal combustion engine
WO2008070307A2 (en) Antiwear agent and lubricating composition thereof
EP2655580B1 (en) Lubricating composition containing a detergent
US20150247102A1 (en) Lubricating composition containing an antiwear agent
US9765275B2 (en) Composition containing ester compounds and a method of lubricating an internal combustion engine
WO2009085800A1 (en) Lubricating composition containing detergent
CA2742292C (en) Lubrication of internal combustion engines in the presence of water contaminant
EP3452566B1 (en) Lubricants for use in boosted engines
EP2721128A1 (en) Lubricating composition containing an ester of an aromatic carboxylic acid
EP2513272B1 (en) Lubricating composition containing an antiwear agent

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200880017335.7

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08755509

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2008755509

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2010509454

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 2688098

Country of ref document: CA

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20097027028

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 12598104

Country of ref document: US