EP2467459A1 - Composition anti-usure et procédé de lubrification d'un moteur à combustion interne - Google Patents

Composition anti-usure et procédé de lubrification d'un moteur à combustion interne

Info

Publication number
EP2467459A1
EP2467459A1 EP10745707A EP10745707A EP2467459A1 EP 2467459 A1 EP2467459 A1 EP 2467459A1 EP 10745707 A EP10745707 A EP 10745707A EP 10745707 A EP10745707 A EP 10745707A EP 2467459 A1 EP2467459 A1 EP 2467459A1
Authority
EP
European Patent Office
Prior art keywords
lubricating composition
formula
acid
compound
lubricating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10745707A
Other languages
German (de)
English (en)
Inventor
Matthew D. Gieselman
John K. Pudelski
Patrick E. Mosier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lubrizol Corp
Original Assignee
Lubrizol Corp
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 Lubrizol Corp filed Critical Lubrizol Corp
Publication of EP2467459A1 publication Critical patent/EP2467459A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/04—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen, halogen, and oxygen
    • C10M2211/044—Acids; Salts or esters thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
    • C10M2215/082—Amides containing hydroxyl groups; Alkoxylated derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/086—Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/043—Mannich bases
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/043—Ammonium or amine salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/047—Thioderivatives not containing metallic elements
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/12—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of organic compounds, e.g. with PxSy, PxSyHal or PxOy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/42—Phosphor free or low phosphor content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/43—Sulfur free or low sulfur content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/45—Ash-less or low ash content
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/26—Two-strokes or two-cycle engines

Definitions

  • the invention provides a lubricating composition containing an antiwear package.
  • the invention further relates to a method of lubricating an internal combustion engine by lubricating the engine with the lubricating composition.
  • lubricating oils It is well known for lubricating oils to contain a number of additives (including antiwear agents, antioxidants, dispersants, or detergents) used to protect internal combustion engines from wear, oxidation, soot deposits and acid 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 may also contain a 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.
  • ZDDP zinc dialkyldithiophosphate
  • the phosphorus from ZDDP is also believed to be relatively volatile and with the coming introduction of the GF-5 specification, tighter limits on emissions of phosphorus may be required. However, reducing the levels of antiwear additives such as ZDDP is likely to increase wear and result in other detrimental performance of an engine.
  • 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.
  • WO 2006/044411 discloses a low-sulphur, low-phosphorus, low-ash lubricant composition containing a tartrate ester, or amide having 1 to 150 carbon atoms per ester of amide group.
  • the lubricant composition is suitable for lubricating an internal combustion engine.
  • WO 2006/04441 1 does not disclose compositions as disclosed herein.
  • a lubricating composition and method as disclosed herein is capable of providing acceptable levels of at least one of (i) phosphorus emissions (typically reducing or preventing emissions), (ii) sulphur emissions (typically reducing or preventing emissions), (iii) friction performance, and (iv) wear and/or extreme pressure performance (typically reducing or preventing).
  • the invention provides a lubricating composition comprising an oil of lubricating viscosity and an antiwear package, wherein the antiwear package comprises:
  • a salt of a sulphur-free phosphorus-containing compound includes amine salts, ammonium salts, metal salts and mixtures thereof, ("ammonium salts” include mono-, di-, tri-, or tetraalkyl ammonium salts as well as unsubstituted ammonium salts.)
  • the antiwear package may allow for a reduction or elimination in the amount of zinc dialkyldithiophosphate antiwear additives.
  • the invention provides a lubricating composition comprising an oil of lubricating viscosity and an antiwear package, wherein the antiwear package comprises: (a) an antiwear agent which may be represented by a compound of Formula (Ia) and/or (Ib):
  • n' is 0 to 10 for Formula (Ib), and 1 to 10 for Formula (Ia);
  • p 1 to 5;
  • X is independently -CH 2 -, >CHR 4 or >CR 4 R 5 , >CHOR 6 , or >C(CO 2 R 6 ) 2 , -CH 3 , -CH 2 R 4 or -CHR 4 R 5 , -CH 2 OR 6 , -CH(CO 2 R 6 ) 2 , >C(OR6 ⁇ CO 2 R 6 , >CHCO 2 R 6 , or ⁇ C-R 6 (where ⁇ equals three valences, and may only apply to Formula (Ia)) or mixtures thereof to fulfill the valence of Formula (Ia) and/or (Ib) (typically the compound of Formula (Ia) or (Ib) has at least one X that is hydroxyl-containing (e.g., >CHOR 6 , wherein R 6 is hydrogen));
  • R 1 and R 2 are independently hydrocarbyl groups, typically containing 1 to 150, 4 to 30, or 6 to 24 carbon atoms;
  • R 3 is a hydrocarbyl group
  • R 4 and R 5 are independently keto-containing groups (such as acyl groups), ester groups or hydrocarbyl groups;
  • R 6 is independently hydrogen or a hydrocarbyl group, typically containing 1 to 150 carbon atoms.
  • a salt of a sulphur-free phosphorus-containing compound that is typically oil-soluble.
  • the salt includes amine salts, ammonium salts, metal salts and mixtures thereof.
  • n and m may be independently integers of 1 to 5;
  • X may be an aliphatic or alicyclic group, or an aliphatic or alicyclic group containing an oxygen atom in the carbon chain, or a substituted group of the foregoing types, said group containing up to 6 carbon atoms and having n+m available points of attachment;
  • each Y may be independently -O-, >NH, or >NR* or two Ys together representing the nitrogen of an imide structure R-N ⁇ formed between two carbonyl groups; and each R and R 1 may be independently hydrogen or a hydrocarbyl group, provided that at least one R or R 1 group is a hydrocarbyl group; each R 2 may be independently hydrogen, a hydrocarbyl group or an acyl group, further provided that at least one -OR 2 group is located on a carbon atom within X that is ⁇ or ⁇ to at least one of the -C(O)-Y-R groups.
  • the compound derived from the hydroxy- carboxylic acid may be derived from tartaric acid or glycolic acid, (typically tartaric acid).
  • the derivative of hydro xycarboxylic acid includes imide, di-ester, di-amide, or ester-amide derivatives of tartaric acid, citric acid, or mixtures thereof.
  • the derivative of hydroxycarboxylic acid includes an imide, a di-ester, a di-amide, or an ester- amide derivative of tartaric acid.
  • the compound Formula (Ia) and/or (Ib) may be derived from hydroxycarboxylic acids such as tartaric acid, citric acid, or mixtures thereof.
  • the compound Formula (Ia) and/or (Ib) is derived from citric acid and R 1 and R 2 contain at least 6 or at least 8 carbon atoms up to 150, or 6 to 30, or 8 to 24 carbon atoms.
  • the compound Formula (Ia) and/or (Ib) is derived from tartaric acid and R 1 and R 2 contain 4 to 30, or 6 to 24 carbon atoms.
  • the compound Formula (Ia) and/or (Ib) may be derived from, e.g., malonic acid, oxalic acid, chlorophenyl malonic acid, or mixtures thereof.
  • component (b) of the lubricating composition may be a salt of a sulphur-free phosphorus-containing compound selected from the group consisting of sulphur-free metal salts of hydrocarbyl-substituted phosphorus-containing compounds and phosphorylated dispersants.
  • the lubricating compositions disclosed herein contain 0 ppm to 1000 ppm, 0 ppm to 500 ppm, or 5 ppm to 300 ppm, or 20 ppm to 250 ppm of molybdenum.
  • the invention provides a method for lubricating an internal combustion engine comprising supplying to the engine a lubricating composition as disclosed herein.
  • the lubricating composition defined for the method contains the salt of a sulphur-free phosphorus-containing compound which may be selected from the group consisting of a sulphur-free metal salt of a hydrocarbyl-substituted phosphorus-containing compound, a phosphorylated dispersant, a hydroxy-substituted di- ester of phosphoric acid, a phosphorylated hydroxy- substituted di- or tri- ester of phosphoric acid or salt, and mixtures thereof.
  • a sulphur-free phosphorus-containing compound which may be selected from the group consisting of a sulphur-free metal salt of a hydrocarbyl-substituted phosphorus-containing compound, a phosphorylated dispersant, a hydroxy-substituted di- ester of phosphoric acid, a phosphorylated hydroxy- substituted di- or tri- ester of phosphoric acid or salt, and mixtures thereof.
  • the invention provides for the use of a lubricating composition as disclosed herein for providing acceptable levels of at least one of (i) phosphorus emissions (typically reducing or preventing emissions), (ii) sulphur emissions (typically reducing or preventing emissions), (iii) friction performance, and (iv) wear and/or extreme pressure performance (typically reducing or preventing).
  • the present invention provides a lubricating composition and a method for lubricating a mechanical device as disclosed above.
  • the mechanical device is an internal combustion engine.
  • the antiwear package includes two or more antiwear agents as disclosed above.
  • the antiwear package may be present at 0.01 wt % to 10 wt %, or 0.05 wt % to 10 wt %, or 0.05 wt % to 5 wt % of the lubricating composition.
  • the derivative of a hydro xycarboxylic acid may be present at 0.005 wt % to 10 wt %, or 0.025 to 5 wt %, or 0.25 to 2.5 wt % of the lubricating composition.
  • Antiwear Agent Represented by a Compound of Formula (Ia) and/or (Ib))
  • the antiwear agent represented by a compound of Formula (Ia) and/or (Ib) may be a derivative of a hydroxycarboxylic acid.
  • one antiwear agent includes a derivative of a hydroxycarboxylic acid.
  • the derivative of a hydroxycarboxylic acid typically a tartrate, may also function as rust and corrosion inhibitor, friction modifier, antiwear agent and demulsifier.
  • the derivative of a hydroxycarboxylic acid may also have friction modifying properties.
  • the derivative of a hydroxycarboxylic acid may be ashless (i.e., does not contain metal in amounts greater than those associated with contaminant amounts).
  • Derivatives of the hydroxycarboxylic acid include imides, di-esters, di-amides, di-imides (applicable for tetra-acids and higher), ester-amides, ester- imides (applicable for tri-acids and higher, such as citric acid), or imide-amides (applicable for tri-acids and higher, such as citric acid).
  • the antiwear agent includes imides, di-esters, di-amides, or ester-amides.
  • the antiwear agent may be derived from at least one of a hydroxy-carboxylic acid di-ester, a hydroxy-carboxylic acid di-amide, a hydroxy-carboxylic acid di-imide (applicable for tetra-acids and higher), a hydroxy-carboxylic acid ester-amide, a hydroxy-carboxylic acid ester-imide (applicable for tri-acids and higher, such as citric acid), and a hydroxycarboxylic acid imide-amide (applicable for tri-acids and higher, such as citric acid).
  • the antiwear agent may be derived from at least one of the group consisting of a hydroxy-carboxylic acid di-ester, a hydroxy- carboxylic acid di-amide, and a hydroxy-carboxylic acid ester-amide.
  • Examples of a suitable a hydroxycarboxylic acid include citric acid, tartaric acid, malic acid (or hydroxy-succinic acid), mandelic acid, lactic acid, glycolic acid, hydroxy-propionic acid, hydroxyglutaric acid, or mixtures thereof.
  • the antiwear agent may be derived from tartaric acid, citric acid, hydroxy-succinic acid, dihydroxy mono-acids, mono-hydroxy diacids, or mixtures thereof.
  • the antiwear agent includes a compound derived from tartaric acid.
  • US Patent Application 2005/198894 discloses suitable hydroxycarboxylic acid compounds, and methods of preparing the same.
  • the antiwear agent includes imide, di-esters, di- amides, ester-amide derivatives of tartaric acid.
  • the antiwear agent may be represented by a compound of Formula (Ia) and/or (Ib) as defined above:
  • n' is 0 to 10, 0 to 6, or 0 to 4 for Formula (Ib), and for Formula (Ia) 1 to 4, or 1 to 2;
  • p is 1 to 5, or 1 to 2, or 1;
  • X is independently -CH 2 -, >CHR 4 or >CR 4 R 5 , >CHOR 6 , or >C(CO 2 R 6 ) 2 , -CH 3 , -CH 2 R 4 or CHR 4 R 5 , -CH 2 OR 6 , -CH(CO 2 R 6 ) 2 , >C(OR6 ⁇ CO 2 R 6 , >CHCO 2 R 6 , or ⁇ C-R 6 (where ⁇ equals three valences, and may only apply to Formula (Ia)) or mixtures thereof to fulfill the valence of Formula (Ia) and/or (Ib) (typically the compound of Formula (Ia) or (Ib) has at least one X that is hydroxyl-containing (i.e., >CHOR 6 , wherein R 6 is hydrogen));
  • R 1 and R 2 are independently hydrocarbyl groups, typically containing 1 to 150, 4 to 30, or 6 to 20, or 10 to 20, or 11 to 18 carbon atoms;
  • R 3 is a hydrocarbyl group
  • R 4 and R 5 are independently keto- groups, ester groups or hydrocarbyl groups
  • R 6 is independently hydrogen or a hydrocarbyl group, typically containing 1 to 150, or 4 to 30 carbon atoms.
  • the di-esters, di-amides, di-imides (applicable for tetra-acids and higher), ester-amide, ester-imide (applicable for tri-acids and higher, such as citric acid), imide-amide (applicable for tri-acids and higher, such as citric acid) compounds may be derived from a compound of Formula (Ia) and/or (Ib).
  • the di-esters, di-amides, ester-amide, compounds may be derived from a compound of Formula (Ia) and/or (Ib).
  • the compound of Formula (Ib) contains an imide group.
  • the compound of Formula (Ia) and/or (Ib) has n, X, and R 1 , R 2 and R 6 defined as follows: n is 1 to 2, X is >CHOR 6 ; and R 1 and R 2 are independently hydrocarbyl groups containing 4 to 30 carbon atoms, and R 6 is independently hydrogen or a hydrocarbyl group containing 4 to 30 carbon atoms.
  • Y and Y' are both -O-.
  • the compound of Formula (Ia) and/or (Ib) has n, X, Y, Y' and R 1 , R 2 and R 6 defined as follows: n is 1 to 2, X is >CHOR 6 ; Y and Y' are both -O-, and R 1 and R 2 are independently hydrocarbyl groups containing 4 to 30 carbon atoms, and R 6 is independently hydrogen or a hydrocarbyl group containing 4 to 30 carbon atoms.
  • the di-esters, di-amides, di-imides (applicable for tetra-acids and higher), ester-amide, ester-imide (applicable for tri-acids and higher, such as citric acid), imide-amide (applicable for tri-acids and higher, such as citric acid) compounds of Formula (Ia) and/or (Ib) may be prepared by reacting a polycarboxylic acid (such as tartaric acid), with an amine or alcohol, optionally in the presence of a known esterification catalyst.
  • the amine or alcohol typically has sufficient carbon atoms to fulfill the requirements of R 1 and/or R 2 as defined in Formula (Ia) and/or (Ib).
  • R 1 and R 2 may be independently linear or branched hydrocarbyl groups. In one embodiment the hydrocarbyl groups may be branched. In one embodiment the hydrocarbyl groups may be linear.
  • the R 1 and R 2 may be incorporated into Formula (Ia) and/or (Ib) by either an amine or an alcohol.
  • the alcohol includes both monohydric alcohol and polyhydric alcohol. In one embodiment the alcohol is branched.
  • the antiwear agent may be derived from a compound of Formula (Ib).
  • 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 may be 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.
  • the antiwear agent may be derived from tartaric acid.
  • the tartaric acid used for preparing the tartrates of the invention may be commercially available (for instance, obtained from Sargent Welch), and it is likely to exist in one or more isomeric forms such as d-tartaric acid, 1-tartaric acid, d, 1-tartaric acid (racemic mixture) or mesotartaric acid, often depending on the source (natural) or method of synthesis (e.g., from maleic acid).
  • These derivatives may 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.
  • 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 (e.g., mineral oil, or synthetic oil) in which it is intended to function to an extent which permits the solution to exhibit one or more of the desired properties.
  • oil e.g., mineral oil, or synthetic oil
  • 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 salt of a sulphur-free phosphorus-containing compound may be selected from the group consisting of a sulphur-free metal or amine salt of a hydrocarbyl-substituted phosphorus-containing compound, a phosphorylated dispersant, a hydroxy-substituted di- ester of phosphoric acid, a phosphorylated hydroxy- substituted di- or tri- ester of phosphoric acid, and mixtures thereof.
  • an amine salt of a sulphur-free phosphorus- containing compound may be a salt of either (i) a hydroxy-substituted di- ester of phosphoric acid, or (ii) a phosphorylated hydroxy-substituted di- or tri- ester of phosphoric acid.
  • the amine salt of a sulphur-free phosphorus-containing compound may be represented Formula (2):
  • a and A' are independently H, or a hydrocarbyl group containing 1 to 30 carbon atoms;
  • each R and R" group are independently a hydrocarbyl group
  • each R' is independently R, H, or a hydroxyalkyl group
  • Y is independently R', or a group represented by RO(RO)P(O)- CH(A')CH(A)- (such as RO(RO)P(O)-CH 2 CH(CH 3 )-);
  • n and n are both positive non-zero integers, with the proviso that the sum of (m+n) is equal to 4; M is a metal ion;
  • t is an integer varying from 1 to 4 (or 1 to 2);
  • q and e are fractions, whose total provides complete valence to satisfy t, with the proviso that q is in the range of 0.1 to 1.5 (or 0.1 to 1), and e is in the range of 0 to 0.9.
  • the amine salt of a sulphur-free phosphorus-containing compound may be represented by Formula (2a):
  • a and A' are independently H, or a hydrocarbyl group containing 1 to 30 carbon atoms;
  • each R and R" group are independently a hydrocarbyl group
  • each R' is independently R, H, or a hydroxyalkyl group
  • Y is independently R', or a group represented by RO(RO)P(O)- CH(A')CH(A)- (such as RO(RO)P(O)-CH 2 CH(CH 3 )-);
  • n and n are both positive non-zero integers, with the proviso that the sum of (m+n) is equal to 4.
  • the compound represented by Formula (2) or Formula (2a) has x' equal to 1.
  • the compound represented by Formula (2) or Formula (2a) has x' is equal to 0. [0060] In one embodiment the compound represented by Formula (2) or
  • Formula (2a) has m equal to 2; and n equal to 2.
  • Formula (2a) has m equal to 3; and n equal to 1.
  • a and A' independently contain 1 to 10, or 2 to 6, or 2 to 4 carbon atoms.
  • R, R' and R" all independently contain 1 to 30, or 1 to 20, or 4 to 20 carbon atoms. In one embodiment up to half of the R' groups may be hydrogen.
  • R" contains 8 to 26, or 10 to 20, or 13 to 19 carbon atoms.
  • the amine phosphate disclosed therein may be a mono- or di- hydrocarbyl-substituted ester of a phosphorus compound salted with an amine.
  • Each hydrocarbyl-substituted ester group may contain 4 to 40 or 6 to 20 carbon atoms.
  • Examples of suitable compounds are also disclosed in Examples P-4 to P-8 of US Patent 6,468,946 (see paragraphs [0060] to [0064]).
  • the reactions described in P-4 to P-8 of US Patent 6,468,946 may also be repeated with other alcohols, including saturated or unsaturated alcohols containing 12 to 15, or 16 to 18 or 20 to 24 carbon atoms.
  • a useful alcohol is a C 18 alcohol.
  • the compound of Formula (2) or Formula (2a) includes amine salts of a primary amine, a secondary amine, a tertiary amine, or mixtures thereof.
  • the primary amine includes a tertiary-aliphatic primary amine.
  • suitable primary amines include ethylamine, propylamine, butylamine, 2-ethylhexylamine, octylamine, and dodecylamine, as well as such fatty amines as n-octylamine, n-decylamine, n-dodecylamine, n- tetradecylamine, n-hexadecylamine, n-octadecylamine and oleyamine.
  • Other useful fatty amines include commercially available fatty amines such as
  • Armeen® "Armeen®” amines (products available from Akzo Chemicals, Chicago, Illinois), such as Armeen C, Armeen O, Armeen OL, Armeen T, Armeen HT,
  • Armeen S and Armeen SD wherein the letter designation relates to the fatty group, such as coco, oleyl, tallow, or stearyl groups.
  • suitable secondary amines include dimethylamine, diethylamine, dipropylamine, dibutylamine, diamylamine, dihexylamine, diheptylamine, methylethylamine, ethylbutylamine, bis-2-ethylhexylamine, N- methyl-1-amino-cyclohexane, Armeen® 2C and ethylamylamine.
  • the secondary amines may be cyclic amines such as piperidine, piperazine and morpholine.
  • tertiary amines include tri-n-butylamine, tri-n- octylamine, tri-decylamine, tri-laurylamine, tri-hexadecylamine, tri-2-ethylhexyl amine, and dimethyloleylamine (Armeen® DMOD).
  • the amines may be in the form of a mixture.
  • suitable mixtures of amines include (i) an amine with 11 to 14 carbon atoms on tertiary alkyl primary groups, (ii) an amine with 14 to 18 carbon atoms on tertiary alkyl primary groups, or (iii) an amine with 18 to 22 carbon atoms on tertiary alkyl primary groups.
  • tertiary alkyl primary amines include tert-butylamine, tert-hexylamine, tert-octylamine (such as 1,1-dimethylhexylamine), tert-decylamine (such as 1,1-dimethyloctylamine), tertdodecylamine, tert-tetradecylamine, tert-hexadecylamine, tert- octadecylamine, tert-tetracosanylamine, and tert-octacosanylamine.
  • a useful mixture of amines includes "Primene®
  • Primene® 81R and Primene® JMT may be mixtures of CI l to C 14 tertiary alkyl primary amines and C 18 to C22 tertiary alkyl primary amines respectively.
  • the metal ion of Formula (2) may be a mono- or di- valent metal, or mixtures thereof. In one embodiment the metal ion may be divalent.
  • the metal of the metal ion includes lithium, sodium, potassium, calcium, magnesium, barium, copper, nickel, tin or zinc. [0075] In one embodiment the metal of the metal ion includes lithium, sodium, calcium, magnesium, or zinc. In one embodiment the metal of the metal ion may be zinc.
  • t is equal to 1, when the compound of Formula (2) is an amine salt or a metal salt of a monovalent metal.
  • t is equal to 2, when the compound of Formula (2) is a metal salt of a divalent metal.
  • q is in the range of 0.5 to 1; and e is in the range of O to 0.5.
  • the compound of Formula (2) is free of a metal ion (e is equal to zero; and q is equal to one).
  • t is equal to 1
  • e is equal to 1
  • q is equal to 1.
  • the sulphur-free amine salt of a phosphorus- containing compound is obtained/obtainable by a process comprising: reacting an amine with either (i) a hydroxy-substituted di-ester of phosphoric acid, or (ii) a phosphorylated hydroxy-substituted di- or tri- ester of phosphoric acid.
  • the sulphur- free amine salt of a phosphorus- containing compound is obtained/obtainable by a process comprising: reacting an amine with either (i) a hydroxy-substituted di-ester of phosphoric acid, or (ii) a phosphorylated hydroxy-substituted di- or tri- ester of phosphoric acid.
  • the salt of a hydroxy-substituted di- ester of phosphoric acid may be prepared by a process comprising:
  • salting the hydroxy-substituted di- ester of phosphoric acid is reacted with an amine and/or metal.
  • the hydroxy-substituted di- ester of phosphoric acid of (ii) may be further reacted at least once more, by repeating step (i) above, with a phosphating agent (typically forming a phosphorylated hydroxy-substituted di- or tri- ester of phosphoric acid), before salting with an amine and/or metal (as in step (iii) above).
  • a phosphating agent typically forming a phosphorylated hydroxy-substituted di- or tri- ester of phosphoric acid
  • steps (i) and (ii) may be repeated at least once more, optionally followed by step (i) before salting with an amine and/or metal (as in step (iii) above).
  • the salts may be prepared by a process comprising performing the steps (i),(ii), and (iii); or (i),(ii),(i), and (iii); or (i),(ii),(i),(ii), and (iii); (i),(ii),(i),(i),(i), and (iii), or (i),(ii),(i),(i),(i), (ii), and (iii), or (i),(ii),(i),(i),(i),(i),(i) and (iii), or (i),(ii),(i),(i),(i),(i),(i),(i) and (iii), or (i),(ii),(i),(i),(i),(i),(i),(i),(i
  • the reaction product yields 1 wt % to 99 wt %, or 20 wt % to 80 wt %, or 35 wt % to 75 wt %, of the sulphur-free amine salt of a phosphorus-containing compound of the invention.
  • the mole ratio in step (i) of the monophosphate to di-phosphate includes ranges of 1 : 10 to 10: 1, or 1 :5 to 5: 1 , or 1 :2 to 2: 1, or 1 : 1.
  • the mole ratio (based on the amount of phosphorus) in step (i) of alkylene oxide to the mono- and/or di- phosphate ester of step (i) includes ranges of 0.6:1 to 1.5:1, or 0.8:1 to 1.2:1, including 1 :1.
  • alkylene oxide includes ethylene oxide, propylene oxide or butylene oxide; the mole ratio of alkylene oxide to hydro xy-substituted di- ester of phosphoric acid in step (ii) includes 1 :1.
  • alkylene oxide includes Cs and higher alkylene oxide; and the mole ratio of alkylene oxide to the hydroxy-substituted di- ester of phosphoric acid in step (ii) includes broader ranges because the alkylene oxides are less volatile under reaction conditions.
  • steps (i) to (iii), in different embodiments may be carried out at a reaction temperature in a range of 3O 0 C to 14O 0 C, or 4O 0 C to HO 0 C, or 45 0 C to 9O 0 C.
  • the process may be carried out at reduced pressure, atmospheric pressure or above atmospheric pressure. In one embodiment the process may be carried out at atmospheric pressure or above atmospheric pressure. [0092] In one embodiment the process may be carried out in an inert atmosphere. Examples of a suitable inert atmosphere include nitrogen, argon, or mixtures thereof.
  • the alkylene oxide contains 2 to 10, or 2 to
  • the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof. In one embodiment the alkylene oxide includes propylene oxide.
  • the alcohol contains 1 to 30, or 4 to 24, or
  • the alcohol may be linear or branched.
  • the alcohol may be saturated or unsaturated.
  • Examples of a suitable alcohol include hexanol, heptanol, octanol, nonanol, dodecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, octadecenol (oleyl alcohol), nonadecanol, eicosyl-alcohol, or mixtures thereof.
  • Examples of a suitable alcohol include for example, 4-methyl-2-pentanol, 2-ethylhexanol, isooctanol, or mixtures thereof.
  • Epal® 610 and Epal® 810 of Ethyl Corporation Linevol® 79, Linevol® 911 and Dobanol® 25 L of Shell AG; Lial® 125 of Condea Augusta, Milan;
  • Useful amines include amine salts of a primary amine, a secondary amine, a tertiary amine, or mixtures thereof. A more detailed description of useful amines is defined above.
  • the amine salt of a phosphoric acid may be prepared by the methodology described in International Publication WO 2008/094759. In particular Preparative Examples 1 to 4 described in paragraphs [0151 to [0158]. Sulphur-Free Metal Salt of a Hydrocarbyl-Substituted Phosphorus-Containing Compound
  • the salt of a sulphur-free phosphorus-containing compound is known and may be prepared as is disclosed in EP 287 618, US Patent 2,228,658, US Patent 4,431,552 and US Patent 2,310,175.
  • Examples of the salt of sulphur-free phosphorus-containing compound disclosed therein include a metal hydrocarbyl-substituted phosphonate, a metal hydro carbyl- substituted phosphinate, a metal hydrocarbyl-substituted phosphite, a metal hydrocarbyl- substituted phosphonite, a metal hydrocarbyl-substituted phosphinite, or mixtures thereof.
  • the phosphorus atom of the hydrocarbyl- substituted phosphorus-containing compound is pentavalent.
  • the sulphur-free metal salt of a hydrocarbyl- substituted phosphorus-containing compound is a metal hydrocarbyl-substituted phosphonate or mixtures thereof.
  • the salt of a sulphur-free phosphorus-containing compound is a phosphorylated dispersant.
  • the phosphorylated dispersant may be prepared by reacting an inorganic phosphorus acid or anhydride with a nitrogen-containing dispersant. The resultant phosphorylated dispersant is believed to form an amine salt of the nitrogen-containing dispersant and the counterion is derived from the phosphorylating agent.
  • the nitrogen- containing dispersant is ashless. It is desirable to ensure the reaction of the inorganic phosphorus acid or anhydride with the nitrogen-containing dispersant produces a product that incorporates the phosphorus into the dispersant instead of forming insoluble phosphorus particulates. If solid particulates form, the resultant product is likely to be hazy and less stable. The use of such a product may reduce the effects observed by the present invention.
  • Ashless dispersants are typically known, prior to mixing in a lubricating oil composition, not to contain ash-forming metals and they do not normally contribute any ash forming metals when added to a lubricant and polymeric dispersants. Ashless dispersants are characterised by a polar group attached to a relatively high molecular weight hydrocarbon chain.
  • Examples of inorganic phosphorus acids or anhydride which are useful in forming the salt of a sulphur-free phosphorus-containing compound include phosphorous acid, phosphoric acid (H3PO4), hypophosphoric acid, phosphorus trioxide (P2O3), phosphorus tetraoxide (P2O4), and phosphoric anhydride (P2O5, or P4O10).
  • the inorganic phosphorus acids or anhydride may be either is phosphorous acid (H 3 PO 3 ) or phosphoric acid (H 3 PO 4 ).
  • the inorganic, oil-insoluble phosphorus containing acids may be reacted with the ashless dispersant which contains basic nitrogen or one or more free hydroxyl groups.
  • the resulting product is believed to be oil-soluble.
  • the nitrogen-containing dispersants include: (i) hydrocarbyl-substituted succinimides; (ii) mixed ester/amides of hydrocarbyl-substituted succinic acid made using alkanols, amines, and/or aminoalkanols; (iii) Mannich dispersants which are condensation products of hydrocarbyl-substituted phenols, formaldehyde and polyethylene polyamines (described in U.S. Patents 3,368,972; 3,413,374; 3,539,633; 3,649,279; 3,798,247 and 3,803,039); and (iv) mixtures thereof.
  • Typical ashless dispersants include N-substituted long chain alkenyl succinimides.
  • N-substituted long chain alkenyl succinimides include polyisobutylene succinimide with number average molecular weight of the polyisobutylene substituent in the range 350 to 5000, 500 to 3000, or 550 to 2500.
  • Succinimide dispersants and their preparation are disclosed, for instance in US Patent 3,172,892 or US Patent 4,234,435 and in EP 0355895.
  • Succinimide dispersants are typically the imide formed from a polyamine, typically a poly(ethyleneamine).
  • the invention further comprises at least one dispersant derived from polyisobutylene succinimide with number average molecular weight in the range 350 to 5000, 500 to 3000, or 550 to 2500.
  • the polyisobutylene succinimide may be used alone or in combination with other dispersants. 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, re- refined oils or mixtures thereof.
  • a more detailed description of unrefined, refined and re-refined oils is provided in International Publication WO2008/147704, paragraphs [0054] to [0056].
  • a more detailed description of natural and synthetic lubricating oils is described in paragraphs [0058] to [0059] respectively of WO2008/147704.
  • Synthetic oils may also be produced by Fischer-Tropsch reactions and typically may be hydroisomerised Fischer- Tropsch hydrocarbons or waxes.
  • 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 April 2008 version of "Appendix E - API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils", section 1.3 Sub-heading 1.3. "Base Stock Categories”.
  • the oil of lubricating viscosity may be an API Group I, or Group II, or Group III, or Group IV oil.
  • the oil of lubricating viscosity may be an API Group II or Group III oil.
  • 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 compound of the invention 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 the additives disclosed hereinabove) 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 these additives 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 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.
  • performance additives include metal deactivators, viscosity modifiers (such as hydrogenated copolymers of styrene-butadiene, ethylene-propylene copolymers, or mixtures thereof), detergents (such as salicylates, sulphonates, salixarates, phenates, or mixtures thereof), friction modifiers (such as glycerol monooleate), antiwear agents (such as zinc dialkyldithiophosphates), corrosion inhibitors, dispersants (typically succinimides), dispersant viscosity modifiers, extreme pressure agents, antioxidants (including alkylated diphenylamines (typically di-nonyl diphenylamine, octyl diphenylamine, di-octyl diphenylamine), hindered phenols, oil-soluble molybdenum compounds, or mixtures thereof), foam inhibitors,
  • viscosity modifiers such as hydrogenated copoly
  • the lubricating composition further comprises at least one of a viscosity modifier, an antioxidant, an overbased detergent, a succinimide dispersant (other than the phosphorylated dispersant of the invention), an antiwear agent (other than those described herein as part of the invention), or mixtures thereof.
  • the lubricating composition is free of zinc dihydrocarbyl dithiophosphate. In one embodiment the lubricating composition further includes zinc dihydrocarbyl dithiophosphate.
  • a hindered phenol antioxidant is an ester and may include, e.g., IrganoxTM L-135 from Ciba or an addition 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
  • an addition 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.
  • the lubricating composition further contains an oil-soluble molybdenum compound.
  • the 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 dithio carbamates, 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 oil-soluble molybdenum compound is a molybdenum dithiocarbamate.
  • Suitable examples of molybdenum dithiocarbamates which may be used as an antioxidant include commercial materials sold under the trade names such as Molyvan 822TM and MolyvanTM A from R.T. Vanderbilt Co., Ltd., and
  • the mechanical device is an internal combustion engine.
  • the internal combustion engine may be a diesel fueled engine, a gasoline fueled engine, a natural gas fueled engine or a mixed gasoline/alcohol fueled engine. In one embodiment the internal combustion engine may be a diesel fueled engine and in another embodiment a gasoline fueled 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.
  • the internal combustion engine contains components of an aluminium-alloy.
  • the aluminium- alloy includes aluminium silicates, aluminium oxides, or other ceramic materials.
  • the aluminium-alloy is an aluminium-silicate surface.
  • 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
  • the phosphorus content may be 0.2 wt % or less, or 0.1 wt % or less, or 0.085 wt % or less, or even
  • the phosphorus content may be 100 ppm to 1000 ppm, or 200 ppm to 600 ppm.
  • the total sulphated ash content may be 2 wt % or less, or 1.5 wt % or less, or
  • the sulphated ash content may be 0.05 wt % to 0.9 wt %, or
  • 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 0.07 wt % or less, and
  • the lubricating composition is suitable for a 2- stroke or a 4-stroke marine diesel internal combustion engine.
  • the marine diesel combustion engine is a 2-stroke engine.
  • the antiwear package may contain the compound of Formula (Ia) and/or (Ib) (or in one embodiment the derivative of a hydroxycarboxylic acid) in an internal combustion engine lubricant at an amount in the range of 0.005 wt % to 10 wt %, or 0.025 to 5 wt %, or 0.25 to 2.5 wt % of the lubricating composition.
  • the antiwear package may contain the salt of a sulphur-free phosphorus-containing compound in an internal combustion engine lubricant at an amount in the range of 0.005 wt % to 10 wt %, or 0.025 to 5 wt %, or 0.25 to
  • Phosphorylated Hydroxyalkyl Ester of Thiophosphoric Acid Phosphorus pentoxide (144 grams) is added in two portions one hour apart to 1 176 grams of hydroxypropyl O,O-di(4-methyl-2-pentyl)phosphorodithioate (prepared by reacting di(4-methyl-2-pentyl)-phosphorodithioic acid with about 1.1 moles of propylene oxide at 54°C and removing excess propylene oxide by vacuum stripping). The mixture is heated at 71 0 C for 6 hours to give an acidic intermediate (132Og). This intermediate is neutralised by adding 555 g of a
  • Ci 2 -i 4 -alkyl amine over two hours at 49°C. After heating to 77°C the material is vacuum stripped to give the product.
  • Example 1 (EXl) is an internal combustion lubricant containing (i)
  • a amine phosphate prepared in a similar manner to P-4 as is described in US Patent 6,468,946, except the alcohol employed is a Cl 8 alcohol, (ii) a tartrate diester of a C 6 to C 15 alcohol, and (iii) other conventional engine oil additives including antioxidants, viscosity modifiers, succinimide dispersants, glycerol monooleate friction modifiers, foam inhibitors, pour point depressants, and overbased detergents.
  • the lubricant contains about 500 ppm of phosphorus.
  • Example 2 (EX2) is similar to Example 1, except 0.64 wt % of the product of Preparative Example 1 above is employed.
  • the lubricant contains about 500 ppm of phosphorus.
  • Comparative Example 1 (CEl) is similar to Example 2, except the product of Preparative Example 1 is replaced with a material prepared from
  • the lubricant contains about 500 ppm of phosphorus.
  • Comparative Example 2 (CE2) is similar to Example 1, except the lubricant does not contain the tartrate diester of a C 6 to C 15 alcohol.
  • the lubricant contains about 500 ppm of phosphorus.
  • Comparative Example 3 contains (i) 0.59 wt % of the product of PCEl, and (ii) other conventional engine oil additives including antioxidants, viscosity modifiers, succinimide dispersants, glycerol monooleate friction modifiers, foam inhibitors, pour point depressants, and overbased detergents.
  • the lubricant contains about 500 ppm of phosphorus.
  • Comparative Example 4 contains (i) 0.64 wt % of the product of Preparative Example 1 above is employed, and (ii) other conventional engine oil additives including antioxidants, viscosity modifiers, succinimide dispersants, glycerol monooleate friction modifiers, foam inhibitors, pour point depressants, and overbased detergents.
  • the lubricant contains about 500 ppm of phosphorus.
  • HFRR high frequency reciprocating rig
  • Each sample is treated with 1 wt % cumene hydroperoxide.
  • HFRR conditions for the evaluations are 50Og load, 75 minute duration, 1000 micrometer stroke, 20 hertz frequency, and isothermal temperature profile at 105 0 C. 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 percent film thickness is based on the measurement of electrical potential between an upper and a lower metal test plate in the HFRR.
  • the film thickness is 100%, there is a high electrical potential for the full length of the 1000 micrometre stroke, suggesting no metal to metal contact.
  • a film thickness of 0% there is no electrical potential suggesting continual metal to metal contact between the plates.
  • the upper and lower metal test plate have a degree of metal to metal contact as well as other areas with no metal to metal contact.
  • the lubricating composition containing both (i) the tartrate ester and (ii) the salt of a sulphur-free phosphorus-containing compound is capable of providing an internal combustion engine with acceptable levels of wear performance and formation of a film.
  • Example CE5 is a lubricant composition containing (i) a commercially available zinc dialkyldithiophosphate (ZDDP) known to be employed in an internal combustion engine lubricant, and (ii) other conventional engine oil additives including antioxidants, viscosity modifiers, succinimide dispersants, glycerol monooleate friction modifiers, foam inhibitors, pour point depressants, and overbased detergents.
  • ZDDP zinc dialkyldithiophosphate
  • other conventional engine oil additives including antioxidants, viscosity modifiers, succinimide dispersants, glycerol monooleate friction modifiers, foam inhibitors, pour point depressants, and overbased detergents.
  • the lubricant contains about 500 ppm of phosphorus.
  • CE5 is evaluated in the HFRR in a similar way as described above. The results obtained for CE5 indicate a wear scar of 260 ⁇ m and a film thickness of 29 %. Comparing CE5 to EX2 indicates
  • CE5 to EXl indicates that the invention lubricant (EXl) has performance approaching commercially available ZDDP containing lubricants.
  • EXl invention lubricant
  • EXl has increased film thickness formation relative to CE5.
  • EX2 has improved performance over CEl to CE5 in both wear reduction and increased film thickness formation.
  • EXl is improved over comparative examples CEl to CE4 in both wear reduction and increased film thickness. Further EXl is has wear performance approaching that of CE5 without the need to employ ZDDP.
  • Example 3 is similar to EXl, except 1 wt % of butyl citrate is used instead of the tartrate diester of a C 6 to C 15 alcohol.
  • Example 4 is similar to EX2, except 1 wt % of butyl citrate is used instead of the tartrate diester of a C 6 to C 15 alcohol.
  • Comparative Example 6 is similar to CEl, except 1 wt % of butyl citrate is used instead of the tartrate diester of a C 6 to C 15 alcohol.
  • EX3, EX4 and CE6 are evaluated in the HFRR in a similar way as described above.
  • the HFRR wear result obtained for EX3, EX4 and CE6 is 412 ⁇ m, 397 ⁇ m and 404 ⁇ m respectively.
  • the film thickness result obtained for EX3, EX4 and CE6 is 2 %, 2 % and 3 % respectively.
  • DPI Phosphorylated Dispersant 1
  • Example 5 (EX5) is a 5W-30 lubricant containing (i) 2.8 wt % of the product of DPI , (ii) 1 wt % of a tartrate diester of a C 6 to C 15 alcohol, and (iii) other conventional engine oil additives including antioxidants, viscosity modifiers, succinimide dispersants, glycerol monooleate friction modifiers, foam inhibitors, pour point depressants, and overbased detergents.
  • the lubricant contains about 500 ppm of phosphorus.
  • Example 6 is similar to EX5, except 2.3 wt % of the product of DP2 is used instead of DPI .
  • the lubricant contains about 500 ppm of phosphorus.
  • Comparative Example 7 is similar to EX5, except it does not contain 1 wt % of a tartrate diester of a C6 to C 15 alcohol.
  • Examples EX5 to EX6 and comparative example CE7 are evaluated for wear using a high frequency reciprocating rig (HFRR) by the methodology described above. The results obtained are:
  • 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, including aliphatic, alicyclic, and aromatic substituents; 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; and hetero substituents, that is, substituents which similarly have a predominantly hydrocarbon character but contain other than carbon in a ring or chain.
  • hydrocarbyl substituent or “hydrocarbyl group” is described in paragraphs [0118] to [0119] of International Publication WO2008147704.

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

L'invention porte sur une composition lubrifiante contenant une huile de viscosité lubrifiante et un ensemble anti-usure. L'ensemble anti-usure contient un dérivé d'un acide hydroxycarboxylique; et un sel d'un composant exempt de soufre et contenant du phosphore. Le sel comprend des sels d'amine, des sels d'ammonium, des sels de métaux et des mélanges de ces sels. L'invention porte aussi sur un procédé pour céder la composition lubrifiante à un moteur à combustion interne.
EP10745707A 2009-08-18 2010-08-17 Composition anti-usure et procédé de lubrification d'un moteur à combustion interne Withdrawn EP2467459A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US23472509P 2009-08-18 2009-08-18
PCT/US2010/045682 WO2011022347A1 (fr) 2009-08-18 2010-08-17 Composition anti-usure et procédé de lubrification d'un moteur à combustion interne

Publications (1)

Publication Number Publication Date
EP2467459A1 true EP2467459A1 (fr) 2012-06-27

Family

ID=43088160

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10745707A Withdrawn EP2467459A1 (fr) 2009-08-18 2010-08-17 Composition anti-usure et procédé de lubrification d'un moteur à combustion interne

Country Status (6)

Country Link
US (1) US20120202727A1 (fr)
EP (1) EP2467459A1 (fr)
CN (1) CN102753661B (fr)
BR (1) BR112012003696A2 (fr)
CA (1) CA2772243A1 (fr)
WO (1) WO2011022347A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9969950B2 (en) * 2012-07-17 2018-05-15 Infineum International Limited Lubricating oil compositions containing sterically hindered amines as ashless TBN sourcces
CN105524683A (zh) * 2014-09-28 2016-04-27 中国石油化工股份有限公司 磷化无灰分散剂、其制备方法及提高润滑油动摩擦系数的方法
CN105038905B (zh) * 2015-07-09 2017-10-31 太原理工大学 一种润滑油、润滑油添加剂及其制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2288679A1 (fr) * 2008-03-19 2011-03-02 The Lubrizol Corporation Composition anti-usure, et procédé de lubrification d'équipement de ligne cinématique

Family Cites Families (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2228658A (en) 1938-11-21 1941-01-14 Standard Oil Co Compounded mineral oil
US2308502A (en) * 1940-08-02 1943-01-19 Standard Oil Co Compounded oil
US2310175A (en) 1941-01-13 1943-02-02 Standard Oil Co California Compounded mineral oil
DE1248643B (de) 1959-03-30 1967-08-31 The Lubrizol Corporation, Cleveland, Ohio (V. St. A.) Verfahren zur Herstellung von öllöslichen aeylierten Aminen
US3368972A (en) 1965-01-06 1968-02-13 Mobil Oil Corp High molecular weight mannich bases as engine oil additives
US3539633A (en) 1965-10-22 1970-11-10 Standard Oil Co Di-hydroxybenzyl polyamines
US3413374A (en) 1966-05-04 1968-11-26 Toyo Rayon Co Ltd Disproportionation of toluene
US3691077A (en) * 1968-09-26 1972-09-12 Robert Earl Wann Lubricant composition
US3649279A (en) 1970-01-15 1972-03-14 Eastman Kodak Co Photographic compositions with a thiosemicarbazone solubilizing agent
US3803039A (en) 1970-07-13 1974-04-09 Standard Oil Co Oil solution of aliphatic acid derivatives of high molecular weight mannich condensation product
US3798247A (en) 1970-07-13 1974-03-19 Standard Oil Co Oil soluble aliphatic acid derivatives of molecular weight mannich condensation products
US4326972A (en) 1978-06-14 1982-04-27 The Lubrizol Corporation Concentrates, lubricant compositions and methods for improving fuel economy of internal combustion engine
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
US4237022A (en) 1979-10-01 1980-12-02 The Lubrizol Corporation Tartarimides and lubricants and fuels containing the same
FR2512458A1 (fr) 1981-09-10 1983-03-11 Lubrizol Corp Compositions, concentres, compositions lubrifiantes et procedes pour augmenter les economies de combustible dans les moteurs a combustion interne
US4431552A (en) 1982-11-26 1984-02-14 Chevron Research Company Lubricant composition containing an alkali-metal borate and a mixture of phosphates, monothiophosphates and dithiophosphates in a critical ratio
EP0287618B1 (fr) 1986-10-21 1992-12-09 The Lubrizol Corporation Sels metalliques solubles dans l'huile d'esters d'acide phosphorique
US4952328A (en) 1988-05-27 1990-08-28 The Lubrizol Corporation Lubricating oil compositions
GB8818711D0 (en) 1988-08-05 1988-09-07 Shell Int Research Lubricating oil dispersants
US5338470A (en) 1992-12-10 1994-08-16 Mobil Oil Corporation Alkylated citric acid adducts as antiwear and friction modifying additives
AU4860999A (en) 1998-07-06 2000-01-24 Lubrizol Corporation, The Mixed phosphorus compounds and lubricants containing the same
US6559105B2 (en) 2000-04-03 2003-05-06 The Lubrizol Corporation Lubricant compositions containing ester-substituted hindered phenol antioxidants
US7696136B2 (en) 2004-03-11 2010-04-13 Crompton Corporation Lubricant compositions containing hydroxy carboxylic acid and hydroxy polycarboxylic acid esters
US7651987B2 (en) 2004-10-12 2010-01-26 The Lubrizol Corporation Tartaric acid derivatives as fuel economy improvers and antiwear agents in crankcase oils and preparation thereof
US7807611B2 (en) 2004-10-12 2010-10-05 The Lubrizol Corporation Tartaric acid derivatives as fuel economy improvers and antiwear agents in crankcase oils and preparation thereof
US20060276352A1 (en) * 2005-06-02 2006-12-07 James N. Vinci Oil composition and its use in a transmission
CA2666097A1 (fr) 2006-10-23 2008-06-12 The Lubrizol Corporation Agent anti-usure et composition lubrifiante de celui-ci
WO2008067529A2 (fr) * 2006-11-30 2008-06-05 Rockline Industries, Inc. Couvercle de distribution à bouton poussoir
US20080182770A1 (en) 2007-01-26 2008-07-31 The Lubrizol Corporation Antiwear Agent and Lubricating Compositions Thereof
WO2008147704A1 (fr) 2007-05-24 2008-12-04 The Lubrizol Corporation Composition lubrifiante contenant un agent anti-usure
WO2008147701A1 (fr) * 2007-05-24 2008-12-04 The Lubrizol Corporation Procédé de lubrification d'une surface composite de silicate d'aluminium avec un lubrifiant comprenant un agent anti-usure dépourvu de soufre, de phosphore, sans cendre
FR2924439B1 (fr) * 2007-12-03 2010-10-22 Total France Composition lubrifiante pour moteur quatre temps a bas taux de cendres
US20120172265A1 (en) * 2008-12-09 2012-07-05 The Lubrizol Corporation Lubricating Composition Containing a Compound Derived from a Hydroxy-carboxylic Acid

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2288679A1 (fr) * 2008-03-19 2011-03-02 The Lubrizol Corporation Composition anti-usure, et procédé de lubrification d'équipement de ligne cinématique

Also Published As

Publication number Publication date
CA2772243A1 (fr) 2011-02-24
CN102753661A (zh) 2012-10-24
BR112012003696A2 (pt) 2016-03-29
US20120202727A1 (en) 2012-08-09
CN102753661B (zh) 2015-09-16
WO2011022347A1 (fr) 2011-02-24

Similar Documents

Publication Publication Date Title
EP2463358B1 (fr) Composition de lubrification contenant un agent anti-usure sans cendres basé sur un dérivé d'acide hydroxypolycarboxylique et un composé de molybdène
EP2467457B1 (fr) Compositions lubrifiantes contenant un additif anti usure
US9540585B2 (en) Lubricating composition containing an antiwear agent
US20100093573A1 (en) Lubricating Composition Containing Sulphur, Phosphorus and Ashfree Antiwear Agent and Amine Containing Friction Modifier
EP3578625B1 (fr) Composition lubrifiante et dispersants associés ayant un effet bénéfique sur la stabilité à l'oxydation
EP2675874B1 (fr) Procédé de lubrification d'une chaîne cinématique
US20120202727A1 (en) Antiwear Composition and Method of Lubricating an Internal Combustion Engine
EP2721128B1 (fr) Composition lubrifiante contenant un ester d'un acide carboxylique aromatique

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20120314

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20130111

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20161210