US20170051226A1 - Use of a lubricant composition for reducing knocking - Google Patents

Use of a lubricant composition for reducing knocking Download PDF

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Publication number
US20170051226A1
US20170051226A1 US15/306,302 US201515306302A US2017051226A1 US 20170051226 A1 US20170051226 A1 US 20170051226A1 US 201515306302 A US201515306302 A US 201515306302A US 2017051226 A1 US2017051226 A1 US 2017051226A1
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Prior art keywords
carbon atoms
group
saturated
alkyl group
hydrogen atom
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US15/306,302
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Inventor
Nicholas Obrecht
Steve FAURE
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TotalEnergies Marketing Services SA
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Total Marketing Services SA
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Assigned to TOTAL MARKETING SERVICES reassignment TOTAL MARKETING SERVICES ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: OBRECHT, NICOLAS, FAURE, Steve
Publication of US20170051226A1 publication Critical patent/US20170051226A1/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/12—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M127/00—Lubricating compositions characterised by the additive being a non- macromolecular hydrocarbon
    • C10M127/04—Lubricating compositions characterised by the additive being a non- macromolecular hydrocarbon well-defined aromatic
    • 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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/02—Well-defined hydrocarbons
    • C10M105/04—Well-defined hydrocarbons aliphatic
    • C—CHEMISTRY; METALLURGY
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    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/16—Ethers
    • C—CHEMISTRY; METALLURGY
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    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
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    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/02—Well-defined aliphatic compounds
    • C10M2203/024—Well-defined aliphatic compounds unsaturated
    • C—CHEMISTRY; METALLURGY
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    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/06—Well-defined aromatic compounds
    • C—CHEMISTRY; METALLURGY
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    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
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    • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
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    • C10M2207/02—Hydroxy compounds
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    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds used as base material
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal salts
    • C—CHEMISTRY; METALLURGY
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    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/02—Unspecified siloxanes; Silicones
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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    • 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
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/18—Anti-foaming property
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/54—Fuel economy
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/76—Reduction of noise, shudder, or vibrations
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
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    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
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Definitions

  • the present invention relates to the field of lubricants, more particularly to the field of the engine lubricants. More particularly, the present invention relates to the use of a lubricant composition in order to reduce knock in a vehicle engine, said lubricant composition comprising at least one base oil and at least one organic anti-knock compound.
  • the lubricant composition according to the invention thus makes it possible to reduce, or even to eliminate knock in a vehicle engine, preferably a motor vehicle engine, while retaining good lubrication properties.
  • the present invention also relates to a lubricating process implementing this composition.
  • the present invention also relates to a process for reducing or even eliminating knock in a vehicle engine, preferably a motor vehicle engine, utilizing this lubricant composition.
  • the present invention also relates to the use of an organic compound in a lubricant composition in order to reduce or even eliminate knock in a vehicle engine, preferably a motor vehicle engine.
  • the present invention also relates to the use of a composition of the additive-concentrate type comprising at least one organic compound in order to reduce or even eliminate knock in a vehicle engine, preferably a motor vehicle engine, utilizing said organic compound.
  • Knock is a phenomenon which occurs in a positive ignition engine of a vehicle, and more particularly in a positive ignition engine of motor vehicles and which is due to the auto-ignition of the fuel upstream of the flame front in the combustion chamber.
  • This auto-ignition propagates at very high speed in the combustion chamber and causes high-frequency vibrations in the gaseous mass, and thermal overload of the engine which may even result serious mechanical incidents.
  • Combustion is a compromise between the speed of propagation of the flame front originating from the spark plug and the auto-ignition delay time of the fuel.
  • knock occurs in the areas distant from the spark plug and most often close to the piston and the cylinder.
  • a lubricant and more particularly an engine lubricant, is used in the cylinders in order to reduce friction as well as the risks of wear.
  • the proximity of the engine lubricant to the areas where knock appears opens up the possibility of interaction between the lubricant and the combustion.
  • lubricants making it possible to attenuate or even to reduce engine knock have been sought.
  • U.S. Pat. Nos. 2,763,613 and 2,898,359 have in particular described the use of anti-knock compounds selected from organometallic compounds, and more particularly ferrocene-type compounds in a lubricant composition.
  • document WO2004/101717 describes the use of manganese-based organometallic compounds in a lubricant composition in order to reduce the knock phenomenon in an engine.
  • the use of such organometallic compounds promotes deposits in the combustion chamber and can thus lead to abnormal combustion such as pre-ignition which can cause significant mechanical malfunction(s). Furthermore, they can present a risk to human health.
  • An object of the invention is thus the use of a lubricant composition in order to reduce knock in a vehicle engine, preferably a motor vehicle engine, said lubricant composition comprising:
  • a compound of formula (I) as defined above in a lubricant composition makes it possible for the lubricant composition, once utilized in an engine, to reduce or even to eliminate the knock phenomenon in the engine.
  • the present invention makes it possible to formulate lubricant compositions having both a good stability and good properties of reduction or even elimination of the knock phenomenon once utilized in an engine.
  • the lubricant compositions according to the invention have good properties of reduction or even elimination of the knock phenomenon once utilized in an engine without needing to add a high content of anti-knock compound in the lubricant composition.
  • the lubricant compositions according to the invention have good properties of reduction or even elimination of the knock phenomenon once utilized in an engine without needing to add thereto other anti-knock additives, and in particular no anti-knock additives selected from the organometallic compounds.
  • the lubricant compositions according to the invention have good properties of reduction or even elimination of the knock phenomenon once utilized in an engine and the formulation of which is easy to implement.
  • the lubricant compositions according to the invention have good properties of reduction or even elimination of the knock phenomenon once utilized in an engine while making it possible to reduce or even to eliminate the risk of deposits in the combustion chamber.
  • the lubricant composition essentially consists of:
  • the invention also relates to an engine oil comprising a lubricant composition as defined above.
  • the invention also relates to the use of a lubricant composition as defined above for the lubrication of vehicle engines, preferentially motor vehicle engines.
  • the invention also relates to the use of a lubricant composition as defined above in order to reduce or even eliminate knock in engines, preferentially motor vehicle engines.
  • the invention also relates to a lubricating process of a vehicle engine, preferably a motor vehicle engine, said process comprising at least one step of bringing a mechanical part of the engine into contact with a lubricant composition as defined above.
  • the invention also relates to a process for reducing or even eliminating knock in a vehicle engine, preferentially motor vehicle engines, comprising at least one step of bringing a mechanical part of the engine of the vehicle into contact with a lubricant composition as defined above.
  • the invention also relates to the use of a compound of formula (I) as defined above in a lubricant composition in order to reduce or even eliminate knock in engines, preferentially motor vehicle engines.
  • the invention also relates to the use of a composition of the additive-concentrate type in a lubricant composition comprising at least one base oil in order to reduce or even eliminate knock in engines, preferentially motor vehicle engines, said composition of the additive-concentrate type comprising:
  • At least one additive selected from the detergents, friction modifiers, anti-wear additives, dispersants, extreme-pressure additives, antioxidants, viscosity index improver polymers, flow point improvers, anti-foaming agents, thickeners and mixtures thereof.
  • the percentages indicated below correspond to percentages by weight of active ingredient.
  • the lubricant composition comprises at least one compound of formula (I):
  • the compound of formula (I) as defined above comprises no metal nor any metallic derivative.
  • the compound of formula (I) as defined above is not an organometallic compound.
  • the compound of formula (I) as defined above comprises at least one R1 to R6 group different from a hydrogen atom.
  • the compound of formula (I) as defined above is different from benzene.
  • the lubricant composition comprises at least one compound of formula (I) as defined above in which R1 represents a hydrogen atom.
  • the lubricant composition comprises at least one compound of formula (I) as defined above in which:
  • R1 represents a hydrogen atom
  • R2 represents a hydrogen atom, a saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl group, comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, advantageously from 1 to 3 carbon atoms,
  • R3 represents a hydrogen atom, a saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl group, comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, advantageously from 1 to 3 carbon atoms,
  • R4 represents a hydrogen atom, a saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl group, comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, advantageously from 1 to 3 carbon atoms,
  • R5 represents a hydrogen atom, a saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl group, comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, advantageously from 1 to 3 carbon atoms,
  • R6 represents a hydrogen atom, a saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl group, comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, advantageously from 1 to 3 carbon atoms,
  • At the most one of the R2 to R6 groups represents a hydrogen atom.
  • the lubricant composition comprises at least one compound of formula (I) as defined above in which R1 represents a saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl group, comprising from 1 to 10 carbon atoms, an —OR7 group, an —NR8R9 group, R7, R8 and R9 being as defined above.
  • the lubricant composition comprises at least one compound of formula (I) as defined above in which:
  • R1 represents a saturated, linear or branched alkyl group, comprising from 1 to 5 carbon atoms, preferably from 1 to 3 carbon atoms, advantageously a methyl or ethyl group,
  • R2 represents a hydrogen atom or a saturated, linear or branched alkyl group, comprising from 1 to 5 carbon atoms, preferably from 1 to 3 carbon atoms, advantageously a methyl or ethyl group,
  • R3 represents a hydrogen atom or a saturated, linear or branched alkyl group, comprising from 1 to 5 carbon atoms, preferably from 1 to 3 carbon atoms, advantageously a methyl or ethyl group,
  • R4 represents a hydrogen atom or a saturated, linear or branched alkyl group, comprising from 1 to 5 carbon atoms, preferably from 1 to 3 carbon atoms, advantageously a methyl or ethyl group,
  • R5 represents a hydrogen atom or a saturated, linear or branched alkyl group, comprising from 1 to 5 carbon atoms, preferably from 1 to 3 carbon atoms, advantageously a methyl or ethyl group,
  • R6 represents a hydrogen atom or a saturated, linear or branched alkyl group, comprising from 1 to 5 carbon atoms, preferably from 1 to 3 carbon atoms, advantageously a methyl or ethyl group,
  • R2 to R6 groups represent a saturated, linear or branched alkyl group, comprising from 1 to 5 carbon atoms, preferably from 1 to 3 carbon atoms, advantageously a methyl or ethyl group.
  • the lubricant composition comprises at least one compound of formula (I) as defined above in which R5 represents a hydrogen atom.
  • the lubricant composition comprises at least one compound of formula (I) as defined above in which R6 represents a hydrogen atom.
  • the lubricant composition comprises a compound of formula (I) as defined above in which R1 represents:
  • the lubricant composition comprises a compound of formula (I) as defined above in which R2 represents:
  • the lubricant composition comprises a compound of formula (I) as defined above in which R3 represents:
  • the lubricant composition comprises a compound of formula (I) as defined above in which R4 represents:
  • the lubricant composition comprises at least one compound of formula (I) in which: R1 represents:
  • the lubricant composition comprises at least one compound of formulae (Ia) to (If):
  • the lubricant composition comprises at least one compound of formulae (Ia) to (Ic):
  • R1 represents:
  • the lubricant composition comprises at least one compound of formulae (Ia) to (Ic):
  • the lubricant composition comprises at least one compound of formulae (Ia) to (Ic) as defined above in which:
  • the lubricant composition comprises at least one compound of formulae (Ia) to (Ic):
  • the lubricant composition comprises at least one compound of formulae (Ia) to (Ic):
  • the lubricant composition comprises at least one compound of formulae (Ia) to (Ic):
  • the lubricant composition comprises at least one compound of formulae (Ia) to (Ic):
  • the lubricant composition comprises at least one compound of formulae (Ia) to (Ic):
  • the lubricant composition used according to the invention comprises at least one compound of formulae (Ia) to (Ic) as defined above in which:
  • the content by weight of the compound of formula (I) ranges from 0.5 to 25%, preferably from 1 to 20%, advantageously from 5 to 15% with respect to the total weight of the lubricant composition.
  • the compound of formula (I) can be presented in a pure form.
  • pure form according to the invention is meant that the compound of formula (I) is single-component and comprise no other component other than the compound of formula (I) or is not combined with another compound.
  • the compound of formula (I) can be encapsulated.
  • the compound of formula (I) can be presented in the form of a capsule or of a microcapsule comprising a minimal content of the compound of formula (I), this minimal content being selected so that the content by weight of the compound of formula (I) ranges from 0.5 to 25%, preferably from 1 to 20%, advantageously from 5 to 15% with respect to the total weight of the lubricant composition.
  • the capsules or microcapsules comprising the compound of formula (I) can be selected from any type of capsules or microcapsules known to a person skilled in the art.
  • the capsules or microcapsules can in particular be constituted by a polymeric envelope selected from the polyurethanes, polyureas, polystyrenes, polyesters, polyamides or copolymers thereof, the polyacrylonitriles, vinyl resins, formaldehyde-based resins or also aminoplast resins.
  • compound (I) will be released out of the capsules or microcapsules when the capsules or microcapsules are subjected to physical-chemical stresses, and more particularly when the capsules or microcapsules are subjected to high temperatures, for example temperatures greater than 150° C. as can be encountered in the areas close to the piston, or when the capsules or microcapsules are subjected to strong shear stresses, which is generally the case in an engine, corresponding for example to values of 10 to 100 million reciprocal seconds (s ⁇ 1 ), or also when the capsules or microcapsules are subjected to variations in the acidity or basicity of the surrounding medium, and more particularly to variations in acidity as can occur in the piston/liner zone.
  • examples of capsules or microcapsules that can be used in the present invention are in particular described in documents WO2010/134044, U.S. Patent Publication No. 2013/0146009 or WO2014/046876.
  • compound (I) can be released by volatilization.
  • the volatilization of the compound of formula (I) can in particular be implemented by adjustment of the distillation curve of the lubricant composition.
  • the use of a compound of formula (I) can be mentioned, which is more volatile than the remainder of the lubricant composition and which makes it possible to extract the compound of formula (I) in the areas subjected to temperatures greater than the boiling point of the compound of formula (I) but less than the boiling point of the lighter components of the remainder of the lubricant composition.
  • the compound of formula (I) can be synthesized in situ in the lubricant composition.
  • the lubricant compositions used according to the invention can contain any type of lubricant base oil, mineral, synthetic or natural, animal or vegetable suited to their use.
  • the base oil or oils used in the lubricant compositions used according to the present invention can be oils of mineral or synthetic origin of Groups I to V according to the classes defined in the API classification (or their equivalents according to the ATIEL classification) as summarized below, alone or in a mixture.
  • Viscosity Saturates Sulphur index content content (VI) Group I Mineral oils ⁇ 90% >0.03% 80 ⁇ VI ⁇ 120 Group II ⁇ 90% ⁇ 0.03% 80 ⁇ VI ⁇ 120 Hydrocracked oils Group III ⁇ 90% ⁇ 0.03% ⁇ 120 Hydrocracked or hydro-isomerized oils Group IV Poly Alpha Olefins (PAO) Group V Esters and other bases not included in bases of Groups I to IV
  • the mineral base oils used according to the invention include any type of bases obtained by atmospheric and vacuum distillation of crude oil, followed by refining operations such as solvent extraction, deasphalting, solvent dewaxing, hydrotreatment, hydrocracking and hydroisomerization, hydrofinishing.
  • the base oils of the lubricant compositions used according to the invention can also be synthetic oils, such as certain esters of carboxylic acids and alcohols, or poly alpha olefins.
  • the poly alpha olefins used as base oils are for example obtained from monomers having 4 to 32 carbon atoms (for example octene, decene), and a viscosity at 100° C. comprised between 1.5 and 15 cSt according to the standard ASTM D445.
  • Their weight-average molecular weight is typically comprised between 250 and 3000 according to the standard ASTM D5296. Mixtures of synthetic oils and mineral oils can also be used.
  • a particular lubricating base for producing the lubricating compositions according to the invention except that they must have properties, in particular in terms of viscosity, viscosity index, sulphur content, oxidation resistance, suitable for use in a gearbox, in particular in a motor vehicle gearbox, in particular in a manual gearbox.
  • the lubricating bases represent at least 50% by weight, relative to the total weight of the lubricating composition, preferentially at least 60%, or also at least 70%. Typically, they represent between 75 and 99.9% by weight, with respect to the total weight of the lubricant compositions according to the invention.
  • the lubricant compositions comprise mineral bases of Group I and/or III, or synthetic bases of Group IV according to the API classification.
  • the lubricant compositions have a kinematic viscosity at 100° C. measured according to the standard ASTM D445 ranging from 3 to 25 cSt, preferably from 5 to 22 cSt, advantageously from 5 to 13 cSt.
  • the lubricant compositions have a viscosity index (VI) greater than or equal to 130, preferentially greater than or equal to 140, advantageously greater than or equal to 150 measured according to the standard ISO 2909.
  • the lubricant compositions used according to the invention can in addition also contain at least one additive selected from the detergents, anti-wear additives, extreme-pressure additives, dispersants, antioxidants, flow point improvers, anti-foaming agents, thickeners, viscosity index improver polymers and mixtures thereof.
  • the anti-wear and extreme-pressure additives protect the surfaces subject to friction by the formation of a protective film adsorbed onto these surfaces.
  • anti-wear additives exists, but the category most widely used in the lubricant compositions, in particular for engine oil, is that of the phosphorus- and sulphur-containing additives, such as the metallic alkylthiophosphates, in particular the zinc alkylthiophosphates, and more specifically the zinc dialkyldithiophosphates or ZnDTPs.
  • the amine phosphates are also anti-wear additives which can be used in the lubricant compositions used according to the invention.
  • the phosphorus provided by these additives acts as a poison on the catalytic systems of motor vehicles as these additives generate ashes.
  • the anti-wear and extreme-pressure additives can be present in the lubricant composition at levels ranging from 0.01 to 6%) by weight, preferentially from 0.05 and 4%, preferentially from 0.1% to 2% with respect to the total weight of the lubricant composition.
  • the friction modifier additive can be a compound providing the metal elements or an ash-free compound.
  • the transition metal complexes such as Mo, Sb, Sn, Fe, Cu, Zn, W can be mentioned, the ligands of which can be hydrocarbon-containing compounds containing oxygen, nitrogen, sulphur or phosphorus atoms, and in particular the molybdenum dithiocarbamates.
  • the ash-free friction modifiers are of organic origin and can be selected from the monoesters of fatty acids and polyols, alkoxylated amines, alkoxylated fatty amines, fatty epoxides, borated fatty epoxides; fatty amines or glycerol esters of fatty acids.
  • fatty is meant, within the meaning of the present invention, a hydrocarbon group comprising from 10 to 24 carbon atoms.
  • the friction modifier additive can be present at levels ranging from 0.01 to 5% by weight, preferentially from 0.1 to 2% with respect to the total weight of the lubricant composition.
  • the antioxidant additives slow down the degradation of the lubricant compositions in service, in particular of the engine oils in service, degradation which can in particular result in the formation of deposits, the presence of sludges, or an increase in the viscosity of the lubricant composition, in particular of the engine oil.
  • the antioxidant additives act in particular as radical inhibitors or hydroperoxide destroyers.
  • the antioxidants commonly used the phenolic-type or amine-type antioxidants and phosphorus- and sulphur-containing antioxidants can be mentioned. Some of these antioxidants, for example the phosphorus- and sulphur-containing additives, may generate ashes.
  • the phenolic antioxidants may be ash-free, or be in the form of neutral or basic metal salts.
  • the antioxidant agents can in particular be selected from the sterically hindered phenols, the sterically hindered phenols esters and the sterically hindered phenols comprising a thioether bridge, diphenylamines, the diphenylamines substituted with at least one C1-C12 alkyl group, the N,N′ dialkyl aryl diamines and combinations thereof.
  • sterically hindered phenol is meant within the meaning of the present invention a compound comprising a phenol group of which at least one vicinal carbon of the carbon bearing the alcohol function is substituted by at least one C1-C10 alkyl group, preferably a C1-C6 alkyl group, preferably, a C4 alkyl group, preferably by the tert-butyl group.
  • the amine compounds are another class of antioxidants that can be used, optionally in combination with the phenolic antioxidants.
  • Typical examples are the aromatic amines of formula R25R26R27N, in which R25 represents an aliphatic group or an optionally substituted aromatic group, R26 represents an optionally substituted aromatic group, R27 represents a hydrogen atom, an alkyl group, an aryl group or a group of formula R28S(O) z R29, where R28 represents an alkylene group or an alkenylene group, R29 represents an alkyl group, an alkenyl group or an aryl group and z represents an integer equal to 0, 1 or 2.
  • Sulphur-containing alkyl phenols or their alkali and alkaline-earth metal salts can also be used as antioxidants.
  • antioxidants are that of the copper-containing compounds, for example the copper thio- or dithiophosphates, salts of copper and of carboxylic acids, dithiocarbamates, sulphonates, phenates, copper acetylacetonates. Copper I and II, succinic acid or anhydride salts can also be used.
  • the lubricant composition used according to the invention can contain all types of antioxidant additives known to a person skilled in the art.
  • ash-free antioxidants are used.
  • the lubricant composition used according to the invention can comprise from 0.5 to 2% of at least one antioxidant additive by weight with respect to the total weight of the lubricant composition.
  • Detergent additives reduce in particular the formation of deposits on the surface of the metal parts by dissolving the by-products of oxidation and combustion.
  • the detergents that can be used in the lubricant composition according to the invention are well known to a person skilled in the art.
  • the detergents commonly used in the formulation of lubricant compositions can be anionic compounds comprising a long lipophilic hydrocarbon-containing chain and a hydrophilic head.
  • the associated cation is typically a metal cation of an alkali or alkaline-earth metal.
  • the detergents are preferentially selected from the alkali or alkaline-earth metal salts of carboxylic acids, sulphonates, salicylates, naphthenates, as well as the salts of phenates.
  • the alkali or alkaline-earth metals are preferentially calcium, magnesium, sodium or barium.
  • These metal salts can contain the metal in an approximately stoichiometric quantity or in excess (in a quantity greater than the stoichiometric quantity). In the latter case, these detergents are referred to as overbased detergents.
  • the excess metal providing the detergent with its overbased character is present in the form of metal salts which are insoluble in oil, for example carbonate, hydroxide, oxalate, acetate, glutamate, preferentially carbonate.
  • the lubricant composition according to the invention can comprise from 0.5 to 4% by weight of detergent, with respect to the total weight of the lubricant composition.
  • the pour point depressant additives in particular improve the low-temperature behaviour of the lubricant compositions, by slowing down the formation of paraffin crystals.
  • the alkyl polymethacrylates, polyacrylates, polyarylamides, polyalkylphenols, polyalkylnaphthalenes, alkylated polystyrenes can be mentioned.
  • the lubricant composition used according to the invention can further comprise at least one dispersant.
  • the dispersants can be selected from the groups formed by the Mannich base(s), the succinimides and derivatives thereof, in particular the borated succinimides.
  • the lubricant composition used according to the invention can comprise from 0.2 to 10%) by weight of dispersants with respect to the total weight of the lubricant composition.
  • the viscosity index improver polymers can be selected from the polymer esters, the copolymers based on ethylene, in particular the ethylene/propylene copolymers and ethylene/ ⁇ -olefin copolymers, the homopolymers or copolymers of styrene, butadiene or isoprene, hydrogenated or not hydrogenated, the polymethacrylates (PMA).
  • the lubricant composition used according to the invention can comprise from 1 to 15% by weight of viscosity index improver polymers with respect to the total weight of the lubricant composition.
  • the anti-foaming additives can be selected from the polyacrylates or silicon-containing compounds and derivatives thereof, and in particular the polysiloxanes.
  • the lubricant composition comprises:
  • the lubricant composition comprises:
  • the lubricant composition essentially consists of:
  • the lubricant composition essentially consists of:
  • the lubricant composition is not an emulsion. In another embodiment of the invention, the lubricant composition is anhydrous.
  • An object of the invention is an engine oil comprising a lubricant composition used according to the invention. All the characteristics and preferences presented above for the lubricant composition also apply to the engine oil used according to the invention.
  • the engine oil can be of 0W-16, 0W-20 and 5W-30 grade according to the SAEJ300 classification, characterized by a kinematic viscosity at 100° C. (KV100) ranging from 5.6 to 12.5 cSt measured according to the international standard ASTM D445.
  • the engine oil can be characterized by a viscosity index, calculated according to the international standard ISO 2909, greater than or equal to 130, preferably greater than or equal to 150.
  • base oils having a sulphur content of less than 0.3%) for example mineral oils of Group III, and sulphur-free synthetic bases, preferentially of Group IV, or mixtures thereof can advantageously be used.
  • An object of the invention is also the use of a lubricant composition as defined above for the lubrication of vehicle engines, preferentially motor vehicle engines, advantageously motor vehicle engines with positive ignition.
  • a object of the invention is also the use of a lubricant composition as defined above in order to reduce or even eliminate knock in engines, preferentially motor vehicle engines, advantageously motor vehicle engines with positive ignition.
  • An object of the invention is also the use of a lubricant composition as defined above in order to reduce the fuel consumption of vehicles, in particular motor vehicles. All the characteristics and preferences presented above for the lubricant composition also apply to the above uses.
  • An object of the invention is also a lubricating process for a vehicle engine, preferably a motor vehicle engine, advantageously of a motor vehicle engine with positive ignition, said process comprising at least one step of bringing a mechanical part of the engine into contact with a lubricant composition as defined above.
  • An object of the invention is also a process for reducing or even eliminating knock in a vehicle engine, preferentially motor vehicle engines, advantageously motor vehicle engines with positive ignition comprising at least one step of bringing a mechanical part of the engine of the vehicle into contact with a lubricant composition as defined above.
  • the reduction or even the elimination of engine knock can be assessed by any method known to a person skilled in the art.
  • the reduction or even the elimination of engine knock by the use of a lubricant composition can in particular be assessed by measuring the power development of the engine and by measuring the development of the ignition advance parameter in the presence of the lubricant composition.
  • An object of the invention is also a process for reducing the fuel consumption of a vehicle, in particular of a motor vehicle comprising at least one step of bringing a mechanical part of the engine of the vehicle into contact with a lubricant composition as defined above. All the characteristics and preferences presented above for the lubricant composition also apply to the above processes.
  • the vehicles can comprise a two- or four-stroke internal combustion engine with positive ignition.
  • the engines can be gasoline engines intended to be supplied with standard gasoline or natural gas.
  • standard gasoline is meant within the meaning of the present invention engines which are supplied with a fuel obtained after refining an oil of mineral origin (such as petroleum for example).
  • the engines can also be gasoline engines modified to be supplied with a fuel based on oils originating from renewable materials such as fuels based on alcohol.
  • the vehicles can be light vehicles such as automobiles and motor cycles.
  • the vehicles can also be lorries, construction machinery.
  • An object of the invention is also the use of a compound of formula (I) as defined above in a lubricant composition in order to reduce or even eliminate knock in engines, preferentially motor vehicle engines, advantageously motor vehicle engines with positive ignition. All the characteristics and preferences presented above for the lubricant composition also apply to the above use.
  • An object of the invention is also a composition of the additive-concentrate type comprising:
  • At least one additive selected from the detergents, the friction modifiers, anti-wear additives, dispersants, extreme-pressure additives, antioxidants, viscosity index improver polymers, flow point improvers, anti-foaming agents, thickeners and mixtures thereof.
  • a lubricant composition No. 1 is prepared from the following compounds:
  • base oil 3 trimethylolpropane ester having a kinematic viscosity at 100° C. measured according to the standard ASTM D445 equal to 4.5 mm 2 /s,
  • additive package mixture comprising a calcium salicylate as detergent, a zinc dithiophosphate as anti-wear agent, a borated succinimide dispersant, a phenolic anti-oxidant, an amine anti-oxidant (alkylated diphenylamine), a polysiloxane derivative as anti-foaming agent, a molybdenum dithiocarbamate as friction modifier and a polymethacrylate as pour point improver.
  • the lubricant composition No. 1 is described in Table II: the percentages indicated are percentages by weight.
  • a compound of formula (I) used according to the invention was added to the lubricant composition No. 1 in order to obtain the lubricant compositions No. 2 and No. 3, the compound of formula (I) being:
  • meta-toluidine (marketed by the company Sigma-Aldrich) of formula:
  • the lubricant compositions No. 2 and No. 3 are described in Table III: the percentages indicated are percentages by weight.
  • the impact of the lubricant compositions No. 1 to No. 3 was assessed according to the method described below.
  • a turbocharged 1.6 litre capacity positive ignition engine was equipped with accelerometers close to each cylinder making it possible to detect the appearance of knock.
  • the engine control analyzes this information and reduces the ignition advance parameter in the event of knock appearing. Otherwise, if the combustion proceeds without the appearance of knock, the engine computer increases the ignition advance in order to improve the engine efficiency and to increase the power measured at the engine output.
  • the engine was installed in a test cell of where the speed and the power output of the engine was measured using an electromagnetic brake.
  • the control parameters such as the engine speed, quantity of gasoline injected, ignition advance and engine power were recorded during the test.
  • the temperature of the engine coolant was maintained at 94° C. at the engine inlet and the oil temperature was maintained at 99° C. at the engine inlet.
  • the tests were carried out under full load and the engine speed swept was extended from 3000 to 8500 rpm.
  • the lubricant composition No. 1 was used as reference oil in order to verify the stability of the engine behaviour.
  • the impact of lubricant compositions No. 2 and No. 3 on the knock phenomenon was observed by measuring the power development of the engine and by measuring the development of the ignition advance parameter by comparing each of these two lubricant compositions with the lubricant composition No. 1.
  • the engine power is expressed in horsepower (hp).
  • the ignition advance is expressed in crankshaft degrees (°V).
  • a difference of at least one hp regarding the power and a difference of at least 0.4°V are considered as significant and therefore allow the benefit of the lubricant composition on the reduction in the knock phenomenon to be validated.
  • the lubricant composition No. 2 was tested in the test described above, preceded and followed by the lubricant composition No. 1.
  • the power and ignition advance improvement is determined with respect to the average of the results obtained on the lubricant composition No. 1 before and after the test with the lubricant composition No. 2.
  • the lubricant composition No. 3 was tested in the test described above, preceded and followed by the lubricant composition No. 1.
  • the power and ignition advance improvement is determined with respect to the average of the results obtained on the lubricant composition No. 1 before and after the test with the lubricant composition No. 3.

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US15/306,302 2014-04-25 2015-04-21 Use of a lubricant composition for reducing knocking Abandoned US20170051226A1 (en)

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FR1453752A FR3020377B1 (fr) 2014-04-25 2014-04-25 Composition lubrifiante comprenant un compose anti-cliquetis
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PCT/EP2015/058615 WO2015162137A1 (fr) 2014-04-25 2015-04-21 Utilisation d'une composition lubrifiante pour diminuer le cliquetis

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JP2017513995A (ja) 2017-06-01
KR20160147911A (ko) 2016-12-23
EP3134495A1 (fr) 2017-03-01
KR102392304B1 (ko) 2022-05-02
MX2016014018A (es) 2017-01-11
EP3134495B1 (fr) 2020-09-02
WO2015162137A1 (fr) 2015-10-29
FR3020377B1 (fr) 2020-11-27
FR3020377A1 (fr) 2015-10-30

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