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
  • 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
  • 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
  • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
  • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
  • C10M107/22—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M107/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol, aldehyde, ketonic, ether, ketal or acetal radical
• • 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
  • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
  • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
  • C10M107/30—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M107/32—Condensation polymers of aldehydes or ketones; Polyesters; Polyethers
  • C10M107/34—Polyoxyalkylenes
• • 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
  • C10M2207/02—Hydroxy compounds
  • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
• • 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
  • C10M2207/02—Hydroxy compounds
  • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/26—Overbased carboxylic acid salts
  • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
• • 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
  • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
  • C10M2209/1033—Polyethers, i.e. containing di- or higher polyoxyalkylene groups 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
  • 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
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
  • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
  • C10M2219/066—Thiocarbamic type compounds
  • C10M2219/068—Thiocarbamate metal salts
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/02—Viscosity; Viscosity index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/02—Pour-point; Viscosity index
• • 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
  • C10N2030/74—Noack Volatility
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines

Definitions

• the present invention relates to engine lubricating compositions, in particular for automobile, gasoline or diesel engines.
• Lubricating compositions used as motor oil conventionally comprise from 50 to 90% of base oils, which may be of mineral, synthetic or natural origin, and additives. These additives are typically detergents, dispersants, antioxidants, viscosity index (VI) improving polymers, friction modifiers, pour point depressants, defoamers, etc.
• base oils which may be of mineral, synthetic or natural origin
• additives are typically detergents, dispersants, antioxidants, viscosity index (VI) improving polymers, friction modifiers, pour point depressants, defoamers, etc.
• the synthetic bases are for example polyalphaolefins, GTL bases obtained for example by Fischer Tropsch processes, or certain esters.
• PAG polyalkylene glycols
• PAG bases in motor oils, especially for automotive engines, has a certain number of interests, in particular because of their good tribological and rheological properties, but also because they are polar bases.
• PAGs are mainly known for their use as base fluids in compressor oils in refrigerant systems.
• the state of the The technique contains some examples of other uses of PAGs, for example in motor oils, for example automobile engines or marine engines.
• WO2009 / 134716 discloses a motor vehicle oil comprising at least one polyalkylene glycol base oil adapted for use in a motor vehicle, combined with an additive package comprising derivatives of aspartic acid, and optionally, antiwear additives, anti-corrosion, antioxidants, friction modifiers, defoamers. No mention is made of the presence of detergent additives in said compositions.
• Requirement WO2009 / 134638 discloses a lubricating composition for an internal combustion engine comprising polyalkylene glycols obtained by copolymerization of ethylene oxide and alkylene oxide having up to 12 carbon atoms, comprising between 1 and 50 alkylene oxide units, and optionally an improving polymer of VI. No mention is made of other additives present in the compositions disclosed.
• Requirement FR 2817874 discloses functional fluids for automobiles, especially for automotive engines, comprising polyalkylene glycol bases and a reducing agent, which may be urea. These PAGs are in particular obtained from ethylene oxide and propylene oxide. No specific mention is made of other PAG bases or other additives used in combination with PAG bases.
• the patent US 5,885,555 discloses a composition for the formulation of dentifrices comprising polyalkylene glycol and methyl salicylate, called "wintergreen". This latter compound is in no way similar to the salicylate detergents used in lubricating compositions, for example in motor oils, where the benzene nucleus of salicylic acid comprises hydrocarbon substituents with sufficiently long chains to constitute the lipophilic part of the detergent.
• compositions for transmissions in marine applications comprising a base oil which can be a synthetic or natural oil.
• the synthetic oils may be polyalphaolefins (PAO), various esters of (di) carboxylic acids and alcohols or polyols, alkylbenzene bases, polysilicones, polymeric or copolymeric olefins, polyphenols, diphenyl etheralkyls, diphenylsulphidealalkyls, polyalkylene glycols, FischerTropsch bases.
• PAO polyalphaolefins
• various esters of (di) carboxylic acids and alcohols or polyols alkylbenzene bases
• polysilicones polymeric or copolymeric olefins
• polyphenols diphenyl etheralkyls, diphenylsulphidealalkyls, polyalkylene glycols, FischerTropsch bases.
• These compositions may also comprise at least one metal detergent, which may
• Requirement JP 2007 204451 discloses a polyalkylene glycol which is a tetraether obtained by polymerization of propylene oxide, as well as a diether, for use as a base oil in lubricating compositions, especially for motor oils, and in the presence of certain additives, especially detergents.
• the disclosed tetraethers have a relatively low molecular weight, and a low kinematic viscosity at 100 ° C. Their use in engine oil formulations therefore requires their use in combination with other base oils; these tetraethers contain only propylene oxide units, which does not give them a high solubility in oils.
• solubilization or the suspension in these tetraether bases of additives having a lipophilic portion may pose a problem.
• the diether is when it consists of 3 long carbon chains (C6 to C14), delimited by two ether functions.
• the two oxygens of ether functions are distant from 5 carbon atoms.
• These bases are therefore not polyalkylene glycol, where, by nature, the oxygen atoms are distant from 2 carbon atoms, which corresponds to the attack of the epoxy function of the alkylene oxides during the polymerization. It is expected that their behavior, especially in terms of polarity, will not offer the same benefits as the PAG engine formula.
• US 2620302 discloses an engine lubricating composition
• an engine lubricating composition comprising 1,2-polypropylene glycol, a mineral oil, 1 to 10% of a metal phenate and 0.1 to 1% of zinc dithiocarbamate.
• the Noack volatility measured according to the CEC L 40-93 standard is typically less than 15%, preferably less than 13%. It is typically between 8 and 15%, or between 10 and 13%.
• the present invention therefore relates to lubricating compositions comprising these specific combinations of PAG bases and additives, as well as to their use as motor oil, especially motor vehicles.
• the present invention also relates to the use of these additives, or packages of additives containing them, in engine oil formulations comprising PAG bases.
• the present invention also relates to the use of these additives, or packages of additives containing them, to reduce the Noack volatility of PAG bases measured according to CEC standard L 40-93.
• the polyalkylene glycol base oil (s) is (are) such that the alcohol (s) making it possible to obtain them comprise from 8 to 12 carbon atoms.
• the polyalkylene glycol base oil (s) (a) are such that the alcohol (s) making it possible to obtain them are chosen from monoalcohols, preferentially from 2-ethylhexanol and / or decanol, preferentially decanol.
• the polyalkyleneglycol base oil (s) (a) have a carbon to oxygen mass ratio of at least 3: 1, preferably between 3: 1 and 6: 1.
• the Noack volatility of the composition according to the invention, measured according to the standard CEC L 40-93 is less than 15%, preferably less than 13%.
• the base or bases (a) have a molar mass measured according to the ASTM D2502 standard of between 300 and 1000, preferably between 350 and 600 grams per mole.
• the kinematic viscosity of the polyalkylene glycol bases at 100 ° C. is between 1 and 12 cSt, preferentially between 3 and 7, preferentially between 3, 5 and 6, 5 cSt.
• the polyalkylene glycol base oil (s) (a) is the major component.
• the composition comprises from 20 to 90%, preferably from 25 to 85% of polyalkylene glycol base oil (s) (a).
• the composition comprises at least one salicylate as detergent (b).
• the composition is free of sulfonate detergent.
• the composition is free of anti-wear additive of the dithiophosphate type, in particular zinc dithiophosphate.
• the composition further comprises an amino antioxidant and / or a phenolic antioxidant.
• Another subject of the invention relates to the use of a lubricating composition as defined above as engine oil, preferably as an engine oil for motor vehicles, gasoline or diesel.
• the polyalkylene glycol bases are the polyalkylene glycol bases (a) as defined above.
• the additive package is free of anti-wear additives of the dithiophosphate type, in particular zinc dithiophosphate.
• the additive package it is free of sulfonate detergents.
• the engine lubricant mainly comprises the polyalkylene glycol bases (a) as defined above.
• the engine lubricant exclusively comprises the polyalkylene glycol bases (a) as defined previously as base oils.
• the engine lubricant comprises from 20 to 90%, preferably from 25 to 85% of polyalkylene glycol base oil (s) as defined above.
• Another subject of the invention also relates to the use of at least one additive chosen from salicylates and phenates, in order to reduce the Noack volatility measured according to the CEC standard L 40-93, base oils of polyalkylene glycol type, obtained from alkylene oxides comprising from 3 to 8 carbon atoms, of which at least one butylene oxide, preferably wherein the polyalkylene glycol bases are as defined above.
• base oils of polyalkylene glycol type obtained from alkylene oxides comprising from 3 to 8 carbon atoms, of which at least one butylene oxide, preferably wherein the polyalkylene glycol bases are as defined above.
• the engine is a motor for motor vehicles, preferably gasoline or diesel.
• the polyalkylene glycol bases (a) compositions according to the invention have properties suitable for use in a motor oil. These are polymers or copolymers (statistics or blocks) of alkylene oxides, for example prepared according to the known methods described in the application WO 2009/134716 on page 2 line 26 to page 4 line 12, for example by etching an alcohol initiator on the epoxy bond of an alkylene oxide and propagating the reaction.
• the polyalkylene glycol (PAG) bases of the compositions according to the invention correspond to the general formula (A): where Y 1 and Y 2 are, independently of one another, hydrogen, or a hydrocarbon group, for example an alkyl or alkylphenyl group, having 1 to 30 carbon atoms, n represents an integer greater than or equal to at 2, preferably less than 60, preferably between 5 and 30, preferably between 7 and 15, x represents one or more integers between 1 and n, the groups R 2x-1 and R 2x are, independently of one another, hydrogen, or hydrocarbon radicals, comprising between 1 and 6 carbon atoms, preferably alkyl, and R 2x is preferably hydrogen, the sum of the carbon number of R 2x-1 and R 2x is between 1 and 6. For at least one value of x, the sum of the carbon number of R 2x-1 and R 2x is equal to 4.
• the alkylene oxides used for the PAG bases of the compositions according to the invention contain between 3 and 8 carbon atoms, of which at least one butylene oxide, the said butylene oxide being 1,2-butylene oxide or 2, Butylene 3-oxide, preferably 1,2-butylene oxide.
• the PAG obtained (in part) from ethylene oxide do not have a sufficient lipophilic character to be used in engine oil formulations.
• they can not be used in combination with other mineral, synthetic or natural base oils.
• Neutral or overbased detergents which are essential for the formulation of lubricants which guarantee engine cleanliness, can not be solubilized or suspended in these PAG bases obtained (partly) from ethylene oxide.
• alkylene oxides comprising more than 8 carbon atoms is also not desired because, to produce bases having the molar mass and therefore the targeted viscosimetric grade for the motor applications, then there will be a number of reduced monomers (n low in formula (A) above), with long R2x-1 and R2x side chains. This adversely affects the overall linear character of the PAG molecule and leads to viscosity indices (VI) that are too low for engine oil application.
• their viscosity index VI is greater than 100, preferably greater than 120.
• compositions according to the invention are obtained from alkylene oxides comprising at least one butylene oxide.
• the butylene oxide (BO) and propylene oxide (PO) copolymers are used because they have both the good tribological and rheological properties of the PAG containing ethylene oxide units and / or polypropylene, and good solubility in conventional mineral, synthetic, and natural bases, and other oily compounds.
• bases are prepared conventionally, by reaction of one or more alcohols with a mixture of butylene oxide and propylene oxide.
• PAGs prepared with a mixture of butylene oxide and oxide are used in the compositions according to the invention.
• PAG bases prepared with a mixture where this ratio is between 3: 1 and 1: 1 are particularly well miscible and soluble in the other base oils, including Group IV synthetic oils.
• the PAG bases of the compositions according to the invention are prepared from alcohol containing from 8 to 12 carbon atoms. 2-ethylhexanol and dodecanol, alone or in a mixture, and in particular dodecanol, are particularly preferred since the PAG bases prepared from these alcohols have very low traction coefficients.
• the PAG bases of the compositions according to the invention are such that their molar carbon to oxygen ratio is greater than 3: 1, preferably between 3: 1 and 6: 1. This gives said PAG bases polarity and viscosity index properties particularly suitable for use in motor oil.
• the molar mass, measured according to the ASTM D2502 standard, of the PAG bases of the compositions according to the invention is preferably between 300 and 1000 grams per mole (g / mol), preferably between 350 and 600 g / mol (that is why they contain a limited number of alkylene oxide units n as described above in formula (A)).
• KV100 kinematic viscosities at 100 ° C.
• KV100 generally of between 1 and 2 cSt and 12 cSt at 100 ° C., preferably between 3 and 7 cSt, preferentially between 3.5 and 6.5 cSt, or between 4 and 4 cSt. 6 cSt or between 3.5 and 4.5 cSt.
• the KV100 of the compositions is measured according to ASTM D445.
• the PAG bases are preferably used as light bases in the automotive engine lubricating compositions according to the invention, where they are preferably combined with VI viscosity index improving polymers and / or other heavier bases.
• PAG (a) bases KV100 approximately between 2 and 6.5 cSt
• SAEJ300 because the heavier PAG (a) bases have cold properties (high CCS) which do not easily reach these grades.
• the PAG (a) bases in particular those with KV100 values between 3.5 and 4.5 cSt, of the order of 4 cSt, have Noack volatilities according to the CEC standard L 40-93 of the order of 35 to 40%, which is very high, and can not be caught up in the formula with improving polymers of viscosity index VI or other less volatile bases.
• the lubricant compositions according to the invention preferentially have a Noack volatility, measured according to the CEC L 40-93 standard, of less than 15%, preferably less than 13%. It is typically between 8 and 15%, or between 10 and 13%.
• the base (s) PAG (a) is the majority base (s).
• the weight percentage of the base PAG (a), or the mass percentage of the cumulative PAG (a) bases is greater than the mass percentage of each of the other bases present in the compositions according to the invention; the percentages by weight being expressed relative to the total weight of lubricating composition.
• the base (s) PAG (a) is the (the) component (s) majority (s).
• the weight percentage of the base PAG (a), or the mass percentage of the cumulative PAG (a) bases is greater than the mass percentage of each of the other components present in the compositions. according to the invention; the percentages by weight being expressed relative to the total weight of lubricating composition.
• the base or bases PAG (a) represent between 20% and 90% by weight, preferably between 25% and 85% by weight, preferably between 30 and 80% by weight. or between 50 and 75% by weight of the lubricating compositions according to the invention.
• the detergents used in the lubricant compositions according to the present invention are well known to those skilled in the art.
• the detergents commonly used in the formulation of lubricating compositions are typically anionic compounds comprising a long lipophilic hydrocarbon chain (typically comprising at least 9, preferably at least 12 carbon atoms) and a hydrophilic head.
• the associated cation is typically a metal cation of an alkali metal, preferably lithium, sodium or potassium.
• the detergents (b) of the compositions according to the invention are chosen from alkali metal or alkaline-earth metal salts of the salicylate and phenate type.
• metal salts may contain the metal in an approximately stoichiometric amount.
• neutral detergents typically have a BN, measured according to ASTM D2896, less than 150 mg KOH / g, or less than 100, or even less than 80 mg KOH / g.
• BN is high, greater than 150 mg KOH / g, typically between 200 and 700 mg KOH / g, generally between 250 and 450 mg KOH / g.
• the excess metal providing the overbased detergent character is in the form of oil insoluble metal salts, for example carbonate, hydroxide, oxalate, acetate, glutamate, preferably carbonate.
• the overbased detergents are thus in the form of micelles composed of insoluble metal salts maintained in suspension in the lubricating composition by the detergents in the form of oil-soluble metal salts.
• the lubricating compositions according to the invention contain at least one salicylate detergent or at least one alkali or alkaline earth metal phenate detergent, neutral or overbased with the above-mentioned oil-insoluble metal salts. According to one embodiment, they contain at least one salicylate detergent and at least one phenate detergent.
• the amounts of detergents included in the lubricant compositions according to the invention are adjusted so that the BN of said compositions, measured according to the ASTM D2896 standard, is between 3 and 12 mg of KOH per gram of lubricant, preferentially understood. between 5 and 10, preferably between 6 and 9 mg of KOH per gram of lubricant.
• the amount of phenate and / or salicylate detergents included in the lubricating compositions according to the invention is between 0.2 and 2%, preferably between 0.5 and 2% by weight.
• the salicylates and phenates used as detergents (b) in the lubricating compositions according to the invention are prepared from salicylic acid and phenol derivatives corresponding respectively to formulas (I) and (II) below: where X 1 , X 2 , X 3 , X 4 , X 5 are either hydrogen, or hydrocarbon radicals, preferably alkyl, or alkylaryl, or arylalkyl, and at least one of X 1 , X 2 , X 3 , X 4 , X 5 is a hydrocarbon radical having sufficient carbon atoms (typically at least about 9 carbon atoms, preferably at least 12 carbon atoms), to give the salicylate an oil-soluble character, and M is an alkali metal.
• One of the groups X 1 to X 5 may for example be an alkyl group, linear or branched comprising at least 9 carbon atoms, preferably between 10 and 160, preferably between 12 and 40, preferably between 14 and 28 carbon atoms.
• at least one of the groups X 1 to X 5 is a linear alkyl comprising at least 9 carbon atoms, preferably between 10 and 160, preferably between 12 and 40, preferentially between 14 and 28 atoms or between 18 and 24 carbon atoms.
• These detergents may be neutral or overbased with oil-insoluble alkali metal salts such as carbonates, hydroxides, oxalates, acetates, glutamates.
• oil-insoluble alkali metal salts such as carbonates, hydroxides, oxalates, acetates, glutamates.
• the detergents (b) of the compositions according to the invention may be salicylates, neutral or overbased, corresponding to formulas (III), (IV), (V), below, where X 1 , X 2 , X 3 , X 4 , X 5 are as defined above, and X 6 and X 7 also have the same meaning, M 1 is an alkali metal, preferably selected from sodium, potassium, lithium, and M 2 is an alkaline earth metal, preferably selected among calcium or magnesium.
• the detergents of formula (III) and the methods for producing them are described, for example, in the application EP 1548 089 .
• the detergents of formula (IV) and (V) and the methods for producing them are for example described in the applications US 6,348,438 , and WO 2004/041767 , and EP 0786 448 .
• Requirement WO 2004/009747 also describes alkaline earth metal salicylate detergents usable as detergent (b) in the compositions according to the invention.
• the detergents (b) of the compositions according to the invention may be phenates, neutral or overbased, corresponding to formulas (VI), (VII), (VIII), below, where X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 are as defined above, and X 8 and X 9 also have the same meaning, M 1 is an alkali metal, preferably selected from sodium, potassium, lithium, and M 2 is an alkaline earth metal, preferably selected from calcium or magnesium.
• Sulfurized derivatives of the salicylates and phenates described above can also be used as detergents (b). These sulfurized derivatives and methods for producing them are for example described in the applications EP 2,055,761 and EP 0786 448 . This latter application also describes mixed detergents phenates salicylates sulfurized compounds, corresponding to formula (IX), which can also be used as detergents (b) in the compositions according to the invention.
• X 1 to X 7 are as defined above
• M 2 and M 3 are alkaline earth metals, preferably selected from calcium or magnesium.
• salicylate and phenate detergents (b) may be used alone or as a mixture. They may be present in combination with other detergents known to those skilled in the art, such as for example other carboxylates.
• other detergents known to those skilled in the art, such as for example other carboxylates.
• compositions according to the invention are free of sulfonate detergents.
• the lubricant compositions according to the invention may contain one or more dithiocarbamate additives (c).
• Dithiocarbamates are well known to those skilled in the art as multifunctional additives for lubricants, providing in particular antiwear properties, but also antioxidant, extreme pressure and friction modifier.
• Dithiocarbamates used in the compositions according to the invention are for example described in the applications EP 1 730 107 , WO 2005/007786 , the patent US 4,997,969 .
• compositions according to the invention may also contain molybdenum dithiocarbamates, friction modifier additives for motor oils well known to those skilled in the art.
• organometallic friction modifiers molybdenum dithiocarbamate can for example satisfy the formula (XI): where X11, X12, X13, X14 are alkyl chains, preferably having 8 to 13 carbon atoms.
• dithiocarbamates (c) may be used alone or as a mixture. They may be present in combination with other antiwear, extreme pressure or friction modifier additives known to those skilled in the art. However, it is preferable to avoid the presence of anti-wear additives of the dithiophosphate type, in particular zinc dithiophosphates, which are difficult to solubilize in the PAG bases, in particular when the PAG base (s) constitute the (the) only base oils. of the composition, or the majority base oil (s), or when the PAG base (s) constitute at least 20% by weight of the lubricating composition.
• anti-wear additives of the dithiophosphate type in particular zinc dithiophosphates
• compositions according to the invention are free from anti-wear of the dithiophosphate type, in particular zinc dithiophosphates.
• the lubricant compositions according to the invention may optionally comprise amine or phenolic antioxidants, alone or as a mixture.
• the phenolic antioxidants of the compositions according to the invention are phenols substituted on at least one of their ortho positions, preferably both, with alkyl groups comprising from 1 to 10 carbon atoms, for example methyl, isopropyl or tert-butyl groups, preferentially from 1 to 3 carbon atoms. They can also be used in the form of dimers.
• the aminated antioxidants of the compositions according to the invention are secondary amines in which the nitrogen atom is connected to at least one aryl group.
• the lubricating compositions according to the present invention may comprise, in combination with the PAG bases (a) described above, one or more other base oils, which may be oils of mineral or synthetic origin 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 as a mixture.
• oils may be oils of vegetable, animal or mineral origin.
• the mineral base oils of the compositions according to the invention include all types of bases obtained by atmospheric and vacuum distillation of crude oil, followed by refining operations such as solvent extraction, desalphating, solvent dewaxing, hydrotreatment, hydrocracking and hydroisomerization, hydrofinishing.
• the other base oils of the compositions according to the present invention can also be synthetic oils, such as certain esters of carboxylic acids and of alcohols, GTL bases which can be obtained by hydroisomerization of a Fisher-Tropsch wax, or polyalphaolefins.
• the polyalphaolefins used as base oils for example, are obtained from monomers having from 4 to 32 carbon atoms (for example octene, decene), and have a viscosity at 100 ° C of between 1.5 and 15 cSt. Their weight average molecular weight is typically between 250 and 3000.
• the lubricant compositions according to the present invention have a kinematic viscosity at 100 ° C. of between 5.6 and 16.3 Cst, measured by the ASTM D445 standard (grade SAE 20, 30 and 40), preferably between 9, 3 and 12.5 cSt (grade 30).
• the compositions according to the present invention are grade 5W or OW multigrade oils according to the SAEJ300 classification.
• compositions according to the present invention also preferably have a VI viscosity index greater than 130, preferably greater than 150, preferably greater than 160.
• the lubricant compositions according to the invention may also contain any type of additive adapted to their use, in particular as motor oil, preferably a motor vehicle engine.
• all the additives for example those described above, including the detergents (b), the dithiocarbamates (c), the antioxidants (d) are preferably used in the usual mass contents of the formulas for motor oils.
• Table 1 provides PAG base oils and minerals, alone or mixed.
• A is a polyalkylene glycol base (PAG), obtained from alkylene oxides, in particular butylene oxide, in particular butylene oxide (BO) and propylene oxide (PO), with a mass ratio 50/50 BO / PO, molar mass 388 g / mol according to ASTM D2502, kinematic viscosity at 100 ° C (KV100) of 3,982 mm 2 / s according to ASTM D445, viscosity number ( VI) of 118. Its Noack volatility is very high (39.4%), compared to that of a mixture of Group III mineral bases (see table 1, A1, Noack of 11.2%). A base mixture PAG A with mineral bases group III makes it possible to obtain an intermediate Noack volatility (see table 1, A2, Noack of 22%).
• PAG polyalkylene glycol base
• Table 2 relates to compositions comprising PAG bases alone or in the presence of additives.
• compositions B1 and B3 are compositions according to the invention containing an additive package which comprises a salicylate detergent, an anti-dithiocarbamate anti-oxidant, an amino antioxidant and a phenolic antioxidant.
• an additive package which comprises a salicylate detergent, an anti-dithiocarbamate anti-oxidant, an amino antioxidant and a phenolic antioxidant.
• Their Noack volatility is of the order of magnitude of that of known engine oils.
• Composition B1 comprises a mixture of PAG bases and Group III mineral bases comparable to the A2 base mixture.
• Composition B2 also comprises a mixture of PAG bases and Group III mineral bases comparable to the A2 base mixture.
• B2 does not include salicylate or phenate additives, and is not according to the invention.
• B2 on the other hand, comprises a viscosity VI improving polymer.
• Compositions C to K contain PAG base A combined with various additives.
• compositions F and G are compositions according to the invention.
• Their Noack volatility is of the order of magnitude of those of light base oils conventionally used in the formulation of engine oils.
• the samples H, J, K also have a Noack volatility strongly lower compared to the base A, thanks to the respective presence of dithiocarbamate, antioxidant amine, phenolic antioxidant, and confirm the possibility of using these additives according to the invention to lower the Noack volatility of a PAG base comprising at least one butylene oxide unit.
• L is a polyalkylene glycol (PAG) base, obtained from ethylene oxide and propylene oxide, with a molar mass of 388 g / mol, a KV 100 of 3,981 mm 2 / s, and a viscosity index of VI 119. Its volatility Noack is very high (37.4%).
• PAG polyalkylene glycol
• composition M which contains the base L and a phenolic antioxidant, has its volatility greatly reduced, at a level of the order of magnitude of those of the light base oils conventionally used in the formulation of motor oils.
• Sample N demonstrates that base L does not solubilize salicylate detergents.
• O is a polyalkylene glycol base (PAG), obtained from propylene oxide (100% PO), with a molecular weight of 750 g / mol, of KV100 6 cSt, with a viscosity index VI 179.
• PAG polyalkylene glycol base
• Composition P contains base O and 1% phenate detergent.
• Sample P demonstrates that the base O which does not contain butylene oxide units, does not solubilize detergents, especially phenates, unlike the base A in sample F.
• Composition B5 comprises base O in a motor oil formulation. Again, this sample, B5 shows that the base O does not solubilize the packets of additives traditionally used and / or that the base O is not compatible with the base oils traditionally used.
• composition B4 which comprises the base L in a motor oil formulation.

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