• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    The present application relates to a lubricating composition comprising: - an oil chosen from polyalkyl glycols (PAG or polyalkylene glycols), and - a nitrogen compound chosen from amine phosphates or amine tungstates. This lubricant composition is particularly useful for the lubrication of a vehicle engine, preferably a motor vehicle.
    公开号:FR3048976A1
    申请号:FR1652188
    申请日:2016-03-15
    公开日:2017-09-22
    发明作者:Laura Broutin；Nicolas Obrecht；Nadjet Khelidj-Suedmeyer
    申请人:Total Marketing Services SA；Dow Global Technologies LLC；
    IPC主号:
    专利说明:

    LUBRICATING COMPOSITION BASED ON POLYALKYLENE GLYCOLS
    The present application relates to the field of lubricating compositions, especially lubricating compositions for a vehicle engine, in particular for a motor vehicle engine. In particular, the present application relates to lubricating compositions based on polyalkyl glycols (PAG or polyalkylene glycols) for the lubrication of a vehicle engine, especially a motor vehicle. Energy efficiency and reduced fuel consumption of automotive engines is a growing concern. It is known that engine lubricants used in said vehicles have an important role in this regard.
    To formulate "fuel-eco" lubricants or fuel economizers, it is known to play on the viscosity of the lubricating bases used. It is also known to use viscosity index (VI) improving polymers, or to use friction modifiers. However, the viscosity index improvers have the disadvantage of degrading the engine cleanliness of the lubricating compositions in which they are employed. However, current engines have high thermal stresses that cause significant deposition phenomena. The deposits are related to the chemical transformation of the lubricant in the parts closest to the combustion chamber and therefore the hottest ones.
    "Fuel-Eco" lubricating compositions based on polyalkylated glycols (PAG or polyalkylene glycols) have been described in document WO 2013/164449, said compositions also having good properties of engine cleanliness.
    However, the use of these PAGs can sometimes cause an increase in the wear of the mechanical parts of the engine, and therefore a degradation of the durability of said engine.
    There is therefore an interest in providing a lubricant composition, especially a lubricating composition for motor vehicle engines, to meet all or part of the disadvantages of the prior art.
    An object of the present invention is to provide a lubricant composition based on PAG, in particular a lubricant composition based on PAG for motor vehicle engines, having improved anti-wear properties.
    Another object of the present invention is to provide a lubricant composition based on PAG, especially a PAG lubricant composition for motor vehicle engine, having both improved anti-wear properties and "Fuel-Eco" properties. > satisfactory.
    Another object of the present invention is to provide a lubricating composition based on PAG, especially a PAG lubricant composition for a motor vehicle engine, having both improved anti-wear properties and does not degrade engine cleanliness.
    Another object of the present invention is to provide a lubricant composition based on PAG, especially a PAG lubricant composition for a motor vehicle engine, having improved anti-wear properties, "Fuel-Eco" properties that are satisfactory and not degrading engine cleanliness.
    Another object of the invention is to provide a lubricant composition based on PAG, in particular a lubricant composition based on PAG for motor vehicle engine, having improved anti-wear properties and easy to formulate.
    In order to meet the above objectives and disadvantages mentioned in the state of the art, the present invention proposes a lubricating composition comprising: an oil chosen from polyalkylated glycols (PAGs or polyalkylene glycols), and a nitrogen compound chosen from amine phosphates or amine tungstates.
    Particularly advantageously, the lubricant composition of the present invention is a lubricant composition for an engine, preferably a vehicle, more preferably a motor vehicle.
    The nitrogenous compound according to the invention may be chosen from amine phosphates.
    Preferably, the nitrogenous compound according to the invention is an amine phosphate chosen from • compounds of formula (IA)
    in which: R1 represents a linear or branched alkyl group comprising from 2 to 10 carbon atoms, preferentially from 3 to 9 carbon atoms, more preferably from 5 to 8 carbon atoms; R2 represents a linear or branched alkyl group comprising from 8 to 15 carbon atoms, preferentially from 9 to 14 carbon atoms, more preferably from 10 to 14 carbon atoms; Compounds of formula (IB)
    in which: R1 represents a linear or branched alkyl group comprising from 2 to 10 carbon atoms, preferentially from 3 to 9 carbon atoms, more preferably from 5 to 8 carbon atoms; R2 represents a linear or branched alkyl group comprising from 8 to 15 carbon atoms, preferentially from 9 to 14 carbon atoms, more preferably from 10 to 14 carbon atoms; A mixture of at least one compound of formula (IA) and at least one compound of formula (IB)
    More preferably, the nitrogenous compound according to the invention is an amine phosphate chosen from • compounds of formula (IA)
    in which: R1 represents a linear alkyl group comprising from 2 to 10 carbon atoms, preferentially from 3 to 9 carbon atoms, more preferably from 5 to 8 carbon atoms; R2 represents a linear or branched alkyl group comprising from 8 to 15 carbon atoms, preferentially from 9 to 14 carbon atoms, more preferably from 10 to 14 carbon atoms; Compounds of formula (IB)
    in which: R1 represents a linear alkyl group comprising from 2 to 10 carbon atoms, preferentially from 3 to 9 carbon atoms, more preferably from 5 to 8 carbon atoms; R2 represents a linear or branched alkyl group comprising from 8 to 15 carbon atoms, preferentially from 9 to 14 carbon atoms, more preferably from 10 to 14 carbon atoms; A mixture of at least one compound of formula (IA) and at least one compound of formula (IB)
    Also more preferably, the nitrogen compound according to the invention is an amine phosphate selected from • compounds of formula (IA)
    in which: R1 represents a branched alkyl group comprising from 2 to 10 carbon atoms, preferentially from 3 to 9 carbon atoms, more preferably from 5 to 8 carbon atoms; R2 represents a linear or branched alkyl group comprising from 8 to 15 carbon atoms, preferentially from 9 to 14 carbon atoms, more preferably from 10 to 14 carbon atoms; Compounds of formula (IB)
    in which: R1 represents a branched alkyl group comprising from 2 to 10 carbon atoms, preferentially from 3 to 9 carbon atoms, more preferably from 5 to 8 carbon atoms; R2 represents a linear or branched alkyl group comprising from 8 to 15 carbon atoms, preferentially from 9 to 14 carbon atoms, more preferably from 10 to 14 carbon atoms; A mixture of at least one compound of formula (IA) and at least one compound of formula (IB)
    Also more preferably, the nitrogen compound according to the invention is an amine phosphate selected from • compounds of formula (IA)
    in which: R1 represents a linear or branched alkyl group comprising from 2 to 10 carbon atoms, preferentially from 3 to 8 carbon atoms, more preferably from 4 to 7 carbon atoms; R2 represents a linear alkyl group comprising from 8 to 15 carbon atoms, preferentially from 9 to 14 carbon atoms, more preferably from 10 to 14 carbon atoms; Compounds of formula (IB)
    in which: R1 represents a linear or branched alkyl group comprising from 2 to 10 carbon atoms, preferentially from 3 to 8 carbon atoms, more preferably from 4 to 7 carbon atoms; R2 represents a linear alkyl group comprising from 8 to 15 carbon atoms, preferentially from 9 to 14 carbon atoms, more preferably from 10 to 14 carbon atoms; A mixture of at least one compound of formula (IA) and at least one compound of formula (IB)
    Also more preferably, the nitrogen compound according to the invention is an amine phosphate selected from • compounds of formula (IA)
    in which: R1 represents a linear or branched alkyl group comprising from 2 to 10 carbon atoms, preferentially from 3 to 8 carbon atoms, more preferably from 4 to 7 carbon atoms; R2 represents a branched alkyl group comprising from 8 to 15 carbon atoms, preferentially from 9 to 14 carbon atoms, more preferably from 10 to 14 carbon atoms; Compounds of formula (IB)
    in which: R1 represents a linear or branched alkyl group comprising from 2 to 10 carbon atoms, preferentially from 3 to 8 carbon atoms, more preferably from 4 to 7 carbon atoms; R2 represents a branched alkyl group comprising from 8 to 15 carbon atoms, preferentially from 9 to 14 carbon atoms, more preferably from 10 to 14 carbon atoms; A mixture of at least one compound of formula (IA) and at least one compound of formula (IB)
    Advantageously, the nitrogen compound is a mixture of at least one compound of formula (IA) and at least one compound of formula (IB) in which: - R1 represents a hexyl or ethylhexyl group, - R2 represents a grouping linear or branched alkyl comprising from 11 to 14 carbon atoms, preferentially a linear or branched C 13 -alkyl group.
    The nitrogenous compound according to the invention may be chosen from amine tungstates.
    Amine tungstates according to the invention and their process of preparation are described in international patent application WO-2008/116099 or in international patent application WO-2013/077948.
    Also preferably, the nitrogenous compound according to the invention is chosen from: - amine tungstates obtained from at least one fatty amine comprising at least one linear alkyl group comprising from 8 to 15 carbon atoms, preferably from 9 to 14 carbon atoms, more preferably 10 to 14 carbon atoms, - amine tungstates obtained from at least one fatty amine comprising at least one branched alkyl group comprising from 8 to 15 carbon atoms, preferentially from 9 to 14 carbon atoms, more preferably from 10 to 14 carbon atoms, - a mixture of at least one amine tungstate obtained from at least one fatty amine comprising at least one linear alkyl group comprising from 8 to to 15 carbon atoms, preferably 9 to 14 carbon atoms, more preferably 10 to 14 carbon atoms and an amine tungstate obtained from at least one fatty amine comprising at least one branched alkyl group comprising from 8 to 15 carbon atoms, preferentially from 9 to 14 carbon atoms, more preferably from 10 to 14 carbon atoms.
    More preferably, the nitrogenous compound is a mixture of at least one amine tungstate obtained from at least one fatty amine comprising at least one linear alkyl group comprising from 11 to 14 carbon atoms, preferentially a C13 group. linear or branched alkyl and an amine tungstate obtained from at least one fatty amine comprising at least one branched alkyl group comprising from 11 to 14 carbon atoms, preferentially a linear or branched C 13 -alkyl group.
    As examples of nitrogenous compounds according to the invention, mention may be made of the product Irgalube 349 sold by the company BASF or the product Vanlube W-324® sold by the company Vanderbilt.
    Preferably, the lubricating composition according to the invention comprises from 0.1 to 3%, preferably from 0.1 to 2%, more preferably from 0.4 to 1.5% by weight of nitrogenous compound.
    According to the invention, the PAG of the lubricant composition according to the invention may be a block polymer or a random polymer.
    The PAG according to the invention comprises alkyl groups whose length of the hydrocarbon chains may vary. According to the invention, the length of the hydrocarbon chains is defined by a mean value of the number of carbon atoms.
    Preferably, the PAG of the composition according to the invention PAG is a block polymer of formula (II) or a random polymer of formula (II)
    (II) wherein R3 represents a linear or branched CrCso-alkyl group, preferably a linear or branched C4-C12-alkyl group; n represents a number ranging from 2 to 60, preferably from 5 to 30 or from 7 to 15; R4 and R5, which may be identical or different, independently represent a hydrogen atom or a C1-C2-alkyl group.
    For the PAG according to the invention, n can represent a number ranging from 2 to 60, preferably ranging from 5 to 30 or from 7 to 15.
    For a preferred PAG according to the invention, R3 represents a linear or branched C4-C12-alkyl group, R4 and R5 are different and independently represent a hydrogen atom or a linear CrC2-alkyl group and n represents a number ranging from 7 at 15.
    Also preferably, the PAG of the composition according to the invention is a block polymer of formula (MA) or a random polymer of formula (MA)
    wherein R3 represents a linear or branched C1-C30-alkyl group, preferably a linear or branched C4-C12-alkyl group; m represents a number ranging from 2 to 60, preferably from 5 to 30 or from 7 to 15; R6 and R7 represent a hydrogen atom; or R6 represents a hydrogen atom and R7 represents a methyl group; or R6 represents a methyl group and R7 represents a hydrogen atom; or R6 and R7 represent a methyl group; or R6 represents an ethyl group and R7 represents a hydrogen atom; or R6 represents a hydrogen atom and R7 represents an ethyl group.
    For the PAG according to the invention, m may represent a number ranging from 2 to 60, preferably ranging from 5 to 30 or from 7 to 15.
    For a preferred PAG according to the invention, R3 represents a linear or branched C4-C12-alkyl group, R6 and R7 are different and independently represent a hydrogen atom, a methyl group or an ethyl group and m represents a number ranging from 7 to 15.
    Also preferably, the PAG of the composition according to the invention is a block polymer of formula (MB) or a random polymer of formula (MB)
    in which R3 represents a linear or branched CrCso-alkyl group, preferably a linear or branched C4-C12-alkyl group, more preferably a linear or branched C8-C12-alkyl group; p and q independently represent a number ranging from 1 to 30, preferably from 2 to 15 or from 2 to 8; R8 and R9 represent a hydrogen atom; or R8 represents a hydrogen atom and R9 represents a methyl group; or R8 represents a methyl group and R9 represents a hydrogen atom; or R8 and R9 represent a methyl group; or R8 represents an ethyl group and R9 represents a hydrogen atom; or R8 represents a hydrogen atom and R9 represents an ethyl group; R10 and R11 represent a hydrogen atom; or R10 represents a hydrogen atom and R11 represents a methyl group; or R10 represents a methyl group and R11 represents a hydrogen atom; or R10 and R11 represent a methyl group; or R10 represents an ethyl group and R11 represents a hydrogen atom; or R10 represents a hydrogen atom and R11 represents an ethyl group.
    For the PAG according to the invention, p and q may independently represent a number ranging from 1 to 30, preferably from 2 to 15 or from 2 to 8.
    As particular PAGs according to the invention, mention may be made of PAGs for which R8, R9, R10 and R11 represent a hydrogen atom; or the PAGs for which R8 and R10 represent a hydrogen atom and R9 and R11 represent a methyl group; or the PAGs for which R8 and R10 represent a hydrogen atom and R9 and R11 represent an ethyl group; or the PAGs for which R8 and R10 represent a hydrogen atom, R9 represents a methyl group and R11 represents an ethyl group; or the PAGs for which R8 and R10 represent a hydrogen atom, R9 represents an ethyl group and R11 represents a methyl group; or the PAGs for which R8, R9 and R11 represent a hydrogen atom and R10 represents a methyl group; or the PAGs for which R8, R10 and R11 represent a hydrogen atom and R9 represents a methyl group.
    For a preferred PAG according to the invention, R3 represents a linear or branched C4-C12-alkyl group, R8, R10 and R11 represent a hydrogen atom and R9 represents a methyl group, p represents a number ranging from 3 to 5, for example 4.5, and q represents a number ranging from 1 to 3, for example 2.
    For a more preferred PAG according to the invention, R3 represents a linear or branched C8-C12-alkyl group, R8 represents a hydrogen atom and R9 represents a methyl group, R10 represents a hydrogen atom and R11 represents an ethyl group. , p represents a number ranging from 3 to 8, for example 5, and q represents a number ranging from 3 to 8, for example 4.
    More preferably, the PAG of the composition according to the invention is a block polymer of formula (III) or a random polymer of formula (III)
    in which R3 represents a linear or branched C4-C12-alkyl group, preferably a linear or branched C4-alkyl group; p represents a number ranging from 1 to 30, preferably from 2 to 15 or from 2 to 8; q represents a number ranging from 1 to 30, preferably from 1 to 10.
    Examples of PAG of formula (III) include the products of the Synalox 50-B® range marketed by Dow Chemical.
    More particularly preferably, the PAG of the composition according to the invention is a block polymer of formula (IV) or a random polymer of formula (IV)
    wherein R3 represents a linear or branched C8-C12-alkyl group; p represents a number ranging from 2 to 6; q represents a number ranging from 2 to 5.
    The PAG used for the composition according to the invention may be prepared by reacting at least one alcohol-type initiator comprising from 1 to 30 carbon atoms with the epoxy bonding of one or more alkylene oxides and then propagation of the reaction. to obtain these polymers. The preferred alkylene oxides are ethylene oxide, propylene oxide and butylene oxide. Methods for preparing PAG of formula (IV) are described in international patent application WO-2012/070007 or in international patent application WO-2013/164449.
    More particularly preferably, the PAG of the composition according to the invention is a block polymer of formula (V) or a random polymer of formula (V)
    in which R3 represents a linear or branched C4-C12-alkyl group, preferentially a linear or branched C4-alkyl group; r represents a number ranging from 2 to 60, preferably from 5 to 30 or from 7 to 15.
    As examples of PAG of formula (V), mention may be made of the products of the Synalox 100-B® range marketed by Dow Chemical.
    More preferably, the PAG is a block polymer of formula (VI) or a random polymer of formula (VI)
    wherein R12 represents a linear or branched C₁ C Csoalkyl group, preferably a linear or branched C8-C15 alkyl group; s and t independently represent an average number ranging from 1 to 5.
    For a preferred PAG according to the invention, R12 represents a group chosen from a linear C8-alkyl group; a branched C8-alkyl group; a linear Cg-alkyl group; a branched C9-alkyl group; a linear C10-alkyl group; C10-branched alkyl; a linear C n -alkyl group; a branched Cn-alKÿl group; a linear C12-alkyl group; a C12-branched alkyl group; a linear C13-alkyl group; a branched C13-alkyl group; a linear C14-alkyl group; a branched C14-alkyl group; a linear C15-alkyl group; a branched C15-alkyl group.
    For a preferred PAG according to the invention: s is greater than or equal to t; or s represents an average number ranging from 2 to 4.5; or t represents an average number ranging from 1.5 to 4.
    For a preferred PAG according to the invention: s represents an average number ranging from 2.5 to 3.5; or t represents an average number ranging from 2 to 3.
    For a preferred PAG according to the invention: s represents an average number equal to 2.5 and t represents an average number equal to 2; where s represents an average number equal to 3.5 and t represents an average number equal to 2.8.
    For a preferred PAG according to the invention: its kinematic viscosity at 100 ° C., measured according to ASTM D445 standard, ranges from 2.5 to 4.5 mm 2s.sup.-1, or whose viscosity index is greater than 160 or is between 160 and 210, or has a pour point of less than -40 ° C, or its dynamic viscosity (CCS) at -35 ° C as measured by ASTM D5293 is less than 1,200 mPa.s.
    Methods for preparing PAG of formula (VI) are described in application WO-2016/016362.
    Preferably, the lubricant composition according to the invention comprises from 1 to 99.5% by weight of PAG.
    More preferably, the lubricating composition according to the invention comprises from 1 to 30%, preferably from 1 to 20%, more preferably from 1 to 15% by weight of PAG. In a more preferred manner, the lubricating composition according to the invention comprises from 40 to 99.5%, preferably from 50 to 99.5%, more preferably from 60 to 99.5%, even more preferably from 70 to 99%, 5%, advantageously 80 to 99.5% by weight of PAG.
    In addition to a PAG and a nitrogen compound selected from amine phosphates or amine tungstates, the lubricating composition according to the invention may comprise a base oil.
    In general, the lubricating composition according to the invention may comprise any type of lubricating base oil, mineral, synthetic or natural, animal or plant adapted to its use.
    The base oils used in the lubricant compositions according to the invention can therefore be oils of mineral or synthetic origins belonging to groups I to V according to the classes defined in the API classification (or their equivalents according to the ATIEL classification) (Table A ) or their mixtures.
    Table A
    The mineral base oils which can be used for the lubricating composition 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, desalting, dewaxing with solvent, hydrotreatment, hydrocracking, hydroisomerization and hydrofinishing. Mixtures of synthetic and mineral oils can also be used.
    There is generally no limitation on the use of different lubricating bases to make the lubricating compositions according to the invention, except that they must have properties, in particular viscosity, viscosity index, sulfur content. and oxidation resistance, especially adapted for use for engines or for vehicle transmissions.
    The base oils of the lubricating compositions according to the invention may also be chosen from synthetic oils, such as certain carboxylic acid esters and alcohols, as well as from polyalphaolefins. The polyalphaolefins used as base oils are, for example, obtained from monomers comprising from 4 to 32 carbon atoms, for example from octene or decene, and whose viscosity at 100 ° C. is between 1.5 and 15mrrf.s "1 according to ASTM D445.The average molecular weight thereof is generally between 250 and 3000 according to ASTM D5296.
    Advantageously according to the invention, the base oil can be chosen from Group III oils, Group IV oils and Group V oils.
    Advantageously, the lubricating composition according to the invention may comprise at least 50% by weight of base oils relative to the total mass of the composition. More advantageously, the lubricant composition according to the invention may comprise at least 60% by weight, or even at least 70% by weight, of base oils relative to the total mass of the composition. More particularly advantageously, the lubricant composition according to the invention may comprise from 50, 60 or 70 to 99.9% by weight, or 50, 60 or 70 to 90% by weight, of one or more base oils. relative to the total mass of the composition.
    The lubricating composition according to the invention may also comprise at least one additional additive. Many additional additives can be used for the lubricant composition according to the invention. The additional additives preferred for the lubricating composition according to the invention are chosen from detergent additives, anti-wear additives different from compounds chosen from amine phosphates or amine tungstates, friction-modifying additives, extreme additives. pressure, dispersants, pour point depressants, defoamers, thickeners, and mixtures thereof.
    Preferably, the lubricating composition according to the invention comprises at least one inorganic friction modifier chosen from organomolybdenum compounds, preferably from molybdenum dithiocarbamates and their derivatives.
    Preferably, the lubricating composition according to the invention comprises from 0.1 to 2% by weight, preferably from 0.1 to 1.5% by weight, more preferably from 0.5 to 1.5% by weight of modifiers. inorganic friction.
    There is a wide variety of additional anti-wear additives different from the compounds selected from amine phosphates or amine tungstates.
    The additional antiwear additives may be chosen from phospho-sulfur additives such as metal alkylthiophosphates, in particular zinc alkylthiophosphates, and more specifically zinc dialkyldithiophosphates or ZnDTPs. The preferred compounds have the formula Zn ((SP (S) (OR) (ORO)) 2, in which R13 and R14, which may be identical or different, independently represent an alkyl group, preferably an alkyl group comprising from 1 to 18 carbon atoms. .
    Advantageously, the lubricant composition according to the invention may comprise from 0.01 to 6% by weight, preferably from 0.05 to 4% by weight, more preferably from 0.1 to 2% by weight relative to the mass. total lubricating composition, additional anti-wear additives.
    The lubricating composition according to the invention may comprise at least one organic friction modifying additive. The organic friction modifier additive may be selected from monoesters of fatty acids and polyols, alkoxylated amines, alkoxylated fatty amines, fatty epoxides, borate fatty epoxides; fatty amines or fatty acid glycerol esters. According to the invention, the fatty compounds comprise at least one hydrocarbon group comprising from 10 to 24 carbon atoms.
    Advantageously, the lubricant composition according to the invention may comprise at least one antioxidant additive. The antioxidant additive generally serves to retard the degradation of the lubricating composition in service. This degradation can notably result in the formation of deposits, the presence of sludge or an increase in the viscosity of the lubricant composition.
    Antioxidant additives act in particular as radical inhibitors or destroyers of hydroperoxides. Among the antioxidant additives commonly used, mention may be made of antioxidant additives of phenolic type, antioxidant additives of amine type, antioxidant phosphosulfur additives. Some of these antioxidant additives, for example phosphosulfur antioxidant additives, can be ash generators. Phenolic antioxidant additives may be ash-free or may be in the form of neutral or basic metal salts. The antioxidant additives may especially be chosen from sterically hindered phenols, sterically hindered phenol esters and sterically hindered phenols comprising a thioether bridge, diphenylamines, diphenylamines substituted by at least one C 1 -C 12 alkyl group, and Ν, Ν '-dialkyl-aryl diamines and mixtures thereof.
    Preferably, according to the invention, the sterically hindered phenols are chosen from compounds comprising a phenol group in which at least one vicinal carbon of the carbon bearing the alcohol function is substituted by at least one C 1 -C 10 alkyl group, preferably an alkyl group. in C 1 -C 6, preferably a C 4 alkyl group, preferably by the ter-butyl group.
    Amino compounds are another class of antioxidant additives that can be used, optionally in combination with phenolic antioxidant additives. Examples of amine compounds are aromatic amines, for example aromatic amines of formula NRaRbRc in which Ra represents an optionally substituted aliphatic or aromatic group, Rb represents an optionally substituted aromatic group, Rc represents a hydrogen atom, an alkyl group, an aryl group or a group of the formula RdS (O) zRe wherein Rd represents an alkylene group or an alkenylene group, Re represents an alkyl group, an alkenyl group or an aryl group and z represents 0, 1 or 2 .
    Sulfurized alkyl phenols or their alkali and alkaline earth metal salts can also be used as antioxidant additives.
    Another class of antioxidant additives is copper compounds, for example copper thio- or dithio-phosphates, copper and carboxylic acid salts, dithiocarbamates, sulphonates, phenates, copper acetylacetonates. Copper salts I and II, succinic acid or anhydride salts can also be used.
    The lubricant composition according to the invention may contain all types of antioxidant additives known to those skilled in the art.
    Also advantageously, the lubricating composition according to the invention comprises from 0.5 to 2% by weight relative to the total weight of the composition, of at least one antioxidant additive.
    The lubricant composition according to the invention may also comprise at least one detergent additive. The detergent additives generally make it possible to reduce the formation of deposits on the surface of the metal parts by dissolving the secondary oxidation and combustion products.
    The detergent additives that may be used in the lubricant composition according to the invention may be anionic compounds comprising a long lipophilic hydrocarbon chain and a hydrophilic head. The associated cation may be a metal cation of an alkali metal or alkaline earth metal. The detergent additives are preferably chosen from the alkali metal or alkaline earth metal salts of carboxylic acids, the sulphonates, the salicylates, the naphthenates and the phenate salts. The alkali and alkaline earth metals are preferably calcium, magnesium, sodium or barium. These metal salts generally comprise the metal in stoichiometric quantity or in excess, therefore in an amount greater than the stoichiometric amount. It is then overbased detergent additives; the excess metal bringing the overbased character to the detergent additive is then generally in the form of an oil insoluble metal salt, for example a carbonate, a hydroxide, an oxalate, an acetate, a glutamate, preferably a carbonate .
    Advantageously, the lubricant composition according to the invention may comprise from 2 to 4% by weight of detergent additive relative to the total mass of the lubricating composition.
    Also advantageously, the lubricant composition according to the invention may also comprise at least one pour point depressant additive.
    By slowing the formation of paraffin crystals, pour point depressant additives generally improve the cold behavior of the lubricant composition according to the invention.
    As examples of pour point depressant additives, mention may be made of alkyl polymethacrylates, polyacrylates, polyarylamides, polyalkylphenols, polyalkylnaphthalenes and alkylated polystyrenes.
    Advantageously, the lubricant composition according to the invention may also comprise at least one dispersing agent. The dispersing agent may be chosen from Mannich bases, succinimides and their derivatives.
    Also advantageously, the lubricating composition according to the invention may comprise from 0.2 to 10% by weight of dispersing agent relative to the total mass of the lubricating composition.
    Advantageously, the lubricating composition may also comprise at least one viscosity index improving polymer. Examples of viscosity index improver polymers include polymeric esters, homopolymers or copolymers, hydrogenated or non-hydrogenated, of styrene, butadiene and isoprene, polymethacrylates (PMA).
    Also advantageously, the lubricating composition according to the invention may comprise from 1 to 15% by weight relative to the total weight of the viscosity index improving lubricant composition.
    Preferably, the lubricating composition according to the invention is used for lubricating an engine, preferably a vehicle, more preferably a motor vehicle.
    Thus, the present invention also relates to the use of a lubricant composition according to the invention for lubricating an engine, preferably a vehicle, more preferably a motor vehicle.
    More preferably, the present invention also relates to the use of a lubricant composition according to the invention for lubricating a vehicle engine, more preferably a motor vehicle.
    The present invention also relates to a method of lubricating a motor vehicle, preferably motor vehicle, comprising at least one step of contacting said motor with the lubricant composition according to the invention.
    The present invention also relates to the use of a nitrogen compound selected from amine phosphates or amine tungstates for improving the anti-wear properties of a lubricating composition comprising an oil selected from PAG. All the characteristics and preferences relating to the nitrogen compound and to the PAG described above apply to this use.
    The present invention will now be illustrated by means of non-limiting examples. Example 1: Lubricating compositions according to the invention
    Lubricating compositions according to the invention are prepared according to Table 1 below (the compositions are given by weight (g)).
    In the compositions below: - PAG 1: PAG comprising propylene oxide and butylene oxide units and an -OH terminus (corresponding to formula (IV) with p »2.8 and q« 2.2) - PAG 2: PAG comprising propylene oxide and butylene oxide units and a -OCH 3 terminus (corresponding to formula (VI) with s "3.5 and t" 2.8) - PAG 3 (Synalox 50-15B® sold by DOW CHEMICAL): PAG based on ethylene oxide units and propylene oxide units - PAG 4 (Synalox 100-20B® marketed by DOW CHEMICAL): PAG based on propylene oxide units - PAG 5: PAG comprising propylene oxide and butylene oxide units and an -OH terminus (corresponding to formula (IV) with p "5 and q = 4) - nitrogen compound 1 (Irgalube 349® marketed by BASF): mixture of compound of formula (IA) and compound of formula (IB) in which R 1 represents a hexyl or ethylhexyl group and R 2 is an alkyl group comprising from 11 to 14 carbon atoms. Nitrogen compound 2 (Vanlube W-324® sold by Vanderbilt): mixture of at least one amine tungstate obtained from at least one fatty amine comprising at least one linear alkyl group comprising from 11 to 14 atoms of carbon and an amine tungstate obtained from at least one fatty amine comprising at least one branched alkyl group comprising from 11 to 14 carbon atoms - friction modifier (Sakuralube 525® marketed by the company Adeka): molybdenum dithiocarbamate - base oil (Yubase 4 + ® sold by the company SK): base oil group III (kinematic viscosity of 4.1 mm 2 / s measured at 100 ° C. according to ASTM D445) - polymer 1 (Viscoplex 6-565® sold by the company Evonik): polymethacrylate-polymer 2 (SV203® sold by the company Infineum): hydrogenated polyisoprene / styrene (PISH) - additive package: succinimide dispersant, anti-wear of ty zinc dithiophosphate, calcium salicylate detergent, phenolic antioxidant, diphenylamine antioxidant
    Table 1
    Example 2: Evaluation of the anti-wear properties
    This assessment is based on a procedure based on ASTM D2670 requiring the use of a FALEX tribometer and whose test conditions are described below.
    - specimens: FALEX steel - Break-in time: 300 s - Test duration: 180 min
    - Break-in charge: 445 N
    - Test load: 1335 N - Speed: 290 rpm - Ambient temperature
    The results are shown in Table 2 and are expressed in pm; the lower the value obtained, the better the anti-wear properties of the evaluated composition
    Table 2
    The results show that the lubricant compositions according to the invention (compositions 1 to 8) have good anti-wear properties.
    It should be noted that the improvement of the anti-wear properties is actually obtained: - in the presence or in the absence of additional base oils, - in the presence or in the absence of additional additives.
    权利要求:
    Claims (13)
    [1" id="c-fr-0001]
    A lubricating composition comprising an oil selected from polyalkyl glycols (PAGs or polyalkylene glycols) and a nitrogen compound selected from amine phosphates or amine tungstates.
    [2" id="c-fr-0002]
    2. Composition according to claim 1 for which the nitrogenous compound is an amine phosphate selected from: • compounds of formula (IA)

    in which: R1 represents a linear or branched alkyl group comprising from 2 to 10 carbon atoms, preferentially from 3 to 9 carbon atoms, more preferably from 5 to 8 carbon atoms; R2 represents a linear or branched alkyl group comprising from 8 to 15 carbon atoms, preferentially from 9 to 14 carbon atoms, more preferably from 10 to 14 carbon atoms; Compounds of formula (IB)

    in which: R 1 represents a linear or branched alkyl group comprising from 2 to 10 carbon atoms, preferentially from 3 to 9 carbon atoms, more preferably from 5 to 8 carbon atoms; R2 represents a linear or branched alkyl group comprising from 8 to 15 carbon atoms, preferentially from 9 to 14 carbon atoms, more preferably from 10 to 14 carbon atoms; A mixture of at least one compound of formula (IA) and at least one compound of formula (IB)
    [3" id="c-fr-0003]
    3. Composition according to claim 1 wherein the nitrogen compound is chosen from: - amine tungstates obtained from at least one fatty amine comprising at least one linear alkyl group comprising from 8 to 15 carbon atoms, preferably from 9 to 14 carbon atoms, more preferably 10 to 14 carbon atoms, - amine tungstates obtained from at least one fatty amine comprising at least one branched alkyl group comprising from 8 to 15 carbon atoms, preferentially from 9 to 14 carbon atoms, more preferably from 10 to 14 carbon atoms, - a mixture of at least one amine tungstate obtained from at least one fatty amine comprising at least one linear alkyl group comprising from 8 to to 15 carbon atoms, preferably 9 to 14 carbon atoms, more preferably 10 to 14 carbon atoms and an amine tungstate obtained from at least one amine grease comprising at least one branched alkyl group comprising from 8 to 15 carbon atoms, preferentially from 9 to 14 carbon atoms, more preferably from 10 to 14 carbon atoms.
    [4" id="c-fr-0004]
    4. Composition according to one of claims 1 to 3 wherein the PAG is a block polymer of formula (II) or a random polymer of formula (II)

    wherein R3 represents a linear or branched CrCso-alkyl group, preferably a linear or branched C4-C12-alkyl group; n represents a number ranging from 2 to 60, preferably from 5 to 30 or from 7 to 15; R4 and R5, which may be identical or different, independently represent a hydrogen atom or a C1-C2-alkyl group.
    [5" id="c-fr-0005]
    5. Composition according to one of claims 1 to 4 wherein the PAG is selected from o a block polymer of formula (MA) or a random polymer of formula (MA)

    wherein R3 represents a linear or branched C1-C30-alkyl group, preferably a linear or branched C4-C12-alkyl group; m represents a number ranging from 2 to 60, preferably from 5 to 30 or from 7 to 15; R6 and R7 represent a hydrogen atom; or R6 represents a hydrogen atom and R7 represents a methyl group; or R6 represents a methyl group and R7 represents a hydrogen atom; or R6 and R7 represent a methyl group; or R6 represents an ethyl group and R7 represents a hydrogen atom; or R6 represents a hydrogen atom and R7 represents an ethyl group; a block polymer of formula (IIB) or a random polymer of formula (IIB)

    in which R3 represents a linear or branched C1-C30-alkyl group, preferably a linear or branched C4-C12-alkyl group, more preferably a linear or branched C8-C12-alkyl group; p and q independently represent a number ranging from 1 to 30, preferably from 2 to 15 or from 2 to 8; R8 and R9 represent a hydrogen atom; or R8 represents a hydrogen atom and R9 represents a methyl group; or R8 represents a methyl group and R9 represents a hydrogen atom; or R8 and R9 represent a methyl group; or R8 represents an ethyl group and R9 represents a hydrogen atom; or R8 represents a hydrogen atom and R9 represents an ethyl group; R10 and R11 represent a hydrogen atom; or R10 represents a hydrogen atom and R11 represents a methyl group; or R10 represents a methyl group and R11 represents a hydrogen atom; or R10 and R11 represent a methyl group; or R10 represents an ethyl group and R11 represents a hydrogen atom; or R10 represents a hydrogen atom and R11 represents an ethyl group.
    [6" id="c-fr-0006]
    6. Composition according to one of claims 1 to 5 wherein the PAG is selected from - a block polymer of formula (III) or a random polymer of formula (III)

    in which R3 represents a linear or branched C4-C12-alkyl group, preferentially a linear or branched C4-alkyl group; p represents a number ranging from 1 to 30, preferably from 2 to 15 or from 2 to 8; q represents a number ranging from 1 to 30, preferably from 1 to 10, or - a block polymer of formula (IV) or a random polymer of formula (IV)

    wherein R3 represents a linear or branched C8-C12-alkyl group; p represents a number ranging from 2 to 6; q represents a number ranging from 2 to 5. - a block polymer of formula (V) or a random polymer of formula (V)

    in which R3 represents a linear or branched C4-C12-alkyl group, preferably a linear or branched C4-alkyl group; r represents a number ranging from 2 to 60, preferably from 5 to 30 or from 7 to 15.
    [7" id="c-fr-0007]
    7. Composition according to one of claims 1 to 3 wherein the PAG is a block polymer of formula (VI) or a random polymer of formula (VI)

    wherein R12 represents a linear or branched C1-C30-alkyl group, preferably a linear or branched C8-C15 alkyl group; s and t independently represent an average number ranging from 1 to 5.
    [8" id="c-fr-0008]
    8. Composition according to one of claims 1 to 7 comprising 1 to 99.5% by weight of PAG.
    [9" id="c-fr-0009]
    9. Composition according to any one of claims 1 to 8 comprising: - from 1 to 30%, preferably from 1 to 20%, more preferably from 1 to 15% by weight of PAG; from 40 to 99.5%, preferably from 50 to 99.5%, more preferably from 70 to 99.5% by weight of PAG.
    [10" id="c-fr-0010]
    10. Composition according to one of claims 1 to 9 comprising from 0.1 to 3%, preferably from 0.1 to 2%, more preferably from 0.4 to 1.5% by weight of nitrogen compound.
    [11" id="c-fr-0011]
    11. Composition according to one of claims 1 to 10 comprising a lubricating base oil.
    [12" id="c-fr-0012]
    12. Composition according to one of claims 1 to 11 further comprising a friction modifier selected from organomolydène compounds, preferably selected from molybdenum dithiocarbamates and their derivatives.
    [13" id="c-fr-0013]
    13. Use of a lubricant composition according to one of claims 1 to 12 for the lubrication of an engine or for the lubrication of an automobile engine.
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    同族专利:
    公开号 | 公开日
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    MX2018011045A|2019-01-24|
    FR3048976B1|2020-02-07|
    CN109072121A|2018-12-21|
    JP2019508562A|2019-03-28|
    KR20180126478A|2018-11-27|
    EP3430109A1|2019-01-23|
    US10982169B2|2021-04-20|
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    法律状态:
    2017-02-13| PLFP| Fee payment|Year of fee payment: 2 |
    2017-09-22| PLSC| Publication of the preliminary search report|Effective date: 20170922 |
    2018-02-23| PLFP| Fee payment|Year of fee payment: 3 |
    2019-02-21| PLFP| Fee payment|Year of fee payment: 4 |
    2020-02-25| PLFP| Fee payment|Year of fee payment: 5 |
    2021-02-10| PLFP| Fee payment|Year of fee payment: 6 |
    2022-02-10| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1652188A|FR3048976B1|2016-03-15|2016-03-15|LUBRICATING COMPOSITION BASED ON POLYALKYLENE GLYCOLS|
    FR1652188|2016-03-15|FR1652188A| FR3048976B1|2016-03-15|2016-03-15|LUBRICATING COMPOSITION BASED ON POLYALKYLENE GLYCOLS|
    BR112018068691A| BR112018068691A2|2016-03-15|2017-03-15|lubricant composition and use of a lubricant composition|
    PCT/EP2017/056058| WO2017157979A1|2016-03-15|2017-03-15|Polyalkylene glycol-based lubricant composition|
    MX2018011045A| MX2018011045A|2016-03-15|2017-03-15|Polyalkylene glycol-based lubricant composition.|
    JP2018548392A| JP2019508562A|2016-03-15|2017-03-15|Lubricating compositions based on polyalkylene glycols|
    KR1020187026779A| KR102372804B1|2016-03-15|2017-03-15|Polyalkylene glycol-based lubricating composition|
    CN201780017795.9A| CN109072121A|2016-03-15|2017-03-15|Lubricating composition based on polyalkylene glycol|
    EP17710009.6A| EP3430109A1|2016-03-15|2017-03-15|Polyalkylene glycol-based lubricant composition|
    US16/084,823| US10982169B2|2016-03-15|2017-03-15|Polyalkylene glycol-based lubricant composition|
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