• 专利附录
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    • 专利摘要:
    The present invention relates to a lubricating composition comprising - at least one base oil, - at least one organomolybdenum compound, - at least one totally or partially neutralized amine salt, the amine corresponding to the following formula (I) RN (X ) -Y (I) and the use of this composition to reduce friction between two surfaces.
    公开号:FR3048433A1
    申请号:FR1651804
    申请日:2016-03-03
    公开日:2017-09-08
    发明作者:Raphaele Iovine；Catherine Charrin
    申请人:Total Marketing Services SA；
    IPC主号:
    专利说明:

    The invention relates to the field of lubricating compositions, especially lubricating compositions for transmission or for motor and in particular for engines of motor vehicles. One of the objectives of the lubricating compositions is to reduce the phenomena of friction and wear of mechanical parts in contact and movement relative to each other. Lubricating compositions have the particular objective of limiting these phenomena of friction in the engines of vehicles, including motor vehicle engines. In addition, the use of carbon coating in engines, especially motor vehicles, is expanding. There is therefore an interest in being able to propose lubricating compositions making it possible to reduce friction phenomena for both the steel / steel contacts, the carbon / carbon coating and the steel / carbon coating. Generally, to limit friction phenomena, friction modifiers may be incorporated into the lubricating compositions. In particular, it is known to add fatty amines as friction modifiers. However, these amines can have a detrimental effect on the joints, in particular the joints of the mechanical parts, and in particular the polymeric joints, especially fluorinated ones. Indeed, these amines can be at the origin of an accelerated degradation of the mechanical properties of the joints.
    It is also known to use organomolybdenum compounds to reduce the phenomena of friction, more particularly in the contacts between two steel surfaces. However, it is known to those skilled in the art that the use of organomolybdenum compounds, in particular organomolybdenum compounds comprising a dithiocarbamate group, may cause worsening of the wear phenomena of mechanical parts. It has also been observed that the organomolybdenum compounds present in a lubricant can degrade or even peel off a carbon coating present on a surface and that this degradation can be accentuated with the increase in the content of organomolybdenum compounds in the lubricant.
    There is therefore an interest in providing lubricating compositions which, while reducing the phenomena of friction, particularly in the presence of surfaces having a carbon coating, have a moderate impact on other engine components, and especially on the joints.
    Furthermore, one of the objectives of the lubricant compositions is also to improve the engine performance and therefore to allow fuel savings.
    An object of the present invention is therefore to provide a lubricant composition for reducing friction phenomena, especially in the presence of surfaces having a carbon coating and having a limited impact on the degradation of seals including engine seals, including engines vehicle, for example a motor vehicle.
    Another object of the present invention is to provide such a composition to reduce friction phenomena for both steel / steel contacts, carbon / carbon coating and steel / carbon coating.
    Another object of the present invention is to provide such a composition also to reduce fuel consumption. Still other objects will appear on reading the description of the invention which follows.
    In order to meet these objectives and the disadvantages of known lubricating compositions, the present invention provides a lubricating composition comprising: at least one base oil, at least one organomolybdenum compound, at least one totally or partially neutralized amine salt, amine having the following formula (I): RN (X) -Y (I) wherein R is a linear or branched, fully or partially saturated hydrocarbon group comprising from 2 to 24 carbon atoms, preferably from 4 to 24 more preferably from 14 to 24, especially from 16 to 24, for example from 18 to 24 carbon atoms; X represents a hydrogen atom, a hydrocarbon group, linear or branched, totally or partially saturated, comprising from 1 to 24 carbon atoms, preferably from 1 to 10 carbon atoms, especially from 1 to 8 carbon atoms, a benzyl group, or a group of the formula -R 1 - [NH-R 4] n -NH 2; Y represents a hydrogen atom, a hydrocarbon group, linear or branched, totally or partially saturated, comprising from 1 to 24 carbon atoms, preferably from 1 to 10 carbon atoms, especially from 1 to 8 carbon atoms, a benzyl group, or a group of the formula -R 1 - [NH-R 4] n -NH 2; n represents an integer of 0 to 3, preferably 0 to 2, preferably 0 or 1; and R 1, which may be identical or different, represent a linear or branched alkyl group comprising from 2 to 4 carbon atoms, preferably from 2 to 3 carbon atoms, preferably CH 2 CH 2 or CH 2 CH 2 CH 2; at least one of X or Y represents a hydrogen atom or -R ^ - [NH-R% -NH2; at least one of X, Y or R represents a hydrocarbon group, linear or branched, totally or partially saturated, comprising from 4 to 24 carbon atoms, preferably from 14 to 24 carbon atoms, in particular from 16 to 24 atoms carbon, for example from 18 to 24 carbon atoms; the acid neutralizing the amine is chosen from monoacids of formula (II) R'COOH (II) in which R 'represents a linear or branched hydrocarbon group, totally or partially saturated, comprising from 2 to 24.
    Surprisingly, the inventors have pointed out that the combination of the totally or partially neutralized amine salt according to the invention and of an organomolybdenum compound makes it possible to limit the friction phenomena for both the steel / steel contacts and the carbon / carbon coating. carbon and steel / carbon coating and having little impact or limited impact on joint degradation. Moreover, the inventors have also demonstrated that the amine salts partially or totally neutralized according to the invention had a better compatibility with the joints, in particular the joints of the engines, in particular motors of motor vehicles, than the corresponding amines. not neutralized. In the context of the present application, the seals are the seals used in engine design, generally polymer seals, in particular preferably fluorinated elastomer seals. In particular, a lubricating composition comprising at least one partially or totally neutralized amine salt according to the invention makes it possible to limit the wear of the joints of the engines, in particular engines of motor vehicles, in contrast to non-neutralized amines. The amine, intended to be neutralized, which is used in the composition of the invention, is preferably an amine corresponding to the following formula (Ia): RN (X) -R '- [NHR% -NH 2 ( la) in which R, X, R 1 and n are as defined above, and at least one of X or R represents a linear or branched, fully or partially saturated hydrocarbon group comprising from 4 to 24 carbon atoms, preferably from 14 to 24 carbon atoms, especially from 16 to 24 carbon atoms, for example from 18 to 24 carbon atoms.
    Preferably, in the compounds of formula (I) or (la) according to the invention: R represents a hydrocarbon group, linear or branched, totally or partially saturated, comprising from 14 to 24, in particular from 16 to 24, for example from 18 to 24 carbon atoms; and X represents a hydrogen atom, a linear or branched alkyl group comprising from 2 to 8 carbon atoms, a benzyl group, or a group of the formula -R 1 - [NH-R 4] n -NH 2.
    Preferably, in the compounds of formula (I) or (la) according to the invention: R represents a hydrocarbon group, linear or branched, totally or partially saturated, comprising from 14 to 24, in particular from 16 to 24, for example from 18 to 24 carbon atoms; and X represents a hydrogen atom or a group of the formula -R 1 - [NH-R 4] n -NH 2.
    Preferably, in the compounds of formula (I) according to the invention: R represents a hydrocarbon group, linear or branched, totally or partially saturated, comprising from 14 to 24, in particular from 16 to 24, for example from 18 to 24 atoms of carbon ; Y is -R ^ - [NH-R% -NH2; n = 0; R 1 is CH 2 CH 2 CH 2; and X represents CH2CH2CH2NH2 or H.
    Preferably, in the compounds of formula (Ia) according to the invention: R represents a hydrocarbon group, linear or branched, totally or partially saturated, comprising from 14 to 24, in particular from 16 to 24, for example from 18 to 24 atoms of carbon; n = 0; R 1 is CH 2 CH 2 CH 2; and X represents CH2CH2CH2NH2 or H.
    In a particularly preferred manner, the amine is chosen from the following amines: RNHCH 2 CH 2 CH 2 CNH 2 with R represents a hydrocarbon group, linear or branched, totally or partially saturated, comprising from 16 to 18 carbon atoms; or N (R) (CH 2 CH 2 CH 2 NH 2) (CH 2 CH 2 CH 2 NH 2) with R represents a hydrocarbon group, linear or branched, totally or partially saturated, comprising from 16 to 18 carbon atoms.
    In the context of the present invention, the acid, which makes it possible to neutralize the amine of formula (I) or (la) defined above in the form of a salt, is preferably chosen from the acids of formula (II) ) in which R 'represents a hydrocarbon group, linear or branched, totally or partially saturated, comprising from 7 to 24 carbon atoms, preferably from 10 to 24, for example from 14 to 20, in particular from 16 to 20 carbon atoms .
    In a particularly preferred manner, the acid which makes it possible to neutralize the amine of formula (I) or (Ia) is oleic acid. The amine used in the composition of the invention is totally or partially neutralized. Preferably, the molar ratio between the number of moles of nitrogen atom in the amine and the number of moles of acid functional group of formula (II) is between 9: 1 and 1: 1, preferably between 5: 1 and 1: 1.
    By organomolybdenum compound according to the invention is meant any organomolybdenum compound soluble in an oil, especially in a base oil.
    The organomolybdenum compound according to the present invention may be chosen from organic complexes of molybdenum such as carboxylates, esters, molybdenum amides, obtainable by reaction of molybdenum oxide or ammonium molybdates with fatty substances. , glycerides, fatty acids or fatty acid derivatives (esters, amines, amides, etc.).
    Preferably, the organomolybdenum compound of the invention is chosen from sulfur and phosphorus-free molybdenum complexes, with amide ligands, mainly prepared by reaction of a molybdenum source, which may be, for example, trioxide of molybdenum, and an amine derivative, and of fatty acids comprising, for example, from 4 to 28 carbon atoms, preferably from 8 to 18 carbon atoms, such as for example the fatty acids contained in vegetable or animal oils .
    The synthesis of such compounds is for example described in US4889647, EP0546357, US5412130, EP1770153.
    In a preferred embodiment of the invention, the organomolybdenum compound is chosen from organic complexes of molybdenum obtained by reaction of: (i) a mono-, di- or tri-glyceride fatty substance, or fatty acid, (ii) an amine source of formula (A):
    In which: X 'represents an oxygen atom or a nitrogen atom, - represents an oxygen atom or a nitrogen atom, - n and m represent 1 when X' or X 'represent an atom of oxygen, n and m represent 2 when X 'or X' represent a nitrogen atom, (iii) and a molybdenum source selected from molybdenum trioxide or molybdates, preferably ammonium molybdate, in an amount of sufficient to provide 0.1 to 30% molybdenum based on the total weight of complex.
    In one embodiment of the invention, the organic molybdenum complex may comprise from 2 to 8.5% by weight of molybdenum with respect to the weight of complex.
    In a preferred embodiment of the invention, the organic molybdenum complex consists of at least one of the compounds of formula (NI) or (IV), alone or as a mixture:
    wherein: X 'represents an oxygen atom or a nitrogen atom; X represents an oxygen atom or a nitrogen atom; η represents 1 when represents an oxygen atom and m represents 1 when X represents an oxygen atom; n represents 2 when X 'represents a nitrogen atom and m represents 2 when X 1 represents a nitrogen atom;
    R 1 represents a linear or branched, saturated or unsaturated alkyl group comprising from 3 to 30 carbon atoms, preferentially from 3 to 20 carbon atoms, advantageously from 7 to 17 carbon atoms;
    (IV) wherein: X 'represents an oxygen atom or a nitrogen atom; X represents an oxygen atom or a nitrogen atom; n represents 1 when X 'represents an oxygen atom and m represents 1 when X represents an oxygen atom; n represents 2 when X 1 represents a nitrogen atom and m represents 2 when X 1 represents a nitrogen atom;
    R 1 represents a linear or branched, saturated or unsaturated alkyl group comprising from 3 to 30 carbon atoms, preferably from 3 to 20 carbon atoms, advantageously from 7 to 17 carbon atoms; R2 represents a linear or branched, saturated or unsaturated alkyl group comprising from 3 to 30 carbon atoms, preferably from 3 to 20 carbon atoms, advantageously from 7 to 17 carbon atoms.
    In one embodiment of the invention, the organic molybdenum complex is prepared by reaction of: (i) a mono, di or tri glyceride fatty substance, or fatty acid, (ii) diethanolamine or 2- (2-aminoethyl) aminoethanol, (iii) and a molybdenum source selected from molybdenum trioxide or molybdates, preferentially ammonium molybdate, in an amount sufficient to provide 0.1 to 20.0 mol% of molybdenum. ratio to the weight of complex.
    In a preferred embodiment of the invention, the organic molybdenum complex consists of at least one compound of formula (III-a) or (III-b), alone or as a mixture:
    (lll-a) in which
    R 1 represents a linear or branched, saturated or unsaturated alkyl group comprising from 3 to 30 carbon atoms, preferably from 3 to 20 carbon atoms, advantageously from 7 to 17 carbon atoms,
    (III-b) in which R 1 represents a linear or branched, saturated or unsaturated alkyl group comprising from 3 to 30 carbon atoms, preferably from 3 to 20 carbon atoms, advantageously from 7 to 17 carbon atoms.
    As examples of sulfur-free molybdenum complexes according to the invention, mention may be made of Molyvan 855® sold by the company Vanderbilt.
    In another embodiment, the organomolybdenum compound may be selected from molybdenum dithiophosphates or molybdenum dithiocarbamates.
    In a preferred embodiment of the invention, the organomolybdenum compound is chosen from molybdenum dithiocarbamates.
    The molybdenum dithiocarbamate compounds (Mo-DTC compounds) are complexes formed of a metal ring bound to one or more ligands, the ligand being a dithiocarbamate group of alkyls. These compounds are well known to those skilled in the art.
    In one embodiment of the invention, the Mo-DTC compound may comprise from 1 to 40%, preferably from 2 to 30%, more preferably from 3 to 28%, advantageously from 4 to 15% by weight of molybdenum, relative to the total mass of Mo-DTC compound. In another embodiment of the invention, the Mo-DTC compound may comprise from 1 to 40%, preferably from 2 to 30%, more preferably from 3 to 28%, advantageously from 4 to 15% by weight of sulfur. , relative to the total mass of Mo-DTC compound.
    In another embodiment of the invention, the Mo-DTC compound may be chosen from those whose nucleus has two molybdenum atoms (also called dimeric Mo-DTC) and those whose nucleus has three molybdenum atoms (also called Trimeric Mo-DTP).
    In another embodiment of the invention, the trimeric Mo-DTC compounds correspond to the formula MoaSkLn in which: k represents an integer at least equal to 4, preferably ranging from 4 to 10, advantageously from 4 to 7, n is an integer from 1 to 4, and L being an alkyl dithiocarbamate group comprising from 1 to 100 carbon atoms, preferably from 1 to 40 carbon atoms, preferably from 3 to 20 carbon atoms.
    Examples of trimeric Mo-DTC compounds according to the invention include the compounds and methods for their preparation as described in WO 98/26030 and US 2003/022954.
    In a preferred embodiment of the invention, the Mo-DTC compound is a dimeric Mo-DTC compound.
    Examples of dimeric Mo-DTC compounds include compounds and methods for their preparation as described in EP 0757093, EPI 0719851, EP 0743354 or EP 1013749.
    The dimeric Mo-DTC compounds generally correspond to the compounds of formula (V):
    (V) wherein:
    Rs, R4, R5, Re, which may be identical or different, independently represent a hydrocarbon group chosen from alkyl, alkenyl, aryl, cycloalkyl or cycloalkenyl groups, X3, X4, X5 and Xe, which may be identical or different, independently represent an oxygen atom; or a sulfur atom.
    Alkyl group in the sense of the invention means a hydrocarbon group, linear or branched, saturated or unsaturated, comprising from 1 to 24 carbon atoms.
    In one embodiment of the invention, the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, stearyl, icosyl, docosyl, tetracosyl, triacontyl, 2-ethylhexyl, 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldodecyl , 2-octyldodecyl, 2-decyltetradecyl, 2-dodecylhexadecyl, 2-hexadecyloctadecyl, 2-tetradecyloctadecyl, myristyl, palmityl and stearyl.
    For the purposes of the present invention, the term "alkenyl group" means a linear or branched hydrocarbon group comprising at least one double bond and comprising from 2 to 24 carbon atoms. The alkenyl group may be chosen from vinyl, allyl, propenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl and oleic.
    Aryl group within the meaning of the present invention means a polycyclic aromatic hydrocarbon or an aromatic group, substituted or not with an alkyl group. The aryl group may comprise from 6 to 24 carbon atoms.
    In one embodiment, the aryl group may be selected from the group consisting of phenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, phenylphenyl, benzylphenyl, phenylstyrene, p-cumylphenyl and the like. naphthyl.
    For the purpose of the present invention, the cycloalkyl groups and the cycloalkenyl groups may be chosen, in a non-limiting manner, from the group consisting of cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl. Cycloalkyl groups and cycloalkenyl groups may comprise from 3 to 24 carbon atoms.
    In a preferred embodiment of the invention, R3, R4, R5 and Re, which may be identical or different, independently represent an alkyl group comprising from 4 to 18 carbon atoms or an alkenyl group comprising from 2 to 24 carbon atoms.
    In one embodiment of the invention, X3, X4, X5 and Xe may be the same and may be a sulfur atom.
    In another embodiment of the invention, X3, X4, X5 and Xe may be the same and may be an oxygen atom.
    In another embodiment of the invention, X3 and X4 may represent a sulfur atom and X5 and Xe may represent an oxygen atom.
    In another embodiment of the invention, X3 and X4 may represent an oxygen atom and X5 and Xe may represent a sulfur atom.
    In another embodiment of the invention; the ratio in number of sulfur atoms relative to the number of oxygen atoms (S / O) of the compound Mo-DTC may vary from (1/3) to (3/1).
    In another embodiment of the invention, the Mo-DTC compound of formula (V) may be chosen from a symmetrical Mo-DTC compound, an asymmetric Mo-DTC compound and their combination.
    By symmetrical Mo-DTC compound according to the invention is meant a Mo-DTC compound of formula (V) in which the groups R3, R4, R5 and Re are identical.
    By asymmetric Mo-DTC compound according to the invention is meant a Mo-DTC compound of formula (V) in which the R3 and R4 groups are identical, the R5 and Re groups are identical and the R3 and R4 groups are different from the groups R5 and Re-
    In a preferred embodiment of the invention, the Mo-DTC compound is a mixture of at least one symmetrical Mo-DTC compound and at least one asymmetric Mo-DTC compound.
    In one embodiment of the invention, R3 and R4, which are identical, represent an alkyl group comprising from 5 to 15 carbon atoms and R5 and Re, which are identical and different from R3 and R4, represent an alkyl group comprising from 5 to 15 carbon atoms. carbon atoms.
    In a preferred embodiment of the invention, R3 and R4, which are identical, represent an alkyl group comprising from 6 to 10 carbon atoms and R5 and Re represent an alkyl group comprising from 10 to 15 carbon atoms.
    In another preferred embodiment of the invention, R3 and R4, which are identical, represent an alkyl group comprising from 10 to 15 carbon atoms and R5 and Re represent an alkyl group comprising from 6 to 10 carbon atoms.
    In another preferred embodiment of the invention, R3, R4, R5 and Re, which are identical, represent an alkyl group comprising from 5 to 15 carbon atoms, preferably from 8 to 13 carbon atoms.
    Advantageously, the compound Mo-DTC is chosen from the compounds of formula (V) in which: X 3 and X 4 represent an oxygen atom, X 5 and X are a sulfur atom, R 3 represents an alkyl group comprising 8 carbon atoms or an alkyl group comprising 13 carbon atoms, - R4 represents an alkyl group comprising 8 carbon atoms or an alkyl group comprising 13 carbon atoms, - R5 represents an alkyl group comprising 8 carbon atoms or an alkyl group comprising 13 carbon atoms, - Re represents an alkyl group comprising 8 carbon atoms or an alkyl group comprising 13 carbon atoms.
    Thus, advantageously, the Mo-DTC compound is chosen from compounds of formula (V-a)
    wherein the groups R3, R4, R5 and Re are as defined for formula (V).
    More advantageously, the compound Mo-DTC is a mixture of: - a Mo-DTC compound of formula (Va) in which R3, R4, R5 and Re represent an alkyl group comprising 8 carbon atoms, - a Mo-DTC compound of formula (Va) in which R3, R4, R5 and Re represent an alkyl group comprising 13 carbon atoms, and - a Mo-DTC compound of formula (Va) in which R3, R4 represent a grouping alkyl comprising 13 carbon atoms and R5 and Re represent an alkyl group comprising 8 carbon atoms, and / or - a Mo-DTC compound of formula (Va) in which R3, R4 represent an alkyl group comprising 8 carbon atoms and R5 and Re represent an alkyl group comprising 13 carbon atoms.
    Examples of Mo-DTC compounds that may be mentioned are Molyvan L®, Molyvan 807® or Molyvan 822® products marketed by RT Vanderbilt Compagny® or Sakura-lube 200®, Sakura-lube 165® and Sakura-lube products. 525® or Sakura-lube 600® marketed by the company Adeka.
    Preferably, the lubricating composition of the invention comprises from 0.05 to 5%, preferably from 0.1 to 2%, by weight of the amine salt partially or totally neutralized with respect to the total weight of the composition.
    Preferably, the lubricating composition of the invention comprises from 0.01 to 3%, preferably from 0.05 to 3%, for example from 0.1 to 2%, by weight of organomolybdenum compound relative to the total weight of the composition.
    In general, the lubricating composition according to the invention may comprise any type of mineral lubricating base oil, synthetic or natural, animal or vegetable, known to those skilled in the art.
    The base oils used in the lubricant compositions according to the invention may 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 ATI EL classification) (Table A ) or their mixtures.
    Table A
    The mineral base oils according to the invention include all types of base oils obtained by atmospheric and vacuum distillation of crude oil, followed by refining operations such as solvent extraction, desalphating, solvent dewaxing, hydrotreatment, hydrocracking. , hydroisomerization and hydrofinition.
    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. , oxidation resistance, suitable 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, and 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 According to ASTM D445, their average molecular weight is generally between 250 and 3000 according to the ASTM D5296 standard.
    Preferably, the base oils of the present invention are chosen from the above base oils whose aromatic content is between 0 and 45%, preferably between 0 and 30%. The aromatic content of the oils is measured according to UV Burdett method. Without wishing to be bound by any theory, the aromaticity of the base oil is a character that makes it possible to optimize the operation of the polymer as a function of temperature. The choice of a low aromatic oil allows an optimum at a higher temperature.
    Advantageously, the lubricant composition according to the invention comprises at least 50% by weight of base oils relative to the total mass of the composition.
    More advantageously, the lubricating composition according to the invention comprises 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 comprises from 60 to 99.5% by weight of base oils, preferably from 70 to 99.5% by weight of base oils, relative to total mass of the composition.
    Many additives can be used for this lubricant composition according to the invention.
    The preferred additives for the lubricating composition according to the invention are chosen from detergent additives, anti-wear additives, friction modifying additives other than organomolybdenum compounds, extreme pressure additives and dispersants. pour point improvers, defoamers, thickeners, and mixtures thereof.
    Preferably, the lubricating composition according to the invention comprises at least one antiwear additive, at least one extreme pressure additive or their mixtures.
    Anti-wear additives and extreme pressure additives protect friction surfaces by forming a protective film adsorbed on these surfaces.
    There is a wide variety of anti-wear additives. In a preferred manner for the lubricating composition according to the invention, the anti-wear additives are chosen from phosphosulfur 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) (OR 1)) 2, in which R 1 and R 2, which may be identical or different, independently represent an alkyl group, preferably an alkyl group containing from 1 to 18 carbon atoms.
    Amine phosphates are also anti-wear additives which can be used in the lubricating composition according to the invention. However, the phosphorus provided by these additives can act as a poison of the catalytic systems of automobiles because these additives are ash generators. These effects can be minimized by partially substituting amine phosphates with non-phosphorus additives, such as, for example, polysulfides, especially sulfur-containing olefins.
    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, anti-wear additives and extreme pressure additives.
    Advantageously, the lubricant composition according to the invention may comprise at least one additional friction modifier additive different from the organomolybdenum compounds. The additional friction modifier additive may be selected from a compound providing metal elements and an ash free compound. Among the compounds providing metal elements, mention may be made of transition metal complexes such as Sb, Sn, Fe, Cu, Zn, the ligands of which may be hydrocarbon compounds comprising oxygen, nitrogen, sulfur or of phosphorus. The ashless friction modifier additives are generally of organic origin and may be selected from monoesters of fatty acids and polyols, fatty epoxides, borate fatty epoxides; or glycerol esters of fatty acid. According to the invention, the fatty compounds comprise at least one hydrocarbon group comprising from 10 to 24 carbon atoms.
    Advantageously, the lubricating composition according to the invention may comprise from 0.01 to 2% by weight or from 0.01 to 5% by weight, preferably from 0.1 to 1.5% by weight or 0.1 at 2% by weight relative to the total mass of the lubricant composition, friction modifier additive.
    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 N, N '-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 carrying the alcohol function is substituted with at least one C 1 -C 10 alkyl group, preferably an alkyl group. in Ci-Ce, preferably a C4 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 in which R 1 represents an optionally substituted aliphatic or aromatic group, R 1 represents an optionally substituted aromatic group, R represents a hydrogen atom, hydrogen, an alkyl group, an aryl group or a group of the formula R®S (O) zR ^ in which R® represents an alkylene group or an alkenylene group, R ^ 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.
    Advantageously, the lubricating composition comprises at least one ash-free antioxidant additive.
    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 can be used in the lubricant composition according to the invention are generally known to those skilled in the art. The detergent additives 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.
    The lubricating composition of the present invention may also comprise at least one additional viscosity index improving polymer. As examples of additional viscosity index improving polymers, there may be mentioned polymeric esters, homopolymers or copolymers, hydrogenated or non-hydrogenated, styrene, butadiene and isoprene, polymethacrylates (PMA).
    The present invention also relates to the use of a lubricant composition according to the invention for the lubrication of mechanical parts, especially in transmissions and / or motor vehicles, preferably motor vehicles.
    The composition according to the invention is used in particular to reduce the friction between two surfaces, in particular between two steel surfaces, between two surfaces covered with carbon or between a steel surface and a surface covered with carbon, in particular in a vehicle engine, preferentially of a motor vehicle.
    In the context of the present invention, the term "carbon coating" means any coating comprising carbon. Carbon coating includes diamond coatings and more particularly nanodiamond coatings. These coatings can in particular be in the form of at least one nanocrystalline diamond layer having a purity ranging from 70 to 99%. Preferably, the carbon coatings are chosen from nanodiamond coatings in the form of at least one nanocrystalline diamond layer having a purity ranging from 70 to 99%, preferably ranging from 70 to 97%, advantageously from 75% and a thickness ranging from 0.1 to 3 μm, preferably ranging from 0.5 to 2 μm, advantageously 1.5 μm.
    These carbon coatings may also be chosen from DLC (Diamond Like Carbon) type coatings. Any type of DLC coating can be used. In general, the DLCs comprise a set of families of amorphous materials essentially containing carbon. Among these families, the hydrogenated DLCs, in particular the α-C: Hs, and the non-hydrogenated DLCs, in particular a-C or ta-C, are used.
    DLCs have properties that vary depending on their content of sp3 hybridized carbons and their hydrogen content. Some DLC variants may be doped with metal elements, such as iron, chromium or tungsten.
    Compared to diamond coatings, DLC coatings are generally less mechanically and thermally resistant because they are amorphous materials. On the other hand, they are generally less rough and above all can be deposited at low temperature on most substrates. Preferably, the DLCs are hydrogenated DLCs, in particular a-C: H containing from 10 to 40% hydrogen.
    Advantageously, the use of the lubricant composition according to the invention makes it possible not to aggravate or even reduce the wear between two surfaces, in particular between two steel surfaces, between two surfaces covered with carbon or between a steel surface and a steel surface. surface covered with carbon, especially in a vehicle engine, preferably a motor vehicle.
    The present invention also relates to the use of the lubricant composition according to the invention for reducing the fuel consumption of vehicles, especially motor vehicles.
    Advantageously, the inventors have also demonstrated that the partially or totally neutralized amine salts according to the invention have a better compatibility with the joints, in particular the joints of the engines, in particular motor vehicle engines, than the amines. corresponding non-neutralized. In the context of the present application the seals are the seals used in the engine design, generally polymeric joints, especially elastomeric seals. preferably fluorinated. In particular, the composition of the invention makes it possible to limit the wear of engine seals, in particular motor vehicle engines, as compared to un-neutralized amines.
    Thus, the present invention also relates to the use of the composition according to the invention to, in addition, reduce the deterioration of seals contained in a vehicle engine, preferably automobile.
    The present invention also relates to a method for lubricating mechanical parts, especially in transmissions and / or engines of vehicles, especially motor vehicles, comprising at least one step of contacting at least one piece with a lubricating composition according to the invention. 'invention.
    The present invention also relates to a method for reducing friction between two surfaces of a vehicle engine, in particular a motor vehicle, comprising at least one step of contacting at least one of the surfaces with a lubricant composition according to the invention. The surfaces are as defined above. In particular, the method relates to the reduction of friction between two steel surfaces, two surfaces covered with carbon or a steel surface and a surface covered with carbon. Advantageously, the method according to the invention makes it possible not to aggravate or reduce wear between two surfaces, in particular between two steel surfaces, between two surfaces covered with carbon or between a steel surface and a surface covered with carbon, in particular in a vehicle engine, preferably a motor vehicle. The invention also relates to a method for reducing the fuel consumption of a vehicle, preferably of a motor vehicle, comprising at least one step of contacting a mechanical part of the vehicle engine with a lubricating composition as defined above.
    The engines according to the invention may be internal combustion engines with two or four strokes. The engines may be gasoline engines or diesel engines intended to be powered by gasoline or conventional diesel. For the purposes of the present invention, the term "conventional gasoline" or "conventional diesel" means engines that are powered by a fuel obtained after refining an oil of mineral origin (such as oil for example). The engines may also be gasoline engines or diesel engines modified to be powered by a fuel based on oils derived from renewable materials such as alcohol-based fuels or biodiesel fuel.
    The vehicles according to the invention may be light vehicles such as automobiles and motorcycles. Vehicles can also be heavy trucks, construction machinery, ships.
    Transmissions according to the invention may be transmissions used in light vehicles such as automobiles, including gearboxes.
    The transmissions according to the invention may also be transmissions used in heavy goods vehicles, construction machinery, especially gearboxes or bridges.
    Transmissions according to the invention may also be transmissions used in industrial machines, including gearboxes or boxes for wind turbines. The invention also relates to the use of a combination of a totally or partially neutralized amine salt, as defined above, and of at least one organomolybdenum compound, in a lubricating composition comprising at least one base oil for reducing friction between two surfaces, in particular between two steel surfaces, between a steel surface and a surface covered with carbon or between two surfaces covered with carbon, in an engine, in particular a vehicle engine, in particular a motor vehicle . The above use also makes it possible not to aggravate or even reduce the wear between two steel surfaces, between a steel surface and a surface covered with carbon, or between two surfaces covered with carbon, in particular in a motor. vehicle, preferably a motor vehicle. The invention will now be described using non-limiting examples.
    EXAMPLE 1 Preparation of Lubricating Compositions According to the Invention, Comparative Lubricating Compositions and Evaluation of the Compatibility of these Compositions with the Seals Used in Motor Vehicle Engines
    A reference lubricant composition 1 is prepared according to Table 1 below (the composition is given by weight (g)). - Base oil 1: NI group base oil (kinematic viscosity at 40 ° C measured according to ASTM D445 = 20 mm / sec) - Base oil 2: Group III base oil (40 ° kinematic viscosity) C measured according to ASTM D445 = 25 mm = / s) - Viscosity index improver: hydrogenated styrene / isoprene polymer - Package of additives: anti-wear type zinc dithiophosphate, anti-oxidant type diphenylamine, calcium salicylate type detergent (P6660® sold by the company Infineum). Pour point depressant: polymethacrylate (Lubrizol 7748® marketed by Lubrizol). Amine 1: neutralized fatty diamine (Duomeen TDO® marketed by Akzo) Nobel) - Amine 2: non-neutralized fatty diamine (Duomeen T® marketed by the company Akzo Nobel) - friction modifier: molybdenum dithiocarbamate (Sakuralube 525® sold by the company Adeka)
    Table 1
    Lubricating compositions according to the invention and comparative are prepared according to Table 2 below (the compositions are given by weight (g)).
    Table 2
    The compatibility of the lubricating compositions prepared with RE1 type elastomer seals are evaluated according to the CEC-L-39-T96 standard and the results obtained are shown in Table 3.
    Table 3
    The results show that the lubricant compositions according to the invention (composition 1) comprising a combination of a neutralized amine and an organomolybdenum compound have a better compatibility with the seals used in the engines, in particular with the fluorinated elastomer seals compared to lubricating compositions comprising a combination of an unneutralized amine and an organomolybdenum compound (Comparative Composition 1).
    EXAMPLE 2 Preparation of Lubricating Compositions According to the Invention, Comparative Lubricating Compositions and Evaluation of Their Friction Reduction Properties on a DLC / Steel Contact
    A reference lubricant composition 2 is prepared according to Table 4 below (the composition is given by weight (g)). - Base oil: Group III base oil (kinematic viscosity at 40 ° C measured according to ASTM D445 = 19 mm / sec) - Viscosity index improver: hydrogenated styrene / isoprene polymer - Package of additives : dispersant, phenate-type detergents, carboxylate and calcium sulphonate - Pour point depressant: polymethacrylate (Viscoplexl-358® sold by the company Evonik) - Amine 1: neutralized fatty diamine (Duomeen TDO® sold by the company Akzo Nobel - Amine 2: non-neutralized fatty diamine (Duomeen T® sold by Akzo Nobel) - Amine 3: Neutralized fatty triamine (Armolube 312® marketed by Akzo Nobel) - Amine 4: non-neutralized fatty triamine (Triameen YT®) sold by Akzo Nobel) - friction modifier: molybdenum dithiocarbamate (Sakuralube 525® marketed by the company Adeka)
    Table 4
    Lubricating compositions according to the invention and comparative are prepared in accordance with Table 5 below (the compositions are given by weight (g)).
    Table 5
    A first test is used to evaluate the friction properties of a lubricating composition.
    The coefficient of friction is thus evaluated using a linear DLC ball / steel plane tribometer under the following conditions: - nature of the steel: 100c6, - nature of the DLC coating of the beads: hydrogenated DLC a: CH containing between 31 and 33% hydrogen and having a molar ratio (sp ^ carbon / carbon sp ^) equal to 55/45, - thickness of the DLC layer: 1.5μ, - temperature: 110 ° C, - normal charge of 5N , - 10mm stroke.
    A second test for evaluating the friction properties of a lubricating composition is also used, which makes it possible to characterize the friction of the engine at operating points representative of the points scanned during a NEDC (New European Cycle) certification cycle. Driving or New European Driving Cycle in English).
    The engine of the test is a RENAULT brand H4BT engine corresponding to a 3-cylinder, multi-point indirect injection gasoline engine meeting the EURO 5 standards.
    The unlit heat engine is driven by an electric generator at the desired speed. The fluids (coolant and lubricant) are conditioned in temperature since the combustion does not take place in this type of tests. A measurement of the torque provided by the electric generator to drive the heat engine is performed at each operating point. Comparing the drive torques of the motor with different lubricants makes it possible to identify those having the best properties in friction.
    The operating points of the test are as follows: Engine speed in rpm: 4000-3500-3000-2500-2000-1500-1000-750
    - Temperature of the lubricant regulated at the ramp: 40 ° C-60 ° C-90 ° C-110 ° C - Temperature of the regulated water at the exit of the motor: 40 ° C-60 ° C-90 ° C-100 ° At the end of this test, the lower the values obtained, the better the friction reduction properties of the lubricant tested.
    The characteristics of the lubricating compositions prepared are evaluated and the results obtained are shown in Table 6.
    Table 6
    The results show that the lubricant compositions according to the invention (compositions 2 and 3) comprising a combination of a neutralized amine and an organomolybdenum compound have at least equivalent or even improved friction-reducing properties, especially on DLC contacts. steel, with respect to lubricating compositions comprising a combination of an unneutralized amine and an organomolybdenum compound (comparative compositions 3 and 4).
    权利要求:
    Claims (16)
    [1" id="c-fr-0001]
    1.- lubricating composition comprising: at least one base oil, at least one organomolybdenum compound, at least one amine salt totally or partially neutralized, the amine corresponding to the following formula (I): RN (X) -Y (I) in which R is a linear or branched, totally or partially saturated hydrocarbon-based group comprising from 2 to 24 carbon atoms, preferably from 4 to 24, more preferably from 14 to 24, in particular from 16 to 24, by example of 18 to 24 carbon atoms; X represents a hydrogen atom, a linear or branched, totally or partially saturated hydrocarbon-based group comprising from 1 to 24 carbon atoms, preferably from 1 to 10 carbon atoms, especially from 1 to 8 carbon atoms, and benzyl group, or a group of formula -R ^ - [NH-R% -NH2; Y represents a hydrogen atom, a hydrocarbon group, linear or branched, totally or partially saturated, comprising from 1 to 24 carbon atoms, preferably from 1 to 10 carbon atoms, especially from 1 to 8 carbon atoms, a benzyl group, or a group of formula -R ^ - [NH-R% -NH2; n represents an integer of 0 to 3, preferably 0 to 2, preferably 0 or 1; R 1 and R 2, which may be identical or different, represent a linear or branched alkyl group comprising from 2 to 4 carbon atoms, preferably from 2 to 3 carbon atoms, preferably CH 2 CH 2 or CH 2 CH 2 CH 2; at least one of X or Y represents a hydrogen atom or -R '' - [NH-R% -NH2; at least one of X, Y or R represents a hydrocarbon group, linear or branched, totally or partially saturated, comprising from 4 to 24 carbon atoms, preferably from 14 to 24 carbon atoms, in particular from 16 to 24 atoms carbon, for example from 18 to 24 carbon atoms; the acid neutralizing the amine is chosen from monoacids of formula (II) R'COOH (II) in which R 'represents a linear or branched hydrocarbon group, totally or partially saturated, comprising from 2 to 24.
    [2" id="c-fr-0002]
    2. - The composition of claim 1, wherein the amine has the following formula (la): RN (X) -R '- [NHR 2] n -NH 2 (la) in which R, X, R R ^ and n have the meanings given in claim 1, at least one of X or R represents a hydrocarbon group, linear or branched, totally or partially saturated, comprising from 4 to 24 carbon atoms, preferably from 14 to 24 atoms carbon, especially from 16 to 24 carbon atoms, for example from 18 to 24 carbon atoms.
    [3" id="c-fr-0003]
    3. - Composition according to any one of claims 1 or 2, wherein: R represents a hydrocarbon group, linear or branched, totally or partially saturated, comprising from 14 to 24, in particular from 16 to 24, for example from 18 to 24 carbon atoms; X represents a hydrogen atom, a linear or branched alkyl group comprising from 2 to 8 carbon atoms, a benzyl group, or a group of formula -R '- [NH-R 4] n -NH 2.
    [4" id="c-fr-0004]
    4. - Composition according to any one of claims 1 to 3, wherein: R represents a hydrocarbon group, linear or branched, totally or partially saturated, comprising from 14 to 24, in particular from 16 to 24, for example from 18 to 24 carbon atoms; X represents a hydrogen atom or a group of formula -R ^ - [NH-R% -NH2.
    [5" id="c-fr-0005]
    5. - Composition according to any one of claims 1 to 4, wherein: R represents a hydrocarbon group, linear or branched, totally or partially saturated, comprising from 14 to 24, in particular from 16 to 24, for example from 18 to 24 carbon atoms; Y is -R ^ - [NH-R% -NH2; n = 0; R 1 is CH 2 CH 2 CH 2; and X represents CH2CH2CH2NH2 or H.
    [6" id="c-fr-0006]
    6. - Composition according to any one of claims 1 to 5 wherein the molar ratio between the number of moles of nitrogen in the amine and the acid of formula (II) is between 9: 1 and 1: 1, preferably between 5: 1 and 1: 1.
    [7" id="c-fr-0007]
    7. - Compositions according to any one of claims 1 to 6, wherein R 'represents a hydrocarbon group, linear or branched, totally or partially saturated, comprising from 7 to 24 carbon atoms, preferably from 10 to 24, by example of 14 to 20, especially 16 to 20 carbon atoms.
    [8" id="c-fr-0008]
    8. - Composition according to any one of claims 1 to 7 wherein the organomolybdenum compound is a molybdenum dithiocarbamate compound.
    [9" id="c-fr-0009]
    9. - Composition according to any one of claims 1 to 8, wherein the amine is selected from the following amines: RNHCH2CH2CH2CNH2 with R represents a hydrocarbon group, linear or branched, totally or partially saturated, comprising from 16 to 18 atoms of carbon ; or N (R) (CH 2 CH 2 CH 2 NH 2) (CH 2 CH 2 CH 2 NH 2) with R represents a hydrocarbon group, linear or branched, totally or partially saturated, comprising from 16 to 18 carbon atoms.
    [10" id="c-fr-0010]
    10. - Composition according to any one of claims 1 to 9 comprising from 0.05 to 5%, preferably from 0.1 to 2%, by weight of the neutralized amine relative to the total weight of the composition.
    [11" id="c-fr-0011]
    11. - Composition according to any one of claims 1 to 10 comprising from 0.01 to 3%, preferably from 0.05 to 3%, for example from 0.1 to 2%, by weight of organomolybdenum compound relative to to the total weight of the composition.
    [12" id="c-fr-0012]
    12. - Composition according to any one of claims 1 to 8 further comprising at least one anti-wear additive, preferably selected from phosphorus compounds, sulfur or phosphosulfur, preferably selected from zinc dithiophosphate.
    [13" id="c-fr-0013]
    13. - Use of a lubricant composition according to any one of claims 1 to 12 for reducing friction between two steel surfaces in a vehicle engine, preferably automobile.
    [14" id="c-fr-0014]
    14. - Use of a lubricant composition according to any one of claims 1 to 12 for reducing friction between a steel surface and a carbon-coated surface in a vehicle engine, preferably automobile.
    [15" id="c-fr-0015]
    15. - Use of a lubricant composition according to any one of claims 1 to 12 for reducing friction between two carbon-coated surfaces in a vehicle engine, preferably automobile.
    [16" id="c-fr-0016]
    16. -Use according to one of claims 13 to 15 to further reduce the deterioration of seals contained in a vehicle engine, preferably automobile.
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    同族专利:
    公开号 | 公开日
    FR3048433B1|2020-03-13|
    JP2019507230A|2019-03-14|
    EP3423551A1|2019-01-09|
    CN108699474A|2018-10-23|
    KR102329180B1|2021-11-19|
    WO2017149119A1|2017-09-08|
    KR20180122337A|2018-11-12|
    JP6889175B2|2021-06-18|
    CN108699474B|2021-05-11|
    BR112018016701A2|2018-12-26|
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    法律状态:
    2017-02-22| PLFP| Fee payment|Year of fee payment: 2 |
    2017-09-08| PLSC| Publication of the preliminary search report|Effective date: 20170908 |
    2018-02-20| PLFP| Fee payment|Year of fee payment: 3 |
    2019-02-20| PLFP| Fee payment|Year of fee payment: 4 |
    2020-02-20| PLFP| Fee payment|Year of fee payment: 5 |
    2021-03-23| PLFP| Fee payment|Year of fee payment: 6 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1651804|2016-03-03|
    FR1651804A|FR3048433B1|2016-03-03|2016-03-03|LUBRICATING COMPOSITION BASED ON NEUTRALIZED AMINES AND MOLYBDENE|FR1651804A| FR3048433B1|2016-03-03|2016-03-03|LUBRICATING COMPOSITION BASED ON NEUTRALIZED AMINES AND MOLYBDENE|
    CN201780012826.1A| CN108699474B|2016-03-03|2017-03-03|Lubricant composition based on neutralized amine and molybdenum|
    EP17708269.0A| EP3423551A1|2016-03-03|2017-03-03|Lubricant composition based on neutralized amines and molybdenum|
    KR1020187024969A| KR102329180B1|2016-03-03|2017-03-03|Lubricant composition based on neutralized amine and molybdenum|
    PCT/EP2017/055006| WO2017149119A1|2016-03-03|2017-03-03|Lubricant composition based on neutralized amines and molybdenum|
    JP2018545592A| JP6889175B2|2016-03-03|2017-03-03|Lubricating composition based on neutralized amines and molybdenum|
    BR112018016701-0A| BR112018016701A2|2016-03-03|2017-03-03|use of a lubricant composition|
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