Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
  • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
  • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
  • C10M133/16—Amides; Imides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
  • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
  • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
  • C10M2215/064—Di- and triaryl amines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/14—Containing carbon-to-nitrogen double bounds, e.g. guanidines, hydrazones, semicarbazones
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/22—Heterocyclic nitrogen compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
  • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
  • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
  • C10M2219/066—Thiocarbamic type compounds
  • C10M2219/068—Thiocarbamate metal salts
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
  • C10N2040/252—Diesel engines

Definitions

• the present invention relates to additive compositions for reducing the corrosivity of motor oils, in particular for diesel engines, with respect to metals and non-ferrous metals, principally copper, lead, tin and aluminum etc. and their alloys.
• a motor lubricant has a very wide variety of additives, to enable it to reach the high performance levels required by users.
• organometallic friction modifiers such as, for example, organomolybdenum compounds or derivatives thereof.
• molybdenum, and / or non-"metal" or “ashless” organic friction modifiers which are generally fatty substances and may be fatty esters, amines or fatty amides, fatty acids, fatty alcohols. .
• U.S. Patent Application No. 5,614,483 discloses the use of carbodiimides, optionally in combination with calcium sulfonate, amine or phenolic antioxidants, passivants for non-ferrous metals, antiwear, extreme pressure additives, viscosity, antifoams, dispersants, detergents, to reduce aggression vis-à-vis the lead, zinc, or steel hydraulic oils containing esters as the base oil.
• This document does not disclose any specific combination of carbodiimide with the aforementioned additives, nor the possibility of using such combinations in motor oils containing organic and / or organometallic friction modifiers, to reduce their corrosivity to copper. , lead and tin.
• Patent Application EP 0992571 describes the combination of a carbodiimide with a specific phenylnaphthylamine (excluding other diarylamines), and optionally with a copper passivator which may be a triazole or a thiadiazole, in a base oil which can be mineral or synthetic, for example of the ester type, said oil may contain additives such as: amine or phenolic antioxidants, VI improvers, sulfur, phosphorus or phosphorus sulfur anti-wear or extreme pressure, metal thiophosphates or thiocarbamates, antitussels, such as carboxylic acids, sulfonate detergents, phenates or metal carboxylates, for improving the oxidation stability of such oils.
• a base oil which can be mineral or synthetic, for example of the ester type
• said oil may contain additives such as: amine or phenolic antioxidants, VI improvers, sulfur, phosphorus or phosphorus sulfur anti-wear or extreme pressure, metal thiophosphat
• Patent application WO 2008/095805 discloses additive compositions comprising borated triazoles and esters and optionally amine phosphates for reducing corrosivity to copper, lead and tin of lubricating compositions containing friction modifiers, which may be lycerol monoleate, or an organomolybdenum compound.
• the examples of this application do not specify which are the friction modifiers contained in the reference oils, whose corrosivity is reduced.
• additive compositions involve a possible addition of phosphorus which can lead to the production of ash and catalyst poisons, detrimental to the aftertreatment systems installed on vehicles (especially diesel vehicles).
• the Applicant has found that the introduction, in motor oils comprising friction modifiers, organic and / or organometallic, an additive composition comprising one or more carbodiimides, amine or phenolic antioxidants, azole compounds, and neutral sulfonate-type anticorrosive additives, allowed to inhibit the corrosiveness of said oils vis-à-vis non-ferrous metals.
• the additive compositions according to the invention have a synergistic effect on reducing the corrosivity of these oils vis-à-vis non-ferrous metals.
• the present invention relates to additive compositions comprising:
• R 1 is an aliphatic or aromatic mono group, substituted or unsubstituted, comprising from 2 to 20 carbon atoms,
• R2 is either hydrogen, an aliphatic group, or an aromatic mono, substituted or unsubstituted, comprising from 2 to 20 carbon atoms,
• R3 is either hydrogen or an aliphatic or monoaromatic group, substituted or unsubstituted, condensed or not, comprising from 2 to 20 carbon atoms.
• At least one antioxidant chosen from secondary amines whose nitrogen atom is connected to at least one aryl group, or from phenols substituted on at least one of their ortho position, preferably both, by alkyl groups comprising 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms, and their dimers.
• the additive compositions according to the invention comprise, as compound (c), at least one carbodiimide wherein X and Y each carry 2 or 3 substituents, in ortho, or ortho and para, with respect to the carbodiimide group, and wherein at least one of these substituents is a branched aliphatic chain having at least 3 carbon atoms or a cycloaliphatic substituent having 5 to 6 carbon atoms.
• the additive compositions according to the invention comprise, as compound (a), at least one benzotriazole of formula (V):
• R6 and R7 are, independently of one another, hydrocarbon groups having from 1 to 30 carbon atoms, preferably from 2 to 20 carbon atoms, linear, branched or cyclic, and which may contain an atom of oxygen, sulfur or nitrogen.
• the additive compositions according to the invention comprise, as compound (b), at least one neutral dialkylbenzene or dialkyinaphthalene sulfonate of an alkali or alkaline earth metal, the alkyl substituents of which contain from 7 to 12 carbon atoms.
• the compound (b) has a BN, measured according to the ASTM D2892 standard, less than 20, preferably less than 15 mg of KOH / gram.
• the secondary amines optionally present as compound (d) are chosen from secondary amines of formula of formula R8-NH-R9, where R8 and R9 are independently one of the other :
• a phenyl group optionally substituted, preferably para to the amine function, with alkyl or alkenyl groups containing from 1 to 10 carbon atoms, preferably from 1 to 3 carbon atoms,
• a naphthyl group optionally substituted, with alkyl or alkenyl groups comprising from 1 to 10 carbon atoms, preferably from 1 to 3 carbon atoms, or else R8 is a phenyl group, and R9 forms with the nitrogen atom; of the amino function and the R8 ring a C6 heterocycle, optionally substituted with alkyl groups.
• the secondary amines optionally present as compound (d) in the additive compositions according to the invention are chosen from diphenylamines, preferably having their phenyl groups substituted in the ortho group by alkyl or alkenyl groups containing from 1 to 10, preferentially from 1 to 3 carbon atoms, unsubstituted phenylnaphthylamine, phenylnaphthylamines substituted by at most 2 alkyl or alkenyl groups having from 1 to 10, preferably from 1 to 3 carbon atoms.
• the additive compositions according to the invention comprise at least one secondary amine as compound (d).
• the percentages by weight [a], [b], [c] and [d] of the compounds (a), (b), (c) and (d) are present in synergistically effective ratios, and / or verify:
• [C]: [b] is between 1 and 10, preferably between 2 and 5,
• [d] is between 1 and 10, preferably between 2 and 5.
• the present invention also relates to lubricating compositions containing such additive compositions.
• the subject of the present invention is lubricant compositions for an engine, preferably for a diesel engine, comprising an additive composition as described above, one or more base oils, and at least one friction modifier, which may be:
• At least one organometallic friction modifier preferably chosen from organomolybdenum or organotungstate compounds, preferentially molybdenum dithiocarbamates,
• At least one organic friction modifier selected from fatty amines, fatty alcohols, fatty acids, fatty acid esters, preferentially glycerol esters such as mono-, di- or tri heptanoate, oleate, stearate, isostearate, linoleate, glycerol caprylate, citrates, tartrates, malates, lactates, mandelates, glycolates, hydroxypropionates, hydroxyglutarates, and their derivatives.
• organic friction modifier selected from fatty amines, fatty alcohols, fatty acids, fatty acid esters, preferentially glycerol esters such as mono-, di- or tri heptanoate, oleate, stearate, isostearate, linoleate, glycerol caprylate, citrates, tartrates, malates, lactates, mandelates, glycolates, hydroxypropionates, hydroxyglutarates, and their derivatives
• the lubricant compositions according to the invention comprise between 0.8% and 5% by weight, preferably between 1 and 1.5% by weight of friction modifiers.
• the lubricant compositions according to the invention comprise at least 0.8% and 5% by weight, preferably between 1 and 1.5% by weight of organic friction modifiers.
• the lubricant compositions according to the invention comprise between 0 and 0.5% by weight, preferably between 0.01% and 0.3% by weight of organometallic friction modifier.
• the amount of additive composition as described above is such that the compound (c) represents from 0.5 to 4%, preferentially from 0.8 to 3 , 5% by weight, preferably from 1 to 3% by weight of said lubricating compositions.
• the present invention also relates to the use of an additive composition as described above to reduce the corrosiveness vis-à-vis copper, lead and tin, measured according to ASTM D6594, a hu an engine, preferably for a diesel engine, comprising at least one friction modifier which may be:
• At least one organometallic friction modifier preferably chosen from organomolybdenum or organotungstate compounds, preferentially molybdenum dithiocarbamates,
• At least one organic friction modifier selected from fatty amines, fatty alcohols, fatty acids, fatty acid esters, preferentially glycerol esters such as mono-, di- or triheptanoate, oleate, stearate, isostearate, linoleate, glycerol caprylate, citrates, tartrates, malates, lactates, mandelates, glycolates, hydroxypropionates, hydroxyglutarates, and their derivatives.
• organic friction modifier selected from fatty amines, fatty alcohols, fatty acids, fatty acid esters, preferentially glycerol esters such as mono-, di- or triheptanoate, oleate, stearate, isostearate, linoleate, glycerol caprylate, citrates, tartrates, malates, lactates, mandelates, glycolates, hydroxypropionates, hydroxyglutarates, and their derivatives.
• the present invention is, finally, relating to a use as described above, wherein the engine oil is a motor oil, preferably for diesel engine, comprising the friction modifier or modifiers described above.
• the engine oil is a motor oil, preferably for diesel engine, comprising the friction modifier or modifiers described above.
• R 1 is an aliphatic or aromatic mono group, substituted or unsubstituted, comprising from 2 to 20 carbon atoms,
• R2 is either hydrogen, an aliphatic group, or an aromatic mono, substituted or unsubstituted, comprising from 2 to 20 carbon atoms,
• R3 is either hydrogen or an aliphatic or monoaromatic group, substituted or unsubstituted, condensed or not, comprising from 2 to 20 carbon atoms.
• X and Y are substituted at the two ortho positions from the carbodiimide group, and optionally at the para position of said group.
• the substituents can be C 2 -C 20 alkyl or cycloalkyl groups, such as the ethyl, propyl, isopropyl, butyl, tert-butyl, cyclohexyl or dodecyl groups, or aryl or aralkyl groups with 6 to 15 carbon atoms, such as phenyl or tolyl, benzyl, naphthyl ...
• these substituents are aliphatic substituents comprising at least 3 carbon atoms, branched or cyclic.
• X and Y each carry 2 or 3 substituents ortho or ortho and para with respect to the carbodiimide group, and wherein at least one of these substituents is a branched aliphatic chain having at least 3 carbon atoms. or a cycloaliphatic substituent having 5 to 6 carbon atoms.
• Particularly preferred compounds include N, N'-di (2,6-diisopropylphenyl) carbodiimide or N, N'-di (2,4,6-triisopropylphenyl) carbodiimide.
• X and Y are as defined above, with the substituents defined above, and p is an integer between 0 and 100, preferably between 0 and 50, preferentially between 0 and 40.
• Carbodiimides, their dimers, oligomers and polymers may be used alone or in admixture.
• the additive compositions according to the invention comprise one or more compounds comprising an azole heterocycle, optionally comprising a sulfur atom (thiaazoles).
• diazoles or triazoles 124 or 123 triazoles
• thiaazoles such as benzothiaazoles, mercaptobenzothiazoles, thiadiazoles, dimercaptothiadiazoles, etc.
• the triazoles 1, 2,4 may be, for example, the metal passivatives described in US Pat. No. 4,734,209, column 1, and column 2, lines 1 to 35, of formula (II):
• R4 and R5 are, independently of one another, C1-C20 alkyl, C3-C20 alkenyl, C5-C12 cycloalkyl, C7-C13 aralkyl, C6-C10 aryl, or both form with the nitrogen atom to which they are attached a C5, C6 or C7 heterocycle, or R4 and R5 are groups of formula (II): R3X [(alkylene) O] n (alkylene) -
• Alkylene C1-C12 alkylene radical
• n is either 0 or an integer between 1 and 6, or R4 is as described above and R5 is a radical of formula (III) (III)
• R5 is a radical of formula (III) and R4 a radical of formula (IV):
• Preferred triazoles are, for example, benzotriazole, of formula (V):
• R6 and R7 are, independently of one another, hydrocarbon groups having from 1 to 30 carbon atoms, preferably from 2 to 20 carbon atoms, linear, branched or cyclic, and which may contain an atom of oxygen, sulfur or nitrogen.
• Components (d) are phenols, or secondary amines, whose amino and phenol function is sterically hindered, well known to those skilled in the art for their antioxidant action in lubricants.
• the phenolic antioxidants of the compositions according to the invention are phenols substituted on at least one of their ortho positions, preferably both, with alkyl groups comprising from 1 to 10 carbon atoms, for example methyl, isopropyl or tert-butyl groups, preferentially from 1 to 3 carbon atoms. They can also be used in the form of dimers.
• the aminated antioxidants of the compositions according to the invention are secondary amines in which the nitrogen atom is connected to at least one aryl group.
• they are secondary amines of formula R8-NH-R9, where R8 and R9 are, independently of one another:
• a phenyl group optionally substituted, preferably para to the amine function, with alkyl or alkenyl groups containing from 1 to 10 carbon atoms, preferably from 1 to 3 carbon atoms,
• a naphthyl group optionally substituted, with alkyl or alkenyl groups containing from 1 to 10 carbon atoms, preferably from 1 to 3 carbon atoms.
• R8 is a phenyl group, and R9 forms with the nitrogen atom of the amino function and the R8 ring a C6 heterocycle, optionally substituted with alkyl groups.
• metal sulfonates used in the additive compositions according to the present invention are well known to those skilled in the art for their inhibitory action of corrosion of ferrous metals in lubricants.
• alkyl benzene or alkyl naphthalene sulfonates of alkali and alkaline earth metals whose alkyl chain or chains contain from 7 to 12 carbon atoms, preferably from 8 to 10 carbon atoms.
• the preferred sulfonates are dialkyl benzene or dialkyl naphthalenes whose alkyl chains contain from 7 to 12 carbon atoms, preferably from 8 to 10 carbon atoms.
• the preferred alkali and alkaline earth metals are calcium, barium, magnesium, zinc, preferentially calcium.
• sulfonates act on the surface of metal parts by creating a protective film by reaction with metal surfaces. They are distinguished from sulphonates used as detergents in oils, for example engine oils, or marine engine oils, which act within the oil, thanks to their micellar structure and their reserve of basicity provided by overbasing, for example metal carbonates.
• the basicity provided is characterized by BN or "Base Number", measured according to ASTM D2896, in mg KOH / gram of detergent.
• the detergents typically have a BK greater than 80 mg KOH / gram of detergent or greater than 150, up to and including up to 4000 mg KOH / gram of detergent.
• the sulfonates themselves have very little intrinsic basicity and must be overbased when used as detergents.
• the sulfonates When used as anticorrosive, on the contrary, the sulfonates must not be overbased (they must be "neutral"), to be able to act on the surface and to bind to the metal surfaces of the parts to be protected.
• the sulphonates When used as anticorrosion, the sulphonates have a basicity according to ASTM D2896 almost nil, less than 30, preferably less than 20, or even less than 15 mg of KOH / g of sulphonates.
• the sulphonates used as detergents typically have alkyl chains containing from 18 to 24 carbon atoms, longer than those of the sulphonates of the compositions according to the invention according to the invention. These long chains make it possible to keep the micelles of overbased detergents in suspension in the oil, which distinguishes them from the anticorrosion sulfonates according to the invention.
• the compounds (a), (b), (c) and (d) are present in synergistically effective amounts in the additive compositions according to the invention.
• the ratios between the mass percentages of the compounds (a), (b), (c) and (d) respectively denoted [a], [b], [c] and [ d] satisfy the following three conditions:
• [c] is between 10 and 100, preferably between 20 and 50,
• [b] is between 1 and 10, preferably between 2 and 5,
• [d] is between 1 and 10, preferably between 2 and 5.
• An advantage of the additive compositions according to the invention is to reduce the corrosivity with respect to copper, lead or tin of lubricating compositions containing a high percentage of organic and / or organometallic friction modifiers, for example between 0.8 and 5% by weight, or between 0.9 and 2% by weight, or between 1 and 1.5% by weight.
• a high percentage of organic and / or organometallic friction modifiers for example between 0.8 and 5% by weight, or between 0.9 and 2% by weight, or between 1 and 1.5% by weight.
• molybdenum organic friction modifiers when the lubricating compositions contain only molybdenum organic friction modifiers, this can still represent between 400 and 2500 ppm of molybdenum, or between 450 and 1000 ppm, or between 500 and 1500 ppm of molybdenum.
• the additive composition reduces the corrosivity, vis-à-vis non-ferrous metals mentioned above, of lubricating compositions themselves having a "fuel eco" effect or fuel economy.
• Another advantage of the additive compositions according to the invention is to reduce the corrosivity with respect to copper, lead or tin of lubricating compositions containing a high percentage of organic friction modifiers, for example comprising between 0.degree. , 5% and 5% by weight, preferably between 0.8 and 5% by weight, or between 0.7% and 4% by weight, or between 0.9 and 2% by weight, or between 1% and 1%. , 5% by weight of organic friction modifiers.
• the additive compositions according to the invention reduce the corrosivity, vis-à-vis the non-ferrous metals mentioned above, of lubricating compositions whose effect "fuel eco” or fuel economy, is obtained essentially or exclusively with organic MF, and therefore with a zero or reduced rate (for example between 0 and 0.5% by weight or between 0.01% and 0.3% by weight) of organometallic friction modifiers generating ash.
• the lubricant compositions according to the invention are motor oils, preferably for diesel engines, comprising an additive composition comprising the components (a), (b), (c), and (d) described above, organic friction modifiers and and / or organometallic and all types of lubricating bases, polymer, viscosity index improver, and other additives adapted to their use.
• the amount of additive composition is such that the compound (c) represents from 0.5 to 4%, preferably from 0.8 to 3.5% by weight, or from 1 to 3% by weight of said lubricating compositions.
• the lubricating compositions according to the invention contain organometallic or organic friction modi fi cators known to those skilled in the art and commonly used in the formulation of motor oils.
• the metal compounds are, for example, complexes of transition metals such as Mo, W, Fe, Cu, Zn, or metals such as Sb, Sn, the ligands of which may be hydrocarbon compounds containing oxygen atoms, nitrogen , sulfur or phosphorus.
• transition metals such as Mo, W, Fe, Cu, Zn
• metals such as Sb, Sn
• the ligands of which may be hydrocarbon compounds containing oxygen atoms, nitrogen , sulfur or phosphorus.
• organic compounds containing tungsten or molybdenum may be particularly effective, such as for example molybdenum dithiocarbamates or MoDTC and will be preferred in the lubricant compositions according to the invention.
• the organic friction modifiers are, for example, fatty alcohols, fatty acids, fatty amines, fatty esters. These compounds can optionally be mono or polyethoxylated. Polyethoxyethers of unsaturated fatty acids are thus used as organic friction modifiers. Borated derivatives of fatty esters can also be used as friction modifiers.
• the fatty esters may be esters of polyols and of fatty acids, for example mono-, di- or triheptanoate, oleate, stearate, isostearate, linoleate, glycerol caprylate, preferentially glycerol monooleate and monoisostearate.
• C2-C8 monoalcohol esters and polyacids such as citrates, tartrates, malates, lactates, mandelates, glycolates, hydroxypropionates, hydroxyglutarates or their borated derivatives, are also used as organic friction modifiers.
• organic friction modifiers may also be fatty amides, such as oleyamides, for example used in combination with glycerol oleates.
• Fatty amines used as organic friction modifiers are often derived from natural vegetable oils, for example coconut oil, palm oil, olive oil, peanut oil, rapeseed oil, sunflower oil, soybean oil, cotton oil, flax, beef tallow, ...
• the preferred organic friction modifiers in the lubricant compositions according to the invention are glycerol esters, fatty amines, citrates, as described above. These friction modifiers can be used alone or in a mixture.
• the lubricating compositions according to the invention may contain exclusively one or more organic MF, which contributes to their "ashless” or ashless character, or exclusively one or more organometallic MFs, or a mixture of one or more organic MFs with one or more organic MFs. or more organometallic MFs.
• Friction modifying additives are generally present at levels of between 0.01 and 5%, preferably 0.01 and 1.5%, in engine lubricants.
• Lubricating bases ⁇ Lubricating bases:
• the lubricant compositions according to the present invention comprise one or more base oils. These bases generally represent at least 50% by weight of the lubricating compositions, generally greater than 70% and up to 85% or more.
• the base oil (s) used in the compositions according to the present invention may be oils of mineral or synthetic origin of groups I to VI according to the classes defined in the API (American Petroleum Institute) classification, alone or as a mixture.
• the mineral base oils according to the invention include all types of bases obtained by atmospheric and vacuum distillation of crude oil, followed by refining operations.
• the base oils of the compositions according to the present invention may also be synthetic oils, such as certain esters of carboxylic acids and alcohols, or polyalphaolefins.
• oils can also be oils of natural, vegetable or animal origin.
• the viscosity index improving polymers make it possible to guarantee a good cold behavior and a minimum viscosity at high temperature, in particular to formulate multi-grade oils.
• the introduction of these compounds into the lubricating compositions allows them to achieve viscosity index (VI) values giving them good fuel eco properties or fuel economy.
• these compounds include polymeric esters, olefins copolymers (OCP), homopolymers or copolymers of styrene, butadiene or isoprene, polymethacrylates (PMA). They are conventionally present at levels of the order of 0 to 40%, preferably 5 to 15% by weight, in the lubricant compositions for a four-stroke engine.
• the additives can be added individually, or in the form of additives, guaranteeing a certain level of performance to the lubricating compositions, as required, for example for a diesel lubricant ACEA (European car manufacturers) or JASO (Japan Automobile Organization Standards).
• ACEA European car manufacturers
• JASO Japanese Automobile Organization Standards
• Dispersants generally representing between 5 and 8% by weight of the lubricating compositions.
• Dispersants such as succinimides, PIB (polyisobutene) succinimides, Mannich bases ensure the maintenance in suspension and evacuation of insoluble solid contaminants formed by the secondary oxidation products that are formed when the engine oil is in use.
• Antioxidants generally represent between 0.5 and 2% by weight of the lubricating compositions. Antioxidants delay the degradation of oils in service, which can result in the formation of deposits, the presence of sludge, or an increase in the viscosity of the oil. They act as free radical inhibitors or destroyers of hydroperoxides. Among the commonly used antioxidants are phenolic antioxidants, sterically hindered amines.
• antioxidants are that of oil-soluble copper compounds, for example copper thio or dithiophosphate, copper and carboxylic acid salts, copper dithiocarbamates, sulphonates, phenates, acetylacetonates. Copper salts I and II, succinic acid or anhydride are used.
• Antiwear additives generally representing between 1 and 2% by weight of the lubricating compositions.
• the anti-wear additives protect the friction surfaces by forming a protective film adsorbed on these surfaces.
• the most commonly used is Zinc di thiophosphate or DTPZn. This category also contains various phosphorus, sulfur, nitrogen, chlorine and boron compounds.
• Detergents generally represent between 2 and 4% by weight of the lubricating compositions
• the detergents are typically alkali metal or alkaline earth metal salts of carboxylic acids, sulfonates, salicylates, naphthenates, as well as the salts of phenates.
• BN typically have a BN according to ASTM D2896 greater than 40, or 80 mg KOH / gram of detergent, and are most often overbased, with BN values typically of the order of 150 and more, or even 250 or 400 or more. (expressed as mg KOH per gram of detergent).
• a reference engine oil (grade 0W30) according to the SAE J300 classification (Society of American Engineers) has been prepared. It contains a blend of API Group III mineral base oils and ATIEL (American Petroleum Institute, Technical Association of the European Lubricants Industry), a diesel engine oil additive package including dispersants , anti-wear, detergents, antioxidants, antifoam, providing the performance levels required by the ACEA (Association of European Automakers) or the JASO (Japan Automobile Standards Organization), and a polymer improving VI, copolymer d alkyl methacrylates.
• API Group III mineral base oils and ATIEL American Petroleum Institute, Technical Association of the European Lubricants Industry
• a diesel engine oil additive package including dispersants , anti-wear, detergents, antioxidants, antifoam, providing the performance levels required by the ACEA (Association of European Automakers) or the JASO (Japan Automobile Standards Organization)
• a polymer improving VI, copolymer d alkyl methacrylates
• This reference motor oil A was additivated with an organometallic friction modifier (molybdenum dithiocarbamate), with an organic friction modifier (fatty amine), and with a mixture of these two friction modifiers, to formulate the oils respectively.
• an organometallic friction modifier molecular pressure modifier (molybdenum dithiocarbamate)
• an organic friction modifier fatty amine
• a mixture of these two friction modifiers to formulate the oils respectively.
• oils A, B and C have in turn been added with amine antioxidants, metal soaps, carbodiimides, benzotriazole, alone or as a mixture, to formulate oils D to M.
• oils F, L and M comprise an additive composition according to the invention.
• Table 1 groups together the compositions and properties of these different oils.
• MoDTC organometallic friction modifier
• oil ref the reference containing no friction modifier
• the addition of some of the components of the additive composition according to the invention makes it possible to reduce the corrosivity with respect to copper, but has an adverse effect on the corrosiveness with respect to the lead (oils D and E, compare to oil A).
• an additive composition according to the invention (comprising a diphenylamine, a calcium sulphonate, a carbodiimide and a triazole) makes it possible to reduce the corrosivity with respect to copper and lead, while now the absence of corrosiveness vis-à-vis the tin (oil F).
• the oil B containing an organic friction modifier (fatty amine), without additivation according to the invention, becomes very corrosive with respect to copper and lead compared to the reference containing no MF (oil ref). .
• oil B of diphenylamine further accentuates the corrosivity with respect to copper and lead (oilG).
• carbodiimide to oil B makes it possible to reduce the corrosion with respect to copper, but the corrosivity with respect to lead remains high, although it is lower than reference B (oil I compared to oil B).
• an additive composition according to the invention (comprising a diphenylamine, a calcium sulphonate, a carbodiimide and a triazole) makes it possible to obtain excellent results, and reduces the corrosivity of the oil containing an MF organic at the level of the reference oil without MF (Oil L, to compare with oil ref).
• the oil C containing an organic friction modifier (fatty amine) and an organometallic friction modifier (MoDTC), without additivation according to the invention, becomes very corrosive towards the copper, and sees its corrosivity vis-à-vis the - Lead also increase, compared to the reference containing no MF (oil ref).
• an organic friction modifier fatty amine
• MoDTC organometallic friction modifier
• an additive composition according to the invention (comprising a diphenylamine, a calcium sulphonate, a carbodiimide and a triazole) makes it possible to obtain excellent results, and reduces the corrosivity of the oil containing an MF organometallic and an organic MF at or below that of the reference oil without MF (Oil M, to compare with oil ref).
• oils F, L and M show no corrosivity with respect to tin (and others) and pass the requirements of the test, as well as oil D and E.
• Another engine oil also grade 0W30 according to the SAE J300 classification (Society of American Engineers), has been prepared. It contains a mixture of Group III and IV Mineral Base Oils according to the classification of ⁇ and ATIEL (American Petroleum Institute, Technical Association of the European Lubricants Industry), a diesel engine oil additive package including dispersants, anti-wear, detergents, antioxidants, antifoam, providing the performance levels required by the ACEA (European Manufacturers Association). Automobiles) or the JASO (Japan Automobile Standards Organization), and a polymer improving VI, LZ7418A alkyl methacrylate copolymer.
• SAE J300 classification Society of American Engineers
• This oil has been additivated with an organic friction modifier (fatty amine), amine antioxidants, metal soaps, carbodiimides, benzotriazole, alone or as a mixture, to formulate oils N to R.
• the oil R comprises an additive composition according to US Pat. 'invention.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Lubricants (AREA)

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• 2009
  • 2009-12-18 FR FR0959258A patent/FR2954346B1/fr not_active Expired - Fee Related
• 2010
  • 2010-12-20 EP EP10810891A patent/EP2513273A1/fr not_active Withdrawn
  • 2010-12-20 CA CA2784431A patent/CA2784431A1/fr not_active Abandoned
  • 2010-12-20 WO PCT/IB2010/055964 patent/WO2011073960A1/fr active Application Filing
  • 2010-12-20 KR KR1020127017458A patent/KR20120123304A/ko not_active Application Discontinuation
  • 2010-12-20 US US13/516,845 patent/US20120329690A1/en not_active Abandoned
  • 2010-12-20 CN CN201080057761.0A patent/CN102812113B/zh not_active Expired - Fee Related
  • 2010-12-20 BR BR112012014827A patent/BR112012014827A2/pt not_active IP Right Cessation
  • 2010-12-20 JP JP2012543991A patent/JP5703309B2/ja not_active Expired - Fee Related
  • 2010-12-20 MX MX2012007051A patent/MX2012007051A/es unknown
  • 2010-12-20 RU RU2012127870/04A patent/RU2012127870A/ru not_active Application Discontinuation

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