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
  • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
  • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
  • C10M137/04—Phosphate esters
• • 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
  • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
  • C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
  • C10M135/36—Heterocyclic sulfur, selenium or tellurium compounds the ring containing sulfur and carbon with nitrogen or oxygen
• • 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
  • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
  • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
  • C10M137/04—Phosphate esters
  • C10M137/10—Thio derivatives
  • C10M137/105—Thio derivatives not containing metal
• • 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
  • C10M141/10—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 phosphorus-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
  • C10M153/00—Lubricating compositions characterised by the additive being a macromolecular compound containing phosphorus
  • C10M153/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • 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
  • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
  • C10M169/04—Mixtures of base-materials and additives
  • C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular 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
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/003—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
  • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
  • C10M2219/106—Thiadiazoles
• • 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
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
  • C10M2223/04—Phosphate esters
  • C10M2223/047—Thioderivatives not containing metallic elements
• • 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
  • C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/04—Molecular weight; Molecular weight distribution
• • 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
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • 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
  • C10N2030/40—Low content or no content compositions
  • C10N2030/43—Sulfur free or low sulfur content compositions
• • 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
  • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives

Definitions

• the present invention relates to the field of lubricating compositions, in particular for motor vehicles, in particular for lubricating the transmission components of motor vehicles, in particular the gears of the transmissions of thermal or electric motors.
• Flaking occurs after a long time of aging, preceding visible deterioration.
• the mechanisms are not well known, but the phenomenon starts with the initiation of cracks at a certain depth under the surface, these cracks propagate, and when cracks normal to the surface are created, scales are detached suddenly.
• the prevention of this phenomenon passes by a reduction of the stresses of contact thanks to an appropriate geometry of the parts, and by the reduction of the frictions, by avoiding adhesion.
• the lubricating composition intervenes in this prevention process, mainly through the physico-chemical reactivity of its additives.
• Sulphur, phosphorus or borate anti-wear and extreme pressure additives are generally added to give transmission oils protective properties against chipping.
• the other additives present in the lubricating composition can also have an impact, positive or negative, on the propagation of cracks inside the parts and therefore on the spalling phenomenon.
• the lubricating composition used in the transmission components may deteriorate.
• WO 2010/126760 describes a lubricating composition comprising a base oil and a polymer of phosphorus ester type comprising the product of the condensation reaction of an acid or phosphorus ester with a diol where the two hydroxy functions are separated by a chain. from 4 to 100 carbon atoms.
• Document WO 2016/089565 describes a lubricating composition comprising a base oil and a phosphite ester composition comprising the product of the condensation reaction of a phosphorus acid or ester with at least two diols.
• the present invention relates to a lubricating composition
• a lubricating composition comprising:
• each of R 1 , R 2 , R 3 and R 4 can be chosen independently of each other from C1-C20 alkyl, C3-C22 alkenyl, C6-C40 cycloalkyl, C7-C40 cycloalkenyl, Cl -20 methoxy alkyl glycol ethers and Y-OH;
• Y is chosen from the groups C2-C40 alkylene, C2-C40 alkyl lactone, -R 7 -N(R 8 )-R 9 - , in which R 7 , R 8 and R 9 are independently of each other chosen from hydrogen, C1-C20 alkyl, C3-C22 alkenyl, C6-C40 cycloalkyl, C7-C40 cycloalkenyl, Cl -20 methoxy alkyl glycol ethers,
• - m is an integer ranging from 2 to 100
• the polymer of formula (I) has a weight-average molecular mass of less than 30,000 g/mol, preferably ranging from 5,000 to 20,000 g/mol.
• the phosphite polymer represents from 0.01 to 10% by weight of the total weight of the lubricating composition.
• the lubricating composition comprises from 5 to 9150 ppm by weight of phosphorus, preferably from 5 to 4500 ppm by weight of phosphorus, relative to the total weight of the lubricating composition.
• the lubricating composition further comprises at least one anti-wear additive chosen from phosphorus anti-wear, sulfur anti-wear, phospho-sulfur anti-wear, phospho-amine anti-wear, sulphur-amine anti-wear, and mixtures thereof.
• the lubricating composition comprises from 0.01 to 5% by weight of anti-wear additive(s) chosen from phosphorus anti-wear, sulfur anti-wear, phospho-sulfur anti-wear, phospho-amine anti-wear, sulphur-amine anti-wear, and their mixture, relative to the total weight of the lubricating composition.
• anti-wear additive(s) chosen from phosphorus anti-wear, sulfur anti-wear, phospho-sulfur anti-wear, phospho-amine anti-wear, sulphur-amine anti-wear, and their mixture, relative to the total weight of the lubricating composition.
• the lubricating composition comprises from 5 to 4000 ppm by weight of sulfur, preferably from 7 to 1000 ppm by weight of sulfur, more preferably from 10 to 800 ppm by weight of sulfur, relative to the total weight of the lubricating composition.
• the lubricating composition comprises: from 70 to 99% by weight of one or more base oil(s), and from 0.01 to 10% by weight of phosphite polymer, optionally from 0.01 to 5% by weight of anti-wear additive(s) chosen from phosphorus anti-wear, sulfur anti-wear, phospho-sulfur anti-wear, phospho-amine anti-wear, sulfur-amine anti-wear, and their mixture, optionally from 1 to 30% by weight of one or more functional additives, preferably chosen from viscosity index improver additives, antioxidant additives, antifoam additives, dispersants, detergents, modifier additives of viscosity, and their mixture, relative to the total weight of the lubricating composition.
• anti-wear additive(s) chosen from phosphorus anti-wear, sulfur anti-wear, phospho-sulfur anti-wear, phospho-amine anti-wear, sulfur-amine anti-wear, and their mixture
• one or more functional additives preferably chosen from viscosity index improver additives, antioxidant additives,
• the invention also relates to the use of a phosphite polymer in a lubricating composition comprising at least one base oil, to improve the load capacity of the lubricating composition, the phosphite polymer corresponding to the formula (I): [Chem 1 ] in which,
• each of R 1 , R 2 , R 3 and R 4 can be chosen independently of each other from C1-C20 alkyl, C3-C22 alkenyl, C6-C40 cycloalkyl, C7-C40 cycloalkenyl, Cl -20 methoxy alkyl glycol ethers and Y-OH;
• Y is chosen from the groups C2-C40 alkylene, C2-C40 alkyl lactone, -R 7 -N(R 8 )-R 9 - , in which R 7 , R 8 and R 9 are independently of each other chosen from hydrogen, C1-C20 alkyl, C3-C22 alkenyl, C6-C40 cycloalkyl, C7-C40 cycloalkenyl, Cl -20 methoxy alkyl glycol ethers,
• - m is an integer ranging from 2 to 100
• - n is an integer ranging from 1 to 1000.
• the invention also relates to the use of the composition according to the invention, for lubricating at least one mechanical part of a motor vehicle, preferably present in a transmission member of a motor vehicle, preferably a gear of a motor vehicle.
• the lubricating composition according to the invention has the advantage of having very good properties for reducing the phenomenon of flaking, in particular when it is implemented under heavy load and high speed.
• the lubricating composition according to the invention also has good durability.
• the expressions “between ... and !, “ranging from ... to ! and “varying from ... to " are equivalent and are intended to mean that the Terminals are included unless otherwise stated.
• the present invention relates to a lubricating composition
• a lubricating composition comprising:
• the lubricating composition according to the invention comprises at least one phosphite polymer corresponding to formula (I):
• each of R 1 , R 2 , R 3 and R 4 can be chosen independently of each other from C1-C20 alkyl, C3-C22 alkenyl, C6-C40 cycloalkyl, C 7 -C 40 cycloalkenyl , methoxy glycol alkyl ethers, Cl - 20 and Y-OH (serving terminal group);
• Y is selected from the group alkylene, C 2 -C 40 alkyl lactone C 2 -C 40, -R 7 -N (R 8) - R 9 - wherein R 7, R 8 and R 9 are independently from each other chosen from hydrogen, C1-C20 alkyl, C3-C22 alkenyl, C6-C40 cycloalkyl, C7-C40 cycloalkenyl, C1-20 methoxy alkyl glycol ethers,
• - m is an integer ranging from 2 to 100
• alkyl is understood to mean a linear or branched noncyclic hydrocarbon-based chain, saturated, optionally comprising one or more heteroatoms, such as oxygen, nitrogen or sulfur atoms.
• the alkyls consist of carbon and hydrogen atoms.
• alkenyl is understood to mean a linear or branched non-cyclic hydrocarbon-based, unsaturated chain, optionally comprising one or more heteroatoms, such as oxygen, nitrogen or sulfur atoms.
• the alkenyls consist of carbon and hydrogen atoms.
• cycloalkyl means a saturated monocyclic or polycyclic group optionally having one or more alkyl or alkenyl substituents, said ring(s) may themselves be substituted by one or more heteroatoms, such as atoms of oxygen, nitrogen or sulfur.
• the cycloalkyls consist of carbon and hydrogen atoms.
• cycloalkenyl means a monocyclic or polycyclic unsaturated group optionally having one or more alkyl or alkenyl substituents, said ring(s) may themselves be substituted by one or more heteroatoms, such as atoms of oxygen, nitrogen or sulfur.
• the cycloalkenyls consist of carbon and hydrogen atoms.
• a “Ci-Cj” group is a group comprising from i to j carbon atoms.
• the Y group is chosen from alkylene comprising from 2 to 20 carbon atoms, preferably from 2 to 12 carbon atoms, more preferably from 2 to 8 carbon atoms.
• m ranges from 4 to 100.
• the phosphite polymer of formula (I) has a weight-average molecular mass of less than 30,000 g/mol, preferably ranging from 3,000 to 20,000 g/mol.
• the weight average molecular mass can be measured by size exclusion chromatography.
• the phosphite polymer of formula (I) has a number-average molecular mass of less than 10,000 g/mol, preferably ranging from 1000 to 5000 g/mol.
• the number average molecular weight can be measured by size exclusion chromatography.
• the phosphite polymer of formula (I) has a polydispersity index ranging from 1 to 5, preferably ranging from 2 to 4.
• the phosphite polymer of formula (I) contains less than 2% by weight, preferably less than 1% by weight, or even less than 0.7% by weight of (alkyl)phenol group, relative to the total weight of the phosphite polymer of formula (I).
• the phosphite polymer of formula (I) is completely free of aromatic groups other than (alkyl)phenol groups.
• the phosphite polymer is in liquid form.
• the phosphite polymer has a phosphorus content ranging from 0.5 to 20% by weight, preferably from 1 to 10% by weight, relative to the total weight of the phosphite polymer.
• the phosphite polymer used in the invention can be obtained according to the process described in the document WO2011102861.
• the polymer can be obtained according to the process described in paragraphs 27 to 32 of this document.
• the synthesis of the polymers of formula (I) generally involves transesterification in which triphenyl phosphite (or any other suitable alkyl or aryl phosphite) may be reacted with a saturated or unsaturated alcohol or a polyethylene ether or of polypropylene glycol and a diol or a polymer diol H(OY) m OH where Y and m are as defined above with an appropriate basic catalyst at a temperature between 20°C and 250°C, and preferably at a temperature between between 50°C and 185°C.
• Non-limiting examples of saturated or unsaturated alcohols include decyl, isodecyl, lauryl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, stearyl, isostearyl , oleic, monohydroxylated glycol ethers.
• the lubricating composition according to the invention comprises from 0.01 to 10% by weight of phosphite polymer(s), relative to the total weight of the lubricating composition.
• Base oil(s) Base oil
• the lubricating composition according to the invention comprises one or more base oils, preferably in a content of at least 70% by weight, preferably ranging from 70 to 99% by weight, more preferably from 80 to 98% by weight , preferably from 85 to 95% by weight, relative to the total weight of the lubricating composition.
• base oils can be chosen from the base oils conventionally used in the field of lubricating oils, such as mineral, synthetic or natural, animal or vegetable oils or mixtures thereof.
• the base oils of the lubricating compositions considered according to the invention may in particular be oils of mineral or synthetic origin belonging to groups I to V according to the classes defined in the API classification (or their equivalents according to the ATIEL classification) and presented in Table 1 below or mixtures thereof.
• Mineral base oils include all types of base oils obtained by atmospheric and vacuum distillation of crude oil, followed by refining operations such as solvent extraction, de-alpha removal, solvent dewaxing, hydrotreating, hydrocracking, hydroisomerization and hydrofinishing .
• Blends of synthetic and mineral oils, which may be biosourced, can also be used.
• the base oils of the compositions used according to the invention can also be chosen from synthetic oils, such as certain esters of carboxylic acids and alcohols, polyalphaolefins (PAO), and polyalkylene glycol (PAG) obtained by polymerization or copolymerization of alkylene oxides comprising from 2 to 8 carbon atoms, in particular from 2 to 4 carbon atoms.
• synthetic oils such as certain esters of carboxylic acids and alcohols, polyalphaolefins (PAO), and polyalkylene glycol (PAG) obtained by polymerization or copolymerization of alkylene oxides comprising from 2 to 8 carbon atoms, in particular from 2 to 4 carbon atoms.
• the PAOs used as base oils are for example obtained from monomers comprising from 4 to 32 carbon atoms, for example from octene or decene.
• the weight average molecular weight of PAO can vary quite widely. Preferably, the weight-average molecular mass of the PAO is less than 600 Da.
• the weight-average molecular mass of the PAO can also range from 100 to 600 Da, from 150 to 600 Da, or even from 200 to 600 Da.
• the base oil or oils of the lubricating composition according to the invention can be chosen from group II or III base oils.
• the oil or base oils of the composition implemented according to the invention are chosen from polyalphaolefins (PAO), polyalkylene glycol (PAG) and esters of carboxylic acids and alcohols.
• PAO polyalphaolefins
• PAG polyalkylene glycol
• esters of carboxylic acids and alcohols are chosen from polyalphaolefins (PAO), polyalkylene glycol (PAG) and esters of carboxylic acids and alcohols.
• the anti-wear additives optionally used in the lubricating composition according to the invention are chosen from phosphorus anti-wear, sulfur anti-wear, phospho-sulphur anti-wear, and mixtures thereof. It should be noted that the anti-wear additive optionally added to the lubricating composition according to the invention will typically be different from the phosphite polymer of formula (I).
• a "phosphorus anti-wear” will designate an anti-wear comprising at least one phosphorus atom and not comprising sulfur, said phosphorus anti-wear may optionally comprise one or more nitrogen atoms (in addition carbon and hydrogen atoms). In this case, it can then be referred to as "phosphorus-amine anti-wear”.
• a "sulfur anti-wear” will designate an anti-wear comprising at least one sulfur atom and not comprising phosphorus, said phosphorus anti-wear may optionally comprise one or more nitrogen atoms (in addition carbon and hydrogen atoms). In this case, it can then be referred to as “sulphur-amine anti-wear”.
• a "phosphor-sulfur anti-wear” will designate an anti-wear comprising at least one phosphorus atom and at least one sulfur atom, said phospho-sulphur anti-wear may optionally comprise one or more atoms nitrogen (in addition to carbon and hydrogen atoms). In this case, it can then be referred to as “sulphur-amine anti-wear”.
• phosphorus anti-wear additives of phosphates, phosphites and phosphonates. These terms denote both phosphoric, phosphorous and phosphonic acids, their mono, di and triesters, for example alkyl phosphates, alkyl phosphonates, and their salts, for example amines.
• the phospho-sulfur anti-wear additives optionally used in the present invention can be (mono or di) thiophosphates and thiophosphites, these terms including thiophosphoric and thiophosphorous acids, the esters of these acids, their salts, dithiophosphites and dithiophosphates.
• salts of esters of thiophosphoric acid and of thiophosphorous acid are those obtained by reaction with a nitrogenous compound such as ammonia or an amine or zinc oxide or zinc chloride.
• the anti-wear additive(s) used in the invention are chosen from phospho-sulfur anti-wear, sulfur-amine anti-wear, and mixtures thereof.
• the lubricating composition according to the invention may comprise from 0.01 to 5% by weight of anti-wear additive(s), preferably from 0.05 to 3% by weight of additive(s). ) anti-wear, relative to the total weight of the lubricating composition.
• the quantity of anti-wear additives may be adapted in order to obtain a phosphorus content ranging from 5 to 9150 ppm by weight in the lubricating composition.
• the phosphorus content in the lubricating composition according to the invention ranges from 5 to 4500 ppm by weight, relative to the total weight of the lubricating composition.
• the inventors have discovered that the combination of the phosphite polymer of formula (I) and a phosphorus, sulfur or phospho-sulfur anti-wear additive makes it possible to increase the durability of the lubricating composition comprising said combination.
• the lubricating composition according to the invention may also further comprise all types of functional additives, distinct from the phosphite polymer and anti-wear additives defined in the context of the present invention, suitable for use in a lubricant for motor vehicles, in particular for manual or automatic transmission of motor vehicles.
• Such additives can be chosen from detergents, dispersants, antioxidants, pour point depressants, anti-foaming agents, heat improvers. viscosity index, and mixtures thereof.
• composition according to the invention comprises at least one functional additive chosen from detergents, dispersants, antioxidants, pour point depressants, antifoaming agents, viscosity index improvers, and mixtures thereof.
• these additional functional additives represent (in total) from 1 to 30% by weight, preferably from 1.5 to 25% by weight, preferably from 2 to 20% by weight, of the weight total of the lubricating composition.
• additives can be introduced separately and/or in the form of a mixture similar to those already available for sale for formulations of commercial lubricants for vehicle engines, with a performance level as defined by T ACEA (Association European Automobile Manufacturers) and/or TAPI (American Petroleum Institute), well known to those skilled in the art.
• T ACEA Association European Automobile Manufacturers
• TAPI American Petroleum Institute
• the lubricating composition according to the invention may comprise at least one antioxidant additive.
• the antioxidant additive generally makes it possible to delay the degradation of the composition in service. This degradation can in particular result in the formation of deposits, in the presence of sludge or in an increase in the viscosity of the composition.
• Antioxidant additives act in particular as free radical inhibitors or destroyers of hydroperoxides.
• antioxidant additives commonly employed, mention may be made of antioxidant additives of the phenolic type, antioxidant additives of the amine type, phosphosulfur antioxidant additives. Some of these antioxidant additives, for example phosphosulfur antioxidant additives, can be ash generators.
• the phenolic antioxidant additives may be ash-free or may be in the form of neutral or basic metal salts.
• the antioxidant additives can in particular be chosen from sterically hindered phenols, sterically hindered phenol esters and sterically hindered phenols comprising a thioether bridge, diphenylamines, diphenylamines substituted with at least one CI 2 alkyl group, N,N '-dialkyl-aryl-diamines and mixtures thereof.
• the sterically hindered phenols are chosen from compounds comprising a phenol group of which at least one carbon vicinal to the carbon bearing the alcohol function is substituted by at least one Ci-Cio alkyl group, preferably an alkyl group C I -C O , preferably a C4 alkyl group, preferably by the tert-butyl group.
• Amino compounds are another class of antioxidant additives that can be used, possibly in combination with phenolic antioxidant additives.
• amino compounds are aromatic amines, for example aromatic amines of formula NR 10 R U R 12 in which R 10 represents an aliphatic group or an optionally substituted aromatic group, R 11 represents an optionally substituted aromatic group, R 12 represents a hydrogen atom, an alkyl group, an aryl group or a group of formula R 13 S(0) z R 14 in which R 13 represents an alkylene group or an alkenylene group, R 14 represents an alkyl group, a 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.
• antioxidant additives are that of copper compounds, for example copper thio- or dithio-phosphates, salts of copper and carboxylic acids, dithiocarbamates, sulphonates, phenates, copper acetylacetonates. Copper I and II salts, succinic acid or anhydride salts can also be used.
• copper compounds for example copper thio- or dithio-phosphates, salts of copper and carboxylic acids, dithiocarbamates, sulphonates, phenates, copper acetylacetonates.
• Copper I and II salts, succinic acid or anhydride salts can also be used.
• the lubricating composition according to the invention may contain all types of antioxidant additives known to those skilled in the art.
• the lubricating composition according to the invention comprises at least one ash-free antioxidant additive.
• the lubricating composition according to the invention may comprise from 0.5 to 2% by weight of at least one antioxidant additive, relative to the total weight of the composition.
• the lubricating composition according to the invention may also comprise at least one detergent additive.
• Detergent additives generally reduce the formation of deposits on the surface of metal parts by dissolving secondary products of oxidation and combustion.
• detergent additives which can be used in the lubricating composition according to the invention are generally known to those skilled in the art.
• Detergent additives can be anionic compounds comprising a long lipophilic hydrocarbon chain and a hydrophilic head.
• the associated cation can be a metal cation of an alkali or alkaline earth metal.
• the detergent additives are preferably chosen from alkali metal or alkaline-earth metal salts of carboxylic acids, sulfonates, salicylates, naphthenates, as well as phenate salts.
• the alkali and alkaline-earth metals are preferably calcium, magnesium, sodium or barium.
• These metallic salts generally comprise the metal in a stoichiometric quantity or else in excess, therefore in a quantity greater than the narrow stoichiometric quantity.
• These are then overbased detergent additives; the excess metal providing 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, preferentially a carbonate .
• the lubricating composition suitable for the invention may for example comprise from 0.5 to 4% by weight of detergent additive, relative to the total weight of the composition.
• the lubricating composition according to the invention may comprise at least one dispersing agent.
• the dispersant will make it possible to ensure the maintenance in suspension and the evacuation of the insoluble solid contaminants constituted by the secondary products of oxidation which are formed when the lubricating composition is in service.
• the dispersing agent can be chosen from Mannich bases or compounds of succinimide type, such as polyisobutylene succinimide (PIBSI).
• PIBSI polyisobutylene succinimide
• the lubricating composition according to the invention may, for example, comprise from 0.2 to 10% by weight of dispersing agent(s), relative to the total weight of the composition.
• the lubricating composition according to the invention may also comprise at least one antifoaming agent.
• the antifoaming agent can be chosen from silicones.
• the lubricating composition according to the invention may comprise from 0.01 to 2% by mass or from 0.01 to 5% by mass, preferably from 0.1 to 1.5% by mass or from 0.1 to 2% by mass of agent antifoam, relative to the total weight of the composition.
• the lubricating composition according to the invention may also comprise at least one pour point depressant additive (also called “PPD” agents for “Pour Point Depressant” in English).
• pour point depressants By slowing down the formation of paraffin crystals, pour point depressants generally improve the cold behavior of the composition.
• pour point depressant additives mention may be made of polyalkyl methacrylates, polyacrylates, polyarylamides, polyalkylphenols, polyalkylnaphthalenes, alkylated polystyrenes.
• the lubricating composition according to the invention may also comprise at least one viscosity index improver (VI improver).
• VI improvers include polymethacrylates, polyisobutenes or fatty acid esters. When they are present, these additives can represent from 1 to 25% by weight, of the total weight of the lubricating composition.
• the phosphite polymer and, where appropriate, the anti-wear and extreme-pressure additive can be added to an oil or mixture of base oils, then the other optional additional additives, added .
• the phosphite polymer and, where applicable, the anti-wear and extreme-pressure additive can be added to a pre-existing conventional lubricant formulation, comprising in particular one or more base oils, and optionally additional additives.
• the phosphite polymer and, where appropriate, the anti-wear and extreme-pressure additive defined in the present invention can be combined with one or more additional additives when they are present, and the "package" of additives thus formed added to an oil or a mixture of base oils.
• the lubricating composition according to the invention has a kinematic viscosity, measured at 40° C. according to the ASTM D445 standard, ranging from 5 to 300 mm 2 /s, in particular from 10 to 25 mm 2 /s.
• the lubricating composition according to the invention has a kinematic viscosity, measured at 100° C. according to the ASTM D445 standard, ranging from 1 to 20 mm 2 /s, in particular from 2 to 15 mm 2 /s.
• the lubricating composition according to the invention comprises, or even consists of:
• viscosity index modifiers optionally one or more additional additives chosen from viscosity index modifiers, detergents, dispersants, antioxidants, pour point depressants, anti-foaming agents and mixtures thereof.
• the lubricating composition according to the invention comprises, or even consists of:
• one or more functional additives preferably chosen from index modifiers viscosifiers, detergents, dispersants, antioxidants, pour point depressants, antifoaming agents and mixtures thereof.
• the lubricating composition according to the invention comprises from 5 to 9150 ppm by weight of phosphorus, preferably from 5 to 4500 ppm by weight of phosphorus, relative to the total weight of the lubricating composition.
• the lubricating composition according to the invention comprises from 5 to 4000 ppm by weight of sulfur, preferably from 7 to 1000 ppm by weight of sulfur, more preferably from 10 to 800 ppm by weight of sulfur, by relative to the total weight of the lubricating composition.
• the present invention also relates to the use of the phosphite polymer as defined previously in a lubricating composition comprising at least one base oil, in order to improve the load capacity of said lubricating composition.
• the present invention also relates to the use of the lubricating composition according to the invention for lubricating the transmissions of motor vehicles, in particular the gears of the transmissions.
• Transmissions can be manual or automatic transmissions.
• the lubricating composition according to the invention is used to reduce the wear of a mechanical part of a motor vehicle transmission, in particular of a motor vehicle gear.
• the lubricating composition according to the invention makes it possible to reduce the wear of the gears of the transmissions.
• the lubricating composition according to the invention is used to reduce the spalling of a mechanical part of a motor vehicle transmission, in particular of a motor vehicle gear.
• the lubricating composition according to the invention is used to both reduce wear and reduce spalling of a mechanical part of a motor vehicle transmission, in particular of a vehicle gear. automobiles.
• the invention also relates, according to another of its aspects, to a method for lubricating at least one part of a transmission of a motor vehicle, in particular a gear of a motor vehicle, comprising at least one step bringing at least said part into contact with a lubricating composition as described above.
• the invention also relates, according to another of its aspects, to a process for improving the durability of a lubricating composition, said process comprising a step of mixing at least one phosphite polymer of formula (I) as defined in the present invention, with at least one base oil, preferably said polymer is further mixed with an anti-wear additive as defined in the present invention.
• All of the characteristics and preferences described for the lubricating composition according to the invention as well as for its uses also apply to these processes.
• the particular, advantageous or preferred characteristics of the composition according to the invention make it possible to define uses according to the invention which are also particular, advantageous or preferred.
• Example 1 Preparation of the lubricating compositions
• the lubricating compositions were prepared by mixing the ingredients at a temperature of approximately 40° C., according to methods well known to those skilled in the art.
• the lubricating compositions which were prepared and tested are detailed in Table 2 below.
• the elemental phosphorus and sulfur contents were calculated according to the elemental contents in the ingredients and are also indicated in Table 2 in ppm by weight. Finally, the kinematic viscosities at 40°C and at 100°C were determined by the ASTM D445 method and are indicated in Table 2.
• the base oils are group III base oils
• the phosphite polymer corresponds to formula (I) and comprises 4.50% by weight of phosphorus and zero sulphur, it has a weight-average molecular mass of approximately 10,000 g/mol and a number-average molecular mass of approximately 3000 g/mol, it can be obtained for example according to the method described in example 2 of document WO 2011/102861,
• the phosphorus anti-wear is a tert-butylphenyl phosphate (not corresponding to formula (I)), comprising 8.10% by weight of phosphorus and zero sulfur, - the phospho-sulfur anti-wear is of the phosphorothionate and comprises 9.30% by weight phosphorus and 19.80% by weight sulfur,
• the sulphur-amine anti-wear is of the dimercaptothiadiazole type, and comprises 30% by weight of sulfur and 4.04% by weight of nitrogen,
• the dispersant is a PIBSI dispersant comprising 3.20% by weight of nitrogen and zero boron, zero sulfur and zero phosphorus,
• - G antioxidant is an alkylated diphenylamine antioxidant
• the detergent is an overbased calcium sulfonate detergent
• the additive package contains a pour point improver and a defoamer.
• composition Cil according to the invention has a better load capacity than the composition CCI.
• Compositions CI2, C3 and C4 exhibit very good load capacity. These load capacity values demonstrate the very good durability of the lubricating composition, in particular for use in transmissions.

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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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• 2020
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• 2021
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  • 2021-07-19 EP EP21745344.8A patent/EP4185674A1/de active Pending
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