Patent Application
20230287290
The present invention relates to the field of lubricant compositions, in particular for automotive vehicles and more especially for lubrication of the transmission components of automotive vehicles, particularly the gearing of the transmissions of internal combustion engines or electric motors.
The transmission components of automotive vehicles operate under a heavy load and high speeds. The oils for these transmissions must therefore have particularly good performance to protect parts against wear and fatigue, and in particular to protect the teeth of gearing against the phenomenon of spalling.
Spalling occurs after a long ageing time which precedes visible deterioration. The mechanisms are ill-known, but the phenomenon starts with initiation of cracking at a certain depth below the surface, these cracks propagate and when normal cracking occurs on the surface there is sudden fall-off of parts of material.
The prevention of this phenomenon requires a reduction in contact stresses by means of appropriate geometry of the parts, and a reduction in friction to prevent adhesion. A lubricant composition takes part in this process of prevention chiefly via the physicochemical reactivity of the additives included therein.
In general, the addition is made of sulfur-, phosphorus- or boron-containing antiwear and extreme pressure additives which impart protective properties to transmission oils against spalling. The other additives contained in a lubricant composition can also have a negative or positive impact on the propagation of cracking inside parts, and hence on the phenomenon of spalling.
Throughout its service life, a lubricant composition used in transmission components can start to deteriorate.
It is therefore one objective of the present invention to provide a composition allowing lubrication of the components of manual or automatic transmissions, in particular the gearing of transmissions of internal combustion engines or electric motors, said composition also having good durability.
Document WO 2010/126760 describes a lubricant composition comprising a base oil and a polymer of phosphorus ester type comprising the condensation reaction product of an acid or phosphorus ester with a diol in which the two hydroxy functions are separated by a chain of 4 to 100 carbon atoms.
Document WO 2016/089565 describes a lubricant composition comprising a base oil and a phosphite ester composition comprising the condensation reaction product of an acid or phosphorus ester with at least two diols.
These two documents do not relate to properties of load-carrying capacity and do not specifically describe the phosphite polymer of formula (I) such as defined in the present invention.
More specifically, the present invention relates to a lubricant composition comprising:
In one embodiment of the invention, the polymer of formula (I) has a weight average molecular weight lower than 30000 g/mol, preferably ranging from 5000 to 20000 g/mol.
In one embodiment of the invention, the phosphite polymer represents from 0.01 to 10% by weight of the total weight of the lubricant composition.
In one embodiment, the lubricant 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 lubricant composition.
In one embodiment, the lubricant composition also comprises at least one antiwear additive selected from among phosphorus antiwear additives, sulfur antiwear additives, sulfur-phosphorus antiwear additives, phosphorus-amine antiwear additives, sulfur-amine antiwear additives, and mixtures thereof.
In one embodiment, the lubricant composition comprises from 0.01 to 5% by weight of antiwear additives selected from among phosphorus antiwear additives, sulfur antiwear additives, sulfur-phosphorus antiwear additives, phosphorus-amine antiwear additives, sulfur-amine antiwear additives, and mixtures thereof, relative to the total weight of the lubricant composition.
In one embodiment, the lubricant 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 lubricant composition.
In one embodiment, the lubricant composition comprises:
The invention also concerns the use of a phosphite polymer in a lubricant composition comprising at least one base oil, to improve the load-carrying capacity of the lubricant composition, the phosphite polymer replying to formula (I):
The invention also concerns the use of the lubricant composition of the invention to lubricate at least one mechanical part of an automotive vehicle, preferably contained in a transmission component of an automotive vehicle, and preferably the gearing of an automotive vehicle.
The lubricant composition of the invention has the advantage of exhibiting very good properties to reduce the phenomenon of spalling, in particular when used under a heavy load and under high speeds.
The lubricant composition of the invention additionally has good durability.
In the remainder hereof, the expressions «between . . . and . . . », «ranging from . . . to . . . » and «varying from . . . to . . . » are equivalent and are intended to indicate that the limits are included, unless otherwise stated.
Unless otherwise stated, the quantities in a product are expressed by weight, relative to the total weight of the product.
The present invention concerns a lubricant composition comprising;
The lubricant composition of the invention comprises at least one phosphite polymer meeting formula (I):
In the meaning of the present invention, by «alkyl» it is meant a linear or branched, non-cyclic saturated hydrocarbon chain optionally comprising one or more heteroatoms such as oxygen, nitrogen or sulfur atoms. Preferably, the alkyls are formed of carbon atoms and hydrogen.
In the meaning of the present invention, by «alkenyl» it is meant a linear or branched, non-cyclic unsaturated hydrocarbon chain optionally comprising one or more heteroatoms such as oxygen, nitrogen or sulfur atoms. Preferably, the alkenyls are formed of carbon atoms and hydrogen atoms.
In the meaning of the present invention, by «cycloalkyl» it is meant a saturated monocyclic or polycyclic group optionally having one or more alkyl or alkenyl substituents, said ring(s) can themselves be substituted by one or more heteroatoms such as oxygen, nitrogen or sulfur atoms. Preferably, the cycloalkyls are formed of carbon atoms and hydrogen atoms.
In the meaning of the present invention, by «cycloalkenyl» it is meant an unsaturated monocyclic or polycyclic group optionally having one or more alkyl or alkenyl substituents, said ring(s) can themselves be substituted by one or more heteroatoms such as oxygen, nitrogen or sulfur atoms. Preferably, the cycloalkenyls are formed of carbon atoms and hydrogen atoms.
In the meaning of the present invention, a «Ci-Cj group» is a group having from i to j carbon atoms.
In one preferred embodiment, the Y group is selected from among alkylenes having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms.
In one embodiment, m ranges from 4 to 100.
In one embodiment the phosphite polymer of formula (I) has a weight average molecular weight lower than 30000 g/mol, preferably ranging from 3000 to 20000 g/mol. Weight average molecular weight can be measured by size exclusion chromatography.
In one embodiment, the phosphite polymer of formula (I) has a number average molecular weight lower than 10000 g/mol, preferably ranging from 1000 to 5000 g/mol. Number average molecular weight can be measured by size exclusion chromatography.
In one embodiment, the phosphite polymer of formula (I) has a polydispersity index ranging from 1 to 5, preferably ranging from 2 to 4.
Preferably, the phosphite polymer of formula (I) contains less than 2% by weight, preferably less than 1% by weight, even less than 0.7% by weight of (alkyl)phenol group, relative to the total weight of the phosphite polymer in formula (I).
Preferably, the phosphite polymer of formula (I) is fully free of aromatic groups differing from the (alkyl)phenol groups.
Typically, the phosphite polymer is in liquid form.
In one embodiment, 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 with the method described in document WO2011102861. In particular, the polymer can be obtained with the method described in paragraphs 27 to 32 of this document.
The synthesis of polymers of formula (I) generally implies a transesterification in which triphenyl phosphite (or any other suitable alkyl or aryl phosphite) can be reacted with a saturated or unsaturated alcohol, or a polyethylene or polypropylene glycol ether, and a diol or a diol polymer H(OY)mOH where m and Y are such as previously defined, with a suitable basic catalyst at a temperature of between 20° C. and 250° C., and preferably at a temperature of between 50° C. and 185° C. Among nonlimiting examples of saturated or unsaturated alcohols, mention can be made of decyl, isodecyl, lauryl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, stearyl, isostearyl, oleic alcohols, monohydroxylated glycol ethers.
Preferably, the lubricant composition of the invention comprises from 0.01 to 10% by weight of phosphite polymer(s) relative to the total weight of the lubricant composition.
The lubricant composition of the invention comprises one or more base oils, preferably in an amount of at least 70% by weight, preferably ranging from 70 to 99% by weight, more preferably from 80 to 98% by weight, and further preferably from 85 to 95% by weight, relative to the total weight of the lubricant composition.
These base oils can be selected from among base oils conventionally used in the field of lubricant oils, such as mineral, synthetic or natural animal or vegetable oils, or mixtures thereof.
It can be a mixture of several base oils, for example a mixture of two, three or four base oils.
The base oils of the lubricant compositions under consideration in the invention can in particular be oils of mineral or synthetic origin belonging to Groups I to V of the groups defined by the API classification (or the equivalents thereof in the ATIEL classification) and are given in Table 1 below, or mixtures thereof.
Mineral base oils include all types of base oils obtained by atmospheric or vacuum distillation of crude oil, followed by refining operations such as solvent extraction, deasphalting, solvent dewaxing, hydrotreatment, hydrocracking, hydroisomerization, and hydrofinishing.
Mixtures of synthetic and mineral oils, possibly being biosourced, can also be used.
There is generally no limitation as to the use of different base oils to form the compositions used in the invention, other than the fact that they must have properties in particular in terms of viscosity, viscosity index or oxidation resistance that are adapted for use in the propulsion systems of an electric or hybrid vehicle.
The base oils of the compositions used in the invention can also be selected from among synthetic oils, such as some esters of carboxylic acids and alcohols, polyalphaolefins (PAOs), and polyalkylene glycols (PAGs) obtained by polymerization or copolymerization of alkylene oxides having 2 to 8 carbon atoms, in particular 2 to 4 carbons atoms.
The PAOs used as base oils are obtained for example from monomers having 4 to 32 carbon atoms, for example from octene or decene. The weight average molecular weight of the PAO can vary widely. Preferably, the weight average molecular weight of the PAO is lower than 600 Da. The weight average molecular weight of the PAO can also range from 100 to 600 Da, from 150 to 600 Da, or from 200 to 600 Da.
Advantageously, the base oil or oils of the lubricant composition of the invention can be selected from among the base oils in Group II or Group III.
In one alternative embodiment, the base oil or oils of the composition used in the invention are selected from among polyalphaolefins (PAOs), polyalkylene glycols (PAG) and the esters of carboxylic acids and of alcohols.
The antiwear additives optionally used in the lubricant composition of the invention, are selected from among phosphorus antiwear additives, sulfur antiwear additives, sulfur-phosphorus antiwear additives, and mixtures thereof.
It is to be noted that the antiwear additive optionally added to the lubricant composition of the invention typically differs from the phosphite polymer of formula (I).
In the meaning of the present invention, a «phosphorus antiwear additive» shall designate an antiwear additive comprising at least one phosphorus atom and not comprising sulfur, said phosphorus antiwear additive may optionally comprise one or more nitrogen atoms (in addition to carbon and hydrogen atoms). In this case, it can be designated a «phosphorus-amine antiwear additive».
In the meaning of the present invention, a «sulfur antiwear additive» shall designate an antiwear additive comprising at least one sulfur atom and not comprising phosphorus, said sulfur antiwear additive may optionally comprise one or more nitrogen atoms (in addition to carbon and hydrogen atoms). In this case it can be designated a «sulfur-amine antiwear additive».
In the meaning of the present invention, a «sulfur-phosphorus antiwear additive» shall designate an antiwear additive comprising at least one phosphorus atom and at least one sulfur atom, said sulfur-phosphorus antiwear additive may optionally comprise one or more nitrogen atoms (in addition to carbon and hydrogen atoms). In this case, it can be designated a «sulfur-phosphorus-amine antiwear additive».
Among phosphorus antiwear additives, mention can be made of phosphates, phosphites, and phosphonates. These terms designate phosphoric, phosphorous, phosphonic acids as well as the mono-, di- and triesters thereof, for example alkyl phosphates, alkyl phosphonates, and the salts thereof e.g. amine salts.
The sulfur-phosphorus antiwear 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, the salts thereof, dithiophosphites and dithiophosphates.
As examples of sulfur-phosphorus antiwear additives, mention can be made of monobutylthiophosphates, monooctylthiophosphates, monolaurylthiophosphates, dibutylthiophosphates, dilaurylthiophosphates, tributylthiophosphates, trioctylthiophosphates, triphenylthiophosphates, monooctylthiophosphites, trilaurylthiophosphates, monolaurylthiophosphites, monobutylthiophosphites, dibutylthiophosphites, dilaurylthiophosphites, tributylthiophosphites, trioctylthiophosphites, triphenylthiophosphites, trilaurylthiophosphites and the salts thereof.
Examples of the ester salts of thiophosphoric acid and thiophosphorous acid are those obtained by reaction with a nitrogen-containing compound such as ammonia or an amine or zinc oxide or zinc chloride.
In one particular embodiment, the antiwear additive(s) used in the invention are selected from among sulfur-phosphorus antiwear additives, sulfur-amine antiwear additives, and mixtures thereof.
For example, the lubricant composition of the invention may comprise from 0.01 to 5% by weight of antiwear additive(s), preferably from 0.05 to 3% by weight of antiwear additive(s), relative to the total weight of the lubricant composition.
The quantity of antiwear additives can be adapted to obtain a phosphorus content ranging from 5 to 9150 ppm by weight in the lubricant composition. Preferably, the phosphorus content in the lubricant composition of the invention ranges from 5 to 4500 ppm by weight, relative to the total weight of the lubricant composition.
The inventors have discovered that the combination of the phosphite polymer of formula (I) with a phosphorus, sulfur or sulfur-phosphorus antiwear additive allows an increase in the durability of the lubricant composition comprising said combination.
The lubricant composition of the invention may also comprise any type of additional functional additive differing from the phosphite polymer and antiwear additives defined in the context of the present invention, and which are adapted for use in a lubricant for automotive vehicles, in particular for manual or automatic transmissions of automotive vehicles.
Such additives, known to persons skilled in the art in the field of lubrication of automotive vehicles, can be selected from among detergents, dispersants, antioxidants, pour point depressants, defoaming agents, viscosity index improvers and mixtures thereof.
Advantageously, the composition of the invention comprises at least one functional additive selected from among detergents, dispersants, antioxidants, pour point depressants, defoaming agents, viscosity index improvers and mixtures thereof.
Typically, when present, these additional functional additives (together) represent from 1 to 30% by weight, preferably from 1.5 to 25% by weight, more preferably from 2 to 20% by weight of the total weight of the lubricant composition.
These additives can be added alone and/or in the form of a mixture such as those already available for sale in formulations of commercial lubricants for automotive vehicles, having a performance level such as defined by the European Automobile Manufacturers' Association (ACEA) and/or the American Petroleum Institute (API), well known to persons skilled in the art.
The lubricant composition of the invention may comprise at least one antioxidant additive.
The antioxidant additive generally allows delaying of degradation of the composition in service. This degradation can particularly translate as the formation of deposits, the presence of sludge or an increase in the viscosity of the composition.
Antioxidant additives generally act as radical inhibitors or hydroperoxide decomposers. Among the antioxidants commonly used, mention can be made of antioxidants of phenolic type, antioxidants of amine type, antioxidants containing sulfur and phosphorus. Some of these antioxidants, for example those comprising sulfur and phosphorus, can generate ash. Phenolic antioxidant additives can be ash-free or can be in the form of neutral or basic metal salts. The antioxidant additives can be selected in particular from among sterically hindered phenols, sterically hindered phenol esters, sterically hindered phenols comprising a thioether bridge, diphenylamines, diphenylamines substituted by at least one C1 to C12 alkyl group, N,N′-dialkyl-aryl-diamines, and mixtures thereof.
Preferably, in the invention, the sterically hindered phenols are selected from among compounds comprising a phenol group in which at least one vicinal carbon of the carbon atom carrying the alcohol function is substituted by at least one C1 to C10 alkyl group, preferably a C1 to C6 alkyl group, more preferably a C4 alkyl group, preferably a tert-butyl group.
Amine compounds form another class of antioxidant additives which can be used, optionally in combination with phenolic antioxidant additives. Examples of amine compounds are aromatic amines e.g. aromatic amines having the formula NR10R11R12 in which R10 is an optionally substituted aliphatic group or aromatic group, R11 is an optionally substituted aromatic group, R12 is a hydrogen atom, an alkyl group, an aryl group or a group of formula R13S(O)zR14 where R13 is an alkylene or alkenylene group, R14 is an alkyl group, an alkenyl group or an aryl group and z is 0, 1 or 2.
Sulfurized alkyl-phenols or the alkali or alkaline-earth metal salts thereof can also be used as antioxidant additives.
Another class of antioxidant additives includes copper-containing compounds, for example copper thio- or dithio-phosphates, the salts of copper and carboxylic acids, copper acetylacetonates, dithiocarbamates, sulfonates, phenates. The salts of copper I and II, the salts of succinic acid or anhydride can also be used.
The lubricant compositions of the invention may also comprise any type of antioxidant additive known to skilled persons.
Advantageously, the lubricant composition comprises at least one ash-free antioxidant additive.
The lubricant composition of 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 lubricant composition of the invention may also comprise at least one detergent additive.
Detergent additives generally allow a reduction in the forming of deposits on the surface of metal parts, by dissolving the secondary products of oxidation and combustion.
The detergent additives able to be used in the lubricant composition of the invention are generally known to persons skilled in the art. The 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 selected from among the alkali or alkaline-earth metal salts of carboxylic acids, sulfonates, salicylates, naphthenates, and phenate salts. The alkali and alkaline-earth metals are preferably calcium, magnesium, sodium or barium.
These metal salts generally comprise the metal in stoichiometric amount or else in excess, hence in an amount greater than the stoichiometric amount. They are then overbased detergent additives; the excess metal imparting the overbased nature to the detergent additive is then generally in the form of an oil-insoluble metal salt, for example a carbonate, hydroxide, oxalate, acetate, glutamate, preferably a carbonate.
The lubricant composition suitable for the invention may comprise for example from 0.5 to 4% by weight of detergent additive, relative to the total weight of the composition.
In addition, the lubricant composition of the invention may comprise at least one dispersing agent. Typically, the dispersant will allow the ensured maintaining in suspension and evacuation of solid insoluble contaminants formed by the secondary products of oxidation which are formed when the lubricant composition is in service.
The dispersing agent can be selected from among Mannich bases or compounds of succinimide type, such as polyisobutylene succinimides (PIBSIs).
The lubricant composition of the invention may comprise for example from 0.2 to 10% by weight of dispersing agent(s), relative to the total weight of the composition.
The lubricant composition of the invention may also comprise at least one defoaming agent.
The defoaming agent can be selected from among silicones.
The lubricant composition of the invention may comprise from 0.01 to 2% by weight, or from 0.01 to 5% by weight, preferably 0.1 to 1.5% by weight, or 0.1 to 2% by weight of defoaming agent, relative to the total weight of the composition.
The lubricant composition of the invention may also comprise at least one pour point depressant additive (PPD).
By slowing the formation of paraffin crystals, pour point depressant additives generally improve the cold properties of the composition. As examples of pour point depressant additives, mention can be made of alkyl polymethacrylates, polyacrylates, polyarylamides, polyalkylphenols, polyalkylnaphthalenes, alkylated polystyrenes.
The lubricant composition of the invention may also comprise at least one additive improving the viscosity index (VI improver). As examples of VI improvers, mention can be made of polymethacrylates, polyisobutenes or fatty acid esters. When present, these additives can represent from 1 to 25% by weight of the total weight of the lubricant composition.
In terms of the formulation of said lubricant composition, the phosphite polymer and optionally the antiwear and extreme pressure additive can be added to a base oil or mixture of base oils, followed by the other additional additives which may optionally be added.
Alternatively, the phosphite polymer and optionally the antiwear and extreme pressure additive can be added to a conventional pre-existing lubricant formulation which particularly comprises one or more base oils and optionally additional additives.
Alternatively, the phosphite polymer and optionally the antiwear and extreme pressure additive defined in the invention can be combined with one or more additional additives, when included, and the «package» of additives thus formed can be added to a base oil or mixture of base oils.
Advantageously, the lubricant composition of the invention has kinematic viscosity, measured at 40° C. according to standard ASTM D445, which ranges from 5 to 300 mm2/s, in particular from 10 to 25 mm2/s.
Advantageously, the lubricant composition of the invention has kinematic viscosity, measured at 100° C. according to standard ASTM D445, which ranges from 1 to 20 mm2/s, in particular from 2 to 15 mm2/s.
In one particular embodiment, the lubricant composition of the invention comprises, or even is constituted by:
In one particular embodiment, the lubricant composition of the invention comprises, or even is constituted by:
In one embodiment, the lubricant composition of 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 lubricant composition.
In one embodiment, the lubricant composition of the invention comprises from 5 to 4000 ppm by weight of sulfur, preferably from 7 to1000 ppm by weight of sulfur, more preferably 10 to 800 ppm by weight of sulfur, relative to the total weight of the lubricant composition.
The present invention also concerns the use of the phosphite polymer such as previously defined in a lubricant composition comprising at least one base oil, to improve the load-carrying capacity of said lubricant composition.
A further subject of the present invention is the use of the lubricant composition of the invention to lubricate the transmissions of automotive vehicles, in particular the gear of transmissions. The transmissions can be manual or automatic transmissions.
Preferably, the lubricant composition of the invention is used to reduce the wear of a mechanical part of the transmission of automotive vehicles, in particular a gear of automotive vehicles. Therefore, in this embodiment, the lubricant composition of the invention allows the wear of transmission gears to be reduced.
Preferably, the lubricant composition of the invention is used to reduce spalling of a mechanical part of the transmission of an automotive vehicle, in particular spalling of a gear in automotive vehicles.
In one advantageous embodiment, the lubricant composition of the invention is used both to reduce wear and to reduce the spalling of a mechanical part of the transmission of automotive vehicles, in particular a gear of automotive vehicles.
In another aspect, the invention further concerns a method for lubricating at least one part of a transmission of an automotive vehicle, in particular a gear of an automotive vehicle, which comprises at least one step of contacting at least said part with a lubricant composition such as previously described.
In another aspect, the invention further concerns a method for improving the durability of a lubricant composition, said method comprising a step of mixing at least one phosphite polymer of formula (I) such as defined in the present invention with at least one base oil, preferably said polymer is also mixed with an antiwear additive such as defined in the present invention.
All the characteristics and preferences described for the lubricant composition of the invention and for the uses thereof, also apply to these methods.
In the invention, the particular, advantageous or preferred characteristics of the composition of the invention allow the defining of the uses of the invention which are also particular, advantageous or preferred.
The invention is now described by means of the following examples evidently given for illustration purposes and not limiting the invention.
The lubricant compositions were prepared by mixing the ingredients at a temperature of about 40° C., following methods well known to those skilled in the art. The prepared and tested lubricant compositions are detailed in Table 2 below.
The elemental content of phosphorus and sulfur was calculated as a function of the elemental composition of the ingredients, and is also given in Table 2 in ppm by weight.
Finally, the kinematic viscosities at 40° C. and at 100° C. were determined with the ASTM D445 method and are given in Table 2.
1%
1%
1%
1%
In the compositions in Table 2:
The scuffing load-carrying capacity of the lubricant compositions described in Table 2 was tested with the FZG A/8,3/90 method (according to standard ISO 14635-1). The results are given in Table 3 below.
With iso-phosphorus content, composition CI1 of the invention exhibits better load-carrying capacity than composition CC1.
Compositions CI2, CI3 and CI4 exhibit very good load-carrying capacity. These load-carrying capacities show the very good durability of the lubricant composition, in particular for use in transmissions.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2007723 | Jul 2020 | FR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2021/070072 | 7/19/2021 | WO |
