EP3377599A1 - Détergents alkylphénols toxicologiquement acceptables utilisés en tant que modificateurs de frottement dans des huiles lubrifiantes automobiles - Google Patents

Détergents alkylphénols toxicologiquement acceptables utilisés en tant que modificateurs de frottement dans des huiles lubrifiantes automobiles

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Publication number
EP3377599A1
EP3377599A1 EP16804973.2A EP16804973A EP3377599A1 EP 3377599 A1 EP3377599 A1 EP 3377599A1 EP 16804973 A EP16804973 A EP 16804973A EP 3377599 A1 EP3377599 A1 EP 3377599A1
Authority
EP
European Patent Office
Prior art keywords
detergent
lubricant
alkylphenol
hydrocarbyl
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP16804973.2A
Other languages
German (de)
English (en)
Inventor
Blayne M. MCKENZIE
Gary M. Walker
James P. Roski
Ewan E. Delbridge
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lubrizol Corp
Original Assignee
Lubrizol Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lubrizol Corp filed Critical Lubrizol Corp
Publication of EP3377599A1 publication Critical patent/EP3377599A1/fr
Withdrawn legal-status Critical Current

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    • 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
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    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04—Hydroxy compounds
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    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
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    • C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
    • 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
    • C10N2040/044—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions
    • 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

Definitions

  • the disclosed technology relates to the use of toxicologically acceptable hydrocarbyl- (e.g. alkyl-) phenol detergents and their salts in automotive lubricating oils, such as, for example, automatic or manual transmissions.
  • hydrocarbyl- e.g. alkyl-
  • phenol detergents and their salts such as, for example, automatic or manual transmissions.
  • Phenol-based detergents are known. Among these are phenates based on phenolic monomers, linked with sulfur bridges or alkylene bridges such as methylene linkages derived from formaldehyde.
  • the phenolic monomers themselves are typically substituted with an aliphatic hydrocarbyl group to provide a measure of oil solubility.
  • the hydrocarbyl groups may be alkyl groups, and, historically, dodecylphenol (or propylene tetramer-substituted phenol) has been widely used.
  • An early reference to basic sulfurized polyvalent metal phenates is U.S. Patent 2,680,096, Walker et al., June 1, 1954; see also U. S. Patent 3,372, 1 16, Meinhardt, March 5, 1968.
  • alkylphenol detergents which are based on phenols alkylated with oligomers of propylene, specifically propylene tetramer (or tetrap- ropenyl), may contain residual alkyl phenol species.
  • alkyl-substituted phenol detergents for uses in lubricants, fuels, and as industrial additives, which contain a reduced or eliminated amount of dodecylphenol component and other substituted phenols having propylene oligomer substituents of 10 to 15 carbon atoms.
  • the products should have similar oil-solubility parameters as phenates prepared from C I 0- 15 propylene oligomers.
  • It comprises a salt of a reaction product of (1) an olefin having at least 10 carbon atoms, where greater than 90 mole % of the olefin is a linear C20-C30 n-alpha olefin, and wherein less than 10 mole % of the olefin is a linear olefin of less than 20 carbon atoms, and less than 5 mole % of the olefin a branched chain olefin of 18 carbons or less, and (2) a hydroxyaromatic compound.
  • U. S. Application 201 1/0190185, Sinquin et al, August 4, 201 1 discloses an overbased salt of an oligomerized alkylhydroxyaromatic compound.
  • the alkyl group is derived from an olefin mixture comprising propylene oligomers having an initial boiling point of at least about 195 °C and a final boiling point of greater than 325 °C.
  • the propylene oligomers may contain a distribution of carbon atoms that comprise at least about 50 weight percent of C14 to C20 carbon atoms.
  • U. S. Application 201 1/0124539, Sinquin et al, May 26, 201 1 discloses an overbased, sulfurized salt of an alkylated hydroxyaromatic compound.
  • the alkyl sub- stituent is a residue of at least one isomerized olefin having from 15 to about 99 wt. % branching.
  • the hydroxyaromatic compound may be phenol, cresols, xylenols, or mixtures thereof.
  • U. S. Application 201 1/01 18160, Campbell et al., May 19, 201 1 discloses an alkylated hydroxyaromatic compound substantially free of endocrine disruptive chemicals.
  • An alkylated hydroxyaromatic compound is prepared by reacting a hydroxyaromatic compound with at least one branched olefinic propylene oligomer having from about 20 to about 80 carbon atoms.
  • Suitable hydroxyaromatic compounds include phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol, and the like.
  • U. S. Application 2010/0029529 discloses an overbased salt of an oligomerized alkylhydroxyaromatic compound.
  • the alkyl group is derived from an olefin mixture comprising propylene oligomers having an initial boing point of at least about 195 °C and a final boiling point of no more than about 325 °C.
  • Suitable hydroxyaromatic compounds include phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol, and the like.
  • U.S. Application 2008/0269351 discloses an alkylated hydroxyaromatic compound substantially free of endocrine disruptive chemicals, prepared by reacting a hydroxyaromatic compound with a branched olefinic oligomer having from about 20 to about 80 carbon atoms.
  • WO/PCT application 2013/059173 discloses an overbased salt of an oligomerized alkylhydroxyaromatic compound.
  • the alkyl group is a combination of very short hydrocarbyl group (i.e. 1 to 8 carbon atoms) and a long hydrocarbyl group (at least about 25 carbon atoms).
  • Suitable compounds incude those made from a mixture of para-cresol and polyisobutylene-substituted phenol.
  • R may be an alkyl group of 1 to 60 carbon atoms, e.g., 9 to 18 carbon atoms. It is understood that R 1 will normally comprise a mixture of various chain lengths, so that the foregoing numbers will normally represent an average number of carbon atoms in the R 1 groups (number average).
  • the disclosed technology therefore, solves the problem of providing a tox- icologically acceptable alkylphenol detergent in a driveline device by supplying to the device an alkyl phenol as described herein.
  • the transmission lubricant can include an oil of lubricating viscosity, from about 0.1 to about 5 wt% of a dispersant, and from about 0.1 to about 5 wt% of a detergent.
  • the detergent in the transmission lubricant can include from about 0.01 to about 2 wt% of an alkylphenol detergent that has at least one unit of an alkyl-substituted phenol wherein the alkyl group is derived from oligomers of an olefin compound containing 3 to 8 carbon atoms, wherein the olefin- derived alkyl group comprises at least 30 mol percent of an olefin with 4 or more carbon atoms.
  • the alkylphenol detergent can be a sulfur-bridged phen- ate, a sulfur-free alkylene-bridged phenate, a salicylate, or mixtures thereof.
  • alkylphenol detergent can include one or more alkali metals, one or more alkaline earth metals, or mixtures thereof.
  • the alkylphenol detergent can be overbased, and in an even further embodiment the overbased alkylphenol detergent can have a metal ratio of at least 1.5, at least 5, or at least 7.
  • the alkyl group of the alkylphenol detergent can include oligomers of n-butene, where the alkyl group can be a hydrocarbyl group of 12 to 48 carbon atoms.
  • the alkylphenol detergent can be an overbased sulfur-coupled alkylphenol detergent with a metal ratio of at least 1.5.
  • the alkylphenol detergent can include a sulfur- bridged phenate represented by the structure
  • the alkylphenol detergent can be a neutral or overbased salt of alkylsalicylic acid.
  • the alkylphenol detergent can be an alkyl sal icy late represented by the structure where R can be an aliphatic hydrocarbyl group derived from oligomers of n-butene, higher alphaolefins, or mixtures thereof, and wherein the hydrocarbyl group contains 8 to 48 carbon atoms.
  • the oil of lubricating viscosity in the lubricant can include comprises at least one API Group I, II, III ,IV, or V, lubricant or mixtures thereof.
  • the lubricant can additionally include at least one of a phosphorus-containing antiwear agent comprising a non-ionic phosphorus compound; an amine salt of a phosphorus compound; a calcium-containing detergent; another friction modifier; a sulphur-containing extreme pressure agent; a sulphur-containing corrosion inhibitor; or combinations thereof.
  • the lubricant can further include from about 0.05 to about 3 wt% of a C2-C 18 di- or tri-hydro- carbyl phosphite, based on the total weight of said lubricant.
  • the lubricant can include less than 2000 ppm zinc based on the total weight of said lubricant.
  • the lubricant can be substantially free of, to free of, a phenol alkylated with oligomers of propylene.
  • the lubricant composition can include the oil of lubricating viscosity; a thiadiazole; a phosphorous containing antiwear agent; the dispersant; the detergent; and the alkylphenol detergent.
  • the lubricant composition can include the oil of lubricating viscosity; a thiadiazole; a phosphorous containing antiwear agent; the dispersant; the detergent; and the alkylphenol detergent.
  • the lubricant composition can include the oil of lubricating viscosity; a zinc dialkyl dithiophosphate antiwear agent; the dispersant; the detergent and the alkylphenol detergent.
  • the off-highway vehicle can be a farm-tractor vehicle or a construction vehicle.
  • the lubricant composition can include the oil of lubricating viscosity; the dispersant; the detergent (including the alkylphenol detergent); a sulfurized olefin; a thiadiazole; and a phosphorous containing antiwear agent.
  • wt% refers to the weight percent of the material referred to based on a total weight of the composition within which the material is included.
  • the disclosed technology provides a lubricating composition for automotive gears, such as transmissions, including an alkylphenol detergent, as well as methods for lubricating automotive gears and a use as disclosed herein.
  • One of the materials of the presently disclosed technology may be a bridged alkylphenol compound.
  • Such materials in general, their methods of preparation, and use in lubricants are well known from, for instance, the above-referenced U. S. Patent 2,680,096, Walker et al. They may be prepared starting from alkyl phenol such as alkylphenols derived from oligomers of n-butene, or mixtures thereof, any of which are readily available as starting materials.
  • alkylation of phenol and its homologues is well known, typically by catalyzed reaction of an olefin, often an a-olefm, with phenol (or with salicylic acid or another homologue, as the case may be). Alkylation of phenol is described in greater detail in the Kirk-Othmer Encyclopedia of Chemical Technology, third edition (1978) vol. 2, pages 82-86, John Wiley and Sons, New York.
  • alkyl (or more generally, hydrocarbyl) phenols to form oligo- meric species, is also well known. They may be condensed, for instance, with formaldehyde or with other aldehydes or ketones such as acetone to form methylene (or alkylene) bridged structures, as described on pages 76-77 of the above cited Kirk- Othmer reference. If condensation with an aldehyde or ketone is intended, it is desirable that the aldehyde or ketone not be a C 12 species, to avoid the formation of any C 12 substituted phenolic materials.
  • the material may be an aldehyde of 8 or fewer carbon atoms, such as 1 to 4, or 1 or 2, or a single carbon atom (formaldehyde).
  • the length of the resulting oligomeric chain of phenolic and alkylene units will depend to some extent on the molar ratio of the reactants, as is well known. Thus an equimolar amount of phenol and formaldehyde provides a condensate with a relatively longer oligomeric chain than that obtained when there is a stoichiometric excess of one species or the other.
  • carbon- and oxygen- containing linkages may also be formed, such as those of the general structure -CH 2 - O-CH2- or homologues in which the hydrogens are replaced by alkyl groups. These may be formed by the condensation of more than a single aldehyde or ketone group.
  • Such structures are known, for example, from U.S. Patent 6,310,009, see col. 2 lines 14-17 and col. 6 lines 1-45.
  • the linking groups prepared form aldehydes or ketones may be generally described as "carbon-containing" bridging groups, e.g., an alkylene bridge or an ether bridge.
  • Substituted phenols may also be linked together to make sulfur bridged species, which may include bridges of single sulfur atoms ( -S-) or multiple sulfur atoms (e.g., -S x - where x may be 2 to 8, typically 2 or 3).
  • Sulfurized phenols may be prepared by reaction with active sulfur species such as sulfur monochloride or sulfur dichloride as described on pages 79-80 of the Kirk-Othmer reference or with elemental sulfur, as described, for instance, in US 2,680,096.
  • Sulfurization (with sulfur) may be conducted in the presence of a basic metal compound such as calcium hydroxide or calcium oxide, thus preparing a metal salt, as described in greater detail, below.
  • the phenol (A) may be a hydrocarbyl-substituted phenol which may be prepared by mixing a hydrocarbon and a phenol at a temperature of about 50-200 °C in the presence of a suitable catalyst such as aluminum trichloride (col. 2 line 51 of US 3,410,798, and following text).
  • a suitable catalyst such as aluminum trichloride (col. 2 line 51 of US 3,410,798, and following text).
  • the alkyl group is derived from a polyolefin compound comprising n-butene (also referred to as 1 -butene) monomers, higher al- pha-olefins, or mixtures thereof.
  • suitable alpha-olefins include isobutylene, 1-pentene, 1 -hexene, 1-heptene, 1-octene, 1-nonene, 1 -decene, and mixtures thereof.
  • the alkyl group of the alkylphenol is a polyolefin compound comprising at least 25 mol % 1-butene, at least 50 mol % 1 -butene, or at least 75 mol % 1 -butene. In one embodiment, the alkyl group of the alkylphenol consists of oligomers or polymers of 1 -butene.
  • Suitable polyolefins include oligomers or polymers of n-butene.
  • a butene polymer or oligomer containing 8 to 48 carbon atoms would contain 2 to 12 butene monomer units.
  • An n-butene polymer or oligomer containing 12 to 32 carbon atoms would contain 3 or 8 n-butene monomer units. Further details of alkylation are disclosed in the above-cited Kirk-Othmer reference.
  • the alkylphenol from which the detergent may be derived may be characterized as a phenol substituted with one or more alkyl groups derived from a polyolefin or oligomerized olefin as described above.
  • the alkylphenol may contain one or more alkyl groups derived from an oligomer (or polymer) of n-butene.
  • the alkylphenol may be C 8 to C 48 alkylphenol, a C 12 to C32 alkylphenol, a C 16 to C24 alkylphenol, or mixtures thereof, wherein the alkyl groups are oligomers of n-butene.
  • the alkylphenol-containing detergent may be a sulfur-bridged phenate detergent, a sulfur-free alkylene-bridged phenate detergent, or mixtures thereof.
  • Detergents of this type are ionic (usually metal) salts of bridged phenolic compounds.
  • the bridged phenolic compound material may be represented by the structure
  • each y may be, in the case of formula I, 1 but more generally from 1 to 4, especially 1 or 2, and each R may be an aliphatic hydrocarbyl group derived from oligomers of n-butene, higher alphaolefins, or mixtures thereof, and wherein the hydrocarbyl group contains 8 to 48 carbon atoms.
  • the average number of carbon atoms in all the R groups, combined may be 16 to 320 (or 20 to 220, or 24 to 120).
  • the average number of carbon atoms in all R groups, combined may also be from about 16 to about 100 (or 20 to 50, or 24 to 36, or 14 to 20 or 18 to 36).
  • each X may be, independently, a carbon-containing bridge, or an alkylene group, or a methylene group, or a bridge of 1 or more sulfur atoms represented by S y , where y may be 1 to 4, especially 1 or 2.
  • n may, in certain embodiments, be 0 to 8, or 1 to 6, or 1 to 4, or 2 to 4. That is, the bridged material may, in these embodiments, contain 2 to 10 bridged phenolic groups, or 3 to 7, or 3 to 5, or 4 such groups. Since n may be zero, it may be evident that throughout this specification, the expression "oligomeric" may be interpreted to include dimeric species.
  • the expression "dimeric or oligomeric” may be used to express this concept, which may include, as above, as an example, 0 to 8 interior units bracketed by [ ] n or 2 to 10 units overall.
  • one or two of the R groups are aliphatic hydrocarbyl groups containing 30 to 200 or 35 to 80 carbon atoms and the remainder of the R groups are methyl groups.
  • the sulfur-bridged alkylphenol-containing detergent may be an oligomer of p-(tetrabutenyl)phenol.
  • a sulfur-bridged oligomer of oligobu- tenylphenol may be represented by the structure (III)
  • n 0 to 4
  • m 0 to 7, or for example, from 1 to 3 or 4.
  • the alkylene-bridged phenate detergent may be a saligenin detergent.
  • a saligenin detergent contains a bridged-alkyl phenol compound that may be an alkylene coupled alkylphenol represented by the structure
  • each R may be an aliphatic hydrocarbyl group derived from oligomers of n-bu- tene, higher alphaolefins, or mixtures thereof, and wherein the hydrocarbyl group contains 8 to 48 carbon atoms;
  • the each bridging group (X) may be independently a carbon-containing bridge, or a hydrocarbylether linkage (such as -CH 2 - O-CH2-), or an alkylene group, or a methylene group;
  • each Y may be independently -CHO or -CH2OH; wherein the -CHO groups comprise at least about 10 mole percent of the X and Y groups; and n may be an integer from 1 to 10.
  • the alkylene-bridged phenate detergent may be a salixarate detergent.
  • a salixarate detergent contains a bridged-alkyl phenol compound that may be an alkylene coupled alkylphenol that may be further bridged or coupled to salicylic acid.
  • the bridged phenol of a salixarate may be represented by the structure (V)
  • R may be an aliphatic hydrocarbyl group derived from oligomers of n-butene, higher alphaolefins, or mixtures thereof, and wherein the hydrocarbyl group contains 8 to 48 carbon atoms; where the each bridging group (X) may be independently a carbon-containing bridge, or an alkylene group, or a methylene group; and n may be an integer from 1 to 10
  • the bridged alkylphenol detergents may be neutral or overbased or super- based.
  • Such overbased detergents are generally single phase, homogeneous Newtonian systems characterized by a metal and/or ammonium content in excess of that which would be present for neutralization according to the stoichiometry of the metal or ammonium and the particular acidic organic compound reacted with the metal or ammonium compound.
  • the overbased materials are typically prepared by reacting an acidic material (typically an inorganic acid or lower carboxylic acid such as carbon dioxide) with a mixture of bridged alkylphenol compounds (referred to as a substrate), a stoichiometric excess of a metal base, typically in a reaction medium of an one inert, organic solvent (e.g., mineral oil, naphtha, toluene, xylene) for the acidic organic substrate. Typically also a small amount of promoter such as a phenol or alcohol is present, and in some cases a small amount of water.
  • the acidic organic substrate will normally have a sufficient number of carbon atoms to provide a degree of solubility in oil.
  • the overbased bridged-phenol detergent may be a metal-containing detergent, an amine or ammonium containing detergent, or mixtures thereof.
  • the overbased metal-containing detergent may be zinc, sodium, calcium or magnesium salts of a phenate, sulfur containing phenate, salixa- rate or saligenin.
  • the overbased detergent comprises a salt of an alkylamine or quaternary ammonium compound.
  • TBN total base number
  • the alkylphenol-containing detergent may be an alkyl sal icy late or salicylate detergent.
  • a salicylate detergent may be a neutral or over- based metal salt of alkylsalicylic acid.
  • Alkylsalicylic acid may be represented by the formula (VI) where R may be an aliphatic hydrocarbyl group derived from oligomers of n-butene, higher alphaolefins, or mixtures thereof, and wherein the hydrocarbyl group contains 8 to 48 carbon atoms.
  • the alkylsalicylate may be a neutral or nearly neutral salt of alkylsalicylic acid; by nearly neutral, it is meant that there is an excess of base of no more than 15 mol percent, i.e. if the salt is metal-containing, the metal ratio is 1.15 or less.
  • the neutral salt of the alkylsalicylic acid may be an amine or ammonium salt, a metal salt, or mixtures thereof.
  • Amines suitable for use in the preparation of the neutral amine salted alkylsalicylate are not overly limited and may include any alkyl amine, though generally are fatty acid amines derived from fatty carboxylic acids.
  • the alkyl group present in the amine may contain from 10 to 30 carbon atoms, or from 12 to 18 carbon atoms, and may be linear or branched. In some embodiments the alkyl group may be linear and unsaturated.
  • Typical amines include pentadecylamine, octadecylamine, cetyla- mine, oleylamine, decylamine, dodecylamine, dimethyldodecylamine, tridecylamine, heptadecylamine, octadecylamine, stearylamine, and any combination thereof.
  • the fatty acid derived amine salt of an alkylsalicylic acid may be a salt of oleylamine.
  • the amine may be a gamma-aminoester compound; aminoesters of this type may be derived from Michael addition of a primary amine to an alkyl diester of itaconic acid represented by the formula
  • R 1 and R 2 are hydrocarbyl groups containing 2 to 30 carbon atoms
  • R 3 is a hydrocarbyl group containing 4 to 50 carbon atoms.
  • R 3 of the ami- noester compound is an alkyl group that has at least one hydrocarbyl group substituted at the 1-, or 2-position of the alkyl group.
  • the aminoester is dibutyl 2-(((2-ethylhexyl)-amino)methyl)succinate.
  • the neutral salt of the alkylsalicylic acid may be a quaternary ammonium salt, also referred to as a quaternary nitrogen compound.
  • Quaternary nitrogen compounds are characterized in that the nitrogen atom is four- coordinate; this results in a cationic species that is not protic, i.e. an acidic proton is not released under basic conditions.
  • Quaternary nitrogen compounds may be characterized as falling into two large groups, four coordinate tetrahydrocarbyl ammonium compounds, for example tetrabutylammonium, and three coordinate aromatic compounds, for example N-hydrocarbylpyridinium.
  • the quaternary nitrogen salt may comprise the reaction product of (a) hydrocarbyl-substituted compound having a tertiary amino group and (b) a quaternizing agent suitable for converting the tertiary amino group of (a) to a quaternary nitrogen, wherein the quaternizing agent may be chosen from dialkyl sulfates, benzyl halides, hydrocarbyl substituted carbonates; hydrocarbyl epoxides in combination with an acid or mixtures thereof.
  • the quaternary nitrogen salt comprises the reaction product of (i) at least one compound chosen from: a polyalkene-substituted amine having at least one tertiary amino group and/or a Mannich reaction product having a tertiary amino group; and (ii) a quaternizing agent.
  • the alkylphenol-containing detergents may be metal-containing detergents.
  • Metal-containing detergents may be neutral, or very nearly neutral, or overbased.
  • An overbased detergent contains a stoichiometric excess of a metal base for the acidic organic substrate. This is also referred to as metal ratio.
  • the term "metal ratio” is the ratio of the total equivalents of the metal to the equivalents of the acidic organic compound.
  • a neutral metal salt has a metal ratio of one.
  • a salt having 4.5 times as much metal as present in a normal salt will have metal excess of 3.5 equivalents, or a ratio of 4.5.
  • the term "metal ratio” is also explained in standard textbook entitled “Chemistry and Technology of Lubricants", Third Edition, Edited by R. M. Mortier and S. T. Orszulik, Copyright 2010, page 219, sub-heading 7.25.
  • the overbased metal-containing alkylphenol detergent may be calcium or magnesium overbased detergent.
  • the over- based detergent may comprise a calcium alkylphenol detergent with a metal ratio of at least 1.5, at least 3, at least 5, or at least 7.
  • the overbased calcium alkylphenol detergent may have a metal ratio of 1.5 to 25, 2.5 to 20 or 5 to 16.
  • the alkylphenol detergent may be described as having TBN.
  • Overbased phenates and salicylates typically have a total base number of 120 to 600 mg KOH/g, or 150 to 550 mg KOH/g, or 180 to 350 mg KOH/g.
  • the amount of the alkylphenol-containing detergent present in a lubricant composition may be defined as the amount necessary to deliver an amount, or range of amounts, of TBN to the lubricant composition.
  • the alkylphenol-containing detergent may be present in a lubricant composition in amount to deliver 0.5 to 10 TBN to the composition, or 1 to 7 TBN, or 1.5 to 5 TBN to the composition.
  • Overbased detergents may also be defined as the ratio of the neutral detergent salt, also referred to as detergent soap, and the detergent ash.
  • the overbased detergent may have a weight ratio of ash to soap of 3 : 1 to 1 :8, or 1.5 : 1 to 1 :4.1, or 1.3 : 1 to 1 :3.4.
  • the product of the disclosed technology may beneficially be used as an additive in a lubricant.
  • the amount of the alkylphenol detergent in a transmission lubricant may be 0.01 to 2 percent by weight, on an oil-free basis, but including the calcium carbonate and other salts present in an overbased composition, or from about 0.1 to about 1.75 wt%, or about 0.2 to about 1.5.
  • a lubricant composition may contain alkylphenol-containing detergents different from that of the disclosed technology in an amount of from about 0.1 to 1.5 weight percent, or 0.2 to 1.25, or 0.3 to 1 weight percent, and is free of or substantially free of an alkylphenol-containing detergent derived from alkylphenol which is derived from oligomers of propylene, especially tetrapropenyl. "Substantially free of in this case means no more than 0.01 weight percent or an amount considered to arise through contamination or other unintentional means.
  • the lubricating composition comprises an oil of lubricating viscosity.
  • oils include natural and synthetic oils, oil derived from hydrocracking, hydro- genation, and hydrofinishing, unrefined, refined, re-refined oils or mixtures thereof.
  • a more detailed description of unrefined, refined and re-refined oils is provided in International Publication WO2008/147704, paragraphs [0054] to [0056] (a similar disclosure is provided in US Patent Application 2010/197536, see [0072] to [0073]).
  • Synthetic oils may also be produced by Fischer-Tropsch reactions and typically may be hydroisom- erized Fischer-Tropsch hydrocarbons or waxes. In one embodiment oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure as well as other gas-to- liquid oils.
  • Oils of lubricating viscosity may also be defined as specified in April 2008 version of "Appendix E - API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils", section 1.3 Sub-heading 1.3. "Base Stock Categories”. The API Guidelines are also summarized in US Patent US 7,285,516 (see column 1 1, line 64 to column 12, line 10).
  • the oil of lubricating viscosity may be an API Group I to III mineral oil, a Group IV synthetic oil, or a Group V naphthenic or ester synthetic oil, or mixtures thereof.
  • the oil of lubricating viscosity may be an API Group II, Group III mineral oil, or a Group IV synthetic oil, or mixtures thereof.
  • Group 11+ refers to Group II base oils, to a generally recognized (but not officially identified by the API) as having a Viscosity Index of 1 10-1 19 and lower volatility than other Group II oils.
  • the oil of lubricating viscosity may be a Group III+ base oil, a term which refers to a Group III base oil having a Viscosity Index greater than or equal to 130.
  • Group III+ base oils are generally known in the art and are described in an article published in 'Lube Report' (see “SK Sees Group III Shortfall", by Nancy DeMarco. The article may be obtained from h j v/ ⁇ v ⁇ .a3 ⁇ 4ei uhc c >n i :i cdi I i 'M t !/sk 3 ⁇ 4ees - xm : 3 ⁇ 4hor; ! ;: i i . pdi '
  • the amount of the oil of lubricating viscosity present is typically the balance remaining after subtracting from 100 weight % the sum of the amount of the additives of the disclosed technology and the other performance additives.
  • the lubricating composition may be in the form of a concentrate and/or a fully formulated lubricant. If the lubricating composition of the disclosed technology (comprising the additives disclosed herein) is in the form of a concentrate which may be combined with additional oil to form, in whole or in part, a finished lubricant), the ratio of the of these additives to the oil of lubricating viscosity and/or to diluent oil include the ranges of 1 :99 to 99: 1 by weight, or 80:20 to 10: 90 by weight. Typically the lubricating composition of the disclosed technology comprises at least 50 weight %, or at least 60 weight %, or at least 70 weight %, or at least 80 weight % of an oil of lubricating viscosity.
  • a lubricant composition may be prepared by adding the alkylphenol detergent described herein above to an oil of lubricating viscosity, optionally in the presence of other performance additives (as described herein below).
  • the lubricant composition may further include other additives.
  • the invention provides a lubricant composition further comprising at least one of a dispersant, an antiwear agent, a dispersant viscosity modifier, a friction modifier, a viscosity modifier, an antioxidant, an overbased detergent (other than the alkylphenol detergent described above), a foam inhibitor, a demulsifier, a pour point depressant or mixtures thereof.
  • the invention provides a lubricant composition further comprising at least one of a polyisobutylene succinimide dispersant, an antiwear agent, a corrosion inhibitor, a dispersant viscosity modifier, a friction modifier, a viscosity modifier (typically a polymethacrylate having linear, comb or star architecture), an antioxidant (including phenolic and aminic antioxidants), an overbased detergent (including overbased sulphonates, phenates, and salicylates other than the alkylphenol detergent described above), or mixtures thereof.
  • a polyisobutylene succinimide dispersant typically a polymethacrylate having linear, comb or star architecture
  • an antioxidant including phenolic and aminic antioxidants
  • an overbased detergent including overbased sulphonates, phenates, and salicylates other than the alkylphenol detergent described above
  • each other performance additive and chemistry of the other performance additive will depend on type of driveline device being lubricated.
  • common additives across each driveline lubricant includes viscosity modifiers, dispersants, foam inhibitors, corrosion inhibitors, pour point depressants, demul- sifiers, and seal swell agents.
  • Viscosity modifiers may be included in the lubricant composition. Viscosity modifiers are usually polymers, including polyisobutenes, polymethacrylic acid esters, diene polymers, polyalkylstyrenes, esterified styrene-maleic anhydride copolymers, alkenylarene-conjugated diene copolymers, and polyolefins. Multifunctional viscosity improvers, which also have dispersant and/or antioxidancy properties are known and may optionally be used. The amount of viscosity modifier may range from 0.1 to 70 wt %, or 1 to 50 wt %, or 2 to 40 wt %. Typically the viscosity modifier may be a polymethacrylate, or mixtures thereof.
  • the lubricant may comprise a dispersant, which may be a nitrogen-containing dispersants, for example a hydrocarbyl substituted nitrogen containing additive.
  • Suitable hydrocarbyl substituted nitrogen containing additives include ashless dispersants and polymeric dispersants. Ashless dispersants are so-named because, as supplied, they do not contain metal and thus do not normally contribute to sulfated ash when added to a lubricant. However they may, of course, interact with ambient metals once they are added to a lubricant which includes metal-containing species. Ashless dispersants are characterized by a polar group attached to a relatively high molecular weight hydrocarbon chain. Examples of such materials include succin- imide dispersants, Mannich dispersants.
  • the dispersant may be post-treated with other reagents, or not post-treated.
  • the dispersant may be post-treated with urea, thiourea, dimercaptothiadiazoles, carbon disulphide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, and phosphorus compounds.
  • a succinimide dispersant may optionally be post-treated by conventional methods by a reaction with any of a variety of other agents.
  • the polyamine may be an alkylenepolyamine.
  • the alkylenepolyamine may include an ethylenepolyamine, a propylenepolyamine, a butylenepolyamine, or mixtures thereof.
  • propylenepolyamine include propylenediamine, di- propylenetri amine and mixtures thereof.
  • the polyamine is chosen from ethylenediamine, diethyl enetri amine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexa- mine, polyamine still bottoms and mixtures thereof.
  • the lubricating composition may have an antiwear additive comprising a phosphate amine salt.
  • the C2-C18 (or C 2 to C 8 or Ci 6 -Ci 8 ) di- or tri -hydrocarbyl phosphite, or mixtures thereof may be represented by the formula:
  • R 6 , R 7 and R 8 may be a hydrocarbyl group containing at least 4 carbon atoms and the other may be hydrogen or a hydrocarbyl group.
  • R 6 , R 7 and R 8 are all hydrocarbyl groups.
  • the hydrocarbyl groups may be alkyl, cycloalkyl, aryl, acyclic or mixtures thereof.
  • the compound may be a tri -hydrocarbyl substituted phosphite i.e., R 6 , R 7 and R 8 are all hydrocarbyl groups and in some embodiments may be alkyl groups.
  • the di- or tri -hydrocarbyl phosphite comprises dibutyl phosphite or oleyl phosphite.
  • Foam inhibitors that may be useful in the compositions include polysilox- anes, copolymers of ethyl acrylate and 2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers including fluorinated polysiloxanes, trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propyl- ene oxide) polymers.
  • pour point depressants that may be useful in the compositions include polyalphaolefins, esters of maleic anhydride-styrene copolymers, poly(meth)acry- lates, polyacrylates or polyacrylamides.
  • Demulsifiers include trialkyl phosphates, and various polymers and copolymers of ethylene glycol, ethylene oxide, propylene oxide, or mixtures thereof.
  • Seal swell agents include sulpholene derivatives Exxon Necton-37TM (FN 1380) and Exxon Mineral Seal OilTM (FN 3200).
  • the invention provides a lubricant composition comprising:
  • a thiadiazole typically present at 0.05 to 1 wt %, or 0.07 to 0.7 wt %, or 0.1 to 0.3 wt %, or 0.15 to 0.25 wt %),
  • a dispersant typically present at 0.1 to 5 wt %, or 0.3 to 4 wt %, or 1 to 3 wt %, or 0.1 to 3 wt %),
  • a phosphorus-containing antiwear agent chosen from (i) a non-ionic phosphorus compound, which may be a hydrocarbyl phosphite; or (ii) an amine salt of a phosphorus compound,
  • a detergent typically present in an amount to deliver 1 10 to 700ppm, 130 to 600ppm, 150 to 500ppm or 160 to 400ppm calcium; and wherein from about 0.01 to about 2 wt%, or from about 0.1 to about 1.75 wt%, or about 0.2 to about 1.5 wt% of the detergent comprises alkylphenol detergent described herein.
  • the manual transmission may have synchromesh, or in another embodiment the manual transmission does not have a synchromesh.
  • the synchromesh may be composed of aluminum, steel, bronze, molybdenum, brass (sintered or non-sintered), carbon in the form of fibers, graphitic material (optionally in combination with a cellulosic material), or a cellulosic material, or a phenolic resin.
  • the lubricant may comprise 0.03 to 1.0 wt %, or 0.1 to 0.6 wt %, or 0.2 to 0.5 wt % of calcium.
  • the detergent may be calcium or magnesium based, and the detergent may have at least 200 TBN, or 250 to 1000, or 450 to 900 or 650 to 800 mg KOH/g on an oil free basis.
  • the detergent is a calcium based detergent.
  • the lubricant may have 100 to 2000ppm, 150 to 1500ppm, 200 to 1000, or
  • an antiwear agent i.e., delivered by zinc dialkyl dithiophosphate or another phosphorus-containing antiwear agent.
  • the invention provides a method of lubricating a manual transmission comprising supplying to the manual transmission a lubricant composition comprising: an oil of lubricating viscosity,
  • a thiadiazole typically present at 0.05 to 1 wt %, or 0.07 to 0.7 wt %, or 0.1 to 0.3 wt %, or 0.15 to 0.25 wt %),
  • a dispersant typically present at 0.1 to 5 wt %, or 0.3 to 4 wt %, or 1 to 3 wt %, or 0.1 to 3 wt %),
  • a phosphorus-containing antiwear agent chosen from (i) a non-ionic phosphorus compound, which may be a hydrocarbyl phosphite; or (ii) an amine salt of a phosphorus compound,
  • a detergent typically present in an amount to deliver 1 10 to 700ppm, 130 to 600ppm, 150 to 500ppm or 160 to 400ppm calcium; and wherein from about 0.01 to about 2 wt%, or from about 0.1 to about 1.75 wt%, or about 0.2 to about 1.5 wt% of the detergent comprises alkylphenol detergent described herein.
  • the thiadiazole compound may include mono- or di -hydrocarbyl substituted 2,5-dimercapto-l,3,4-thiadiazole compounds.
  • Examples of a thiadiazole include 2,5-dimercapto-l,3,4-thiadiazole, or oligomers thereof, a hydrocarbyl-substi- tuted 2,5-dimercapto-l,3,4-thiadiazole, a hydrocarbylthio-substituted 2,5-dimer- capto-l,3,4-thiadiazole, or oligomers thereof.
  • oligomers of hydrocarbyl-substi- tuted 2,5-dimercapto-l,3,4-thiadiazole typically form by forming a sulphur-sulphur bond between 2,5-dimercapto-l,3,4-thiadiazole units to form oligomers of two or more of said thiadiazole units.
  • thiadiazole compounds may also be used in the post treatment of dispersants as mentioned below in the formation of a dimercapto- thiadiazole derivative of a polyisobutylene succinimide.
  • Examples of a suitable thiadiazole compound include at least one of a di- mercaptothiadiazole, 2,5-dimercapto-[l,3,4]-thiadiazole, 3,5-dimercapto-[l ,2,4]- thiadiazole, 3,4-dimercapto-[l ,2,5]-thiadiazole, or 4-5-dimercapto-[l,2,3]-thiadia- zole.
  • the lubricant may contain a detergent aside from the aklylphenol detergent described above.
  • the detergent may be neutral or overbased, typically overbased.
  • the detergent may be calcium or magnesium containing, typically calcium containing.
  • Another component of the disclosed lubricant can be an overbased, carbonated calcium or magnesium arylsulphonate detergent having a total base number (TBN) of at least 640 as calculated on an oil-free basis, or a mixture of such detergents.
  • Detergents in general are typically overbased materials, otherwise referred to as over- based or superbased salts, which are generally homogeneous Newtonian systems having by a metal content in excess of that which would be present for neutralization according to the stoichiometry of the metal and the detergent anion.
  • the amount of excess metal is commonly expressed in terms of metal ratio, that is, the ratio of the total equivalents of the metal to the equivalents of the acidic organic compound.
  • Overbased materials are prepared by reacting an acidic material (such as carbon dioxide) with an acidic organic compound, an inert reaction medium (e.g., mineral oil), a stoichiometric excess of a metal base, and a promoter such as a phenol or alcohol.
  • the acidic organic material will normally have a sufficient number of carbon atoms, to provide oil-solubility.
  • Overbased detergents may be characterized by Total Base Number (TBN), the amount of strong acid needed to neutralize all of the material's basicity, expressed as mg KOH per gram of sample.
  • TBN is a very well-known parameter that is described in ASTM D 4739. Since overbased detergents are commonly provided in a form which contains diluent oil, for the purpose of this document, TBN is to be recalculated to an oil-free basis.
  • Various detergents may have a TBN of 100 to 1000, or 150 to 800, or, 400 to 700.
  • the detergents may have a TBN of at least 640, for instance, 650 to 1000, or even 680 to 800. In each case, the units are mg KOH/g.
  • the detergent is an overbased calcium sulphonate detergent, but other metals may also be present, whether in a sulphonate detergent (for example, an overbased magnesium arylsulphonate detergent) or a different detergent substrate (for example, an overbased calcium phenate detergent).
  • the metal compounds generally useful in making the basic metal salts are generally any Group 1 or Group 2 metal compounds (CAS version of the Periodic Table of the Elements). Examples include alkali metals such as sodium, potassium, lithium, copper, magnesium, calcium, barium, zinc, and cadmium. In one embodiment the metals are sodium, magnesium, or calcium.
  • the anionic portion of the salt may be hydroxide, oxide, carbonate, borate, or nitrate.
  • the detergents may be calcium or magnesium detergents, typically prepared using calcium or magnesium oxide or calcium or magnesium hydroxide. Since the detergents of particular interest are carbonated detergents, they will be materials that have been treated with carbon dioxide. Such treatment leads to more efficient incorporation of basic metal into the composition. Formation of high TBN detergents involving reaction with carbon dioxide is disclosed, for instance, in US 7,238,651, Kocsis et al., July 3, 2007, see, for instance, examples 10-13 and the claims. Other detergents, however, may also optionally be present, which need not be carbonated or need not be so highly overbased (i.e., of lower TBN).
  • the overbased calcium or magnesium arylsulphonate detergent is present as the predominant amount by weight of the metal detergents, that is, at least 50 weight percent or at least 60 or 70 or 80 or 90 weight percent of the metal -containing detergents, on an oil free basis.
  • the lubricants may contain an overbased sulphonate detergent.
  • Suitable sulphonic acids include sulphonic and thiosulphonic acids, including mono- or poly- nuclear aromatic or cycloaliphatic compounds.
  • Certain oil-soluble sulphonates may be represented by R 2 -T-(S0 3 " ) a or R 3 -(S0 3 " )b, where a and b are each at least one; T is a cyclic nucleus such as benzene or toluene; R 2 is an aliphatic group such as alkyl, alkenyl, alkoxy, or alkoxyalkyl; (R 2 )-T typically contains a total of at least 15 carbon atoms; and R 3 is an aliphatic hydrocarbyl group typically containing at least 15 carbon atoms.
  • the groups T, R 2 , and R 3 may also contain other inorganic or organic substit- uents; they may also be described as hydrocarbyl groups.
  • the sulphonate detergent may be a predominantly linear alkylbenzenesulphonate detergent as described in paragraphs [0026] to [0037] of US Patent Application 2005-065045.
  • the linear alkyl (or hydrocarbyl) group may be attached to the benzene ring anywhere along the linear chain of the alkyl group, but often in the 2, 3, or 4 position of the linear chain, and in some instances predominantly in the 2 position.
  • the alkyl (or hydrocarbyl) group may be branched, that is, formed from a branched olefin such as propylene or 1-butene or isobutene.
  • Sulphonate detergents having a mixture of linear and branched alkyl groups may also be used.
  • the carbonated calcium or magnesium arylsulpho- nate detergent may be based on an alkylated and sulphonated benzene; in another embodiment, it may be based on an alkylated and sulphonated toluene.
  • the detergent is a mon- oalkylbenzenemonosulphonate, and in another embodiment it is a monoalkyltolu- enemonosulphonate.
  • alkyl group it may contain a sufficient number of carbon atoms to impart oil-solubility to the detergent, such as at least 8 carbon atoms, or 10 to 100 carbon atoms, or 10 to 50 carbon atoms, or 12 to 36 carbon atoms, or 14 to 24 or 16 to 20 or alternatively about 18 carbon atoms. If more than one alkyl group (other than methyl) is present, each alkyl group may have the afore-described number of carbon atoms, or all the alkyl groups together may have in total the afore-described number of carbon atoms, (e.g., two C 12 alkyl groups for a total of 24 carbon atoms in the alkyl groups).
  • overbased material that may additionally be present (that is, in addition to the alkylphenol detergent described above) in certain embodiments of the present invention is an overbased phenate detergent.
  • an overbased phenate detergent Certain commercial grades of calcium or magnesium sulphonate detergents contain minor amounts of calcium or magnesium phenate detergents to aid in their processing or for other reasons and may contain, for instance, 4% phenate substrate content and 96% sulphonate substrate content.
  • the phenols useful in making phenate detergents may be represented by (R 1 )a-Ar-(OH)b, where R 1 is an aliphatic hydrocarbyl group of 4 to 400 or 6 to 80 or 6 to 30 or 8 to 25 or 8 to 15 carbon atoms; Ar is an aromatic group such as benzene, toluene or naphthalene; a and b are each at least one, the sum of a and b being up to the number of displaceable hydrogens on the aromatic nucleus of Ar, such as 1 to 4 or 1 to 2. There is typically an average of at least 7 or 8 aliphatic carbon atoms provided by the R 1 groups for each phenol compound, and in some instances about 12 carbon atoms.
  • Phenate detergents are also sometimes provided as sulphur-bridged species or as methylene-bridged species.
  • Sulphur-bridged species may be prepared by reacting a hydrocarbyl phenol with sulphur.
  • Methylene-bridged species may be prepared by re- acting a hydrocarbyl phenol with formaldehyde (or a reactive equivalent such as paraformaldehyde). Examples include sulphur-bridged dodecylphenol (overbased Ca salt) and methyl ene-coupled heptylphenol.
  • an optional, additional overbased material is an overbased saligenin detergent.
  • Overbased saligenin detergents are commonly over- based magnesium salts which are based on saligenin derivatives.
  • a general example of such a saligenin derivative may be represented by the formula:
  • X is -CHO or -CH 2 OH
  • Y is -CH 2 - or -CH 2 OCH 2 -
  • the -CHO groups typically comprise at least 10 mole percent of the X and Y groups
  • M is hydrogen, ammonium, or a valence of a metal ion (that is, if M is multivalent, one of the valences is satisfied by the illustrated structure and other valences are satisfied by other species such as anions or by another instance of the same structure)
  • Ri is a hydrocarbyl group of 1 to 60 carbon atoms
  • m is 0 to typically 10
  • each p is independently 0, 1 , 2, or 3, provided that at least one aromatic ring contains an R 1 substituent and that the total number of carbon atoms in all R 1 groups is at least 7.
  • one of the X groups may be hydrogen.
  • M is a valence (or equivalent) of a Mg ion or a mixture of Mg and hydrogen.
  • Saligenin detergents are disclosed in greater detail in U. S. Patent 6,3 10,009, with special reference to their methods of synthesis (Column 8 and Example 1) and preferred amounts of the various species of X and Y (Column 6).
  • Salixarate detergents are overbased materials that may be represented by a compound comprising at least one unit of formula (I) or formula (II):
  • R 3 is hydrogen, a hydrocarbyl group, or a valence of a metal ion;
  • R 2 is hydroxyl or a hydrocarbyl group, and j is 0, 1, or 2;
  • R 6 is hydrogen, a hydrocarbyl group, or a hetero- substituted hydrocarbyl group; either R 4 is hydroxyl and R 5 and R 7 are independently either hydrogen, a hydrocarbyl group, or hetero-sub- stituted hydrocarbyl group, or else R 5 and R 7 are both hydroxyl and R 4 is hydrogen, a hydrocarbyl group, or a hetero- substituted hydrocarbyl group; provided that at least one of R 4 , R 5 , R 6 and R 7 is hydrocarbyl containing at least 8 carbon atoms; and wherein the molecules on average contain at least one of unit (I) or (III) and at least one of unit (II) or (
  • the divalent bridging group "A,” which may be the same or different in each occurrence, includes -CH2- and - CH2OCH2- , either of which may be derived from formaldehyde or a formaldehyde equivalent (e.g., paraform, formalin).
  • Salixarate derivatives and methods of their preparation are described in greater detail in U.S. patent number 6,200,936 and PCT Publication WO 01/56968. It is believed that the salixarate derivatives have a predominantly linear, rather than mac- rocyclic, structure, although both structures are intended to be encompassed by the term "salixarate.”
  • a salixarate detergent may contain a portion of molecules represented (prior to neutralization) by the structure:
  • R groups are independently hydrocarbyl groups containing at least 8 carbon atoms.
  • Glyoxylate detergents are also optional overbased materials. They are based on an anionic group which, in one embodiment, may have the structure:
  • each R is independently an alkyl group containing at least 4 or 8 carbon atoms, provided that the total number of carbon atoms in all such R groups is at least 12 or 16 or 24.
  • each R may be an olefin polymer substituent.
  • the acidic material upon from which the overbased glyoxylate detergent is prepared is the condensation product of a hydroxyaromatic material such as a hydrocarbyl -substituted phenol with a carboxylic reactant such as glyoxylic acid or another omega-oxoalkanoic acid.
  • an overbased detergent is an overbased salicylate, e,g., an alkali metal or alkaline earth metal salt of a substituted salicylic acid.
  • the salicylic acids may be hydrocarbyl -substituted wherein each substituent contains an average of at least 8 carbon atoms per substituent and 1 to 3 substituents per molecule.
  • the sub- stituents may be polyalkene substituents.
  • the hydrocarbyl substituent group contains 7 to 300 carbon atoms and may be an alkyl group having a molecular weight of 150 to 2000.
  • Overbased salicylate detergents and their methods of preparation are disclosed in U. S. Patents 4,719,023 and 3,372, 116.
  • overbased detergents may include overbased detergents having a Mannich base structure, as disclosed in U.S. Patent 6,569,818.
  • the hydrocarbyl substituents on hydroxy- substituted aromatic rings in the above detergents are free of or substantially free of C 12 aliphatic hydrocarbyl groups (e.g., less than 1%, 0.1%, or 0.01% by weight of the substituents are C 12 aliphatic hydrocarbyl groups).
  • such hydrocarbyl substituents contain at least 14 or at least 18 carbon atoms.
  • the lubricant may further include an additional phosphorus containing material and may include a metal salt of a phosphorus acid.
  • Metal salts may have the formula:
  • R 8 and R 9 are independently hydrocarbyl groups containing 3 to 30 carbon atoms, are readily obtainable by heating phosphorus pentasulfide (P2S5) and an alcohol or phenol to form an 0,0-dihydrocarbyl phosphorodithioic acid.
  • the alcohol which reacts to provide the R 8 and R 9 groups may be a mixture of alcohols, for instance, a mixture of isopropanol and 4-methyl-2-pentanol, and in some embodiments a mixture of a secondary alcohol and a primary alcohol, such as isopropanol and 2-ethylhexanol.
  • the resulting acid may be reacted with a basic metal compound to form the salt.
  • the metal M having a valence n, generally is aluminum, tin, manganese, cobalt, nickel, zinc, or copper, and in many cases, zinc, to form zinc dialkyldithiophosphates.
  • Such materials are well known and readily available to those skilled in the art of lubricant formulation. Suitable variations to provide low phosphorus volatility are disclosed, for instance, in US published application 2008-0015129, see, e.g., claims.
  • amines may also be used in the invention.
  • a useful mixture of amines is "Primene® 81R” and “Primene® JMT.
  • Primene® 81R and Primene® JMT are mixtures of C l l to C 14 tertiary alkyl primary amines and C 18 to C22 tertiary alkyl primary amines respectively.
  • the hydrocarbyl amine salt of an alkylphosphoric acid ester is the reaction product of a C 14 to C 18 alkylated phosphoric acid with Primene 81RTM (produced and sold by Rohm & Haas) which is a mixture of C I 1 to C14 tertiary alkyl primary amines.
  • hydrocarbyl amine salts of dialkyldithiophosphoric acid esters include the reaction product(s) of isopropyl, methyl-amyl (4-methyl-2-pentyl or mixtures thereof), 2-ethylhexyl, heptyl, octyl or nonyl dithiophosphoric acids with ethylene diamine, morpholine, or Primene 81RTM, and mixtures thereof.
  • the dithiophosphoric acid may be reacted with an epoxide or a glycol. This reaction product is further reacted with a phosphorus acid, anhydride, or lower ester.
  • the epoxide includes an aliphatic epoxide or a styrene oxide.
  • useful epoxides include ethylene oxide, propylene oxide, butene oxide, octene oxide, dodecene oxide, styrene oxide and the like.
  • the epoxide is Propylene oxide.
  • the glycols may be aliphatic glycols having from 1 to about 12, or from about 2 to about 6, or about 2 to about 3 carbon atoms.
  • the dithiophosphoric acids, glycols, epoxides, inorganic phosphorus reagents and methods of reacting the same are described in U. S. Patent numbers 3, 197,405 and 3,544,465.
  • dithiophosphoric acid is prepared by adding phosphorus pentoxide (about 64 grams) at about 58 °C over a period of about 45 minutes to about 514 grams of hydroxypropyl 0,0-di(4- methyl-2-pentyl)phosphorodithioate (prepared by reacting di(4-methyl-2-pentyl)- phosphorodithioic acid with about 1.3 moles of propylene oxide at about 25 °C ). The mixture is heated at about 75 °C for about 2.5 hours, mixed with a diatomaceous earth and filtered at about 70 °C. The filtrate contains about 1 1.8% by weight phosphorus, about 15.2% by weight sulfur, and an acid number of 87 (bromophenol blue).
  • the additional phosphorus containing material may provide 1 % to 90 %, or 10 to 80 %, or 20 to 70 % of the total amount of phosphorus to the lubricant. In one embodiment the additional phosphorus containing material is present, and in one embodiment the additional phosphorus containing material is present is absent.
  • the lubricant may further include an antioxidant, or mixtures thereof.
  • the Antioxidant may include molybdenum compounds such as molybdenum dithiocarba- mates, sulphurised olefins, hindered phenols, aminic compounds such as alkylated diphenylamines (typically di-nonyl diphenylamine, octyl diphenylamine, or di-octyl diphenylamine).
  • the antioxidant may be present at 0 to 3 wt %, or 0.1 to 2.5 wt %, or 0.2 to 1.5 wt %.
  • the invention provides a lubricant composition comprising:
  • a dispersant typically present at 0.01 to 5 wt %, or 0.05 to 3 wt %, or 0.1 to 3 wt %, or or 0.1 to 2 wt %,
  • a friction modifier typically present at 0 to 4 wt %, or 0.1 to 4 wt %, 0.2 to 3 wt %, 0.3 to 3 wt %, 0.25 to 2.5 wt%. In one embodiment the friction modifier is present, and in an alternative embodiment the friction modifier is not present.
  • the invention provides a method of lubricating an automatic transmission comprising supplying to the automatic transmission a lubricant composition comprising:
  • a dispersant typically present at 0.5 to 3 wt %, or 1 to 2.5 wt %, or 1.5 to 4 wt %, or 1.5 to 3 wt %,
  • a phosphorus-containing antiwear agent chosen from (i) a non-ionic phosphorus compound, which may be a hydrocarbyl phosphite; or (ii) an amine salt of a phosphorus compound,
  • a thiadiazole typically present at 0.1 to 0.5 wt %,or 0.2 to 0.4 wt %, or 0.25 to 0.35 wt %.
  • a detergent typically present in an amount to deliver 40 to 700ppm, 50 to 600ppm, 60 to 500ppm or 70 to 250ppm calcium; and wherein from about 0.01 to about 2 wt%, or from about 0.1 to about 1.75 wt%, or about 0.2 to about 1.5 wt% of the detergent comprises alkylphenol detergent described herein, and
  • a friction modifier typically present at 0 to 4 wt %, or 0.1 to 4 wt %, 0.2 to 3 wt %, 0.3 to 3 wt %, 0.25 to 2.5 wt%. In one embodiment the friction modifier is present, and in an alternative embodiment the friction modifier is not present.
  • the automatic transmission includes continuously variable transmissions (CVT), infinitely variable transmissions (IVT), Toroidal transmissions, continuously slipping torque converted clutches (CSTCC), stepped automatic transmissions or dual clutch transmissions (DCT).
  • CVT continuously variable transmissions
  • IVT infinitely variable transmissions
  • CSTCC continuously slipping torque converted clutches
  • DCT dual clutch transmissions
  • the calcium-containing detergent may be an overbased detergent, a non- overbased detergent, or mixtures thereof. Typically the detergent may be overbased.
  • Patents describing the preparation of overbased calcium-containing detergents include U.S. patents 2,501,73 1 ; 2,616,905; 2,616,91 1 ; 2,616,925; 2,777,874; 3,256, 186; 3,384,585; 3,365,396; 3,320, 162; 3,3 18,809; 3,488,284; and 3,629, 109.
  • TBN values quoted and associated range of TBN is on "an as is basis,” i.e., containing conventional amounts of diluent oil.
  • Conventional amounts of diluent oil typically range from 30 wt % to 60 wt % (often 40 wt % to 55 wt %) of the detergent component.
  • the calcium-containing detergent may be a non-overbased detergent (may also be referred to as a neutral detergent).
  • the TBN of a non-overbased may be 20 to less than 200, or 30 to 100, or 35 to 50 mg KOH/g.
  • the TBN of a non-overbased calcium-containing detergent may also be 20 to 175, or 30 to 100 mg KOH/g.
  • the TBN may be lower (for example 0 to 50 mg KOH/g, or 10 to 20 mg KOH/g).
  • the calcium-containing detergent may be an overbased detergent, which may have a TBN of greater than 200 mg KOH/g (typically 250 to 600, or 300 to 500 mg KOH/g).
  • the calcium-containing detergent may be formed by the reaction of a basic calcium compound and an acidic detergent substrate.
  • the acidic detergent substrate may include an alkyl phenol, an aldehyde-coupled alkyl phenol, a sulphurised alkyl phenol, an alkyl aromatic sulphonic acid (such as, alkyl naphthalene sulphonic acid, alkyl toluene sulphonic acid or alkyl benzene sulphonic acid), an aliphatic carboxylic acid, a calixarene, a salixarene, an alkyl salicylic acid, or mixtures thereof.
  • the metal basic compound is used to supply basicity to the detergent.
  • the basic calcium compound is a compound of a hydroxide or oxide of the metal.
  • the oxides and/or hydroxides may be used alone or in combination.
  • the oxides or hydroxides may be hydrated or dehydrated, although hydrated is typical.
  • the basic calcium compound may be calcium hydroxide, which may be used alone or mixtures thereof with other metal basic compounds. Calcium hydroxide is often referred to as lime.
  • the metal basic compound may be calcium oxide which may be used alone or mixtures thereof with other metal basic compounds.
  • the detergent when the alkyl phenol, the aldehyde-coupled alkyl phenol, and the sulphurised alkyl phenol are used to prepare a calcium-containing detergent, the detergent may be referred to as a calcium phenate.
  • the calcium phenate may be an alkyl phenate, an aldehyde-coupled alkyl phenate, a sulphurised alkyl phenate, or mixtures thereof.
  • the TBN of a calcium phenate may vary from less 200, or 30 to 175 typically 150 to 175) mg KOH/g for a neutral phenate to 200 or more to 500, or 210 to 400 (typically 230 to 270) mg KOH/g for an overbased phenate.
  • the alkyl group of a phenate (i.e., an alkyl phenate) may contain 4 to 80, or 6 to 45, or 8 to 20, or 9 to 15 carbon atoms.
  • the calcium-containing detergent may be a sulphonate, or mixtures thereof.
  • the sulphonate may be prepared from a mono- or di- hydro- carbyl-substituted benzene (or naphthalene, indenyl, indanyl, or bicyclopentadienyl) sulphonic acid, wherein the hydrocarbyl group may contain 6 to 40, or 8 to 35 or 9 to 30 carbon atoms.
  • the hydrocarbyl group may be derived from polypropylene or a linear or branched alkyl group containing at least 10 carbon atoms.
  • a suitable alkyl group include branched and/or linear decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl, nonodecyl, eicosyl, un-eicosyl, do-eicosyl, tri-eicosyl, tetra-eicosyl, penta-eicosyl, hexa-eicosyl or mixtures thereof.
  • the hydrocarbyl-substituted sulphonic acid may include polypropene benzenesulphonic acid and/or C 16-C24 alkyl benzenes
  • a calcium sulphonate detergent may be a predominantly linear alkylbenzene sulphonate detergent having a metal ratio of at least 8 as is described in paragraphs [0026] to [0037] of US Patent Application 2005065045 (and granted as US 7,407,919).
  • the linear alkyl group may be attached to the benzene ring anywhere along the linear chain of the alkyl group, but often in the 2, 3 or 4 position of the linear chain, and in some instances predominantly in the 2 position.
  • a calcium sulphonate detergent may have TBN of less than 100, or less than 75, typically 20 to 50 mg KOH/g, or 0 to 20 mg KOH/g.
  • a calcium sulphonate detergent may have a TBN greater than 200, or 300 to 550, or 350 to 450 mg KOH/g.
  • the detergent may be borated or non-borated.
  • the calcium-containing detergent may be an overbased calcium sulphonate, an overbased calcium phenate, or mixtures thereof.
  • the detergent may be an overbased calcium sulphonate.
  • the calcium-containing detergent may be in a mixture with a having zinc-, barium-, sodium-, or magnesium- containing detergent.
  • the zinc-, barium-, sodium-, or magnesium- containing detergent is also well known in the art and described in the same references describing a calcium-containing detergent.
  • the TBN and metal ratios may however, differ slightly.
  • the zinc-, barium-, sodium-, or magnesium- containing detergent may be a phenate, a sulphur-containing phenate, sulphonate, salixarate or salicylate.
  • a zinc-, barium-, sodium-, or magnesium- containing detergent may be a magnesium phenate, a magnesium sulphur-containing phenate, or a magnesium sulphonate.
  • the lubricant composition may include a friction modifier, typically at least two friction modifiers. Useful friction modifiers are described below.
  • the friction modifier may be formed by the condensation of the hydroxyalkyl compound with an acylating agent or an amine.
  • an acylating agent or an amine.
  • the friction modifier disclosed in US Patent Application 60/725360 may be an amide represented by the formula R 1 R 2 N-C(0)R 3 , wherein R 1 and R 2 are each independently hydrocarbyl groups of at least 6 carbon atoms and R 3 is a hydroxyalkyl group of 1 to 6 carbon atoms or a group formed by the condensation of said hydroxyalkyl group, through a hydroxyl group thereof, with an acylating agent.
  • R 1 and R 2 are each independently hydrocarbyl groups of at least 6 carbon atoms and R 3 is a hydroxyalkyl group of 1 to 6 carbon atoms or a group formed by the condensation of said hydroxyalkyl group, through a hydroxyl group thereof, with an acylating agent.
  • Preparative Examples are disclosed in Examples 1 and 2 (paragraphs 68 and 69).
  • the amide of a hydroxylalkyl compound is prepared by reacting glycolic acid, that is, hydroxyacetic acid, HO-CH2-COOH with an amine
  • the friction modifier may be a secondary or tertiary amine being represented by the formula R 4 R 5 NR 6 , wherein R 4 and R 5 are each independently an alkyl group of at least 6 carbon atoms and R 6 is hydrogen, a hydrocarbyl group, a hydroxyl-containing alkyl group, or an amine-containing alkyl group.
  • R 4 and R 5 are each independently an alkyl group of at least 6 carbon atoms and R 6 is hydrogen, a hydrocarbyl group, a hydroxyl-containing alkyl group, or an amine-containing alkyl group.
  • the friction modifier may be derived from the reaction of a carboxylic acid or a reactive equivalent thereof with an aminoalcohol, wherein the friction modifier contains at least two hydrocarbyl groups, each containing at least 6 carbon atoms.
  • An example of such a friction modifier includes the reaction product of isostearic acid or an alkyl succinic anhydride with tris-hydroxymethylamino- methane. A more detailed description of such a friction modifier is disclosed in International Publication WO04/007652) in paragraphs 8 and 9 to 14.
  • the friction modifier includes fatty amines, borated glycerol esters, fatty acid amides, non-borated fatty epoxides, borated fatty epoxides, alkoxylated fatty amines, borated alkoxylated fatty amines, metal salts of fatty acids, fatty imidazolines, metal salts of alkyl salicylates (may also be referred to as a detergent), metal salts of sulphonates (may also be referred to as a detergent), condensation products of carboxylic acids or polyalkylene-polyamines, or amides of hydroxyalkyl compounds.
  • the friction modifier includes a fatty acid ester of glycerol.
  • the final product may be in the form of a metal salt, an amide, an imidazoline, or mixtures thereof.
  • the fatty acids may contain 6 to 24, or 8 to 18 carbon atoms.
  • the fatty acids may branched or straight-chain, saturated or unsaturated.
  • Suitable acids include 2-ethylhexanoic, decanoic, oleic, stearic, isostearic, palmitic, myristic, palmitoleic, linoleic, lauric, and linolenic acids, and the acids from the natural products tallow, palm oil, olive oil, peanut oil, corn oil, and Neat' s foot oil.
  • the fatty acid is oleic acid.
  • the metal typically the metal includes zinc or calcium; and the products include overbased and non-over- based products. Examples are overbased calcium salts and basic oleic acid-zinc salt complexes which may be represented by the general formula Zn401eate 6 0.
  • the condensation product When in the form of an amide, the condensation product includes those prepared with ammonia, or with primary or secondary amines such as diethylamine and diethanolamine.
  • the condensation product of an acid with a diamine or polyamine such as a polyethylenepolyamine.
  • the friction modifier is the condensation product of a fatty acid with C8 to C24 atoms, and a polyalkylene polyamine, and in particular, the product of isostearic acid with tetra- ethylenepentamine.
  • the friction modifier includes those formed by the condensation of the hydroxyalkyl compound with an acylating agent or an amine.
  • the friction modifier disclosed in WO2007/044820 includes an amide represented by the formula R 12 R 13 N-C(0)R 14 , wherein R 12 and R 13 are each independently hydrocarbyl groups of at least 6 carbon atoms and R 14 is a hydroxyalkyl group of 1 to 6 carbon atoms or a group formed by the condensation of said hydroxyalkyl group, through a hydroxyl group thereof, with an acylating agent.
  • the amide of a hydrox- ylalkyl compound is prepared by reacting glycolic acid, that is, hydroxyacetic acid, HO-CH2-COOH with an amine.
  • the friction modifier includes a reaction product of a di-cocoalkyl amine (or di-cocoamine) with glycolic acid.
  • the friction modifier includes compounds prepared in Preparative Examples 1 and 2 of WO 2008/014319.
  • the friction modifier includes an alkoxylated alcohol.
  • alkoxylated alcohols A detailed description of suitable alkoxylated alcohols is described in paragraphs 19 and 20 of US Patent Application 2005/0101497.
  • the alkoxylated amines are also described in US Patent 5,641,732 in column 7, line 15 to column 9, line 25.
  • the friction modifier includes a hydroxyl amine compound as defined in column 37, line 19, to column 39, line 38 of US Patent 5,534, 170.
  • the hydroxyl amine includes borated as such products are described in column 39, line 39 to column 40 line 8 of US Patent 5,534, 170.
  • the friction modifier includes an alkoxylated amine e.g., an ethoxylated amine derived from 1.8 % EthomeenTM T-12 and 0.90 % TomahTM PA-1 as described in Example E of US Patent 5,703,023, column 28, lines 30 to 46.
  • alkoxylated amine compounds include commercial alkoxylated fatty amines known by the trademark "ETHOMEEN” and available from Akzo Nobel.
  • ETHOMEENTM C/12 bis[2-hydroxyethyl]-coco-amine
  • ETHOMEENTM C/20 poly- yoxyethylene[10]cocoamine
  • ETHOMEENTM S/12 bis[2-hydroxyethyl]soyamine
  • ETHOMEENTM T/12 bis[2-hydroxyethyl]-tallow-amine
  • ETHOMEENTM T/15 polyoxyethylene-[5]tallowamine
  • ETHOMEENTM 0/12 bis[2-hydroxyethyl]oleyl- amine
  • ETHOMEENTM 18/12 bis[2— hydroxy ethyl] octadecylamine
  • ETHOMEENTM 18/25 polyoxyethylene[15]octadecylamine.
  • Fatty amines and ethoxylated fatty amines are also described in U.S. Patent 4,741,848.
  • the friction modifier includes a polyol ester as described in US Patent 5,750,476 column 8, line 40 to column 9, line 28.
  • the friction modifier includes a low potency friction modifier as described in US Patent 5,840,662 in column 2, line 28 to column 3, line 26. US Patent 5,840,662 further discloses in column 3, line 48 to column 6, line 25 specific materials and methods of preparing the low potency friction modifier.
  • the friction modifier includes a reaction product of an isomerised alkenyl substituted succinic anhydride and a polyamine as described in US Patent 5,840,663 in column 2, lines 18 to 43. Specific embodiments of the friction modifier described in US Patent 5,840,663 are further disclosed in column 3, line 23 to column 4, line 35. Preparative examples are further disclosed in column 4, line 45 to column 5, line 37 of US Patent 5,840,663.
  • the friction modifier includes an alkylphosphonate mono- or di- ester sold commercially by Rhodia under the trademark Duraphos® DMODP.
  • the condensation of a fatty acid and a polyamine typically result in the formation of at least one compound chosen from hydrocarbyl amides, hydrocarbyl imidazolines and mixtures thereof.
  • the condensation products are hydrocarbyl imidazolines.
  • the condensation products are hydrocarbyl amides.
  • the condensation products are mixtures of hydrocarbyl imidazolines and hydrocarbyl amides.
  • the condensation product is a mixture of hydrocarbyl imidazolines and hydrocarbyl amides.
  • the fatty acid may be derived from a hydrocarbyl carboxylic acid.
  • the hydrocarbyl group may be alkyl, cycloalkyl, or aryl, although alkyl is typical, and the hydrocarbyl groups may be linear or branched.
  • the fatty acid contains 8 or more, 10 or more, more 13 or 14 or more carbon atoms (including the carbon of the carboxy group).
  • the fatty acid contains 8 to 30, 12 to 24, or 16 to 18 carbon atoms.
  • Other suitable carboxylic acids may include the polycarboxylic acids or carboxylic acids or anhydrides having from 2 to 4 carbonyl groups, typically 2.
  • the polycarboxylic acids may include succinic acids and anhydrides and Diels-Alder reaction products of unsaturated monocarboxylic acids with unsaturated carboxylic acids (such as acrylic, methacrylic, maleic, fumaric, crotonic and itaconic acids).
  • unsaturated monocarboxylic acids such as acrylic, methacrylic, maleic, fumaric, crotonic and itaconic acids.
  • the fatty carboxylic acids include fatty monocarboxylic acids containing 8 to 30, 10 to 26, or 12 to 24 carbon atoms.
  • Suitable fatty acids may include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, eicosic acid and, tall oil acids.
  • the fatty acid is stearic acid, which may be used alone or in combination with other fatty acids.
  • One or both friction modifiers may in one embodiment be nitrogen-containing compounds, typically both friction modifiers are nitrogen-containing.
  • one of friction modifiers is the condensation product of a fatty acid with C8 to C24 atoms, and a polyalkylene polyamine, and in particular, the product of isostearic acid with tetraethylenepentamine.
  • the phosphorus-containing compound may be a non-ionic phosphorus compound.
  • the phosphorus-containing compounds comprise two or more (possibly up to four) non-ionic phosphorus compounds.
  • the non- ionic phosphorus compound may have an oxidation of +3 or +5.
  • the different embodiments comprise phosphite ester, phosphate esters, or mixtures thereof.
  • the phosphorus-containing compound comprises a non-ionic phosphorus compound (a C 4-6 hydrocarbyl phosphite) and an amine salt of a phosphorus acid or ester.
  • the phosphorus-containing compound comprises a non-ionic phosphorus compound that is a C 4 -6 hydrocarbyl phosphite, or mixtures thereof.
  • the C 4-6 hydrocarbyl phosphite includes those represented by the formula:
  • each R' " may be independently hydrogen or a hydrocarbyl group having 4 to 6 carbon atoms, typically 4 carbon atoms, with the proviso that at least one of the R' ' ' groups is hydrocarbyl.
  • the C 4-6 hydrocarbyl phosphite comprises dibutyl phosphite.
  • the C 4-6 hydrocarbyl phosphite may deliver at least 175 ppm, or at least 200 ppm of the total amount of phosphorus delivered by the phosphorus-containing compounds.
  • the C 4- 6 hydrocarbyl phosphite may deliver at least 45 wt %, or 50 wt % to 100 wt %, or 50 wt % to 90 wt % or 60 wt % to 80 wt % of the total amount of phosphorus from the phosphorus-containing compound.
  • the phosphorus-containing compounds may comprise a second phosphite whose formula is similar to that disclosed above, except R'" may contain 2 to 40, 8 to 24 or 1 1 to 20 carbon atoms, with the proviso that the second phosphite is not a C4-6 hydrocarbyl phosphite.
  • hydrocarbyl groups examples include propyl, dodecyl, butadecyl, hexadecyl, octadecyl, propenyl, dodecenyl, butadecenyl, hexa- deencyl, or octadecenylgroups.
  • alk(en)yl is intended to include moieties that have an alkyl and/or alkenyl group.
  • the phosphorus-containing compounds include a mixture of a C4-6 hydrocarbyl phosphite (typically dibutyl phosphite) and a C 12-18 alk(en)yl hydrogen phosphite and optionally phosphoric acid. In different embodiments the phosphoric acid is present or absent.
  • the phosphorus-containing compounds include a mixture of a C4-6 hydrocarbyl phosphite (typically dibutyl phosphite) and a C 16-18 alk(en)yl hydrogen phosphite.
  • the alk(en)yl hydrogen phosphite be may an alkyl hydrogen phosphite, and alkenyl hydrogen phosphite, or a mixture of alkenyl hydrogen phosphite and alkyl hydrogen phosphite.
  • the alk(en)yl hydrogen phosphite be may a mixture of alkenyl hydrogen phosphite and alkyl hydrogen phosphite and optionally phosphoric acid.
  • the phosphoric acid may be present or absent.
  • the phosphorus-containing compounds include a mixture of a C4-6 hydrocarbyl phosphite (typically dibutyl phosphite) and a Cn-14 alk(en)yl hydrogen phosphite.
  • the alk(en)yl hydrogen phosphite be may an alkyl hydrogen phosphite, and alkenyl hydrogen phosphite, or a mixture of alkenyl hydrogen phosphite and alkyl hydrogen phosphite.
  • the alk(en)yl hydrogen phosphite may be a mixture of alkenyl hydrogen phosphite and alkyl hydrogen phosphite and optionally phosphoric acid.
  • the phosphorus-containing compounds include a mixture of a C4-6 hydrocarbyl phosphite (typically dibutyl phosphite) and phosphoric acid.
  • the lubricant composition in one embodiment includes a package that comprises a phosphorus-containing compound and a non-ionic phosphorus compound that is a hydrocarbyl phosphite.
  • the lubricant composition further comprises a C 8 -2o hy- drocarbyl phosphite, or a C 12 . 18 hydrocarbyl phosphite, or C 16 -i8 hydrocarbyl phosphite.
  • the lubricant composition includes an amine antioxidant.
  • the amine antioxidant may be a phenyl-a-naphthylamine (PANA) or a hydrocarbyl substituted diphenylamine, or mixtures thereof.
  • the hydrocarbyl substituted diphenylamine may include mono- or di- C 4 to C 16 -, or C 6 to C 12-, or C9- alkyl diphenylamine.
  • the hydrocarbyl substituted diphenylamine may be octyl diphenylamine, or di-octyl diphenylamine, dinonyl diphenylamine, typically dinonyl diphenylamine.
  • the amine antioxidant may be present at 0.2 wt % to 1.2 wt %, or 0.3 wt % to 1.0 wt %, or 0.4 wt % to 0.9 wt % or 0.5 wt % to 0.8 wt %, of the lubricant composition.
  • the lubricant composition be optionally include at least one other antix- odiant that is known and includes sulphurised olefins, hindered phenols, molybdenum dithiocarbamates, and mixtures thereof.
  • the hindered phenol antioxidant often contains a secondary butyl and/or a tertiary butyl group as a sterically hindering group.
  • the phenol group is often further substituted with a hydrocarbyl group and/or a bridging group linking to a second aromatic group.
  • Suitable hindered phenol antioxidants include 2,6-di- tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl- 2,6-di-tert-butylphenol.
  • the hindered phenol antioxidant may be an ester and may include, e.g., IrganoxTM L-135 from Ciba, or butyl 3-(3,5-di-tert- butyl-4-hydroxyphenyl)propanoate.
  • the secondary antioxidant may be present at 0.1 wt % to 1 wt %, or 0.2 wt % to 0.9 wt % or 0.1 wt % to 0.4 wt %, or 0.4 wt % to 1.0 wt %, of the lubricant composition.
  • the alkylphenol detergents described herein can be employed in off-high- way vehicles, such as, for example, farm tractors and construction vehicles. Such vehicles often have a common sump that lubricates not only the transmission but also the gears, axles, and hydraulics in the vehicle.
  • the invention includes a lubricant composition comprising:
  • a dispersant typically present at 0.1 to 3 wt %, or 0.1 to 2.5 wt %, or 0.2 to 2 wt %,
  • a detergent typically present in an amount to deliver 10 to 2600ppm, 100 to 2300ppm, 200 to 2000ppm calcium; and wherein from about 0.01 to about 2 wt%, or from about 0.1 to about 1.75 wt%, or about 0.2 to about 1.5 wt% of the detergent comprises alkylphenol detergent described herein.
  • the invention includes a method of lubricating an off- highway vehicle comprising supplying to the vehicle a lubricant composition comprising:
  • a dispersant typically present at 0.1 to 3 wt %, or 0.1 to 2.5 wt %, or 0.2 to 2 wt %,
  • a phosphorus-containing antiwear agent chosen from (i) a non-ionic phosphorus compound, which may be a hydrocarbyl phosphite, such as a zinc dialkyldithio- phosphate; or (ii) an amine salt of a phosphorus compound,
  • a detergent typically present in an amount to deliver 10 to 2600ppm, 100 to 2300ppm, 200 to 2000ppm calcium; and wherein from about 0.01 to about 2 wt%, or from about 0.1 to about 1.75 wt%, or about 0.2 to about 1.5 wt% of the detergent comprises alkylphenol detergent described herein.
  • the off-highway vehicle lubricated typically has a wet-brake, a transmission, a hydraulic, a final drive, a power take-off system. These parts are typically lubricated by a single lubricant supplied from a common sump.
  • the transmission may be a manual transmission or an automatic transmission.
  • the calcium-containing detergent may be an overbased detergent, a non- overbased detergent, or mixtures thereof. Typically the detergent may be overbased.
  • the phosphorus-containing antiwear agent may include zinc dialkyldithi- ophosphate, a non-ionic phosphorus compound, which may be a hydrocarbyl phosphite; (i) a non-ionic phosphorus compound, which may be a hydrocarbyl phosphite; or (ii) an amine salt of a phosphorus compound, or mixtures thereof.
  • the lubricant composition disclosed herein contains no zinc dialkyldithiophosphate.
  • the lubricant composition disclosed herein contains zinc dialkyldithiophosphate.
  • the phosphorus-containing compound may be a non-ionic phosphorus compound.
  • the phosphorus-containing compounds comprise two or more (possibly up to four) non-ionic phosphorus compounds.
  • the non- ionic phosphorus compound may have an oxidation of +3 or +5.
  • the different embodiments comprise phosphite ester, phosphate esters, or mixtures thereof.
  • the phosphorus-containing compound comprises a non-ionic phosphorus compound (a C 4-6 hydrocarbyl phosphite) and an amine salt of a phosphorus acid or ester.
  • the phosphorus-containing compound comprises a non-ionic phosphorus compound that is a C 4 -6 hydrocarbyl phosphite, or mixtures thereof.
  • the C 4-6 hydrocarbyl phosphite includes those represented by the formula:
  • each R' " may be independently hydrogen or a hydrocarbyl group having 4 to 6 carbon atoms, typically 4 carbon atoms, with the proviso that at least one of the R' ' ' groups is hydrocarbyl.
  • the C 4-6 hydrocarbyl phosphite comprises dibutyl phosphite.
  • the C 4-6 hydrocarbyl phosphite may deliver at least 175 ppm, or at least 200 ppm of the total amount of phosphorus delivered by the phosphorus-containing compounds.
  • the C 4 -6 hydrocarbyl phosphite may deliver at least 45 wt %, or 50 wt % to 100 wt %, or 50 wt % to 90 wt % or 60 wt % to 80 wt % of the total amount of phosphorus from the phosphorus-containing compound.
  • the phosphorus-containing compounds may comprise a second phosphite whose formula is similar to that disclosed above, except R'" may contain 2 to 40, 8 to 24 or 1 1 to 20 carbon atoms, with the proviso that the second phosphite is not a C 4 -6 hydrocarbyl phosphite.
  • suitable hydrocarbyl groups include propyl, dodecyl, butadecyl, hexadecyl, octadecyl, propenyl, dodecenyl, butadecenyl, hexa- deencyl, or octadecenylgroups.
  • alk(en)yl is intended to include moieties that have an alkyl and/or alkenyl group.
  • the phosphorus-containing compounds include a mixture of a C4-6 hydrocarbyl phosphite (typically dibutyl phosphite) and a C 12-18 alk(en)yl hydrogen phosphite and optionally phosphoric acid. In different embodiments the phosphoric acid is present or absent.
  • the phosphorus-containing compounds include a mixture of a C4-6 hydrocarbyl phosphite (typically dibutyl phosphite) and a C 16-18 alk(en)yl hydrogen phosphite.
  • the alk(en)yl hydrogen phosphite be may an alkyl hydrogen phosphite, and alkenyl hydrogen phosphite, or a mixture of alkenyl hydrogen phosphite and alkyl hydrogen phosphite.
  • the alk(en)yl hydrogen phosphite be may a mixture of alkenyl hydrogen phosphite and alkyl hydrogen phosphite and optionally phosphoric acid.
  • the phosphoric acid may be present or absent.
  • the phosphorus-containing compounds include a mixture of a C4-6 hydrocarbyl phosphite (typically dibutyl phosphite) and a Cn-14 alk(en)yl hydrogen phosphite.
  • the alk(en)yl hydrogen phosphite be may an alkyl hydrogen phosphite, and alkenyl hydrogen phosphite, or a mixture of alkenyl hydrogen phosphite and alkyl hydrogen phosphite.
  • the alk(en)yl hydrogen phosphite may be a mixture of alkenyl hydrogen phosphite and alkyl hydrogen phosphite and optionally phosphoric acid.
  • the phosphorus-containing compounds include a mixture of a C4-6 hydrocarbyl phosphite (typically dibutyl phosphite) and phosphoric acid.
  • the lubricant composition in one embodiment includes a package that comprises a phosphorus-containing compound and a non-ionic phosphorus compound that is a hydrocarbyl phosphite.
  • the lubricant composition further comprises a C 8 -2o hydrocarbyl phosphite, or a C 12 . 18 hydrocarbyl phosphite, or C 16 -i8 hydrocarbyl phosphite, as described above.
  • the amine salt of a phosphorus acid may be derived from an amine salt of a phosphate.
  • the amine salt of the phosphorus acid may be represented by the formula:
  • R 3 and R 4 may be independently hydrogen or hydrocarbon typically containing 4 to 40, or 6 to 30, or 6 to 18, or 8 to 18 carbon atoms, with the proviso that at least one is a hydrocarbon group;
  • R 5 , R 6 , R 7 and R 8 may be independently hydrogen or a hydrocarbyl group, with the proviso that at least one is a hydrocarbyl group.
  • hydrocarbon groups of R 3 and/or R 4 may be linear, branched, or cyclic.
  • Examples of a hydrocarbon group for R 3 and/or R 4 include straight-chain or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl.
  • Examples of a cyclic hydrocarbon group for R 3 and/or R 4 include cyclo- pentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclopentyl, dimethylcyclopentyl, methyl ethyl cycl op entyl, diethylcyclopentyl, methyl- cyclohexyl, dimethylcyclohexyl, methylethylcyclohexyl, diethylcyclohexyl, methyl- cycloheptyl, dimethyl cycloheptyl, methylethylcycloheptyl, and diethyl cycloheptyl.
  • the phosphate may be an amine salt of a mixture of monoalkyl and dialkyl phosphoric acid esters.
  • the monoalkyl and dialkyl groups may be linear or branched.
  • the amine salt of a phosphorus acid may be derived from an amine such as a primary amine, a secondary amine, a tertiary amine, or mixtures thereof.
  • the amine may be aliphatic, or cyclic, aromatic or non-aromatic, typically aliphatic.
  • the amine includes an aliphatic amine such as a tertiary-aliphatic primary amine.
  • suitable primary amines include ethylamine, propylamine, butylamine, 2-ethylhexylamine, bis-(2-ethylhexyl)amine, octylamine, and dodecyla- mine, as well as such fatty amines as n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecyl amine and oleyamine.
  • fatty amines include commercially available fatty amines such as "Armeen®” amines (products available from Akzo Chemicals, Chicago, Illinois), such as Armeen C, Armeen O, Armeen OL, Armeen T, Armeen HT, Armeen S and Armeen SD, wherein the letter designation relates to the fatty group, such as coco, oleyl, tallow, or stearyl groups.
  • suitable secondary amines include dimethylamine, diethyla- mine, dipropylamine, dibutylamine, diamylamine, dihexylamine, diheptylamine, methyl ethylamine, ethylbutyl amine, N-methyl-l -amino-cyclohexane, Armeen® 2C and ethyl amyl amine.
  • the secondary amines may be cyclic amines such as piperidine, piperazine and morpholine.
  • tertiary amines include tri-n-butylamine, tri-n-octylamine, tri-decylamine, tri-lauryl amine, tri-hexadecylamine, and dimethyloleylamine (Armeen® DMOD).
  • the amines are in the form of a mixture.
  • suitable mixtures of amines include (i) a tertiary alkyl primary amine with 1 1 to 14 carbon atoms, (ii) a tertiary alkyl primary amine with 14 to 18 carbon atoms, or (iii) a tertiary alkyl primary amine with 18 to 22 carbon atoms.
  • tertiary alkyl primary amines include tert-butyl amine, tert-hexyl amine, tert-octyl amine (such as 1,1-dimethylhexylamine), tert-decylamine (such as 1,1 -dimethyl octylamine), tertdodecylamine, tert-tetradecylamine, tert-hexadecylamine, tert-octadecylamine, tert-tetracosanyl amine, and tert-octacosanylamine.
  • a useful mixture of amines is "Primene® 81R” or “Primene® JMT.
  • Primene® 81R and Primene® JMT are mixtures of C l l to C 14 tertiary alkyl primary amines and C 18 to C22 tertiary alkyl primary amines respectively.
  • the amine salt of a phosphorus acid may be prepared as is described in US Patent 6,468,946.
  • Column 10, lines 15 to 63 describes phosphoric acid esters formed by reaction of phosphorus compounds, followed by reaction with an amine to form an amine salt of a phosphate hydrocarbon ester.
  • Column 10, line 64, to column 12, line 23, describes preparative examples of reactions between phosphorus pentoxide with an alcohol (having 4 to 13 carbon atoms), followed by a reaction with an amine (typically Primene®81 -R) to form an amine salt of a phosphate hydrocarbon ester.
  • the sulphur-containing extreme pressure agent may be an olefin sulphide, or mixtures thereof.
  • the olefin sulphide may include a polysulphide or a sulphurised olefin such as sulphurised isobutylene, or mixtures thereof.
  • the olefin sulphide includes a polysulphide.
  • the olefin sulphide includes sulphurized isobutylene.
  • the olefin sulphide includes a mixture of a sulphurised isobutylene and a polysulphide.
  • At least 50 wt % of the polysulphide molecules are a mixture of tri- or tetra- sulphides. In other embodiments at least 55 wt %, or at least 60 wt % of the polysulphide molecules are a mixture of tri- or tetra- sulphides.
  • the polysulphide includes a sulphurised organic polysulphide from oils, fatty acids or ester, olefins or polyolefins.
  • Oils which may be sulfurized include natural or synthetic oils such as mineral oils, lard oil, carboxylate esters derived from aliphatic alcohols and fatty acids or aliphatic carboxylic acids (e.g., myristyl oleate and oleyl oleate), and synthetic unsaturated esters or glycerides.
  • natural or synthetic oils such as mineral oils, lard oil, carboxylate esters derived from aliphatic alcohols and fatty acids or aliphatic carboxylic acids (e.g., myristyl oleate and oleyl oleate), and synthetic unsaturated esters or glycerides.
  • Fatty acids include those that contain 8 to 30, or 12 to 24 carbon atoms.
  • Examples of fatty acids include oleic, linoleic, linolenic, and tall oil.
  • Sulphurised fatty acid esters prepared from mixed unsaturated fatty acid esters such as are obtained from animal fats and vegetable oils, including tall oil, linseed oil, soybean oil, rapeseed oil, and fish oil.
  • the polysulphide includes olefins derived from a wide range of alkenes.
  • the alkenes typically have one or more double bonds.
  • the olefins in one embodiment contain 3 to 30 carbon atoms. In other embodiments, olefins contain 3 to 16, or 3 to 9 carbon atoms.
  • the sulphurised olefin includes an olefin derived from propylene, isobutylene, pentene or mixtures thereof.
  • the polysulphide comprises a polyolefin derived from polymerising by known techniques, an olefin as described above.
  • the polysulphide includes dibutyl tetrasulphide, sulphurised methyl ester of oleic acid, sulphurised alkylphenol, sulphurised dipentene, sulphurised dicyclopentadiene, sulphurised terpene, and sulphurised Diels-Alder ad- ducts.
  • the lubricant may also include a sulphur-containing corrosion inhibitor.
  • the sulphur-containing corrosion inhibitor may be a thiadiazole compound, or mixtures thereof.
  • the thiadiazole compound may include mono- or di-hydrocarbyl substituted 2,5-dimercapto-l,3,4-thiadiazole compounds.
  • Examples of a thiadiazole include 2,5-dimercapto-l,3,4-thiadiazole, or oligomers thereof, a hydrocarbyl-substi- tuted 2,5-dimercapto-l,3,4-thiadiazole, a hydrocarbylthio-substituted 2,5-dimer- capto-l,3,4-thiadiazole, or oligomers thereof.
  • oligomers of hydrocarbyl-substi- tuted 2,5-dimercapto-l,3,4-thiadiazole typically form by forming a sulphur-sulphur bond between 2,5-dimercapto-l,3,4-thiadiazole units to form oligomers of two or more of said thiadiazole units.
  • thiadiazole compounds may also be used in the post treatment of dispersants as mentioned below in the formation of a dimercapto- thiadiazole derivative of a polyisobutylene succinimide.
  • Examples of a suitable thiadiazole compound include at least one of a di- mercaptothiadiazole, 2,5-dimercapto-[l,3,4]-thiadiazole, 3,5-dimercapto-[l ,2,4]- thiadiazole, 3,4-dimercapto-[l ,2,5]-thiadiazole, or 4-5-dimercapto-[l,2,3]-thiadia- zole.
  • condensation product is intended to encompass esters, amides, imides and other such materials that may be prepared by a condensation reaction of an acid or a reactive equivalent of an acid (e.g., an acid halide, anhydride, or ester) with an alcohol or amine, irrespective of whether a condensation reaction is actually performed to lead directly to the product.
  • an acid e.g., an acid halide, anhydride, or ester
  • a particular ester may be prepared by a transesterification reaction rather than directly by a condensation reaction.
  • the resulting product is still considered a condensation product.
  • each chemical component described is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material, that is, on an active chemical basis, unless otherwise indicated.
  • each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade.
  • hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
  • hydrocarbyl groups include:
  • hydrocarbon substituents that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic- substituted aromatic substituents, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring);
  • aliphatic e.g., alkyl or alkenyl
  • alicyclic e.g., cycloalkyl, cycloalkenyl
  • aromatic-, aliphatic-, and alicyclic- substituted aromatic substituents as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring);
  • substituted hydrocarbon substituents that is, substituents containing non- hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy);
  • hetero substituents that is, substituents which, while having a predominantly hydrocarbon character, in the context of this invention, contain other than carbon in a ring or chain otherwise composed of carbon atoms and encompass substituents as pyridyl, furyl, thienyl and imidazolyl.
  • Heteroatoms include sulfur, oxygen, and nitrogen.
  • no more than two, or no more than one, non-hydrocarbon substitu- ent will be present for every ten carbon atoms in the hydrocarbyl group; alternatively, there may be no non-hydrocarbon substituents in the hydrocarbyl group.
  • the term "about” means that a value of a given quantity is within ⁇ 20% of the stated value. In other embodiments, the value is within ⁇ 15% of the stated value. In other embodiments, the value is within ⁇ 10% of the stated value. In other embodiments, the value is within ⁇ 5% of the stated value. In other embodiments, the value is within ⁇ 2.5% of the stated value. In other embodiments, the value is within ⁇ 1% of the stated value.
  • the term "substantially” means that a value of a given quantity is within ⁇ 10% of the stated value. In other embodiments, the value is within ⁇ 5% of the stated value. In other embodiments, the value is within ⁇ 2.5%) of the stated value. In other embodiments, the value is within ⁇ 1% of the stated value.
  • the transitional term "comprising,” which is synonymous with “including,” “containing,” or “characterized by,” is inclusive or open-ended and does not exclude additional, un-recited elements or method steps.
  • the term also encompass, as alternative embodiments, the phrases “consisting essentially of and “consisting of,” where “consisting of excludes any element or step not specified and “consisting essentially of permits the inclusion of additional un-recited elements or steps that do not materially affect the essential or basic and novel characteristics of the composition or method under consideration.

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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)

Abstract

La technologie selon l'invention concerne l'utilisation de détergents hydrocarbyl (par ex., alkyl-)phénols toxicologiquement acceptables et leurs sels dans des huiles lubrifiantes automobiles telles que, par exemple, pour des transmissions automatiques ou manuelles.
EP16804973.2A 2015-11-17 2016-11-15 Détergents alkylphénols toxicologiquement acceptables utilisés en tant que modificateurs de frottement dans des huiles lubrifiantes automobiles Withdrawn EP3377599A1 (fr)

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US201562256325P 2015-11-17 2015-11-17
PCT/US2016/062031 WO2017087384A1 (fr) 2015-11-17 2016-11-15 Détergents alkylphénols toxicologiquement acceptables utilisés en tant que modificateurs de frottement dans des huiles lubrifiantes automobiles

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US (1) US20180355273A1 (fr)
EP (1) EP3377599A1 (fr)
CN (1) CN108463543A (fr)
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WO (1) WO2017087384A1 (fr)

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WO2017087384A1 (fr) 2017-05-26
US20180355273A1 (en) 2018-12-13
CA3005091A1 (fr) 2017-05-26
CN108463543A (zh) 2018-08-28

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