Lubricant additive composition for electric vehicle

Abstract

The disclosed technology relates to lubricant additives containing dispersants, corrosion inhibitors, phosphorus antiwear agents, antioxidants, and sulfur-free detergents. The disclosed technology also relates to a lubricating composition containing a lubricant additive, where the lubricating composition is used to lubricate a transmission of an electric vehicle, and in particular for a gearbox.

Description

Background Technology

[0001] The disclosed technology relates to a lubricating composition for electric vehicle powertrains (especially gearboxes for electric vehicles), the lubricant additive composition comprising an oil having a lubricating viscosity, a dispersant, a corrosion inhibitor, a phosphorus anti-wear agent, an antioxidant, and a sulfur-free detergent.

[0002] Electric vehicles and hybrid electric vehicles may include a power source (such as a conventional internal combustion engine, like a gasoline or diesel engine, and / or a battery power source coupled to an electric motor) in conjunction with a transmission for transmitting power to the vehicle's wheels. The transmission may include an electric motor coupled to the wheels and / or a gear reduction unit. In some applications, a lubricant reservoir containing a lubricant composition for lubricating the electric motor and the power gear reduction unit is provided.

[0003] In electric and hybrid electric vehicle applications, lubricating fluids come into contact with components of electric motors as well as components of traditional internal combustion engine gear reduction units. Therefore, suitable fluids must be applicable to a wide variety of vehicle components. For example, lubricating fluids may come into contact with the electrical windings in the motor stator and the gears in the mechanical parts of the transmission. Thus, suitable fluids for these applications must not only possess conventional lubricating properties but also be compatible with electronic components.

[0004] For a fluid to be suitable for electrical components, it must simultaneously provide good lubrication, conductivity, and cooling properties. Typically, due to the aggregation of additives commonly used in such conventional fluids, one or more of the desired properties required for electric and hybrid electric applications are compromised, thus these conventional fluids may not be suitable for electric or hybrid electric vehicles.

[0005] However, lubricants must still provide adequate lubrication, including, for example, dispersibility, cleanliness, anti-wear properties, and corrosion resistance. Similarly, maintaining low-viscosity fluids for these vehicles is desirable to improve vehicle efficiency. Therefore, new lubricant compositions are needed to achieve these often competing results. Summary of the Invention

[0006] The disclosed technology provides a lubricant additive composition containing a dispersant, a corrosion inhibitor, a phosphorus anti-wear agent, an antioxidant, and a sulfur-free detergent. Lubricants containing the lubricant additive composition may have a viscosity of 1 cSt to 32 cSt at 100°C, as measured by ASTM D445.

[0007] Lubricant additive compositions can be mixed with base oils such as API Group III base oils, Group IV base oils, or mixtures thereof to prepare lubricating compositions.

[0008] A lubricating composition containing a lubricant additive composition can be used in methods of lubricating an electric vehicle by supplying the lubricating composition to the drivetrain of the electric vehicle. In some cases, this method can be used where the drivetrain does not include a shift clutch. In some cases, the lubricant additive provides improvements in dispersibility, cleanliness, anti-wear properties, oxidation properties (control), and corrosion resistance. Detailed Implementation

[0009] The preferred features and implementation schemes will now be described in a non-restrictive manner.

[0010] One aspect of this technology is a lubricant additive composition. The lubricant additive composition can be used in conjunction with a base oil in a lubrication composition to provide lubrication in the powertrain of an electric vehicle. The lubricant additive composition may, in particular, include sufficient amounts of at least a dispersant, a corrosion inhibitor, an anti-wear additive, an antioxidant, and a sulfur-free detergent.

[0011] dispersant

[0012] Dispersants may include, for example, "succinimide dispersants," which are carboxyl dispersants prepared by reacting a hydrocarbon-substituted succinic anhydride or its reactive equivalent with an amine such as poly(ethylene amine); "amine dispersants," which are reaction products of relatively high molecular weight aliphatic or alicyclic halides with amines (such as polyalkylene polyamines); "Mannich dispersants," i.e., reaction products of alkylphenols wherein the alkyl group contains at least 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines); and "ester dispersants," which are similar to the above-described succinimide dispersants, except that they may be considered to be prepared by reacting a hydrocarbon acylated agent with an aliphatic polyol (such as glycerol, pentaerythritol, or sorbitol), as described in U.S. Patent 3,381,022.

[0013] Another class of ashless dispersants are high molecular weight esters. These substances are similar to the succinimides described above, except that they can be considered to be prepared by reacting a hydrocarbon acylating agent with an aliphatic polyol (such as glycerol, pentaerythritol, or sorbitol). Such substances are described in more detail in U.S. Patent 3,381,022. Aromatic succinates can also be prepared as described in U.S. Patent Publication 2010 / 0286414. In some cases, these ester-type dispersants can be post-treated with an amine (such as poly(ethylene amine)).

[0014] Post-treated dispersants may also be used. Post-treated dispersants are typically obtained by reacting a carboxylic acid (e.g., succinimide), amine, or Mannich dispersant with a reagent such as urea, thiourea, carbon disulfide, aldehyde, ketone, carboxylic acid, alkyl-substituted succinic anhydride, nitriles, epoxides, boron compounds such as boric acid (to produce “boronized dispersants” as described above), phosphorus compounds such as phosphoric acid or anhydride, 2,5-dimercaptothiadiazole (DMTD), or an aromatic diacid (such as terephthalic acid) having an acid group at the 1, 3, or 1, 4 position on the benzene ring.

[0015] Boronized dispersants are typically obtained by reacting a carboxylic acid (e.g., succinimidyl), amine, or Mannich dispersant with a boron compound reagent such as boric acid (to produce a "boronized dispersant"). Dispersants and their production methods are well known in the art. Boronized dispersants may be additionally functionalized with sulfur or phosphorus fractions. The dispersant component in a boonized dispersant may be a mixture of multiple dispersants of different types; optionally, at least one may be a succinimidyl dispersant. In one embodiment, the boonized dispersant may be a boronized polyisobutylene succinimidyl dispersant, wherein its polyisobutylene fraction may have a number average molecular weight of 750 to 2200, or 750 to 1600, or 950 to 1550. One or more boronized dispersants may be prepared having an N:CO ratio of 0.9:1 to 1.6:1, or 0.95:1 to 1.5:1, or 1:1 to 1.4:1. The amount of borate dispersant in the composition may be, for example, from 0.05% to 2.0% by weight. In other embodiments, the amount is from 0.1% to 1.0% or from 0.15% to 0.75% of the final blend fluid formulation. In concentrates, this amount will become proportionally higher.

[0016] Mixtures of dispersants may also be used. The nitrogen content of the dispersant may be greater than or equal to about 11,000 ppm, or greater than or equal to about 11,500 ppm, or greater than or equal to about 12,000 ppm by weight of the dispersant.

[0017] The total amount of one or more dispersants or combinations thereof in the composition (whether or not post-treated (e.g., borated or non-borated)) may be, for example, 0.01% to 3% by weight, or, for example, 0.025% to 2.75% by weight, or 0.05% to 2.5% by weight, or 1% to 2.5% by weight, although the amount will be proportionally higher on a concentrate basis. In terms of the degree to which the dispersant is borated, the dispersant may provide the composition with less than 250 ppm of boron, or less than 200 ppm of boron, or even less than 150 ppm of boron, or less than 100 ppm of boron, or less than 90 ppm of boron, or even less than 80 ppm of boron, and in some cases, less than 70 ppm of boron.

[0018] In some embodiments, the dispersant can be prepared by a method involving the presence of small amounts of chlorine or other halogens, as described in U.S. Patent 7,615,521 (see, for example, columns 4, lines 18-60 and Preparation Example A). Such dispersants typically have some carbocyclic structure at the connection between the hydrocarbon substituent and the acidic or amide “head” group. In other embodiments, the dispersant can be prepared by a thermal method involving an “ene” reaction without the use of any chlorine or other halogens, as described in U.S. Patent 7,615,521; dispersants prepared in this manner are typically derived from high vinylidene (i.e., greater than 50% terminal vinylidene) polyisobutylene (see columns 4, lines 61-5, lines 30 and Preparation Example B). Such dispersants typically do not contain the aforementioned carbocyclic structure at the connection point. In some embodiments, the dispersant can be prepared by radical catalytic polymerization of high vinylidene polyisobutylene with an alkene-bonded unsaturated acylating agent, as described in U.S. Patent 8,067,347.

[0019] The dispersant can also be a graft copolymer, which is the product of the condensation reaction of an olefin polymer to which a carboxylic acid (or equivalent) functional group is grafted, and the grafted olefin reacts with a monoamine or polyamine that may have a single primary amino group. If the olefin polymer is an ethylene / propylene copolymer, then the polyamine is not poly(ethyleneamine).

[0020] The polymer substrate will be an olefin polymer, such as those described above. The olefin polymer substrate used in the derived graft copolymer will contain grafted carboxylic acid functional groups or reactive equivalents of carboxylic acid functional groups (e.g., acid anhydrides or esters). The reactive carboxylic acid functional groups will typically exist as side groups attached via, for example, a grafting process.

[0021] Alkene-bonded unsaturated carboxylic acids are typically grafted onto the polymer backbone. These substances attached to the polymer usually contain at least one alkene bond (before the reaction) and at least one carboxylic acid (or its anhydride) group, or a polar group that can be converted into the said carboxyl group by oxidation or hydrolysis. Maleic anhydride or its derivatives are suitable. Grafting them onto olefin polymers (e.g., ethylene copolymers or terpolymers) yields two carboxylic acid functional groups. Examples of additional unsaturated carboxylic acids include maleic anhydride, itaconic anhydride, or corresponding dicarboxylic acids such as maleic acid, fumaric acid, and their esters, as well as cinnamic acid and its esters.

[0022] Alkenyl unsaturated carboxylic acids can be grafted onto polymers (such as ethylene / propylene copolymers). Radical-induced grafting of alkenyl unsaturated carboxylic acids can also be carried out in solvents (such as hexane or mineral oil). This can be done at high temperatures ranging from 100°C to 250°C, for example 120°C to 190°C, or 150°C to 180°C, for example above 160°C.

[0023] Suitable free radical initiators include peroxides, hydroperoxides, and azo compounds, typically those with boiling points greater than about 100°C and thermally decompose within the grafting temperature range to provide free radicals. Representative examples of these free radical initiators include azobisisobutyronitrile (AIBN) and 2,5-dimethyl-hex-3-yne-2,5-bis-tert-butylperoxide. The amount of initiator can be from 0.005% to 1% by weight of the reaction mixture solution. Grafting can be carried out under an inert atmosphere, such as under nitrogen cover. The resulting polymer intermediate is characterized by the presence of carboxylic acid acylation functional groups within its structure.

[0024] In an alternative embodiment, an unsaturated carboxylic acid (such as maleic anhydride) can first condense with a monoamine or polyamine that typically has a single primary amino group (as described below), and the condensation product itself is subsequently grafted onto the polymer backbone in a similar manner to that described above.

[0025] The amount of reactive carboxylic acids on the polymer chain, and especially the amount of grafted carboxylic acids on the chain, is typically 0.5% to 8% by weight, or 1% to 7% by weight, or 1.5% to 6% by weight, or in some embodiments 2% to 5% by weight, based on the weight of the polymer backbone. In some embodiments, the amount of reactive carboxylic acids on the polymer chain, and especially the amount of grafted carboxylic acids on the chain, can be about 1% to about 2% by weight, or in other embodiments about 2% to 3% by weight, or about 3% to 4% by weight, or 4% to 5% by weight. These figures represent the amount of carboxylic acid-containing species, particularly referring to maleic anhydride as the grafting material. As will be apparent to those skilled in the art, this amount can be adjusted to account for carboxylic acid-containing species having higher or lower molecular weights or higher or lower amounts of acid functional groups per molecule. Grafting can be to a certain extent an acid-functionalized polymer that provides a total acid value (TAN, according to ASTM D664) of 5 mg KOH / g to 100 mg KOH / g, 10 mg KOH / g to 80 mg KOH / g, or 15 mg KOH / g to 75 mg KOH / g, or 20 mg KOH / g to 70 mg KOH / g, or about 20 mg KOH / g to about 60 mg KOH / g or 65 mg KOH / g.

[0026] Acidic polymers react with monoamines or polyamines, typically having a single primary amino group. If the olefin polymer is an ethylene / propylene copolymer, then the polyamine is not poly(ethyleneamine). The reaction may consist of a condensation to form an imide, amide, or semiamide, or amide ester (assuming a portion of the alcohol also reacts), or an amine salt. The primary amino group will typically condense to form an amide or, in the case of maleic anhydride, an imide. It should be noted that in some embodiments, the amine will have a single primary amino group, that is, it will not have two or more primary amino groups (except for a negligible amount of additional primary amino groups that may be present throughout the amine composition, e.g., less than 5% or 2% or 1% or 0.5%, or 0.01% to 0.1%, especially 1% or less, such as 0.01% to 1% of amino groups being primary amino groups). This characteristic minimizes the amount of crosslinking that would otherwise be possible. Poly(ethyleneamine) can generally and in an oversimplified manner be described as H2N-(C2H4-NH-). n -C2H4-NH2, where n can be, for example, 2 to 6. These typically have an average of about 2 primary amino groups, and therefore are generally undesirable for use in the functionalization of ethylene / propylene copolymers, thereby minimizing or avoiding any undesirable crosslinking. In those embodiments where the polyamine is not poly(ethyleneamine), the amine component used to prepare the condensation product will be free of or substantially free of poly(ethyleneamine), such as less than 5% by weight, or less than 1% by weight, or 0.01% by weight to 0.1% by weight of the amine component being poly(ethyleneamine).

[0027] Suitable primary amines may include aromatic amines, such as amines in which the carbon atom of the aromatic ring structure is directly attached to the amino nitrogen. Amines may be monoamines or polyamines. The aromatic ring will typically be a mononuclear aromatic ring (i.e., a ring derived from benzene), but may include fused aromatic rings, such as those derived from naphthalene. Examples of aromatic amines include aniline, N-alkylaniline (such as N-methylaniline) and N-butylaniline, di-(p-methylphenyl)amine, naphthylamine, 4-aminodiphenylamine, N,N-dimethylphenyldiamine, 4-(4-nitrophenylazo)aniline (Disperse Orange 3), sulfadiazine, 4-phenoxyaniline, 3-nitroaniline, 4-aminoacetaniline, phenyl 4-amino-2-hydroxybenzoate (phenylaminosalicylate), N-(4-amino-5-methoxy-2-methyl-phenyl)-benzamide (Glass Violet B), N-(4-amino-2,5-dimethoxy-phenyl)-benzamide (Glass Blue RR), N-(4-amino-2,5-diethoxy-phenyl)-benzamide (Glass Blue BB), N-(4-aminophenyl)-benzamide, and 4-phenylazoaniline. Other examples include p-ethoxyaniline, p-dodecylaniline, cyclohexyl-substituted naphthylamine, and thiophene-substituted aniline. Other suitable aromatic amines include amino-substituted aromatic compounds and amines in which the amine nitrogen is part of the aromatic ring, such as 3-aminoquinoline, 5-aminoquinoline, and 8-aminoquinoline. Also included are aromatic amines such as 2-aminobenzimidazole, which contain a secondary amino group directly attached to the aromatic ring and a primary amino group attached to the imidazole ring. Other amines include N-(4-anilinophenyl)-3-aminobutyramide (i.e., φ-NH-φ-NH-COCH2CH(CH3)NH2). Additional aromatic amines include aminocarbazole, aminoindole, aminopyrrole, aminoinzolone, aminopteridine, mercaptotriazole, aminophenithiazine, aminopyridine, aminopyrazine, aminopyrimidine, pyridine, pyrazine, pyrimidine, aminothiadiazole, aminothiothiadiazole, and aminobenzotriazole. Other suitable amines include 3-amino-N-(4-anilinophenyl)-N-isopropylbutyramide and N-(4-anilinophenyl-3-{(3-aminopropyl)-(cocoyl)amino}butyramide. Other usable aromatic amines include various aromatic amine dye intermediates containing multiple aromatic rings linked by, for example, amide structures. Examples include substances with the general formula φ-CONH-φ-NH2, wherein the phenyl group may be substituted. Suitable aromatic amines include those in which the amine nitrogen is a substituent on an aromatic carboxylic acid compound, i.e., the nitrogen is not sp. within the aromatic ring. 2 Hybridization.

[0028] Amines can also be non-aromatic, or in other words, amines in which the amino nitrogen is not directly attached to a carbon atom of an aromatic ring, or amines in which the amine nitrogen is not part of an aromatic ring, or amines in which the amine nitrogen is not a substituent on an aromatic carboxylic acid compound. In some cases, such non-aromatic amines can be considered aliphatic or cycloaliphatic. Such amines can be straight-chain or branched, or functionalized with certain functional groups. Non-aromatic amines can include monoamines having, for example, one to eight carbon atoms, such as methylamine, ethylamine, and propylamine, as well as various higher amines. Diamines or polyamines can also be used, and will generally have only a single primary amino group. Examples include dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, dibutylaminoethylamine, 1-(2-aminoethyl)piperidine, 1-(2-aminoethyl)pyrrolidone, N,N-dimethylethylamine; 3-(dimethylamino)-1-propylamine; O-(2-aminopropyl)-O′-(2-methoxyethyl)polypropylene glycol; N,N-dimethyldipropylenetriamine, aminoethylmorpholine, 3-morpholinopropylamine; aminoethyl ethylidene urea, and aminopropylmorpholine.

[0029] In some embodiments, non-aromatic amines can be used alone or in combination with each other or in combination with aromatic amines. In some embodiments, the amount of aromatic amines may be trace compared to the amount of non-aromatic amines, or in some cases, the composition may be substantially free of or contain no aromatic amines.

[0030] In some embodiments, the grafted olefin polymer may have a nitrogen content of 0.05 wt% to 3 wt%, or 0.1 wt% to 2.5 wt%, or 0.15 wt% to 2 wt%, or 0.2 wt% to 1.75 wt%, or 0.25 wt% to 1.6 wt%, calculated using ASTM D5291.

[0031] Corrosion inhibitors

[0032] Corrosion inhibitors can also be described as metal passivators or yellow metal passivators.

[0033] Examples of corrosion inhibitors include triazoles, such as benzotriazole and 1,2,4-triazole, benzimidazole, or mixtures thereof. In one embodiment, the corrosion inhibitor comprises benzotriazole. In another embodiment, the corrosion inhibitor comprises bis(2-ethylhexyl)-[1,2,4-triazol-1-yl)methyl]amine.

[0034] The triazole comprises a triazole having a hydrocarbon group substituted at at least one of the following ring positions: 1-, 2-, 4-, 5-, 6-, or 7-. In various embodiments, the hydrocarbon group contains 1 to about 30, 1 to about 15, or 1 to about 16 carbon atoms. In one embodiment, the corrosion inhibitor comprises tolyltriazole. In one embodiment, the hydrocarbon triazole substituted at position 4-, 5-, 6-, or 7- further reacts with aldehydes and amines.

[0035] Examples of suitable alkylbenzotriazoles that also react with aldehydes and amines include N,N-bis(2-ethylhexyl)-aryl-methyl-1H-benzotriazole-1-methylamine, N,N-bis(2-ethylhexyl)-4-methyl-1H-benzotriazole-1-methylamine, N,N-bis(2-ethylhexyl)-4-methyl-1H-benzotriazole-1-methylamine, 2H-benzotriazole-2-methylamine, N-(4-methoxyphenyl)-1H-benzotriazole-1-methylamine, and N,N-bis(dodecyl) Alkyl-1H-benzotriazole-1-methylamine, N-(1H-benzotriazole-1-ylmethyl)-N-(2-ethylhexyl)-1H-benzotriazole-1-methylamine, N-methyl-N-phenyl-1H-benzotriazole-1-methylamine, 4,5,6,7-tetrahydro-N,N-di-tetrazyl-1H-benzotriazole-1-methylamine, N,N-di-octadecyl-1H-benzotriazole-1-methylamine, 5-methyl-N,N-dioctyl-1H-benzotriazole-1-methylamine, N,N-Dibutyl-1H-benzotriazole-1-methylamine, N-(4-methylphenyl)-1H-benzotriazole-1-methylamine, N,N-bis(2-ethylhexyl)-1H-benzotriazole-1-methylamine, N,N-dioctyl-2H-benzotriazole-2-methylamine, N-dodecyl-1H-benzotriazole-1-methylamine, N-phenyl-1H-benzotriazole-1-methylamine, N,N-bisdodecyl-4,5,6,7-tetrahydro-1H-benzotriazole-1-methylamine The corrosion inhibitor comprises amines, N,N-bis(2-ethylhexyl)-5-methyl-1H-benzotriazole-1-methylamine, N-octadecyl-1H-benzotriazole-1-methylamine, N,N-bisdodecyl-2H-benzotriazole-2-methylamine, N,N-dioctyl-1H-benzotriazole-1-methylamine, N-(2-ethylhexyl)-1H-benzotriazole-1-methylamine, 4,5,6,7-tetrahydro-N,N-bistetradecyl-1H-benzotriazole-1-methylamine, or mixtures thereof. In one embodiment, the corrosion inhibitor comprises N,N-bis(2-ethylhexyl)-4-methyl-1H-benzotriazole-1-methylamine or N,N-bis(2-ethylhexyl)-aryl-methyl-1H-benzotriazole-1-methylamine.

[0036] Examples of suitable alkyl 1,2,4-triazoles that also react with amines include N,N-bis(1-methylethyl)-1H-1,2,4-triazole-1-methylamine, N,N-diisobutyl-1H-1,2,4-triazole-1-methylamine, N,N-dicyclohexyl-1H-1,2,4-triazole-1-methylamine, N,N-bis(2-ethylhexyl)-1H-1,2,4-triazole-1-methylamine, 1-((1H-1,2,4-triazole- 1-yl)methyl)piperidine, N,N-bis(tetranyl)-1H-1,2,4-triazol-1-methylamine, N,N-dimethyl-1-(1H-1,2,4-triazol-1-yl)methylamine, N,N-dibutyl-1H-1,2,4-triazol-1-methylamine, N,N-dicocoyl-1-(1H-1,2,4-triazol-1-yl)methylamine, N-((1H-1,2,4-triazol-1-yl)methyl)oct-3-amine.

[0037] In various embodiments, the corrosion inhibitor is triazole. The triazole corrosion inhibitor may be present alone or in mixtures with other triazole corrosion inhibitors or other azole corrosion inhibitors, ranging from about 0.005% by weight or 0.01% by weight to about 0.1% by weight, or about 0.03% by weight to about 0.08% by weight, or about 0.04% by weight to about 0.068% by weight, or about 0.045% by weight to about 0.057% by weight of the lubricant additive composition.

[0038] Phosphorus anti-wear compounds

[0039] The lubricant additive composition contains at least one phosphorus anti-wear compound. The phosphorus anti-wear compound may be an acid, salt, or ester. In one embodiment, the phosphorus anti-wear compound is in the form of two or three, or a mixture of two to four (usually two or three) phosphorus anti-wear compounds. In some embodiments, the phosphorus anti-wear compound is in the form of a mixture of phosphite esters and phosphate amine compounds.

[0040] In some embodiments, the phosphorus anti-wear compound is a phosphite. Suitable phosphites include those having at least one hydrocarbon group with 3 or 4 or more, or 8 or more, or 12 or more carbon atoms. The phosphite can be a monoalkyl-substituted phosphite, a dialkyl-substituted phosphite, or a trialkyl-substituted phosphite.

[0041] In one embodiment, the phosphite is sulfur-free, i.e., the phosphite is not a thiophosphite.

[0042] Phosphites can be represented by the following formula:

[0043]

[0044] At least one R may be a hydrocarbon group containing at least three carbon atoms, and the other R groups may be hydrogen. In one embodiment, two of the R groups are hydrocarbon groups, and the third is hydrogen. In one embodiment, each R group is a hydrocarbon group, i.e., the phosphite is a trialkyl-substituted phosphite. The hydrocarbon group may be alkyl, cycloalkyl, aryl, acyclic, or a mixture thereof.

[0045] The R hydrocarbon group can be straight-chain or branched, usually straight-chain, and can be saturated or unsaturated, usually saturated.

[0046] In one embodiment, the phosphorus anti-wear compound may be a C3-8 hydrocarbon ester of phosphite or a mixture thereof, wherein each R may independently be hydrogen or a hydrocarbon group having 3 to 8, or 4 to 6 carbon atoms, typically 4 carbon atoms. Typically, C3-8 hydrocarbon esters of phosphite include dialkyl esters of phosphite, wherein each R is 1 to 14 carbon atoms, or 2 to 12 carbon atoms, or 3 to 8, or 4 to 6 carbon atoms. Dialkyl esters of phosphite may be, for example, dibutyl phosphite or dioleyl phosphite. C3-8 hydrocarbon esters or C3-8 dialkyl esters of phosphite may deliver at least 175 ppm or at least 200 ppm of the total phosphorus delivered by the phosphorus anti-wear compound. C3-8 alkyl esters or dialkyl esters of phosphite can deliver at least 45% by weight, or 50% to 100% by weight, or 50% to 90% by weight, or 60% to 80% by weight of the total phosphorus in the phosphorus anti-wear compound.

[0047] In one embodiment, the phosphorus anti-wear compound may be a C12-24 hydrocarbon ester of phosphorous acid or a mixture thereof, wherein each R may independently be hydrogen or a hydrocarbon group having 12 to 24, or 14 to 20, carbon atoms, typically 16 to 18 carbon atoms. Typically, C12-24 hydrocarbon esters of phosphorous acid include C16-18 dialkyl esters of phosphorous acid. Examples of alkyl groups for R3, R4, and R5 include octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, octadecenyl, nonadecanyl, eicosyl, or mixtures thereof. The C12-24 hydrocarbon ester or C12-24 dialkyl ester of phosphorous acid may be present in the lubricant additive composition at about 0.05% by weight to about 1.0% by weight, or about 0.1% by weight to about 0.5% by weight, of the lubricant additive composition.

[0048] In some embodiments, the phosphorus-containing compound may include C3-8 alkyl esters of phosphorous acid and C12-14 alkyl esters of phosphorous acid.

[0049] The phosphorus anti-wear compound may include 0.1% to 2% by weight of the additive composition, or even 0.1% to 1.8% by weight, or 0.1% to 1.4% or 1.6% by weight, or even 0.1% to 1% or 1.2% by weight of the lubricant additive composition. The phosphorus anti-wear compound may include 0.1% to 0.5% by weight of the additive composition, or even 0.1% to 0.4% by weight, or 0.1% to 0.2% by weight of the lubricant additive composition.

[0050] The phosphorus anti-wear compound may be a phosphite composition, which is the product of the reaction of monomeric phosphorous acid or its ester with at least two alkylene glycols, such as a condensation product. In one embodiment, the aforementioned phosphite does not contain zinc.

[0051] "Monomer" phosphorous acid or ester refers to phosphorous acid or ester that typically contains one phosphorus atom and can react with glycols to form oligomers, polymers, or other condensation compounds. The monomeric phosphorous acid or its ester can be phosphorous acid itself (H3PO3), although monomeric esters such as dialkyl phosphites can also be used for ease of handling or other reasons. One or more alkyl groups can be relatively low molecular weight groups having 1 to 6 or 1 to 4 carbon atoms, such as methyl, ethyl, propyl, or butyl, so that the alcohol produced upon reaction with alkylene glycols can be readily removed. An exemplary phosphate ester is dimethyl phosphite; other phosphate esters include diethyl phosphite, dipropyl phosphite, dioleyl phosphite, and dibutyl phosphite. Sulfur-containing analogs (e.g., thiophosphonites) may also be used. Other esters include trialkyl phosphonates. Mixtures of dialkyl phosphonates and trialkyl phosphonates are also available. As mentioned above, in these substances, the alkyl groups can be the same or different, and typically each alkyl group independently has 1 to 6 or 1 to 4 carbon atoms.

[0052] The monomeric phosphate or ester will react or condense with at least two alkylene glycols to form a phosphorus-based anti-wear compound, which may include a polymeric (or oligomeric) phosphate ester and optionally a monomeric substance. The first alkylene glycol (i) will be a 1,4-, 1,5-, or 1,6-alkylene glycol. That is, there will be two hydroxyl groups separated by chains of 4, 5, or 6 carbon atoms, respectively, in a 1, 4, 1, 5, or 1, 6 relationship. The first hydroxyl group may literally be on a single carbon atom, that is, on a carbon atom of the α-diol, or it may be on a higher-numbered carbon atom. For example, the glycol may also be 2,5-diol, or 2,6-diol, or 2,7-diol, or 3,6-diol, or 3,7-diol or 3,8-diol, as will be apparent to those skilled in the art. The alkylene glycol may be branched (e.g., alkyl-substituted) or unbranched, and in one embodiment is unbranched. Unbranched, i.e., branched diols (α,ω-diols), include 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. Branched or substituted diols include 1,4-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 3,3-dimethyl-1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, and 2,5-dimethyl-2,5-hexanediol. Diols having one or more secondary hydroxyl groups (such as 2,5-hexanediol) can be called branched or substituted diols, even if the carbon chain itself can be straight. The position of the hydroxyl group at the 1,4, 1,5, or 1,6 positions (that is, positions relative to each other or literal positions) can facilitate oligomerization with phosphorus substances rather than the formation of cyclic structures (which would be sterically disadvantageous). In some embodiments, the first alkylene glycol may be 1,6-hexanediol.

[0053] If desired, the first alkylene dihydroxy compound (diol) may have additional hydroxyl groups, that is, more than two per molecule, or exactly two hydroxyl groups. In one embodiment, exactly two hydroxyl groups are present per molecule. If more than two hydroxyl groups are present, and fewer than four atoms are present separating any one of the hydroxyl groups, care should be taken to ensure that there is no excessive cyclization that could interfere with the polymerization reaction. Furthermore, care should be taken to avoid over-branching or cross-linking of the product, which can lead to the formation of an undesirable gel. Such problems can be avoided by carefully controlling the reaction conditions, such as controlling the reagent ratios and order of addition, performing the reaction under appropriate dilution conditions, and reacting under low acidity conditions. These conditions can be determined by those skilled in the art through routine experiments only.

[0054] Phosphorous acid or its ester also reacts with the second alkylene glycol (ii). The second alkylene glycol is an alkyl-substituted 1,3-propanediol, wherein one or more of the alkyl substituents are located on one or more carbon atoms of the propylene unit, and the total number of carbon atoms in the alkyl-substituted 1,3-propanediol is 5 to 12, 6 to 12, 7 to 11, or 8 to 18, or in some embodiments, 9. That is, the alkyl-substituted 1,3-propanediol can be represented by the following general formula:

[0055]

[0056] The R groups may be the same or different, and may be hydrogen or alkyl groups, provided that at least one R is an alkyl group and the total number of carbon atoms in the R groups is 2 to 9 or 3 to 9, such that the total number of carbon atoms in the diol will be 5 to 12 or 6 to 12, respectively, and the same applies to other ranges of total carbon. By analogy with the 1,4-diol, 1,5-diol, or 1,6-diol mentioned above, the 1,3-diol mentioned herein refers to two hydroxyl groups in a 1,3 relationship with each other, that is, separated by a chain of 3 carbon atoms. Therefore, 1,3-diol may also be referred to as 2,4-diol or 3,5-diol. If the 1,3-diol has one or more secondary hydroxyl groups, then such a molecule will be considered a substituted diol. In one embodiment, the number of alkyl substituents is 2, and the total number of carbon atoms in the molecule is 9. Suitable substituents may include, for example, methyl, ethyl, propyl, and butyl (in the form of their various possible isomers).

[0057] Examples of second alkylene glycols may include 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butylpropane-1,3-diol, 2-ethylhexane-1,3-diol, 2,2-dibutylpropane-1,3-diol, 2,2-diisobutylpropane-1,3-diol, 2-methyl-2-propylpropane-1,3-diol, 2-propyl-propane-1,3-diol, 2-butylpropane-1,3-diol, 2-pentylpropane-1,3-diol, 2-methyl-2-propylpropane-1,3-diol, 2,2-diethylpropane-1,3-diol, 2,2,4-trimethylpentane-1,3-diol, 2-methylpentane-2,4-diol, 2,4'-dimethyl-2,4'-pentanediol, and 2,4'-hexanediol. It should be noted that, for clarity, some of the aforementioned nomenclatures emphasize the propan-1,3-diol structure of the molecule. For example, 2-pentylpropan-1,3-diol can also be named 2-hydroxymethylhept-1-ol, but the latter nomenclature does not so clearly indicate the 1,3-property of the diol.

[0058] The relative molar ratio of the first alkylene glycol (i) to the second alkylene glycol (ii) may be 30:70 to 65:35, or alternatively, 35:65 to 60:40, or 40:60 to 50:50, or 40:60 to 45:55. If the ratio is less than about 30:70, the resulting product may not fully exhibit the benefits of the disclosed technology, and if the ratio is greater than about 65:35, its compatibility with other components in the lubricant formulation may be reduced.

[0059] The ratio of the relative molar amount of the monomeric phosphorous acid or its ester (a) to the total molar amount of the alkylene glycol (b) can be 0.9:1.1 to 1.1:0.9, or 0.95:1.05 to 1.05:0.95, or 0.98:1.02 to 1.02:0.98, or about 1:1. Reactions carried out at approximately equimolar ratios tend to promote the formation of oligomers or polymers. A precise 1:1 ratio can theoretically lead to the formation of extremely long chains and thus very high molecular weights. However, in practice, this is not usually achievable because competing reactions and incomplete reactions will provide materials with lower degrees of polymerization, and a portion of the material will be in the form of cyclic monomers.

[0060] The reaction products will typically consist of a mixture of individual substances, including some oligomers or polymers and cyclic monomers. The cyclic monomers may contain one phosphorus atom and an alkylene group primarily derived from 1,3-diol(ii), as 1,3-diols are capable of participating in the formation of oligomers or cyclic esters. The oligomers or polymers typically contain 2 or 3 to 20 phosphorus atoms, or alternatively 5 to 10 phosphorus atoms, linked together by alkylene groups derived from diols(i) and (ii), and may exhibit a relatively preferential incorporation of 1,4-, 1,5-, or 1,6-diols, which are less likely to cyclize with phosphorus to form cyclic monomers.

[0061] The product may be a mixture of substances that can be represented by the structure shown:

[0062]

[0063] Where x and y represent the relative amounts of the two diols incorporated into the oligomer. The structures shown are not intended to indicate that the polymer is necessarily a block polymer, as the structures represented by the x brackets and y brackets may be more or less randomly distributed, influenced by or dependent on the availability of various diol reactants. Each X is independently a terminal group, which may be, for example, an alkyl group (such as methyl) or a hydrogen atom or a diol-derived structure terminated with an OH group. In the above schemes, diene (i) is chosen as 1,6-hexanediol and diene (ii) is chosen as 2-butyl-2-ethyl-1,3-propanediol for illustrative purposes only. Corresponding structures and mixtures will be formed using different diols (i) and (ii).

[0064] The relative amounts of oligomers and cyclic monomers in the reaction mixture will depend to some extent on the specific diol and reaction conditions chosen. For the reaction products prepared from 1,6-hexanediol and 2-butyl-2-ethyl-1,3-propanediol, as shown in the structures above, the amounts of oligomers can be approximated as shown in the table below:

[0065] mol% 1,6-diol 30 40 50 60 65 % oligomers by weight 52 58 62 70 71

[0066] Furthermore, the amount of cyclic monomer can be 100% minus the percentage of oligomers. It is also possible to prepare a mixture of oligomers and cyclic monomers having the aforementioned weight percentages, regardless of the specific diol used. In some embodiments, 55 to 60% by weight of the product is in oligomeric form, and 45 to 40% is in cyclic monomer form. In some embodiments, the relative amounts of cyclic monomers and oligomers are 1:3 to 1:1 by weight, or alternatively, 1:3 to 1:0.8.

[0067] The condensation reaction between phosphoric acid or an ester and a diol can be achieved by mixing the reagents and heating until the reaction is substantially complete. Typically, the first and second alkylene glycols can be mixed with the phosphorus compound simultaneously or almost simultaneously (i.e., usually before the reaction with one of the alkylene glycols is complete). Small amounts of a basic substance, such as sodium methoxide, may also be present. If a methyl ester of phosphorous acid is used as the reagent, the substantial completion of the reaction corresponds to the cessation of methanol precipitation and distillation from the reaction mixture. Suitable temperatures include those in the range of 100°C to 140°C, such as 110°C to 130°C or 115°C to 120°C. If the reaction temperature used exceeds about 140°C, there is a risk that the desired product may not form in a useful yield or with useful purity, as competing reactions may occur. Typically, the reaction time can be up to 12 hours, depending on the temperature, applied pressure (if any), stirring, and other variables. In some cases, reaction times of 2 to 8 hours or 4 to 6 hours may be suitable.

[0068] If desired, other monomers may be included in the reaction mixture. Specifically, the inclusion of polycarboxylic acids such as dicarboxylic acids is sometimes considered beneficial. For example, the inclusion of relatively small amounts of tartaric acid or citric acid can provide products with useful properties. The amount of polycarboxylic acid or dicarboxylic acid may be suitable for incorporating at least one or about one polycarboxylic acid or dicarboxylic acid monomer unit into each oligomer molecule of the product. In practice, the amount of polycarboxylic acid or dicarboxylic acid added to the reaction mixture may be higher than this. Without intending to be bound by any theory, it is believed that when a small amount of tartaric acid is present, it can be incorporated as a terminal unit of the polymer and can condense with the OH group of an alkylene glycol via an ester bond. Such materials can exhibit good properties in terms of abrasion protection, corrosion inhibition, and sealing performance. Suitable polycarboxylic acids (or their esters or anhydrides) include maleic acid, fumaric acid, tartaric acid, citric acid, phthalic acid, terephthalic acid, malonic acid (e.g., esters), succinic acid, malic acid, adipic acid, oxalic acid, sebacic acid, dodecanoic acid, glutaric acid, and glutamic acid. Another class of monomers that may be included are monocarboxylic acids containing a reactive hydroxyl group, or reactive equivalents of such materials, such as acid anhydrides, esters, or lactones. Examples include glyoxylic acid, caprolactone, valproic acid, and hydroxystearic acid.

[0069] The amount of the aforementioned phosphite product used in the lubricant may be sufficient to provide 0.01 to 0.3 or 0.1% by weight to the composition, or in other embodiments, 0.02 to 0.07% by weight or 0.025 to 0.05% by weight of phosphorus. Of course, the actual amount of product corresponding to these phosphorus amounts will depend on its phosphorus content. Suitable amounts of the ester product in the lubricant additive composition may be 0.01% to 1.0% by weight, or 0.02% to 0.5% by weight, or 0.03% to 0.30% by weight, or even 0.05% to 0.25% by weight.

[0070] While each of the aforementioned phosphorus anti-wear compounds may be present alone in the lubricant additive composition, the lubricant additive composition may also include a mixture of two or more. In some embodiments, the phosphorus-containing compound may include C3-8 hydrocarbon esters of phosphorous acid and phosphite ester products. In some embodiments, the phosphorus-containing compound may include each of C3-8 hydrocarbon esters of phosphorous acid, C12 to C24 hydrocarbon esters of phosphorous acid, and phosphite ester products. In any case, the phosphorus anti-wear compound shall be present in an amount delivering 100 ppm to 4000 ppm of phosphorus to the lubricant additive composition. In some embodiments, at least one phosphorus anti-wear compound may be present in an amount delivering 125 ppm to 1000 ppm of phosphorus or 150 ppm to 800 ppm of phosphorus to the lubricant additive composition.

[0071] As otherwise described, the lubricant additive composition may comprise a substantially sulfur-free alkyl phosphate. In this salt composition, in contrast to the orthophosphate (or monomeric phosphate) structure, at least 30 mol% of phosphorus atoms are in an alkyl pyrophosphate structure. The percentage of phosphorus atoms in the pyrophosphate structure may be 30 mol% to 100 mol%, or 40 mol% to 90 mol%, or 50 mol% to 80 mol%, or 55 mol% to 70 mol%, or 55 mol% to 65 mol%. The remaining phosphorus atoms may be in an orthophosphate structure or may consist partially of unreacted phosphoric acid or other phosphorus substances. In one embodiment, up to 60 mol% or up to 50 mol% of phosphorus atoms are in a monoalkyl orthophosphate salt structure or a dialkyl orthophosphate salt structure.

[0072] A substantially sulfur-free alkyl phosphate present in pyrophosphate form (sometimes referred to as the POP structure). In some embodiments, at least 80 mol% or at least 85%, 90%, 95%, or 99% of the alkyl group in the alkyl phosphate will be a primary alkyl group. In some embodiments, the alkyl group will have 4 to 22 carbon atoms, or 4 to 20 carbon atoms, or 4 to 18 carbon atoms, or even 4 to 12 carbon atoms, or 5 to 10 carbon atoms, or 6 to 8 carbon atoms. Such groups include 2-butyl, 2-pentyl, 3-pentyl, 3-methyl-2-butyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methyl-2-pentyl, and other such primary groups and their isomers having 6, 7, 8, 9, 10, 11, or 12 carbon atoms. In some embodiments, the alkyl group will have a methyl branch at the α-position of the group, for example, a 4-methyl-2-pentyl (also known as 4-methylpentyl-2-yl) group.

[0073] Such alkyl (including cycloalkyl) groups are typically generated by reacting phosphorus pentoxide (referred to herein as P2O5, although it is recognized that a more likely structure may be derived from P4O) with one or more corresponding alcohols. 10 The reaction (represented by) is used to provide it. Therefore, alkyl phosphates can be prepared by reacting phosphorus pentoxide with a primary alcohol having 4 to 12 carbon atoms and then reacting the product with a salting material, as described in further detail below.

[0074] Although it is possible to separate the pyrophosphate from the orthoester if desired, it is also possible, and is commercially preferred, to use the reaction mixture without separating the components.

[0075] In one embodiment, the phosphorus anti-wear compound may include a phosphorus-containing acid, salt, or ester, or a mixture thereof. In one embodiment, the phosphorus anti-wear compound is in the form of a mixture.

[0076] Phosphorus anti-wear compounds may include those derived from phosphoric acid, phosphorous acid, thiophosphoric acid, thiophosphorous acid, or mixtures thereof.

[0077] In one embodiment, the phosphorus anti-wear compound may include: (i) a nonionic phosphorus compound; (ii) an amine salt of a phosphorus compound; or (hi) an ammonium salt of a phosphorus compound.

[0078] In one embodiment, the phosphorus anti-wear compound may include an ammonium salt or amine salt of a phosphorus-containing acid or ester.

[0079] Amino salts of phosphoric acid or esters include phosphate esters and their amine salts; dialkyl dithiophosphate esters and their amine salts; amine salts of phosphites; and amine salts containing phosphate carboxylic esters, ethers and amides; and mixtures thereof.

[0080] The alkyl group of the phosphorus anti-wear compound can be 2 to 12 carbon atoms, or 3 to 10 carbon atoms, or 4 to 8 carbon atoms.

[0081] Amino salts of phosphates or esters can be used alone or in combination.

[0082] In one embodiment, the amine salt of phosphate or ester includes a partial amine salt, or a partial amine-metal salt compound, or a mixture thereof.

[0083] Pyrophosphates, phosphate esters, or mixtures of phosphate esters react with salifying materials. The salifying materials can be metals to form metal salts or amines to form amine salts.

[0084] The metals in the metal salt include aluminum, calcium, magnesium, strontium, chromium, iron, cobalt, nickel, zinc, tin, lead, manganese, silver, or mixtures thereof. In one embodiment, the metal is zinc.

[0085] The amine in an amine salt can be derived from R 2 3N represents, where each R 2 Independently a hydrogen or hydrocarbon group, or an ester-containing or ether-containing group, provided that at least one R 2 The functional group is a hydrocarbon group, an ester group, or an ether group (i.e., not NH3). Suitable hydrocarbon amines include primary amines having 1 to 18 carbon atoms, or 3 to 12 or 4 to 10 carbon atoms, such as methylamine, ethylamine, propylamine, isopropylamine, butylamine and its isomers, pentylamine and its isomers, hexylamine and its isomers, heptylamine and its isomers, octylamine and its isomers, such as isooctylamine and 2-ethylhexylamine, as well as higher amines. Other primary amines include dodecylamine, aliphatic amines (such as n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine, and oleylamine). Other useful aliphatic amines include commercially available aliphatic amines, such as... Amines (available from Akzo Chemicals, Chicago, Illinois), such as...

[0086] C O、 OL, T, HT, S and SD, where the letter name involves fatty groups, such as coconut oil, oil, tallow, or stearin groups.

[0087] Secondary amines that can be used include dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, methylethylamine, ethylbutylamine, bis-2-ethylhexylamine, N-methyl-1-amino-cyclohexane, 2C and ethylpentylamine. Secondary amines can be cyclic amines, such as piperidine, piperazine, and morpholine.

[0088] Suitable tertiary amines include tri-n-butylamine, tri-n-octylamine, tri-decylamine, tri-laurhodium, tri-hexadecylamine, and dimethyloleylamine. DMOD). Triisodecylamine or tridecylamine and their isomers may be used.

[0089] Examples of mixtures of amines include (i) amines having 11 to 14 carbon atoms on a tertiary alkyl primary group, (ii) amines having 14 to 18 carbon atoms on a tertiary alkyl primary group, or (iii) amines having 18 to 22 carbon atoms on a tertiary alkyl primary group. Other examples of tertiary alkyl primary amines include tertiary butylamine, tertiary hexylamine, tertiary octylamine (such as 1,1-dimethylhexylamine), tertiary decylamine (such as 1,1-dimethyloctylamine), tertiary dodecylamine, tertiary tetradecylamine, tertiary hexadecylamine, tertiary octadecylamine, tertiary tetradecylamine, and tertiary octadecylamine. In one embodiment, a useful amine mixture includes " 81R or " JMT. 81R and JMT (both manufactured and sold by Rohm & Haas) can be a mixture of C11 to C14 tertiary alkyl primary amines and C18 to C22 tertiary alkyl primary amines, respectively.

[0090] In one embodiment, the amine salt of the phosphate or ester as described above may include a concentration of about C. n To approximately C 14 Amines or mixtures thereof with tertiary alkyl primary groups. In one embodiment, the amine salt of the phosphorus compound comprises amines having about C 14 To approximately C 18 Amines of tertiary alkyl primary amines or mixtures thereof. In one embodiment, the amine salt of the phosphorus compound comprises a group having a concentration of about C. 18 To approximately C 22 Amines of tertiary alkyl primary amines or mixtures thereof.

[0091] In one embodiment, the amine salt of the phosphate or ester as described above may be C 14 To C 18 Alkylated phosphoric acid and 81R (produced and marketed by Rohm & Haas) is a reaction product, said 81R is C 11 To C 14 A mixture of tertiary alkyl primary amines. In other embodiments, the amine may be an ester-containing amine, such as an N-alkyl-substituted γ- or δ-amino (thio) ester, which is therefore a secondary amine. One or both of the O atoms in the ester group may be replaced by sulfur, but sulfur atoms may generally be absent.

[0092] One or more additional substituents or groups may be present at the α, β, γ, or δ positions of the amino ester. In one embodiment, no such substituents are present. In another embodiment, a substituent is present at the β position. That is, the substituent at the β position of the chain may include an ester, thioester, carbonyl, or hydrocarbon group. This is to be understood as encompassing similar structures of δ-amino esters.

[0093] In one embodiment, the material may be a methyl succinate diester having an amine substitution on the methyl group. In some embodiments, the material will be or will contain 2-((alkyl)-aminomethyl succinate dialkyl ester (which may also be referred to as dialkyl 2-((alkyl)aminomethyl succinate).

[0094] The N-alkyl-substituted γ-amino esters or γ-amino thioesters disclosed herein can be prepared by Michael addition of a primary amine, typically having a branched alkyl group as described above, with an vinyl unsaturated ester or thioester of the type described above. In this case, the vinyl unsaturation will be between the β and γ carbon atoms of the ester.

[0095] The N-alkyl-substituted δ-amino esters or δ-aminothioesters disclosed herein can be prepared by reductive amination of esters of 5-oxygen-substituted carboxylic acids or 5-oxygen-substituted thiocarboxylic acids. They can also be prepared by amination of esters of 5-halogen-substituted carboxylic acids or 5-halogen-substituted thiocarboxylic acids, or by reductive amination of esters of 2-amino-substituted adipic acid, or by alkylation of esters of 2-amino adipic acid.

[0096] Further detailed descriptions of N-substituted γ-amino esters and their synthesis can be found in Lubrizol's WO2014 / 074335, filed May 15, 2014. Further detailed descriptions of N-substituted δ-amino esters and their synthesis can be found in Lubrizol's PCT application PCT / US2015 / 027958, filed April 28, 2015, and US 61 / 989306, filed May 6, 2015.

[0097] Any type of amine will react to neutralize one or more acidic groups on the phosphate ester component, which will contain pyrophosphate as described above, as well as any orthophosphate that may be present.

[0098] When the amine salt is the amine salt of the above-mentioned phosphate ester, the amount of amine salt used in the lubricant may be from 0.05% to 2.0% by weight, or from 0.75% to 1.5% by weight, or from 0.1% to 1.2% by weight.

[0099] The amount of phosphorus anti-wear agent is suitable for supplying phosphorus to the lubricant formulation at a rate of 200 parts by weight per million to 3,000 parts by weight per million (ppm).

[0100] When the lubricant composition is substantially free of sulfur (less than 250 parts per million, or less than 100 parts per million, or less than 50 parts per million, or less than 25 parts per million, or even completely free of sulfur), the phosphorus anti-wear agent may be a phosphate, which is suitable for providing phosphorus to the lubricant formulation in amounts of 100 parts per million to 5,000 parts per million, or 125 parts per million to 3,000 parts per million, or 125 parts per million to 2,000 parts per million, or 125 parts per million to 2,000 parts per million, or 100 parts per million to 200 parts per million.

[0101] antioxidants

[0102] The lubricant additive composition may also include antioxidants, such as aromatic amine antioxidants, hindered phenolic antioxidants (including ester-containing hindered phenolic antioxidants), and sulfurized olefin antioxidants. These antioxidants may be present in amounts from 0.01% to 5% by weight, or from 0.15% to 3% by weight, or from 0.2% to 1.5% by weight, or from 0.2% to 1% by weight, or from 0.25% to 0.7% by weight.

[0103] In one embodiment, the lubricant additive composition of the present invention comprises an arylamine antioxidant. The arylamine antioxidant may be phenyl-α-naphthylamine (PANA), or a hydrocarbon-substituted diphenylamine, or a mixture thereof. The hydrocarbon-substituted diphenylamine may comprise mono- or di-C4 to C16-, or C6 to C12-, or C9-alkyl diphenylamines. For example, the hydrocarbon-substituted diphenylamine may be octyl diphenylamine or dioctyl diphenylamine, dinonyl diphenylamine, and typically dinonyl diphenylamine.

[0104] When present, arylamine antioxidants may be present in 0.1% to 1.2% by weight, or 0.15% to 0.8% by weight, or 0.2% to 0.6% by weight, or 0.3% to 0.5% by weight of the lubricant additive composition.

[0105] Hindered phenolic antioxidants often contain sec-butyl and / or tert-butyl groups as sterically hindered groups. The phenolic group is typically further substituted with a hydrocarbon group and / or a bridging group connected to a second aromatic group. Examples of suitable hindered phenolic 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. In one embodiment, the hindered phenolic antioxidant may be an ester and may include, for example, Irganox derived from Ciba. TM L-135 or butyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

[0106] If present, the hindered phenolic antioxidant may be present in 0.1% to 1% by weight, or 0.2% to 0.9% by weight, or 0.1% to 0.4% by weight, or 0.4% to 1.0% by weight of the lubricant additive composition.

[0107] Antioxidants also include sulfurized olefins, such as monosulfides or disulfides, or mixtures thereof. These materials typically have sulfur bonds containing one to ten sulfur atoms, such as one to four, one, or two sulfur atoms. Substances that can be sulfurized to serve as sulfurized antioxidants in lubricant additive compositions may include oils, fatty acids and esters, olefins and polyolefins prepared therefrom, terpenes, or Diels-Alder adducts. Details of methods for preparing certain such sulfurized substances can be found in U.S. Patents 3,471,404 and 4,191,659.

[0108] sulfur-free detergent

[0109] The lubricant additive composition also includes a sulfur-free detergent composition. The sulfur-free detergent may be selected from salicylates, phenolates, or salicylate detergents. Typically, this detergent is a metal-containing detergent, wherein the metal may be sodium, potassium, calcium, magnesium, or a mixture thereof.

[0110] The sulfur-free metal-containing detergent used in this invention can be a highly alkaline detergent, a non-highly alkaline detergent, or a mixture thereof. Typically, the detergent is highly alkaline.

[0111] The preparation of metal-containing detergents is known in the art. Patents describing the preparation of highly alkaline metal-containing detergents include U.S. Patents 2,501,731; 2,616,905; 2,616,911; 2,616,925; 2,777,874; 3,256,186; 3,384,585; 3,365,396; 3,320,162; 3,318,809; 3,488,284; and 3,629,109.

[0112] Detergents containing metals can be non-alkaline detergents (also known as neutral detergents). The TBN (total nitrate content) of non-alkaline detergents can be from 20 mg KOH / g to less than 200 mg KOH / g, or from 30 mg KOH / g to 100 mg KOH / g, or from 35 mg KOH / g to 50 mg KOH / g. The TBN of non-alkaline detergents containing metals can also be from 20 mg KOH / g to 175 mg KOH / g, or from 30 mg KOH / g to 100 mg KOH / g.

[0113] As used herein, the TBN values ​​and ranges cited are based "as is," i.e., containing a typical amount of diluent oil. A typical amount of diluent oil is typically between 30% and 60% by weight (typically 40% to 55% by weight) of the detergent component.

[0114] Detergents containing metals can be highly alkaline detergents with a TBN, for example, greater than 200 mg KOH / g (typically 250 mg KOH / g to 600 mg KOH / g, or 300 mg KOH / g to 500 mg KOH / g).

[0115] Highly alkaline metal-containing detergents can be formed by reacting an alkaline metal compound (e.g., an alkaline metal compound containing sodium, potassium, calcium, or magnesium) with an acidic detergent matrix. The acidic detergent matrix may include alkyl salicylic acid.

[0116] Alkaline metal compounds are used to provide alkalinity to detergents. Alkaline metal compounds are compounds of metal hydroxides or oxides.

[0117] Oxides and / or hydroxides may be used alone or in combination. Oxides or hydroxides may be hydrated or dehydrated, although hydration is typical. In one embodiment, the alkali metal compound may be calcium hydroxide, which may be used alone or in combination with other metal alkali compounds. Calcium hydroxide is commonly referred to as lime. In one embodiment, the calcium alkali compound may be calcium oxide, which may be used alone or in combination with other metal alkali compounds.

[0118] Salicylate detergents are typically derived from p-alkylphenols or usually alkylphenols. These types of alkylphenols are carboxylated to form salicylate detergents. Suitable alkyl salicylates include those alkylated with oligomers of propylene, oligomers of butene, especially tetramers and pentamers of n-butene, and those alkylated with α-olefins, isomerized α-olefins, and polyolefins such as polyisobutylene.

[0119] The detergent can be borated or non-borated.

[0120] The chemical structure of salicylate detergents is known to those skilled in the art. The standard textbook entitled "Chemistry and Technology of Lubricants," third edition, edited by RMMortier and STOrszulik, copyright 2010, pp. 220-223, provides a general disclosure of the detergents and their structures under subheading 7.2.6.

[0121] In one embodiment, the sulfur-free metal-containing detergent may be a detergent containing sodium, potassium, calcium, or magnesium, or a mixture thereof. Such detergents and their preparation are well known in the art, but may also include those developed thereafter. However, the TBN and metal ratio may vary slightly. More detailed descriptions of the terms "metal ratio," TBN, and "soap content" are known to those skilled in the art and are explained in standard textbooks, such as "Lubricant Chemistry and Processes," 3rd edition, edited by RMMortier and STOrszulik, copyright 2010, pp. 219-220, under the category of detergents in subheading 7.2.5.

[0122] In one embodiment of the invention, the detergent is a calcium-containing detergent. In one embodiment, the detergent comprises or is composed of a calcium salicylate detergent. The calcium-containing detergent is included in an amount delivering up to 2000 ppm of calcium, or 100 ppm to 1000 ppm, or 100 ppm to 600 ppm of calcium, or 100 ppm to 250 ppm, or even 400 ppm to 750 ppm of calcium to the composition.

[0123] Other additives

[0124] Lubricant additive compositions may contain additives other than those listed above.

[0125] The lubricant additive composition may also contain a poly(meth)acrylate polymer viscosity modifier. As used herein, the following ranges of viscosity modifiers are measured by GPC using polystyrene standards in the range of 350 to 100,000 weight average molecular weight.

[0126] In one embodiment, the lubricant additive composition comprises a linear poly(meth)acrylate polymer with a weight-average molecular weight of 5,000 to 25,000 or 8,000 to 20,000.

[0127] The linear poly(meth)acrylate polymer may be present in the lubricant additive composition in amounts of about 0.1 wt% to about 5 wt%, or 0.1 wt% to 4 wt%, or 0.2 wt% to 3 wt%, or 0.5 wt% to 3 wt%, or 1.0 wt% to 4 wt%, 0.6 wt% to 4 wt%, or 0.75 wt% to 3 wt%, or 0.2 wt% to 0.75 wt%.

[0128] Poly(meth)acrylate polymers can be derived from monomer compositions comprising: (a) 50% to 95% or 60% to 80% by weight of alkyl (meth)acrylate, wherein the alkyl groups of the (meth)acrylate have 10 to 15 carbon atoms; (b) 1% to 40% or 4% to 35% by weight of alkyl (meth)acrylate, wherein the alkyl groups of the (meth)acrylate have 1 to 9 carbon atoms; (c) 1% to 10% or 1% to 8% by weight of a monomer having dispersant functionality; (d) 0% to 4%, 0% to 2% or 0% by weight of a vinyl aromatic monomer (typically styrene); and (e) 0% to 9% or 0% to 6% by weight of alkyl (meth)acrylate, wherein the alkyl groups of the (meth)acrylate have 16 to 18 carbon atoms. In one embodiment, the linear polymer may contain 0% to 20% by weight of 16 to 18 alkyl esters of (meth)acrylate.

[0129] In one embodiment, the linear polymer comprises a poly(meth)acrylate (typically polymethacrylate) whose units are derived from a mixture of alkyl methacrylate monomers, wherein (a) the monomer contains 8 to 24, 10 to 18, or 12 to 15 carbon atoms in the alcohol-derived portion of the ester group, and (b) the monomer contains 6 to 11, 8 to 11, or 8 carbon atoms in the alcohol-derived portion of the ester group, and has a 2-(C1-4 alkyl) substituent, and optionally at least one monomer selected from the group consisting of: (meth)acrylates containing 1 to 7 carbon atoms in the alcohol-derived portion of the ester group and being different from (meth)acrylates (a) and (b); vinyl aromatic compounds (or vinyl aromatic monomers); and nitrogen-containing vinyl monomers; provided that no more than 60% by weight, or no more than 50% by weight, or no more than 35% by weight of the ester contains no more than 10 carbon atoms in the alcohol-derived portion of the ester group. This type of linear polymer is described in more detail in paragraphs

[0019] and

[0031] through

[0067] of US 6,124,249 or EP 0937769A1. (When written as R'C(=O)-OR, "alcohol-derived moiety" refers to the "-OR" portion of the ester, regardless of whether it is actually prepared by reaction with an alcohol). Optionally, the linear polymer may additionally contain a third monomer. The third monomer may be styrene or a mixture thereof. The third monomer may be present in amounts of 0% to 25% of the polymer composition, or 1% to 15% of the composition, 2% to 10% of the composition, or even 1% to 3% of the composition.

[0130] Typically, the molar ratio of ester(a) to ester(b) in the copolymer is in the range of 95:5 to 35:65, or 90:10 to 60:40, or 80:20 to 50:50.

[0131] The ester is typically an aliphatic ester, and typically an alkyl ester. In one embodiment, the ester of (a) may be a C12-15 alkyl ester of (meth)acrylate, and the ester of (b) may be 2-ethylhexyl (meth)acrylate.

[0132] In one embodiment, the ester group in ester (a) contains a branched alkyl group. The ester group may contain 2% to 65%, or 5% to 60%, of an ester group having a branched alkyl group. The branched alkyl group may be β-branched and may contain 8 to 60, 8 to 30, or 8 to 16 carbon atoms. For example, the branched alkyl group may be derived from 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol, 2-octyldodecanol, 2-decyltetradecanol, or mixtures thereof, or commercially available alcohols, such as those available from Sasol. Branched Guerbert alcohol.

[0133] The C1-4 alkyl substituents can be any isomer of methyl, ethyl, propyl, and butyl.

[0134] The weight-average molecular weight of linear poly(meth)acrylates can be 45,000 or less, or 35,000 or less, or 25,000 or less, or 8,000 to 25,000, or 10,000 to 35,000, or 12,000 to 20,000.

[0135] Linear polymers can be referred to as viscosity modifiers or dispersant viscosity modifiers because they can exhibit dispersant functionality. The term "dispersant viscosity modifier" as used herein does not include dispersants, which are a separate class of compounds. Linear polymers can be used as standalone viscosity modifiers (or dispersant viscosity modifiers) in the presence of 0.5% to 4% by weight of a linear (meth)acrylic acid polymer viscosity modifier with dispersant functionality, wherein the linear polymer has a weight-average molecular weight of 5,000 to 25,000 or 10,000 to 20,000, and wherein the oil having lubricating viscosity has a kinematic viscosity of 4 cSt to 6 cSt (mm² / s) at 100°C and a viscosity index of 120 to 150.

[0136] In one embodiment, the lubricant additive composition may contain only two linear polymer viscosity modifiers having dispersant functionality, wherein the linear polymers have a weight-average molecular weight of 5,000 to 25,000 or 10,000 to 20,000.

[0137] In one embodiment, the lubricant additive composition may comprise 0.1% to 4% (or 0.2% to 3%) of a linear (meth)acrylic acid polymer viscosity modifier having dispersant functionality, wherein the linear polymer has a weight-average molecular weight greater than 25,000 to 400,000 (or up to 350,000), or 30,000 to 150,000. A linear (meth)acrylic acid polymer with a weight-average molecular weight greater than 25,000 to 400,000 (or up to 350,000) may be considered chemically similar to a linear (meth)acrylic acid polymer with a weight-average molecular weight of 5,000 to 25,000, except for the difference in weight-average molecular weight.

[0138] The lubricant additive composition may include a linear polymer viscosity modifier having dispersant functionality, comprising: 0.1 wt% to 5 wt% (or 1 wt% to 4 wt%) of a linear (meth)acrylic acid polymer viscosity modifier having dispersant functionality, wherein the linear polymer has a weight-average molecular weight of 10,000 to 20,000; and 0.1 wt% to 4 wt% (or 1 wt% to 3 wt%) of a linear (meth)acrylic acid polymer viscosity modifier having dispersant functionality, wherein the linear polymer has a weight-average molecular weight of greater than 20,000 to 250,000 (or 30,000 to 150,000).

[0139] As described below, the molecular weight of viscosity modifiers has been determined using known methods, such as GPC analysis using polystyrene standards. Methods for determining the molecular weight of polymers are well-known. For example, these methods are described in: (i) P.J. Flory, “Principles of star polymer Chemistry”, Cornell University Press (1953), Chapter VII, pp. 266–315; or (ii) “Macromolecules, an Introduction to star polymer Science”, edited by F.A. Bovey and F.H. Winslow, Academic Press (1979), pp. 296–312.

[0140] In one embodiment, the lubricant additive may also include a boron-containing compound.

[0141] The lubricant additive composition may contain a boron-containing compound in an amount sufficient to provide the lubricant additive composition with about 75 ppm to about 500 ppm of boron, or about 85 ppm to about 450 ppm, or about 95 ppm to about 350 ppm of boron, or about 100 ppm to about 400 ppm of boron.

[0142] Boron can be transported through various types of boron-containing compounds.

[0143] Boron-containing compounds can be used as dispersants for post-treatment with boron sources.

[0144] Boron-containing compounds may include boron-containing friction modifiers, such as boronized aliphatic epoxides, boronized glycerides, and boronized alkoxylated aliphatic amines.

[0145] Boron-containing compounds may also include boronized detergents. Boronized detergents may include, for example, highly basic boronized materials, as described in U.S. Patents 5,403,501 and 4,792,410.

[0146] Boron-containing compounds may also include borate esters. Borate esters may be compounds represented by one or more of the following formulas:

[0147]

[0148] Each R can be independently a hydrocarbon group as defined herein, and any two adjacent R groups can together form a cyclic group. Mixtures of two or more of the foregoing may be used. The total number of carbon atoms in the R groups in each formula should be sufficient to dissolve the compound in a base oil. Typically, the total number of carbon atoms in the R groups is at least about 3, and in one embodiment at least about 5, and in another embodiment at least about 8. There is no limit to the required total number of carbon atoms in the R groups, but a practical upper limit is the absence of about 400 or about 500 carbon atoms.

[0149] In embodiments, each R can independently be a hydrocarbon group containing 1 to 14, 2 to 13, or even 3 to 10 or 12 carbon atoms, provided that the sum of the total number of carbon atoms in all Rs is 3 or more, preferably 4 or more, and even more preferably 6 or more. In some embodiments, each R can independently be a C3 to C22, C3 to C18, or C3 to C12 alkyl group. Examples of useful R groups include isopropyl, n-butyl, isobutyl, pentyl, 4-methyl-2-pentyl, 2-ethyl-1-hexyl, isooctyl, decyl, dodecyl, 2-propylheptyl, tetradecyl, 2-pentenyl, dodecenyl, phenyl, naphthyl, alkylphenyl, etc.

[0150] Suitable examples of borate esters include, for example, tripropyl borate, tributyl borate, tripentyl borate, trihexyl borate, triheptyl borate, trioctyl borate, trinonyl borate, and tridecyl borate. Other examples of borate esters may include, for example, compounds of formula I, wherein each R is independently a C3 to C22, or C3 to C18, or C3 to C12 alkyl group, such as, for example, tri-2-ethylhexyl borate, tri(2-propylheptyl) borate, and mixtures thereof. In one embodiment, the borate ester may be a C8 borate ester or a C10 borate ester. In one embodiment, the borate ester may be tri(2-propylheptyl) borate. In some embodiments, the borate ester may be tri-2-ethylhexyl borate.

[0151] In one embodiment, the borate-treated ester may be represented by the formula B(OC5H11)3 or B(OC4H9)3. In one embodiment, the borate-treated ester may be tributyl borate.

[0152] In one embodiment, the boronized ester may be a phenolic compound represented by the following formula:

[0153]

[0154] In Formula VII: R1, R2, R3, and R4 are independently hydrocarbon groups having 1 to about 12 carbon atoms; and R5 and R6 are independently alkylene groups having 1 to about 6 carbon atoms, and in one embodiment are alkylene groups having about 2 to about 4 carbon atoms, and in another embodiment are alkylene groups having about 2 or about 3 carbon atoms. In one embodiment, R1 and R2 independently contain 1 to about 6 carbon atoms, and in one embodiment are each tert-butyl groups. In one embodiment, R3 and R4 are independently hydrocarbon groups having about 2 to about 12 carbon atoms, and in one embodiment are hydrocarbon groups having about 8 to about 10 carbon atoms. In one embodiment, R5 and R6 are independently --CH2CH2-- or --CH2CH2CH2--.

[0155] In one embodiment, the boronized ester may be a compound represented by the following formula:

[0156]

[0157] In Formula IX, each R is independently a hydrogen or hydrocarbon group. Each hydrocarbon group may contain one to about 12 carbon atoms, and in one embodiment may contain one to about four carbon atoms. An example is 2,2'-oxy-bis-(4,4,6-trimethyl-1,3,2-dioxoborhexane).

[0158] Boronate esters may be used in the lubricant additive composition in amounts of about 0.2% or 0.3% to about 2.0% by weight, or in some cases about 0.35% to 2.0% by weight, and in one embodiment about 0.25% to about 1.0% by weight, and in another embodiment about 0.25% to about 0.75% by weight.

[0159] In one embodiment, the lubricant additive composition may include a polyol and an ester of an aliphatic carboxylic acid containing 12 to 24 carbon atoms.

[0160] Polyols include diols, triols, and alcohols having a higher number of OH groups. Polyols include: ethylene glycol, including diethylene glycol, triethylene glycol, and tetraethylene glycol; propylene glycol, including dipropylene glycol, tripropylene glycol, and tetrapropylene glycol; glycerol; butylene glycol; hexanediol; sorbitol; arabinitol; mannitol; sucrose; fructose; glucose; cyclohexanediol; erythritol; and pentaerythritol, including dipentaerythritol and tripentaerythritol; preferably, diethylene glycol, triethylene glycol, glycerol, sorbitol, pentaerythritol, and dipentaerythritol.

[0161] Aliphatic carboxylic acids that form esters are acids containing 12 to 24 carbon atoms. These acids are characterized by the general formula R1-(CO)OH, where R1 is a hydrocarbon group, which can be a straight-chain hydrocarbon group, a branched hydrocarbon group, a cyclic hydrocarbon group, or a mixture thereof. Preferably, it is a straight-chain hydrocarbon group containing 12 to 24 carbon atoms, for example, a straight-chain hydrocarbon group with 14 to 20 or 16 to 18 carbon atoms. These acids can also be used in combination with acids having more or fewer carbon atoms.

[0162] Typically, the acid R1-(CO)OH is a monocarboxylic acid because polycarboxylic acids tend to form polymer products if the reaction conditions and amounts of reactants are not carefully controlled. However, mixtures of monocarboxylic acids and small amounts of dicarboxylic acids or anhydrides can be used to prepare esters. Examples of carboxylic acids include dodecanoic acid, stearic acid, lauric acid, behenic acid, and oleic acid.

[0163] The aforementioned esters are, in particular, monoesters of such polyols and such carboxylic acids. Preferred esters are monooleic glycerides. It should be understood that, as with other such materials, monooleic glycerides are commercially available in grades comprising mixtures of such materials, including glycerol, oleic acid, other long-chain acids, dioleic acid glycerides, and trioleic acid glycerides. Commercially available materials are believed to contain approximately 60 ± 5% by weight of the chemical substance “monooleic acid glycerides,” 35 ± 5% of dioleic acid glycerides, and less than approximately 5% of trioleic acid esters and oleic acid. The amounts of monoesters described below are calculated based on the actual corrected amounts of polyol monoesters present in any such mixture.

[0164] The amount of the aforementioned ester in the lubricant additive composition is typically on the order of about 0.01% by weight to about 1.0% by weight of the lubricant additive composition, but may also be about 0.05% by weight to about 0.5% by weight, or 0.8% by weight, or about 0.1% by weight to about 0.6% by weight.

[0165] In addition to the aforementioned esters, the lubricant additive composition may also contain alcohols and esters of aliphatic carboxylic acids containing about 4 to about 8 carbon atoms.

[0166] Alcohols include both monohydric alcohols and polyhydric alcohols (i.e., polyols). The carbon atoms in alcohols can be straight-chained, branched, or a mixture thereof.

[0167] The appropriate polyols are the same as those described above.

[0168] When branched, the alcohol can be a Gerbert alcohol or a mixture thereof. Gerbert alcohols may have alkyl groups including: 1) alkyl groups containing C15-16 polymethylene groups, such as 2-C1-15 alkyl-hexadecyl groups (e.g., 2-octylhexadecyl) and 2-alkyl-octadecyl groups (e.g., 2-ethyloctadecyl, 2-tetradecyl-octadecyl, and 2-hexadecyloctadecyl); 2) alkyl groups containing C13-14 polymethylene groups, such as 1-C1-15 alkyl-tetradecyl groups (e.g., 2-hexyltetradecyl, 2-decyltetradecyl, and 2-undecyltridecyl) and 2-C1-15 alkyl-hexadecyl groups (e.g., 2-ethyl-hexadecyl and 2-dodecylhexadecyl); 3) alkyl groups containing C10-12 polymethylene groups, such as 2-C1-15 alkyl-dodecyl groups (e.g., 2-octyldodecyl) and 2-C1-15 alkyl-dodecyl groups (2-hexyldodecyl and 2-octyl... 4) Alkyl groups containing C6-9 polymethylene groups, such as 2-C1-15 alkyl-tetradecyl groups (e.g., 2-hexyltetradecyl and 2-decyltetradecyl); 5) Alkyl groups containing C1-5 polymethylene groups, such as 2-(3-methylhexyl). -7-methyl-decyl and 2-(1,4,4-trimethylbutyl)-5,7,7-trimethyl-octyl groups; and 6) and mixtures of two or more branched alkyl groups, such as alkyl residues of carbonyl synthetic alcohols corresponding to propylene oligomers (from hexamer to undeterminer), ethylene / propylene (molar ratio 16:1-1:11) oligomers, isobutylene oligomers (from pentamer to octamer), and C5-17α-olefin oligomers (from dimer to hexamer).

[0169] Examples of suitable branched monohydric alcohols include 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol, 2-octyldodecanol, 2-decyltetradecanol, isotridecanol, isooctanol, oleyl alcohol, Guerbert alcohol, or mixtures thereof. Examples of linear monohydric alcohols include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanool, or mixtures thereof. In one embodiment, the monohydric alcohol contains 6 to 30, 8 to 20, or 8 to 15 carbon atoms (typically 8 to 15 carbon atoms).

[0170] Aliphatic carboxylic acids that form esters are acids containing 4 to 8 carbon atoms. Although aliphatic, aliphatic carboxylic acids may contain olefinically unsaturated groups along their C4 to C8 alkyl backbone. Furthermore, these acids can be monocarboxylic acids, dicarboxylic acids, acid anhydrides, or mixtures thereof. Examples of carboxylic acids include, for instance, succinic acid, maleic acid, fumaric acid, pentenoic acid, glutaric acid, adipic acid, citralic acid, mesonic acid, pimelic acid, octanoic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, etc.

[0171] Particularly preferred esters may be adipates, such as, for example, C8-13 or C8-12 adipates, such as diisooctyl adipate or ditridecyl adipate. Other esters may include, for example, pentaerythritol esters, neopentyl esters, and trimethylol esters.

[0172] The amount of the aforementioned ester in the lubricant additive composition is typically on the order of about 0.1 wt% to about 3.0 wt% of the lubricant additive composition, but may also be about 0.2 wt% to about 2.5 wt% or about 0.3 wt% to about 2.0 wt%.

[0173] Carboxylic acid esters are prepared by a well-known reaction of at least one carboxylic acid (or its reactive equivalent, such as an ester, halide, or anhydride) with at least one of the aforementioned hydroxyl compounds.

[0174] Another component of the lubricant additive composition may be a metal deactivator. Examples of such materials include 2,5-dimercapto-1,3,4-thiadiazole and / or its derivatives. Such materials are described in European Patent Publication 0761805, which is incorporated herein by reference.

[0175] The metal deactivators used in this paper reduce the corrosion of metals such as copper. Metal deactivators are also known as metal passivators. These metal deactivators are typically nitrogen- and / or sulfur-containing heterocyclic compounds, such as dimercaptothiadiazole, triazole, aminomercaptothiadiazole, imidazole, thiazole, tetraazole, hydroxyquinoline, oxazoline, imidazoline, thiophene, indole, indazole, quinoline, benzoxazine, dithiol, oxazole, oxtriazole, pyridine, piperazine, triazine, and any one or more derivatives thereof. The metal deactivator preferably contains at least one triazole, which may be substituted or unsubstituted. Examples of suitable compounds are benzotriazoles, alkyl-substituted benzotriazoles (e.g., tolyltriazole, ethylbenzotriazole, hexylbenzotriazole, octylbenzotriazole, etc.), aryl-substituted benzotriazoles (e.g., phenol benzotriazole, etc.), and alkylaryl or aralkyl-substituted benzotriazoles and substituted benzotriazoles, wherein the substituents may be hydroxyl, alkoxy, halogen (especially chlorine), nitro, carboxyl, and carboxyalkoxy. Preferably, the triazole is a benzotriazole or alkylbenzotriazole wherein the alkyl group contains 1 to about 20 carbon atoms, preferably 1 to about 8 carbon atoms. Benzotriazoles and tolyltriazoles are useful.

[0176] In one embodiment, the metal deactivator is the reaction product of a dispersant and a dimercaptothiadiazole. Dispersants are generally characterized as reaction products of carboxylic acids with amines and / or alcohols. These reaction products are commonly used as dispersants in the lubricant field and are sometimes collectively referred to as dispersants, although they may have other uses besides or as substitutes for dispersants. Carboxylic acid dispersants include succinimidyl dispersants, ester dispersants, etc. Succinimidyl dispersants are generally the reaction products of polyamines with alkenyl succinic anhydrides or acids. Ester dispersants are the reaction products of alkenyl succinic anhydrides or acids with polyol compounds. The reaction products can then be further treated with amines such as polyamines. Examples of useful dispersants are disclosed in U.S. Patent Nos. 3,219,666 and 4,234,435, which are incorporated herein by reference. Useful dispersants also include ashless dispersants discussed below. Typically, the reaction between the dispersant and the dimercaptothiadiazole occurs by mixing the dispersant and heating to a temperature above about 100°C. U.S. Patent Nos. 4,140,643 and 4,136,043 describe compounds prepared by reacting such dispersants with dimercaptothiadiazoles. These patents are incorporated herein by reference for their disclosure of dispersants, dimercaptothiadiazoles, methods of reacting the two, and products obtained from such reactions.

[0177] In one embodiment, the metal deactivator is the reaction product of phenol and dimercaptothiadiazole. The phenol is preferably an alkylphenol, wherein the alkyl group contains at least about 6, preferably from 6 to about 24, more preferably from about 6 or about 7 to about 12 carbon atoms. The aldehyde is preferably an aldehyde or aldehyde synthon containing 1 to about 7 carbon atoms, such as formaldehyde. Preferably, the aldehyde is formaldehyde or paraformaldehyde. The aldehyde, phenol, and dimercaptothiadiazole are typically reacted by mixing them at temperatures up to about 150°C, preferably from about 50°C to about 130°C, in a molar ratio of about 0.5 moles to about 2 moles of phenol and about 0.5 moles to about 2 moles of aldehyde per mole of dimercaptothiadiazole. Preferably, the three reagents react in equal molar amounts.

[0178] In one embodiment, the metal deactivator is a bis(alkyldithio)thiadiazole. Preferably, each alkyl group is independently an alkyl, aryl, or aralkyl group having 6 to about 24 carbon atoms. Each alkyl group may be independently tert-octyl, nonyl, decyl, dodecyl, or ethylhexyl. The metal deactivator may be bis-2,5-tert-octyl-dithio-1,3,4-thiadiazole or a mixture thereof with 2-tert-octylthio-5-mercapto-1,3,4-thiadiazole. These materials are commercially available under the trade name Amoco 150 from Amoco Chemical Company. These dithiothiadiazole compounds are disclosed as component (d) in PCT Publication WO 88 / 03551, which is incorporated herein by reference for the dithiothiadiazole compounds disclosed therein. In a preferred embodiment, the metal deactivator is a dimercaptothiadiazole derivative. Specific examples are given below in D-1 and D-2.

[0179] Example D-1

[0180] Oxidative coupling of 2,5-dimercapto-1,3,4-thiadiazole with tert-nonylthiol; 100% chemical, 36% S, 64% N.

[0181] Example D-2

[0182] Heptaylphenol was coupled with 2,5-dimercapto-1,3,4-thiadiazole using formaldehyde (thiadiazole was generated in situ); 20% oil, 17.75% S, 5.5% N.

[0183] When used, the amount of metal deactivator in the lubricant additive composition is typically in the range of about 0.01% by weight to about 0.5% by weight of the lubricant additive composition. In some embodiments, the amount of metal deactivator may be in the range of about 0.02% by weight to about 0.42% by weight, or about 0.03% by weight to about 0.33% by weight, or about 0.04% by weight to about 0.24% by weight of the lubricant additive composition.

[0184] Another component of the present invention may be a borate epoxide containing 12 to 24 carbon atoms. This material can also be described as a borate ester of a vicinal diol containing 12 to 24 carbon atoms. Such materials can be represented by the following structures:

[0185]

[0186] Where R 1 R 2 R 3 and R 4Each R group is independently a hydrogen or aliphatic free radical, or any two thereof together with one or more carbon atoms to which they are attached to form a cyclic free radical. Preferably, at least one of the R groups may be an alkyl group containing at least 8 or at least 10 carbon atoms. In one embodiment, one of the R groups is such an alkyl group, and the remaining R groups are hydrogen. Boronized epoxides are described in detail in U.S. Patent No. 4,584,115. Boronized epoxides are generally prepared by reacting an epoxide with a boron source such as boric acid or boron trioxide. Boronized epoxides are not epoxides themselves, but rather ring-opening boron-containing reaction products of epoxides. Suitable epoxides include C 14-16 Or C 14-18 Or C 16-18 A commercially available mixture of epoxides, available from Elf-Atochem or Union Carbide, can be prepared from the corresponding olefin by known methods. Purified epoxides, such as 1,2-epoxyhexadecane, are available from Aldrich Chemicals. The borate compound is prepared by blending the boron compound and the epoxide and heating at a suitable temperature (typically 80 to 250 °C) until the desired reaction occurs. Inert liquids, such as toluene, xylene, or dimethylformamide, can be used as the reaction medium. Water is formed during the reaction and is typically distilled off. A basic reagent can be used to catalyze the reaction. Preferred borate epoxides are borate epoxides primarily consisting of a 16-carbon olefin. The amount of the borate epoxide can be 0.01 or 0.05 to 0.5 or 1.0 parts by weight of the composition, or alternatively, 0.1 to 0.9%.

[0187] The lubricant additive composition preferably exhibits a conductivity of up to 1 x 10⁻⁹ S / cm at 100°C and 500V, as measured by ASTM D2624, or a conductivity of 9.5 x 10⁻¹⁰ S / cm, or 9 x 10⁻¹⁰ S / cm, or 8.5 x 10⁻¹⁰ S / cm, or 8 x 10⁻¹⁰ S / cm, or 7.0 x 10⁻¹⁰ S / cm, or 6.5 x 10⁻¹⁰ S / cm, or 6.0 x 10⁻¹⁰ S / cm, or 5.5 x 10⁻¹⁰ S / cm, or 5.0 x 10⁻¹⁰ S / cm. Very preferably, the lubricant additive composition does not have conductivity, but can practically achieve a conductivity on the order of 4.0 x 10⁻¹⁰ or 4.5 x 10⁻¹⁰ at 100°C.

[0188] In one embodiment, the lubricant additive composition is substantially free of friction modifiers. In some embodiments, the lubricant additive composition is completely free of friction modifiers.

[0189] When added to base oils, lubricant additive compositions can be in concentrate form and / or fully formulated lubricant form. That is, lubricant additive compositions can be added to base oils to prepare lubricating compositions.

[0190] base oil

[0191] Base oils can be defined according to the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five groups of base oils are as follows: Group I (sulfur content >0.03 wt% and / or <90 wt% saturated, viscosity index 80-120); Group II (sulfur content <0.03 wt% and >90 wt% saturated, viscosity index 80-120); Group III (sulfur content <0.03 wt% and >90 wt% saturated, viscosity index >120); Group IV (all polyalphaolefins (PAOs)); and Group V (all other oils not included in Groups I, II, III, or IV). Base oils may include, for example, API Group I, II, III, IV oils or mixtures thereof.

[0192] Typically, base oils are API Group I, II, III, IV oils, or mixtures thereof. Alternatively, base oils may be API Group II, III, IV oils, or mixtures thereof.

[0193] In one implementation, the base oil can be prepared via a Fischer-Tropsch gas-liquid synthesis process and other gas-liquid oils.

[0194] In one embodiment, the base oil may be an API Group IV oil. The amount of Group IV oil may be 0% to 20% by weight, or 0.1% to 20% by weight, or 1% to 15% by weight, or 5% to 10% by weight of the lubricant additive composition.

[0195] The amount of base oil present is typically the balance remaining after subtracting the total amount of the lubricant additives of the present invention from 100% by weight. If the lubricant additive composition is in the form of a concentrate (which can be combined with the base oil to form a finished lubricant in whole or in part), the ratio of the lubricant additive composition to the base oil and / or diluent oil includes, by weight, a range of 1:99 to 99:1, or 2:98 to 98:2, or 5:95 to 95:5, or 10:90 to 90:10, or 15:85 to 85:15, or 20:80 to 80:20.

[0196] According to ASTM D445, a lubricating composition containing a lubricant additive composition may have a kinematic viscosity of 10 cSt to 30 cSt, or for example 14 cSt to 25 cSt, or even 15 cSt to 22 cSt, or 9 cSt to 25 cSt or 22 cSt, or for example 10 cSt to 25 cSt or 22 cSt, or even 14 cSt to 25 cSt or 22 cSt, or 18 cSt to 22 cSt at 40°C.

[0197] According to ASTM D445, a lubricating composition containing a lubricant additive composition may have a kinematic viscosity of 2 cSt to 25 cSt at 100°C. According to ASTM D445, a lubricating composition containing a lubricant additive composition may have a kinematic viscosity of 2 cSt to 15 cSt at 100°C. According to ASTM D445, a lubricating composition containing a lubricant additive composition may have a kinematic viscosity of 2 cSt to 12 cSt at 100°C. According to ASTM D445, a lubricating composition containing a lubricant additive composition may have a kinematic viscosity of 2 cSt to 9 cSt at 100°C. According to ASTM D445, a lubricating composition containing a lubricant additive composition may have a kinematic viscosity of 2 cSt to 7 cSt at 100°C. According to ASTM D445, a lubricating composition containing a lubricant additive composition may have a kinematic viscosity of 2 cSt to 6 cSt at 100°C. According to ASTM D445, a lubricating composition containing a lubricant additive composition may have a kinematic viscosity of 2 cSt to 4 cSt at 100°C.

[0198] When the lubricant additive composition is in the form of a lubricating composition, it will be suitable for lubricating the drivetrain of electric vehicles, and in particular the gearbox of the electric motor in the electric vehicle. Specifically, the lubricant additive composition will be suitable for lubricating the transmission in a vehicle with an electric motor, which may be a fully electric vehicle or a hybrid electric vehicle having both an electric motor and an engine powered by hydrocarbons or other fuels.

[0199] Specifically, the disclosed technology provides a method for lubricating a power transmission device, the method comprising supplying the power transmission device with a lubricating composition as described herein, i.e., a lubricating composition containing a base oil, a succinimide dispersant, a azole corrosion inhibitor, a phosphorus anti-wear compound, and an antioxidant, and allowing the power transmission device to operate for a sufficient time to allow the lubricating composition to achieve the improved results described herein.

[0200] Specifically, the disclosed technology provides a method for lubricating a power transmission device, the method comprising supplying the power transmission device with a lubricating composition as described herein, i.e., a lubricating composition containing a base oil, a succinimide dispersant, a azole corrosion inhibitor, a phosphorus anti-wear compound, an antioxidant, and a viscosity modifier, and allowing the power transmission device to operate for a sufficient time to allow the lubricating composition to achieve the improved results described herein.

[0201] A drivetrain power transmission device may include at least two gears, such as in a vehicle's gearbox (e.g., a manual transmission), in a shaft or differential, or in other drivetrain power transmission devices. The drivetrain power transmission device may also include bearings. The rolling elements of the bearings may be cylindrical or spherical in design. Lubricated gears may include hypoid gears, spiral bevel gears, or more commonly, quasi-hypoid gears, such as quasi-hypoid gears in a driveshaft. Shafts may have gear ratios from 2:1 to 8:1, and the diameter of the gear ring may be approximately 13 cm to 64 cm. Shafts may be combined with an open differential or some type of traction enabling device. Shafts may be part of a drivetrain with one or more driveshafts, such as in a tandem or triplex design, where the shafts may be coupled to a power distributor. Applications of these shafts include light-duty, medium-duty, and heavy-duty vehicles (e.g., professional or long-haul transportation services) and can be used on or off-road. Shafts may originate from conventional petroleum-powered vehicles, electrically powered vehicles, or their hybrid counterparts. An electric drive shaft can combine an electric motor, power electronics, and a transmission into a single unit, directly powering the vehicle's axle.

[0202] Therefore, one aspect is a method for lubricating an electric vehicle, which includes supplying a lubricating composition containing a lubricant additive composition as described herein to the drivetrain of the electric vehicle and operating the drivetrain.

[0203] On the other hand, there is a method for lubricating a transmission, particularly a method for lubricating a transmission in a vehicle with an electric motor, which includes supplying a lubricating composition containing a lubricant additive composition as described herein to the transmission and operating the transmission.

[0204] The lubricant should be able to meet its expected requirements during the normal operation of the power transmission device in the drive system.

[0205] The lubricant additive composition is applicable to transmissions including automatic transmissions and dual-clutch transmissions. The transmission may or may not include a shift clutch, and where the transmission includes a shift clutch, the clutch may be a dry clutch or a wet clutch. In one embodiment, the lubricant can be used in a transmission that does not contain a shift clutch. In another embodiment, the lubricant additive composition can be used in a transmission with a wet clutch. In yet another embodiment, the lubricant additive composition can be used in a transmission with a dry clutch.

[0206] The drivetrain may be a manual transmission, which may or may not include a synchronizer system or a shaft. In one embodiment, the drivetrain includes a synchronizer or a shaft.

[0207] In one embodiment, the drivetrain includes a synchronizer. The synchronizer system may have operating surfaces made of brass, carbon, molybdenum, phenolic resin, or sintered metal (typically bronze) or mixtures thereof.

[0208] As used herein, the term "condensation product" is intended to cover esters, amides, imides, and other materials of this kind that can be prepared by the condensation reaction of an acid or its reaction equivalent (e.g., an acid halide, anhydride, or ester) with an alcohol or amine, regardless of whether the condensation reaction actually takes place to directly produce the product. Thus, for example, a particular ester may be prepared by transesterification rather than directly by a condensation reaction. The resulting product is still considered a condensation product.

[0209] Unless otherwise stated, the amounts of each chemical component described do not include any solvents or diluents that are commonly found in commercial substances, i.e., based on active chemicals. However, unless otherwise stated, each chemical or composition mentioned herein should be interpreted as a commercial-grade substance that may contain isomers, byproducts, derivatives, and other such substances generally understood to be present in commercial-grade forms.

[0210] As used herein, the terms "hydrocarbon substituent" or "hydrocarbon group" are used in their common sense, as is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly bonded to the rest of the molecule and exhibiting predominantly hydrocarbon characteristics. Examples of hydrocarbon groups include:

[0211] Hydrocarbon substituents, namely 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 by another part of the molecule (e.g., two substituents together form a ring).

[0212] Substituted hydrocarbon substituents, i.e. substituents containing non-hydrocarbon groups, in the context of this invention, do not alter the primary hydrocarbon properties of the substituent (e.g., halogens (especially chlorine and fluorine), hydroxyl groups, alkoxy groups, mercapto groups, alkyl mercapto groups, nitro groups, nitroso groups, and thiooxy groups).

[0213] Heterosubstituents are substituents that, while possessing predominantly hydrocarbon characteristics in the context of this invention, contain substituents other than carbon atoms in a ring or chain composed of additional carbon atoms, and encompass substituents such as pyridyl, furanyl, thiophene, and imidazolyl. Heteroatoms include sulfur, oxygen, and nitrogen. Typically, for every ten carbon atoms in a hydrocarbon group, there will be no more than two or no more than one non-hydrocarbon substituent; alternatively, non-hydrocarbon substituents may be absent from the hydrocarbon group.

[0214] It is known that some of the substances described above can interact in the final formulation, such that the composition of the final formulation may differ from those initially added. For example, metal ions (e.g., metal ions in detergents) can migrate to other acidic or anionic sites of other molecules. The resulting products, including those formed when the compositions of the present invention are used for their intended purpose, may not be easily described. However, all such modifications and reaction products are included within the scope of the present invention; the present invention includes compositions prepared by mixing the aforementioned components.

[0215] As used herein, the term "about" means that the value of a given quantity is within ±20% of the stated value. In other embodiments, the value is within ±15% of the specified value. In other embodiments, the value is within ±10% of the specified value. In other embodiments, the value is within ±5% of the specified value. In other embodiments, the value is within ±2.5% of the specified value. In other embodiments, the value is within ±1% of the specified value.

[0216] Additionally, as used herein, the term "substantially" means that a given number of values ​​are within ±10% of a specified value. In other embodiments, the value is within ±5% of the specified value. In other embodiments, the value is within ±2.5% of the specified value. In other embodiments, the value is within ±1% of the specified value.

[0217] In different embodiments, the lubricating composition may have the composition described in the table below:

[0218]

[0219] The invention described herein can be used to lubricate automatic transmissions used in hybrid electric vehicles, as can be better understood with reference to the following terms:

[0220] Clause 1: A lubricant composition comprising: (a) an oil having a lubricating viscosity; (b) a dispersant; (c) a triazole corrosion inhibitor; (d) a phosphorus-containing anti-wear compound; (e) an antioxidant; and (f) a sulfur-free detergent; wherein the lubricant composition contains not more than 40 ppm sulfur, or not more than 30 ppm sulfur, or not more than 20 ppm sulfur.

[0221] Clause 2: The lubricant composition according to Clause 1, wherein the sulfur-free detergent comprises or is composed of a salicylate detergent.

[0222] Clause 3: A lubricant composition according to any of the preceding clauses, wherein the sulfur-free detergent comprises or is composed of calcium salicylate, and the calcium salicylate detergent is present in an amount sufficient to deliver up to 2000 ppm, or 100 ppm to 1000 ppm, or 100 ppm to 600 ppm, or 100 ppm to 250 ppm, or 400 ppm to 750 ppm of calcium to the lubricant composition.

[0223] Clause 4: The lubricant composition according to any of the preceding clauses, wherein the phosphorus anti-wear compound comprises a dialkyl phosphite having the following formula:

[0224]

[0225] R3 and R4 are independently alkyl groups having 1 to 24 carbon atoms.

[0226] Clause 5: The lubricant composition according to Clause 4, wherein the dialkyl phosphite comprises or is composed of dibutyl hydrogen phosphite.

[0227] Clause 6: The lubricant composition according to any of the preceding clauses, wherein the phosphorus-containing anti-wear compound comprises or is composed of phosphonates.

[0228] Clause 7: The lubricant composition according to the preceding clause, wherein the phosphonate comprises (a) a monomeric phosphorous acid or its ester and (b) a reaction product of at least two alkylene glycols: a first alkylene glycol (i) having two hydroxyl groups in a 1,4, 1,5, or 1,6 relationship; and a second alkylene glycol (ii) being an alkyl-substituted 1,3-propanediol, wherein one or more alkyl substituents are located on one or more carbon atoms of a propylene unit, and the total number of carbon atoms in the alkyl-substituted 1,3-propanediol is about 5 to about 12; wherein the relative molar ratio of the monomeric phosphorous acid or its ester (a) to all the alkylene glycols (b) is about 0.9:1.1 to about 1.1:0.9; and wherein the relative molar ratio of the first alkylene glycol (i) to the alkyl-substituted 1,3-propanediol (ii) is about 30:70 to about 65:35.

[0229] Clause 8: The lubricant composition according to any of the preceding clauses, wherein the dispersant comprises or is composed of a succinimide dispersant having a number average molecular weight of 750 to 2200, or 750 to 1600, or 950 to 1550.

[0230] Clause 9: A lubricant composition according to any one of Clauses 1 to 7, wherein the dispersant comprises or is composed of an olefin polymer dispersant.

[0231] Clause 10: The lubricant composition according to Clause 9, wherein the dispersant comprises or is composed of an ethylene / propylene copolymer dispersant.

[0232] Clause 11: A lubricant composition according to any one of Clauses 1 to 8, wherein the dispersant comprises a borate-modified PIB succinimide dispersant having a number average molecular weight of 1000.

[0233] Clause 12: The lubricant composition according to Clause 11, wherein the dispersant comprises a non-boronized PIB succinimide dispersant having a number average molecular weight of 1550.

[0234] Clause 13: A lubricant composition according to any of the preceding clauses, wherein the dispersant comprises polyisobutylene succinic anhydride (PIBSA) prepared by a thermal process.

[0235] Clause 14: The lubricant composition according to any of the preceding clauses, wherein the triazole corrosion inhibitor comprises or is composed of 1,2,4-triazole.

[0236] Clause 15: The lubricant composition according to any of the preceding clauses, wherein the triazole corrosion inhibitor comprises N,N-bis(2-ethylhexyl)-[(1,2,4-triazol-1-yl)methyl]amine or is composed of N,N-bis(2-ethylhexyl)-[(1,2,4-triazol-1-yl)methyl]amine.

[0237] Clause 16: A lubricant composition according to any one of Clauses 1 to 13, wherein the triazole corrosion inhibitor comprises or is composed of a toluenetriazole derivative.

[0238] Clause 17: The lubricant composition according to any one of claims 1 to 13, wherein the triazole corrosion inhibitor comprises or is composed of bis(2-ethylhexyl)-[(1,2,4-triazol-1-yl)methyl]amine or bis(2-ethylhexyl)-[(1,2,4-triazol-1-yl)methyl]amine.

[0239] Clause 18: A lubricant composition according to any of the preceding clauses, wherein the antioxidant comprises or is composed of arylamine antioxidants.

[0240] Clause 19: A lubricant composition according to any of the preceding clauses, wherein the antioxidant comprises or is composed of phenyl-α-naphthylamine (PANA).

[0241] Clause 20: A lubricant composition according to any of the preceding clauses, wherein the antioxidant comprises or consists of a hydrocarbon-substituted diphenylamine.

[0242] Clause 21: The lubricant composition according to any of the preceding clauses, wherein the antioxidant is selected from the group consisting of octyl diphenylamine, dioctyl diphenylamine, dinonyl diphenylamine, or mixtures thereof.

[0243] Clause 22: A lubricant composition according to any of the preceding clauses, wherein the lubricant composition comprises: 0.5% to 5% by weight of a dispersant; 0.01% to 0.11% by weight of a triazole corrosion inhibitor; 0.05% to 2% by weight of a phosphorus anti-wear compound; 0.2% to 1.2% by weight of an antioxidant; and 0.1% to 1.0% by weight of a sulfur-free detergent.

[0244] Clause 23: A lubricant composition according to any of the preceding clauses, wherein the lubricant composition comprises: 1.0 wt% to 3 wt% of a dispersant; 0.01 wt% to 0.11 wt% of a triazole corrosion inhibitor; 0.05 wt% to 1 wt% of a phosphorus anti-wear compound; or 0.2 wt% to 1.0 wt% of an antioxidant; and 0.2 wt% to 0.8 wt% of a sulfur-free detergent.

[0245] Clause 24: A lubricant composition according to any of the preceding clauses, wherein the lubricant composition comprises: 0.2% to 3% by weight of a dispersant; 0.01% to 0.11% by weight of a triazole corrosion inhibitor; 0.1% to 0.5% by weight of a phosphorus anti-wear compound; or 0.2% to 0.7% by weight of an antioxidant; and / or 0.2% to 0.5% by weight of a sulfur-free detergent.

[0246] Clause 25: A lubricant composition according to any of the preceding clauses, wherein the lubricant composition comprises: 1% to 2% by weight of a dispersant; 0.01% to 0.11% by weight of a triazole corrosion inhibitor; 1% to 2% by weight of a phosphorus anti-wear compound; 0.2% to 0.4% by weight of an antioxidant; and 0.2% to 0.5% by weight of a sulfur-free detergent.

[0247] Clause 26: A lubricant composition according to any of the preceding clauses, wherein the lubricant composition is substantially free of borate esters.

[0248] Clause 27: A lubricant composition according to any of the preceding clauses, wherein the oil having a lubricating viscosity is selected from the group consisting of API Group III base oils, Group IV base oils, or mixtures thereof.

[0249] Clause 28: A lubricant composition according to any of the preceding clauses, wherein the viscosity of the lubricant composition is 1 cSt to 32 cSt at 100°C, as measured by ASTM D445.

[0250] Clause 29: A lubricant composition according to any of the preceding clauses, wherein the viscosity of the lubricant composition is 1.5 cSt to 15 cSt, as measured by ASTM D445.

[0251] Clause 30: A lubricant composition according to any of the preceding clauses, wherein the viscosity of the lubricant composition is 2 cSt to 12 cSt at 100°C, as measured by ASTM D445.

[0252] Clause 31: A lubricant composition according to any of the preceding clauses, wherein the oil having a lubricating viscosity comprises or is composed of API Group III base oils.

[0253] Clause 32: A lubricant composition according to any of the preceding clauses, wherein the oil having a lubricating viscosity comprises or is composed of API IV base oils.

[0254] Clause 33: The lubricating composition according to any of the preceding clauses, wherein the phosphorus anti-wear agent is present in an amount sufficient to deliver 100 parts / million to 5000 parts / million of phosphorus to the composition.

[0255] Clause 34: A method of lubricating an electric vehicle, the method comprising supplying a lubricant composition according to any of the preceding clauses to the drivetrain of the electric vehicle and operating the drivetrain.

[0256] Clause 35: A method for reducing wear in said electric vehicle by supplying a lubricant composition according to any one of Clauses 1 to 33 to the drivetrain.

[0257] Clause 36: Use of any one of Clauses 1 to 33 for reducing wear in the drivetrain of an electric vehicle.

[0258] Clause 37: Any lubricating composition that can be used directly as described in Clauses 1 to 33 for the purpose of reducing corrosion.

[0259] Example

[0260] Prepare lubricating compositions according to Table 1 below.

[0261] Table 1 (Weight is for oil-free - base oil added to 100%)

[0262]

[0263]

[0264] 1 Amines C9-diphenylamine

[0265] 2 C14 dialkylamides of α-hydroxy acids

[0266] 3 1000Mn borate-modified PIB succinimide (3.8% N, 0.81% B)

[0267] 4 1550Mn non-boronized PIB succinimide (1.41% N)

[0268] 5 polyalkylsiloxane

[0269] 6 dibutyl hydrogen phosphite

[0270] 7 A condensation product of monomeric phosphorous acid or its ester with at least two alkylene glycols.

[0271] 8Amine salts of C14-C18 dialkyl hydrogen phosphates and C12-C14 tertiary alkylamines

[0272] 9 Bis(2-ethylhexyl)-[1,2,4-triazol-1-yl)methyl]amine

[0273] The FE8 roller bearing test is used to evaluate the effects of lubricants on the frictional behavior and wear of various bearings, including cylindrical roller thrust bearings, under operating conditions. For this test, two test cylindrical roller thrust bearings 81212 are mounted in the FE8 test apparatus, subjected to axial bearing loads, operated at a specific speed, and maintained at the test temperature.

[0274] The lubricating compositions from Table 1 were evaluated under FE8 roller bearing testing using equipment and test procedures according to DIN 51819T1-T3. Tests were performed in duplicate to confirm the results. The test conditions are listed below, and the results are summarized in Table 2.

[0275] condition

[0276] • Test parameters

[0277] Axial load 800kN

[0278] • Speed ​​7.5 rpm

[0279] · Fluid volume 4 liters

[0280] • Temperature 80℃ (at the housing gasket)

[0281] • Cage material: brass

[0282] • Oil flow rate: 0.1 L / min (per bearing)

[0283] • Test duration: 2 runs × 80 hours

[0284] Table 2

[0285] Example 1 3 6 FE-8 bearing wear results Component wear (mg) 52.0 -0.5 9.9 Cage wear (mg) 106.7 12.0 47.8 Inner rail wear (mg) 95.6 0.2 20.9 Outer rail wear (mg) 97.9 -0.3 17.2

[0286] In wear tests, the weight loss of bearing components reflects the lubricant's ability to protect the bearing. Formulations containing salicylates perform better than those containing sulfonates.

[0287] Copper corrosion testing was conducted using the ZF Copper Corrosion Test procedure, in which a weighed copper sample block was placed in test oil and heated to 150°C for 168 hours under air purging at 83 mL / min. At the end of the test, the copper weight loss of the sample block, the percentage of copper in the test emissions, and the visual rating (ASTM D-130) were measured. The results are summarized in Table 3.

[0288] Table 3

[0289]

[0290] Example 2, which contains a non-boronicized dispersant, showed a higher copper weight loss at the end of the test than Examples 4 and 5, which contain a non-boronicized dispersant and calcium salicylate detergent, as indicated by the amount of copper measured in the test fluid at the end of the test.

[0291] Each of the foregoing references is incorporated herein by reference, including any prior application claiming priority thereto, whether or not specifically listed above. Any reference to any reference is not an admission that the reference conforms to the prior art or constitutes general knowledge of a person skilled in the art in any jurisdiction. Unless expressly stated in the examples or otherwise, all numerical quantities of matter, reaction conditions, molecular weight, number of carbon atoms, etc., specified in this specification should be understood to be modified by the word “about.” It should be understood that the upper and lower limits of the quantities, ranges, and proportions described herein can be combined independently. Similarly, the ranges and quantities of each element of the invention can be used in conjunction with the ranges or quantities of any other element.

[0292] As used herein, the transitional term “comprising,” synonymous with “comprising,” “containing,” or “characterized in,” is inclusive or open-ended and does not exclude additional, unlisted elements or method steps. However, in every use of “comprising” herein, it is intended that the term also cover the phrases “consistently composed of” and “composed of” as alternative embodiments, wherein “consisting of” excludes any elements or steps not specified, and “consisting of” allows the inclusion of additional, undescribed elements or steps that do not substantially affect the essential or essential and novel characteristics of the composition or method under consideration.

[0293] As used herein, “substantially free” means that the amount of the substance under consideration is below the amount that would affect fluid-related properties in a measurable manner. “Substantially free” can also mean that the substance under consideration was not intentionally added to the composition, but does not exclude the presence of such a material as a contaminant. “Substantially free” can also mean that the substance under consideration may be present in amounts below the detection limits of standard test methods now known to or developed by those skilled in the art. In some embodiments, “substantially free” may mean less than 10 ppm by weight or even less than 5 ppm by weight.

[0294] While certain representative embodiments and details have been shown to illustrate the purpose of this invention, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the scope of the invention. In this regard, the scope of the invention is defined only by the following claims.

Claims

1. A lubricant composition comprising: (a) An oil with lubricating viscosity; (b) Dispersant; (c) Triazole corrosion inhibitor; (d) Phosphorus-containing anti-wear compounds; (e) Antioxidants; and (f) Sulfur-free detergents; The lubricant composition contains no more than 40 ppm sulfur, or no more than 30 ppm sulfur, or no more than 20 ppm sulfur.

2. The lubricant composition according to claim 1, wherein the sulfur-free detergent comprises or is composed of a salicylate detergent.

3. The lubricant composition according to any of the preceding claims, wherein the sulfur-free detergent comprises or is composed of calcium salicylate.

4. The lubricant composition of claim 3, wherein the calcium salicylate detergent is present in an amount sufficient to deliver up to 2000 ppm, or 100 ppm to 1000 ppm, or 100 ppm to 600 ppm, or 100 ppm to 250 ppm, or 400 ppm to 750 ppm of calcium to the lubricant composition.

5. The lubricant composition according to any of the preceding claims, wherein the phosphorus anti-wear compound comprises a dialkyl phosphite.

6. The lubricant additive composition according to claim 5, wherein the dialkyl phosphite has the following formula: R3 and R4 are independently alkyl groups having 1 to 24 carbon atoms.

7. The lubricant composition of claim 5, wherein the dialkyl phosphite comprises or is composed of dibutyl hydrogen phosphite.

8. The lubricant composition according to any one of claims 1 to 4, wherein the phosphorus-containing anti-wear compound comprises or is composed of phosphonates.

9. The lubricant composition according to claim 8, wherein the phosphonate comprises a reaction product of the following substances: (a) Monomer phosphorous acid or its ester, and (b) At least two alkylene glycols: A first alkylene glycol (i) having two hydroxyl groups in a 1,4, 1,5, or 1,6 relationship; The second alkylene glycol (ii) of alkyl-substituted 1,3-propanediol, wherein one or more alkyl substituents are located on one or more carbon atoms of the propylene unit, and the total number of carbon atoms in the alkyl-substituted 1,3-propanediol is about 5 to about 12. The relative molar ratio of the monomeric phosphorous acid or its ester (a) to all alkylene glycols (b) is approximately 0.9:1.1 to approximately 1.1:0.9; and The relative molar ratio of the first alkylene glycol (i) to the alkyl-substituted 1,3-propanediol (ii) is about 30:70 to about 65:

35.

10. The lubricant composition according to any of the preceding claims, wherein the dispersant comprises or is composed of a succinimide dispersant.

11. The lubricant composition of claim 10, wherein the dispersant comprises or is composed of a succinimide dispersant having a number average molecular weight of 750 to 2200, or 750 to 1600, or 950 to 1550.

12. The lubricant composition according to any one of claims 1 to 9, wherein the dispersant comprises or is composed of an olefin polymer dispersant.

13. The lubricant composition of claim 12, wherein the dispersant comprises or is composed of an ethylene / propylene copolymer dispersant.

14. The lubricant composition according to any of the preceding claims, wherein the dispersant comprises a borate dispersant.

15. The lubricant composition according to any of the preceding claims, wherein the dispersant comprises a non-boronized dispersant.

16. The lubricant composition according to any of the preceding claims, wherein the triazole corrosion inhibitor comprises or is composed of 1,2,4-triazole.

17. The lubricant composition according to any of the preceding claims, wherein the triazole corrosion inhibitor comprises N,N-bis(2-ethylhexyl)-[(1,2,4-triazol-1-yl)methyl]amine or is composed of N,N-bis(2-ethylhexyl)-[(1,2,4-triazol-1-yl)methyl]amine.

18. The lubricant composition according to any one of claims 1 to 15, wherein the triazole corrosion inhibitor comprises or is composed of a toluenetriazole derivative.

19. The lubricant composition according to any one of claims 1 to 15, wherein the triazole corrosion inhibitor comprises or is composed of bis(2-ethylhexyl)-[(1,2,4-triazol-1-yl)methyl]amine.

20. The lubricant composition according to any of the preceding claims, wherein the antioxidant comprises or is composed of arylamine antioxidants.

21. The lubricant composition according to any of the preceding claims, wherein the antioxidant comprises or is composed of phenyl-α-naphthylamine (PANA).

22. The lubricant composition according to any of the preceding claims, wherein the antioxidant comprises or consists of a hydrocarbon-substituted diphenylamine.

23. The lubricant composition according to any of the preceding claims, wherein the antioxidant is selected from the group consisting of octyl diphenylamine, dioctyl diphenylamine, dinonyl diphenylamine, or mixtures thereof.

24. The lubricant composition according to any preceding claim, wherein the lubricant composition comprises: The dispersant is present in amounts of 0.5% to 5% by weight, or 1.0% to 3% by weight, or 0.2% to 3% by weight, or 1% to 2% by weight. 0.01% to 0.11% by weight of the triazole corrosion inhibitor; The phosphorus anti-wear compound in amounts of 0.05 wt% to 2 wt%, or 0.05 wt% to 1 wt%, or 0.1 wt% to 0.5 wt%, or 1.0 wt% to 2 wt%; The antioxidant is present in amounts of 0.2 wt% to 1.2 wt%, or 0.2 wt% to 1.0 wt%, or 0.2 wt% to 0.7 wt%, or 0.2 wt% to 0.4 wt%. The sulfur-free detergent is present in amounts of 0.1% to 1.0% by weight, or 0.2% to 0.8% by weight, or 0.2% to 0.5% by weight.

25. The lubricant composition according to any of the preceding claims, wherein the lubricant composition is substantially free of borate esters.

26. The lubricant composition according to any of the preceding claims, wherein the oil having a lubricating viscosity is selected from the group consisting of API Group III base oils, API Group IV base oils, or mixtures thereof.

27. The lubricant composition according to any of the preceding claims, wherein the viscosity of the lubricant composition at 100°C is 1 cSt to 32 cSt, or 1.5 cSt to 15 cSt, or 2 cSt to 12 cSt, as measured by ASTM D445.

28. The lubricant composition according to any of the preceding claims, wherein the oil having a lubricating viscosity comprises or is composed of API Group III base oils.

29. The lubricant composition according to any of the preceding claims, wherein the oil having a lubricating viscosity comprises or is composed of API IV base oils.

30. The lubricating composition according to any of the preceding claims, wherein the phosphorus anti-wear agent is present in an amount sufficient to deliver 100 parts / million to 5000 parts / million of phosphorus to the composition.

31. A method of lubricating an electric vehicle, the method comprising supplying a lubricant composition according to any one of the preceding claims to the drivetrain of the electric vehicle and operating the drivetrain.

32. A method for reducing wear in an electric vehicle by supplying the drivetrain with a lubricant composition according to any one of claims 1 to 30.

33. Use of the lubricating composition according to any one of claims 1 to 30 for reducing wear in the powertrain of an electric vehicle.

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