Lubricant additive composition for electric vehicles

Abstract

The disclosed technology relates to lubricating additives containing dispersants, corrosion inhibitors, phosphite-based anti-wear agents, antioxidants, and sulfur-free detergents. The technology of this disclosure also relates to lubricating compositions containing lubricating additives, which are used to lubricate the transmissions of electric vehicles, and in particular for use in gearboxes. The lubricating 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.

Description

[Technical Field]

[0001] The disclosed technology relates to a lubricating composition for use in the driveline of an electric vehicle, particularly in the gearbox, wherein the lubricating additive composition contains an oil of lubricating viscosity, a dispersant, a corrosion inhibitor, a phosphorus-based wear inhibitor, an antioxidant, and a sulfur-free detergent. [Background technology]

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

[0003] In electric and hybrid electric vehicle applications, the lubricating fluid may come into contact with components of the electric motor as well as components of conventional combustion engine gear reduction units. Therefore, a suitable fluid must be applicable across a wide variety of vehicle components. For example, the lubricating fluid may come into contact with electric windings in the motor stator, as well as gears in the mechanical parts of the transmission. Thus, a suitable fluid for these applications must not only possess conventional lubrication 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 performance. Often, one or more of the desired properties required for electrical and hybrid electric applications are impaired due to the accumulation of additives commonly used in such conventional fluids, and therefore, these conventional fluids may not be suitable for electric or hybrid electric vehicles.

[0005] However, lubricants still need to provide adequate lubrication, including, for example, dispersibility, cleanliness, wear resistance, and corrosion resistance. Similarly, it is desirable to maintain low viscosity fluids in such vehicles in order to improve their efficiency. Therefore, new lubrication compositions are needed to achieve these often competing results. [Overview of the Initiative] [Means for solving the problem]

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

[0007] The lubricating additive composition can be mixed with a base oil such as an API Group III base oil, a Group IV base oil, or a mixture thereof to prepare a lubricating composition.

[0008] Lubricating compositions containing lubricating additives can be used in methods of lubricating electric vehicles by supplying them to the drive lines of electric vehicles. In some examples, this method can be used when the drive line does not include a transmission clutch. In some examples, the lubricating additives improve dispersibility, detergency, wear resistance, oxidation performance (controlled), and corrosion resistance. [Modes for carrying out the invention]

[0009] Various preferred features and embodiments are described below by non-limiting examples.

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

[0011] The dispersants may include, for example, a "succinimide dispersant," which is a type of carboxylic acid dispersant prepared by the reaction of hydrocarbyl-substituted succinic anhydride or its reactive equivalent with an amine such as poly(ethyleneamine); an "amine dispersant," which is a reaction product of a relatively high molecular weight aliphatic or alicyclic halide and an amine (e.g., polyalkylene polyamine); and an "ester dispersant," which is similar to the succinimide dispersant described above, except that it may be considered to be prepared by the reaction of an alkylphenol containing at least 30 carbon atoms in the alkyl group with an aldehyde (especially formaldehyde) and an amine (especially polyalkylene polyamine) with a hydrocarbyl acylating agent and a polyhydric aliphatic alcohol (e.g., glycerol, pentaerythritol, or sorbitol), as described in U.S. Patent No. 3,381,022.

[0012] Another class of ashless dispersants are high molecular weight esters. These materials are similar to the succinimides described above, except that they may be prepared by the reaction of a hydrocarbyl acylating agent with a polyhydric aliphatic alcohol, such as glycerol, pentaerythritol, or sorbitol. Such materials are described in detail in U.S. Patent No. 3,381,022. Aromatic succinic acid esters can also be prepared, as described in U.S. Patent Publication No. 2010 / 0286414. In some examples, these ester-type dispersants can be post-treated with an amine such as poly(ethyleneamine).

[0013] The post-treated dispersants can also be used. The post-treated dispersants are generally obtained by reacting carboxylic acids (such as succinimides), amines, or Mannich dispersants with reagents such as urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds such as boric acid (to obtain the above-mentioned "borated dispersants"), phosphorus compounds such as phosphoric acid or anhydrides, 2,5-dimercaptothiadiazole (DMTD), or aromatic dicarboxylic acids having acidic groups at the 1,3 or 1,4 positions on the benzene ring (such as terephthalic acid).

[0014] The borated dispersants are generally obtained by reacting carboxylic acids (such as succinimides), amines, or Mannich dispersants with boron compound reagents such as boric acid (to obtain the "borated dispersants"). The dispersants and their manufacturing methods are well-known in the art. The borated dispersants can be further functionalized at the sulfur or phosphorus moieties. The dispersant components in the borated dispersants can be a mixture of multiple dispersants of different types, and optionally, at least one can be a succinimide dispersant. In one embodiment, the borated dispersant can be a borated polyisobutylene succinimide dispersant whose polyisobutylene moiety can have a number average molecular weight of 750 to 2200, or 750 to 1600, or 950 to 1550. The borated dispersants can be prepared to have 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 the borated dispersant in the composition can be, for example, 0.05 to 2.0 weight percent. In other embodiments, the amount is 0.1 to 1.0 percent or 0.15 to 0.75 percent of the final blend fluid formulation. In concentrates, the amount will be proportionally higher.

[0015] Mixtures of dispersants can also be used. The dispersants can have a nitrogen content of about 11,000 ppm or more, or about 11,500 ppm or more, or about 12,000 ppm or more by weight of the dispersant.

[0016] Regardless of whether post-treatment is performed (e.g., boro-oxidized or non-boro-oxidized), the total amount of dispersants or combinations thereof in the composition may be, for example, 0.01 to 3 weight percent of the final blended fluid formulation, or, for example, 0.025 to 2.75 weight percent, or 0.05 to 2.5 weight percent, or 1 to 2.5 weight percent, but in concentrates, the amount increases proportionally. Up to the extent that the dispersant is boro-oxidized, 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.

[0017] In certain embodiments, the dispersant may be prepared by a process involving the presence of small amounts of chlorine or other halogens, as described in U.S. Patent No. 7,615,521 (see, for example, column 4, lines 18-60 and Preparation Example A). Such dispersants typically have several carbon-cyclic structures in the bonding of hydrocarbyl substituents to acidic or amide "head" groups. In other embodiments, the dispersant may be prepared by a thermal process involving an "ene" reaction without the use of chlorine or other halogens, as described in U.S. Patent No. 7,615,521. Dispersants produced in this way are often derived from high-vinylidene (i.e., more than 50% terminal vinylidene) polyisobutylene (see, column 4, lines 61-5, line 30 and Preparation Example B). Such dispersants typically do not contain the above-mentioned carbon-cyclic structures at the bonding points. In certain embodiments, the dispersant may be prepared by free-radical catalytic polymerization of high-vinylidene polyisobutylene with an ethylenically unsaturated acylating agent, as described in U.S. Patent No. 8,067,347.

[0018] The dispersant can be a graft copolymer that is a condensation reaction product of an olefin polymer grafted with a carboxylic acid (or equivalent) functional group, and the grafted olefin reacts with a monoamine or polyamine that can have a single primary amino group. When the olefin polymer is an ethylene / propylene copolymer, the polyamine is not a poly(ethyleneamine).

[0019] The polymer substrate is an olefin polymer as described above. The olefin polymer substrate used in the derivatized graft copolymer contains a graft carboxylic acid functionality or a reactive equivalent of the carboxylic acid functionality (e.g., an acid anhydride or ester). The reactive carboxylic acid functionality will typically be present as a pendant group bonded, for example, by a graft process.

[0020] The ethylenically unsaturated carboxylic acid material is usually radically grafted onto the polymer backbone. These materials bonded to the polymer usually contain at least one ethylene bond (before reaction) and at least one (such as two) carboxylic acid (or its acid anhydride) group or a polar group convertible to the above carboxyl group by oxidation or hydrolysis. Maleic anhydride or its derivatives are preferred. It is grafted onto an olefin polymer (such as an ethylene copolymer or terpolymer) to provide two carboxylic acid functionalities. Examples of additional unsaturated carboxylic acid materials include maleic anhydride, itaconic anhydride, or the corresponding dicarboxylic acids such as maleic acid, fumaric acid and their esters, as well as cinnamic acid and its esters.

[0021] The ethylenically unsaturated carboxylic acid material can be radically grafted onto a polymer (such as an ethylene / propylene copolymer). The free radical induced graft of the ethylenically unsaturated carboxylic acid material can also be carried out in a solvent such as hexane or mineral oil. This can be carried out at a high temperature in the range of 100 °C to 250 °C, for example, 120 °C to 190 °C, or 150 °C to 180 °C, for example, above 160 °C.

[0022] Possible free radical initiators include peroxides, hydroperoxides, and azo compounds, typically having boiling points higher than about 100°C, which thermally decompose within the graft temperature range to provide free radicals. Representative examples of these free radical initiators include azobisisobutyronitrile and 2,5-dimethyl-hexa-3-in-2,5-bis-tertiary butyl peroxide. The initiator can be used in amounts of 0.005% to 1% by weight, based on the weight of the reaction mixture solution. Grafting can be carried out in an inert atmosphere, such as under a nitrogen blanket. The resulting polymer intermediate is characterized by having a carboxylic acid acylation function within its structure.

[0023] In another embodiment, an unsaturated carboxylic acid material such as maleic anhydride is first condensed with a monoamine or polyamine, which typically has a single primary amino group (described below), and then the condensation product itself is grafted onto a polymer backbone in a manner similar to that described above.

[0024] The amount of reactive carboxylic acid on the polymer chain, particularly the amount of graft carboxylic acid on the chain, is typically 0.5–8 weight percent, or 1–7 weight percent, or 1.5–6 weight percent, based on the weight of the polymer backbone, or 2–5 weight percent in some embodiments. In some embodiments, the amount of reactive carboxylic acid on the polymer chain, particularly the amount of graft carboxylic acid on the chain, can be about 1–2 weight percent, or in other embodiments about 2–3 weight percent, or about 3–4 weight percent, or 4–5 weight percent. These figures represent the amount of carboxyl-containing species, with particular reference to maleic anhydride as the graft material. As will be apparent to those skilled in the art, these amounts can be adjusted to account for carboxyl-containing species having a higher or lower molecular weight per molecule, or having a higher or lower amount of acid-functionality. The graft may be of a degree that provides an acid-functionalized polymer having a total acid number (TAN according to ASTM D664) of 5–100, 10–80, or 15–75, or 20–70, or about 20–60 or 65 mgKOH / g.

[0025] Acid-containing polymers typically react with monoamines or polyamines having a single primary amino group. If the olefin polymer is an ethylene / propylene copolymer, its polyamine is not poly(ethyleneamine). The reaction may consist of condensation to form imides, amides, or halfamides or amide esters (assuming some alcohol also reacts) or amine salts. Primary amino groups usually condense to form amides, or imides in the case of maleic anhydride. Note that in certain embodiments, the amine has a single primary amino group, i.e., does not have two or more primary amino groups (however, additional primary amino groups in the total amine component are not significant, although perhaps in very small amounts, such as less than 5%, or less than 2%, or less than 1%, or less than 0.5%, or less than 0.01-0.1%, especially less than 1%, e.g., 0.01-1%) of the primary amine groups). This feature minimizes the amount of crosslinking that may otherwise occur. Poly(ethyleneamine) is generally, and in an oversimplified way, H2N-(C2H4-NH-) n These can be represented as -C2H4-NH2, where n is, for example, 2 to 6. Since these typically have about two primary amino groups on average, their use is typically undesirable for the functionalization of ethylene / propylene copolymers, and therefore undesirable crosslinking can be minimized or avoided. In embodiments where the polyamine is not poly(ethyleneamine), the amine component used in the production of the condensation product is poly(ethyleneamine) or substantially poly(ethyleneamine), for example, less than 5% by weight of the amine component is poly(ethyleneamine), or less than 1%, or 0.01 to 0.1% by weight.

[0026] Suitable primary amines may include aromatic amines such as those in which the carbon atoms of the aromatic ring structure are directly bonded to the amino nitrogen. The amine may be a monoamine or a polyamine. The aromatic ring is typically a mononuclear aromatic ring (i.e., derived from benzene), but may also include a condensed aromatic ring, such as one derived from naphthalene. Examples of aromatic amines include aniline, N-alkylanilines such as N-methylaniline, N-butylaniline, di-(para-methylphenyl)amine, naphthylamine, 4-aminodiphenylamine, N,N-dimethylphenylenediamine, 4-(4-nitrophenylazo)aniline (Disperse Orange 3), sulfamethazine, 4-phenoxyaniline, 3-nitroaniline, 4-aminoacetanilide, 4-amino-2-hydroxybenzoate phenyl ester (aminosalicylate phenyl), N-(4-amino-5-methoxy-2-methylphenyl)-benzamide (Fast Violet B), N-(4-amino-2,5-dimethoxyphenyl)-benzamide (Fast Blue RR), N-(4-amino-2,5-diethoxyphenyl)-benzamide (Fast Blue BB), N-(4-amino-phenyl)-benzamide, and 4-phenylazoaniline. Other examples include para-ethoxyaniline, para-dodecylaniline, cyclohexyl-substituted naphthylamines, and thienyl-substituted anilines. Other suitable examples of aromatic amines include amino-substituted aromatic compounds, as well as amines in which the amine nitrogen is part of the aromatic ring, such as 3-aminoquinoline, 5-aminoquinoline, and 8-aminoquinoline. Aromatic amines such as 2-aminobenzimidazole, which contains one secondary amino group directly bonded to the aromatic ring and a primary amino group bonded to the imidazole ring, are also mentioned. Other amines include N-(4-anilinophenyl)-3-aminobutanamide (i.e., φ-NH-φ-NH-COCH2CH(CH3NH2)).Additional aromatic amines include aminocarbazole, aminoindole, aminopyrrole, aminoindazolinone, aminoperimidine, mercaptotriazole, aminophenothiazine, aminopyridien, aminopyrazine, aminopyrimidine, pyridine, pyrazine, pyrimidine, aminothiadiazole, aminothiothiadiazole, and aminobenzothiazoazole. Other suitable amines include 3-amino-N-(4-anilinophenyl)-N-isopropylbutanamide and N-(4-anilinophenyl)-3-{(3-aminopropyl)-(cocoalkyl)amino}butanamide. Other aromatic amines that can be used include, for example, various aromatic amine dye intermediates containing multiple aromatic rings linked by an amide structure. Examples include materials with a general structure of φ-CONH-φ-NH2, which may be phenyl group substituted. Suitable aromatic amines are those in which the amine nitrogen is a substituent on the aromatic carboxylic acid compound, i.e., the nitrogen is sp. within the aromatic ring. 2 It includes unmixed ingredients.

[0027] Amines may also be non-aromatic, or in other words, amines in which the amino nitrogen is not directly bonded to a carbon atom of an aromatic ring, or the amine nitrogen is not part of an aromatic ring, or the amine nitrogen is not a substituent of an aromatic carboxylic acid compound. In some cases, such non-aromatic amines may be considered aliphatic or alicyclic. Such amines may be linear, branched, or functionalized with some functional group. Non-aromatic amines can include monoamines having 1 to 8 carbon atoms, such as methylamine, ethylamine, and propylamine, as well as various higher amines. Diamines or polyamines may also be used, usually having 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; aminoethylethyleneurea and aminopropylmorpholine.

[0028] In certain embodiments, non-aromatic amines can be used alone, in combination with each other, or in combination with aromatic amines. In some embodiments, the amount of aromatic amine may be small compared to the amount of non-aromatic amine, or in some examples, the composition may be substantially free of or free of aromatic amines.

[0029] In certain embodiments, the grafted olefin polymer may have a nitrogen content of 0.05 to 3 weight percent, or 0.1 to 2.5, or 0.15 to 2, or 0.2 to 1.75, or 0.25 to 1.6 weight percent, as calculated using ASTM D5291. Corrosion inhibitor

[0030] Corrosion inhibitors may also be described as metal deactivators or yellow metal passivators.

[0031] 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-triazole-1-yl)methyl]amine.

[0032] The triazole includes a triazole containing a hydrocarbyl substitution at at least one of the 1st, 2nd, 4th, 5th, 6th, or 7th ring positions. In different embodiments, the hydrocarbyl group contains 1 to about 30 carbon atoms, or 1 to about 15 carbon atoms, or 1 to about 16 carbon atoms. In one embodiment, the corrosion inhibitor includes a tolyltriazole. In one embodiment, a hydrocarbyltriazole substituted at the 4th, 5th, 6th, or 7th position is further reacted with an aldehyde and an amine.

[0033] Suitable examples of hydrocarbylbenzotriazoles for further reaction with aldehydes and amines include N,N-bis(2-ethylhexyl)-ar-methyl-1H-benzotriazole-1-methaneamine, N,N-bis(2-ethylhexyl)-4-methyl-1H-benzotriazole-1-methaneamine, N,N-bis(2-ethylhexyl)-4-methyl-1H-benzotriazole-1-methaneamine, 2H-benzotriazole-2-methaneamine, N-(4-methoxyphenyl)-1H-benzotriazole-1-methaneamine, N N-didodecyl-1H-benzotriazole-1-methamine, N-(1H-benzotriazol-1-ylmethyl)-N-(2-ethylhexyl)-1H-benzotriazol-1-methamine, N-methyl-N-phenyl-1H-benzotriazol-1-methamine, 4,5,6,7-tetrahydro-N,N-ditridecyl-1H-benzotriazol-1-methamine, N,N-dioctadecyl-1H-benzotriazol-1-methamine, 5-methyl-N,N-dioctyl-1H-benzotriazol-1-methamine N,N-dibutyl-1H-benzotriazole-1-methaneamine, N-(4-methylphenyl)-1H-benzotriazole-1-methaneamine, N,N-bis(2-ethylhexyl)-1H-benzotriazole-1-methaneamine, N,N-dioctyl-2H-benzotriazole-2-methaneamine, N-dodecyl-1H-benzotriazole-1-methaneamine, N-phenyl-1H-benzotriazole-1-methaneamine, N,N-didodecyl-4,5,6,7-tetrahydro-1H-benzotriazole-1-methaneamine Examples include N,N-bis(2-ethylhexyl)-5-methyl-1H-benzotriazole-1-methaneamine, N-octadecyl-1H-benzotriazole-1-methaneamine, N,N-didodecyl-2H-benzotriazole-2-methaneamine, N,N-dioctyl-1H-benzotriazole-1-methaneamine, N-(2-ethylhexyl)-1H-benzotriazole-1-methaneamine, 4,5,6,7-tetrahydro-N,N-ditetradecyl-1H-benzotriazole-1-methaneamine, or mixtures thereof.In one embodiment, the corrosion inhibitor comprises N,N-bis(2-ethylhexyl)-4-methyl-1H-benzotriazole-1-methaneamine or N,N-bis(2-ethylhexyl)-ar-methyl-1H-benzotriazole-1-methaneamine.

[0034] Suitable examples of hydrocarbyl 1,2,4-riazoles for further reaction with amines include N,N-bis(1-methylethyl)-1H-1,2,4-triazole-1-methaneamine, N,N-diisobutyl-1H-1,2,4-triazole-1-methaneamine, N,N-dicyclohexyl-1H-1,2,4-triazole-1-methaneamine, N,N-bis(2-ethylhexyl)-1H-1,2,4-triazole-1-methaneamine, and 1-((1H-1,2,4-triazole-1-methaneamine). Examples include azol-1-yl)methyl)piperidine, N,N-bis(tridecyl)-1H-1,2,4-triazole-1-methaneamine, N,N-dimethyl-1-(1H-1,2,4-triazol-1-yl)methaneamine, N,N-dibutyl-1H-1,2,4-triazol-1-methaneamine, N,N-dicoco-1-(1H-1,2,4-triazol-1-yl)methaneamine, and N-((1H-1,2,4-triazol-1-yl)methyl)octane-3-amine.

[0035] In various embodiments, the corrosion inhibitor is a triazole. The triazole corrosion inhibitor may be present alone or in mixtures with other triazoles or other azole corrosion inhibitors in amounts ranging from about 0.005 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, etc., of the lubricating additive composition. Phosphorus wear-resistant compounds

[0036] The lubricating additive composition contains at least one phosphorus-resistant compound. The phosphorus-resistant compound may be an acid, a salt, or an ester. In one embodiment, the phosphorus-resistant compound is in the form of two or three, or a mixture of two to four (typically two or three) phosphorus-resistant compounds. In some embodiments, the phosphorus-resistant compound is in the form of a mixture of a phosphite and a phosphateamine compound.

[0037] In some embodiments, the phosphorus wear-resistant compound is a phosphite. Preferred phosphites include those having at least one hydrocarbyl group having 3 or 4 or more, or 8 or more, or 12 or more carbon atoms. The phosphite may be a monohydrocarbyl-substituted phosphite, a dihydrocarbyl-substituted phosphite, or a trihydrocarbyl-substituted phosphite.

[0038] In one embodiment, the phosphite does not contain sulfur. That is, the phosphite is not a thiophosphite.

[0039] Phosphite can be expressed by the following formula: [ka] In the formula, at least one R may be a hydrocarbyl group containing at least three carbon atoms, and the other R group may be hydrogen. In one embodiment, two of the R groups are hydrocarbyl groups and the third is hydrogen. In one embodiment, each R group is a hydrocarbyl group, i.e., the phosphite is a trihydrocarbyl-substituted phosphite. The hydrocarbyl groups may be alkyl, cycloalkyl, aryl, acyclic, or mixtures thereof.

[0040] The R-hydrocarbyl group can be linear or branched, typically linear, and saturated or unsaturated, typically saturated.

[0041] In one embodiment, the phosphorus wear-resistant compound may be a C3-C8 hydrocarbyl phosphite or a mixture thereof, where each R is independently hydrogen or a hydrocarbyl group having 3-8 or 4-6 carbon atoms, typically 4. Typically, the C3-C8 hydrocarbyl phosphite includes a dialkyl phosphite where each R has 1-14 carbon atoms, 2-12 carbon atoms, or 3-8 or 4-6 carbon atoms. The dialkyl phosphite may be, for example, a dibutyl phosphite or a dioleyl phosphite. The C3-C8 hydrocarbyl phosphite or C3-C8 dialkyl phosphite can deliver at least 175 ppm, or at least 200 ppm, of the total amount of phosphorus delivered by the phosphorus wear-resistant compound. C3-C8 hydrocarbyl phosphites or C3-C8 dialkyl phosphites 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 amount of phosphorus from the phosphorus wear-resistant compound.

[0042] In one embodiment, the phosphorus wear-resistant compound may be a C12-C24 hydrocarbyl phosphite or a mixture thereof, where each R is independently a hydrogen atom or a hydrocarbyl group having 12-24 or 14-20 carbon atoms, typically 16-18 carbon atoms. Typically, C12-C24 hydrocarbyl phosphites include C16-C18 dialkyl phosphites. Examples of alkyl groups for R3, R4, and R5 include octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl, nonadecyl, eicosyl, or mixtures thereof. C12-C24 hydrocarbyl phosphites or C12-C24 dialkyl phosphites may be present in the lubricating additive composition in an amount of about 0.05% to about 1.0% by weight, or about 0.1% to about 0.5% by weight.

[0043] In some embodiments, the phosphite-containing compound may include both C3-C8 and C12-C14 hydrocarbyl phosphites.

[0044] The phosphorus wear-resistant compound may contain phosphite in an amount of 0.1 to 2% by weight of the additive composition, or further in an amount of 0.1 to 1.8% by weight, or 0.1 to 1.4 or 1.6% by weight, or further in an amount of 0.1 to 1 or 1.2% by weight of the lubricating additive composition. The phosphorus wear-resistant compound may contain phosphite in an amount of 0.1 to 0.5% by weight of the additive composition, or further in an amount of 0.1 to 0.4% by weight or 0.1 to 0.2% by weight of the lubricating additive composition.

[0045] The phosphorus wear-resistant compound may be a phosphite ester composition, which is a reaction product, such as a condensation product, of a monomer phosphite or its ester with at least two alkylenediols. In the embodiment, the aforementioned phosphite ester does not contain zinc.

[0046] A "monomer" phosphite or ester typically refers to a phosphite or ester containing one phosphorus atom, which can react with diols to form oligomers, polymers, or other condensed species. Monomer phosphite or its esters may be phosphite itself (H3PO3), but monomeric partial esters such as dialkyl phosphites may be used for ease of handling or other reasons. The alkyl group(s) may be relatively low molecular weight groups with 1 to 6 or 1 to 4 carbon atoms, such as methyl, ethyl, propyl, or butyl, thereby allowing for the easy removal of alcohols produced during reaction with alkylenediols. An exemplary phosphite is dimethyl phosphite, and others include diethyl phosphite, dipropyl phosphite, dioleil phosphite, and dibutyl phosphite. Sulfur-containing analogs can also be used (e.g., thiophosphite). Other esters include trialkyl phosphites. Mixtures of dialkyl phosphites and trialkyl phosphites may also be useful. In these substances, the alkyl groups may be the same or different, and each may independently have typically 1 to 6 or 1 to 4 carbon atoms as described above.

[0047] A monomer phosphoric acid or ester reacts or condenses with at least two alkylenediols to form phosphorus wear-resistant compounds, which include polymer (or oligomer) phosphorus esters and optionally monomer species. The first alkylenediol(i) is 1,4-alkylenediol, 1,5-alkylenediol, or 1,6-alkylenediol. That is, there are two hydroxyl groups that are 1,4, 1,5, or 1,6 in relation to each other, separated by chains of 4, 5, or 6 carbon atoms, respectively. The first hydroxyl group may be literally on one carbon atom, i.e., on the α-carbon of the diol, or on a higher numbered carbon atom. For example, the diol may also be a 2,5-, or 2,6-, or 2,7-diol, or a 3,6-, or 3,7-, or 3,8-diol, as will be apparent to those skilled in the art. The alkylenediol may be branched (e.g., alkyl-substituted) or unbranched, and in one embodiment it is unbranched. Unbranched, or linear, 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 with one or more secondary hydroxyl groups, even if the carbon chain itself is linear (such as 2,5-hexanediol), can be called branched or substituted diols. The location of the hydroxyl group at positions 1,4, 1,5, or 1,6 (i.e., relative to each other or literal positions) may help promote oligomerization with phosphorus species rather than the formation of a periodic structure (which is sterically undesirable). In certain embodiments, the first alkylenediol may be 1,6-hexanediol.

[0048] The first alkylenedihydroxy compound (diol) may optionally contain additional hydroxyl groups, i.e., more than two, or exactly two, per molecule. In one embodiment, exactly two hydroxyl groups are present per molecule. If there are more than two hydroxyl groups, care must be taken to ensure that there is no excessive cyclization that could hinder the polymerization reaction if there are fewer than four atoms separating any of the hydroxyl groups. Care should also be taken to avoid excessive branching or crosslinking in the product, which could lead to undesirable gel formation. Such problems can be avoided by careful control of the reaction conditions, e.g., control of the ratios of reagents and the order of their addition, carrying out the reaction under suitable dilution conditions, and reacting under low acid conditions. These conditions can be determined by those skilled in the art using only routine experiments.

[0049] Phosphorous acid or esters also react with a second alkylenediol (ii). The second alkylenediol is an alkyl-substituted 1,3-propylenediol in which one or more of its alkyl substituents are located on one or more carbon atoms of the propylene unit, and the total number of carbon atoms of the alkyl-substituted 1,3-propylenediol is 5 to 12, 6 to 12, 7 to 11, 8 to 18, or 9 in certain embodiments. That is, an alkyl-substituted 1,3-propylenediol can be represented by the following general formula: [ka] In the formula, the various 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 group is 2 to 9 or 3 to 9, so that the total number of carbon atoms in the diol is 5 to 12 or 6 to 12, respectively, and so on for other ranges of total carbon atoms. Similar to the 1,4-diols, 1,5-diols, or 1,6-diols described above, the reference to 1,3-diols here means that the two hydroxyl groups are in a 1,3 relationship with each other, i.e., separated by a chain of three carbon atoms. Thus, 1,3-diols may also be called 2,4-diols or 3,5-diols. If a 1,3-diol has one or more secondary hydroxyl groups, such a molecule will be considered a substituted diol. In one embodiment, there are two alkyl substituents and the total number of carbon atoms in the molecule is 9. Suitable substituents may include, for example, methyl, ethyl, propyl, and butyl (and their various possible isomers).

[0050] Examples of a second type of alkylenediol 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-propylpropane-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 some of the aforementioned nomenclature emphasizes the propane-1,3-diol structure of the molecule for clarity. For example, 2-pentylpropane-1,3-diol is sometimes called 2-hydroxymethylheptan-1-ol, but the latter nomenclature does not so clearly illustrate the 1,3-property of the diol.

[0051] The relative molar amounts of the first alkylenediol (i) and the second alkylenediol (ii) may be in a ratio of 30:70 to 65:35, or 35:65 to 60:40, or 40:60 to 50:50, or 40:60 to 45:55. If the ratio is less than approximately 30:70, the resulting product may not fully exhibit the advantages of the disclosed technology, and if it is greater than approximately 65:35, its compatibility with other components in the lubricant formulation may be reduced.

[0052] The relative molar amounts of the monomer phosphorous acid or its ester (a) and the total molar amount of alkylenediol (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 approximately 1:1. Reactions in nearly equimolar ratios tend to promote oligomer or polymer formation. A precise 1:1 ratio theoretically leads to the formation of very long chains, resulting in very high molecular weights. However, in practice, this is typically not achieved because competing reactions and reaction imperfections provide materials with lower degrees of polymerization, and certain parts of the material take the form of cyclic monomers.

[0053] The reaction products typically consist of a mixture of individual species, including several oligomer or polymer species and cyclic monomer species. The cyclic monomer species may contain one phosphorus atom and one alkylene group, mainly derived from 1,3-diol(ii), since the 1,3-diol can be involved in either oligomerization or cyclic esterification. The oligomer or polymer species may typically contain 2 or 3 to 20 phosphorus atoms, or 5 to 10 phosphorus atoms, bonded together by alkylene groups derived from diol(i) and (ii), and may show relative preference for the incorporation of 1,4-diol, 1,5-diol, or 1,6-diol, which are not readily cyclized with phosphorus to form cyclic monomer species.

[0054] The product may be a mixture of species that can be represented by the following structures: [ka] In the formulas, x and y represent the relative amounts of the two diols incorporated into the oligomer. The structures represented by x and y in parentheses may be distributed more or less randomly, influenced by or depending on the availability of various diol reactants; therefore, the structures shown are not intended to indicate that the polymer is necessarily a block polymer. Each X is independently a terminal group, which may be a diol-derived moiety that can be terminated with, for example, an alkyl group (e.g., methyl), or hydrogen, or an OH group. In the scheme above, for illustrative purposes only, diene (i) is selected to be 1,6-hexanediol, and diene (ii) is selected to be 2-butyl-2-ethyl-1,3-propanediol. Using different diols (i) and (ii), the corresponding structures and mixtures are formed.

[0055] The relative amounts of oligomeric species and cyclic monomer species in the reaction mixture will depend to some extent on the specific diol selected and the reaction conditions. In the case of a reaction product prepared from 1,6-hexanediol and 2-butyl-2-ethyl-1,3-propanediol, as shown in the structure above, the amount of oligomeric product may be approximately as shown in the table below. [Table A] Furthermore, the amount of cyclic monomer may be 100% minus the proportion of oligomer. Regardless of the specific diol used, mixtures having the above weight % of oligomer and cyclic monomer can be usefully prepared. In certain embodiments, 55–60 weight percent of the product is in oligomeric form and 45–40 percent is in cyclic monomer form. In some embodiments, the relative amount of cyclic monomer species to oligomeric species is 1:3–1:1 or 1:3–1:0.8 by weight.

[0056] Condensation reactions between phosphoric acid or esters and diols can be achieved by mixing the reagents and heating until the reaction is substantially complete. Typically, the first and second alkylenediols can be mixed simultaneously with or nearly simultaneously with the phosphorus compound, i.e., typically before the reaction with one of the alkylenediols is complete. Small amounts of basic materials, such as sodium methoxide, may also be present. When methyl ester of phosphorous acid is used as the reagent, substantial completion of the reaction can correspond to the generation of methanol from the reaction mixture and the cessation of distillation. Preferred temperatures include 100–140°C, for example, in the range of 110–130°C or 115–120°C. If reaction temperatures above approximately 140°C are used, competitive reactions may occur, and there is a risk that the desired product may not be formed in a useful yield or useful purity. The reaction time can typically be up to 12 hours, depending on the temperature, the pressure applied (if any), stirring, and other variables. In some examples, reaction times of 2–8 hours or 4–6 hours may be appropriate.

[0057] If necessary, other monomers may be included in the reaction mixture. In particular, the inclusion of polycarboxylic acids, such as dicarboxylic acids, may be considered beneficial. For example, the inclusion of relatively small amounts of tartaric acid or citric acid may provide useful properties to the product. The amount of polyacid or diacid may be suitable for incorporating at least one or approximately one poly or dicarboxylic acid monomer unit per molecule of the product oligomer. The amount of polyacid or diacid actually added to the reaction mixture may be greater than this amount. Although not intended to be theoretical, it is thought that in the presence of small amounts of tartaric acid, it may be incorporated as a terminal unit of the polymer and possibly condensed via an ester bond with the OH group of the alkylenediol. Such materials may exhibit good performance in terms of wear protection and corrosion inhibition, as well as sealing properties. Suitable polyacids (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, dodecanediic acid, glutaric acid, and glutamic acid. Other types of monomers that may be included are monocarboxylic acids containing a reactive hydroxyl group, or reactive equivalents of such materials such as anhydrides, esters, or lactones. Examples include glyoxylic acid, caprolactone, valerolactone, and hydroxystearic acid.

[0058] The amount of the above-mentioned phosphite ester product used in the lubricant may be sufficient to provide the composition with 0.01 to 0.3 or 0.1 weight percent of phosphorus, or in other embodiments, 0.02 to 0.07 weight percent or 0.025 to 0.05 weight percent of phosphorus. Of course, the actual amount of product corresponding to these amounts of phosphorus depends on its phosphorus content. Suitable amounts of the ester product in the lubricant additive composition may be 0.01 to 1.0 weight percent, or 0.02 to 0.5 weight percent, or 0.03 to 0.30 weight percent, or even 0.05 to 0.25 weight percent.

[0059] Each of the phosphorus-resistant compounds described above may be present in the lubrication additive composition as is, but the lubrication additive composition may also contain a mixture of two or more compounds. In some embodiments, the phosphorous acid-containing compound may include C3-C8 hydrocarbyl phosphites and phosphite ester products. In some embodiments, the phosphorous acid-containing compound may include each of C3-C8 hydrocarbyl phosphites, C12-C24 hydrocarbyl phosphites, and phosphite ester products. In any case, the phosphorus-resistant compound must be present in an amount that delivers 100-4000 ppm of phosphorus to the lubrication additive composition. In some embodiments, at least one phosphorus-resistant compound may be present in an amount that delivers 125-1000 ppm of phosphorus, or 150-800 ppm of phosphorus to the lubrication additive composition.

[0060] The lubricating additive composition may contain substantially sulfur-free alkyl phosphates, as further described. In this salt composition, at least 30 mole percent of the phosphorus atoms are alkyl pyrophosphate structures, as opposed to orthophosphate (or monomeric phosphoric acid) structures. The percentage of phosphorus atoms in the pyrophosphate structures may be 30 to 100 mole%, or 40 to 90%, 50 to 80%, 55 to 70%, or 55 to 65%. The remaining amount of phosphorus atoms may be orthophosphate structures, or may consist of partially unreacted phosphates or other phosphorus species. In one embodiment, up to 60 or up to 50 mole percent of the phosphorus atoms are mono- or di-alkyl-orthophosphate salt structures.

[0061] Substantially sulfur-free alkyl phosphate salts exist in pyrophosphate form (sometimes called POP structure). In certain embodiments, at least 80 mole percent, or at least 85, 90, 95, or 99 percent, of the alkyl group in the alkyl phosphate salt are primary alkyl groups. In some embodiments, the alkyl group may have 4 to 22, or 4 to 20, or 4 to 18, or even 4 to 12 carbon atoms, or 5 to 10, 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 having 6, 7, 8, 9, 10, 11, or 12 carbon atoms and their isomers. In some embodiments, alkyl groups may have a methyl branch at the α-position of the group, one example being the 4-methyl-2-pentyl (also known as 4-methylpenta-2-yl) group.

[0062] Such alkyl (including cycloalkyl) groups are typically produced by the reaction of the corresponding alcohol or multiple alcohols with phosphorus pentoxide (referred to as P2O5 herein, but a more likely structure is P4O 10 (It is recognized that it can be represented as follows). Therefore, alkyl phosphate salts can be prepared by the reaction of phosphorus pentoxide with a primary alcohol having 4 to 12 carbon atoms, and the reaction of the product with a salting material, as will be described in more detail below.

[0063] Pyrophosphate esters can be isolated from orthoesters as needed, but it is also possible, and commercially preferable, to use the reaction mixture without separating the components.

[0064] In one embodiment, the phosphorus-resistant compound may include a phosphorus-containing acid, salt, or ester, or a mixture thereof. In one embodiment, the phosphorus-resistant compound may be in the form of a mixture.

[0065] Phosphorus-based wear-resistant compounds may include those derived from phosphoric acid, phosphorous acid, thiophosphate, thiophosphate, or mixtures thereof.

[0066] In one embodiment, the phosphorus wear-resistant 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.

[0067] In one embodiment, the phosphorus-resistant compound may include an ammonium salt or amine salt of a phosphorus-containing acid or ester.

[0068] Examples of amine salts of phosphorus acids or esters include phosphate esters and their amine salts, dialkyldithiophosphate esters and their amine salts, amine salts of phosphates, and amine salts of phosphorus-containing carboxylic acid esters, ethers, and amides, as well as mixtures thereof.

[0069] The alkyl group of the phosphorus wear-resistant compound may have a length of 2 to 12 carbon atoms, or 3 to 10 or 4 to 8 carbon atoms.

[0070] Amine salts of phosphorus acids or esters can be used alone or in combination.

[0071] In one embodiment, the amine salt of a phosphorus acid or ester includes a partial amine salt, a partial amine-metal salt compound, or a mixture thereof.

[0072] Pyrophosphates, phosphate esters, or mixtures of phosphate esters react with a salting material to form an amine salt. The salting material may be a metal for forming a metal salt, or an amine for forming an amine salt.

[0073] Examples of 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.

[0074] The amine in the amine salt is R 2 It can be expressed as 3N, where each R 2 R is independently a hydrogen atom, a hydrocarbyl group, an ester-containing group, or an ether-containing group, provided that at least one R 2 The group is a hydrocarbyl group, an ester-containing group, or an ether-containing group (i.e., not NH3). Suitable hydrocarbylamines 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), and higher amines. Other primary amines include dodecylamines and fatty amines (such as n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine, and oleylamine). Other useful fatty amines include commercially available fatty amines such as "Armeen®" amines (products available from Akzo Chemicals, Chicago, Ill), e.g., Armeen® C, Armeen® O, Armeen® OL, Armeen® T, Armeen® HT, Armeen® S, and Armeen® SD, where the letters refer to aliphatic groups such as coco, oleyl, talo, or stearyl groups.

[0075] Examples of secondary amines that can be used include dimethylamine, diethylamine, dipropylamine, dibutylamine, diamylamine, dihexylamine, diheptylamine, methylethylamine, ethylbutylamine, bis-2-ethylhexylamine, N-methyl-1-aminocyclohexane, Armeen® 2C, and ethylamylamine. Secondary amines may also be cyclic amines such as piperidine, piperazine, and morpholine.

[0076] Suitable tertiary amines include tri-n-butylamine, tri-n-octylamine, tri-decylamine, tri-laurylamine, tri-hexadecylamine, and dimethyloleylamine (Armeen® DMOD). Triisodecylamine or tridecylamine and their isomers can be used.

[0077] Examples of amine mixtures include (i) amines having 11 to 14 carbon atoms in the tertiary alkyl primary group, (ii) amines having 14 to 18 carbon atoms in the tertiary alkyl primary group, or (iii) amines having 18 to 22 carbon atoms in the tertiary alkyl primary group. Other examples of tertiary alkyl primary amines include tert-butylamine, tert-hexylamine, tert-octylamine (such as 1,1-dimethylhexylamine), tert-decylamine (such as 1,1-dimethyloctylamine), tert-dodecylamine, tert-tetradecylamine, tert-hexadecylamine, tert-octadecylamine, tert-tetracosanylamine, and tert-octacosanylamine. In one embodiment, useful mixtures of amines include "Primene® 81R" or "Primene® JMT". Primene® 81R and Primene® JMT (both manufactured and sold by Rohm & Haas) can be mixtures of C11 - C14 tertiary alkyl primary amines and C18 - C22 tertiary alkyl primary amines, respectively.

[0078] In one embodiment, the amine salt of the phosphoric acid or ester as described above may include an amine having a tertiary alkyl primary group of about C n to about C 14 or a mixture thereof. In one embodiment, the amine salt of the phosphorus compound may include an amine having a tertiary alkyl primary amine of about C 14 to about C 18 or a mixture thereof. In one embodiment, the amine salt of the phosphorus compound is about C18 ~About C 22 It contains amines having a tertiary alkyl primary amine or mixtures thereof.

[0079] In one embodiment, the amine salt of phosphoric acid or ester as described above is C 11 ~C 14 Primene® 81R (produced and sold by Rohm & Haas), a mixture of tertiary alkyl primary amines, and C 14 ~C 18 It may be a reaction product of alkylated phosphoric acid. In other embodiments, the amine may be an ester-containing amine such as an N-hydrocarbyl-substituted γ- or δ-amino(thio) ester, and therefore a secondary amine. One or both of the oxygen atoms of the ester group may be replaced by sulfur, but typically the sulfur atoms may not be present.

[0080] One or more further 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 hydrocarbyl group. It is understood that similar structures for δ-aminoesters are included.

[0081] In one embodiment, the material may be a methyl succinate diester having an amine substitution on a methyl group. In a particular embodiment, the material may be or contain 2-((hydrocarbyl)-aminomethylsuccinate dihydrocarbyl ester (which may also be referred to as dihydrocarbyl 2-((hydrocarbyl)aminomethylsuccinate).

[0082] The N-hydrocarbyl-substituted γ-aminoester or γ-aminothioester materials disclosed herein can typically be prepared by Michael addition of a primary amine having the branched hydrocarbyl group described above to an ethylenically unsaturated ester or thioester of the same type as described above. In this example, the ethylenically unsaturated portion is between the β-carbon and γ-carbon atoms of the ester.

[0083] The N-hydrocarbyl-substituted δ-aminoester or δ-aminothioester materials disclosed herein may be prepared by reductive amination of esters of 5-oxy-substituted carboxylic acids or 5-oxy-substituted thiocarboxylic acids. They may 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 hexanedioic acid, or by alkylation of esters of 2-aminohexanedioic acid.

[0084] Details of N-substituted γ-aminoesters and their synthesis can be found in International Publication No. 2014 / 074335, Lubrizol, May 15, 2014. Details of N-substituted δ-aminoesters and their synthesis can be found in International Application PCT / US2015 / 027958 (Lubrizol, filed April 28, 2015) and U.S. Patent Application No. 61 / 989306 (filed May 6, 2015).

[0085] Any type of amine reacts to neutralize the acidic groups on the phosphate ester components, including the pyrophosphate esters and any orthophosphate esters that may be present.

[0086] When the amine salt is an amine salt of the above-mentioned phosphate ester, the amount of amine salt used in the lubricant may be 0.05 to 2.0% by weight, or 0.75 to 1.5% by weight, or 0.1 to 1.2% by weight.

[0087] The amount of phosphite-based anti-wear agent may be suitable for providing phosphorus to the lubricant formulation in an amount of 200 to 3000 parts per million by weight (ppm).

[0088] If the lubricant composition is substantially sulfur-free (less than 250 ppm, or less than 100 ppm, or less than 50 ppm, or less than 25 ppm, or even completely sulfur-free), then the phosphite-anti-wear agent may be a suitable phosphate for providing phosphite to the lubricant compound in amounts of 100 to 5000 ppm, or 125 to 3000 ppm, or 125 to 2000 ppm, or 125 to 2000 ppm, or 100 to 200 ppm. Antioxidants

[0089] The lubricating additive composition may also contain antioxidants, such as aromatic amine antioxidants, hindered phenol antioxidants including ester-containing hindered phenol antioxidants, and sulfurized olefin antioxidants. These antioxidants may be present in amounts of 0.01 to 5, or 0.15 to 3, or 0.2 to 1.5, or 0.2 to 1, or 0.25 to 0.7 weight percent.

[0090] In one embodiment, the lubricating additive composition of the present invention contains an arylamine antioxidant. The arylamine antioxidant may be phenyl-α-naphthylamine (PANA), a hydrocarbyl-substituted diphenylamine, or a mixture thereof. Examples of hydrocarbyl-substituted diphenylamines include mono- or di-C4-C16 alkyldiphenylamines, C6-C12 alkyldiphenylamines, or C9 alkyldiphenylamines. For example, the hydrocarbyl-substituted diphenylamine may be octyldiphenylamine, dioctyldiphenylamine, dinonyldiphenylamine, typically dinonyldiphenylamine.

[0091] If present, the arylamine antioxidant may be present in an amount of 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 lubricating additive composition.

[0092] Hindered phenol antioxidants often contain secondary and / or tertiary butyl groups as sterically hindering groups. The phenol group is often further substituted with a hydrocarbyl group and / or a crosslinking group that bonds to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenol antioxidant may be an ester, such as Irganox® L-135 from Ciba, or butyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate.

[0093] If present, the hindered phenol antioxidant may be present in an amount of 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 lubricating additive composition.

[0094] Antioxidants include sulfurized olefins such as monosulfides, disulfides, or mixtures thereof. These materials generally have sulfide bonds containing 1 to 10, for example, 1 to 4, or 1 or 2 sulfur atoms. Materials that can be sulfurized for use as sulfurized antioxidants in lubricating additive compositions include oils, fatty acids and esters, olefins and polyolefins made therefrom, terpenes, or Diels-Alder adducts. Details of methods for preparing such sulfurized materials can be found in U.S. Patents No. 3,471,404 and No. 4,191,659. Sulfur-free cleaning agents

[0095] The lubricating additive composition also includes a sulfur-free cleaning agent composition. The sulfur-free cleaning agent may be selected from salicylate, phenate, or salixalate cleaning agents. Typically, such cleaning agents are metal-containing cleaning agents, and this metal may be sodium, potassium, calcium, magnesium, or a mixture thereof.

[0096] The sulfur-free metal-containing detergent used in the present invention may be an overbasic detergent, a non-overbasic detergent, or a mixture thereof. Typically, the detergent is overbasic.

[0097] The preparation of metal-containing detergents is known in the art. Patents describing the preparation of perbasic metal-containing detergents include U.S. Patents Nos. 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.

[0098] The metal-containing detergent may be a non-perbasic detergent (sometimes called a neutral detergent). The TBN of a non-perbasic detergent may be 20 to less than 200 mg, or 30 to 100 mg, or 35 to 50 mg KOH / g. Alternatively, the TBN of a non-perbasic metal-containing detergent may be 20 to 175 mg, or 30 to 100 mg KOH / g.

[0099] When used herein, the cited TBN values ​​and associated TBN ranges are "as is," i.e., containing the conventional amount of diluent oil. The conventional amount of diluent oil is typically in the range of 30% to 60% (often 40% to 55% by weight) of the detergent component.

[0100] The metal-containing cleaning agent may be, for example, an overbasic cleaning agent having TBN greater than 200 mg KOH / g (typically 250-600 or 300-500 mg KOH / g).

[0101] Overbasic metal-containing detergents can be formed, for example, by the reaction of a basic metal compound containing sodium, potassium, calcium, or magnesium with an acidic detergent substrate. The acidic detergent substrate may include alkyl salicylic acid.

[0102] Basic metal compounds are used to supply basicity to cleaning agents. Basic metal compounds are compounds of metal hydroxides or oxides.

[0103] Oxides and / or hydroxides can be used alone or in combination. Oxides or hydroxides can be hydrated or dehydrated, but hydration is typical. In one embodiment, the basic metal compound may be calcium hydroxide, which can be used alone or in mixtures with other metal basic compounds. Calcium hydroxide is often called lime. In one embodiment, the calcium basic compound may be calcium oxide, which can be used alone or in mixtures with other metal basic compounds.

[0104] Salicylate detergents are typically derived from p-hydrocarbylphenols, or generally from alkylphenols. These alkylphenols are carboxylated to form salicylate detergents. Suitable alkyl salicylates include alkylated propylene oligomers, butene oligomers, particularly those with n-butene tetramers and pentamers, and those with alkylated alpha-olefins, isomerized alpha-olefins, and polyolefins such as polyisobutylene.

[0105] The cleaning agent does not need to be boric or not.

[0106] The chemical structure of salicylate cleaning agents is known to those skilled in the art. A general disclosure of such cleaning agents and their structure is provided on pages 220-223 of the standard textbook entitled "Chemistry and Technology of Lubricants," 3rd edition, edited by RMMortier and STOrszulik, copyright 2010, under subheading 7.2.6.

[0107] In one embodiment, a sulfur-free metal-containing detergent may be a sodium, potassium, calcium, or magnesium-containing detergent, or a mixture thereof. Such detergents and their preparations are well known in the art, but may also include those to be developed in the future. However, the ratio of TBN to metal may vary slightly. A more detailed explanation of the terms "metal ratio," "TBN," and "soap content" is known to those skilled in the art and is described in standard textbooks, for example, pages 219-220 of subheading 7.2.5 in "Chemistry and Technology of Lubricants," Third Edition, Edited by RMMortier and STOrszulik, Copyright 2010. Classification of detergents.

[0108] In one embodiment, the cleaning agent is a calcium-containing cleaning agent. In one embodiment, the cleaning agent contains or comprises a calcium salicylate. The calcium-containing cleaning agent is included in the composition in an amount sufficient to deliver 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 further 400 ppm to 750 ppm of calcium. Other additives

[0109] The lubricating additive composition may contain additives in addition to those listed above.

[0110] The lubricating additive composition may also contain poly(meth)acrylate polymer viscosity modifiers. When used herein, the following viscosity modifier ranges are determined by GPC using polystyrene standards having a weight-average molecular weight in the range of 350 to 100,000.

[0111] In one embodiment, the lubricating additive composition comprises a linear poly(meth)acrylate polymer having a weight-average molecular weight of 5,000 to 25,000, or 8,000 to 20,000.

[0112] Linear poly(meth)acrylate polymers may be present in the lubricating additive composition in amounts of about 0.1% to about 5% by weight, or 0.1% to 4% by weight, or 0.2% to 3% by weight, or 0.5% to 3% by weight, or 1.0% to 4% by weight, or 0.6% to 4% by weight, or 0.75% to 3% by weight, or 0.2% to 0.75% by weight.

[0113] The poly(meth)acrylate polymer comprises (a) 50% to 95% by weight, or 60% to 80% by weight, of alkyl(meth)acrylate, wherein the alkyl group of the (meth)acrylate has 10 to 15 carbon atoms, and (b) 1% to 40% by weight, or 4% to 35% by weight, of alkyl(meth)acrylate, wherein the alkyl group of the (meth)acrylate has 1 to 9 carbon atoms. A monomer composition comprising (c) 1% to 10% by weight, or 1% to 8% by weight, of a dispersant-functional monomer; (d) 0% to 4% by weight, or 0% to 2% by weight, or 0% by weight, of a vinyl aromatic monomer (typically styrene); and (e) 0% to 9% by weight, or 0% to 6% by weight, of an alkyl (meth)acrylate, wherein the alkyl group of the (meth)acrylate has 16 to 18 carbon atoms. In one embodiment, the linear polymer may contain 0% to 20% by weight of 16 to 18 alkyl (meth)acrylate.

[0114] In one embodiment, the linear polymer contains a poly(meth)acrylate (typically polymethacrylate) having units derived from a mixture of alkyl(meth)acrylate ester monomers different from (a) and (b), vinyl aromatic compounds (or vinyl aromatic monomers), and nitrogen-containing vinyl monomers, provided that 60% or less by weight of the ester, or 50% or less by weight of the ester, or 35% or less by weight of the ester, contains 10 or fewer carbon atoms in the alcohol derivative of the ester group. This type of linear polymer is described in detail in U.S. Patent No. 6,124,249 or European Patent Application Publication No. 0937769(A1), paragraphs

[0019] and

[0031] -

[0067] (wherein “alcohol-derived portion” is written as R’C(=O)-OR, it refers to the “-OR” portion of an ester, regardless of whether it is actually prepared by reaction with an alcohol). Optionally, the linear polymer may further 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%, 2% to 10%, or even 1% to 3% of the composition.

[0115] 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.

[0116] Esters are usually aliphatic esters, typically alkyl esters. In one embodiment, the ester of (a) may be a C12-C15 alkyl (meth)acrylate, and the ester of (b) may be a 2-ethylhexyl (meth)acrylate.

[0117] In one embodiment, the ester group in ester (a) contains a branched alkyl group. The ester group may contain 2-65% or 5-60% of ester groups having a branched alkyl group. The branched alkyl group may be β-branched and may contain 8-60, 8-30, or 8-16 carbon atoms. For example, the branched alkyl group may be derived from commercially available alcohols such as 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol, 2-octyldodecanol, 2-decyltetradecanol, or mixtures thereof, or Isofol® branched Guerbet alcohols available from Sasol.

[0118] The C1-C4 alkyl substituents can be any isomer of methyl, ethyl, propyl, and butyl.

[0119] The weight-average molecular weight of linear poly(meth)acrylate may 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.

[0120] Linear polymers may exhibit dispersant functionality and may therefore be referred to as viscosity modifiers or dispersible viscosity modifiers. References to “dispersible viscosity modifiers” herein exclude dispersants, which are a distinct class of compounds. Linear polymers may be used as the only viscosity modifier (or dispersible viscosity modifier) ​​present in 0.5% to 4% by weight linear (meth)acrylic 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, and the lubricating viscosity oils have a kinematic viscosity of 4 to 6 cSt (mm² / s) and a viscosity index of 120 to 150 at 100°C.

[0121] In one embodiment, the lubricating additive composition may contain only two linear polymer viscosity modifiers having dispersant functionality, and the linear polymer has a weight-average molecular weight of 5,000 to 25,000 or 10,000 to 20,000.

[0122] In one embodiment, the lubricating additive composition may contain 0.1% to 4% (or 0.2% to 3% by weight) of a linear (meth)acrylic polymer viscosity modifier having dispersant functionality, wherein the linear polymer has a weight-average molecular weight of over 25,000 to 400,000 (or up to 350,000) or 30,000 to 150,000. A linear (meth)acrylic polymer with a weight-average molecular weight of 25,000 to 400,000 (or up to 350,000) may be considered chemically similar to a linear (meth)acrylic polymer with a weight-average molecular weight of 5,000 to 25,000, except that it has a different weight-average molecular weight.

[0123] The lubricating additive composition may contain a linear polymer viscosity modifier having dispersant functionality, comprising 0.1% to 5% (or 1% to 4% by weight) of a linear (meth)acrylic 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% to 4% (or 1% to 3% by weight) of a linear (meth)acrylic polymer viscosity modifier having dispersant functionality, and the linear polymer has a weight-average molecular weight of over 20,000 to 250,000 (or 30,000 to 150,000).

[0124] As described below, the molecular weight of the viscosity modifier was determined using known methods such as GPC analysis using a polystyrene standard. Methods for determining the molecular weight of polymers are well known. These methods are described, for example, as follows: (i) PJ Flory, "Principles of star polymer Chemistry", Cornell University Press 91953), Chapter VII, pp 266-315, or (ii) "Macromolecules, an Introduction to star polymer Science", FA Bovey and FH Winslow, Editors, Academic Press (1979), pp 296-312.

[0125] In one embodiment, the lubricating additive may also include a boron-containing compound.

[0126] The lubricating additive composition may contain a boron-containing compound in an amount sufficient to provide about 75 ppm to about 500 ppm of boron relative to the lubricating additive composition, or about 85 to about 450 ppm or about 95 to about 350 ppm of boron, or about 100 to about 400 ppm of boron relative to the lubricating additive composition.

[0127] Boron can be delivered by many types of boron-containing compounds.

[0128] The boron-containing compound may be a dispersant that has been post-treated with a boron source, as described above.

[0129] Boron-containing compounds may include, for example, boron-containing friction modifiers such as borooxide fatty epoxides, borooxide glycerol esters, and borooxide alkoxylated fatty amines.

[0130] Boron-containing compounds may also include boric acid detergents. These boric acid detergents may include, for example, the overbasic boric acid materials described in U.S. Patent Nos. 5,403,501 and 4,792,410.

[0131] Boron-containing compounds may also include borate esters. A borate ester may be a compound represented by one or more of the following formulas: [ka] In the formulas, each R can independently be a hydrocarbyl group, the term as defined herein, and any two adjacent R groups can together form a cyclic group. A mixture of two or more of the above can be used. The total number of carbon atoms in the R groups in each formula must be sufficient to make the compound soluble in the base oil. In general, the total number of carbon atoms in the R groups is at least about 3, at least about 5 in one embodiment, and at least about 8 in another embodiment. There is no limit to the total number of carbon atoms required in the R groups, but a practical upper limit is about 400 or about 500 carbon atoms.

[0132] In embodiments, each R may independently be a hydrocarbyl group containing 1 to 14, 2 to 13, or further 3 to 10 or 12 carbon atoms, provided that the total number of carbon atoms in all R is 3 or more, preferably 4 or more, and more preferably 6 or more. In some embodiments, each R may independently be C3 to C22, C3 to C18, or C3 to C12 alkyl. Examples of useful R groups include isopropyl, n-butyl, isobutyl, amyl, 4-methyl-2-pentyl, 2-ethyl-1-hexyl, isooctyl, decyl, dodecyl, 2-propylheptyl, tetradecyl, 2-pentenyl, dodecenyl, phenyl, naphthyl, alkylphenyl, and the like.

[0133] Preferred 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 include, for example, compounds of formula I, where each R is independently a C3-C22, C3-C18, or C3-C12 alkyl, such as tri-2-ethylhexyl borate, tris(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 tris(2-propylheptyl borate). In some embodiments, the borate ester may be tri-2-ethylhexyl borate.

[0134] In one embodiment, the boro oxide ester can be represented by the formula B(OC5H11)3 or B(OC4H9)3. In one embodiment, the borate ester may be tri-n-butyl borate.

[0135] In one embodiment, the boric acid ester may be a phenol compound represented by the following formula: [ka] In formula VII, R1, R2, R3, and R4 are independently hydrocarbyl groups of 1 to about 12 carbon atoms, and R5 and R6 are independently alkylene groups of 1 to about 6 carbon atoms, in one embodiment about 2 to about 4 carbon atoms, and in one embodiment 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 each is a t-butyl group. In one embodiment, R3 and R4 independently are hydrocarbyl groups of about 2 to about 12 carbon atoms, and in one embodiment about 8 to about 10 carbon atoms. In one embodiment, R5 and R6 independently are -CH2CH2- or -CH2CH2CH2-.

[0136] In one embodiment, the borate ester may be a compound represented by the following formula: [ka] In formula IX, each R is independently either hydrogen or a hydrocarbyl group. Each hydrocarbyl group may contain 1 to about 12 carbon atoms, and in one embodiment, 1 to about 4 carbon atoms. An example is 2,2'-oxy-bis-(4,4,6-thymethyl-1,3,2-dioxaporinane).

[0137] Boric acid ester may be used in the lubricating additive composition in an amount of about 0.2 or 0.3 to about 2.0% by weight, or optionally about 0.35 to 2.0% by weight, in one embodiment about 0.25 to about 1.0% by weight, and in one embodiment about 0.25 to about 0.75% by weight, based on the weight of the lubricating additive composition.

[0138] In one embodiment, the lubricating additive composition may comprise an ester of a polyol and an aliphatic carboxylic acid containing 12 to 24 carbon atoms.

[0139] Polyols include diols, triols, and alcohols with a large number of alcoholic OH groups. Examples of polyhydric alcohols include ethylene glycols such as diethylene glycol, triethylene glycol, and tetraethylene glycol; propylene glycols such as dipropylene glycol, tripropylene glycol, and tetrapropylene glycol; glycerol, butanediol, hexanediol, sorbitol, arabitol, mannitol, sucrose, fructose, glucose, cyclohexanediol, erythritol, and pentaerythritols such as dipentaerythritol and tripentaerythritol. Preferably, these are diethylene glycol, triethylene glycol, glycerin, sorbitol, pentaerythritol, and dipentaerythritol.

[0140] Aliphatic carboxylic acids that form esters are acids containing 12 to 24 carbon atoms. Such acids can be characterized by the following general formula R1-(CO)OH, where R1 is a hydrocarbyl group, which may be a linear hydrocarbyl group, a branched or cyclic hydrocarbyl group, or a mixture thereof. Linear hydrocarbyl groups containing 12 to 24 carbon atoms, for example, 14 to 20 or 16 to 18 carbon atoms, are preferred. Such acids can also be used in combination with acids having more or fewer carbon atoms.

[0141] Generally, if the reaction conditions and the amounts of reactants are not carefully controlled, polycarboxylic acids tend to form polymer products, and therefore, acid R1-(CO)OH is a monocarboxylic acid. However, mixtures of monocarboxylic acids with 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.

[0142] The aforementioned esters are, in particular, monoesters of such polyols and such carboxylic acids. A preferred ester is glycerol monooleate. It should be understood that glycerol monooleate, as in the case of other such materials, in its commercially available grades is a mixture containing materials such as glycerol, oleic acid, other long-chain acids, glycerol dioleate, and glycerol trioleate. Commercial materials are thought to contain about 60 ± 5 wt percent of the chemical species "glycerol monooleate," in addition to 35 ± 5 percent glycerol dioleate, and less than about 5 percent trioleate and oleic acid. The amounts of monoesters described below are calculated based on the actual, modified amount of polyol monoester present in any such mixture.

[0143] The amount of the aforementioned ester in the lubricating additive composition is typically about 0.01 to about 1.0% by weight of the lubricating additive composition, but it may also be about 0.05 to about 0.5 or 0.8, or about 0.1 to about 0.6% by weight.

[0144] In addition to the esters mentioned above, the lubricating additive composition may also contain alcohol esters and aliphatic carboxylic acids containing about 4 to about 8 carbon atoms.

[0145] Alcohols include both monohydric alcohols and polyhydric alcohols (i.e., polyols). The carbon atoms of alcohols can be linear, branched, or a mixture thereof.

[0146] The preferred polyols are the same as those listed above.

[0147] If branched, the alcohol may be a Guerbet alcohol or a mixture thereof. Guerbet alcohols are 1) alkyl groups containing a C15-C16 polymethylene group such as a 2-C1-C15 alkyl-hexadecyl group (e.g., 2-octylhexadecyl) and a 2-alkyl-octadecyl group (e.g., 2-ethyloctadecyl, 2-tetradecyl-octadecyl, and 2-hexadecyloctadecyl), and 2) 1-C1-C15 alkyl-tetradecyl group (e.g., 2-hexyltetradecyl, 2-decyltetradecyl, and 2- 3) alkyl groups containing a C13-C14 polymethylene group, such as undecyltridecyl and 2-C1-C15 alkyl-hexadecyl groups (e.g., 2-ethyl-hexadecyl and 2-dodecylhexadecyl), 2-C1-C15 alkyl-dodecyl groups (e.g., 2-octyldodecyl), 2-C1-C15 alkyl-dodecyl groups (2-hexyldodecyl and 2-octyldodecyl), 2-C1-C15 alkyl-tetradecyl groups (e.g., 2- 4) Alkyl groups containing C10-C12 polymethylene groups such as hexyltetradecyl and 2-decyltetradecyl, 2-C1-C15 alkyl-decyl groups (e.g., 2-octyldecyl), 2,4-di-C1-C15 alkyl-decyl groups (e.g., 2-ethyl-4-butyl-decyl), 3) 2-(3-methylhexyl)-7-methyldecyl and 2-(1,4,4-trimethylbutyl) 6) The alkyl group may contain alkyl groups such as C1-C5 polymethylene groups including -5,7,7-trimethyl-octyl groups, and alkyl groups such as mixtures of two or more branched alkyl groups such as alkyl residues of oxo alcohols corresponding to propylene oligomers (hexamers to decahtamers), ethylene / propylene (molar ratio 16:1 to 1:11) oligomers, isobutene oligomers (pentamers to octamers), and C5-C17 α-olefin oligomers (dimers to hexamers).

[0148] Suitable examples of branched monohydric alcohols include 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol, 2-octyldodecanol, 2-decyltetradecanol, isotridecanol, isooctanool, oleyl alcohol, Guerbet alcohol, or mixtures thereof. Examples of monohydric linear alcohols include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, or mixtures thereof. In one embodiment, the monohydric alcohol contains 6 to 30 carbon atoms, or 8 to 20 carbon atoms, or 8 to 15 carbon atoms (typically 8 to 15 carbon atoms).

[0149] Aliphatic carboxylic acids that form esters are acids containing 4 to 8 carbon atoms. While aliphatic, aliphatic carboxylic acids can contain ethylenically unsaturated compounds along the C4-C8 alkyl group backbone. In addition, such acids may be monocarboxylic acids, dicarboxylic acids, anhydrides, or mixtures thereof. Examples of carboxylic acids include succinic acid, maleic acid, fumaric acid, glutaconic acid, glutaric acid, adipic acid, citraconic acid, mesaconic acid, pimelic acid, suberic acid, butyric acid, valeric acid, caproic acid, enanthic acid, and caprylic acid.

[0150] Particularly preferred esters may be adipic acid esters, such as C8-C13 or C8-C12 adipate esters like diisooctyl adipate or ditridecyl adipate. Other esters may include, for example, pentaerythritol esters, neopentyl esters, and trimethylol esters.

[0151] The amount of the aforementioned ester in the lubricating additive composition is typically about 0.1 to about 3.0% by weight of the lubricating additive composition, but it may also be about 0.2 to about 2.5 or about 0.3 to about 2.0% by weight.

[0152] Carboxylic acid esters are prepared by a well-known reaction between at least one carboxylic acid (or its reactive equivalent, such as an ester, halide, or anhydride) and at least one of the above-mentioned hydroxy compounds.

[0153] Another component of the lubricating additive composition may be a metal deactivator. Examples of such materials include 2,5-dimercapto-1,3,4-thiadiazole and / or derivatives thereof. Such materials are described in European Patent Publication No. 0761805, which is incorporated herein by reference.

[0154] The metal deactivators useful herein reduce the corrosion of metals such as copper. These metal deactivators are also called metal passivators. These metal deactivators are typically nitrogen and / or sulfur-containing heterocyclic compounds, such as dimercaptothiadiazole, triazole, aminomercaptothiadiazole, imidazole, thiazole, tetrazole, hydroxyquinoline, oxazoline, imidazoline, thiophene, indole, indazole, quinoline, benzoxazine, dithiol, oxazole, oxatriazole, pyridine, piperazine, triazine, and any one or more derivatives thereof. The metal deactivator preferably comprises at least one triazole, which may be substituted or unsubstituted. Examples of suitable compounds include benzotriazoles, alkyl-substituted benzotriazoles (e.g., tolyltriazole, ethylbenzotriazole, hexylbenzotriazole, octylbenzotriazole, etc.), aryl-substituted benzotriazoles (e.g., phenolbenzotriazole, etc.), and alkylaryl or arylalkyl-substituted benzotriazoles, as well as substituted benzotriazoles in which the substituents may be hydroxyl, alkoxy, halo (especially chloro), nitro, carboxy, and carboxyalkoxy. Preferably, the triazole is a benzotriazole or alkylbenzotriazole containing an alkyl group with 1 to about 20 carbon atoms, preferably 1 to about 8 carbon atoms. Benzotriazoles and tolyltriazoles are useful.

[0155] In one embodiment, the metal deactivator is a reaction product of a dispersant and dimercaptothiadiazole. Dispersants can generally be characterized as reaction products of carboxylic acids and amines and / or alcohols. These reaction products are commonly used as dispersants in the field of lubricants and are sometimes referred to as dispersants in general, despite the fact that they may have other uses in addition to or instead of as dispersants. Carboxylic acid dispersants include succinimide dispersants, ester-type dispersants, and the like. Succinimide dispersants are generally the reaction of a polyamine with an alkenyl succinic anhydride or acid. Ester-type dispersants are the reaction products of an alkenyl succinic anhydride or acid with a polyol compound. The reaction product may then be further treated with an amine such as a polyamine. Examples of useful dispersants are disclosed in U.S. Patents 3,219,666 and 4,234,435, which are incorporated herein by reference. Useful dispersants also include ashless dispersants, which are discussed below. Generally, the reaction occurs between a dispersant and dimercaptothiadiazole by mixing them and heating to a temperature above about 100°C. U.S. Patents 4,140,643 and 4,136,043 describe compounds prepared by such reactions of dispersants with dimercaptothiadiazole. These patents are incorporated herein by reference with respect to their disclosures of dispersants, dimercaptothiadiazole, methods for reacting these two, and products obtained from such reactions.

[0156] In one embodiment, the metal deactivator is a reaction product of phenol, an aldehyde, and dimercaptothiadiazole. The phenol is preferably an alkylphenol containing at least about 6 alkyl groups, preferably 6 to about 24, more preferably about 6, or about 7 to about 12 carbon atoms. The aldehyde is preferably an aldehyde synthone such as formaldehyde or aldehyde containing 1 to about 7 carbon atoms. Preferably, the aldehyde is formaldehyde or paraformaldehyde. The aldehyde, phenol, and dimercaptothiadiazole are reacted by mixing them at a temperature of up to about 150°C, preferably about 50°C to about 130°C, in a molar ratio of about 0.5 to about 2 moles of phenol and about 0.5 to about 2 moles of aldehyde per mole of dimercaptothiadiazole. Preferably, the three reagents react in equimolar amounts.

[0157] In one embodiment, the metal deactivator is bis(hydrocarbyldithio)thiadiazole. Preferably, each hydrocarbyl group is independently an alkyl, aryl, or aralkyl group having 6 to about 24 carbon atoms. Each hydrocarbyl can independently be t-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 from Amoco Chemical Company under the trade name Amoco 150. These dithiothiadiazole compounds are disclosed as component (d) in PCT Publication WO88 / 03551, which is incorporated by reference to the disclosure of dithiothiadiazole compounds. In a preferred embodiment, the metal deactivator is a dimercaptothiadiazole derivative. The following D-1 and D-2 are specific examples. Example D-1

[0158] Example D-1 2,5-dimercapto-1,3,4-thiadiazole oxidatively bonded to t-nonyl mercaptan, 100% chemical substance, S36%, N64%.

[0159] Example D-2 Heptylphenol conjugated with 2,5-dimercapto-1,3,4-thiadiazole using formaldehyde (thiadiazole is generated in situ), 20% oil, 17.75% sulfur, 5.5% nitrogen.

[0160] When used, the amount of metal deactivator in the lubricating additive composition may generally be in the range of about 0.01 to about 0.5% by weight of the lubricating additive composition. In some embodiments, the amount of metal deactivator may be in the range of about 0.02 to about 0.42% by weight, or about 0.03 to about 0.33% by weight, or about 0.04 to about 0.24% by weight of the lubricating additive composition.

[0161] Another component of the present invention may be a boro oxide epoxide containing 12 to 24 carbon atoms. Alternatively, this material can be described as a borate ester of a vicinal diol containing 12 to 24 carbon atoms. Such a material may be represented by the following structure: [ka] In the formula, R 1 , R 2 , R 3 , and R 4Each of these independently forms a hydrogen or aliphatic radical, or any two of them together with the carbon atoms they are bonded to to form a cyclic radical. Preferably, at least one of the R groups may be an alkyl group containing at least eight or at least ten carbon atoms. In one embodiment, one of the R groups may be such an alkyl group, and the remaining R group may be hydrogen. Epoxide borooxides are described in detail in U.S. Patent No. 4,584,115. Epoxide borooxides are generally prepared by reacting an epoxide with a boron source such as boric acid or boron trioxide. Epoxide borooxide itself is not an epoxide, but is a ring-opening boron-containing reaction product of an epoxide. Suitable epoxides include C 14~16 or C 14~18 or C 16~18 The composition includes commercially available mixtures of epoxides, which can be purchased from Elf-Atochem or Union Carbide and prepared from the corresponding olefins by known methods. Purified epoxy compounds such as 1,2-epoxyhexadecane can be purchased from Aldrich Chemicals. Boroxide compounds are prepared by blending boron compounds with epoxides and heating them 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 reaction media. Water is formed and is typically distilled off during the reaction. The reaction can be catalyzed using alkaline reagents. Preferred borooxide epoxides may be borooxides of mainly 16-carbon olefins. The amount of borooxide epoxide may be 0.01 or 0.05 to 0.5 or 1.0 parts by weight, or 0.1 to 0.9 percent, of the composition.

[0162] The lubricating additive composition exhibits a conductivity of up to 1 × 10⁻⁹ S / cm at 100°C and 500V, as measured by ASTM D2624, or from 9.5 × 10⁻¹⁰ S / cm, or from 9 × 10⁻¹⁰ S / cm, or from 8.5 × 10⁻¹⁰ S / cm, or from 8 × 10⁻¹⁰ S / cm, or from 7.0 × 10⁻¹⁰ S / cm, or from 6.5 × 10⁻¹⁰ S / cm, or from 6.0 × 10⁻¹⁰ S / cm, or from 5.5 × 10⁻¹⁰ S / cm, or from 5.0 as measured by ASTM D2624. It is very preferable that the lubricating additive composition has no conductivity, but practically speaking, a conductivity of about 4.0 × 10⁻¹⁰ or 4.5 × 10⁻¹⁰ at 100°C may be achievable.

[0163] In one embodiment, the lubrication additive composition is substantially free of friction modifiers. In some embodiments, the lubrication additive composition is completely free of friction modifiers.

[0164] The lubricating additive composition may be in the form of a concentrate and / or a fully blended lubricant when added to the base oil. That is, a lubricating composition can be prepared by adding the lubricating additive composition to the base oil. base oil

[0165] Base oils can be defined as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five base oil groups are as follows: Group I (saturated with a sulfur content greater than 0.03 wt% and / or less than 90 wt%; viscosity index 80–120); Group II (saturated with a sulfur content less than 0.03 wt% and more than 90 wt%; viscosity index 80–120); Group III (saturated with a sulfur content less than 0.03 wt% and more than 90 wt%; viscosity index greater than 120); Group IV (all polyalphaolefins (PAOs); and Group V (all others not included in Group I, Group II, Group III, or Group IV). Base oils may include, for example, oils of API Group I, Group II, Group III, Group IV, Group V, or mixtures thereof.

[0166] In many cases, the base oil is an API Group I, Group II, Group III, or Group IV oil, or a mixture thereof. Alternatively, the base oil may be an API Group II, Group III, or Group IV oil, or a mixture thereof.

[0167] In one embodiment, the base oil can be prepared by the Fischer-Tropsch gas liquefaction synthesis procedure and other gas liquefaction oils.

[0168] 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 lubricating additive composition.

[0169] The amount of base oil present is typically the remainder after subtracting the total amount of the lubricating additive composition of the present invention from 100% by weight. If the lubricating additive composition is in the form of a concentrate (which, in whole or in part, can be combined with the base oil to form a finished lubricant), the ratio of the lubricating additive composition to the base oil and / or diluent oil includes the ranges of 1:99 to 99:1 by weight, or 2:98 to 98:2 by weight, or 5:95 to 95:5 by weight, or 10:90 to 90:10 by weight, or 15:85 to 85:15, or 20:80 to 80:20 by weight.

[0170] In a lubricating composition containing a lubricating additive composition, the kinematic viscosity at 40°C according to ASTM D445 may be 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 or 22 cSt, or for example 10 cSt to 25 or 22 cSt, or even 14 cSt to 25 or 22 cSt, or 18 cSt to 22 cSt.

[0171] A lubricating composition containing a lubricating additive composition may have a kinematic viscosity of 2 to 25 cSt at 100°C according to ASTM D445. A lubricating composition containing a lubricating additive composition may have a kinematic viscosity of 2 to 15 cSt at 100°C according to ASTM D445. A lubricating composition containing a lubricating additive composition may have a kinematic viscosity of 2 to 12 cSt at 100°C according to ASTM D445. A lubricating composition containing a lubricating additive composition may have a kinematic viscosity of 2 to 9 cSt at 100°C according to ASTM D445. A lubricating composition containing a lubricating additive composition may have a kinematic viscosity of 2 to 7 cSt at 100°C according to ASTM D445. A lubricating composition containing a lubricating additive composition may have a kinematic viscosity of 2 to 6 cSt at 100°C according to ASTM D445. A lubricating composition containing a lubricating additive composition may have a kinematic viscosity of 2 to 4 cSt at 100°C according to ASTM D445.

[0172] When in the form of a lubricating composition, the lubricating additive composition is suitable for lubricating the driveline of an electric vehicle, particularly the gearbox of the electric motor of an electric vehicle. In particular, the lubricating additive composition is suitable for lubricating the transmission of an electric motor-equipped vehicle, 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.

[0173] In particular, the disclosed technology provides a method for lubricating a driveline power transmission device, comprising supplying a lubricating composition to the driveline power transmission device, as described herein, namely, a base oil, a succinimide dispersant, an azole corrosion inhibitor, a phosphorus wear-resistant compound, and an antioxidant, and operating the driveline power transmission device for a period of time sufficient to allow the lubricating composition to achieve the improved results described herein.

[0174] In particular, the disclosed technology provides a method for lubricating a driveline power transmission unit, comprising supplying a lubricating composition to the driveline power transmission unit, as described herein, namely, a base oil, a succinimide dispersant, an azole corrosion inhibitor, a phosphorus wear-resistant compound, an antioxidant, and a viscosity modifier, and operating the driveline power transmission unit for a period of time sufficient to allow the lubricating composition to achieve the improved results described herein.

[0175] A driveline power transmission may include at least two gears, such as in a vehicle gearbox (e.g., a manual transmission), an axle, a differential, or other driveline power transmission. The driveline power transmission may also include bearings. The rolling elements of the bearings may be cylindrical or ball-shaped by design. Lubricated gears may include unvoided, spiral bevel, or more commonly, hypoid gears, such as those found in drive axles. The gear ratio of the axle may be 2:1 to 8:1, and the diameter of the ring gear may be approximately 13 to 64 cm. The axle may incorporate an open differential or some type of traction-enhancing device. The axle may be part of a drivetrain with one or more drive axles, such as in a tandem or tridem design, and the axle may be coupled with a power distributor. Applications for these axles include small, medium, and heavy vehicles (e.g., professional or line-haul service) and may be used on highways or public roads. The axles may be from conventional petroleum-powered vehicles, electric vehicles, or hybrids thereof. In electric axles, a unit that directly supplies power to the vehicle's axles can combine an electric motor, power electronics, and a transmission.

[0176] Accordingly, one embodiment is a method for lubricating an electric vehicle, comprising supplying a lubricating composition containing the lubricating additive composition described herein to the drive line of the electric vehicle, and operating the drive line.

[0177] Another embodiment is a method for lubricating a transmission, particularly a transmission of a vehicle equipped with an electric motor, comprising supplying a lubricating composition containing the lubricating additive composition described herein to the transmission, and operating the transmission.

[0178] The lubricant should be able to satisfy the expected characteristics of the lubricant during the normal operation of the driveline power transmission system.

[0179] Transmissions in which the lubricating additive composition may be suitable include automatic transmissions and dual-clutch transmissions. The transmission may or may not include a gear shift clutch, and if the transmission includes a gear shift clutch, the clutch may be a dry clutch or a wet clutch. In one embodiment, the lubricant may be used in a transmission that does not house a gear shift clutch. In another embodiment, the lubricating additive composition may be used in a transmission having a wet clutch. In a further embodiment, the lubricating additive composition may be used in a transmission having a dry clutch.

[0180] The driveline device may be a manual transmission that includes or does not include a synchronizer system or an axle. In one embodiment, the driveline device includes a synchronizer or an axle.

[0181] In one embodiment, the driveline device includes a synchronizer. The synchronizer system may have working surfaces made of brass, carbon, molybdenum, phenolic resin, or sintered metal (typically bronze), or mixtures thereof.

[0182] As used herein, the term “condensation product” is intended to encompass other such materials that can be prepared by the condensation reaction of esters, amides, imides, and acids or reactive equivalents of acids (e.g., acid halides, anhydrides, or esters) with alcohols or amines, regardless of whether the condensation reaction is actually carried out to directly yield the product. Therefore, for example, certain esters may be prepared not directly by a condensation reaction, but by a transesterification reaction. The resulting product is still considered a condensation product.

[0183] The amounts of each chemical component described herein are expressed in terms of active chemical substance, excluding any solvents or diluents that may conventionally be present in commercially available substances, unless otherwise indicated. However, unless otherwise indicated, each chemical substance or composition referred to herein should be construed as a commercially available substance that may contain isomers, by-products, derivatives, and other such substances that are commonly understood to be present in commercial grade.

[0184] As used herein, the terms “hydrocarbyl substituent” or “hydrocarbyl group” are used in their ordinary sense as is well known to those skilled in the art. Specifically, they refer to groups having carbon atoms directly bonded to the rest of the molecule and having primarily hydrocarbon properties. Examples of hydrocarbyl groups include:

[0185] Hydrocarbon substituents, i.e., aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, as well as aromatic, aliphatic, and alicyclic substituted aromatic substituents, and cyclic substituents in which the ring is completed via another part of the molecule (e.g., two substituents together form a ring);

[0186] Substitutive hydrocarbon substituents, i.e., substituents in the context of the present invention that contain non-hydrocarbon groups that do not alter the properties of the hydrocarbon (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy);

[0187] Heterosubstituted substituents, in the context of the present invention, are substituents that primarily possess hydrocarbon properties, but otherwise contain non-carbon atoms in a ring or chain composed of carbon atoms, and include substituents as pyridyl, furyl, thienyl, and imidazolyl. Examples of heteroatoms include sulfur, oxygen, and nitrogen. Generally, there are two or fewer, or one or fewer, non-hydrocarbon substituents for every 10 carbon atoms in the hydrocarbyl group, and alternatively, there may be no non-hydrocarbon substituents in the hydrocarbyl group.

[0188] Since some of the materials described above can interact in the final formulation, it is known that the components of the final formulation may differ from those initially added. For example, metal ions (e.g., in detergents) can migrate to other acidic or anionic sites of other molecules. The products formed thereby, including those formed when the composition of the present invention is used in its intended application, may not be readily apparent. Nevertheless, all such modifications and reaction products are within the scope of the present invention. The present invention encompasses compositions prepared by mixing the components described above.

[0189] 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 stated value. In other embodiments, the value is within ±10% of the stated value. In other embodiments, the value is within ±5% of the stated value. In other embodiments, the value is within ±2.5% of the stated value. In other embodiments, the value is within ±1% of the stated value.

[0190] Furthermore, as used herein, the term “substantially” means that a given quantity is within ±10% of the stated value. In other embodiments, the value is within ±5% of the stated value. In other embodiments, the value is within ±2.5% of the stated value. In other embodiments, the value is within ±1% of the stated value.

[0191] In different embodiments, the lubricating composition may have the compositions listed in the following table. [Table B]

[0192] The present invention as described herein is useful for lubricating automatic transmissions for hybrid electric vehicles, which can be better understood by referring to the following provisions.

[0193] Clause 1: A lubricating composition comprising (a) an oil of lubricating viscosity, (b) a dispersant, (c) a triazole corrosion inhibitor, (d) a phosphite-containing wear-resistant compound, (e) an antioxidant, and (f) a sulfur-free detergent, wherein the lubricating composition contains 40 ppm or less of sulfur, or 30 ppm or less of sulfur, or 20 ppm or less of sulfur.

[0194] Clause 2: The lubricant composition according to Clause 1, wherein the sulfur-free cleaning agent includes or consists of a salicylate cleaning agent.

[0195] Clause 3: The lubricant composition according to any one of Clauses 1 to 2, wherein the sulfur-free cleaning agent contains or comprises calcium salicylate, and the calcium salicylate cleaning agent 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.

[0196] Clause 4: The phosphite abrasion-resistant compound is, Formula: [ka] A lubricant composition according to any one of claims 1 to 3, comprising a dialkyl phosphite having, wherein R3 and R4 are independently alkyl groups having 1 to 24 carbon atoms.

[0197] Clause 5: The lubricant composition according to Clause 4, wherein the dialkyl phosphite comprises or consists of dibutylhydrogen phosphite.

[0198] Clause 6: The phosphite-containing wear-resistant compound is a lubricant composition according to any one of Clauses 1 to 5, comprising or consisting of a phosphonate ester.

[0199] Clause 7: The lubricant composition according to any one of Clauses 1 to 6, wherein the phosphonate ester comprises a reaction product of (a) monomer phosphite or an ester thereof and (b) at least two alkylenediols, namely, a first alkylenediol (i) having two hydroxyl groups in a 1,4, 1,5, or 1,6 relationship, and a second alkyl-substituted 1,3-propylenediol (ii) having one or more alkyl substituents on one or more carbon atoms of a propylene unit, and the total number of carbon atoms in the alkyl-substituted 1,3-propylenediol being about 5 to about 12, wherein the relative molar amounts of monomer phosphite or an ester thereof (a) and the alkylenediol (b) are in a ratio of about 0.9:1.1 to about 1.1:0.9, and the relative molar amounts of the first alkylenediol (i) and the alkyl-substituted 1,3-propylenediol (ii) are in a ratio of about 30:70 to about 65:35.

[0200] Clause 8: The lubricant composition according to any one of Clauses 1 to 7, comprising or consisting of a succinimide dispersant having a number average molecular weight of 750 to 2200, or 750 to 1600, or 950 to 1550.

[0201] Clause 9: The dispersant is a lubricant composition according to any one of Clauses 1 to 7, comprising or consisting of an olefin polymer dispersant.

[0202] Clause 10: The lubricant composition according to Clause 9, wherein the dispersant comprises or consists of an ethylene / propylene copolymer dispersant.

[0203] Clause 11: The lubricant composition according to any one of Clauses 1 to 8, comprising a PIB succinimide borooxide dispersant having a number average molecular weight of 1000.

[0204] Clause 12: The lubricant composition according to Clause 11, comprising a non-borooxide PIB succinimide dispersant having a number average molecular weight of 1550.

[0205] Clause 13: The lubricant composition according to any one of Clauses 1 to 12, wherein the dispersant comprises polyisobutylene succinic anhydride (PIBSA) prepared by a thermal process.

[0206] Clause 14: A triazole corrosion inhibitor is a lubricant composition according to any one of Clauses 1 to 13, comprising or consisting of 1,2,4-triazole.

[0207] Clause 15: The lubricant composition according to any one of Clauses 1 to 14, wherein the triazole corrosion inhibitor comprises or consists of N,N-bis(2-ethylhexyl)-[(1,2,4-triazol-1-yl)methyl]amine.

[0208] Clause 16: A triazole corrosion inhibitor is a lubricant composition according to any one of Clauses 1 to 13, comprising or comprising a toltriaazole derivative.

[0209] Clause 17: The lubricant composition according to any one of Clauses 1 to 13, wherein the triazole corrosion inhibitor comprises or consists of bis(2-ethylhexyl)-[(1,2,4-triazol-1-yl)methyl]amine.

[0210] Clause 18: The lubricant composition according to any one of Clauses 1 to 17, wherein the antioxidant comprises or consists of an arylamine antioxidant.

[0211] Clause 19: The lubricant composition according to any one of Clauses 1 to 18, wherein the antioxidant comprises or consists of phenyl-α-naphthylamine (PANA).

[0212] Clause 20: The lubricant composition according to any one of Clauses 1 to 19, wherein the antioxidant comprises or consists of a hydrocarbyl-substituted diphenylamine.

[0213] Clause 21: The lubricant composition according to any one of Clauses 1 to 20, wherein the antioxidant is selected from the group consisting of octyldiphenylamine, dioctyldiphenylamine, dinonyldiphenylamine, or mixtures thereof.

[0214] Clause 22: The lubricant composition according to any one of Clauses 1 to 21, comprising 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 phosphite wear-resistant compound, 0.2% to 1.2% by weight of an antioxidant, and 0.1% to 1.0% by weight of a sulfur-free detergent.

[0215] Clause 23: A lubricant composition according to any one of Clauses 1 to 22, comprising 1.0% to 3% by weight of a dispersant, 0.01% to 0.11% by weight of a triazole corrosion inhibitor, 0.05% to 1% by weight of a phosphite wear-resistant compound, or 0.2% to 1.0% by weight of an antioxidant, and 0.2% to 0.8% by weight of a sulfur-free detergent.

[0216] Clause 24: A lubricant composition according to any one of Clauses 1 to 23, comprising 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 phosphite wear-resistant compound, or 0.2% to 0.7% by weight of an antioxidant, or 0.2% to 0.5% by weight of a sulfur-free detergent.

[0217] Clause 25: The lubricant composition according to any one of Clauses 1 to 24, comprising 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 phosphite wear-resistant compound, 0.2% to 0.4% by weight of an antioxidant, and 0.2% to 0.5% by weight of a sulfur-free detergent.

[0218] Clause 26: The lubricant composition is the lubricant composition according to any one of Clauses 1 to 25, which is substantially free of borate esters.

[0219] Clause 27: The lubricant composition according to any one of Clauses 1 to 26, wherein the oil of lubrication viscosity is selected from the group consisting of API Group III base oils, Group IV base oils, or mixtures thereof.

[0220] Clause 28: A lubricant composition according to any one of Clauses 1 to 27, wherein the viscosity of the lubricant composition is 1 cSt to 32 cSt at 100°C as measured by ASTM D445.

[0221] Clause 29: A lubricant composition according to any one of Clauses 1 to 28, wherein the viscosity of the lubricant composition is 1.5 cSt to 15 cSt as measured by ASTM D445.

[0222] Clause 30: A lubricant composition according to any one of Clauses 1 to 29, wherein the viscosity of the lubricant composition is 2 to 12 cSt at 100°C as measured by ASTM D445.

[0223] Clause 31: The lubricating viscosity oil comprises or consists of an API Group III base oil, as described in any one of Clauses 1 to 30.

[0224] Clause 32: The lubricating viscosity oil comprises or consists of an API Group IV base oil, as described in any one of Clauses 1 to 31.

[0225] Clause 33: The lubricating composition according to any one of Clauses 1 to 32, wherein the phosphite-based anti-wear agent is present in the composition in an amount sufficient to deliver 100 to 5000 ppm of phosphorus to the composition.

[0226] Clause 34: A method for lubricating an electric vehicle, comprising supplying a lubricating composition described in any one of Clauses 1 to 33 to the drive line of the electric vehicle, and operating the drive line.

[0227] Clause 35: A method for reducing wear in a drive line of an electric vehicle by supplying the lubricant composition described in any one of Clauses 1 to 33 to the drive line.

[0228] Clause 36: Use of any one of the lubricating compositions described in Clauses 1 to 33 to reduce wear in the drive lines of electric vehicles.

[0229] Clause 37: Use of any one of the lubricating compositions described in Clauses 1 to 33 to reduce corrosion. [Examples]

[0230] Lubricating compositions were prepared according to Table 1 below. [Table 1] 1 Amine C9 diphenylamine 2 C14 dialkylamides of alpha-hydroxy acids 3 1000Mn borate PIB succinimide (3.8% N, 0.81% B) 4 1550Mn non-borooxide PIB succinimide (1.41%N) 5 Polyalkylsiloxane 6 Dibutylhydrogen phosphite 7 A condensation product of monomeric phosphite or its ester and at least two alkylenediols. 8 Amine salts of C14-C18 dialkyl phosphate hydrogen and C12-C14 tertiary alkylamines 9 Bis(2-ethylhexyl)-[1,2,4-triazol-1-yl)methyl]amine

[0231] The FE8 roller bearing test can be used to evaluate the friction behavior and wear effects of lubricants under various operating conditions for a variety of bearings, including cylindrical roller thrust bearings. To perform this test, two test cylindrical roller thrust bearings 81212 are mounted in the FE8 test apparatus, an axial bearing load is applied, they are operated at a specific speed, and maintained at the test temperature.

[0232] The lubrication compositions listed in Table 1 were evaluated under FE8 roller bearing testing conditions using rigs and test protocols in accordance with DIN 51819 T1-T3. The tests were performed in two succession to confirm the results. The test conditions are listed below, and the results are summarized in Table 2. conditions • Test parameters • Shaft load 800kN ·Speed ​​7.5rpm • Liquid volume: 4 liters • Temperature 80℃ (at the housing washer) • Cage material: Brass • Oil flow rate 0.1 1 / min (each bearing) • Exam period: 2 sessions x 80 hours [Table 2]

[0233] In wear tests, the weight loss of bearing elements reflects the ability of the lubricant to protect the bearing. Formulations containing salicylate detergents performed better than formulations containing sulfonate detergents.

[0234] The copper corrosion test was performed according to the "ZF Copper Corrosion Test" procedure, in which a weighed copper coupon was placed in the test oil and heated at 150°C for 168 hours using an air purge of 83 mL / min. At the end of the test, the weight loss of copper from the coupon, the copper content in the test drain (%), and a visual assessment (ASTM D-130) were measured. The results are summarized in Table 3. [Table 3]

[0235] As indicated by the amount of copper measured in the test fluid at the end of the test, Example 2, which contained a non-borodic dispersant, showed a higher weight loss of copper at the end of the test than Examples 4 and 5, which contained a non-borodic dispersant and a calcium salicylate detergent.

[0236] Each of the documents mentioned above, including any prior application claiming priority, whether or not they are specifically listed above, is incorporated herein by reference. Reference to any document does not constitute an endorsement that such document is eligible as prior art or constitutes the general knowledge of a person skilled in the art in any jurisdiction. Except in the examples or unless otherwise expressly indicated, all quantities in this description specifying amounts of materials, reaction conditions, molecular weights, number of carbon atoms, etc., should be understood to be modified by the word "about." The upper and lower limits of quantities, ranges, and ratios described herein can be combined independently. Similarly, the ranges and quantities for each element of the present invention can be used together with the ranges or quantities for any of the other elements.

[0237] As used herein, the transitional term “comprising,” which is synonymous with “including,” “contains,” or “characterized by,” is inclusive or open-ended and does not exclude additional undescribed elements or method steps. However, in each “comprising” statement herein, the term is also intended to include, as alternative embodiments, the phrases “essentially from” and “consisting of,” where “consisting of” excludes any unspecified elements or steps, and “essentially from” allows the inclusion of additional undescribed elements or steps that do not substantially affect the essential or basic and novel features of the composition or method under consideration.

[0238] As used herein, “substantially absent” means that the amount of the material in question is less than an amount that would affect the relevant performance of the fluid in a measurable manner. “Substantially absent” may also mean that the material in question is not intentionally added to the composition, but does not rule out the presence of such a substance as a contaminant. “Substantially absent” may also mean that the material in question may be present in an amount lower than the detection limits of standard test methods currently known to those skilled in the art or hereafter developed. In some embodiments, “substantially absent” may mean less than 10 ppm by weight, or even less than 5 ppm by weight.

[0239] For the purpose of illustrating the present invention, certain representative embodiments and details have been shown, but 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 should be limited only by the following claims.

Claims

1. A lubricant composition, (a) Lubricating viscosity oil, (b) Dispersant and (c) Triazole corrosion inhibitor, (d) Abrasion-resistant compound containing phosphite, (e) Antioxidants, (f) A cleaning agent that does not contain sulfur, The lubricant composition contains 40 ppm or less of sulfur, or 30 ppm or less of sulfur, or 20 ppm or less of sulfur.

2. The lubricant composition according to claim 1, wherein the sulfur-free cleaning agent includes or consists of a salicylate cleaning agent.

3. The lubricant composition according to any one of claims 1 to 2, wherein the sulfur-free cleaning agent contains or consists of calcium salicylate.

4. The lubricant composition according to claim 3, wherein the calcium salicylate cleaning agent 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 one of claims 1 to 4, wherein the phosphite wear-resistant compound comprises a dialkyl phosphite.

6. The aforementioned dialkylphosphite is given by formula: 【Chemistry 9】 The lubricating additive composition according to claim 5, wherein R3 and R4 are independently alkyl groups having 1 to 24 carbon atoms.

7. The lubricant composition according to claim 5, wherein the dialkyl phosphite includes or consists of dibutylhydrogen phosphite.

8. The lubricant composition according to any one of claims 1 to 4, wherein the phosphite-containing wear-resistant compound includes or consists of a phosphonate ester.

9. The phosphonate ester is (a) monomer phosphite or its ester, (b) at least two alkylenediols, A first alkylenediol (i) having two hydroxyl groups in the relationship 1,4,1,5, or1,6, The reaction product comprises an alkyl-substituted 1,3-propylenediol, 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-propylenediol is about 5 to about 12, and includes a second alkylenediol (ii), The relative molar amounts of monomer phosphite or its ester (a) and the alkylenediol (b) are in a ratio of approximately 0.9:1.1 to approximately 1.1:0.

9. The lubricant composition according to claim 8, wherein the relative molar amounts of the first alkylenediol (i) and the alkyl-substituted 1,3-propylenediol (ii) are in a ratio of about 30:70 to about 65:

35.

10. The lubricant composition according to any one of claims 1 to 9, wherein the dispersant comprises or consists of a succinimide dispersant.

11. The lubricant composition according to claim 10, wherein the dispersant comprises or consists 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 consists of an olefin polymer dispersant.

13. The lubricant composition according to claim 12, wherein the dispersant comprises or consists of an ethylene / propylene copolymer dispersant.

14. The lubricant composition according to any one of claims 1 to 13, wherein the dispersant comprises a borooxide dispersant.

15. The lubricant composition according to any one of claims 1 to 14, wherein the dispersant comprises a non-borodic dispersant.

16. The lubricant composition according to any one of claims 1 to 15, wherein the triazole corrosion inhibitor comprises or consists of 1,2,4-triazole.

17. The lubricant composition according to any one of claims 1 to 16, wherein the triazole corrosion inhibitor comprises or consists 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 consists of a toltriaazole derivative.

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

20. The lubricant composition according to any one of claims 1 to 19, wherein the antioxidant comprises or consists of an arylamine antioxidant.

21. The lubricant composition according to any one of claims 1 to 20, wherein the antioxidant comprises or consists of phenyl-α-naphthylamine (PANA).

22. The lubricant composition according to any one of claims 1 to 21, wherein the antioxidant comprises or consists of a hydrocarbyl-substituted diphenylamine.

23. The lubricant composition according to any one of claims 1 to 22, wherein the antioxidant is selected from the group consisting of octyldiphenylamine, dioctyldiphenylamine, dinonyldiphenylamine, or a mixture thereof.

24. The lubricating composition, A dispersant in an amount 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, A triazole corrosion inhibitor in an amount of 0.01% to 0.11% by weight, A phosphite-resistant abrasion-resistant compound in an amount of 0.05% to 2% by weight, or 0.05 to 1% by weight, or 0.1% to 0.5% by weight, or 1.0 to 2% by weight, The antioxidant in an amount of 0.2% to 1.2% by weight, or 0.2% to 1.0% by weight, or 0.2% to 0.7% by weight, or 0.2% to 0.4% by weight, A lubricant composition according to any one of claims 1 to 23, comprising 0.1% to 1.0% by weight, or 0.2% to 0.8% by weight, or 0.2% to 0.5% by weight of the sulfur-free detergent.

25. The lubricant composition according to any one of claims 1 to 24, wherein the lubricant composition substantially does not contain boric acid ester.

26. The lubricant composition according to any one of claims 1 to 25, wherein the oil having the lubricating viscosity is selected from the group consisting of API Group III base oils, Group IV base oils, or mixtures thereof.

27. The lubricant composition according to any one of claims 1 to 26, wherein the viscosity of the lubricant composition is 1 cSt to 32 cSt, 1.5 cSt to 15 cSt, or 2 to 12 cSt at 100°C when measured by ASTM D445.

28. The lubricant composition according to any one of claims 1 to 27, wherein the oil having the aforementioned lubricating viscosity contains or consists of an API Group III base oil.

29. The lubricant composition according to any one of claims 1 to 28, wherein the oil having the aforementioned lubricating viscosity contains or consists of an API Group IV base oil.

30. The lubricant composition according to any one of claims 1 to 29, wherein the phosphite-based wear-resistant agent is present in an amount sufficient to deliver 100 to 5000 ppm of phosphorus to the composition.

31. A method for lubricating an electric vehicle, comprising supplying a lubricating composition according to any one of claims 1 to 30 to the drive line of the electric vehicle, and operating the drive line.

32. A method for reducing wear in an electric vehicle's drive line by supplying the lubricant composition according to any one of claims 1 to 30 to the drive line of the electric vehicle.

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

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