Lubricating compositions and methods for lubricating driveline devices

Abstract

The invention provides, inter alia, a lubricant formulation containing a sulfur-free poly(meth)acrylate P(M)A polymer, and a method for lubricating a driveline device of a motor vehicle.

Description

Background Technology

[0001] The present invention particularly provides a lubricant formulation containing a sulfur-free poly(meth)acrylate P(M)A polymer, and a method for lubricating a transmission system of a motor vehicle.

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

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

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

[0005] For example, most conductive components in electric and hybrid electric vehicles are made of copper. Sulfur substances present in lubricants can cause copper corrosion. Therefore, from a copper corrosion perspective, sulfur-free formulations would be advantageous. However, lubricants must still provide adequate lubrication, including, for example, dispersibility, cleanliness, and anti-wear properties. Therefore, new lubricant compositions are needed to achieve these often competing results. Summary of the Invention

[0006] Therefore, the disclosed technology solves the problem of P(M)A polymer contributing to sulfur load in transmission system formulations by preparing lubricant formulations containing sulfur-free poly(meth)acrylate (“P(M)A”).

[0007] Therefore, one aspect of this technology relates to a lubricant formulation having a) an oil having a lubricating viscosity and a sulfur-free poly(meth)acrylate (“P(M)A”) polymer.

[0008] In one embodiment, P(M)A may have a number-average molecular weight of about 1000 g / mol to about 25000 g / mol. P(M)A may also optionally contain nitrogen-containing groups.

[0009] The formulation may also contain, for example, a phosphorus anti-wear agent sufficient to provide 100 ppm to 5000 ppm of phosphorus to the composition, and a triazole corrosion inhibitor, such as, for example, 1,2,4-triazole.

[0010] Another aspect of this technology includes a method of lubricating a vehicle's drivetrain by applying the lubricant formulation described herein to the drivetrain and then operating the vehicle. The vehicle may be a hybrid electric vehicle or a fully electric vehicle. Detailed Implementation

[0011] The present invention particularly provides a lubricant formulation having a) an oil having a lubricating viscosity and a sulfur-free poly(meth)acrylate (“P(M)A”) polymer, and a method for lubricating a transmission system device.

[0012] Oil with lubricating viscosity

[0013] One component of the disclosed technology is an oil with lubricating viscosity, also known as a base oil. The base oil can be selected from any of the Group IV base oils listed in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines (2011), i.e.

[0014] Base oil categories sulfur(%) Saturation (%) Viscosity Index

[0015] Class I > 0.03 and / or < 90 80 to less than 120

[0016] Class II ≤0.03 and ≥90 80 to <120

[0017] Class III ≤0.03 and ≥90 ≥120

[0018] All polyalphaolefins (PAOs) in Class IV

[0019] Group V includes all other base oils not included in Group I, II, III, or IV.

[0020] Group I, II, and III are mineral oil base feedstocks. Other generally recognized categories of base oils may be used, even if not formally classified by the American Petroleum Institute (API): Group II+ refers to Group II substances with a viscosity index of 110 to 119 and lower volatility than other Group II oils; and Group III+ refers to Group III substances with a viscosity index greater than or equal to 130. Oils with lubricating viscosity may include natural or synthetic oils and mixtures thereof. Mixtures of mineral and synthetic oils, such as polyalphaolefin oils and / or polyester oils, may be used.

[0021] In one embodiment, the oil having a lubricating viscosity has a kinematic viscosity of 1.5 mm at 100°C according to ASTM D445. 2 / s to 7.5mm 2 / s, or 2mm 2 / s to 7mm 2 / s, or 2.5mm 2 / s to 6.5mm 2 / s, or 3mm 2 / s to 6mm 2 / s. In one embodiment, the oil having a lubricating viscosity comprises a polyalphaolefin having a kinematic viscosity of 1.5 to 7.5 at 100°C according to ASTM D445 or any of the other foregoing ranges.

[0022] Gather ( methyl ) acrylate "P(M)A" polymer

[0023] The use of parentheses indicates that the chemical part contained within the parentheses may or may not be present. For example, the use of (methyl) (throughout the specification) indicates that the methyl chemical part mentioned in the parentheses is optional.

[0024] The P(M)A polymers that can be used in this technology are those prepared in the absence of sulfur. Such P(M)A polymers can be prepared, for example, by free radical polymerization using a sulfur-free addition-fragmentation chain transfer agent.

[0025] α-Methylstyrene dimer (AMSD) can be used as a sulfur-free addition-fragmentation chain transfer agent to prepare P(M)A polymers. Methods for preparing P(M)A polymers are those well known in the art, such as, for example, free radical polymerization or group transfer polymerization. The resulting polymer comprises at least one polymeric dimer of an α-methylstyrene derivative as shown in Formula I.

[0026] R1, R2, R3, R4, R5, and R6 are each independently selected from the following groups: hydrogen, -CH(O), -CN, isocyanate groups and their salts and esters, NR7R8, silanes, halogens, -C(O)OR9, -C(O)NR10R11, -CR12(O), -C(O)OC(O)R13, ​​-C(O)NR14COR15, -OC(O)R16, -OR17, substituted and unsubstituted alkyl groups, substituted and unsubstituted alkenyl groups, substituted and unsubstituted alkenyl groups. Substituted alkynyl groups, and substituted and unsubstituted aryl groups; R7, R8, R9, R10, R11, R12, R13, R14, R15 and R16 are each independently selected from the group consisting of: H, alkyl, aryl, substituted alkyl or substituted aryl; R17 is selected from the group consisting of: alkyl, aryl, substituted alkyl or substituted aryl; R1, R2, R3, R4, R5 and R6 cannot all be hydrogen simultaneously; and alkyl and substituted alkyl groups have chains consisting of 1 to 12 carbons.

[0027] In one implementation, R1, R2, R3, R4, R5, and R6 are each H.

[0028] In one embodiment, P(M)A can be synthesized by catalytic chain transfer polymerization (“CCTP”), wherein the desired (meth)acrylate monomer reacts with a catalytic amount of chain transfer agent. Examples of catalytic chain transfer agents may include, but are not limited to, low-spin Co(II) complexes such as cobalt oxime [J. Am. Chem. Soc., 1984, 106, 5197-5202] and their derivatives.

[0029] Desired monomers for preparing poly(meth)acrylate polymers may include, for example, mixtures of (meth)acrylate monomers containing alkyl groups of varying lengths. The (meth)acrylate monomers may contain alkyl groups that are straight-chain, branched, or aromatic. The alkyl groups may contain 1 to 24 carbon atoms, for example, 1 to 20 carbon atoms.

[0030] The poly(meth)acrylate polymers described herein can be formed from monomers derived from saturated alcohols, such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-methylpentyl methacrylate, 2-propylheptyl methacrylate, 2-butyloctyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, nonyl methacrylate, isooctyl methacrylate, isononyl methacrylate, 2-tert-butylheptyl methacrylate, 3-isopropylheptyl methacrylate, decyl methacrylate, undecyl methacrylate, 5-methylundecyl methacrylate, dodecyl methacrylate, and so on. 2-Methyldodecyl acrylate, tridecyl acrylate, 5-methyltridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, 2-methylhexadecyl acrylate, heptadecanyl acrylate, 5-isopropylheptadecanyl acrylate, 4-tert-butyloctadecyl acrylate, 5-ethyloctadecyl acrylate, 3-isopropyloctadecyl acrylate, octadecyl acrylate, nonadecanyl acrylate, eicosyl acrylate, methacrylates derived from unsaturated alcohols such as oleyl (meth)acrylate; and cycloalkyl (meth)acrylates such as 3-vinyl-2-butylcyclohexyl (meth)acrylate or borneol (meth)acrylate.

[0031] Other examples of monomers used to prepare poly(meth)acrylate polymers may include alkyl (meth)acrylates having long-chain alcohol-derived groups, which can be obtained, for example, by reacting methacrylic acid (through direct esterification) or methyl (meth)acrylate (through transesterification) with long-chain fatty alcohols. These fatty alcohols include Sasol's Nafol. ® 1620, Alfol ® 10. Alfol ® 810, Alfol ® 12. Alfol ® 1012EE, Alfol ® 1014CDC, Alfol ® 1214, Alfol ® 1214GC, Alfol ® 1214HA, Alfol ® 1216 and Lial ® 125; Shell AG's Neodol® 91. Neodol ® 23. Neodol ® 25. Neodol ® 45 and Neodol ® 135; BASF's C13-C15 alcohols, isotrexate alcohol, Hydrenol ® and Lorol ® Kalcol of Kao Corporation ® 2465, Kalcol ® 2470, Kalcol ® 8655 and Ecogreen Oleochemicals' Ecorol ® 80. Ecorol ® 24. Ecorol ® 26. Ecorol ® 28 and Ecorol ® 68. Further examples of monomers include alkyl (meth)acrylates having branched alcohol-derived groups, which can be obtained, for example, by reacting methacrylic acid (by direct esterification) or methyl (meth)acrylate (by transesterification) with Guerbet alcohol. Examples of Guerbet alcohols include 2-butyloctanol, 2-butyldecanol, 2-hexyloctanol, 2-hexyldecanol, 2-octyldecanol, 2-hexyldodecanool, 2-octyldodecanool, 2-decyltetradecanool, 2-dodecylhexadecanool, and 2-tetradecyloctadecanool.

[0032] Aromatic monomers can also be used to prepare poly(meth)acrylate polymers and may contain, for example, benzyl (meth)acrylate. In another embodiment, the aromatic monomer may be selected from phenyl (meth)acrylate, propyl (meth)acrylate, or styrene. Other oil-insoluble (meth)acrylate monomers that are polymerizable in oil are also contemplated for use. Mixtures of these and other oil-insoluble monomers may also be used in this invention.

[0033] P(M)A may optionally contain a nitrogen-containing group. The nitrogen-containing compound may contain aromatic amines, such as amines in which the carbon atom of the aromatic ring structure is directly linked to an amino nitrogen atom. The amine may be a monoamine or a polyamine. The aromatic ring will typically be a mononuclear aromatic ring (i.e., a ring derived from benzene), but may include fused aromatic rings, such as those derived from naphthalene. Examples of aromatic amines include aniline, N-alkylanilines (such as N-methylaniline) and N-butylaniline, di(p-methylphenyl)amine, naphthylamine, 4-aminodiphenylamine, N,N-dimethylphenyldiamine, 4-(4-nitrophenylazo)aniline (Disperse Orange 3), 4-phenoxyaniline, 3-nitroaniline, 4-aminoacetaniline, phenyl 4-amino-2-hydroxybenzoate (phenyl aminosalicylate), N-(4-amino-5-methoxy-2-methyl-phenyl)-benzamide (Glass Violet B), N-(4-amino-2,5-dimethoxy-phenyl)-benzamide (Glass Blue RR), N-(4-amino-2,5-diethoxy-phenyl)-benzamide (Glass Blue BB), N-(4-amino-phenyl)-benzamide, and 4-phenylazoaniline. Other examples include p-ethoxyaniline, p-dodecylaniline, and cyclohexyl-substituted naphthylamines. Examples of other suitable aromatic amines include amino-substituted aromatic compounds and amines in which the amine nitrogen is part of the aromatic ring, such as 3-aminoquinoline, 5-aminoquinoline, and 8-aminoquinoline. Also included are aromatic amines such as 2-aminobenzimidazole, which contain a secondary amino group directly attached to the aromatic ring and a primary amino group attached to the imidazole ring. Other amines include N-(4-anilinophenyl)-3-aminobutyramide (i.e., -NH- -NH-COCH2CH(CH3)NH2). Other aromatic amines include aminocarbazole, aminoindole, aminopyrrole, aminoinzolone, aminopiperidine, aminopyridine, aminopyrazine, aminopyrimidine, pyridine, pyrazine, pyrimidine, and aminobenzotriazole. Other suitable amines include 3-amino-N-(4-anilinophenyl)-N-isopropylbutyramide and N-(4-anilinophenyl)-3-{(3-aminopropyl)-(cocoyl)amino}butyramide. Other usable aromatic amines include various aromatic amine dye intermediates containing multiple aromatic rings linked by, for example, amide structures. Examples include general formulas. -CONH- -NH2 substances in which the phenyl group may be substituted. Suitable aromatic amines include those in which the amine nitrogen is a substituent on the aromatic carboxylic acid compound (i.e., the nitrogen is not sp2 hybridized in the aromatic ring).

[0034] Nitrogen-containing compounds may also include non-aromatic amines, or in other words, amines in which the amino nitrogen is not directly attached to a carbon atom of an aromatic ring, or amines in which the amine nitrogen is not part of an aromatic ring, or amines in which the amine nitrogen is not a substituent on an aromatic carboxylic acid compound. In some cases, such non-aromatic amines may be considered aliphatic or cycloaliphatic. Such amines may be straight-chain, branched, or functionalized with certain functional groups. Non-aromatic amines may include monoamines having, for example, 1 to 8 carbon atoms, such as methylamine, ethylamine, and propylamine, as well as various higher amines. Diamines or polyamines may also be used, and will generally have only a single primary amino group. Examples include dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, dibutylaminoethylamine, 1-(2-aminoethyl)piperidine, 1-(2-aminoethyl)pyrrolidone, N,N-dimethylethylamine; 3-(dimethylamino)-1-propylamine; O-(2-aminopropyl)-O′-(2-methoxyethyl)polypropylene glycol; N,N-dimethyldipropylenetriamine, aminoethylmorpholine, 3-morpholinopropylamine; aminoethyl ethylidene urea, and aminopropylmorpholine.

[0035] In some embodiments, non-aromatic amines can be used alone or in combination with each other or in combination with aromatic amines. In some embodiments, the amount of aromatic amines may be trace compared to the amount of non-aromatic amines, or in some cases, the composition may be substantially free of or contain no aromatic amines.

[0036] In some embodiments, aromatic amines may be used alone or in combination with each other or in combination with non-aromatic amines. In some embodiments, the amount of non-aromatic amines may be trace compared to the amount of aromatic amines, or in some cases, the composition may be substantially free of or contain no non-aromatic amines.

[0037] When measured by gel permeation chromatography (“GPC”), P(M)A can have a number-average molecular weight (“Mn”) of about 1,000 to about 25,000, or about 1,500 to about 22,500, or even about 2,000 to about 20,000, or 2,500 to 17,500, or 3,000 to 15,000. All chromatographic measurements were performed using an Agilent 390-LC MDS instrument equipped with a differential refractive index and a dual-wavelength UV detector. Poly(methyl methacrylate) and polystyrene standards were used for calibration.

[0038] The lubricating composition of the present invention comprises 1% to 35% by weight, or 5% to 30% by weight, or 10% to 25% by weight of P(M)A, as described herein.

[0039] Phosphorus anti-wear compounds

[0040] The lubricant additive composition contains at least one phosphorus anti-wear compound, such as a phosphate, alkyl phosphate, or alkyl phosphite. The phosphorus anti-wear compound may be an acid, salt, or ester. In one embodiment, the phosphorus anti-wear compound is in the form of two or three, or a mixture of two to four (usually two or three) phosphorus anti-wear compounds. In some embodiments, the phosphorus anti-wear compound is in the form of a mixture of phosphite and (thio)phosphoamine compounds.

[0041] In some embodiments, the phosphorus anti-wear compound is a phosphite. Suitable phosphites include those having at least one hydrocarbon group with 3 or 4 or more, or 8 or more, or 12 or more carbon atoms. The phosphite can be a monoalkyl-substituted phosphite, a dialkyl-substituted phosphite, or a trialkyl-substituted phosphite.

[0042] In one embodiment, the phosphite is sulfur-free, i.e., the phosphite is not a thiophosphite.

[0043] Phosphites can be represented by the following formula:

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

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

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

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

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

[0049] The phosphorus anti-wear compound may include 0.1% to 2% by weight of the additive composition, or even 0.2% to 1.8% by weight, or 0.2% to 1.4% or 1.6% by weight, or even 0.2% to 1% or 1.2% by weight of the lubricant additive composition. The phosphorus anti-wear compound may include 0.1% to 0.5% by weight of the additive composition, or even 0.2% to 0.4% by weight, or 0.2% to 0.3% by weight of the lubricant additive composition.

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

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

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

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

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

[0055] The R groups may be the same or different, and may be hydrogen or alkyl groups, provided that at least one R is an alkyl group and the total number of carbon atoms in the R groups is 2 to 9 or 3 to 9, such that the total number of carbon atoms in the diol will be 5 to 12 or 6 to 12, respectively, and the same applies to other ranges of total carbon. By analogy with the 1,4-diol, 1,5-diol, or 1,6-diol mentioned above, the 1,3-diol mentioned herein refers to two hydroxyl groups in a 1,3 relationship with each other, that is, separated by a chain of 3 carbon atoms. Therefore, 1,3-diol can also be called 2,4-diol or 3,5-diol. If the 1,3-diol has one or more secondary hydroxyl groups, then such a molecule will be considered a substituted diol. In one embodiment, the number of alkyl substituents is 2, and the total number of carbon atoms in the molecule is 9. Suitable substituents may include, for example, methyl, ethyl, propyl, and butyl (in their various possible isomers).

[0056] Examples of second alkylene glycols may include 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butylpropane-1,3-diol, 2-ethylhexane-1,3-diol, 2,2-dibutylpropane-1,3-diol, 2,2-diisobutylpropane-1,3-diol, 2-methyl-2-propylpropane-1,3-diol, 2-propyl-propane-1,3-diol, 2-butylpropane-1,3-diol, 2-pentylpropane-1,3-diol, 2-methyl-2-propylpropane-1,3-diol, 2,2-diethylpropane-1,3-diol, 2,2,4-trimethylpentane-1,3-diol, 2-methylpentane-2,4-diol, 2,4'-dimethyl-2,4'-pentanediol, and 2,4'-hexanediol. It should be noted that, for clarity, some of the aforementioned nomenclatures emphasize the propan-1,3-diol structure of the molecule. For example, 2-pentylpropan-1,3-diol can also be named 2-hydroxymethylhept-1-ol, but the latter nomenclature does not so clearly indicate the 1,3-property of the diol.

[0057] The relative molar ratio of the first alkylene glycol (i) to the second alkylene glycol (ii) may be 30:70 to 65:35, or alternatively, 35:65 to 60:40, or 40:60 to 50:50, or 40:60 to 45:55. If the ratio is less than about 30:70, the resulting product may not fully exhibit the benefits of the disclosed technology, and if the ratio is greater than about 65:35, its compatibility with other components in the lubricant formulation may be reduced.

[0058] The ratio of the relative molar amount of the monomeric phosphorous acid or its ester (a) to the total molar amount of the alkylene glycol (b) can be 0.9:1.1 to 1.1:0.9, or 0.95:1.05 to 1.05:0.95, or 0.98:1.02 to 1.02:0.98, or about 1:1. Reactions carried out at approximately equimolar ratios tend to promote the formation of oligomers or polymers. A precise 1:1 ratio can theoretically lead to the formation of extremely long chains and thus very high molecular weights. However, in practice, this is not usually achievable because competing reactions and incomplete reactions will provide substances with lower degrees of polymerization, and a portion of the substance will be in the form of cyclic monomers.

[0059] The reaction products will typically consist of a mixture of individual substances, including oligomers or polymers and cyclic monomers. The cyclic monomers may contain one phosphorus atom and an alkylene group primarily derived from 1,3-diol(ii), as 1,3-diols are capable of participating in the formation of oligomers or cyclic esters. The oligomers or polymers may typically contain two or three to twenty phosphorus atoms, or alternatively five to ten phosphorus atoms, linked together by alkylene groups derived from diols(i) and (ii), and may exhibit a relatively preferential incorporation of 1,4-diols, 1,5-diols, or 1,6-diols, which are less likely to cyclize with phosphorus to form cyclic monomers.

[0060] The product may be a mixture of substances that can be represented by the structure shown:

[0061] (Oligomers)

[0062] add (Cyclic monomeric substances)

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

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

[0065] Furthermore, the amount of cyclic monomer can be 100% minus the percentage of oligomer. It is also possible to prepare a mixture of oligomer and cyclic monomer having the above weight percentages regardless of the specific diol used. In some embodiments, 55% to 60% of the product is in oligomeric form, and 45% to 40% is in cyclic monomer form. In some embodiments, the relative amounts of cyclic monomer and oligomer are 1:3 to 1:1 by weight, or alternatively, 1:3 to 1:0.8.

[0066] The condensation reaction between phosphoric acid or an ester and a diol can be achieved by mixing the reagents and heating until the reaction is substantially complete. Typically, the first and second alkylene glycols can be mixed simultaneously or almost simultaneously (i.e., usually before the reaction with one of the alkylene glycols is complete). Small amounts of a basic substance, such as sodium methoxide, may also be present. If a methyl ester of phosphorous acid is used as the reagent, the substantial completion of the reaction corresponds to the cessation of methanol precipitation and distillation from the reaction mixture. Suitable temperatures include those in the range of 100°C to 140°C, such as 110°C to 130°C or 115°C to 120°C. If the reaction temperature used exceeds about 140°C, there is a risk that the desired product may not form in a useful yield or with useful purity, as competing reactions may occur. Typically, the reaction time can be up to 12 hours, depending on the temperature, applied pressure (if any), stirring, and other variables. In some cases, reaction times of 2 to 8 hours or 4 to 6 hours may be suitable.

[0067] If desired, other monomers may be included in the reaction mixture. Specifically, the inclusion of polycarboxylic acids such as dicarboxylic acids is sometimes considered beneficial. For example, the inclusion of relatively small amounts of tartaric acid or citric acid can provide products with useful properties. The amount of polycarboxylic acid or dicarboxylic acid may be suitable for incorporating at least one or about one polycarboxylic acid or dicarboxylic acid monomer unit into each oligomer molecule of the product. In practice, the amount of polycarboxylic acid or dicarboxylic acid added to the reaction mixture may be higher than this. Without intending to be bound by any theory, it is believed that when a small amount of tartaric acid is present, it can be incorporated as a terminal unit of the polymer and can condense with the OH group of an alkylene glycol via an ester bond. Such substances can exhibit good properties in terms of anti-wear protection, corrosion inhibition, and sealing performance. Suitable polycarboxylic acids (or their esters or anhydrides) include maleic acid, fumaric acid, tartaric acid, citric acid, phthalic acid, terephthalic acid, malonic acid (e.g., esters), succinic acid, malic acid, adipic acid, oxalic acid, sebacic acid, dodecanoic acid, glutaric acid, and glutamic acid. Another class of monomers that may be included are monocarboxylic acids containing a reactive hydroxyl group, or reactive equivalents of such substances, such as acid anhydrides, esters, or lactones. Examples include glyoxylic acid, caprolactone, valproic acid, and hydroxystearic acid.

[0068] The amount of the aforementioned phosphite product used in the lubricant may be sufficient to provide the composition with 0.01% to 0.3% or 0.1% by weight, or in other embodiments, 0.02% to 0.07% or 0.025% to 0.05% by weight of phosphorus. Of course, the actual amount of product corresponding to these phosphorus amounts will depend on its phosphorus content. Suitable amounts of the ester product in the lubricant additive composition may be 0.01% to 1.0% by weight, or 0.02% to 0.5% by weight, or 0.03% to 0.30% by weight, or even 0.05% to 0.25% by weight.

[0069] While each of the above-described phosphorus anti-wear compounds may be present alone in the lubricant additive composition, the lubricant additive composition may also include a mixture of two or more. In some embodiments, the phosphorus-containing compound may include C3-8 hydrocarbon esters of phosphorous acid and phosphite ester products. In some embodiments, the phosphorus-containing compound may include each of C3-8 hydrocarbon esters of phosphorous acid, C12 to C24 hydrocarbon esters of phosphorous acid, and phosphite ester products. In any case, the phosphorus anti-wear compound shall be present in an amount delivering 100 ppm to 4000 ppm of phosphorus to the lubricant additive composition. In some embodiments, at least one phosphorus anti-wear compound may be present in an amount delivering 125 ppm to 3500 ppm of phosphorus or 150 ppm to 3000 ppm of phosphorus to the lubricant additive composition.

[0070] As otherwise described, the lubricant additive composition may comprise a substantially sulfur-free alkyl phosphate. In this salt composition, at least 30 mol% of phosphorus atoms are in an alkyl pyrophosphate structure, in contrast to the orthophosphate (or monomeric phosphate) structure. The percentage of phosphorus atoms in the pyrophosphate structure may be 30 mol% to 100 mol%, or 40 mol% to 90 mol%, or 50 mol% to 80 mol%, or 55 mol% to 70 mol%, or 55 mol% to 65 mol%. The remaining phosphorus atoms may be in an orthophosphate structure or may consist partially of unreacted phosphoric acid or other phosphorus substances. In one embodiment, up to 60 mol% or up to 50 mol% of phosphorus atoms are in a monoalkyl orthophosphate salt structure or a dialkyl orthophosphate salt structure.

[0071] A substantially sulfur-free alkyl phosphate present in pyrophosphate form (sometimes referred to as the POP structure). In some embodiments, at least 80 mol%, or at least 85 mol%, 90 mol%, 95 mol%, or 99 mol% of the alkyl group in the alkyl phosphate will be a primary alkyl group. In some embodiments, the alkyl group will have 4 to 22, or 4 to 20, or 4 to 18, or even 4 to 12 carbon atoms, or 5 to 10 carbon atoms, or 6 to 8 carbon atoms. Such groups include 2-butyl, 2-pentyl, 3-pentyl, 3-methyl-2-butyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methyl-2-pentyl, and other such primary groups and their isomers having 6, 7, 8, 9, 10, 11, or 12 carbon atoms. In some embodiments, the alkyl group will be in the group - A methyl branch at the - position, for example, is a 4-methyl-2-pentyl (also known as 4-methylpentyl-2-yl) group.

[0072] Such alkyl (including cycloalkyl) groups are typically provided by reacting the corresponding one or more alcohols with phosphorus pentoxide (referred to herein as P2O5, although it is recognized that a more likely structure may be represented by P4O10). Thus, alkyl phosphates can be prepared by reacting phosphorus pentoxide with a primary alcohol having 4 to 12 carbon atoms and then reacting the product with a salting agent, as described in further detail below.

[0073] Although it is possible to separate the pyrophosphate from the orthoester if desired, it is also possible and commercially preferred to use the reaction mixture without separating the components.

[0074] Phosphorus anti-wear compounds can also be amine alkyl thiophosphates, wherein the alkyl thiophosphate is represented by the formula (R'O)2PSSH, wherein each R' is independently a hydrocarbon group containing about 3 to about 30, preferably about 3 to at most about 18, or about 3 to at most about 12, or at most about 8 carbon atoms. Examples of R' groups may include isopropyl, isobutyl, n-butyl, sec-butyl, various pentyl, n-hexyl, methyl isobutylcarbonyl, heptyl, 2-ethylhexyl, isooctyl, nonyl, behenyl, decyl, dodecyl, and tridecyl. Exemplary lower alkylphenyl R' groups include butylphenyl, pentylphenyl, heptylphenyl, etc. Examples of mixtures of R' groups include: 1-butyl and 1-octyl; 1-pentyl and 2-ethyl-1-hexyl; isobutyl and n-hexyl; isobutyl and isopentyl; 2-propyl and 2-methyl-4-pentyl; isopropyl and sec-butyl; and isopropyl and isooctyl.

[0075] In one embodiment, the alkyl thiophosphate of an aminoalkyl thiophosphate can be reacted with an epoxide or a polyol (such as glycerol). This reaction product can be used alone or further reacted with phosphoric acid, anhydride, or a lower ester. The epoxide is typically an aliphatic epoxide or styrene oxide. Examples of useful epoxides include ethylene oxide, propylene oxide, butane oxide, octane oxide, dodecane oxide, styrene oxide, etc. Ethylene oxide and propylene oxide are preferred. The polyol is as described above. The diol can be an aliphatic diol having 2 to about 12, or about 2 to about 6, or 2 or 3 carbon atoms. Diols include ethylene glycol, propylene glycol, etc. Alkyl thiophosphates, diols, epoxides, inorganic phosphorus reagents, and methods for reacting them are described in U.S. Patents 3,197,405 and 3,544,465, the disclosures of which are incorporated herein by reference.

[0076] In one embodiment, the phosphorus anti-wear compound may include a phosphorus-containing acid, salt, or ester, or a mixture thereof. In one embodiment, the phosphorus anti-wear compound may be in the form of a mixture.

[0077] Phosphorus anti-wear compounds may include those derived from phosphoric acid, phosphorous acid, thiophosphoric acid, thiophosphorous acid, or mixtures thereof.

[0078] In one embodiment, the phosphorus anti-wear compound may include: (i) a nonionic phosphorus compound; (ii) an amine salt of a phosphorus compound; or (hi) an ammonium salt of a phosphorus compound.

[0079] In one embodiment, the phosphorus anti-wear compound may include an ammonium salt or amine salt of a phosphorus-containing acid or ester.

[0080] Amino salts of phosphoric acid or esters include phosphate esters and their amine salts; dialkyl dithiophosphate esters and their amine salts; amine salts of phosphites; and amine salts containing phosphate carboxylic esters, ethers and amides; and mixtures thereof.

[0081] The alkyl groups of phosphorus anti-wear compounds can be 2 to 12 carbon atoms, or 3 to 10 carbon atoms, or 4 to 8 carbon atoms.

[0082] Amino salts of phosphates or esters can be used alone or in combination.

[0083] In one embodiment, the amine salt of phosphate or ester comprises a partial amine salt, or a partial amine-metal salt compound, or a mixture thereof. In one embodiment, the amine salt of phosphate or ester also contains a sulfur atom in the molecule.

[0084] Pyrophosphates, thiophosphates, phosphate esters, or mixtures of phosphate esters react with salifying agents. The salifying agent can be a metal to form a metal salt or an amine to form an amine salt.

[0085] The metal salts contain metals including aluminum, calcium, magnesium, strontium, chromium, iron, cobalt, nickel, zinc, tin, lead, manganese, silver, or mixtures thereof. In one embodiment, the metal is zinc.

[0086] The amine in an amine salt can be represented by R23N, where each R2 is independently a hydrogen or hydrocarbon group, an ester-containing group, or an ether-containing group, provided that at least one R2 group is a hydrocarbon group, an ester-containing group, or an ether-containing group (i.e., not NH3). Suitable hydrocarbon amines include primary amines having 1 to 18 carbon atoms, 3 to 12 carbon atoms, or 4 to 10 carbon atoms, such as methylamine, ethylamine, propylamine, isopropylamine, butylamine and its isomers, pentylamine and its isomers, hexylamine and its isomers, heptylamine and its isomers, octylamine and its isomers, such as isooctylamine and 2-ethylhexylamine, as well as higher amines. Other primary amines include dodecylamine, aliphatic amines (such as n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine, and oleylamine). Other useful aliphatic amines include commercially available aliphatic amines, such as "Armeen". ® "Amines (available from Akzo Chemicals, Chicago, Ill), such as Armeen..." ® C, Armeen ® O, Armeen ® OL, Armeen ® T, Armeen ® HT, Armeen ® S and Armeen ® SD, where the letter name involves fatty groups, such as coconut oil, oil, tallow, or stearin groups.

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

[0088] Suitable tertiary amines include tri-n-butylamine, tri-n-octylamine, tri-decylamine, tri-laurhodium, tri-hexadecylamine, and dimethyl oleylamine (Armeen). ® DMOD). Tridecylamine or tridecylamine and their isomers may be used.

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

[0090] In one embodiment, the amine salt of the phosphoric acid or ester as described above may comprise an amine or mixture thereof having a tertiary alkyl primary group of about Cn to about C14. In one embodiment, the amine salt of the phosphorus compound comprises an amine or mixture thereof having a tertiary alkyl primary amine of about C14 to about C18. In one embodiment, the amine salt of the phosphorus compound comprises an amine or mixture thereof having a tertiary alkyl primary amine of about C14 to about C18.

[0091] In one embodiment, the amine salt of the phosphoric acid or ester as described above may be a C14 to C18 alkylated phosphoric acid with Primene. ® 81R (produced and marketed by Rohm & Haas), the reaction product of which is Primene ® 81R is a mixture of C11 to C14 tertiary alkyl primary amines. In other embodiments, the amine may be an ester-containing amine, such as an N-alkyl-substituted γ- or ... -Amino (thio) esters, which are therefore secondary amines. One or both of the O atoms in the ester group may be replaced by sulfur, although sulfur atoms may not usually be present.

[0092] In amino esters , , γ or One or more additional substituents or groups may also be present at the site. In one embodiment, no such substituents are present. In another embodiment, at... Substituents are present at this position. That is, in the chain... The substituents at the position can include ester, thioester, carbonyl, or hydrocarbon groups. This will be understood as encompassing... Similar structures to α-amino esters.

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

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

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

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

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

[0098] When the amine salt is the amine salt of the above-mentioned phosphate ester, the amount of amine salt used in the lubricant may be from 0.1% to 2.0% by weight, or from 0.15% to 1.5% by weight, or from 0.15% to 2.5% by weight.

[0099] When the amine salt is the amine salt of the above-mentioned thiophosphate, the amount of the amine salt used in the lubricant may be 0.05% to 0.5% by weight, or 0.1% to 0.3% by weight, or 0.15% to 2% by weight.

[0100] The amount of phosphorus anti-wear agent is suitable for supplying phosphorus to the lubricant formulation at a rate of 100 parts by weight per million to 5,000 parts by weight per million (ppm).

[0101] The phosphorus anti-wear agent can be a phosphate, alkyl phosphate, or alkyl phosphite, which is suitable for supplying phosphorus to lubricant formulations in amounts of 100 ppm to 5000 ppm, or 150 ppm to 4000 ppm, or 200 ppm to 3000 ppm, or 250 ppm to 2000 ppm, or 100 ppm to 1000 ppm, or 1000 ppm to 5000 ppm, 1250 ppm to 4000 ppm, 1500 ppm to 3000 ppm, or 1600 ppm to 2700 ppm.

[0102] Other performance additives

[0103] The lubricating composition can be prepared by optionally adding P(M)A to an oil having a lubricating viscosity in the presence of other performance additives (described below).

[0104] The lubricating compositions of the present invention optionally contain other performance additives, such as, for example, dispersants, antioxidants, corrosion inhibitors (e.g., triazoles), polyethers, detergents, and anti-wear agents, to name just a few.

[0105] Dispersants may include, for example, "succinimide dispersants," which are carboxyl dispersant substances prepared by reacting a hydrocarbon-substituted succinic anhydride or its reactive equivalent with an amine such as poly(ethylene amine); "amine dispersants," which are reaction products of relatively high molecular weight aliphatic or alicyclic halides with amines (such as polyalkylene polyamines); "Mannich dispersants," i.e., reaction products of alkylphenols in which the alkyl group contains at least 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines); and "ester dispersants," which are similar to the above-mentioned succinimide dispersants, except that they can be considered to be prepared by reacting a hydrocarbon acylated agent with an aliphatic polyol (such as glycerol, pentaerythritol, or sorbitol), as described in U.S. Patent 3,381,022.

[0106] Another class of ashless dispersants are high molecular weight esters. These substances are similar to the succinimides described above, except that they can be considered to be prepared by reacting a hydrocarbon acylating agent with an aliphatic polyol (such as glycerol, pentaerythritol, or sorbitol). Such substances are described in more detail in U.S. Patent 3,381,022. Aromatic succinates can also be prepared as described in U.S. Patent Publication 2010 / 0286414. In some cases, these ester-type dispersants can be post-treated with an amine (such as poly(ethylene amine)).

[0107] Post-treatment dispersants may also be used. Post-treatment dispersants are typically obtained by reacting a carboxylic acid (e.g., succinimide), amine, or Mannich dispersant with a reagent such as urea, thiourea, carbon disulfide, aldehyde, ketone, carboxylic acid, hydrocarbon-substituted succinic anhydride, nitriles, epoxides, boron compounds such as boric acid (to produce “boronized dispersants” as described above), phosphorus compounds such as phosphoric acid or anhydride, 2,5-dimercaptothiadiazole (DMTD), or an aromatic diacid (such as terephthalic acid) having an acid group at the 1, 3, or 1, 4 position on the benzene ring.

[0108] Boronized dispersants are typically obtained by reacting a carboxylic acid (e.g., succinimidyl), amine, or Mannich dispersant with a boron compound reagent such as boric acid (to produce a "boronized dispersant"). Dispersants and their production methods are well known in the art. Boronized dispersants may be additionally functionalized with sulfur or phosphorus fractions. The dispersant component in a boonized dispersant may be a mixture of multiple dispersants of different types; optionally, at least one may be a succinimidyl dispersant. In one embodiment, the boonized dispersant may be a boronized polyisobutylene succinimidyl dispersant, wherein its polyisobutylene fraction may have a number average molecular weight of 750 to 2200, or 750 to 1350, or 750 to 1150. One or more boronized dispersants may be prepared having an N:CO ratio of 0.9:1 to 1.6:1, or 0.95:1 to 1.5:1, or 1:1 to 1.4:1. The amount of borate dispersant in the composition may be, for example, from 0.05% to 2.0% by weight. In other embodiments, the amount is from 0.1% to 1.0% or from 0.15% to 0.75% of the final blended fluid formulation. In concentrates, this amount will become proportionally higher.

[0109] Mixtures of dispersants may also be used. The nitrogen content of the dispersant may be greater than or equal to about 11,000 ppm, or greater than or equal to about 11,500 ppm, or greater than or equal to about 12,000 ppm by weight of the dispersant.

[0110] The total amount of one or more dispersants in the composition (whether post-treated (e.g., boronized or non-boronized, but preferably boronized) or a combination thereof) can be, for example, 0.01% to 3% by weight of the final blended fluid formulation, or, for example, 0.025% to 2.75% by weight or 0.05% to 2.5% by weight, although the amount will be proportionally higher on a concentrate basis. In terms of the degree to which the dispersant is boronized, 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.

[0111] In some embodiments, the dispersant can be prepared by a method involving the presence of small amounts of chlorine or other halogens, as described in U.S. Patent 7,615,521 (see, for example, columns 4, lines 18-60 and Preparation Example A). Such dispersants typically have some carbocyclic structure at the connection between the hydrocarbon substituent and the acidic or amide “head” group. In other embodiments, the dispersant can be prepared by a thermal method involving an “ene” reaction without the use of any chlorine or other halogens, as described in U.S. Patent 7,615,521; dispersants prepared in this manner are typically derived from high vinylidene (i.e., greater than 50% terminal vinylidene) polyisobutylene (see columns 4, lines 61-5, lines 30 and Preparation Example B). Such dispersants typically do not contain the aforementioned carbocyclic structure at the connection point. In some embodiments, the dispersant can be prepared by radical catalytic polymerization of high vinylidene polyisobutylene with an alkene-bonded unsaturated acylating agent, as described in U.S. Patent 8,067,347.

[0112] Lubricant formulations may also contain corrosion inhibitors, which may be described as metal passivators or yellow metal passivators.

[0113] Examples of corrosion inhibitors include triazoles, such as benzotriazole and 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, 2-alkyldithiobenzothiazole, 2-(N,N'-dialkyldithiocarbamoyl)benzothiazole, 2,5-bis(alkyldithio)-1,3,4-thiadiazole, 2,5-bis(N,N'-dialkyldithiocarbamoyl)-1,3,4-thiadiazole, derivatives of 2-alkyldithio-5-mercaptothiadiazole, or mixtures thereof. In one embodiment, the corrosion inhibitor comprises benzotriazole. In one embodiment, the corrosion inhibitor comprises 2,5-bis(alkyldithio)-1,3,4-thiadiazole.

[0114] The triazole comprises a triazole having a hydrocarbon-substituted group at at least one of the following ring positions: 1-, 2-, 4-, 5-, 6-, or 7-. In various embodiments, the hydrocarbon group contains 1 to about 30, 1 to about 15, or 1 to about 16 carbon atoms. In one embodiment, the corrosion inhibitor comprises tolyltriazole. In one embodiment, the hydrocarbon-substituted triazole at the 4, 5, 6, or 7 position also reacts with aldehydes and amines.

[0115] Examples of suitable alkylbenzotriazoles that also react with aldehydes and amines include N,N-bis(2-ethylhexyl)-aryl-methyl-1H-benzotriazole-1-methylamine, N,N-bis(2-ethylhexyl)-4-methyl-1H-benzotriazole-1-methylamine, N,N-bis(2-ethylhexyl)-4-methyl-1H-benzotriazole-1-methylamine, 2H-benzotriazole-2-methylamine, N-(4-methoxyphenyl)-1H-benzotriazole-1-methylamine, N,N-bisdodecyl-1H-benzotriazole-1-methylamine, N-(1H-benzotriazole-1-ylmethyl)-N-(2-ethylhexyl)-1H-benzotriazole-1-methylamine, N-methyl-N-phenyl 4,5,6,7-Tetrahydro-N,N-bis(tridecyl-1H-benzotriazole-1-methylamine), N,N-bis(octadecyl-1H-benzotriazole-1-methylamine, 5-methyl-N,N-dioctyl-1H-benzotriazole-1-methylamine, N,N-dibutyl-1H-benzotriazole-1-methylamine, N-(4-methylphenyl)-1H-benzotriazole-1-methylamine, N,N-bis(2-ethylhexyl)-1H-benzotriazole-1-methylamine, N,N-dioctyl-2H-benzotriazole-2-methylamine, N-dodecyl-1H-benzotriazole-1-methylamine, N-phenyl-1H-benzotriazole-1-methylamine N,N-bisdodecyl-4,5,6,7-tetrahydro-1H-benzotriazole-1-methylamine, N,N-bis(2-ethylhexyl)-5-methyl-1H-benzotriazole-1-methylamine, N-octadecyl-1H-benzotriazole-1-methylamine, N,N-bisdodecyl-2H-benzotriazole-2-methylamine, N,N-dioctyl-1H-benzotriazole-1-methylamine, N-(2-ethylhexyl)-1H-benzotriazole-1-methylamine, 4,5,6,7-tetrahydro-N,N-bistetradecyl-1H-benzotriazole-1-methylamine, or mixtures thereof. In one embodiment, the corrosion inhibitor comprises N,N-bis(2-ethylhexyl)-4-methyl-1H-benzotriazole-1-methylamine or N,N-bis(2-ethylhexyl)-aryl-methyl-1H-benzotriazole-1-methylamine.

[0116] Examples of suitable alkyl 1,2,4-triazoles for further reaction with amines include N,N-bis(1-methylethyl)-1H-1,2,4-triazole-1-methylamine, N,N-diisobutyl-1H-1,2,4-triazole-1-methylamine, N,N-dicyclohexyl-1H-1,2,4-triazole-1-methylamine, N, N-bis(2-ethylhexyl)-1H-1,2,4-triazol-1-methylamine, 1-((1H-1,2,4-triazol-1-yl)methyl)piperidine, N,N-bis(tetrazyl)-1H-1,2,4-triazol-1-methylamine, N,N-dimethyl-1-(1H-1,2,4-triazol-1-yl)methylamine, N,N-dibutyl-1H-1,2,4-triazol-1-methylamine, N,N-dicocoyl-1-(1H-1,2,4-triazol-1-yl)methylamine, N-((1H-1,2,4-triazol-1-yl)methyl)oct-3-amine.

[0117] In various embodiments, the corrosion inhibitor is triazole. The triazole corrosion inhibitor may be present alone or in mixtures with other triazole corrosion inhibitors or other azole corrosion inhibitors, ranging from about 0.005% by weight or 0.01% by weight to about 0.1% by weight, or about 0.03% by weight to about 0.08% by weight, or about 0.04% by weight to about 0.068% by weight, or about 0.045% by weight to about 0.057% by weight of the lubricant additive composition.

[0118] In one embodiment, the photoresist can be a thiadiazole, such as 1,3,4-thiadiazole. In another embodiment, the 1,3,4-thiadiazole may contain substituents, such as, for example, alkyl dithioalkyl moieties, at the 2 and 5 positions of the thiadiazole ring. Such photoresists may include those of the following formula:

[0119] R1 and R2 are independently alkyl groups with 1 to 12 carbon atoms.

[0120] In one embodiment, the resist comprises (i) 2,5-bis(alkyldithio)-1,3,4-thiadiazole, (ii) a benzotriazole having a hydrocarbon-substituted ring at at least one of the following ring positions 4-, 5-, 6-, or 7-, or (iii) a benzotriazole having a hydrocarbon-substituted ring at at least one of the following ring positions 1- or 2- (typically benzotriazole is further reacted with aldehydes and amines).

[0121] In one embodiment, the resist comprises 2,5-bis(alkyldithio)-1,3,4-thiadiazole. In different embodiments, the alkyl group of the 2,5-bis(alkyldithio)-1,3,4-thiadiazole contains 1 to about 30, or about 2 to about 25, or 4 to about 20, or about 6 to about 16 carbon atoms. Examples of suitable 2,5-bis(alkyldithio)-1,3,4-thiadiazoles include 2,5-bis(tert-octyldithio)-1,3,4-thiadiazole, 2,5-bis(tert-nonyldithio)-1,3,4-thiadiazole, 2,5-bis(tert-decyldithio)-1,3,4-thiadiazole, 2,5-bis(tert-undecyldithio)-1,3,4-thiadiazole, 2,5-bis(tert-dodecyldithio)-1,3,4-thiadiazole, or mixtures thereof.

[0122] The photoresist can be used alone or in combination with two, three or more photoresists. In one embodiment, the photoresist comprises a mixture of: (i) 2,5-bis(alkyldithio)-1,3,4-thiadiazole, (ii) a benzotriazole having a hydrocarbon-substituted ring group at at least one of the following ring positions: 4-, 5-, 6- or 7-, and (iii) a benzotriazole having a hydrocarbon-substituted ring group at at least one of the following ring positions: 1- or 2- (typically, benzotriazole is further reacted with aldehydes and amines).

[0123] In various embodiments, the corrosion inhibitor is thiadiazole. The thiadiazole corrosion inhibitor may be present alone or in mixtures with other thiadiazole corrosion inhibitors or other azole corrosion inhibitors, ranging from about 0.01% to about 1% by weight, or about 0.05% to about 0.9% by weight, or about 0.1% to about 0.8% by weight, or about 0.2% to about 0.7% by weight, or about 0.2% to about 0.5% by weight, or about 0.25% to about 0.35% by weight, of the lubricant additive composition.

[0124] The lubricant additive composition may also include antioxidants, such as aromatic amine antioxidants, hindered phenolic antioxidants (including ester-containing hindered phenolic antioxidants), and sulfurized olefin antioxidants. These antioxidants may be present in amounts from 0.01% to 5% by weight, or from 0.15% to 3% by weight, or from 0.2% to 1.5% by weight, or from 0.2% to 1% by weight, or from 0.25% to 0.7% by weight.

[0125] In one embodiment, the lubricant additive composition of the present invention comprises an arylamine antioxidant. The arylamine antioxidant may be phenyl-α-naphthylamine (PANA), or a hydrocarbon-substituted diphenylamine, or a mixture thereof. The hydrocarbon-substituted diphenylamine may comprise mono- or di-C4 to C16-, or C6 to C12-, or C9-alkyl diphenylamines. For example, the hydrocarbon-substituted diphenylamine may be octyl diphenylamine or dioctyl diphenylamine, dinonyl diphenylamine, and typically dinonyl diphenylamine.

[0126] When present, arylamine antioxidants may be present in 0.2% to 1.2% by weight, or 0.3% to 1.0% by weight, or 0.4% to 0.9% by weight, or 0.5% to 0.8% by weight of the lubricant additive composition.

[0127] Hindered phenolic antioxidants often contain sec-butyl and / or tert-butyl groups as sterically hindered groups. The phenolic group is typically further substituted with a hydrocarbon group and / or a bridging group connected to a second aromatic group. Examples of suitable hindered phenolic antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol, or 4-butyl-2,6-di-tert-butylphenol or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenolic antioxidant can be an ester and may include, for example, Irganox derived from Ciba. ™ L-135 or butyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

[0128] If present, the hindered phenolic antioxidant may be present in 0.1% to 1% by weight, or 0.2% to 0.9% by weight, or 0.1% to 0.4% by weight, or 0.4% to 1.0% by weight of the lubricant additive composition.

[0129] Antioxidants also include sulfurized olefins, such as monosulfides or disulfides, or mixtures thereof. These substances typically have sulfur bonds containing 1 to 10 sulfur atoms, such as 1 to 4, 1, or 2 sulfur atoms. Substances that can be sulfurized to serve as sulfurized antioxidants in lubricant additive compositions may include oils, fatty acids and esters, olefins and polyolefins prepared therefrom, terpenes, or Diels-Alder adducts. Details of methods for preparing certain such sulfurized substances can be found in U.S. Patents 3,471,404 and 4,191,659.

[0130] In one embodiment, the lubricant additive may also include a boron-containing compound.

[0131] The lubricant additive composition may contain a boron-containing compound in an amount sufficient to provide the lubricant additive composition with about 75 ppm to about 500 ppm of boron, or about 85 ppm to about 450 ppm, or about 95 ppm to about 350 ppm of boron, or about 100 ppm to about 400 ppm of boron.

[0132] Boron can be transported through various types of boron-containing compounds.

[0133] Boron-containing compounds can be used as dispersants for post-treatment with boron sources.

[0134] Boron-containing compounds may include boron-containing friction modifiers, such as boronized aliphatic epoxides, boronized glycerides, and boronized alkoxylated aliphatic amines.

[0135] Boron-containing compounds may also include boronized detergents. Boronized detergents may include, for example, highly basic boronized substances, as described in U.S. Patents 5,403,501 and 4,792,410.

[0136] Boron-containing compounds may also include borate esters. Borate esters may be compounds represented by one or more of the following formulas:

[0137] Each R can be independently a hydrocarbon group as defined herein, and any two adjacent R groups can together form a cyclic group. Mixtures of two or more of the foregoing may be used. The total number of carbon atoms in the R groups in each formula should be sufficient to dissolve the compound in a base oil. Typically, the total number of carbon atoms in the R groups is at least about 3, and in one embodiment at least about 5, and in another embodiment at least about 8. There is no limit to the required total number of carbon atoms in the R groups, but a practical upper limit is the absence of about 400 or about 500 carbon atoms.

[0138] In embodiments, each R may independently be a hydrocarbon group containing 1 to 14, 2 to 13, or even 3 to 10 or 12 carbon atoms, provided that the sum of the total number of carbon atoms in all Rs is 3 or more, preferably 4 or more, and even more preferably 6 or more. In some embodiments, each R may independently be a C3 to C22, C3 to C18, or C3 to C12 alkyl group. Examples of useful R groups include isopropyl, n-butyl, isobutyl, pentyl, 4-methyl-2-pentyl, 2-ethyl-1-hexyl, isooctyl, decyl, dodecyl, 2-propylheptyl, tetradecyl, 2-pentenyl, dodecenyl, phenyl, naphthyl, alkylphenyl, etc.

[0139] Suitable examples of borate esters include, for example, tripropyl borate, tributyl borate, tripentyl borate, trihexyl borate, triheptyl borate, trioctyl borate, trinonyl borate, and tridecyl borate. Other examples of borate esters may include, for example, compounds of formula I, wherein each R is independently a C3 to C22, C3 to C18, or C3 to C12 alkyl group, such as, for example, tri-2-ethylhexyl borate, tri(2-propylheptyl) borate, and mixtures thereof. In one embodiment, the borate ester may be a C8 borate ester or a C10 borate ester. In one embodiment, the borate ester may be tri(2-propylheptyl) borate. In some embodiments, the borate ester may be tri-2-ethylhexyl borate.

[0140] In one embodiment, the borate-treated ester may be represented by the formula B(OC5H11)3 or B(OC4H9)3. In one embodiment, the borate-treated ester may be tributyl borate.

[0141] In one embodiment, the boronized ester may be a phenolic compound represented by the following formula.

[0142] In Formula VII: R1, R2, R3, and R4 are independently hydrocarbon groups having 1 to about 12 carbon atoms; and R5 and R6 are independently alkylene groups having 1 to about 6 carbon atoms, and in one embodiment are alkylene groups having about 2 to about 4 carbon atoms, and in another embodiment are alkylene groups having about 2 or about 3 carbon atoms. In one embodiment, R1 and R2 independently contain 1 to about 6 carbon atoms, and in one embodiment are each tert-butyl groups. In one embodiment, R3 and R4 are independently hydrocarbon groups having about 2 to about 12 carbon atoms, and in one embodiment are hydrocarbon groups having about 8 to about 10 carbon atoms. In one embodiment, R5 and R6 are independently --CH2CH2-- or --CH2CH2CH2--.

[0143] In one embodiment, the boronized ester may be a compound represented by the following formula:

[0144] In Formula IX, each R is independently a hydrogen or hydrocarbon group. Each hydrocarbon group may contain 1 to about 12 carbon atoms, and in one embodiment may contain 1 to about 4 carbon atoms. An example is 2,2'-oxy-bis-(4,4,6-trimethyl-1,3,2-dioxoborhexane).

[0145] Boronate esters may be used in the lubricant additive composition at about 0.2% or 0.3% by weight to about 2.0% by weight, or in some cases about 0.35% to 2.0% by weight, and in one embodiment about 0.25% to about 1.0% by weight, and in another embodiment about 0.25% to about 0.75% by weight.

[0146] In one embodiment, the lubricant additive composition may include a polyol and an ester of an aliphatic carboxylic acid containing 12 to 24 carbon atoms.

[0147] Polyols include diols, triols, and alcohols having a higher number of OH groups. Polyols include: ethylene glycol, including diethylene glycol, triethylene glycol, and tetraethylene glycol; propylene glycol, including dipropylene glycol, tripropylene glycol, and tetrapropylene glycol; glycerol; butylene glycol; hexanediol; sorbitol; arabinitol; mannitol; sucrose; fructose; glucose; cyclohexanediol; erythritol; and pentaerythritol, including dipentaerythritol and tripentaerythritol; preferably, diethylene glycol, triethylene glycol, glycerol, sorbitol, pentaerythritol, and dipentaerythritol.

[0148] Aliphatic carboxylic acids that form esters are acids containing 12 to 24 carbon atoms. These acids are characterized by the general formula R1-(CO)OH, where R1 is a hydrocarbon group, which can be a straight-chain hydrocarbon group, a branched hydrocarbon group, a cyclic hydrocarbon group, or a mixture thereof. Preferably, it is a straight-chain hydrocarbon group containing 12 to 24 carbon atoms, for example, a straight-chain hydrocarbon group with 14 to 20 or 16 to 18 carbon atoms. These acids can also be used in combination with acids having more or fewer carbon atoms.

[0149] Generally, the acid R1-(CO)OH is a monocarboxylic acid because polycarboxylic acids tend to form polymer products if the reaction conditions and amounts of reactants are not carefully controlled. However, mixtures of monocarboxylic acids and small amounts of dicarboxylic acids or anhydrides can be used to prepare esters. Examples of carboxylic acids include dodecanoic acid, stearic acid, lauric acid, behenic acid, and oleic acid.

[0150] The aforementioned esters are, in particular, monoesters of such polyols and such carboxylic acids. Preferred esters are monooleic glycerides. It should be understood that, as with other such substances, monooleic glycerides, in their commercially available grades, are mixtures of such substances including glycerol, oleic acid, other long-chain acids, dioleic acid glycerides, and trioleic acid glycerides. It is believed that commercially available substances comprise about 60 ± 5% by weight of the chemical substance “monooleic acid glycerides,” and 35 ± 5% of dioleic acid glycerides and less than about 5% of trioleic acid esters and oleic acid. The amounts of monoesters described below are calculated based on the actual corrected amounts of polyol monoesters present in any such mixture.

[0151] The amount of the aforementioned ester in the lubricant additive composition is typically on the order of about 0.01% by weight to about 1.0% by weight of the lubricant additive composition, but may also be about 0.05% by weight to about 0.5% by weight, or 0.8% by weight, or about 0.1% by weight to about 0.6% by weight.

[0152] In addition to the aforementioned esters, the lubricant additive composition may also contain alcohols and esters of aliphatic carboxylic acids containing about 4 to about 8 carbon atoms.

[0153] Alcohols include both monohydric alcohols and polyhydric alcohols (i.e., polyols). The carbon atoms in alcohols can be straight-chained, branched, or a mixture thereof.

[0154] The appropriate polyols are the same as those described above.

[0155] When branched, the alcohol can be a Gerbert alcohol or a mixture thereof. Gerbert alcohols may have alkyl groups including: 1) alkyl groups containing C15-16 polymethylene groups, such as 2-C1-15 alkyl-hexadecyl groups (e.g., 2-octylhexadecyl) and 2-alkyl-octadecyl groups (e.g., 2-ethyloctadecyl, 2-tetradecyl-octadecyl, and 2-hexadecyloctadecyl); 2) alkyl groups containing C13-14 polymethylene groups, such as 1-C1-15 alkyl-tetradecyl groups (e.g., 2-hexyltetradecyl, 2-decyltetradecyl, and 2-undecyltridecyl) and 2-C1-15 alkyl-hexadecyl groups (e.g., 2-ethyl-hexadecyl and 2-dodecylhexadecyl); 3) alkyl groups containing C10-12 polymethylene groups, such as 2-C1-15 alkyl-dodecyl groups (e.g., 2-octyldodecyl) and 2-C1-15 alkyl-dodecyl groups (2-hexyldodecyl and 2-octyl). 4) Alkyl groups containing C6-9 polymethylene groups, such as 2-C1-15 alkyl-tetradecyl groups (e.g., 2-hexyltetradecyl and 2-decyltetradecyl); 5) Alkyl groups containing C1-5 polymethylene groups, such as 2-(3-methylhexyl). -7-methyl-decyl and 2-(1,4,4-trimethylbutyl)-5,7,7-trimethyl-octyl groups; and 6) and mixtures of two or more branched alkyl groups, such as alkyl residues of carbonyl synthetic alcohols corresponding to propylene oligomers (from hexamer to undeterminer), ethylene / propylene (molar ratio 16:1-1:11) oligomers, isobutylene oligomers (from pentamer to octamer), and C5-17α-olefin oligomers (from dimer to hexamer).

[0156] Examples of suitable branched monohydric alcohols include 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol, 2-octyldodecanol, 2-decyltetradecanol, isotridecanol, isooctanol, oleyl alcohol, Guerbert alcohol, or mixtures thereof. Examples of linear monohydric alcohols include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanool, or mixtures thereof. In one embodiment, the monohydric alcohol contains 6 to 30, 8 to 20, or 8 to 15 carbon atoms (typically 8 to 15 carbon atoms).

[0157] Aliphatic carboxylic acids that form esters are acids containing 4 to 8 carbon atoms. Although aliphatic, aliphatic carboxylic acids may contain olefinically unsaturated groups along their C4 to C8 alkyl backbone. Furthermore, these acids can be monocarboxylic acids, dicarboxylic acids, acid anhydrides, or mixtures thereof. Examples of carboxylic acids include, for instance, succinic acid, maleic acid, fumaric acid, pentenoic acid, glutaric acid, adipic acid, citralic acid, mesonic acid, pimelic acid, octanoic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, etc.

[0158] Particularly preferred esters may be adipates, such as, for example, C8-13 or C8-12 adipates, such as diisooctyl adipate or ditridecyl adipate. Other esters may include, for example, pentaerythritol esters, neopentyl esters, and trimethylol esters.

[0159] The amount of the aforementioned ester in the lubricant additive composition is typically on the order of about 0.1 wt% to about 3.0 wt% of the lubricant additive composition, but may also be about 0.2 wt% to about 2.5 wt%, or about 0.3 wt% to about 2.0 wt%.

[0160] Carboxylic acid esters are prepared by a well-known reaction of at least one carboxylic acid (or its reactive equivalent, such as an ester, halide, or anhydride) with at least one of the aforementioned hydroxyl compounds.

[0161] Another component of the lubricant additive composition may be a metal deactivator. Examples of such substances include 2,5-dimercapto-1,3,4-thiadiazole and / or its derivatives. Such substances are described in European Patent Publication 0761805, which is incorporated herein by reference.

[0162] The metal deactivators used in this article reduce corrosion of metals such as copper. Metal deactivators are also known as metal passivators. These metal deactivators are typically nitrogen- and / or sulfur-containing heterocyclic compounds, such as dimercaptothiadiazole, triazole, aminomercaptothiadiazole, imidazole, thiazole, tetraazole, hydroxyquinoline, etc. Azoline, imidazoline, thiophene, indole, indazole, quinoline, benzo[a] Azides, dithiols, azole, Triazoles, pyridines, piperazines, triazines, 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 are benzotriazoles, alkyl-substituted benzotriazoles (e.g., tolyltriazole, ethylbenzotriazole, hexylbenzotriazole, octylbenzotriazole, etc.), aryl-substituted benzotriazoles (e.g., phenol benzotriazole, etc.), and alkylaryl or aralkyl-substituted benzotriazoles and substituted benzotriazoles, wherein the substituents may be hydroxyl, alkoxy, halogen (especially chlorine), nitro, carboxyl, and carboxyalkoxy. Preferably, the triazole is a benzotriazole or alkylbenzotriazole wherein the alkyl group contains 1 to about 20 carbon atoms, preferably 1 to about 8 carbon atoms. Benzotriazoles and tolyltriazoles are useful.

[0163] In one embodiment, the metal deactivator is the reaction product of a dispersant and a dimercaptothiadiazole. Dispersants are generally characterized as reaction products of carboxylic acids with amines and / or alcohols. These reaction products are commonly used as dispersants in the lubricant field and are sometimes collectively referred to as dispersants, although they may have other uses besides or as substitutes for dispersants. Carboxylic acid dispersants include succinimidyl dispersants, ester dispersants, etc. Succinimidyl dispersants are generally the reaction products of polyamines with alkenyl succinic anhydrides or acids. Ester dispersants are the reaction products of alkenyl succinic anhydrides or acids with polyol compounds. The reaction products can then be further treated with amines such as polyamines. Examples of useful dispersants are disclosed in U.S. Patent Nos. 3,219,666 and 4,234,435, which are incorporated herein by reference. Useful dispersants also include ashless dispersants discussed below. Typically, the reaction between the dispersant and the dimercaptothiadiazole occurs by mixing the dispersant and heating to a temperature above about 100°C. U.S. Patent Nos. 4,140,643 and 4,136,043 describe compounds prepared by reacting such dispersants with dimercaptothiadiazoles. These patents are incorporated herein by reference for their disclosure of dispersants, dimercaptothiadiazoles, methods of reacting the two, and products obtained from such reactions.

[0164] In one embodiment, the metal deactivator is the reaction product of phenol and dimercaptothiadiazole. The phenol is preferably an alkylphenol, wherein the alkyl group contains at least about 6, preferably 6 to about 24, more preferably about 6 or about 7 to about 12 carbon atoms. The aldehyde is preferably an aldehyde or aldehyde synthon containing 1 to about 7 carbon atoms, such as formaldehyde. Preferably, the aldehyde is formaldehyde or paraformaldehyde. The aldehyde, phenol, and dimercaptothiadiazole are typically reacted by mixing them at a temperature up to about 150°C, preferably about 50°C to about 130°C, in a molar ratio of about 0.5 moles to about 2 moles of phenol and about 0.5 moles to about 2 moles of aldehyde per mole of dimercaptothiadiazole. Preferably, the three reagents react in equal molar amounts.

[0165] In one embodiment, the metal deactivator is a bis(alkyldithio)thiadiazole. Preferably, each alkyl group is independently an alkyl, aryl, or aralkyl group having 6 to about 24 carbon atoms. Each alkyl group may be independently tert-octyl, nonyl, decyl, dodecyl, or ethylhexyl. The metal deactivator may be bis-2,5-tert-octyl-dithio-1,3,4-thiadiazole or a mixture thereof with 2-tert-octylthio-5-mercapto-1,3,4-thiadiazole. These substances are commercially available under the trade name Amoco 150 from Amoco Chemical Company. These dithiothiadiazole compounds are disclosed as component (d) in PCT Publication WO88 / 03551, which is incorporated herein by reference for the dithiothiadiazole compounds disclosed therein. In a preferred embodiment, the metal deactivator is a dimercaptothiadiazole derivative. Specific examples are given below in D-1 and D-2.

[0166] Example D-1

[0167] Oxidative coupling of 2,5-dimercapto-1,3,4-thiadiazole with tert-nonylthiol; 100% chemical, 36% S, 64% N.

[0168] Example D-2

[0169] Heptaylphenol was coupled with 2,5-dimercapto-1,3,4-thiadiazole using formaldehyde (thiadiazole was generated in situ); 20% oil, 17.75% S, 5.5% N.

[0170] When used, the amount of metal deactivator in the lubricant additive composition is typically in the range of about 0.01% by weight to about 0.5% by weight of the lubricant additive composition. In some embodiments, the amount of metal deactivator may be in the range of about 0.02% by weight to about 0.42% by weight, or about 0.03% by weight to about 0.33% by weight, or about 0.04% by weight to about 0.24% by weight of the lubricant additive composition.

[0171] Another component of the present invention may be a borate epoxide containing 12 to 24 carbon atoms. This substance can also be described as a borate ester of a vicinal diol containing 12 to 24 carbon atoms. Such substances can be represented by the following structures.

[0172] R1, R2, R3, and R4 are each independently a hydrogen or aliphatic radical, or any two thereof together with one or more carbon atoms to which they are attached to form a cyclic radical. Preferably, at least one of the R groups may be an alkyl group containing at least 8 or at least 10 carbon atoms. In one embodiment, one of the R groups is such an alkyl group, and the remaining R groups are hydrogen. Boronized epoxides are described in detail in U.S. Patent No. 4,584,115. Boronized epoxides are generally prepared by reacting an epoxide with a boron source such as boric acid or boron trioxide. Boronized epoxides are not epoxides themselves, but rather ring-opening boron-containing reaction products of epoxides. Suitable epoxides include commercially available mixtures of C14-16 or C14-18 or C16-18 epoxides, which are available from Elf-Atochem or Union Carbide, and can be prepared from the corresponding olefins by known methods. Purified epoxides, such as 1,2-epoxyhexadecane, are available from Aldrich Chemicals. Boronized compounds are prepared by blending a boron compound with an epoxide and heating at a suitable temperature (typically 80 to 250 °C) until the desired reaction occurs. Inert liquids, such as toluene, xylene, or dimethylformamide, can be used as the reaction medium. Water is formed during the reaction and is typically distilled off. A basic reagent can be used to catalyze the reaction. Preferred boronized epoxides are boronized epoxides that are primarily 16-carbon olefins. The amount of the boron ester epoxide can be 0.01 or 0.05 to 0.5 or 1.0 parts by weight of the composition, or alternatively, 0.1 to 0.9%.

[0173] The lubricant additive composition may also contain a calcium-containing detergent. Although it is preferred that no calcium-containing detergent is present, the amount of calcium-containing detergent included may be up to 300 ppm of calcium, or 30 ppm to 300 ppm, or 30 ppm to 275 ppm of calcium, or 60 ppm to 250 ppm, or even 60 ppm to 225 ppm of calcium.

[0174] In some implementations, the calcium-containing detergent may be present at 900 ppm or less, or 1 ppm to 900 ppm, or even 5 ppm to 800 ppm, or 10 ppm to 700 ppm, or even 15 ppm to 600 ppm, or 500 ppm.

[0175] Calcium-containing detergents can be highly alkaline, non-alkaline, or mixtures thereof. Typically, the detergent is highly alkaline.

[0176] The preparation of calcium-containing detergents is known in the art. Patents describing the preparation of highly alkaline calcium-containing detergents include U.S. Patents 2,501,731; 2,616,905; 2,616,911; 2,616,925; 2,777,874; 3,256,186; 3,384,585; 3,365,396; 3,320,162; 3,318,809; 3,488,284; and 3,629,109.

[0177] Calcium-containing detergents can be non-alkaline detergents (also known as neutral detergents). The TBN (total nitrate nitrogen) of non-alkaline detergents can be from 20 mg KOH / g to less than 200 mg KOH / g, or from 30 mg KOH / g to 100 mg KOH / g, or from 35 mg KOH / g to 50 mg KOH / g. The TBN of non-alkaline calcium-containing detergents can also be from 20 mg KOH / g to 175 mg KOH / g or from 30 mg KOH / g to 100 mg KOH / g. When non-alkaline calcium-containing detergents are prepared from strong acids such as hydrocarbon-substituted sulfonic acids, the TBN can be even lower (e.g., 0 to 50 mg KOH / g, or 10 to 20 mg KOH / g).

[0178] As used herein, the TBN values ​​and ranges cited are based "as is," i.e., containing a typical amount of diluent oil. A typical amount of diluent oil is typically between 30% and 60% by weight (typically 40% to 55% by weight) of the detergent component.

[0179] Calcium-containing detergents can be highly alkaline, with a TBN, for example, greater than 200 mg KOH / g (typically 250 to 600, or 300 to 500 mg KOH / g).

[0180] Highly alkaline calcium-containing detergents can be formed by the reaction of alkaline calcium compounds and acidic detergent bases. Acidic detergent bases may include alkyl aromatic sulfonic acids (e.g., alkylnaphthalene sulfonic acid, alkyltoluene sulfonic acid, or alkylbenzene sulfonic acid), alkyl salicylic acid, or mixtures thereof.

[0181] Basic calcium compounds are used to provide alkalinity to detergents. Basic calcium compounds are compounds of calcium hydroxide or oxide.

[0182] Oxides and / or hydroxides may be used alone or in combination. Oxides or hydroxides may be hydrated or dehydrated, although hydration is typical. In one embodiment, the basic calcium compound may be calcium hydroxide, which may be used alone or in combination with other basic metal compounds. Calcium hydroxide is commonly referred to as lime. In one embodiment, the basic calcium compound may be calcium oxide, which may be used alone or in combination with other basic metal compounds.

[0183] In one embodiment, the calcium-containing detergent may be a sulfonate or a mixture thereof. The sulfonate may be prepared from a benzene (or naphthalene, indene, indanyl, or dicyclopentadienyl) sulfonic acid with a mono- or di-alkyl substituted group, wherein the alkyl group may contain 6 to 40, 8 to 35, or 9 to 30 carbon atoms.

[0184] The hydrocarbon group may be derived from polypropylene or from a straight-chain or branched alkyl group containing at least 10 carbon atoms. Examples of suitable alkyl groups include branched and / or straight-chain decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, octadecenyl, nonadecanyl, eicosyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, or mixtures thereof.

[0185] In one embodiment, the hydrocarbon-substituted sulfonic acid may include polypropylene benzenesulfonic acid and / or C16-C24 alkylbenzenesulfonic acid or mixtures thereof.

[0186] In one embodiment, the calcium sulfonate detergent may be primarily a linear alkylbenzene sulfonate detergent with a metal ratio of at least 8, as described in paragraphs

[0026] through

[0037] of U.S. Patent Application 2005065045 (and granted US 7,407,919). In some embodiments, the linear alkyl group may be attached to any position along the linear chain of the alkyl group to the benzene ring, but often at the 2, 3, or 4 positions of the linear chain, and in some cases primarily at the 2 position.

[0187] When the detergent is neutral or weakly alkaline, the TBN of calcium sulfonate detergent can be less than 100 mg KOH / g or less than 75 mg KOH / g, usually 20 mg KOH / g to 50 mg KOH / g, or 0 mg KOH / g to 20 mg KOH / g.

[0188] When the alkalinity is high, the TBN of calcium sulfonate detergent can be greater than 200 mg KOH / g, or from 300 mg KOH / g to 550 mg KOH / g, or from 350 mg KOH / g to 450 mg KOH / g.

[0189] Phenolic detergents are typically derived from p-hydroxyphenols or, generally, from alkylphenols. This type of alkylphenol can be combined with sulfur and become highly basic, combined with aldehydes and become highly basic, or carboxylated to form salicylate detergents. Suitable alkyl salicylates include those alkylated with oligomers of propylene, oligomers of butene, especially tetramers and pentamers of n-butene, and those alkylated with α-olefins, isomerized α-olefins, and polyolefins such as polyisobutylene. In one embodiment, the lubricant additive composition comprises less than 0.2% by weight, or less than 0.1% by weight, or even less than 0.05% by weight of a PDDP-derived salicylate detergent. In one embodiment, the lubricant additive composition comprises a salicylate detergent that is not derived from PDDP. In one embodiment, the lubricant additive composition comprises a salicylate detergent prepared from PDDP, such detergent containing less than 1.0% by weight of unreacted PDDP, or less than 0.5% by weight of unreacted PDDP, or substantially free of PDDP.

[0190] The detergent can be borated or non-borated.

[0191] The chemical structures of sulfonate and salicylate detergents are known to those skilled in the art. The standard textbook entitled "Chemistry and Technology of Lubricants," third edition, edited by RM Mortier and ST Orszulik, copyright 2010, pp. 220-223, provides a general disclosure of the detergents and their structures under subheading 7.2.6.

[0192] In one embodiment, the calcium-containing detergent may be highly alkaline calcium sulfonate, highly alkaline calcium salicylate, or a mixture thereof. Typically, the detergent may be highly alkaline calcium sulfonate.

[0193] In one embodiment, the calcium-containing detergent may be mixed with a detergent containing zinc, barium, sodium, or magnesium. Detergents containing zinc, barium, sodium, or magnesium are also well known in the art and are described in the same references describing calcium-containing detergents. However, the TBN and metal ratio may vary slightly. Zinc-, barium-, sodium-, or magnesium-containing detergents may be phenolates, sulfur-containing phenolates, sulfonates, salicylates, or salicylates. Typically, zinc-, barium-, sodium-, or magnesium-containing detergents may be magnesium phenolate, magnesium-sulfur phenolates, or magnesium sulfonate.

[0194] More detailed descriptions of “metal ratio,” TBN, and “soap content” are known to those skilled in the art and are explained in standard textbooks, such as “Lubricant Chemistry and Processes,” 3rd edition, edited by RM Mortier and ST Orszulik, copyright 2010, pp. 219-220, under the category of detergents in subheading 7.2.5.

[0195] The lubricant additive composition preferably exhibits a conductivity of up to 1 × 10⁻⁹ S / cm at 100°C and 500 V, as measured by ASTM D2624, or a conductivity of 9.5 × 10⁻¹⁰ S / cm, or 9 × 10⁻¹⁰ S / cm, or 8.5 × 10⁻¹⁰ S / cm, or 8 × 10⁻¹⁰ S / cm, or 7.0 × 10⁻¹⁰ S / cm, or 6.5 × 10⁻¹⁰ S / cm, or 6.0 × 10⁻¹⁰ S / cm, or 5.5 × 10⁻¹⁰ S / cm, or 5.0 × 10⁻¹⁰ S / cm. Very preferably, the lubricant additive composition does not have conductivity, but can practically achieve a conductivity on the order of 4.0 × 10⁻¹⁰ or 4.5 × 10⁻¹⁰ at 100°C.

[0196] In one embodiment, the lubricant additive composition is substantially free of friction modifiers. In some embodiments, the lubricant additive composition is completely free of friction modifiers.

[0197] When added to base oils, lubricant additive compositions can be in concentrate form and / or fully formulated lubricant form. That is, lubricant additive compositions can be added to base oils to prepare lubricating compositions.

[0198] The sulfur content of the lubricating composition may be 100 ppm or less, or 80 ppm or less, or 60 ppm or less, or 40 ppm or less. In one embodiment, the sulfur content may be in the range of 1 ppm to 100 ppm. In one embodiment, the lubricating composition is sulfur-free.

[0199] In one embodiment, the phosphorus content can be from 100 ppm to 5000 ppm. In another embodiment, the phosphorus content can be from 100 ppm to 4000 ppm, or 200 ppm to 3000 ppm, or even 100 ppm to 2000 ppm, 100 ppm to 1000 ppm, or 200 ppm to 600 ppm. The total sulfated ash content can be from 0.3 wt% to 1.2 wt% or 0.5 wt% to 1.1 wt% of the lubricating composition. In one embodiment, the sulfated ash content can be from 0.5 wt% to 1.1 wt% of the lubricating composition.

[0200] Industrial applications

[0201] P(M)A can be used in methods for lubricating the drivetrain of a vehicle. The method includes applying the disclosed lubricant formulation to the drivetrain and operating the vehicle.

[0202] The transmission system can be, for example, gears, axles, drive shafts, automatic or manual transmissions, or the transmission system of off-highway vehicles (such as agricultural tractors). Such transmission systems are lubricated by gear oil, axle oil, drive shaft oil, traction oil, manual transmission fluid, automatic transmission fluid, or off-highway oils (such as agricultural tractor oil).

[0203] In one embodiment, a method for lubricating a manual transmission is provided, which may or may not include a synchronizer system. In one embodiment, a method for lubricating an automatic transmission is provided. In one embodiment, the present invention provides a method for lubricating a wheel axle.

[0204] The automatic transmissions that the disclosed method can cover include, for example, continuously variable transmissions (CVT), continuously variable transmissions (IVT), toroidal transmissions, continuously sliding torque converter clutches (CSTCC), stepped automatic transmissions, or dual-clutch transmissions (DCT).

[0205] Automatic transmissions may include a continuously slippery torque converter clutch (CSTCC), a wet start and shift clutch, and in some cases, a metal or composite synchronizer. Dual-clutch transmissions or automatic transmissions may also incorporate an electric motor unit.

[0206] Regarding axles and gears, the method may include applying gear oil or axle oil to planetary hub reduction axles, mechanical steering and transmission gearboxes in public vehicles, synchronous meshing gearboxes, power take-off gears, limited-slip axles, and planetary hub reduction gearboxes. The axles may also incorporate an electric motor unit. The electric motor may be located, for example, "in-wheel," on the front or rear axle. The electric motor may also be incorporated into a drive shaft.

[0207] The following examples provide an illustration of the invention. These examples are non-exhaustive and are not intended to limit the scope of the invention.

[0208] Example

[0209] P(M)A 1 – A sulfur-containing poly(methacrylate) copolymer with amine functional groups prepared by free radical polymerization using 1-dodecylthiol as a chain transfer agent.

[0210] P(M)A2 – A sulfur-free poly(methacrylate) copolymer with amine functional groups prepared by free radical polymerization using AMSD as a chain transfer agent. Except for the chain transfer agent, the composition of P(M)A2 is the same as that of P(M)A1.

[0211] P(M)A3 – An amine-free, sulfur-free poly(methacrylate) copolymer prepared by free radical polymerization using AMSD as a chain transfer agent. Except for the amine-containing monomer, the composition of P(M)A3 is the same as that of P(M)A2.

[0212] P(M)A samples were tested using base oil only in concentrate form, as shown in Table 1 below. All components are listed on an oil-free basis.

[0213] Table 1

[0214] Test Results

[0215] Comparing the sulfur content of the fluids, it can be seen that neither sulfur-free P(M)A formulation 2 nor sulfur-free P(M)A formulation 3 has measurable sulfur by method D4951.

[0216] Comparing the viscosity of conventional P(M)A in formulation 1 with the viscosity of sulfur-free P(M)A formulations 2 and 3, it can be seen that they are all equal, demonstrating the equivalence of the polymers.

[0217] The industry standard for Cu corrosion testing is D130. Preparations with sulfur-free P(M)A formulation 2 and sulfur-free P(M)A formulation 3 showed significantly less copper corrosion.

[0218] Comparison of ZF copper corrosion test data shows that for formulations containing sulfur-free P(M)A, the copper content in the solution is lower, and the mass loss of the test specimens is also lower.

[0219] P(M)A samples were tested in fully prepared fluids, as shown in Table 2 below. All components are listed based on an oil-free basis.

[0220] Table 2

[0221] 1 – The additive package contains at least one of the following: antioxidants, dispersants, anti-wear agents, and corrosion inhibitors, as well as combinations thereof.

[0222] Test Description

[0223] Comparing the sulfur content of the fluids, it can be seen that neither sulfur-free P(M)A formulation 5 nor sulfur-free P(M)A formulation 6 increased the sulfur content above the baseline of 47. This confirms the presence of sulfur-free P(M)A.

[0224] Comparing the viscosity of conventional P(M)A in formulation 4 with the viscosity of sulfur-free P(M)A formulations 5 and 6, it can be seen that they are all equal, demonstrating the equivalence of the polymers.

[0225] The industry standard copper corrosion test is D130. Formulations with sulfur-free PMA formulations 5 and 6 exhibit significantly less copper corrosion. In fact, the copper corrosion of sulfur-free PMA without amine functional groups does not exceed the baseline for formulation 7, which has no polymer.

[0226] Comparison of ZF copper corrosion test data shows that for formulations containing sulfur-free P(M)A, the copper content in the solution is lower, and the mass loss of the test specimens is also lower. It is known that some of the substances mentioned above can interact in the final formulation, such that the composition of the final formulation may differ from those initially added. The resulting products, including those formed by using the lubricant compositions of the present invention in their intended use, may not be readily described. However, all such modifications and reaction products are included within the scope of the present invention; the present invention includes lubricant compositions prepared by mixing the above-mentioned components.

[0227] Each document mentioned above is incorporated herein by reference. Unless explicitly stated in the examples or otherwise, all numerical quantities of matter, reaction conditions, molecular weight, number of carbon atoms, etc., specified in this specification should be understood to be modified by the word “about.” Unless otherwise stated, each chemical or composition mentioned herein should be interpreted as a commercial-grade substance that may contain isomers, byproducts, derivatives, and other such substances generally understood to be present in commercial-grade substances. However, unless otherwise stated, the amount of each chemical component does not include any solvents or diluents that are generally present in commercial substances. It should be understood that the upper and lower limits of the amounts, ranges, and proportions described herein can be combined independently. Similarly, the ranges and amounts of each element of the invention can be used in conjunction with the ranges or amounts of any other element.

[0228] As used herein, the term "hydrocarbon substituent" or "hydrocarbon group" is used in its common sense, as is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly connected to the rest of the molecule and having predominantly hydrocarbon properties. Examples of hydrocarbon groups include: hydrocarbon substituents, including aliphatic, alicyclic, and aromatic substituents; substituted hydrocarbon substituents, i.e., substituents containing a non-hydrocarbon group that, in the context of this invention, does not alter the predominantly hydrocarbon properties of the substituent; and heterosubstituents, i.e., substituents that similarly have predominantly hydrocarbon properties but contain non-carbons in a ring or chain. A more detailed definition of the term "hydrocarbon substituent" or "hydrocarbon group" is described in paragraphs

[0118] to

[0119] of International Publication WO2008147704, or in similar definitions in paragraphs

[0137] to

[0141] of published application US 2010-0197536.

[0229] As used herein, the transitional term “comprising,” synonymous with “comprising,” “containing,” or “characterized in,” is inclusive or open-ended and does not exclude additional, unlisted elements or method steps. However, in every use of “comprising” herein, it is intended that the term also cover the phrases “consistently composed of” and “composed of” as alternative embodiments, wherein “consisting of” excludes any elements or steps not specified, and “consisting of” allows the inclusion of additional, undescribed elements or steps that do not substantially affect the essential or essential and novel characteristics of the composition or method under consideration.

[0230] While the invention has been explained with respect to its preferred embodiments, it should be understood that various modifications will become apparent to those skilled in the art upon reading this specification. Therefore, it should be understood that the invention disclosed herein is intended to cover such modifications that fall within the scope of the appended claims.

Claims

1. A lubricant formulation, said lubricant formulation comprising: a. Oils with lubricating viscosity, and b. A sulfur-free poly(meth)acrylate polymer ("PMA") having a number-average molecular weight of about 1,000 g / mol to about 25,000 g / mol and optionally nitrogen-containing groups. c. Sulfur less than 100 ppm and phosphorus from 100 ppm to 5000 ppm.

2. The lubricant formulation according to claim 1, wherein the lubricant formulation further comprises a phosphorus anti-wear agent sufficient to provide 100 ppm to 5000 ppm phosphorus to the composition.

3. The lubricant formulation according to any of the preceding claims, wherein the lubricant formulation further comprises a triazole corrosion inhibitor.

4. The lubricant formulation according to claim 3, wherein the triazole comprises 1,2,4-triazole.

5. The lubricant formulation according to any of the preceding claims, wherein the low molecular weight, sulfur-free poly(meth)acrylate polymer is prepared by reversible addition-fragmentation chain transfer polymerization of (meth)acrylate monomers, optionally one or more of the (meth)acrylate monomers having nitrogen-containing groups.

6. The lubricant formulation according to any of the preceding claims, wherein the low molecular weight, sulfur-free dispersant poly(meth)acrylate polymer comprises: a. (Meth)acrylate backbone, b. Copolymerized amine functional monomers, c. Chain transfer agents having the following structure: Where R 1 R 2 R 3 R 4 R 5 and R 6 Each is independently selected from the following groups: hydrogen, -CH(O), -CN, isocyanate group and its salts and esters, NR 7 R 8 Silanes, halogens, -C(O)OR 9 -C(O)NR 10 R 11 -CR 12 (O), -C(O)OC(O)R 13 -C(O)NR 14 COR 15 -OC(O)R 16 -OR 17 Substituted and unsubstituted alkyl groups, substituted and unsubstituted alkenyl groups, substituted and unsubstituted alkynyl groups, and substituted and unsubstituted aryl groups; R 7 R 8 R 9 R 10 R 11 R 12 R 13 R 14 R 15 and R 16 Each is independently selected from the group consisting of: H, alkyl, aryl, substituted alkyl or substituted aryl; R 17 The group selected is from the group consisting of alkyl, aryl, substituted alkyl, or substituted aryl; and the alkyl and substituted alkyl have a chain consisting of 1 to 12 carbon atoms. The poly(meth)acrylate polymer contains no more than 40 ppm of sulfur, or no more than 30 ppm of sulfur, or no more than 20 ppm of sulfur.

7. The lubricant according to claim 6, wherein at least one of R1, R2, R3, R4, R5, and R6 is hydrogen.

8. The lubricant according to claim 6, wherein the chain transfer agent is α-methylstyrene dimer ("AMSD").

9. A method for lubricating a vehicle's transmission system, the method comprising: a. Applying the lubricant formulation according to any one of claims 1 to 8 to the transmission system. b. Operate the vehicle.

10. The method of claim 9, wherein the vehicle is a hybrid electric vehicle.

11. The method of claim 9, wherein the vehicle is an electric vehicle.

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