Transmission fluid compositions for hybrid and electric vehicle applications

Abstract

A transmission fluid composition contains a major amount of a lubricating oil base oil and a minor amount of an additive package, said additive package comprising: (i) a mixture comprising two or more phosphites and / or phosphates; (ii) one or more thioester compounds; (iii) a detergent comprising calcium salicylate; and (iv) an ashless dispersant based on a metallocene-catalyzed PAO arm-terminated poly(alkyleneamine). Such a transmission fluid can be used to control / mitigate wear in at least partially electric transmissions and / or to cool / insulate electrical / electronic components of at least partially electric drive systems.

Description

Technical Field

[0001] This disclosure relates to lubricant compositions, such as those for use in hybrid vehicles and fully electric vehicles. The lubricant provides lubrication to the mechanical parts in contact with the engine and / or transmission, while also providing necessary cooling and resistive properties when in contact with the electrical / electronic components of the engine and / or transmission. Background Technology

[0002] As part of ongoing efforts to improve vehicle efficiency and reduce environmental impact, automakers are developing so-called "hybrid vehicles." These are vehicles, such as automobiles and larger vehicles, that have two propulsion methods: a combustion engine that runs on gasoline or diesel fuel and an electric motor powered by a battery. The battery can be charged using the combustion engine or through regenerative braking or both.

[0003] Hybrid vehicles may include conventional stepped automatic transmissions, continuously variable transmissions (CVTs), or other common types of transmissions. In a particular type of transmission referred to herein as a "hybrid transmission," electromechanical components such as the electric motor and mechanical components such as reduction gears and drive gears are housed in a single housing and lubricated by a common lubricant. An example of such a hybrid transmission is the electronically controlled continuously variable transmission (ECVT) used by Toyota in its hybrid vehicles. Other vehicle manufacturers use similar configurations. Considering that fully electric vehicle transmissions may also house mechanical components in the same housing as the electrical / electromechanical components, the common lubricant requirements in these vehicles may be similar. Therefore, this disclosure relates to the lubrication of at least partially electric (e.g., hybrid and / or fully electric) transmissions.

[0004] The nature of hybrid or fully electric transmissions places several distinct requirements on the transmission fluid used for their lubrication. Mechanical components, gears, etc., must be adequately protected against wear and corrosion, as in any conventional transmission. However, the presence of electromechanical components means the transmission fluid must also provide electrical insulation (or sufficiently high volume resistivity), good compatibility with the metals (typically copper) present in the electromechanical components, and good cooling capacity. Additionally, for the purpose of improving energy (fuel) consumption efficiency, it is ideal that the transmission fluid used reduces / minimizes energy loss due to drag and friction inherent in the fluid itself. Lower viscosity fluids exhibit lower drag and friction compared to more viscous fluids, but also typically exhibit less effective wear protection. Therefore, simply reducing the viscosity of conventional transmission fluids does not solve the problems encountered when attempting to formulate fluids for at least partially electric transmissions, as the typical additive combinations present in these fluids result in a volume resistivity that is too low for these applications. Thus, it is clear that formulating a transmission fluid that meets all the diverse and competing requirements of at least partially electric transmissions is not a simple task. This disclosure is based on the discovery of a transmission fluid that has a high volume resistivity, thus effectively insulating at least partially the electromechanical components of the electrically driven transmission, and, despite having low viscosity, also provides good wear protection for the mechanical components of the transmission. The competing requirements of good electrical insulation, good wear protection, and even relatively low viscosity are thus met (optionally, good energy efficiency as well).

[0005] Overview

[0006] Accordingly, this disclosure provides a transmission fluid composition comprising a major amount of a lubricating oil base oil and a minor amount of an additive package, the additive package comprising:

[0007] (i) A mixture of compounds containing two or more structures (I):

[0008]

[0009] (ii) Compounds with one or more structures (II):

[0010]

[0011] (iii) Detergents containing calcium salicylate; and

[0012] (iv) Basic nitrogen-containing ashless dispersants comprising one or more structures (III):

[0013]

[0014] In structure (I), groups R1, R2, and R3 (if applicable) may each independently be an alkyl group having 1 to 18 carbon atoms or an alkyl group having 1 to 18 carbon atoms in which the alkyl chain is interrupted by a thioether bond. Specifically, in mixture (i), at least some groups R1, R2, and R3 (if applicable) are alkyl groups having 1 to 18 carbon atoms in which the alkyl chain is interrupted by a thioether bond. In structure (II), groups R4 and R7 may each independently comprise or have an alkyl group having 1 to 12 carbon atoms, and groups R5 and R6, if present, may each independently comprise or have an alkyl bond having 2 to 12 carbon atoms. In structure (III), groups R8 and R9 can each independently be a hydrocarbon group prepared by metallocene-catalyzed polymerization of an α-olefin feedstock comprising 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-octadecene, or mixtures thereof. Also in structure (III), each R... 10 It can be independently composed of hydrogen, acetyl groups, or ethylene carbonate and >NR. 10 The structural part formed by the reaction between them, and x can be 1 to 10, the same for all molecules of structure (III) or the average value of all molecules of structure (III) in a mixture of molecules of structure (III).

[0015] This disclosure also provides the use of such a transmission fluid composition for controlling and / or mitigating wear in a hybrid electric or fully electric-powered transmission lubricated by contacting one or more electrical or electronic components of the drivetrain with such a transmission fluid composition, and simultaneously cooling at least a portion of the electrical or electronic components of the hybrid or fully electric drivetrain in contact with such a composition, and methods for controlling and / or mitigating wear in a hybrid or fully electric transmission lubricated by contacting one or more electrical or electronic components of the drivetrain with such a transmission fluid composition, and simultaneously cooling at least a portion of the electrical or electronic components of the hybrid or fully electric drivetrain in contact with such a composition.

[0016] Detailed Explanation

[0017] It has been found that specific combinations of components (i), (ii), (iii), and (iv) can provide a combination of wear protection and volume resistivity, particularly in lower viscosity formulations, where the individual performance characteristics become more difficult to achieve independently and one performance characteristic is often obtained at the expense of another. However, such combinations of components can also advantageously achieve sufficient wear protection and volume resistivity in medium to high viscosity formulations.

[0018] It is known in the art that phosphorus-containing compounds can provide wear protection for metal surfaces under high loads. Without being bound by theory, it has been suggested that this is a result of the formation of a phosphorus-containing “glass” on the lubricated metal surface. In this disclosure, only component (i) typically contains phosphorus. However, although component (i) is expected to provide suitable wear protection, the presence of phosphorus alone may be insufficient or may be slightly or largely offset by the presence of another component or a mixture of components.

[0019] Furthermore, volume resistivity is known to decrease relatively proportionally with decreasing base oil viscosity. It has also been shown that polar and ionic compounds dissolved or suspended in a base oil or diluent of a given viscosity naturally reduce volume resistivity. Ironically, the functional components of lubricating fluids used in conjunction with transmissions and / or other engine / drivetrain components are often ionic or polar, which typically creates a trade-off. However, for applications where lubricating fluids for mechanical engine components (e.g., drivetrain components like transmissions) also act as coolants for electrical and / or electronic components of engines (e.g., hybrid and / or all-electric engines), the requirements for lubricating fluids are generally limited to providing sufficient short-circuit resistance when in contact with electrical and / or electronic engine components. In some cases, this trade-off leaves a small window for sufficient anti-wear properties for mechanical parts and sufficient resistivity properties for electrical / electronic parts. One objective of this disclosure is to increase (or potentially maximize) this window and thus increase the balance between resistivity and anti-wear properties.

[0020] It has been unexpectedly found that combinations of components (i), (ii), (iii), and (iv), or combinations of components (iv) and (v) (optionally with or without component (iii), but without components (i) and (ii)), can provide a particularly enhanced combination of wear protection (as reflected in the mean life from needle-bearing fatigue tests) and volume resistivity (“VR”; at elevated temperatures). Experiments reported below demonstrate that the combinations of components do not inherently provide both wear and VR benefits simultaneously, but rather can be selectively chosen to provide advantageous benefits relative to various comparative compositions with similar and / or slightly altered component properties.

[0021] Component (i) may advantageously comprise a mixture of compounds with two or more structures (I):

[0022]

[0023] The groups R1, R2, and R3 may each independently comprise or contain an alkyl group having 1 to 18 carbon atoms and / or an alkyl group having 1 to 18 carbon atoms in which the alkyl chain is inserted by a thioether bond, provided that at least some of the groups R1, R2, and R3 may comprise or contain an alkyl group having 1 to 18 carbon atoms in which the alkyl chain is inserted by a thioether bond. The mixture may contain three or more, four or more, or five or more compounds of structure (I).

[0024] In some embodiments, groups R1, R2, and R3 may each independently comprise or have an alkyl group having 4 to 10 carbon atoms and / or an alkyl group having 4 to 10 carbon atoms in which the alkyl chain is inserted by a thioether bond, provided that at least some groups R1, R2, and R3 may comprise or have an alkyl group having 4 to 10 carbon atoms in which the alkyl chain is inserted by a thioether bond.

[0025] When groups R1, R2, and R3 contain alkyl groups (where the alkyl chain is not inserted by a thioether bond), examples may include, but are not limited to, methyl, ethyl, propyl, and butyl, particularly including butyl.

[0026] When groups R1, R2, and R3 contain an alkyl group in which the alkyl chain is inserted by a thioether bond, examples include groups with the structure -R'-SR”, where R' can be –(CH2). n –, where n can be an integer from 2 to 4, and R” can be –(CH2). m –CH3, where m can be an integer from 1 to 15, such as from 1 to 7.

[0027] Specifically, in a mixture of compounds constituting component (i) of structure (I), at least 10% by mass (e.g., at least 20%, at least 30%, or at least 40%) of the mixture comprises compounds of structure (I) in which at least one of R1, R2, and R3 comprises, or in which the alkyl chain is inserted by a thioether bond, an alkyl group having, in particular, the structure -R'-SR", wherein R' may be –(CH2). n –, where n can be an integer from 2 to 4, and R” can be –(CH2). m –CH3, where m can be an integer from 1 to 15, such as from 1 to 7.

[0028] Component (ii) may advantageously comprise one or more compounds of structure (II):

[0029]

[0030] Groups R4 and R7 may each independently comprise or have an alkyl group of 1 to 12 carbon atoms, and R5 and R6 may each independently comprise or have an alkyl bond of 2 to 12 carbon atoms. Specifically, R4 and R7 may each independently comprise or have –(CH2) m –CH3, where m is an integer from 1 to 15, such as from 1 to 7, and R5 and R6 (if they exist) can each contain independently or –(CH2). n - where n is an integer from 2 to 4. The mixture may contain two or more or three or more compounds of structure (II).

[0031] Specifically, the compound of structure (I) (component (i)) and the compound of structure (II) (component (ii)) may each be present in the transmission fluid composition in an amount of 0.04 to 1.0% by mass, for example, 0.05 to 0.8% by mass, 0.05 to 0.5% by mass, or 0.07 to 0.4% by mass, based on the total mass of the composition. Additionally or alternatively, the compound of structure (I) (component (i)) and the compound of structure (II) (component (ii)) may together provide the transmission fluid composition with 80 to 800 parts by mass of phosphorus, for example, 100 to 700 ppm, 150 to 600 ppm, or 200 to 500 ppm, based on the total mass of the composition. The phosphorus content can be measured according to ASTM D5185. Additionally or alternatively, particularly, the mass ratio of the compound of structure (I) (component (i)) to the compound of structure (II) (component (ii)) may be 2:1 to 1:2, 5:3 to 3:5, 3:2 to 2:3, or 4:3 to 3:4.

[0032] Component (iii) may advantageously comprise a calcium salicylate detergent, consist essentially of a calcium salicylate detergent, or be a calcium salicylate detergent. Calcium salicylate detergents are known in the art and may include neutral and / or overbased calcium salts of salicylic acid (such as alkyl salicylic acid).

[0033] Neutral calcium salicylate detergents, and generally neutral detergents, are those detergents that contain a stoichiometric amount of calcium relative to the amount of the (Lewis) acidic structural moiety present in the detergent. Therefore, in general, neutral detergents typically have a relatively low alkalinity compared to their highly alkaline counterparts.

[0034] For example, the term "highly basic" in relation to calcium neutralizers is used to indicate the fact that the calcium component is present in a stoichiometric amount greater than the corresponding (Lewis) acid component. A common method for preparing highly basic salts involves heating a mineral oil solution of acid with a stoichiometric excess of a neutralizing agent (in this case, a calcium neutralizer, such as an oxide, hydroxide, carbonate, bicarbonate, sulfide, or a combination thereof, at a temperature of approximately 50°C) at an appropriate temperature and filtering the resulting product. The use of a "promoter" in the neutralization step to facilitate the incorporation of a large excess of salt / base (in this case, calcium) is also known. Examples of compounds that can be used as promoters include, but are not limited to, phenols such as phenol, naphthol, alkylphenols, thiophenols, sulfurized alkylphenols, and condensation products of formaldehyde with phenols; alcohols such as methanol, 2-propanol, octanol, and Cellosolve. TM alcohol, Carbitol TM Alcohols, ethylene glycol, stearyl alcohol, and cyclohexanol; amines, such as aniline, phenylenediamine, phenothiazine, phenyl-β-naphthylamine, and dodecylamine; and combinations thereof. A particularly efficient method for preparing basic salts involves mixing an acidic substance with an excess of calcium neutralizer and at least one alcohol promoter, and carbonating the mixture at elevated temperatures such as 60 to 200°C.

[0035] Specifically, the calcium salicylate detergent of component (iii) may be present in the transmission fluid composition in an amount of 0.03 to 2.0% by mass, for example, 0.05 to 0.7% by mass, 0.07 to 1.0% by mass, or 0.10 to 1.9% by mass, based on the total mass of the composition. Additionally or alternatively, the calcium salicylate detergent of component (iii) may be sufficient to provide the transmission fluid composition with an amount of calcium of 30 to 2000 parts by mass (ppm), for example, 45 to 450 ppm, 50 to 800 ppm, or 100 to 1800 ppm, based on the mass of the composition. The calcium content can be measured according to ASTM D5185.

[0036] Component (iv) may comprise one or more basic nitrogen-containing ashless dispersants having the following structure (III), essentially composed of one or more basic nitrogen-containing ashless dispersants having the following structure (III), or one or more basic nitrogen-containing ashless dispersants having the following structure (III):

[0037]

[0038] Wherein: R8 and R9 are each independently a hydrocarbon group prepared by metallocene-catalyzed polymerization of α-olefin feedstocks comprising 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-octadecene, or mixtures thereof, such that the dispersant arm or end group of R8 and R9 is a metallocene-catalyzed poly(α-olefin) or mPAO; each R 10 Independently composed of hydrogen, acetyl groups, or ethylene carbonate and >NR 10 The structural part formed by the reaction between them; and x is 1 to 10 and is the average value of all molecules of structure (III) in a mixture of molecules of structure (III).

[0039] In a specific embodiment of structure (III) of component (iv), the α-olefin feedstock comprises 1-octene, 1-decene, 1-dodecene, or a mixture thereof, or is substantially composed of 1-octene, 1-decene, 1-dodecene, or a mixture thereof. Additionally or alternatively, in a specific embodiment of structure (III) of component (iv), each R 10 Independently, it is a hydrogen or acetyl structural moiety. Further additionally or alternatively, in a particular embodiment of the structure (III) of component (iv), x is 3 to 10.

[0040] In a particular embodiment, the mPAO end groups or arms (R1 and R2 structural portions) of component (iv) without ash dispersant can each independently exhibit a number-average molecular weight (Mn) of 300 to 20,000 Daltons as determined by GPC with reference to a linear polystyrene standard, such as 400 to 15,000 Daltons, 450 to 10,000 Daltons, 500 to 8,000 Daltons, 650 to 6,500 Daltons, 800 to 5,000 Daltons, or 900 to 3,000 Daltons; particularly 300 to 20,000 Daltons, 500 to 8,000 Daltons, or 800 to 5,000 Daltons.

[0041] Examples of such additional ashless dispersants may include mPAO-based succinimides, mPAO-based succinamides, mixed esters / amides of mPAO-substituted succinic acid (mPAOSA), and hydroxy esters of mPAO-substituted succinic acid, as well as their reaction products and mixtures.

[0042] Such basic nitrogen-containing ashless dispersants can be used as lubricant additives, and their preparation methods are described in patent literature. Exemplary ashless dispersants of structure (III) may include mPAO-based succinimides and succinamides, wherein each of the mPAO-substituent arms contains more than 36 carbons, for example, more than 40 carbon atoms. These materials can be readily prepared by reacting dicarboxylic acid-functionalized mPAO or anhydride (such as reacted maleic acid)-functionalized mPAO with amine-functionalized molecules. Examples of suitable amines may include polyamines such as polyalkylene polyamines, hydroxylated polyamines, polyoxyethylene polyamines, and combinations thereof. Amine functionality can be provided by polyalkylene polyamines such as tetraethylenepentamine and pentaethylenehexamine. Mixtures in which the average number of nitrogen atoms per polyamine molecule is greater than 7 are also obtained. These are commonly referred to as heavy polyamines or H-PAMs and may be traded under names such as HPA. TM and HPA-X TM Purchased from Dow Chemical, for E-100 TM Purchased from Huntsman Chemical, etc. Examples of hydroxylated polyamines may include N-hydroxyalkyl-alkylene polyamines, such as N-(2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)piperazine, and / or N-hydroxyalkylated alkylene diamines of the type described, for example, in U.S. Patent No. 4,873,009. Examples of polyoxyethylene polyamines may include polyoxyethylene and / or polyoxypropylene diamines and triamines (and their coolidomers) having an average Mn of about 200 to about 5000 Daltons. Products of this type may be traded under the name Jeffamine. TM Purchased.

[0043] As is known in the art, the reaction of amines with mPAO-functionalized dicarboxylic acids and / or anhydrides (suitably, the reactive sites on the mPAO molecule and the reaction products of alkenyl succinic anhydride or maleic anhydride) can be conveniently achieved by heating the reactants together (e.g., in an oil solution). Reaction temperatures of ~100°C to ~250°C and reaction times of ~1 to ~10 hours are typical. The reaction ratios can vary significantly, but a coupling ratio of approximately 1 between the reactants (moles of anhydride functional group / moles of dicarboxylic acid per mole of primary amine functional group) is generally desirable.

[0044] Specifically, the nitrogen-containing ashless dispersant of component (iv) may comprise an mPAO-based succinimide formed from succinic anhydride-functionalized mPAO and polyalkylene polyamines (such as tetraethylenepentamine or H-PAM). The mPAO end groups or arms may each be derived from the metallocene-catalyzed polymerization (oligopolymerization) of the α-olefin feedstock described herein and may each exhibit a number-average molecular weight (Mn) of 500 to 5000 Daltons, for example, 750 to 2500 Daltons. These dispersants, similar to other dispersants known in the art, may be further processed (e.g., with a secondary nitrogen-capping agent, such as acetic anhydride and / or ethylene carbonate, with a boating / boronating agent, and / or with an inorganic acid of phosphorus). Suitable examples of post-treated dispersants are commonly found, for example, in U.S. Patent Nos. 3,254,025, 3,502,677, and 4,857,214.

[0045] Although boronization of dispersants is known and may be desirable, in certain embodiments, the dispersant of component (iv) individually (commonly), and even all components (together) of the additive kit and / or transmission fluid according to this disclosure, may contain less than 200 parts by weight (ppm) of boron based on the total mass of the composition, such as less than 150 ppm boron, less than 100 ppm boron, less than 70 ppm boron, or less than 50 ppm boron.

[0046] Specifically, the nitrogen-containing ashless dispersant of component (iv) may be present in the transmission fluid composition in an amount of 0.50 to 8.0% by mass, for example, 0.75 to 5.0% by mass, 0.90 to 3.5% by mass, or 1.0 to 3.0% by mass, based on the mass of the transmission fluid composition.

[0047] The amount of lubricating oil base oil in the transmission fluid composition according to this disclosure is typically a major amount (i.e., greater than 50% by weight based on the composition), while the total amount of the additive package and each component of the additive package individually typically constitute a minor amount (i.e., less than 50% by weight based on the composition). For example, the transmission fluid composition may contain more than 50% to 99.5%, more than 50% to 99%, more than 50% to 98.5%, more than 50% to 98%, more than 50% to 97.5%, more than 50% to 97%, more than 50% to 96.5%, more than 50% to 96%, more than 50% to 95.5%, more than 50% to 95%, or 60% by weight based on the composition. Up to 99.5%, 60% to 99%, 60% to 98.5%, 60% to 98%, 60% to 97.5%, 60% to 97%, 60% to 96.5%, 60% to 96%, 60% to 95.5%, 60% to 95%, 70% to 99.5%, 70% to 99%, 70% to 98.5%, 70% to 98%, 70% to 97.5%, 70% to 97%, 70% to 96.5%, 70% to 96%, 70% to 95.5%, 70% to 95%, 75% to 99.5%, 75% to 99%, 75% to 98.5%, 75% to 98%, 75% to 97.5%, 75% to 97%, 75% to 96.5%, 75% to 96%, 75% to 95.5%, 75% to 95%, 80% to 99% Lubricating oil base oils comprising 0.5%, 80% to 99%, 80% to 98.5%, 80% to 98%, 80% to 97.5%, 80% to 97%, 80% to 96.5%, 80% to 96%, 80% to 95.5%, or 80% to 95% by weight of the composition, particularly 60% to 99%, 70% to 98%, 75% to 97%, or 80% to 96.5% by weight of the composition. Additionally or alternatively, the transmission fluid composition may contain, based on the weight of the composition, 0.5% to less than 50%, 0.5% to 39%, 0.5% to 34%, 0.5% to 29%, 0.5% to 24%, 0.5% to 19.5%, 0.5% to 14.5%, 0.5% to 11.5%, 0.5% to 9.5%, 0.5% to 7.5%, 0.5% to 6.5%, 0.5% to 5.5%, 0.5% to 5.0%, 0.5% to 4.5%, or 0.5% to 4.0%. 0.5% to 3.5%, 0.5% to 3.0%, 0.5% to 2.5%, 0.5% to 2.0%, 0.5% to 1.5%, 1.9% to less than 50%, 1.9% to 39%, 1.9% to 34%, 1.9% to 29%, 1.9% to 24%, 1.9% to 19.5%, 1.9% to 14.5%, 1.9% to 11.5%, 1.9% to 9.5%, 1.9% to 7.5%, 1.9% to 6.5%, 1.9% to 5.5%, 1.9% to 5.0%, 1.9% to 4.5%, 1.9% to 4.0%, 1.9% to 3.5%, 1.9% to 3.0%, 2.9% to less than 50%, 2.9% to 39%, 2.9% to 34%, 2.9% to 29%, 2.9% to 24%, 2.9% to 19.5%, 2.9% to 14.5%, 2.9% to 11.5%, 2.9% to 9.5%, 2.9% to 7.5%, 2.9% to 6.5%, 2.9% to 5.5%, 2.9% to 5.0%, 2.9% to 4.5%, 2.9% to 4.0%, 3.9% to less than 50%, 3.9% to 39%, 3.9% to 34%, 3 0.9% to 29%, 3.9% to 24%, 3.9% to 19.5%, 3.9% to 14.5%, 3.9% to 11.5%, 3.9% to 9.5%, 3.9% to 7.5%, 3.9% to 6.5%, 3.9% to 5.5%, 3.9% to 5.0%, 4.8% to less than 50%, 4.8% to 39%, 4.8% to 34%, 4.8% to 29%, 4.8% to 24%, 4.8% to 19.5%, 4.8% to 14.5%, 4.8% to 11.5%, 4.8% to 9.5%, 4.8% to 7.5%, 4.8% to 6.5%, 4.8% to 5.5%, 5.8% To below 50%, 5.8% to 39%, 5.8% to 34%, 5.8% to 29%, 5.8% to 24%, 5.8% to 19.5%, 5.8% to 14.5%, 5.8% to 11.5%, 5.8% to 9.5%, 5.8% to 7.5%, 5.8% to 6.5%, 6.7% to below 50%, 6.7% to 39%, 6.7% to 34%, 6.7% to 29%, 6.7% to 24%, 6.7% to 19.5%, 6.7% to 14.5%, 6.7% to 11.5%, 6.7% to 9.5%, 6.7% to 7.5%, 7.6% to below 50%, 7.6% to 3 Additive kit components at concentrations of 9%, 7.6% to 34%, 7.6% to 29%, 7.6% to 24%, 7.6% to 19.5%, 7.6% to 14.5%, 7.6% to 11.5%, 7.6% to 9.5%, 8.5% to less than 50%, 8.5% to 39%, 8.5% to 34%, 8.5% to 29%, 8.5% to 24%, 8.5% to 19.5%, 8.5% to 14.5%, 8.5% to 11.5%, or 8.5% to 9.5%, particularly 1.9% to 29%, 3.9% to 24%, 4.8% to 14.5%, or 5.8% to 11.5% by weight of the composition.

[0048] The base oil for a lubricating oil can be any suitable base oil known in the art. Both natural and synthetic base oils may be suitable. Natural lubricants may include animal fats, vegetable oils (such as castor oil and lard), petroleum, mineral oils, oils derived from coal or shale, and combinations thereof. A particular natural lubricant may include or include mineral oils.

[0049] Suitable mineral oils can include all common mineral oil base oils, including those that are chemically naphthenic or alkanes. Suitable oils can be refined using conventional methods with acids, alkalis, and clay or other reagents (such as aluminum chloride), or they can be extractive oils, for example, produced by solvent extraction with solvents such as phenols, sulfur dioxide, furfural, dichlorodiethyl ether, or combinations thereof. They can be hydrotreated or hydrofined, dewaxed by cooling or catalytic dewaxing processes, hydrocracking, or some combination thereof. Suitable mineral oils can be derived from natural crude oil sources or can consist of isomerized wax materials or residues from other refining processes.

[0050] Synthetic lubricating oil base oils may include hydrocarbon oils and halogenated hydrocarbon oils, such as oligomeric, polymeric and interpolymerized olefins (e.g., polybutene, polypropylene, propylene-isobutylene copolymer, chlorinated polylactenes, poly(1-hexene), poly(1-octene), poly(1-decene), etc. and mixtures thereof); alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2-ethylhexyl)benzene, etc.); polybenzenes (e.g., biphenyl, terphenyl, alkylated polybenzenes, etc.); alkylated diphenyl ethers, alkylated diphenyl sulfides and their derivatives, analogs and homologues, etc.; and combinations and / or reaction products thereof.

[0051] In some embodiments, the oil derived from this class of synthetic oil base stock may contain or be a polyalphaolefin (PAO), including hydrogenated oligomers of alpha-olefins, particularly oligomers of 1-decene, such as those produced by radical, Ziegler catalysis, or cationic catalysis. These may be, for example, oligomers of branched or linear alpha-olefins having 2 to 16 carbon atoms, and specific, non-limiting examples include polypropylene, polyisobutylene, poly-1-butene, poly-1-hexene, poly-1-octene, poly-1-decene, poly-1-dodecene, and mixtures and / or interpolymers / copolymers thereof.

[0052] Synthetic lubricant base oils may additionally or alternatively include alkylene oxide polymers, interpolymers, copolymers, and their derivatives, wherein any (most) terminal hydroxyl groups have been modified by esterification, etherification, etc. Examples of such synthetic oils may be: polyoxyalkylene polymers produced by polymerization of ethylene oxide or propylene oxide; alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ethers with an average Mn of ~1000 Daltons, diphenyl ethers of polypropylene glycol with an average Mn of about 1000 to about 1500 Daltons); and their mono- and polycarboxylic acid esters (e.g., acetate esters, mixed C3-C8 fatty acid esters, C3-C8 esters of tetraethylene glycol). 12 Oxy-acid diesters, or combinations thereof.

[0053] Another suitable class of synthetic lubricant base oils may contain esters of dicarboxylic acids (such as phthalic acid, succinic acid, alkyl succinic acid and alkenyl succinic acid, maleic acid, azelaic acid, octanoic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, etc.) and various alcohols (such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicoyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, complex esters formed by reacting 1 mole of sebacate with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid, and combinations thereof. Preferred types of oils from this class of synthetic oils may include C4 to C6 oils. 12 Adipate esters of alcohols.

[0054] Esters that can be used as base oils for synthetic lubricants may additionally or alternatively include those composed of C5-C64. 12 Those made from monocarboxylic acids, polyols and / or polyol ethers (e.g., neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.) and combinations thereof.

[0055] Lubricating oil base stock can be derived from unrefined oil, refined oil, refined oil, or mixtures thereof. Unrefined oil is obtained directly from natural or synthetic sources (e.g., coal, shale, or tar sand bitumen) without further purification or treatment. Examples of unrefined oil may include shale oil obtained directly from a dry distillation operation, petroleum obtained directly from distillation, or ester oil obtained directly from an esterification process, each or a combination thereof, which may then be used without further processing. Refined oil is similar to unrefined oil, except that it has typically been treated in one or more purification steps to alter its chemical structure and / or improve one or more properties. Suitable purification techniques may include distillation, hydrotreating, dewaxing, solvent extraction, acid or alkali extraction, filtration, and percolation, all known to those skilled in the art. Refined oil can be obtained by treating used and / or refined oil in a process similar to that originally used to obtain refined oil. These refined oils may be referred to as recycled oil or reprocessed oil and may often be further processed using techniques for removing waste additives and oil decomposition products.

[0056] Another class of suitable supplemental or alternative lubricating oil base stocks may include those made from oligomers or waxes derived from natural gas feedstocks. These base stocks can be referred to in many ways, but they are commonly known as Gas-to-Liquid (GTL) or Fischer-Tropsch base stocks.

[0057] The lubricating oil base stock according to this disclosure may be a blend of one or more oils / base stock described herein, whether similar or different in type, and blends of natural and synthetic lubricating oils (i.e. partially synthetic) are explicitly envisioned for use in this disclosure.

[0058] Lubricating oils can be classified according to the American Petroleum Institute (API) publication "Engine Oil Licensing and Certification System", Industry Services Department, 14th edition, December 1996, Appendix 1, December 1998, where the oil classifications are as follows:

[0059] a) Group I base oils contain less than 90% saturates and / or more than 0.03% sulfur and have a viscosity index greater than or equal to 80 and less than 120;

[0060] b) Group II base oils contain 90% or more saturates and 0.03% or less sulfur and have a viscosity index of 80 or more and less than 120;

[0061] c) Group III base oils contain 90% or more saturates and 0.03% or less sulfur and have a viscosity index of 120 or more;

[0062] d) Group IV base oils are polyalphaolefins (PAO); and

[0063] e) Group V base oils include all other base oils not included in Groups I, II, III or IV.

[0064] In one embodiment of this disclosure, the lubricating oil base stock may comprise or contain mineral oil or a mixture of mineral oils, particularly Group II and / or Group III mineral oils (API classification). Additionally or alternatively, the lubricating oil base stock may comprise or contain synthetic oils, such as polyalphaolefin (Group IV) and / or Group V oils. In embodiments where a very low viscosity of the desired formulation is desired (e.g., less than 4.0 cSt or less than 3.5 cSt), it may be advantageous for the lubricating oil base stock to be a Group IV (polyalphaolefin) base stock or a mixture of Group IV base oils, or to contain at least 40% (e.g., at least 50%, at least 60%, at least 70%, at least 80%, or at least 90%) of one or more Group IV base oils by weight.

[0065] Advantageously, the lubricating oil base oils can exhibit a viscosity index (CSI) of 1.0 cSt to 10 cSt, independently or collectively (e.g., 1.0 cSt to 8.1 cSt, 1.0 cSt to 7.2 cSt, 1.0 cSt to 6.5 cSt, 1.0 cSt to 6.0 cSt, 1.0 cSt to 5.5 cSt, 1.0 cSt to 5.0 cSt, 1.0 cSt to 4.5 cSt, 1.0 cSt to 4.0 cSt, 1.0 cSt to 3.5 cSt, 1.5 cSt to 3.3 cSt, 1.0 cSt to 3.0 cSt, 1.0 cSt to 2.5 cSt, 1.0 cSt to 2.0 cSt, 1.5 cSt to 10 cSt, 1.5 cSt to 8.1 cSt, 1.5 cSt). St to 7.2cSt, 1.5cSt to 6.5cSt, 1.5cSt to 6.0cSt, 1.5cSt to 5.5cSt, 1.5cSt to 5.0cSt, 1.5cSt to 4.5cSt, 1.5cSt to 4.0cSt, 1.5cSt to 3.5cSt, 1.5cSt to 3.3cSt, 1.5cSt to 3.0cSt, 1.5cSt to 2.5cSt, 2.0cSt to 10cSt, 2.0cSt to 8.1cSt, 2.0cSt to 7.2cSt, 2.0cSt to 6.5cSt, 2.0cSt to 6.0cSt, 2.0cSt to 5.5cSt, 2.0cSt to 5.0cSt, 2.0 cSt to 4.5cSt, 2.0cSt to 4.0cSt, 2.0cSt to 3.5cSt, 2.0cSt to 3.0cSt, 2.0cSt to 2.5cSt, 2.5cSt to 10cSt, 2.5cSt to 8.1cSt, 2.5cSt to 7.2cSt, 2.5cSt to 6.5cSt, 2.5cSt to 6.0cSt, 2.5cSt to 5.5cSt, 2.5cSt to 5.0cSt, 2.5cSt to 4.5cSt, 2.5cSt to 4.0cSt, 2.5cSt to 3.5cSt, 2.5cSt to 3.0cSt, 2.7cSt to 10cSt, 2.7cSt to 8.1cSt, 2.7 cSt to 7.2cSt, 2.7cSt to 6.5cSt, 2.7cSt to 6.0cSt, 2.7cSt to 5.5cSt, 2.7cSt to 5.0cSt, 2.7cSt to 4.5cSt, 2.7cSt to 4.0cSt, 2.7cSt to 3.5cSt, 2.7cSt to 3.0cSt, 3.0cSt to 10cSt, 3.0cSt to 8.1cSt, 3.0cSt to 7.2cSt, 3.0cSt to 6.5cSt, 3.0cSt to 6.0cSt, 3.0cSt to 5.5cSt, 3.0cSt to 5.0cSt, 3.0cSt to 4.5cSt, 3.0cSt to 4.0cSt, 3.0 cSt to 3.5 cSt, 3.5 cSt to 10 cSt, 3.5 cSt to 8.1 cSt, 3.5 cSt to 7.2 cSt, 3.5 cSt to 6.5 cSt, 3.5 cSt to 6.0 cSt, 3.5 cSt to 5.5 cSt, 3.5 cSt to 5.0 cSt, 3.5 cSt to 4.5 cSt, 3.5 cSt to 4.0 cSt, 4.0 cSt to 10 cSt, 4.0 cSt to 8.1 cSt The kinematic viscosity (KV100) at 100°C, measured according to ASTM D445, is defined as follows: 4.0 cSt to 7.2 cSt, 4.0 cSt to 6.5 cSt, 4.0 cSt to 6.0 cSt, 4.0 cSt to 5.5 cSt, 4 cSt to 5.0 cSt, or 4.0 cSt to 4.5 cSt, particularly 1.0 cSt to 10 cSt, 1.5 cSt to 3.3 cSt, 2.7 cSt to 8.1 cSt, 3.0 cSt to 7.2 cSt, or 2.5 cSt to 6.5 cSt.

[0066] The desired components (i), (ii), (iii), and (iv) may be added individually to the lubricating oil base stock to form the transmission fluid composition, or more conveniently, may be added to the oil as an additive package containing the desired compound dissolved or dispersed in the carrier fluid. Alternatively, two or more components may be added together as an additive package, while one or more other components may be added individually to the lubricating oil base stock and / or the blend used to form the transmission fluid composition. Such an additive package may optionally further contain, or the transmission fluid composition may contain, one or more co-additives as defined below, independent of the additive package.

[0067] Co-additives

[0068] The transmission fluid compositions disclosed herein may optionally include co-additives commonly found in transmission fluids. Suitable co-additives are known to those skilled in the art. Some examples are described herein.

[0069] Added ashless dispersant

[0070] In some embodiments, the additive kit and / or transmission fluid composition may further comprise one or more additional basic nitrogen-containing ashless dispersants of structure (III) different from component (iv). Such additional nitrogen-containing ashless dispersants, when present, may advantageously be of structure (IV):

[0071]

[0072] Where: R 11 and R 12Each is independently a hydrocarbon group (e.g., a polyisobutylene-based structural moiety) with a number-average molecular weight (Mn) of 500 to 5000 Daltons or 750 to 2500 Daltons as determined by GPC using a reference linear polystyrene standard; each R 13 Independently composed of hydrogen, acetyl groups, or ethylene carbonate and >NR 13 The structural moiety formed by the reaction between them (especially the hydrogen or acetyl structural moiety); and y is 1 to 10 (especially 3 to 10) and is the average value of all structural (IV) molecules in a mixture of molecules of structural (IV).

[0073] Examples of such additional ashless dispersants may include polyisobutylene succinimide, polyisobutylene succinamide, mixed esters / amides of polyisobutylene-substituted succinic acid, hydroxy esters of polyisobutylene-substituted succinic acid, and Mannich condensation products of hydrocarbon-substituted phenols, formaldehyde and polyamines, as well as their reaction products and mixtures.

[0074] Such basic nitrogen-containing ashless dispersants are well-known lubricant additives, and their preparation methods are extensively described in patent literature. Exemplary additional dispersants may include polyisobutylene succinimide and succinamide, wherein the polyisobutylene-substituent is a long chain with more than 36 carbon atoms, such as more than 40 carbon atoms. These materials can be readily prepared by reacting a dicarboxylic acid material substituted with polyisobutylene with an amine-functionalized molecule. Examples of suitable amines may include polyamines, such as polyalkylene polyamines, hydroxylated polyamines, and polyoxyethylene polyamines, and combinations thereof. The amine functionality may be provided by polyalkylene polyamines, such as tetraethylenepentamine and pentaethylenehexamine. Mixtures in which the average number of nitrogen atoms per polyamine molecule is greater than 7 are also available. These are commonly referred to as heavy polyamines or H-PAMs and may be traded under names such as HPA. TM and HPA-X TM Purchased from Dow Chemical, for E-100 TM Purchased from Huntsman Chemical, etc. Examples of hydroxylated polyamines may include N-hydroxyalkyl-alkylene polyamines, such as N-(2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)piperazine, and / or N-hydroxyalkylated alkylene diamines of the type described, for example, in U.S. Patent No. 4,873,009. Examples of polyoxyethylene polyamines may include polyoxyethylene and polyoxypropylene diamines and triamines having an average Mn of about 200 to about 2500 Daltons. Products of this type may be traded under the name Jeffamine. TM Purchased.

[0075] It is known in the art that the reaction of amines with polyisobutylene-substituted dicarboxylic acid materials (suitably alkenyl succinic anhydride or maleic anhydride) can be conveniently achieved by heating the reactants together (e.g., in an oil solution). Reaction temperatures of ~100°C to ~250°C and reaction times of ~1 to ~10 hours are typical. The reaction ratio can be significantly varied, but a dicarboxylic acid unit content of approximately 0.1 to approximately 1.0 equivalents per reactive amine-containing reactant is generally used.

[0076] In particular, the additional ashless dispersant, when present, may comprise a polyisobutylene succinic anhydride and a polyalkylene polyamine (such as tetraethylenepentamine or H-PAM). The polyisobutylene group may be derived from polyisobutylene and may exhibit a number average molecular weight (Mn) of approximately 500 to approximately 5000 Daltons, for example, approximately 750 to approximately 2500 Daltons. As is known in the art, these and other dispersants may be post-treated (e.g., with secondary nitrogen end-capping agents, such as acetic anhydride and / or ethylene carbonate, with boating / boronating agents, and / or with phosphoric inorganic acids). Suitable examples can be found, for example, in U.S. Patent Nos. 3,254,025, 3,502,677, and 4,857,214.

[0077] When used, the additional ashless dispersant may be present in an amount of 0.01 to 10% by mass, for example, 0.05 to 7% by mass or 0.1 to 5% by mass, based on the mass of the transmission fluid composition.

[0078] Non-calcium salicylate detergent

[0079] In some embodiments, the additive kit and / or transmission fluid composition may further contain detergents other than calcium salicylate. In other embodiments, the additive kit and / or transmission fluid composition may be substantially free of other detergents besides calcium salicylate in component (iii). In alternative embodiments, the additive kit and / or transmission fluid composition may be substantially free of intentionally added phenolic detergents and / or substantially free of intentionally added sulfonate detergents.

[0080] When the transmission fluid composition contains an additional non-calcium salicylate detergent, it may also be a calcium-containing detergent. These detergents are generally oil-soluble or oil-dispersible enough to remain dissolved or dispersed in the oil to be carried by the oil to their intended point of action. Additional calcium-containing detergents are known in the art and include neutral and highly basic salts of calcium with acidic substances such as sulfonic acids, carboxylic acids, alkylphenols, sulfurized alkylphenols, and mixtures thereof.

[0081] Examples of non-salicylic acid calcium detergents that can be used in the transmission fluid compositions of this disclosure may include, but are not limited to, neutral and / or highly basic salts of such substances, such as calcium phenolate; calcium sulfide phenolate (e.g., wherein each aryl group has one or more aliphatic groups to provide hydrocarbon solubility); calcium sulfonate (e.g., wherein each sulfonic acid structural moiety is attached to an aromatic nucleus, which in turn typically contains one or more aliphatic substituents to provide hydrocarbon solubility); calcium salts of hydrolyzed phosphorus sulfide alkenes (e.g., having 10 to 2000 carbon atoms) and / or hydrolyzed phosphorus sulfide alcohols and / or aliphatic substituted phenolic compounds (e.g., having 10 to 2000 carbon atoms); calcium salts of aliphatic carboxylic acids and / or aliphatic substituted alicyclic carboxylic acids; and combinations thereof and / or reaction products thereof; and many other similar calcium salts of oil-soluble organic acids. If desired, mixtures of neutral and / or highly basic salts of two or more different non-salicylic acid acids (e.g., one or more highly basic calcium phenolate and one or more highly basic calcium sulfonate) may be used.

[0082] Methods for producing oil-soluble neutral and highly alkaline calcium detergents are well known to those skilled in the art and are widely reported in patent literature. Calcium-containing detergents may optionally undergo post-treatment, such as borylation. Methods for preparing borylated detergents are well known to those skilled in the art and are widely reported in patent literature.

[0083] In some embodiments, although not generally preferred, the additional detergent compound may include magnesium-containing detergents, including magnesium-containing salicylates, magnesium-containing phenolates, magnesium-containing sulfonates and / or any other calcium-containing detergents described herein, in any magnesium-containing form, and any mixtures thereof.

[0084] When present, the additional detergent may comprise, consist essentially of, or consist of, neutral or highly alkaline calcium sulfonate detergent and / or neutral or highly alkaline calcium phenolate detergent, or consist of, neutral or highly alkaline calcium sulfonate detergent and / or neutral or highly alkaline calcium phenolate detergent. When present, the combination of calcium salicylate of component (iii) and the additional detergent may collectively provide the transmission fluid composition with 75 to 2500 parts by weight (ppm) of calcium based on the composition, for example, 85 to 1800 ppm, 100 to 1000 ppm, or 120 to 500 ppm. The calcium content may be measured according to ASTM D5185.

[0085] antioxidants

[0086] Antioxidants, sometimes referred to as oxidation inhibitors, can improve the resistance (or reduce susceptibility) of transmission fluid compositions to oxidation. They work by binding to and modifying oxidants (such as peroxides and other free radical-forming compounds) to render them harmless (e.g., by breaking them down) or by inertizing oxidation catalysts or promoters. Oxidative degradation can manifest as sludge in the fluid with increased use, varnish deposits on metal surfaces, and sometimes as increased viscosity.

[0087] Examples of suitable antioxidants include, but are not limited to, copper-containing antioxidants, sulfur-containing antioxidants, aromatic amine and / or amide-containing antioxidants, hindered phenolic antioxidants, dithiophosphates and their derivatives, as well as combinations thereof and certain reaction products. Some antioxidants may be ashless (i.e., virtually free of trace amounts or metal atoms other than contaminants). In a preferred embodiment, one or more antioxidants are present in the transmission fluid composition according to this disclosure. In particular, the transmission fluid composition of this disclosure may comprise a combination of amine antioxidants and hindered phenolic antioxidants.

[0088] Corrosion inhibitor inhibitors)

[0089] Corrosion inhibitors are used to mitigate the corrosion of metals and are often referred to as metal deactivators or metal passivators. Some corrosion inhibitors can also be characterized as antioxidants.

[0090] Suitable corrosion inhibitors may include nitrogen- and / or sulfur-containing heterocyclic compounds, such as triazoles (e.g., benzotriazole), substituted thiadiazoles, imidazoles, thiazoles, tetraazoles, hydroxyquinolines, oxazolines, imidazoles, thiophenes, indoles, indazoles, quinolines, benzoxazines, dithiols, oxazoles, oxatriazoles, pyridines, piperazines, triazines, and any one or more derivatives thereof. A specific corrosion inhibitor is benzotriazole, as shown in the following structure:

[0091]

[0092] Where R 14 C1 to C2 are either nonexistent or can be linear or branched, saturated or unsaturated. 20 Hydrocarbon group or substituted hydrocarbon group. It may contain a ring structure that is alkyl or aryl in nature and / or contain heteroatoms such as N, O or S. Examples of suitable compounds may include benzotriazole, alkyl-substituted benzotriazole (e.g., tolyltriazole, ethylbenzotriazole, hexylbenzotriazole, octylbenzotriazole, etc.), aryl-substituted benzotriazole, alkylaryl- or arylalkyl-substituted benzotriazole, and combinations thereof. For example, the triazole may comprise benzotriazole and / or alkylbenzotriazole, wherein the alkyl group contains 1 to about 20 carbon atoms, or 1 to about 8 carbon atoms. Preferred corrosion inhibitors may comprise benzotriazole and / or tolyltriazole.

[0093] Additionally or alternatively, corrosion inhibitors may include substituted thiadiazoles with the following structures:

[0094]

[0095] Where R 15 and R 16 Independently, it is a hydrogen or hydrocarbon group, which can be aliphatic or aromatic, including cyclic, alicyclic, aralkyl, aryl, and alkylaryl groups. These substituted thiadiazoles are derived from the 2,5-dimercapto-1,3,4-thiadiazole (DMTD) molecule. Many derivatives of DMTD have been described in the art, and any such compound may be included in the transmission fluid used in this disclosure. For example, U.S. Patent Nos. 2,719,125, 2,719,126, and 3,087,937 describe the preparation of various 2,5-bis-(hydrodithio)-1,3,4-thiadiazoles.

[0096] Additionally or alternatively, the corrosion inhibitor may include one or more other DMTD derivatives, such as carboxylic acid esters, wherein R 15 and R 16 It can be attached to the sulfur atom of a sulfide via a carbonyl group. The preparation of these sulfide-containing DMTD derivatives is described, for example, in U.S. Patent No. 2,760,933. DMTD derivatives prepared by the condensation of DMTD with an α-haloaliphatic monocarboxylic acid having at least 10 carbon atoms are described, for example, in U.S. Patent No. 2,836,564. This method produces DMTD derivatives wherein R... 15 and R 16 It is HOOC-CH(R) 17 )-(R 17 (It is a hydrocarbon group). DMTD derivatives, which are further prepared by amidation or esterification of these terminal carboxylic acid groups, are also available.

[0097] The preparation of 2-alkyldithio-5-mercapto-1,3,4-thiadiazole is described, for example, in U.S. Patent No. 3,663,561.

[0098] A specific class of DMTD derivatives may include mixtures of 2-alkyldithio-5-mercapto-1,3,4-thiadiazole and 2,5-bis-alkyldithio-1,3,4-thiadiazole. Such mixtures may be marketed under trade names. 4313 is for sale and available for purchase from Afton Chemical.

[0099] In particular, the transmission fluid composition disclosed herein may contain substituted thiadiazoles, substituted benzotriazoles, or combinations thereof.

[0100] When needed, corrosion inhibitors can be used in any effective amount, but when used, they are typically used in amounts of approximately 0.001 to 5.0% by mass based on the mass of the transmission fluid, such as 0.005 to 3.0% by mass, or 0.01 to 1.0% by mass.

[0101] Friction modifier

[0102] Friction modifiers may include derivatives of polyethylene polyamines and / or ethoxylated long-chain amines. Derivatives of polyethylene polyamines may advantageously include succinimides with a specified structure or may be simple amides.

[0103] Suitable succinimides derived from polyethylene polyamines may include those with the following structures:

[0104]

[0105] Where x+y can be 8 to 15 and z can be 0 or an integer from 1 to 5, specifically, where x+y can be 11 to 15 (e.g., 13) and z can be 1 to 3. More broadly, such friction modifiers can be represented using the following general structure:

[0106]

[0107] Where R 18 and R 19 Each independently is:

[0108]

[0109] Let x+y be 8 to 15 (especially 11 to 15, e.g., 13) and z be 0 or an integer from 1 to 5 (especially an integer from 1 to 5 or an integer from 1 to 3); and where each R 20 Independently composed of hydrogen, acetyl groups, or ethylene carbonate and >NR 20 The structural parts formed by the reaction between them (especially the hydrogen or acetyl structural parts).

[0110] The preparation of such friction modifiers is described, for example, in U.S. Patent No. 5,840,663.

[0111] The above-mentioned succinimide can react with acetic anhydride to form a friction modifier with the following structure (where z = 1) as an example, wherein each R 20 Independently acetyl:

[0112]

[0113] Preparation of such friction modifiers can be found, for example, in U.S. Patent Application Publication No. 2009 / 0005277. Post-reactions with other reagents (e.g., boriding agents) are also known in the art.

[0114] Such succinimide friction modifiers can be used in any effective amount when present. Typically, they can be used in transmission fluids in amounts from 0.1 to 10.0% by mass, for example, 0.5 to 6.0% by mass or 2.0 to 5.0% by mass.

[0115] An example of an alternative simple amide may have the following structure:

[0116]

[0117] Where R 21 and R 22 They can be the same or different alkyl groups. For example, R 21 and R 22 It can be a linear or branched C 14 To C 20 Alkyl group, and m can be an integer from 1 to 5. Specifically, R 21 and R 22 They can all be derived from isostearic acid, and m can be 4.

[0118] When present, such simple amide friction modifiers can be used in any effective amount. Typically, they can be used in transmission fluids in amounts from 0.1 to 5.0% by mass, for example, 0.2 to 4.0% by mass or 0.25 to 3.0% by mass.

[0119] Suitable ethoxylated amine friction modifiers may comprise the reaction products of primary amines and / or diamines with ethylene oxide. The reaction with ethylene oxide may be suitably carried out using stoichiometry so that substantially all primary and secondary amines can be converted to tertiary amines. Such amines may have exemplary structures:

[0120]

[0121] Where R 23 and R 24 It can be an alkyl group containing about 10 to 20 carbon atoms or an alkyl group containing sulfur or oxygen bonds. An exemplary ethoxylated amine friction modifier may include R... 23 and / or R 24 Materials containing 16 to 20 carbon atoms, such as 16 to 18 carbon atoms. This type of material is commercially available and marketed by Akzo Nobel under the trade name... and For sale. Suitable materials from Akzo Nobel may include, in particular, [other materials]. T / 12 and T / 13.

[0122] When present, such ethoxylated amines can be used in any effective amount. Typically, they can be used in transmission fluids in amounts from 0.01 to 2.0% by mass, for example, 0.05 to 0.5% by mass or 0.1 to 0.3% by mass.

[0123] However, in some embodiments where the transmission fluid composition is used in conjunction with a hybrid or all-electric motor, the transmission fluid composition may optionally be substantially free of friction modifiers, or substantially free of friction modifiers of the type described herein.

[0124] molybdenum compounds

[0125] In some embodiments, the additive kit and / or transmission fluid composition may further comprise one or more oil-soluble or oil-dispersible molybdenum-containing compounds, such as oil-soluble or oil-dispersible organomolybdenum compounds. In other embodiments, the additive kit and / or transmission fluid composition may also be substantially free of oil-soluble or oil-dispersible molybdenum-containing compounds.

[0126] Non-limiting examples of such oil-soluble or oil-dispersible organomolybdenum compounds may include, but are not limited to, molybdenum dithiocarbamate, molybdenum dithiophosphate, molybdenum dithiophosphonite, molybdenum xanthate, molybdenum thioxanthate, molybdenum sulfide, and mixtures thereof, particularly one or more of dialkyldithiocarbamate, dialkyldithiophosphate, alkylxanthate, and alkylthioxanthate. Representative alkylxanthate and alkylthioxanthate compounds may be represented by the formula Mo(R) 25 OCS2)4 and Mo(R 25 SCS2)4 indicates that each R 25 It may be an organic group selected independently from alkyl, aryl, aralkyl and alkoxyalkyl, typically having 1 to 30 carbon atoms or 2 to 12 carbon atoms, particularly alkyl groups having 2 to 12 carbon atoms each.

[0127] In some embodiments, the oil-soluble or oil-dispersible organic molybdenum compound may comprise molybdenum dithiocarbamate, such as dialkyl molybdenum dithiocarbamate, and / or may be substantially free of molybdenum dithiophosphate, particularly dialkyl molybdenum dithiophosphate. In some embodiments, any oil-soluble or oil-dispersible molybdenum compound may consist of molybdenum dithiocarbamate (such as dialkyl molybdenum dithiocarbamate) and / or molybdenum dithiophosphate (such as dialkyl molybdenum dithiophosphate) as the sole source of molybdenum atoms in the composition. In any set of embodiments, when present, the oil-soluble or oil-dispersible molybdenum compound may consist substantially of molybdenum dithiocarbamate (such as dialkyl molybdenum dithiocarbamate) as the sole source of molybdenum atoms in the transmission fluid.

[0128] When present, molybdenum compounds can be mononuclear, binuclear, trinuclear, or tetranuclear, particularly including or containing binuclear and / or trinuclear molybdenum compounds.

[0129] Suitable dinuclear or dimeric dialkyl dithiocarbamate molybdenum can be represented, for example, by the following formula:

[0130]

[0131] Where R 26 To R 29 Each of the four hydrocarbon groups (R) can independently represent a straight-chain, branched-chain, or aromatic hydrocarbon group having 1 to 24 carbon atoms, and X1 to X4 can each independently represent an oxygen atom or a sulfur atom. 26 To R 29 They may be the same as or different from each other.

[0132] Suitable trinuclear organomolybdenum compounds may include those of the formula Mo3S k L n Q z Those and their mixtures. In such a trinuclear formula, three molybdenum atoms may be attached to multiple sulfur atoms (S), and k varies from 4 to 7. Additionally, each L can be an independently chosen organic ligand with a sufficient number of carbon atoms to make the compound oil-soluble or oil-dispersible, and n is from 1 to 4. Furthermore, when z is non-zero, Q can be selected from neutral electron-donating compounds such as water, amines, alcohols, phosphine, and / or ethers, where z is from 0 to 5 and includes non-stoichiometric (non-integer) values.

[0133] In such a trinuclear configuration, all ligands (L... n The combination of ligands typically contains at least 21 total carbon atoms (e.g., at least 25, at least 30, or at least 35). However, importantly, the organic groups of the ligands may advantageously collectively exhibit a sufficient number of carbon atoms to make the compound soluble or dispersible in oil. For example, the number of carbon atoms in each ligand L may typically be from 1 to 100, e.g., from 1 to 30 or from 4 to 20.

[0134] Mo3S k L n Q z Trinuclear molybdenum compounds can advantageously exhibit a cationic nucleus surrounded by anionic ligands, as shown by one or both of the following structures:

[0135]

[0136] Such cation nuclei can each have a net charge of +4 (e.g., due to the +4 oxidation state of each Mo atom). Therefore, to dissolve these nuclei, the total charge in all ligands should correspond, in this case, -4. Four monoanion ligands can provide favorable nucleus neutralization. While not wishing to be bound by any theory, it is believed that two or more trinuclear nuclei can be bonded or interconnected by one or more ligands, and these ligands can be polydentate. This includes cases where polydentate ligands have multiple connections to a single nucleus. Oxygen and / or selenium can substitute for a portion of the sulfur atom in either nucleus.

[0137] Non-limiting examples of ligands for the aforementioned trinuclear core may include, but are not limited to, dithiophosphates such as dialkyl dithiophosphates, xanthates such as alkyl xanthates and / or alkyl thioxanthates, dithiocarbamates such as dialkyl dithiocarbamates, and combinations thereof, particularly each comprising or being a dialkyl dithiocarbamate. Additionally or alternatively, the trinuclear molybdenum-containing ligand may independently be one or more of the following:

[0138]

[0139] Where X5, X6, X7, and Y are each independently oxygen or sulfur, Z is nitrogen or boron, and R 30 、R 31 、R 32 、R 33 、R 34 、R 35 and R 36 Each is independently a hydrogen or organic (carbon-containing) structural moiety, such as a hydrocarbon group, which may be the same as or different from each other, especially the same. Exemplary organic structural moieties may include alkyl (e.g., where the carbon atom attached to the remainder of the ligand is primary or secondary), aryl, substituted aryl, alkylaryl, substituted alkylaryl, aralkyl, substituted aralkyl, ether, thioether, or combinations thereof or reaction products, especially alkyl.

[0140] Oil-soluble or oil-dispersible trinuclear molybdenum compounds can be obtained by using a molybdenum source, such as (NH4)2Mo3S, in a suitable liquid / solvent. 13 • n(H₂O) (where n varies from 0 to 2, including non-stoichiometric (non-integer) values) is prepared by reacting with a suitable ligand source, such as tetraalkylthiuram disulfide. It is prepared by reacting molybdenum source (e.g., (NH₄)₂Mo₃S) with a suitable ligand source. 13Other oil-soluble or oil-dispersible trinuclear molybdenum compounds can be formed by reacting a trinuclear molybdenum-sulfur halide salt, such as [M']2[Mo3S7A6] (where M' is a counter ion and A is a halogen such as Cl, Br, or I) with a ligand source (such as a dialkyl dithiocarbamate or dialkyl dithiophosphate) in a suitable liquid / solvent (system). Alternatively, a trinuclear molybdenum-sulfur halide salt, such as [M']2[Mo3S7A6] (where M' is a counter ion and A is a halogen such as Cl, Br, or I), with a ligand source (such as a dialkyl dithiocarbamate or dialkyl dithiophosphate) in a suitable liquid / solvent (system) to form an oil-soluble or oil-dispersible trinuclear molybdenum compound. A suitable liquid / solvent (system) can be, for example, aqueous or organic.

[0141] Other molybdenum precursors may include acidic molybdenum compounds. These compounds react with basic nitrogen compounds as determined by ASTM D-664 or D-2896 titration procedures and are typically hexavalent. Examples may include, but are not limited to, molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, such as sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide, or similar acidic molybdenum compounds or combinations thereof. Therefore, additionally or alternatively, when needed, molybdenum can be provided to the compositions of this disclosure by, for example, molybdenum / sulfur complexes of basic nitrogen compounds as described in U.S. Patent Nos. 4,263,152, 4,285,822, 4,283,295, 4,272,387, 4,265,773, 4,261,843, 4,259,195 and 4,259,194 and / or PCT Publication No. WO 94 / 06897.

[0142] When present, the molybdenum-containing compound may be present in the transmission fluid composition in amounts of 0.1 to 2.0 wt%, 0.1 to 1.5 wt%, 0.2 to 1.2 wt%, or 0.2% to 0.8 wt% based on the total mass of the composition. Additionally or alternatively, when present, the molybdenum-containing compound may provide the transmission fluid composition with 50 to 1000 parts per million, 50 to 800 ppm, 100 to 650 ppm, or 100 to 500 ppm of molybdenum based on the total mass of the composition. The molybdenum content can be measured according to ASTM D5185.

[0143] Zinc-based phosphorus compounds

[0144] In some embodiments, the additive kit and / or transmission fluid composition may further comprise one or more zinc-based phosphorus compounds, such as one or more zinc dithiophosphate compounds. Such compounds are known in the art and are commonly referred to as ZDDP. In other embodiments, the additive kit and / or transmission fluid composition may also be substantially free of zinc-based phosphorus compounds.

[0145] ZDDP compounds can be prepared using known techniques, for example, by first forming dialkyl dithiophosphate (DDPA) (usually by reacting one or more alcohols or phenols with P2S5), and then neutralizing the formed DDPA with a zinc compound. For example, dithiophosphate can be prepared by reacting a mixture of primary and secondary alcohols. Alternatively, dithiophosphate can be prepared where the hydrocarbon group is entirely secondary or entirely primary. Any basic or neutral zinc compound can be used to prepare the zinc salt, but oxides, hydroxides, and carbonates are commonly used. When used, commercial additives often contain excess zinc due to the use of an excess of basic zinc compound in the neutralization reaction.

[0146] Advantageous zinc dialkyl dithiophosphate may comprise or be an oil-soluble salt of dialkyl dithiophosphate, for example, as shown in the following formula:

[0147]

[0148] Where R 37 and R 38 It can be the same or different hydrocarbon groups containing 1 to 18 (e.g., 2 to 12 or 2 to 8) carbon atoms. Examples of said hydrocarbon groups may include one or more of alkyl, alkenyl, aryl, aralkyl, alkylaryl, and alicyclic groups. Exemplary hydrocarbon groups may include, but are not limited to, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, pentyl, n-hexyl, isohexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, benzyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl, and combinations thereof. To obtain and / or maintain oil solubility, each dialkyl dithiophosphate ligand (i.e., a single R...) 37 and R 38 The total number of carbon atoms on the (p) may typically be at least about 5. In particular, zinc dialkyl dithiophosphate may therefore contain or be dialkyl zinc dithiophosphate.

[0149] When desired, one or more ZDDP compounds may be present in the transmission fluid composition in an amount of 0.4 to 5.0% by mass, such as 0.6 to 3.5% by mass, 1.0 to 3.0% by mass, or 1.2 to 2.5% by mass, based on the total mass of the composition. Additionally or alternatively, when present, the ZDDP compound may alone provide the transmission fluid composition with 300 to 4000 parts by mass of phosphorus, such as 500 to 2500 ppm, 750 to 2000 ppm, or 800 to 1600 ppm, based on the total mass of the composition. Further additionally or alternatively, when present, the ZDDP compound may provide the transmission fluid composition with 400 to 4500 parts by mass of zinc, such as 500 to 3000 ppm, 800 to 2600 ppm, or 1000 to 2200 ppm, based on the total mass of the composition. The zinc and phosphorus contents may each be measured according to ASTM D5185.

[0150] Other additives

[0151] Other additives known in the art may be optionally added to the transmission fluid, such as other anti-wear agents, extreme pressure additives, viscosity modifiers, etc. They are typically disclosed, for example, in "Lubricant Additives" by CVSmallheer and R. Kennedy Smith, 1967, pp. 1-11.

[0152] Transmission fluid composition

[0153] As mentioned herein, the transmission fluid composition according to this disclosure may advantageously contain a major amount of lubricating oil base oil and a minor amount of a combination of additives, such as in an additive kit comprising components (i), (ii), (iii), (iv) and optional co-additives, such as corrosion inhibitors, one or more antioxidants, and one or more friction modifiers, as well as others listed herein. Such a transmission fluid composition is advantageously used to control and / or mitigate wear during the operation of vehicle drivetrain components (such as transmissions), and to cool and / or insulate electrical / electronic components of electric or fully electric motors that are also in contact with the fluid composition. Therefore, this disclosure also includes a method for controlling and / or mitigating wear in a transmission driven by a hybrid or fully electric motor and simultaneously cooling at least a portion of the electrical or electronic components of the hybrid or fully electric drivetrain, the method comprising lubricating the transmission with the transmission fluid composition according to this disclosure and contacting one or more electrical or electronic components of the drivetrain with the transmission fluid composition according to this disclosure. Furthermore, this disclosure also provides the use of the transmission fluid composition according to this disclosure, or more particularly the use of an additive package containing a combination of components (i), (ii), (iii) and (iv) or a combination of components (iv) and (v) (optionally with or without component (iii)) in the transmission fluid composition for controlling and / or mitigating wear in a hybrid or all-electric transmission lubricated by the transmission fluid composition and simultaneously cooling at least a portion of the electrical or electronic components of the hybrid or all-electric drivetrain in contact with the transmission fluid composition.

[0154] This transmission fluid composition advantageously exhibits good / excellent volume resistivity when in contact with electrical / electronic components of at least partially electric motors. In this disclosure, the volume resistivity is calculated from conductivity measurements taken using, for example, an EMCEE Model 1152 conductivity probe available from Emcee Electronics, Inc., of Venice, FL, USA, which (i) is factory calibrated according to ASTM D2624-15, or (ii) is used in conjunction with a Baur DTLC device / rig available from Baur GmbH of Sulz, Austria, following the procedures outlined in ASTM D1169-11 (specifying ~80°C and ~500V) and calibrated at ~80°C using Toyota ATF WS automatic transmission fluid (available from Sansone Toyota of Avenel, NJ). Conductivity was measured and resistivity was calculated at approximately 80°C, rather than at approximately 40°C or approximately 20°C, to more closely simulate the operating temperature at which the engine is more likely to experience a short circuit than at low / resting temperatures. At least two or three volume resistivity measurements were performed on each sample to obtain an average volume resistivity value. Advantageously, the transmission fluid composition according to this disclosure can exhibit at least 44.0 MΩ·m (e.g., at least 44.5 MΩ·m, at least 45.0 MΩ·m, at least 45.5 MΩ·m, at least 46.0 MΩ·m, at least 46.5 MΩ·m, at least 47.0 MΩ·m, or at least 47.5 MΩ·m; particularly at least 46.0 MΩ·m or at least 47.0 MΩ·m), and optionally up to 500 MΩ·m (e.g., up to 400 MΩ·m, up to 350 MΩ·m, up to 325 MΩ·m, up to 300 MΩ·m, up to 250 MΩ·m). The average volume resistivity (VR) at ~80°C is 1 MΩ·m, up to 200 MΩ·m, up to 150 MΩ·m, up to 120 MΩ·m, up to 95.0 MΩ·m, up to 90.0 MΩ·m, up to 85.0 MΩ·m, up to 80.0 MΩ·m, up to 76.0 MΩ·m, up to 72.0 MΩ·m, up to 68.0 MΩ·m or up to 65.0 MΩ·m; especially up to 350 MΩ·m, up to 325 MΩ·m, up to 95.0 MΩ·m, up to 72.0 MΩ·m or up to 65.0 MΩ·m.

[0155] Additionally or alternatively, the transmission fluid composition, when used as a lubricant, can advantageously exhibit good / excellent wear properties, particularly through needle-bearing fatigue (NBFT) tests regarding wear life. In this disclosure, although NBFT life can be obtained by various methods, the NBFT life discussed herein uses the apparatus and procedures disclosed in the Examples section. Advantageously, the transmission fluid composition according to this disclosure can exhibit at least 13.0 Megacycles (e.g., at least 13.5 Megacycles, at least 14.0 Megacycles, at least 14.5 Megacycles, at least 15.0 Megacycles, at least 15.5 Megacycles, at least 16.0 Megacycles, at least 16.5 Megacycles, at least 17.0 Megacycles, at least 17.5 Megacycles, at least 18.0 Megacycles, at least 18.5 Megacycles, at least 19.0 Megacycles, at least 19.5 Megacycles, or at least 20.0 Megacycles; particularly at least 13.5 Megacycles, at least 1 4.0 MHz, at least 17.0 MHz, or at least 20.0 MHz), and optionally up to 70.0 MHz (e.g., up to 60.0 MHz, up to 50.0 MHz, up to 40.0 MHz, up to 35.0 MHz, up to 30.0 MHz, up to 27.0 MHz, up to 24.0 MHz, up to 22.0 MHz, up to 21.0 MHz, or up to 20.0 MHz; particularly up to 50.0 MHz, up to 30.0 MHz, up to 24.0 MHz, or up to 22.0 MHz) mean needle roller bearing fatigue (NBFT) life.

[0156] Advantageously, any transmission fluid composition of this disclosure can exhibit a maximum of 10 cSt (e.g., a maximum of 8.0 cSt, a maximum of 7.0 cSt, a maximum of 6.5 cSt, a maximum of 6.0 cSt, a maximum of 5.5 cSt, a maximum of 5.0 cSt, a maximum of 4.5 cSt, a maximum of 4.0 cSt, a maximum of 3.5 cSt, a maximum of 3.0 cSt, a maximum of 2.5 cSt, a maximum of 2.0 cSt, 1.0 cSt to 10 cSt, 1.0 cSt to 8.0 cSt, 1.0 cSt to 7.0 cSt, 1.0 cSt to 6.5 cSt, 1.0 cSt to 6.0 cSt, 1.0 cSt to 5.5 cSt, 1.0 cSt to 5.0 cSt, 1.0 cSt to 4.5 cSt, 1. 0cSt to 4.0cSt, 1.0cSt to 3.5cSt, 1.0cSt to 3.0cSt, 1.0cSt to 2.5cSt, 1.0cSt to 2.0cSt, 1.5cSt to 10cSt, 1.5cSt to 8.0cSt, 1.5cSt to 7.0cSt, 1.5cSt to 6.5cSt, 1.5cSt to 6.0cSt, 1.5cSt to 5.5cSt, 1.5cSt to 5.0cSt, 1.5cSt to 4.5cSt, 1.5cSt to 4.0cSt, 1.5cSt to 3.5cSt, 1.5cSt to 3.0cSt, 1.5cSt to 2.5cSt, 2.0cSt to 10cSt, 2. 0cSt to 8.0cSt, 2.0cSt to 7.0cSt, 2.0cSt to 6.5cSt, 2.0cSt to 6.0cSt, 2.0cSt to 5.5cSt, 2.0cSt to 5.0cSt, 2.0cSt to 4.5cSt, 2.0cSt to 4.0cSt, 2.0cSt to 3.5cSt, 2.0cSt to 3.0cSt, 2.0cSt to 2.5cSt, 2.5cSt to 10cSt, 2.5cSt to 8.0cSt, 2.5cSt to 7.0cSt, 2.5cSt to 6.5cSt, 2.5cSt to 6.0cSt, 2.5cSt to 5.5cSt, 2.5cSt to 5.0cSt, 2 0.5cSt to 4.5cSt, 2.5cSt to 4.0cSt, 2.5cSt to 3.5cSt, 2.5cSt to 3.0cSt, 3.0cSt to 10cSt, 3.0cSt to 8.0cSt, 3.0cSt to 7.0cSt, 3.0cSt to 6.5cSt, 3.0cSt to 6.0cSt, 3.0cSt to 5.5cSt, 3.0cSt to 5.0cSt, 3.0cSt to 4.5cSt, 3.0cSt to 4.0cSt, 3.0cSt to 3.5cSt, 3.5cSt to 10cSt, 3.5cSt to 8.0cSt, 3.5cSt to 7.0cSt, 3.5cSt to 6.5cSt, 3.The kinematic viscosity (KV100) at 100°C, measured according to ASTM D445, is 5 cSt to 6.0 cSt, 3.5 cSt to 5.5 cSt, 3.5 cSt to 5.0 cSt, 3.5 cSt to 4.5 cSt, 3.5 cSt to 4.0 cSt, 4.0 cSt to 10 cSt, 4.0 cSt to 8.0 cSt, 4.0 cSt to 7.0 cSt, 4.0 cSt to 6.5 cSt, 4.0 cSt to 6.0 cSt, 4.0 cSt to 5.5 cSt, 4.0 cSt to 5.0 cSt, or 4.0 cSt to 4.5 cSt), particularly 1.0 cSt to 10 cSt, 2.0 cSt to 8.0 cSt, 1.5 cSt to 3.5 cSt, or 2.5 cSt to 5.0 cSt.

[0157] Alternative formulations

[0158] In some embodiments, instead of specific combinations of components (i), (ii), (iii), and (iv), combinations of components (iv) and (v) (e.g., substantially absent components (i) and (ii)) can alternatively provide a combination of wear protection and volume resistivity. Such alternative embodiments may optionally contain substantially no (e.g., no intentionally added) calcium salicylate detergents, substantially no (e.g., no intentionally added) additional nitrogen-containing ashless dispersants (e.g., having structure (IV)), or both. In some such embodiments of calcium salicylate detergents that are substantially free of component (iii), alternative formulations may optionally also contain substantially no (e.g., no intentionally added) magnesium salicylate detergents, substantially no (e.g., no intentionally added) calcium sulfonate and / or magnesium sulfonate detergents, substantially no (e.g., no intentionally added) calcium phenolate and / or magnesium phenolate detergents, and combinations thereof (in some cases, substantially no (e.g., no intentionally added) detergents of any kind).

[0159] Component (v) may advantageously contain one or more structures having the structure HP(=O)-(OR) 39 )2 dialkyl phosphite compounds, which can react with the structure HO-P-(OR) 39 )2 balance, where each R 39 It may independently contain or not contain thioether bonds of straight-chain, branched, and / or cyclic alkyl, alkenyl, alkadienyl, and / or alkatrienyl groups having 12 to 24 carbon atoms (i.e., phosphorus-containing structures (I) different from component (i), wherein at least some alkyl chains are inserted by thioether bonds). For example, each R 39 The alkyl structural moieties may be the same or different and may each independently contain straight-chain and / or branched alkyl and / or alkenyl groups having 14 to 22 carbon atoms (e.g., 16 to 18 carbon atoms).

[0160] Specifically, when present, the dialkyl phosphite compound of component (v) may be present in the transmission fluid composition in an amount of 0.05 to 2.0% by mass, for example, 0.1 to 1.4% by mass, 0.2 to 1.0% by mass, or 0.25 to 0.8% by mass, based on the total mass of the composition. Additionally or alternatively, specifically, the dialkyl phosphite compound of component (v), when present, may collectively provide the transmission fluid composition with 35 to 2200 parts by mass of phosphorus, for example, 50 to 2000 ppm, 100 to 1000 ppm, or 300 to 750 ppm, based on the total mass of the composition. The phosphorus content can be measured according to ASTM D5185.

[0161] These alternative formulations containing combinations of components (iv) and (v) can advantageously exhibit similar average volume resistivity properties and / or average needle roller bearing fatigue (NBFT) life properties to those formulations containing combinations of components (i), (ii), (iii) and (iv) as described herein.

[0162] Additional Implementation Plan

[0163] Additionally or alternatively, this disclosure may include one or more of the following embodiments.

[0164] Implementation Scheme 1. A transmission fluid composition comprising: a primary amount of a lubricating oil base oil; and a secondary amount of an additive kit, said additive kit comprising: (i) a mixture of compounds comprising two or more structures (i):

[0165]

[0166] Wherein groups R1, R2, and R3 are independently alkyl groups having 1 to 18 carbon atoms or alkyl groups having 1 to 18 carbon atoms wherein the alkyl chain is inserted by a thioether bond, provided that in mixture (i), at least some groups R1, R2, and R3 are alkyl groups having 1 to 18 carbon atoms wherein the alkyl chain is inserted by a thioether bond; (ii) a compound of one or more structures (II):

[0167]

[0168] Wherein groups R4 and R7 are independently alkyl groups having 1 to 12 carbon atoms and R5 and R6 are independently alkyl linkages having 2 to 12 carbon atoms; (iii) detergents containing calcium salicylate; and (iv) basic nitrogen-containing ashless dispersants containing one or more of structures (III):

[0169]

[0170] Wherein: R8 and R9 are each independently a hydrocarbon group prepared by metallocene-catalyzed polymerization of an α-olefin feedstock comprising 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-octadecene, or mixtures thereof (particularly, essentially composed of 1-octene, 1-decene, 1-dodecene, or mixtures thereof); each R 10 Independently composed of hydrogen, acetyl groups, or ethylene carbonate and >NR 10 The structural moiety formed by the reaction between them (especially the hydrogen or acyl structural moiety); and x is 1 to 10 (especially 3 to 10) and is the average value of all molecules of structure (III) in a mixture of molecules of structure (III).

[0171] Implementation Scheme 2. The transmission fluid composition according to Implementation Scheme 1, wherein the compounds of component (i) and component (ii) are each present in the composition in an amount of 0.05 to 0.5% by mass based on the total mass of the composition and / or in a mass ratio of 2:1 to 1:2.

[0172] Implementation Scheme 3. A transmission fluid composition according to Implementation Scheme 1 or Implementation Scheme 2, wherein component (iii) is present in the composition in an amount of 0.05 to 0.7% by mass based on the total mass of the composition, and / or provides the composition with 45 to 450 parts by mass (ppm) of calcium based on the total mass of the composition.

[0173] Implementation Scheme 4. A transmission fluid composition according to any of the foregoing embodiments, wherein component (iii) is free from intentionally added phenolic detergent components and / or free from intentionally added sulfonate detergent components.

[0174] Implementation Scheme 5. A transmission fluid composition according to any of the preceding embodiments, wherein component (iv) is present in the composition in an amount of 0.75 to 5.0% by mass based on the total mass of the composition, and / or wherein the ashless dispersant R8 and R9 structural portions of component (iv) each independently have a number average molecular weight (Mn) of 300 to 20,000 Daltons as determined by GPC with reference to a linear polystyrene standard.

[0175] Implementation Scheme 6. The transmission fluid composition according to any of the foregoing embodiments, further comprising an additional alkaline nitrogen-containing ashless dispersant of structure (IV):

[0176]

[0177] in:

[0178] R 11 and R 12 Each is independently a hydrocarbon group with a number-average molecular weight (Mn) of 500 to 5000 Daltons as determined by GPC using a reference linear polystyrene standard;

[0179] Each R 13 Independently composed of hydrogen, acetyl groups, or ethylene carbonate and >NR 13 The structural parts formed by the reaction between them; and

[0180] y is 3 to 10 and is the average value of all molecules of structure (IV) that are the same for all molecules of structure (IV) or for a mixture of molecules of structure (IV).

[0181] Implementation Scheme 7. The transmission fluid composition according to Implementation Scheme 6, wherein:

[0182] R 11 and R 12 Each is independently a polyisobutylene-based structural moiety having a number-average molecular weight (Mn) of 750 to 2500 Daltons as determined by GPC using a reference linear polystyrene standard; and

[0183] Each R 13 It is an independent hydrogen or acetyl group structural moiety.

[0184] Implementation Scheme 8. The transmission fluid composition according to any one of Implementation Schemes 1-5, which is also substantially free of other basic nitrogen-containing ashless dispersants except for component (iv).

[0185] Implementation Scheme 9. A transmission fluid composition according to any of the preceding embodiments, wherein the composition comprises less than 100 parts by mass (ppm) of boron based on the total mass of the composition.

[0186] Implementation Scheme 10. A transmission fluid composition according to any of the foregoing embodiments, wherein the lubricating oil base oil comprises Group III base oil, Group IV base oil, or a combination thereof.

[0187] Implementation Scheme 11. A transmission fluid composition according to any of the foregoing embodiments, further comprising a substituted thiadiazole, an amine antioxidant, a phenolic antioxidant, a corrosion inhibitor, and a friction modifier having the following structure:

[0188]

[0189] Where R 18 and R 19 Each independently is:

[0190]

[0191] Let x+y be integers from 8 to 15 and z be integers from 1 to 5; and let each of R... 20 Independently composed of hydrogen, acetyl groups, or ethylene carbonate and >NR 20 The structural parts formed by the reaction between them.

[0192] Implementation Scheme 12. A transmission fluid composition according to any of the preceding embodiments, wherein: the lubricating oil base oil exhibits a kinematic viscosity (KV100) of 1.5 cSt to 8.1 cSt at 100°C as measured according to ASTM D445; the composition exhibits a KV100 of 2 cSt to 6.5 cSt as measured according to ASTM D445; the composition exhibits an average volume resistivity of at least 46.0 MΩ·m at approximately 80°C; and the composition exhibits an average needle roller bearing fatigue life of at least 13.0 megacycles.

[0193] Implementation Scheme 13. A transmission fluid composition according to any of the preceding embodiments, wherein the composition exhibits one or more of the following: an average volume resistivity of at least 47.0 MΩ·m at about 80°C and an average needle roller bearing fatigue life of at least 14.0 megacycles; an average volume resistivity of at most 95.0 MΩ·m at about 80°C and an average needle roller bearing fatigue life of at most 30.0 megacycles; and an average volume resistivity of at most 72.0 MΩ·m at about 80°C and an average needle roller bearing fatigue life of at most 25.0 megacycles.

[0194] Implementation Scheme 14. A transmission fluid composition comprising: a major amount of a lubricating oil base oil, such as a Group III base oil, a Group IV base oil, or a combination thereof; and a minor amount of an additive kit, said additive kit comprising: (iv) an alkaline nitrogen-containing ashless dispersant comprising one or more compounds comprising structure (III):

[0195]

[0196] Wherein: R8 and R9 are each independently a hydrocarbon group prepared by metallocene-catalyzed polymerization of an α-olefin feedstock comprising 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-octadecene, or mixtures thereof (particularly, essentially composed of 1-octene, 1-decene, 1-dodecene, or mixtures thereof); each R 10 Independently composed of hydrogen, acetyl groups, or ethylene carbonate and >NR 10The structural moiety formed by the reaction between them (especially the hydrogen or acyl structural moiety); and x is 1 to 10 (especially 3 to 10) and is the average of all molecules of structure (III) in a mixture of molecules of structure (III); and (v) one or more having the structure HP(=O)-(OR) 39 )2 dihydrocarbyl hydrogenphosphite compounds, wherein each R 39 Alkyl groups that independently contain or have 12 to 24 carbon atoms (e.g., 14 to 22 carbon atoms or 16 to 18 carbon atoms).

[0197] Implementation Scheme 15. The transmission fluid composition according to Implementation Scheme 14 further comprises one or more of the following: no intentionally added components (i) and (ii); substantially no intentionally added components (iii); substantially no other alkaline nitrogen-containing ashless dispersants other than component (iv); and less than 50 parts by mass (ppm) of boron based on the total mass of the composition.

[0198] Implementation Scheme 16. The transmission fluid composition according to Implementation Scheme 14 or Implementation Scheme 15, further comprising a substituted thiadiazole, an amine antioxidant, a phenolic antioxidant, a corrosion inhibitor, and at least two friction modifiers, wherein at least one has the following structure:

[0199]

[0200] Where R 18 and R 19 Each independently is:

[0201]

[0202] Let x+y be integers from 8 to 15 and z be integers from 1 to 5; and let each of R... 20 Independently composed of hydrogen, acetyl groups, or ethylene carbonate and >NR 20 The structural parts formed by the reaction between them.

[0203] Implementation Scheme 17. A transmission fluid composition according to any one of Implementation Schemes 14-16, wherein: the lubricating oil base oil exhibits a kinematic viscosity (KV100) of 1.5 cSt to 3.3 cSt at 100 °C as measured according to ASTM D445; the composition exhibits a KV40 of 9.1 cSt to 11.4 cSt as measured according to ASTM D445; the composition exhibits an average volume resistivity of at least 46.0 MΩ·m at approximately 80 °C; the composition exhibits an average volume resistivity of up to 350 MΩ·m at approximately 80 °C; the composition exhibits an average needle roller bearing fatigue life of at least 14.0 megacycles; and optionally, the composition exhibits an average needle roller bearing fatigue life of up to 22.0 megacycles.

[0204] Implementation Scheme 18. A transmission fluid composition according to any one of Implementation Schemes 14-17, wherein component (iv) is present in the composition in an amount of 0.75 to 5.0% by mass based on the total mass of the composition, and / or wherein the ashless dispersant R8 and R9 structural portions of component (iv) each independently have a number average molecular weight (Mn) of 300 to 20,000 Daltons as determined by GPC with reference to a linear polystyrene standard.

[0205] Implementation Scheme 19. A method for controlling or mitigating wear in a transmission driven by a hybrid or all-electric motor and simultaneously cooling at least a portion of electrical or electronic components of a hybrid or all-electric drivetrain, the method comprising lubricating the transmission with a transmission fluid composition according to any of the preceding embodiments and contacting one or more electrical or electronic components of the drivetrain with the transmission fluid composition according to any of the preceding embodiments.

[0206] Implementation Scheme 20. The use of a transmission fluid composition according to any one of Implementation Schemes 1-18 for controlling or mitigating wear in a hybrid or all-electric transmission lubricated with the composition and simultaneously cooling at least a portion of electrical or electronic components of a hybrid or all-electric drive system in contact with the composition.

[0207] The invention will now be described by way of non-limiting embodiments only. Example

[0208] The following components are used to form a transmission fluid composition according to the present disclosure, as well as certain comparative examples.

[0209] The following component (i) compounds constitute at least 3.0% by weight of the total mass of the compounds conforming to structure (I) in the transmission fluid composition according to this disclosure:

[0210]

[0211] There are at least three (3) other compounds in component (i), but the total mass of the compounds constituting structure (I) in the transmission fluid composition is less than 3.0% by weight. Compounds (a) and (c), namely compounds containing alkyl groups in which alkyl chains are inserted by thioether bonds, together constitute more than 40% by weight (e.g., more than 45%) of all components (i) and structure (I) compounds.

[0212] The following component (ii) compounds constitute at least 3.0% by weight of the total mass of the compounds conforming to structure (II) in the transmission fluid composition according to this disclosure:

[0213] C8H 17 -S-C2H4-O-C4H9; and C8H 17 -S-C2H4-O-C2H4-S-C8H 17

[0214] (e)(f).

[0215] The component (ii) contains at least two (2) other compounds, but the total mass of the compounds constituting structure (II) in the transmission fluid composition is less than 3.0% by weight.

[0216] Component (iii) is a highly basic alkyl-substituted calcium salicylate detergent, although some comparative examples in this article were formulated with a highly basic calcium sulfonate-substituted salicylate detergent of component (iii).

[0217] Component (iv) is an ashless dispersant of mPAO-terminated poly(alkyleneamine)succinimide with structure (III):

[0218]

[0219] R8 and R9 are each independently a hydrocarbon group produced by metallocene-catalyzed polymerization of an α-olefin feedstock consisting essentially of 1-octene, 1-decene, 1-dodecene, or mixtures thereof; wherein each R 10 Independently hydrogen; and where x is 3 to 10 and is the same for all molecules of structure (III) or the average of all molecules of structure (III) in a mixture of molecules of structure (III). R8 and R9 each independently have a number-average molecular weight of 500 to 2500 Daltons as determined by GPC with reference to linear polystyrene standards.

[0220] A mixture of compounds of component (i) can be prepared by placing dibutyl phosphite (~194 g, ~2 mol) in a round-bottomed four-necked flask equipped with a reflux condenser, a stir bar, and a nitrogen bubbler. The flask is then purged with nitrogen, sealed, and the stirrer is started. The dibutyl phosphite is then heated to ~150 °C under vacuum and maintained at that temperature, while hydroxyethyl n-octyl sulfide (~280 g, ~2 mol) is added over a period of time, such as about 1 hour. After the addition of hydroxyethyl n-octyl sulfide, heating can continue until no more butanol is formed. The reaction mixture is then cooled to obtain the mixed product.

[0221] The mixture of compounds in component (ii) can be prepared by combining hydroxyethyl n-octyl sulfide (~190 g, ~1 mol) and n-butanol (~74 g, ~1 mol) in a round-bottom four-necked flask equipped with a top receiver, a stir bar, and a nitrogen bubbler. A suitable amount of acid catalyst (e.g., phosphorous acid) can then be added. The flask is then purged with nitrogen, sealed, and the stirrer started. The reaction mixture can then be heated to ~150 °C at approximately atmospheric pressure and maintained therein until ~0.5 mol of water (~9 g) can be collected in the receiver. The reaction mixture can then be cooled to obtain the product.

[0222] Tables 1-2 below detail some of the prepared transmission fluid compositions. The amounts of components (i), (ii), (iii), and (iv) are expressed as % by mass, and the contents of phosphorus, boron, and calcium are expressed as parts per million (ppm) by mass, all based on the mass of the composition. "Other additives" refers to combinations of co-additives commonly found in transmission fluid additive kits and includes, but is not limited to, thiadiazoles, amine antioxidants, phenolic antioxidants, corrosion inhibitors, friction modifiers, and base oil diluents. Any variation in the amount of "other additives" used in the various examples is to balance the amounts of other components and is attributed solely to differences in the amount of base oil diluent. Components (i), (ii), (iii), and (iv), along with other additives, are collectively referred to herein as additive kits. All active (non-diluent) components in the additive kits are used at substantially the same concentration in the various examples. The base oil diluent used to dilute the samples of each additive kit to form the exemplary transmission fluid compositions exhibits ~2.7 cSt (mm). 2 KV100 Group IV base oils (or mixtures of Group IV base oils together) up to 8.1 cSt ( / sec) to ~8.1 cSt.

[0223] Table 1.

[0224]

[0225]

[0226] 1The amount shown is a component comprising ~25-55% by mass of diluent.

[0227] *Take the average of 2-3 measurements.

[0228] Table 2.

[0229]

[0230] 1 The amount shown is a component comprising ~25-55% by mass of diluent.

[0231] 2 Boration

[0232] *Take the average of 2-3 measurements.

[0233] Comparative Examples 1 and 3 represent transmission fluid formulations in which boronized PIB-PAM-PIB dispersant is paired with anti-wear components (i) and (ii), and respectively with calcium salicylate detergent or calcium sulfonate detergent. Similar to Comparative Example 1, Comparative Example 2 is based on calcium salicylate detergent, except that it contains a mixture of boronized and unboronized PIB-PAM-PIB dispersant. Similar to Comparative Example 3, Comparative Example 4 is based on calcium sulfonate detergent, except that it contains a mixture of boronized PIB-PAM-PIB and unboronized mPAO-PAM-mPAO dispersant. However, Example 5 represents an analogue of Comparative Example 4 containing calcium salicylate detergent, which contains both anti-wear components (i) and (ii) and a mixture of unboronized mPAO-PAM-mPAO and boronized PIB-PAM-PIB dispersant. Examples 6A and 6B are similar to Example 5, except that both contain only unborated mPAO-PAM-mPAO and no PIB-PAM-PIB dispersant – the difference between Examples 6A and 6B is the addition of a mixture of diluents with different KV100 values ​​to achieve different full-formulation KV100 values. Examples 7A and 7B are similar to Examples 6A and 6B, respectively, except that the mPAO-PAM-mPAO dispersant is boronized and premixed with the anti-wear components (i) and (ii). The mPAO and PIB arms / end groups of the mPAO-PAM-mPAO and PIB-PAM-PIB dispersants used in the comparative examples and examples each have a number-average molecular weight of 750 to 2500 Daltons as determined by GPC with reference to linear polystyrene standards. In addition, the PAM linkers in the mPAO-PAM-mPAO and PIB-PAM-PIB dispersants used in the comparative examples and examples exhibit an average x (polyalkyleneamine repeating unit value) of 3 to 10.

[0234] KV100 was used to characterize each additive kit / fully formulated composition from Tables 1-2, and the volume resistivity (the reciprocal of volume conductivity) of the fully formulated compositions was measured using an Emcee Model 1152-0007 conductivity probe, available from Emcee Electronics, Inc., of Venice, FL (USA). Test tubes containing ~15-25 mL of sample were immersed in a silicone oil bath (~2 L beaker) heated to ~80°C using a hot plate, with the temperature probe submerged in the oil bath. All samples were degassed in a desiccator for at least 72 hours prior to testing. The silicone oil bath was stirred with a magnetic stirrer at ~300 to ~600 rpm and equilibrated at the elevated temperature for at least 30 minutes prior to measurement. A hydrogen sulfide detector was placed above the test tubes to ensure no significant degradation of the sample had occurred. Each sample was then measured at least twice, with at least 2 minutes between measurements to confirm accuracy.

[0235] As is clearly seen from Tables 1-2, a beneficial ~80°C volume resistivity value (i.e., above a certain threshold) is not inherent, even for combinations of components (i), (ii), (iii), and (iv). For example, it is noted that Example 1 (containing all four components according to this disclosure) exhibits excellent wear performance. The average VR values ​​from Comparative Examples 1-3, which contain no component (iv), are consistently below 44.0 MΩ·m, with no VR measurement equal to or higher than 46.0 MΩ·m. The average VR value from Comparative Example 4, which contains a mixture of calcium sulfonate detergent and dispersant (~30 wt% component (iii) and the balance PIBSA-PAM dispersant), is also below 44.0 MΩ·m, with no VR measurement equal to or higher than 46.0 MΩ·m, while Example 5, containing the same dispersant mixture with calcium salicylate detergent component (iii), exhibits a significantly higher average VR. Examples 6A and 6B, containing calcium salicylate detergent component (iii) and only mPAOSA-PAM dispersant component (iv) without PIBSA-PAM dispersant, both exhibited average VR values ​​higher than the comparative example threshold. Examples 7A and 7B, despite containing the same component classes as in Examples 6A and 6B, exhibited average VR values ​​lower than the comparative example threshold. Although the main (but not the only) difference between Examples 6 and 7 is the boronization of the dispersant, the comparison precisely demonstrates that simply including all components (i), (ii), (iii), and (iv) in the lubricant composition does not inherently produce an average VR value higher than the comparative threshold.

[0236] Tables 3-4 below detail some of the prepared transmission fluid compositions. The amounts of components (i), (ii), (iii), and (iv) are expressed as % by mass, and the contents of phosphorus, boron, and calcium are expressed as parts per million (ppm) by mass, all based on the mass of the composition. "Other additives" refers to combinations of co-additives commonly found in transmission fluid additive kits and includes, but is not limited to, thiadiazoles, amine antioxidants, phenolic antioxidants, corrosion inhibitors, at least one friction modifier, and base oil diluents. Any variation in the amount of "other additives" used in the examples is to balance the amounts of other components and is attributed solely to differences in the amount of base oil diluent. Components (i), (ii), (iii), (iv), and (v), along with other additives, are collectively referred to herein as additive kits. The concentrations of the thiadiazole and antioxidant components in the additive kits remain similar across all examples, while the total concentrations of corrosion inhibitors, friction modifiers, and base oil / diluent sometimes (but not consistently) vary between samples. However, for all examples and comparative examples in Tables 3-4, each additive kit was used at the same treatment rate (same dilution ratio) for the full formulation composition. The base oil diluent used to dilute the various additive kit samples to form exemplary transmission fluid compositions is a Group III or Group IV base oil (or a mixture of Group III and / or Group IV base oils together) exhibiting a KV100 of ~1.5 cSt to ~3.3 cSt, except for Comparative Example 18, whose base oil exhibits a KV100 of ~2.7 cSt to ~8.1 cSt (similar to Comparative Examples 1-4 and Examples 5-7).

[0237] Table 3.

[0238]

[0239] 1 The amount shown is a component comprising ~25-55% by mass of diluent.

[0240] * Only one data point; ^ Only the average of two data points

[0241] Table 4.

[0242]

[0243] 1 The amount shown is a component comprising ~25-55% by mass of diluent.

[0244] Comparative Examples 8 and 9 represent transmission fluid formulations in which different amounts of borated PIB-PAM-PIB dispersant are paired with anti-wear components (i) and (ii), respectively, but without mPAO-PAM-mPAO dispersant component (iv) and without calcium salicylate detergent component (iii) (or even without any detergent). They serve as lower viscosity analogs to Comparative Examples 1-3 above. Examples 10, 11, and 15 show mixtures of borated PIB-PAM-PIB and unbored mPAO-PAM-mPAO (component (iv)) with dispersants of anti-wear components (i) and (ii), but without calcium salicylate detergent component (iii). Examples 11 and 15 contain the same approximate amounts of the same components, but are mixed using different component pre-blends. Examples 12 and 17 show mixtures of unboronized mPAO-PAM-mPAO dispersant component (iv) and dialkyl phosphite component (v), without any anti-abrasion components (i) and (ii) and calcium salicylate detergent component (iii) (or even without any detergent). Examples 13, 14, and 16 are substantially, but not entirely, analogs of the detergents containing calcium salicylate component (iii) of Examples 10, 11, and 15, including anti-abrasion components (i) and (ii) and mixtures of unboronized mPAO-PAM-mPAO dispersant component (iv) and boronized PIB-PAM-PIB dispersant. The mPAO and PIB arms / terminal groups of the mPAO-PAM-mPAO and PIB-PAM-PIB dispersants used in the comparative examples and examples each have a number-average molecular weight of 750 to 2500 Daltons as determined by GPC with reference to linear polystyrene standards. In addition, the PAM connectors within the mPAO-PAM-mPAO and PIB-PAM-PIB dispersants used in the comparative and examples respectively exhibited an average x (polyalkyleneamine repeating unit value) of 3 to 10.

[0245] KV40 was characterized for each additive kit / full formulation composition from Tables 3-4, and the volume resistivity (the reciprocal of volume conductivity) of the full formulation compositions was tested using a Baur DTLC apparatus / rig available from Baur GmbH of Sulz, Austria, following the procedure outlined in ASTM D1169-11 (specifying ~80°C and ~500V).

[0246] The needle roller bearing fatigue (NBFT) life of each additive kit / full formulation composition from Tables 3-4 was also tested. NBFT life can be analyzed using various methods. Here, a modified Falex 4-ball E / P wear tester (available from Falex of Sugar Grove, IL (USA)) was used to test how relatively small volumes (~50 mL) of samples protect bearings from wear. In this modified tester, a bearing (i.e., NSK part#AXK1105) capable of accommodating 30 ball bearings (axially oriented, like numbers around a clock face) was modified by removing two from every five bearings, so that three consecutive bearings were in place, followed by two missing bearing slots, repeated six times (the three consecutive bearings were approximately located at even positions on the clock face, i.e., 12, 2, 4, 6, 8, and 10, while the missing bearing slots were approximately located at odd positions on the same clock face, i.e., 1, 3, 5, 7, 9, and 11), resulting in 18 bearings and 12 empty bearing slots. This modified bearing is placed between the upper and lower bearing races (i.e., NTN part#WS81105 and NSK part#FTRE-2542) and encapsulated in a test cup containing a thermocouple (to verify sample temperature) and an adapter (to connect to the rotating shaft of the wear testing machine), where the sample temperature can be controlled using a heating device. In the needle roller bearing fatigue test, the testing machine shaft rotates at ~2100 rpm while a load is applied to the bearing assembly lubricated by the sample composition. For the first ~26 minutes of the test, a load of ~588 N is applied; for the next ~4 minutes, the load is increased to ~2940 N; after a total of ~30 minutes, the load is further increased to ~8820 N for the remainder of the test. The first ~30 minutes of the test (when a relatively low load is applied) are considered the "break-in" period. The target temperature for this test is nominal ~120°C, although the test begins at approximately room temperature (~20-25°C). The heating element within the adapter provides some heat, but it doesn't need to strictly reach the target temperature—typically, a temperature of at least ~100°C is reached before the load increases to ~8820N. If necessary, an external airflow can be introduced during testing (but usually only after the break-in period) to counteract frictional heat, preventing the bearing thermocouple temperature from overshooting / exceeding ~120°C for too long. The test is terminated only when the vibration threshold is reached. A vibration amplitude baseline is established at frequencies from ~1Hz to ~10kHz after ~45 minutes of the break-in period (i.e., ~75 minutes after entering the test). Exclude frequencies of ~176-654Hz, ~1367-1426Hz, and ~4.492-4.795kHz, and monitor vibration at the remaining frequencies.For almost all other frequencies, the test is terminated when vibration is detected at least 250% above the baseline at that frequency (i.e., when the vibration amplitude exceeds the baseline amplitude by ~250%, the vibration amplitude is approximately 3.5 times or ~350% of the baseline amplitude). However, for vibration frequencies between ~2.3 kHz and ~2.4 kHz (~2305 Hz to ~2402 Hz), the test is terminated only when vibration is detected at least 125% above the baseline at that frequency (i.e., when the vibration amplitude exceeds the baseline amplitude by ~125%, the vibration amplitude is approximately 2.25 times or ~225% of the baseline amplitude). These vibrations are considered to indicate wear (e.g., pitting). Once the test is terminated, the bearing and its assembly are removed and visually inspected (usually under magnification) for signs of pitting. If absolutely no signs of pitting are found during visual inspection, the termination may be premature and the test may be ruled out. Typically, needle roller bearing fatigue (NBFT) life represents the average of 4 to 7 measurements, but more or fewer measurements may be used. NBFT life can be calculated in megacycles (Mcyc) using the dimensions and geometry of the bearing components and the shaft rotation rate to assess the number of cycles per hour, and only the test time of the lubricated bearing under full load (i.e., the test time after break-in, or the total test time in hours minus the initial 30-minute break-in period).

[0247] As is clearly seen from Tables 3-4, beneficial ~80°C volume resistivity values ​​(i.e., above a certain threshold) and beneficial needle roller bearing fatigue life values ​​(and therefore their combination) are not inherent, even if the composition contains a combination of all components (i), (ii), (iii), and (iv). For example, as shown in Examples 12 and 17, even combinations of components (iv) and (v) that do not contain any of components (i), (ii), and (iii) produce very beneficial VR values ​​above the threshold of Comparative Example 18, although beneficial NBFT lifetimes above the threshold of Comparative Example 18 are clearly not inherent (i.e., they appear in Example 17 but not in Example 12). Therefore, combinations of different components may or may not produce a simultaneous combination of VR values ​​that are consistently equal to or higher than 44.0 MΩ·m (e.g., no single VR measurement equal to or higher than 46.0 MΩ·m) and average NBFT lifetimes that are equal to or higher than 13.0 Mcyc (or equal to or higher than 14.0 Mcyc). It is also noteworthy that Comparative Examples 8 and 9 exhibited average VR values ​​below the threshold and NBFT lifetime values ​​above the threshold of Comparative Example 18, as did Examples 10 and 13. However, directly opposite, Examples 11 and 12 exhibited average VR values ​​above the threshold and NBFT lifetime values ​​below the threshold of Comparative Example 18. Only Examples 14-17 achieved average VR values ​​and NBFT lifetime values ​​above the threshold. Examples 14 and 16 contained all components (i), (ii), (iii), and (iv), while Example 15 contained only components (i), (ii), and (iv) (no component (iii), and even essentially no detergent), and Example 17 contained only components (iv) and (v) (essentially no components (i), (ii), and (iii), and even essentially no PIB-based dispersants). Many other possible interpretations can be derived from this data, but the non-inherent correlation between components and properties (especially VR and NBFT lifetime discussed herein) is the most significant.

Claims

1. A transmission fluid composition comprising: The main amount of lubricating base oil; and A minor amount of additive kit, the additive kit comprising: (i) A mixture of compounds containing two or more structures (I): Wherein groups R1, R2 and R3 are independently alkyl groups having 1 to 18 carbon atoms or alkyl groups having 1 to 18 carbon atoms in which alkyl chains are inserted by thioether bonds, provided that in mixture (i), at least some groups R1, R2 and R3 are alkyl groups having 1 to 18 carbon atoms in which alkyl chains are inserted by thioether bonds. (ii) Compounds with one or more structures (II): Wherein groups R4 and R7 are independently alkyl groups having 1 to 12 carbon atoms and R5 and R6 are independently alkyl bonds having 2 to 12 carbon atoms; (iii) Detergents containing calcium salicylate; and (iv) Basic nitrogen-containing ashless dispersants comprising one or more structures (III): in: R8 and R9 are each independently a hydrocarbon group prepared by metallocene-catalyzed polymerization of an α-olefin feedstock comprising 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-octadecene, or mixtures thereof; each R 10 Independently composed of hydrogen, acyl groups, or ethylene carbonate and >NR 10 The structural part formed by the reaction between them; and x is 1 to 10 and is the average value of all molecules of structure (III) in a mixture of molecules of structure (III).

2. The transmission fluid composition according to claim 1, wherein the compounds of components (i) and (ii) are each present in the composition in an amount of 0.05 to 0.5% by mass based on the total mass of the composition and / or in a mass ratio of 2:1 to 1:

2.

3. The transmission fluid composition according to claim 1, wherein component (iii) is present in the composition in an amount of 0.05 to 0.7% by mass based on the total mass of the composition, and / or provides the composition with 45 to 450 parts by mass (ppm) of calcium based on the total mass of the composition.

4. The transmission fluid composition according to claim 2, wherein component (iii) is present in the composition in an amount of 0.05 to 0.7% by mass based on the total mass of the composition, and / or provides the composition with 45 to 450 parts by mass (ppm) of calcium based on the total mass of the composition.

5. The transmission fluid composition according to claim 1, wherein component (iii) is free from intentionally added phenolic detergent components and / or intentionally added sulfonate detergent components.

6. The transmission fluid composition according to claim 2, wherein component (iii) is free from intentionally added phenolic detergent components and / or intentionally added sulfonate detergent components.

7. The transmission fluid composition according to claim 3, wherein component (iii) is free from intentionally added phenolic detergent components and / or intentionally added sulfonate detergent components.

8. The transmission fluid composition according to claim 4, wherein component (iii) is free from intentionally added phenolic detergent components and / or intentionally added sulfonate detergent components.

9. The transmission fluid composition according to claim 1, wherein R8 and R9 are each independently a hydrocarbon group prepared by metallocene-catalyzed polymerization of an α-olefin feedstock consisting of 1-octene, 1-decene, 1-dodecene, or a mixture thereof.

10. The transmission fluid composition according to claim 1, wherein each R 10 It is an independent hydrogen or acetyl group structural moiety.

11. The transmission fluid composition according to claim 1, wherein x is 3 to 10.

12. The transmission fluid composition according to any one of claims 1-11, wherein component (iv) is present in the composition in an amount of 0.75 to 5.0% by mass based on the total mass of the composition, and / or wherein the R8 and R9 structural portions of component (iv) of the ashless dispersant each independently have a number average molecular weight (Mn) of 300 to 20,000 Daltons as determined by GPC with reference to a linear polystyrene standard.

13. The transmission fluid composition according to any one of claims 1-11, further comprising an additional basic nitrogen-containing ashless dispersant of structure (IV): in: R 11 and R 12 Each is independently a hydrocarbon group with a number-average molecular weight (Mn) of 500 to 5000 Daltons as determined by GPC using a reference linear polystyrene standard; Each R 13 Independently composed of hydrogen, acetyl groups, or ethylene carbonate and >NR 13 The structural parts formed by the reaction between them; and y is 3 to 10 and is the average value of all molecules of structure (IV) that are the same for all molecules of structure (IV) or for a mixture of molecules of structure (IV).

14. The transmission fluid composition according to claim 13, wherein: R 11 and R 12 Each is independently a polyisobutylene-based structural moiety having a number-average molecular weight (Mn) of 750 to 2500 Daltons as determined by GPC using a reference linear polystyrene standard; and Each R 13 It is an independent hydrogen or acetyl group structural moiety.

15. The transmission fluid composition according to any one of claims 1-11, further comprising not containing any other alkaline nitrogen-containing ashless dispersant other than component (iv).

16. The transmission fluid composition according to claim 12, further comprising no other alkaline nitrogen-containing ashless dispersant besides component (iv).

17. The transmission fluid composition according to any one of claims 1-11, 14, 16, wherein the composition comprises less than 100 parts by mass (ppm) of boron based on the total mass of the composition.

18. The transmission fluid composition according to any one of claims 1-11, 14, 16, wherein the lubricating oil base oil comprises Group III base oil, Group IV base oil, or a combination thereof.

19. The transmission fluid composition according to any one of claims 1-11, 14, and 16, further comprising a substituted thiadiazole, an amine antioxidant, a phenolic antioxidant, a corrosion inhibitor, and a friction modifier having the following structure: Where R 18 and R 19 Each independently is: Let x+y be integers from 8 to 15 and z be integers from 1 to 5; and let each of R... 20 Independently composed of hydrogen, acetyl groups, or ethylene carbonate and >NR 20 The structural parts formed by the reaction between them.

20. The transmission fluid composition according to any one of claims 1-11, 14, 16, wherein: The lubricating oil base oils exhibit a kinematic viscosity (KV100) of 1.5 cSt to 8.1 cSt at 100°C as measured according to ASTM D445; the composition exhibits a KV100 of 2 cSt to 6.5 cSt as measured according to ASTM D445. The composition exhibits an average volume resistivity of at least 46.0 MΩ·m at approximately 80 °C; and The composition exhibits an average needle roller bearing fatigue life of at least 13.0 megacycles.

21. The transmission fluid composition according to any one of claims 1-11, 14, 16, wherein the composition exhibits one or more of the following: At least 47.0 MΩ·m of average volume resistivity at approximately 80 °C and at least 14.0 megacycles of average needle roller bearing fatigue life; Average volume resistivity of up to 95.0 MΩ·m at approximately 80 °C and average needle roller bearing fatigue life of up to 30.0 megacycles; and The average volume resistivity at approximately 80°C is up to 72.0 MΩ·m, and the average fatigue life of the needle roller bearing is up to 25.0 megacycles.

22. A transmission fluid composition comprising: The main amount of lubricating base oil; and A minor amount of additive kit, the additive kit comprising: (iv) Basic nitrogen-containing ashless dispersants comprising one or more structures (III): in: R8 and R9 are each independently a hydrocarbon group prepared by metallocene-catalyzed polymerization of an α-olefin feedstock comprising 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-octadecene, or mixtures thereof; each R 10 Independently composed of hydrogen, acyl groups, or ethylene carbonate and >NR 10 The structural part formed by the reaction between them; and x is 1 to 10 and is the average value of all molecules of structure (III) in a mixture of molecules of structure (III); and (v) One or more structures having HP(=O)-(OR) 39 )2 dialkyl phosphite compounds, wherein each R 39 Alkyl groups that independently contain or have 12 to 24 carbon atoms The transmission fluid composition further comprises one or more of the following: No components (i) and (ii) were intentionally added; No intentionally added components (iii); There are no other basic nitrogen-containing ashless dispersants besides component (iv); and Boron is present in amounts of less than 50 parts per million (ppm) based on the total mass of the composition.

23. The transmission fluid composition of claim 22, wherein the lubricating oil base oil comprises Group III base oil, Group IV base oil, or a combination thereof.

24. The transmission fluid composition of claim 22, wherein R8 and R9 are each independently a hydrocarbon group prepared by metallocene-catalyzed polymerization of an α-olefin feedstock consisting of 1-octene, 1-decene, 1-dodecene, or a mixture thereof.

25. The transmission fluid composition according to claim 22, wherein each R 10 It is an independent hydrogen or acetyl group structural moiety.

26. The transmission fluid composition of claim 22, wherein x is 3 to 10.

27. The transmission fluid composition according to claim 22, wherein each R 39 Alkyl groups that independently contain or have 14 to 22 carbon atoms.

28. The transmission fluid composition according to claim 22, wherein each R 39 Alkyl groups that independently contain or have 16 to 18 carbon atoms.

29. The transmission fluid composition according to any one of claims 22-28, further comprising a substituted thiadiazole, an amine antioxidant, a phenolic antioxidant, a corrosion inhibitor, and at least two friction modifiers, wherein at least one has the following structure: Where R 18 and R 19 Each independently is: Let x+y be integers from 8 to 15 and z be integers from 1 to 5; and let each of R... 20 Independently composed of hydrogen, acetyl groups, or ethylene carbonate and >NR 20 The structural parts formed by the reaction between them.

30. The transmission fluid composition according to any one of claims 22-28, wherein: The lubricating oil base oils exhibit a kinematic viscosity (KV100) of 1.5 cSt to 3.3 cSt at 100°C as measured according to ASTM D445; the composition exhibits a KV40 of 9.1 cSt to 11.4 cSt as measured according to ASTM D445. The composition exhibits an average volume resistivity of at least 46.0 MΩ·m at approximately 80 °C; The composition exhibits an average volume resistivity of up to 350 MΩ·m at approximately 80 °C; and The composition exhibits an average needle roller bearing fatigue life of at least 14.0 megacycles.

31. The transmission fluid composition according to any one of claims 22-28, wherein: The lubricating oil base oils exhibit a kinematic viscosity (KV100) of 1.5 cSt to 3.3 cSt at 100°C as measured according to ASTM D445; the composition exhibits a KV40 of 9.1 cSt to 11.4 cSt as measured according to ASTM D445. The composition exhibits an average volume resistivity of at least 46.0 MΩ·m at approximately 80 °C; The composition exhibits an average volume resistivity of up to 350 MΩ·m at approximately 80 °C; The composition exhibits an average needle roller bearing fatigue life of at least 14.0 megacycles; and The composition exhibits an average needle roller bearing fatigue life of up to 22.0 megacycles.

32. The transmission fluid composition according to claim 29, wherein: The lubricating oil base oils exhibit a kinematic viscosity (KV100) of 1.5 cSt to 3.3 cSt at 100°C as measured according to ASTM D445; the composition exhibits a KV40 of 9.1 cSt to 11.4 cSt as measured according to ASTM D445. The composition exhibits an average volume resistivity of at least 46.0 MΩ·m at approximately 80 °C; The composition exhibits an average volume resistivity of up to 350 MΩ·m at approximately 80 °C; and The composition exhibits an average needle roller bearing fatigue life of at least 14.0 megacycles.

33. The transmission fluid composition according to claim 29, wherein: The lubricating oil base oils exhibit a kinematic viscosity (KV100) of 1.5 cSt to 3.3 cSt at 100°C as measured according to ASTM D445; the composition exhibits a KV40 of 9.1 cSt to 11.4 cSt as measured according to ASTM D445. The composition exhibits an average volume resistivity of at least 46.0 MΩ·m at approximately 80 °C; The composition exhibits an average volume resistivity of up to 350 MΩ·m at approximately 80 °C; The composition exhibits an average needle roller bearing fatigue life of at least 14.0 megacycles; and The composition exhibits an average needle roller bearing fatigue life of up to 22.0 megacycles.

34. The transmission fluid composition according to any one of claims 22-28, 32, 33, wherein component (iv) is present in the composition in an amount of 0.75 to 5.0% by mass based on the total mass of the composition, and / or wherein the ashless dispersant R8 and R9 structural portions of component (iv) each independently have a number average molecular weight (Mn) of 300 to 20,000 Daltons as determined by GPC with reference to a linear polystyrene standard.

35. A method for controlling or mitigating wear in a transmission driven by a hybrid or all-electric motor and simultaneously cooling at least a portion of electrical or electronic components of a hybrid or all-electric drivetrain, the method comprising lubricating the transmission with a transmission fluid composition according to any one of claims 1-34 and contacting one or more electrical or electronic components of the drivetrain with the transmission fluid composition according to any one of claims 1-34.

36. The use of the transmission fluid composition according to any one of claims 1-34 for controlling or mitigating wear in a hybrid or all-electric transmission lubricated with the composition and simultaneously cooling at least a portion of electrical or electronic components of a hybrid or all-electric drivetrain in contact with the composition.

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