Ashless lubricant composition

Abstract

A lubricant composition that is ashless includes an oil of lubricating viscosity; and about 0.05 to about 3 wt% actives based on a total weight of the composition of a friction modifier that is the reaction product of: (1) a C10-C24 fatty acid; and (2) a triamine.

Description

PCT PATENT APPLICATIONATTORNEY DOCKET NO. 364.1663PCASHLESS LUBRICANT COMPOSITIONCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application No. 63 / 696,133 filed September 18, 2024, which is expressly incorporated by reference herein in its entirety.TECHNICAL FIELD

[0002] The present disclosure generally relates to a lubricant composition that is ashless. More specifically, the lubricant composition includes an oil of lubricating viscosity and a particular friction modifier.BACKGROUND

[0003] Lubricants can be utilized in various industries for various applications, e.g. in machinery, automotive engines, and many other mechanical systems to facilitate a smooth operation and increase longevity of mechanical parts, by reducing friction, wear, and heat between moving surfaces of the mechanical parts. The effectiveness of a lubricant can often be attributed to its active components, e.g. friction modifiers.

[0004] Many conventional friction modifiers exhibit good friction modification performance but only in specific conditions, such as in a particular temperature range, load, and speed. For example, at high temperatures, thermal degradation of these friction modifiers can occur, which may lead to the formation of unwanted by-products, and thus, decrease the effectiveness in friction modification of the lubricant.

[0005] Furthermore, various conventional friction modifiers include rare metals that may be expensive to produce and may not be sustainable considering the increasing environmental and natural resource management standards.

[0006] Bio-lubricants including friction modifiers derived from natural and renewable resources can be desirable alternatives due to their low cost, high abundance and low toxicity. However, bio-lubricants can experience performance shortcomings. Accordingly, there is an opportunity for improvement.BRIEF SUMMARY

[0007] This disclosure provides a lubricant composition that is ashless and that comprises: an oil of lubricating viscosity; and about 0.05 to about 3 wt% actives based on a total weight ofPCT PATENT APPLICATIONATTORNEY DOCKET NO. 364.1663PC the composition of a friction modifier that is the reaction product of: (1) a C10-C24 fatty acid; and (2) a triamine.

[0008] The disclosure also provides a lubricant composition that is ashless and that comprises:A. a Group III base oil; andB. about 0.05 to about 3 wt% actives of a friction modifier based on a total weight of the composition and has the following structure (II):wherein R is a C16-C18 alkyl chain; wherein the composition exhibits a coefficient of friction that is at least 60% less than that of a comparative composition that comprises molybdenum dithiocarbamate in a comparative amount to the friction modifier but is free of the friction modifier, as determined using a Mini Traction machine test conducted at a sliding to rolling ratio of about 50%, a load of about 20 N, and at a temperature of about 120 °C; and wherein the composition exhibits an average wear scar diameter that is at least about 15% less than that of a comparative composition that comprises molybdenum dithiocarbamate in a comparative amount to the friction modifier but is free of the friction modifier, as determined using High- Frequency Reciprocating Rig screening conducted at a temperature of about 120 °C, a frequency of about 20 Hz, and a load of about 1000g.BRIEF DESCRIPTION OF THE DRAWINGS

[0009] The present disclosure will hereinafter be described in conjunction with the following figures, wherein

[0010] FIG. 1 is a collection of Stribeck curves, also described as line plots, of coefficient of friction versus entrainment speed, which can be categorized into three regimes including boundary, mixed, and an elastohydrodynamic lubrication (EHD), of Example 1 and Comparative Example 1, performed at various temperatures;

[0011] FIG. 2 is a second collection of Stribeck curves of Example 1 and Comparative Example 1, performed at the same temperatures as FIG. 1.PCT PATENT APPLICATIONATTORNEY DOCKET NO. 364.1663PCDETAILED DESCRIPTION

[0012] The following detailed description is merely exemplary in nature and is not intended to limit the current composition. Furthermore, there is no intention to be bound by any theory presented in the preceding background or the following detailed description.

[0013] Embodiments of the present disclosure are generally directed to chemical compounds, e.g. friction modifiers, ethoxylated amines, diacids, anhydrides, etc., compositions including the same, and methods for forming the same. For the sake of brevity, conventional techniques related to making such chemical compounds and compositions may not be described in detail herein. Moreover, the various tasks and process steps described herein may be incorporated into a more comprehensive procedure or process having additional steps or functionality not described in detail herein. In particular, various steps in the manufacture of chemical compounds and associated compositions are well-known and so, in the interest of brevity, many conventional steps will only be described briefly herein or will be omitted entirely without providing the well-known process details.

[0014] In this disclosure, the terminology “about” can describe values ± 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10%, in various embodiments. Moreover, it is contemplated that, in various nonlimiting embodiments, it is to be appreciated that all numerical values as provided herein, save for the actual examples, are approximate values with endpoints or particular values intended to be read as “about” or “approximately” the value as recited. It is also contemplated that all isomers and chiral options for each compound described herein are hereby expressly contemplated for use herein in various non-limiting embodiments.

[0015] Throughout this disclosure, the terminology percent "actives" is well recognized in the art and means the percent amount of active or actual compound or molecule present as compared to, for example, a total weight of a diluted solution of a solvent and such a compound. Some compounds, such as a solvent, are not described relative to a percent actives because it is well known to be approximately 100% actives. Any one or more of the values described herein may be alternatively described as percent actives as would be understood by the skilled person.PCT PATENT APPLICATIONATTORNEY DOCKET NO. 364.1663PC

[0016] In various embodiments, the terminology “free of’ describes embodiments that include less than about 5, 4, 3, 2, 1, 0.5, or 0.1, weight percent (or weight percent actives) of the compound or element at issue using an appropriate weight basis as would be understood by one of skill in the art. In other embodiments, the terminology “free of’ describes embodiments that have zero weight percent of the compound or element at issue.

[0017] The terminology “consists essentially of’ may describe various non-limiting embodiments that are free of one or more optional compounds described herein and / or free of one or more chemical compounds, additives, solvents, etc.

[0018] It is to be understood that the subscripts of chemical compounds that are polymeric, e.g. friction modifier, ethoxylated amine, etc., are typically described as average values because the synthesis of chemical compounds typically produces a distribution of various individual molecules.

[0019] The chemical compounds and compositions disclosed herein may suitably comprise, consist of, or consist essentially of the components, elements, and process delineations described herein. The embodiments illustratively disclosed herein suitably may be practiced in the absence of any element which is not specifically disclosed herein.Lubricant Composition:

[0020] This disclosure provides a lubricating composition that is ashless including an oil of lubricating viscosity, and a particular friction modifier. The lubricant composition may be described herein simply as “the composition”. The lubricant composition may be further described as, or may be used as, a lubricant, a lubricator, an engine oil, a motor oil, a transmission fluid, an EV fluid, grease, etc. The lubricant composition may be used to reduce friction and wear in a mechanical system, e.g. a combustion engine, an electric motor, a gearbox, bearings, hydraulic systems, etc. In various embodiments, the lubricant composition may be further defined as a metal working fluid.

[0021] The composition is ashless. The terminology “ashless” may be used to describe a minimal presence of visible inorganic residues (ash), which may include a metal, when the composition is burned, which can negatively affect the performance of mechanical parts. In various embodiments, the composition is free of visible inorganic residues, or ashless. In other embodiments, the composition exhibits minimal visible inorganic residues, which may also be described as ashless.PCT PATENT APPLICATIONATTORNEY DOCKET NO. 364.1663PC

[0022] The composition of this disclosure may also exhibit excellent wear performance, provide good wear protection at comparatively low treat rates, exhibit good oil solubility (e.g. high carbon content), have a comparatively low phosphorous content, and / or low sulfur content, as compared to comparative compositions. The composition may additionally exhibit both good wear performance and low friction coefficients simultaneously, have customizable TBN values, detergency properties, and / or friction modification properties. Moreover, the composition is ashless (low metal content), and can be halogen-, phosphor- and sulfur-free, which can be beneficial in several applications e.g. engine oils, transmission fluids for EVs and hydraulic fluids, that exhibit improved wear performance when compared to compositions that include, for example, an industry standard, e.g. zinc dihydrocarbyl dithiophosphate (ZDDP) and / or molybdenum dithiocarbamate (MoDTC), that exhibit excellent wear performance at comparatively low treat rates, that exhibit both low friction coefficients at various temperatures ( which can be desirable for EV fluids) and low wear performance (contrary to ZDDPs), that exhibit variable friction performance at the same low wear performance (which can be desirable for transmission fluids).

[0023] In various other embodiments, the lubricant composition is combined with an industry standard, including but not limited to ZDDP and / or MoDTC, such that including one or more of the industry standards further provides synergistic effect to the lubricant composition, allowing for good wear performance and low friction coefficients.Oil of Lubricating Viscosity

[0024] The lubricant composition includes an oil of lubricating viscosity. The oil of lubricating viscosity, i.e., an oil exhibiting a viscosity suitable for use in lubricating applications such as those described here, may be alternatively described as a base stock, a base oil, or simply as an oil. This oil is typically the primary liquid constituent of the composition and may be any known in the art. In one embodiment, the oil is described as a base oil and is chosen from natural (vegetable, animal or mineral), synthetic lubricating oils and combinations thereof. The type of oil is not particularly limited and may be any type of oil of lubricating viscosity known in the art.

[0025] In various embodiments, the oil is a Group I, II, III, IV, or V oil as defined in the American Petroleum Institute (API) publication “Engine Oil Licensing and Certification System”, Industry Services Department, Fourteenth Edition, December 1996, Addendum 1,PCT PATENT APPLICATIONATTORNEY DOCKET NO. 364.1663PCDecember 1998. For example, the oil may include less than about 90 percent saturates and / or greater than about 0.03 percent sulfur and has a viscosity index greater than or equal to about 80 and less than about 120.

[0026] In the aforementioned descriptions, saturates may be measured using ASTM D 2007, viscosity index may be determined using ASTM D 2270, sulfur may be measured using ASTM D 2622, ASTM D 4294, ASTM D 4927, ASTM D 3120, or combinations thereof.

[0027] In various embodiments, the oil includes greater than or equal to about 10, about 15, about 20, about 25, about 30, about 35, about 40, about 45, about 50, about 55, about 60, about 65, about 70, about 75, about 80, about 85, about 90, or about 95 wt %, of a Group I, II, III, IV, or V oil, based on the total weight of the oil itself. In various non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above, are hereby expressly contemplated for use herein.

[0028] In other embodiments, the oil is or includes a natural oil which may be chosen from animal and vegetable oils (e.g. castor and lard oil), liquid petroleum oils and hydro refined, solvent-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic- naphthenic types, and combinations thereof. Alternatively, the oil may be derived from coal or shale.

[0029] In other embodiments, the oil is or includes a synthetic lubricating oil which may be chosen from hydrocarbon oils such as polymerized and interpolymerized olefins (e.g. polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(l -hexenes), poly(l -octenes), poly(l -decenes)); alkylbenzenes (e.g. dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzenes); polyphenols (e.g. biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogues and homologues thereof, and combinations thereof.

[0030] In other embodiments, the oil is or includes an ester of a dicarboxylic acid (e.g. phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety of alcohols (e.g. butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol), and combinations thereof. Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate,PCT PATENT APPLICATIONATTORNEY DOCKET NO. 364.1663PC diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid. Other esters include those made from C5 to C12 monocarboxylic acids and polyols, and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol. Still others include esters made from mono carboxylic acids and monoalcohols e.g. methanol, ethanol, etc. Methyl esters often have low viscosities. These monoesters can also be based on alkoxylated alcohols wherein alkoxylate groups are ethylene oxide and / or propylene oxide. Other examples include polyalkylene glycol (PAG) derived oil. These polyalkylene glycols can be used as is or etherified by reaction with alcohols or esterified by reaction with carboxylic acids, particularly mono-acids.

[0031] In other embodiments, the oil is or includes an unrefined, refined or re-refined oil. Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further treatment would be unrefined oil. Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration and percolation are known to those skilled in the art. Re-refined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. Such re-refined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for approval of spent additive and oil breakdown products.

[0032] In other embodiments, the oil is or includes a gas-to-liquid (“GTL”) oil, i.e. the oil may be an oil derived from Fischer-Tropsch synthesized hydrocarbons made from synthesis gas containing H2 and CO using a Fischer-Tropsch catalyst. These hydrocarbons typically require further processing in order to be useful as an oil. For example, they may, by methods known in the art, be hydroisomerized; hydrocracked and hydroisomerized; dewaxed; or hydroisomerized and dewaxed.

[0033] In other embodiments, the volatility of the oil, as measured by the NOACK test (ASTM D5880), is less than or equal to about 16%, about 13.5%, about 12%, about 10%, or about 8%.PCT PATENT APPLICATIONATTORNEY DOCKET NO. 364.1663PCTypically, the viscosity index (VI) of the oil is at least about 95, about 110, about 120, or about 125, or from about 130 to about 140, measured according to ASTM D5880. In various nonlimiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above, are hereby expressly contemplated for use herein.

[0034] In various embodiments, the oil is present in an amount of greater than about 55, about 60, about 65, about 70, about 75, about 80, about 85, or about 90, wt %, based on the total weight of the composition. In other embodiments, the oil is present in an amount of less than about 99, about 98, about 97, about 96, about 95, about 94, about 93, about 92, about 91, or about 90, wt%, based on a total weight of the composition. In still other embodiments, the oil may be present in an amount to balance the amount of the friction modifier (e.g. as described below), such that the total weight is about 100 wt%. Alternatively, the amount of the oil may be such that the amount of the oil, plus the amount of the friction modifier, plus the amount of any one or more additives described herein, is about 100 wt%. In various non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above, are hereby expressly contemplated for use herein.Friction Modifier

[0035] The lubricant composition also includes the friction modifier. The friction modifier may be, include, consist essentially of, or consist of, the reaction product of: (1) a C10-C24 fatty acid; and (2) a triamine. In various embodiments, the terminology “consist essentially of’ describes that the friction modifier is free or, or includes less than about 5, 4, 3, 2, 1, 0.5, or 0.1, wt%, of another reaction product of an acid and an amine that is not that which is described immediately above, and / or free of one or more polymers, additives, fillers, solvents, etc.

[0036] The (1) a C10-C24 fatty acid is not particularly limited and may have any number of carbon atoms from 10-24, e.g. 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, or 24, carbon atoms. In other embodiments the number of carbon atoms is from about 10 to about 24, about 11 to about 23, about 12 to about 22, about 13 to about 21, about 14 to about 20, about 15 to about 19, about 16 to about 18, or about 17 to about 18. In various non-limiting embodiments, all values and ranges of values, including and between those described above, are hereby expressly contemplated for use herein.

[0037] The fatty acid may be a singular fatty acid or may include a combination of two or more fatty acids. For example, the fatty acid may be or include a distribution of fatty acids havingPCT PATENT APPLICATIONATTORNEY DOCKET NO. 364.1663PC various numbers of carbon atoms. In one embodiment, the fatty acid is or include tall oil fatty acid. In another embodiment, the fatty acid is or includes soy fatty acid. Each of these fatty acids may include a mixture of molecules of varying chain length, as is well appreciated in the art. In other embodiments, the fatty acid is chosen from Capric Acid (C10:0), Lauric Acid (C12:0), Myristic Acid (C14:0), Palmitic Acid (C16:0); Palmitoleic Acid (C16:l); Stearic Acid (C18:0); Oleic Acid (C18:l); Linoleic Acid (C18:2); Alpha-Linolenic Acid (C18:3); Arachidic Acid (C20:0); Gadoleic Acid (C20:l); Eicosapentaenoic Acid (EPA) (C20:5); Behenic Acid (C22:0); Erucic Acid (C22:l); Docosahexaenoic Acid (DHA) (C22:6); Lignoceric Acid (C24:0); Nervonic Acid (C24:l), and combinations thereof. In this nomenclature, the “C” number refers to the carbon chain length and the other number refers to the number of double bonds, e.g. (Carbon Chain Length : Number of Double Bonds). In other embodiments, the fatty acid is chosen from flaxseed oil fatty acid; sunflower oil fatty acid; com oil fatty acid; cottonseed oil fatty acid; rapeseed oil fatty acid; safflower oil fatty acid; olive oil fatty acid; and combinations thereof.

[0038] Referring now to the triamine, the triamine is also not particularly limited and may be any known in the art. In various embodiments, the triamine is chosen from diethylenetriamine (DETA), triethylenetetramine (TETA), N-(2-aminoethyl)-l,3-propanediamine (AEPD), isophorone diamine (IPDA), N,N',N''-tris(2-aminoethyl)amine (TREN), tris(2- aminoethyl)amine (TAEA), 1,3,5-triaminopentane (dipropylenetriamine), hexamethylenetriamine (HMTA), and combinations thereof. In one embodiment, the triamine is diethylenetriamine (DETA).

[0039] In other embodiments, the triamine has the structure (I)wherein each of x and y is independently about 1 to about 6. In various embodiments, each of x and y is independently about 1, 2, 3, 4, 5, or 6. In other embodiments, each of x and y is independently from about 1.5 to about 5.5, about 2 to about 5, about 2.5 to about 4.5, about 3 to about 4, or about 3.5 to about 4. In various non- limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above, are hereby expressly contemplated for use herein.PCT PATENT APPLICATIONATTORNEY DOCKET NO. 364.1663PC

[0040] The (1) a C10-C24 fatty acid and the (2) triamine may be reacted at any molar ratio. In various embodiments, the fatty acid and the triamine are reacted at a molar ratio of from about (0.5-1.5:1) to about (1:0.5-1.5). In other embodiments, the molar ratio is from about (0.5-1) : about 1. For example, the molar ratio may be about 0.5:1, about 0.55:1, about 0.6:1, about 0.65:1, about 0.7:1, about 0.75:1, about 0.8:1, about 0.85:1, about 0.9:1, about 0.95:1, or about 1:1, or vice versa. In one embodiment, the molar ratio is about 0.8:1 to about 0.9:1. In various non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above, are hereby expressly contemplated for use herein.

[0041] Referring now to the reaction product of the (1) a C10-C24 fatty acid and the (2) triamine, the reaction product may be an imidazoline. In one embodiment, the imidazoline has the structure (II):wherein R is a C16-C18 alkyl chain. In various embodiments, R has about 16, 17, or 18 carbon atoms. R may be linear, branched, or include a cyclic portion.

[0042] The friction modifier itself can have various physical properties. In various embodiments, the friction modifier itself has a Total Base Number of greater than about 280, 290, 300, etc. mg KOH / g measured according to ASTM D2896. In other embodiments, the TBN is from about 280 to about 300, about 285 to about 295, or about 290 to about 295, mg KOH / g measured according to ASTM D2896. In various non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above, are hereby expressly contemplated for use herein.

[0043] In other embodiments, the friction modifier has a weight average molecular weight (Mw) of from about 300 Da to about 700 Da. In some embodiments, the Mw is from about 350 to about 650, about 400 to about 600, about 450 to about 550, or about 450 to about 500, Da. In various non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above, are hereby expressly contemplated for use herein.PCT PATENT APPLICATIONATTORNEY DOCKET NO. 364.1663PC

[0044] The friction modifier is present in the lubricant composition in an amount of from about 0.05 to about 3 weight percent actives based on a total weight of the composition. In various embodiments, this amount is from about 0.1 to about 1 wt% actives, based on a total weight of the lubricant composition. In still other embodiments, this amount is from about 0.15 to about2.95, about 0.2 to about 2.9, about 0.25 to about 2.85, about 0.3 to about 2.8, about 0.35 to about2.75, about 0.4 to about 2.7, about 0.45 to about 2.65, about 0.5 to about 2.6, about 0.55 to about2.55, about 0.6 to about 2.5, about 0.65 to about 2.45, about 0.7 to about 2.4, about 0.75 to about2.35, about 0.7 to about 2.3, about 0.75 to about 2.25, about 0.8 to about 2.2, about 0.85 to about2.15, about 0.9 to about 2.1, about 0.95 to about 2.05, about 1 to about 2, about 1.05 to about1.95, about 1.1 to about 1.9, about 1.15 to about 1.85, about 1.2 to about 1.8, about 1.25 to about1.75, about 1.3 to about 1.7, about 1.35 to about 1.65, about 1.4 to about 1.6, about 1.45 to about1.55, or about 1.5, weight percent actives based on a total weight of the composition. In various non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above, are hereby expressly contemplated for use herein.Additives

[0045] The lubricant composition may include, or be free of, one or more additives that is not one of the compounds described above. For example, the composition may include, or be free of, one or more additives such as, but not limited to, metal deactivators, viscosity modifiers, detergents, friction modifiers, antiwear agents, corrosion inhibitors, dispersants, dispersant viscosity modifiers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, pour point depressants, seal swelling agents, and any combination or mixture thereof.

[0046] More specifically, the composition may include, or be free of, MoDTC, which may be used as an additional friction modifier. In various embodiments, MoDTC is present in the composition in an amount of from about 0.1 to about 1 wt% actives, based on a total weight of the composition. In other embodiments, MoDTC is present in the composition in an amount of from about 0.2 to about 0.9 wt%, about 0.3 to about 0.8 wt%, about 0.4 to about 0.7 wt%, or about 0.5 to about 0.6 wt%, based on a total weight of the composition. In various non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above, are hereby expressly contemplated for use herein.

[0047] The composition may additionally and optionally include ZDDP, which may be used as an antiwear agent. In various embodiments, ZDDP is present in the composition in an amountPCT PATENT APPLICATIONATTORNEY DOCKET NO. 364.1663PC of from about 0.1 to about 1 wt% actives, based on a total weight of the composition. In other embodiments, ZDDP is present in the composition in an amount of from about 0.2 to about 0.9 wt%, about 0.3 to about 0.8 wt%, about 0.4 to about 0.7 wt%, or about 0.5 to about 0.6 wt%, based on a total weight of the composition. In various non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above, are hereby expressly contemplated for use herein.

[0048] In various embodiments, the composition includes both MoDTC and ZDDP, in a total weight amount of from about 0.2 to about 2 wt%, about 0.3 to about 1.9 wt%, about 0.4 to about 1.8 wt%, about 0.5 to about 1.7 wt%, about 0.6 to about 1.6 wt%, 0.7 to about 1.5 wt%, about 0.8 to about 1.4 wt%, about 0.9 to about 1.3 wt%, about 1 to about 1.2 wt%, or about 1 to about 1.1 wt%, based on a total weight of the composition. In various non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above, are hereby expressly contemplated for use herein.

[0049] In various embodiments, the composition includes from about 0.1 to about 25 wt%, about 1 to about 5 wt%, about 1 to about 4 wt%, about 1 to about 3 wt%, about 1 to about 2 wt%, or about 2 to about 3 wt% of one or more additives, based on a total weight of the composition. In other embodiments, the composition includes from about 5 to about 25 wt%, about 6 to about 24 wt%, about 7 to about 23 wt%, about 8 to about 22 wt%, about 9 to about 21 wt%, about 10 to about 20 wt%, about 11 to about 19 wt%, about 12 to about 18 wt%, about 13 to about 17 wt%, about 14 to about 16 wt%, or about 14 to about 15 wt% of one or more additives, based on a total weight of the composition. In various non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above, are hereby expressly contemplated for use herein.Physical Properties

[0050] In various embodiments, the composition itself can have a cyclic content of at least about 60% as determined using IR spectroscopy. In other embodiments, the cyclic content is at least about 65, 70, or 75%, as determined using IR spectroscopy. Alternatively, the cyclic content may be from about 60 to about 75, about 65 to about 70, %, as determined using IR spectroscopy.PCT PATENT APPLICATIONATTORNEY DOCKET NO. 364.1663PC

[0051] The composition may exhibit a friction coefficient when utilized, which may be used to describe the ability of the composition to reduce friction between two or more surfaces, e.g. parts inside a combustion engine, an electric motor, a gearbox, between bearings, etc.

[0052] The friction coefficient of the composition may be evaluated in comparison to a comparative composition using a standardized method, e.g. ASTM D471, or by using a Mini Traction machine (MTM) test conducted at a sliding rolling ratio of about 50%, a load of about 20 N. The friction coefficient of the lubricant composition may alternatively be measured using various methods and / or instruments, e.g. using a pin-on-disk tribometer, using a four-ball tester, using a reciprocating tribometer, etc. A smaller friction coefficient may indicate an increase in lubrication performance, and thus, a more effective lubricant composition.

[0053] The friction coefficient may be measured at various temperatures, typically from about 40 to about 120 °C, e.g. about 40 °C, about 50 °C, about 60 °C, about 70 °C, about 80 °C, about 90 °C, about 100 °C, about 110 °C, or about 120 °C. Additionally, the friction coefficient may be measured at various entrainment speeds, e.g. about 1 to about 5000 mm / s, about 5 mm / s, about 50 mm / s, about 500 m / s, or about 5000 mm / s. Entrainment speeds may be categorized into lubrication regimes, which are known in art to include a boundary regime, a mixed regime, and a elastohydrodynamic lubrication (EHD) regime.

[0054] The friction coefficient at various conditions, e.g. various temperatures, entrainment speeds and / or lubrication regimes, may be visualized using a Stribeck curve, which may be known in the art as a plot of friction coefficient vs. entrainment speed. In various embodiments, the friction coefficient of the lubricant composition, measured using any of the aforementioned method and / or conditions, may be from about 0.001 to about 0.1. In other embodiments, the friction coefficient is from about 0.001 to about 0.01, about 0.002 to about 0.009, about 0.003 to about 0.008, about 0.004 to about 0.007, or about 0.005 to about 0.006. In other embodiments, the friction coefficient is from about 0.01 to about 0.1, about 0.02 to about 0.09, about 0.03 to about 0.08, about 0.04 to about 0.07, or about 0.05 to about 0.06. In yet other embodiments, the friction coefficient is from about 0.05 to about 0.2, about 0.1 to about 0.19, about 0.11 to about 0.18, about 0.12 to about 0.17, about 0.13 to about 0.16, or about 0.14 to about 0.15. In various non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above, are hereby expressly contemplated for use herein.PCT PATENT APPLICATIONATTORNEY DOCKET NO. 364.1663PC

[0055] In various embodiments, the composition has a friction coefficient, as determined using an MTM test conducted at a sliding to rolling ratio of about 50%, a load of about 20 N, and at a temperature of from about 40 °C to about 120 °C, that is at least about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, or 75, or greater, % less than that of a comparative composition that comprises MoDTC in a comparative amount to the friction modifier but is free of the friction modifier. In other words, when the composition of this disclosure is compared to a comparative composition that includes MoDTC, the instant composition has an improved coefficient of friction as described above. The terminology “in a comparative amount” means that the MoDTC is included in an amount that may or may not be the same weight or molar amount as the friction modifier but is an amount that would be known to be comparative by the skilled person. In various embodiments, such an amount is about ± 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mole or weight % different. It is contemplated that the above values may change depending on the content and type of oil (e.g. oil of lubricating viscosity) that is used for the test. In various non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above, are hereby expressly contemplated for use herein.

[0056] In various embodiments, the composition has a friction coefficient, as determined using an MTM test conducted at a sliding to rolling ratio of about 50%, a load of about 20 N, and at a temperature of from about 40 °C to about 120 °C, that is at least about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, or 75, or greater, % less than that of a comparative composition that comprises ZDDP in a comparative amount to the friction modifier but is free of the friction modifier. In other words, when the composition of this disclosure is compared to a comparative composition that includes ZDDP, the instant composition has an improved coefficient of friction as described above. The terminology “in a comparative amount” means that the ZDDP is included in an amount that may or may not be the same weight or molar amount as the friction modifier but is an amount that would be known to be comparative by the skilled person. In various embodiments, such an amount is about ± 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mole or weight % different. It is contemplated that the above values may change depending on the content and type of oil (e.g. oil of lubricating viscosity) that is used for the test. In various non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above, are hereby expressly contemplated for use herein.PCT PATENT APPLICATIONATTORNEY DOCKET NO. 364.1663PC

[0057] Additionally, the composition may exhibit synergistic effect with another friction modifier and / or an antiwear agent, e.g. MoDTC, ZDDP, etc. such that the composition including the friction modifier and MoDTC and / or ZDDP may exhibit a friction coefficient, as determined using an MTM test at various entrainment speed, e.g. 5 mm / s, 50 mm / s, 500 mm / s, 5000 mm / s, etc., that is at least about 5, 10, 15, 20, 25, 30, 35, 40, 45, or greater, % less than that of a comparative composition that comprises only MoDTC or only ZDDP in a comparative amount to the friction modifier but is free of the friction modifier, or at least about 5, 10, 20, 25, 30, 35, 40, 45, or greater, % less than that of the composition that comprises only the friction modifier but is free of the MoDTC or free of the ZDDP. In various non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above, are hereby expressly contemplated for use herein.

[0058] The composition may also exhibit an average wear scar, which can be used to describe the size of a wear mark left on a test article, such as a ball or a disk. The average wear scar may be measured using any standardized method known in the art, e.g. ASTM D4172, ASTM D975, in various conditions. In various embodiments, the average wear scar exhibited by the composition, measured using a high frequency reciprocating rig (HFRR) test, performed at about 120 °C, a frequency at about 20 Hz, and a load of about 1000 g, is less than about 300, 250, 200, or 150, microns. In other embodiments, the average wear scar is from about 100 to about 300 microns, about 110 to about 290 microns, about 120 to about 270 microns, about 130 to about 260 microns, about 140 to about 250 microns, about 150 to about 240 microns, about 160 to about 230 microns, about 170 to about 220 microns, about 180 to about 210 microns, or about 190 to about 200 microns. In various non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above, are hereby expressly contemplated for use herein.

[0059] The average wear scar of the composition may also be evaluated in comparison to a comparative composition. A smaller scar diameter may indicate a better wear protection performance of the composition. In various embodiments, the composition exhibits an average wear scar diameter, as determined using HFRR screening conducted at a temperature of about 120 °C, a frequency of about 20 Hz, and a load of about 1000g, that is at least about 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30, 35, 40, 45, or greater % less than that of a comparative composition that comprises MoDTC in a comparative amount as the friction modifier, but isPCT PATENT APPLICATIONATTORNEY DOCKET NO. 364.1663PC free of the friction modifier. In other words, when the composition of this disclosure is compared to a comparative composition that includes MoDTC, the instant composition can have improved 4-ball wear preventative performance as described above. The terminology “in a comparative amount” means that the MoDTC is included in an amount that may or may not be the same weight or molar amount as the friction modifier but is an amount that would be known to be comparative by the skilled person. In various embodiments, such an amount is about ± 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mole or weight % different. It is contemplated that the above values may change depending on the content and type of oil (e.g. oil of lubricating viscosity) that is used for the test. In various non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above, are hereby expressly contemplated for use herein.

[0060] In various embodiments, the composition exhibits an average wear scar diameter, as determined using HFRR screening conducted at a temperature of about 120 °C, a frequency of about 20 Hz, and a load of about 1000g, that is at least about 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30, 35, 40, 45, or greater % less than that of a comparative composition that comprises ZDDP in a comparative amount as the friction modifier, but is free of the friction modifier. In other words, when the composition of this disclosure is compared to a comparative composition that includes ZDDP, the instant composition can have improved 4-ball wear preventative performance as described above. The terminology “in a comparative amount” means that the ZDDP is included in an amount that may or may not be the same weight or molar amount as the friction modifier but is an amount that would be known to be comparative by the skilled person. In various embodiments, such an amount is about ± 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mole or weight % different. It is contemplated that the above values may change depending on the content and type of oil (e.g. oil of lubricating viscosity) that is used for the test. In various non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above, are hereby expressly contemplated for use herein.

[0061] The composition is not limited to any particular total base number (TBN). In various embodiments, the composition has a TBN, measured according to ASTM D2896, of from about 4 to about 15, about 5 to about 14, about 6 to about 13, about 7 to about 12, about 8 to about 11, or about 9 to about 10. In various non-limiting embodiments, all values and ranges of values,PCT PATENT APPLICATIONATTORNEY DOCKET NO. 364.1663PC both whole and fractional, including and between those described above, are hereby expressly contemplated for use herein.

[0062] The composition is also not limited relative to viscometric description. For example, in various embodiments the composition may be described as SAE 20WX, SAE 15WX, SAE 10WX, SAE 5WX or SAE OWX, where X represents any one of 20, 30, 40 and 50 wherein the characteristics of the different viscometric grades can be found in the SAE J300 classification. In an embodiment of each aspect, independently of the other embodiments, the composition is in the form of an SAE 10WX, SAE 5WX or SAE OWX, In various embodiments in the form of an SAE 5WX or SAE OWX, wherein X represents any one of 20, 30, 40 and 50. In various embodiments X is 20 or 30. Alternatively, the composition may be described as a transmission / gear oils. Typical transmission oil grades are SAE 80W, 75W-90, 80W-90 and SAE 90. Alternatively, the composition may be described as a hydraulic oil which has ISO viscosity grades and typical ISO grades such as ISO VG 32, ISO VG 46, ISO VHG 68, and ISO VG 100.Method of Forming the Composition

[0063] The composition may be formed by any method known in the art. In various embodiments, the method includes the step of providing the oil of lubricating viscosity, providing the friction modifier, and combining the oil and the friction modifier to form the composition. Alternatively, the method may include the step of providing one or more additives and the step of combining the one or more additives with the oil, the friction modifier, and / or with the combination of the oil and the friction modifier, to form the composition. The method may include batch or continuous steps.Method of Forming the Friction modifier

[0064] The method of forming the friction modifier is not particularly limited and may be any known in the art. The method of forming the composition itself may include one or more steps of the synthesis of the friction modifier. Alternatively, the friction modifier may be formed entirely independently from the method of forming the composition. In such an embodiment, the friction modifier may be provided in an already formed state.EXAMPLESGeneral Procedure For Formation Of Lubricant Compositions and Comparative CompositionsPCT PATENT APPLICATIONATTORNEY DOCKET NO. 364.1663PC

[0065] Various friction modifiers were used to form various lubricant compositions, described herein as Example 1 and two Comparative Examples.

[0066] Example 1 includes an friction modifier (1A), which is synthesized from a reaction of tall oil fatty acid and diethylenetriamine (DETA) in a molar ratio of about 0.8 to about 0.9. Example 1 includes the friction modifier (1A) in an amount of 0.3 wt% actives based on a total weight of the lubricant composition and Group III oils in balance amount.

[0067] The Comparative Example 1 includes a conventional friction modifier including MoDTC, present in an amount of 0.2 wt%, actives based on a total weight of the lubricant composition and Group III oils in balance amount.

[0068] The Comparative Example 2 includes a friction modifier that includes a high- viscosity modified polyester, present in an amount of 0.2 wt%, actives based on a total weight of the lubricant composition and Group III oils in balance amount. The polyester has the approximate following viscosity:Evaluation of Physical Properties of Lubricant Compositions

[0069] The antiwear and friction-reducing performances of Example 1 and the Comparative Examples 1 and 2 were measured following the same procedure.

[0070] Example 1 and the Comparative Examples 1 and 2 were tested for average wear scar using a High Frequency Reciprocating Rig (HFRR) to evaluate the anti- wear properties. The protocol employed was as follows:• Load: 1000 g• Duration: 60 minutes• Frequency: 20 Hz• Standard steel ball on AISI 52100 steel

[0071] Example 1 and the Comparative Examples 1 and 2 were tested for friction coefficient using a Mini Traction machine (MTM) test to evaluate the friction modification properties. The protocol employed was as follows:• Load: 20 NPCT PATENT APPLICATIONATTORNEY DOCKET NO. 364.1663PC• Sliding to rolling ratio: 50%• Frequency: 20 Hz

[0072] The friction coefficient was constantly monitored, and the reported value is the average over three regimes (boundary, mixed and EHD). The average wear scar was measured at the end of the test using optical microscopy, and the reported value is the average of the wear scar diameter on the ball along the horizontal and vertical directions. The results associated with the testing of Example 1 and the Comparative Examples 1 and 2 are reported in Table 1 below.Table 1. Average Friction Coefficient and Average Wear Scar Measured at 120 °C

[0073] The data in Table 1 indicates that Example 1 including the friction modifier exhibits better performance in terms of wear scar diameter compared to Comparative Examples 1 and 2 and friction modification compared to Comparative Example 2, which include industry standards and are free of the friction modifier.

[0074] The friction coefficients of Example 1 and Comparative Example 1, which are measured according to the procedure first described above, can further be visualized in Figures 1 and 2 which are collections of line plots of coefficient of friction versus entrainment speed at various temperatures categorized into regimes of boundary, mixed, and an elastohydrodynamic lubrication (EHD). Each line plot is also known in the art as a Stribeck curve.

[0075] When plotting the coefficient of friction (CoF) against entrainment speed (the average speed at which two surfaces move relative to one another), three distinct lubrication regimes are typically observed: boundary lubrication, mixed lubrication, and elastohydrodynamic (EHD) lubrication. These regimes describe the behavior of the lubricating film between the surfaces and how it influences friction.

[0076] In the boundary lubrication regime, the surfaces are in near or actual contact, with only a thin, molecular film of lubricant present. CoF is typically expected to be relatively high due to solid-to-solid contact between surface asperities (microscopic high points). Lubricant molecules tend to adhere to the surfaces and may form boundary layers, but these layers are too thin to fully separate the surfaces. Friction is dominated by the material properties of thePCT PATENT APPLICATIONATTORNEY DOCKET NO. 364.1663PC surfaces and the effectiveness of the boundary layer. This regime is typically observed at low entrainment speeds or during start-stop operations. The boundary regime generally occurs under high-load and low-speed conditions, e.g. bearings, gears, pumps, transmissions, etc., which can limit the durability of a mechanical component. Figure 1 shows that, in the boundary regimes measured at 40°C, 80°C, and 120°C, Example 1 exhibits approximately the same or a smaller friction coefficient than the Comparative Example 1, which can indicate a more efficient lubrication performance which may be beneficial in different applications, e.g. lubricant for electric vehicles, lubricant for diesel vehicles, etc. This is both superior and unexpected over what would otherwise be predicted by a person of skill in the art.

[0077] In the mixed lubrication regime, both hydrodynamic and boundary lubrication mechanisms are present. There is partial separation of the surfaces, but some asperities still make contact. As speed increases, a thicker lubricant film starts to form, but there is still some surface-to-surface contact. CoF is typically expected to decrease as the hydrodynamic effects begin to dominate and surface contact decreases. Friction is influenced by both the load-bearing capacity of the lubricant film and the remaining solid contacts. In this region, the CoF typically decreases rapidly as the entrainment speed increases, showing a transition from boundary to hydrodynamic lubrication. Again, Figure 1 shows that, in the mixed regimes measured at 40°C, 80°C, and 120°C, Example 1 exhibits smaller friction coefficients than the Comparative Example 1. This again is both superior and unexpected over what would otherwise be predicted by a person of skill in the art.

[0078] In the EHD lubrication regime, a full lubricant film separates the surfaces, preventing direct contact between asperities. The lubricant film is thick enough to support the load, and the surfaces are deformed elastically under pressure. CoF tends to be very low, as surface interaction is eliminated and friction is now primarily due to the viscous shear of the lubricant film. The lubricant is pressurized and the film thickness is sufficient to fully separate the surfaces. This regime occurs at high entrainment speeds and under high loads. The surfaces may elastically deform under the high pressure generated in the contact area, which influences the film thickness. Here, the CoF typically stabilizes and remains low as speed continues to increase, indicating effective separation of the surfaces by the lubricant film. Yet again, Figure 1 shows that, in the mixed regimes measured at 40°C, 80°C, and 120°C, Example 1 exhibits smaller friction coefficients than the Comparative Example 1. This again is both superior andPCT PATENT APPLICATIONATTORNEY DOCKET NO. 364.1663PC unexpected over what would otherwise be predicted by a person of skill in the art. Figure 2 shows the same results as Figure 1 but presented in a visually different manner.

[0079] Overall, the data above show the capability of the friction modifier to significantly improve the wear prevention capability of lubricant compositions while concurrently markedly reducing the coefficient of friction of these compositions. These results are superior to what is known in the art because the results show that these compositions outperform the combined friction and wear performance of lubricant compositions including industry standards, e.g. MoDTC.

[0080] While at least one exemplary embodiment has been presented in the foregoing detailed description, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing an exemplary embodiment. It being understood that various changes may be made in the function and arrangement of elements described in an exemplary embodiment without departing from the scope as set forth in the appended claims.

Claims

PCT PATENT APPLICATIONATTORNEY DOCKET NO. 364.1663PCCLAIMSWhat is claimed is:

1. A lubricant composition that is ashless and that comprises:A. an oil of lubricating viscosity; andB. about 0.05 to about 3 wt% actives based on a total weight of the composition of a friction modifier that is the reaction product of:(1) a C10-C24 fatty acid; and(2) a triamine.

2. The composition of claim 1 wherein the reaction product is an imidazoline.

3. The composition of claim 1 or 2 wherein the triamine has the structure (I)wherein each of x and y is independently about 1 to about 64. The composition of any preceding claim wherein the triamine is diethylene triamine.

5. The composition of any preceding claim wherein the C10-C24 fatty acid is tall oil fatty acid.

6. The composition of any preceding claim wherein the C10-C24 fatty acid is soy fatty acid.

7. The composition of any preceding claim wherein the C10-C24 fatty acid is chosen from flaxseed oil fatty acid; sunflower oil fatty acid; corn oil fatty acid; cottonseed oil fatty acid; rapeseed oil fatty acid; safflower oil fatty acid; olive oil fatty acid; and combinations thereof.PCT PATENT APPLICATIONATTORNEY DOCKET NO. 364.1663PC8. The composition of claim 1 wherein the imidazoline has the structure (II):wherein R is a C16-C18 alkyl chain.

9. The composition of any preceding claim that has a cyclic content of at least about 60% as determined using IR spectroscopy.

10. The composition of any preceding claim wherein the friction modifier has a Total Base Number of greater than about 290 mg KOH / g.

11. The lubricant composition of any preceding claim wherein the friction modifier has a weight average molecular weight (Mw) of from about 300 Da to about 700 Da.

12. The lubricant composition of any preceding claim wherein the friction modifier is present in an amount of from about 0.1 to about 1 wt% actives, based on a total weight of the lubricant composition.

13. The lubricant composition of any preceding claim wherein the fatty acid and the triamine are reacted at a molar ratio of from about 0.8:1 to about 0.9:1.

14. The lubricant composition of any preceding claims exhibiting a coefficient of friction that is at least 60% less than that of a comparative composition that comprises molybdenum dithiocarbamate in a comparative amount to the friction modifier but is free of the friction modifier, as determined using a Mini Traction machine test conducted at a sliding to rolling ratio of about 50%, a load of about 20 N, and at a temperature of about 120 °C.PCT PATENT APPLICATIONATTORNEY DOCKET NO. 364.1663PC15. The lubricant composition of any preceding claims exhibiting an average wear scar diameter that is at least 12% less than that of a comparative composition that comprises molybdenum dithiocarbamate in a comparative amount to the friction modifier but is free of the friction modifier, as determined using High-Frequency Reciprocating Rig screening conducted at a temperature of about 120 °C, a frequency of about 20 Hz, and a load of about 1000g.

16. A lubricant composition that is ashless and that comprises:A. a Group III base oil; andB. about 0.05 to about 3 wt% actives of a friction modifier that has the following structure (II):wherein R is a Ci6-Cis alkyl chain. wherein the composition exhibits a coefficient of friction that is at least 60% less than that of a comparative composition that comprises molybdenum dithiocarbamate in a comparative amount to the friction modifier but is free of the friction modifier, as determined using a Mini Traction machine test conducted at a sliding to rolling ratio of about 50%, a load of about 20 N, and at a temperature of about 120 °C; and wherein the composition exhibits an average wear scar diameter that is at least about 15% less than that of a comparative composition that comprises molybdenum dithiocarbamate in a comparative amount to the friction modifier but is free of the friction modifier, as determined using High-Frequency Reciprocating Rig screening conducted at a temperature of about 120 °C, a frequency of about 20 Hz, and a load of about 1000g.

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