Lubricant composition including a phosphate ester amine salt

Abstract

A lubricant composition is ashless, metal free, and sulfur free and includes an oil of lubricating viscosity and about 0.05 to about 3 wt % actives of a phosphate ester amine salt based on a total weight of the composition. The phosphate ester amine salt is the reaction product of a particular phosphate ester and a particular amine.

Description

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This is a U.S. National-Stage entry under 35 U.S.C. § 371 based on International Application No. PCT / EP2024 / 060452, filed Apr. 17, 2024, which was published under PCT Article 21(2) and which claims the benefit of U.S. Provisional Application No. 63 / 496,738, filed Apr. 18, 2023, which are hereby expressly incorporated herein by reference in their entireties.TECHNICAL FIELD

[0002] The present disclosure generally relates to lubricant compositions that include phosphate ester amine salts. More specifically, the phosphate ester amine salts include naturally derived C8-C18 groups, e.g. cocoyl and tallowyl groups.BACKGROUND

[0003] Amine neutralized phosphate esters are a type of lubricant additive that combines the properties of both phosphate esters and amine salts. They are known to be produced by reacting a phosphate ester with an amine, such as an alkanolamine or an alkyleneamine, to form an amine salt. The resulting amine neutralized phosphate ester combines the anti-wear and anti-oxidant properties of phosphate esters with the friction reduction, detergency and dispersancy properties of amine salts. This can provide enhanced performance in a variety of lubricant applications, particularly in high-temperature, high-load applications where conventional anti-wear additives may not be effective.

[0004] Amine neutralized phosphate esters are typically used in lubricants for gearboxes, hydraulic systems, and other heavy-duty industrial applications. They can help to reduce friction, prevent wear, and protect against rust and corrosion. They can also help to prevent the formation of deposits and sludge, which can improve the overall performance and lifespan of the lubricant. In addition to their lubricant properties, amine neutralized phosphate esters can also act as emulsifiers, allowing them to be used in applications where water contamination may be a concern, such as in marine or off-shore equipment.

[0005] Overall, amine neutralized phosphate esters offer a unique combination of properties that can provide enhanced performance in a variety of lubricant applications. Nevertheless, there remains a need for a significant reduction in friction with concurrent reduction in wear. This enables improvement in the energy efficiency of many mechanical systems, while simultaneously extending the lifetime of mechanical equipment. Ideally, this should be achieved with a low ash content, low phosphor content, and low content of metal containing lubricant additives. All three of these aspects are environmentally important and are needed in modern lubricants but not yet available as properties of a single additive which also provide concurrent friction and wear reduction performance benefits. Therefore, there remains an opportunity to develop improved lubricant compositions having the properties described above. Furthermore, other desirable features and characteristics of the present disclosure will become apparent from the subsequent detailed description of the disclosure and the appended claims, taken in conjunction with the accompanying drawings and this background of the disclosure.BRIEF SUMMARY

[0006] This disclosure provides a lubricant composition that is ashless, metal free, and sulfur free and that comprises:

[0007] (1) an oil of lubricating viscosity; and

[0008] (2) about 0.05 to about 3 wt % actives of a phosphate ester amine salt based on a total weight of the composition, wherein the phosphate ester amine salt is the reaction product of:

[0009] a phosphate ester; and

[0010] an amine;

[0011] wherein the phosphate ester has the following structure (I)whereinR′ has the formula R—O—[(CH2CH2O)m(CH2CH2CH2O)n];R is a naturally derived C8-C18 group;

[0015] m+n is from 3 to 15; and

[0016] R″ is H or independently a second R′;

[0017] wherein the amine has the following structure (II)whereinat least two of R1, R2, and R3 are independently a naturally derived C8-C18 group and R2 is optionally H; orat least one of R1, R2, and R3 is independently a naturally derived C8-C18 group and one or two of R1, R2, and R3 is CH3 or 2-ethylhexyl, or

[0021] R1 a naturally derived C8-C18 group and R3 is H or CH3 or (CH2CH2O)xH, wherein x is from 1 to 3 and R2 is CH2CH2CH2NR42 wherein R4 is H or CH3 or (CH2CH2O)yH, wherein y is from 1 to 3; or

[0022] R1 is a naturally derived C8-C18 group and each of R2 and R3 is (CH2CH2O)xH, wherein x is from 1 to 3.

[0023] In various embodiments, the compositions of this disclosure provide exhibit excellent wear performance, provide good wear protection at comparatively low treat rates, exhibit good oil solubility (e.g. high carbon content), have comparatively low phosphorous content as compared to comparative compositions, exhibit both good wear performance and low friction coefficients simultaneously, have customizable TBN values, detergency properties, and friction modification properties, and can include phosphate ester amine salts that have comparatively low conductivity properties. Combinations of these attributes allow for the formation of excellent engine oils, hydraulic fluids, transmission oils, EV fluids, greases, etc. Moreover, via selection of various amines and phosphate esters of this disclosure, compositions are formed that are ashless, halogen-, sulphur- and metal-free (which can be important 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 sulfur, and optionally include or exclude, for example, ZDDP (industry standard) and / or MoDTC (molybdenum containing friction modifier) and / or DTC (dithiocarbamate), that exhibit excellent wear performance at comparatively low treat rates, that exhibit low P-content which allows for use in engine oil applications, that exhibit both low friction coefficients 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), and that have multifunctionality e.g. relative to AW and TBN boosting / detergency boosting / corrosion inhibition.BRIEF DESCRIPTION OF THE DRAWINGS

[0024] The present disclosure will hereinafter be described in conjunction with the following drawing figures, wherein

[0025] The FIGURE is a plot of coefficient of friction versus wear scar diameter showing the superior combined coefficient of friction and wear prevention performance of various embodiments of this disclosure as described in the Examples.DETAILED DESCRIPTION

[0026] The following detailed description is merely exemplary in nature and is not intended to limit the current lubricant composition. Furthermore, there is no intention to be bound by any theory presented in the preceding background or the following detailed description. Moreover, it is contemplated that, in various non-limiting 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.

[0027] Embodiments of the present disclosure are generally directed to lubricant compositions and methods for forming the same. For the sake of brevity, conventional techniques related to lubricant 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 lubricant compositions are well-known and so, in the interest of brevity, many conventional steps will only be mentioned briefly herein or will be omitted entirely without providing the well-known process details.

[0028] 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 non-limiting 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.

[0029] 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.

[0030] 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. 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.

[0031] 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 polymers, surfactants, additives, solvents, etc.

[0032] It is to be understood that the subscripts of polymers or various groups described herein are typically described as average values because the synthesis of polymers typically produces a distribution of various individual molecules. Therefore, the subscripts may be ranges of values, decimal values, or ranges of decimal values.Lubricant Composition

[0033] This disclosure provides a lubricant composition which may be described herein as the “lubricating composition” or the “composition.” The composition is typically ashless, metal free, and sulfur free. However, these are not strictly independent requirements that must each be met in all circumstances, as will be understood. Moreover, it is contemplated that not all embodiments are ashless and may include some ash content. Having ashless components allow for the preparation of low ash containing lubricants that still provide effective lubrications benefits.

[0034] The terminology “ashless” describes that the composition does not include metallic additives or other materials that leave behind a residue, known as “ash,” when burned. Alternatively, ashless may describe that the composition includes less than 5, 4, 3, 2, 1, 0.5, 0.1, 0.05, or 0.01, weight percent of a metallic additive or other material that would leave behind a residue when burned, based on a total weight of the composition. Similarly, the composition can be metal free. Typically, this means that the composition is free of any metals. Similarly, the term “metal free” may be used to describe that the composition is substantially free from metals. However, it is contemplated that the terminology “metal free” may describe embodiments that the composition includes less than 5, 4, 3, 2, 1, 0.5, 0.1, 0.05, or 0.01, weight percent of a metal, 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.

[0035] In various embodiments, the composition includes an oil of lubricating viscosity and a phosphate amine ester salt. In other embodiments, the composition consists essentially of the oil and the phosphate amine ester salt. In other embodiments, the composition consists of the oil and the phosphate amine ester salt.Oil of Lubricating Viscosity

[0036] 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” or “base oil” or simply “oil” herein. 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) and 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.

[0037] In various embodiments, the oil is a Group III base stock as defined in the American Petroleum Institute (API) publication “Engine Oil Licensing and Certification System”, Industry Services Department, Fourteenth Edition, December 1996, Addendum 1, December 1998. For example, the Group III base stock typically has a viscosity of about 3 to about 12, about 4 to about 10, or about 4.5 to about 8, mm2 / s (cSt) at 100° C. 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. One of skill in the art will understand that these values and ranges exemplify a “lubricating viscosity” as used herein, while also understanding that viscosities outside the ranges may also be used in selecting the oil.

[0038] In various embodiments, the oil may be as described in the American Petroleum Institute (API) publication “Engine Oil Licensing and Certification System”, Industry Services Department, Fourteenth Edition, December 1996, Addendum 1, December 1998. For example, the oil may be a Group I base stock that includes less than about 90 percent saturates and / or greater than about 0.03 percent sulphur and has a viscosity index greater than or equal to 80 and less than 120 using the test methods specified in Table E-1.

[0039] Alternatively, the oil may be a Group II base stock that includes greater than or equal to about 90 percent saturates and less than or equal to about 0.03 percent sulphur and has a viscosity index greater than or equal to 80 and less than 120 using the test methods specified in Table E-1. Alternatively, the oil may be a Group III base stock that includes greater than or equal to about 90 percent saturates and less than or equal to about 0.03 percent sulphur and has a viscosity index greater than or equal to 120 using the test methods specified in Table E-1. Alternatively, the oil may be a Group IV base stock such as an polyalphaolefins (PAO). Alternatively, the oil may be a Group V base stock that includes all other base stocks not included in Group I, II, III, or IV. In the aforementioned descriptions, saturates may be determined using ASTM D 2007, viscosity index may be determined using ASTM D 2270, sulphur may be determined using ASTM D 2622, ASTM D 4294, ASTM D 4927, ASTM D 3120, or combinations thereof.

[0040] In various embodiments, the oil includes greater than or equal to about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95, mass %, of a Group III base stock, based on the total mass of the oil itself. In other embodiments, the oil consists of, or consists essentially of, a Group III base stock. Additives included in the oil may comprise a carrier oil which is not a Group III base stock. 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] 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.

[0042] 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(1-hexenes), poly(1-octenes), poly(1-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.

[0043] 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, 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 mono-alcohols e.g. methanol, ethanol, etc. Methyl esters often have low viscosities. These mono-esters can also be based on alkoxylated alcohols wherein alkoxylate groups are ethylene oxide and / or propylene oxide. Other examples include polyalkylene glycol (PAG) based base stocks. These polyalkylene glycols can be used as is or etherified by reaction with alcohols or esterified by reaction with carboxylic acids, particularly mono-acids.

[0044] 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.

[0045] In other embodiments, the oil is or includes a gas-to-liquid (“GTL”) base 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 a base oil. For example, they may, by methods known in the art, be hydroisomerized; hydrocracked and hydroisomerized; dewaxed; or hydroisomerized and dewaxed.

[0046] In other embodiments, the oil is or includes a Group I, Group II, Group IV or Group V base stocks or base oil blends of the aforementioned base stocks.

[0047] In other embodiments, the volatility of the oil, as measured by the NOACK test (ASTM D5880), is less than or equal to 16%, 13.5%, 12%, 10%, or 8%. Typically, the viscosity index (VI) of the oil is at least 95, 110, 120, or 125, or from about 130 to 140. 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 oil is present in an amount of greater than 55, 60, 65, 70, 75, 80, 85, or 90, mass %, based on the total mass of the composition. In other embodiments, the oil is present in an amount of less than about 99, 98, 97, 96, 95, 94, 93, 92, 91, or 90, mass %, based on the total mass of the composition. In still other embodiments, the oil may be present in an amount to balance the amount of the phosphate ester amine salt (e.g. as described below), such that the total is about 100%. Alternatively, the amount of the oil may be such that the amount of the oil, plus the amount of the phosphate ester amine salt, plus the amount of any one or more additives described herein, is about 100%. 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.Phosphate Ester Amine Salt

[0049] The composition also includes the phosphate ester amine salt. The composition may be alternatively described as a physical mixture of the oil and the phosphate ester amine salt and any optional additives, e.g. those described herein.

[0050] Typically, the phosphate ester amine salt is present in the composition in an amount of from about 0.05 to about 3, about 0.1 to about 3, about 0.5 to about 2.5, about 1 to about 2, about 1.5 to about 2, about 1 to about 1.5, about 0.5 to about 1, about 0.5 to about 1.5, about 0.5 to about 2, about 0.1 to about 1.5, about 0.2 to about 1.4, about 0.3 to about 1.3, about 0.4 to about 1.2, about 0.5 to about 1.1, about 0.6 to about 1, about 0.7 to about 0.9, or about 0.8 to about 0.9, 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.

[0051] The phosphate ester amine salt is the reaction product of a phosphate ester and an amine, each of which is described in greater detail below. It is contemplated that a single phosphate ester or more than one phosphate ester may be utilized. Similarly, a single amine or more than one amine may be utilized. Typically, a combination of phosphate esters are utilized.Phosphate Ester

[0052] The phosphate ester typically has the following structure (I)In this structure, R′ has the formula R—O—[(CH2CH2O)m(CH2CH2CH2O)n]. Moreover, R″ is H or independently a second R′. If R″ is H, then the phosphate ester is a phosphate monoester. If R″ is independently a second R′, then the phosphate ester is a phosphate diester. Typically, a mixture of monoesters and diesters are used.Referring back to R′ in Formula (I), R is a naturally derived C8-C18 group. The terminology “naturally derived” means that the group is not a synthetic group and is derived from a natural source such as a plant or animal source, e.g. from animal fat. Therefore, it is contemplated that the C8-C18 group may be alternatively described as a naturally sourced group or as a group derived from a natural source. Alternatively, the group may be described as a plant based group or as an animal fat based group.

[0054] The naturally derived C8-C18 group may be linear or branched having 8 to 18 carbon atoms so long as it is naturally derived. The group may be saturated or unsaturated or partially unsaturated. In various embodiments, the group has 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms. In other embodiments, the group has 8 to 18, 9 to 17, 10 to 16, 11 to 15, 12 to 14, 10 to 18, 12 to 18, 14 to 18, 16 to 18, 12 to 18, 12 to 16, or 14 to 16 carbon atoms. Non-limiting examples of naturally derived C8-C18 groups include tallowyl groups, oleyl groups, cocoyl groups, etc. The terminology “naturally derived”, which is consistent with the description above, typically means that the C8-C18 groups are derived from suitable fatty acids and alcohols obtained from natural sources such as, for instance, plant or animal esters (e.g. palm oil, rape seed oil, palm kernel oil, coconut oil, babassu oil, soybean oil, castor oil, tallow, tall oil, whale or fish oils, grease, lard, and mixtures thereof). Accordingly, suitable C8-C18 groups include cocoyl, oleyl, tallowyl, tallyl, soyayl, rapeseedyl, palmyl groups and the like. In other embodiments, the naturally derived C8-C18 group is chosen from groups such as C8—Caprylic, C10—Capric, C12—Lauric, C14—Myristic, C15—Pentadecylic, C16—Palmitic, C17—Margaric, C18—Stearic, C14—Myristoleic, C16′—Palmitoleic, C18′—Oleic, C18″—Linoleic, and combinations thereof. Any one or more of these may be utilized herein.

[0055] For example, a tallowyl group can be described as a C16-C18 group since about 95 mol % of its carbon chains fall within this range, whereas a cocoyl group includes a mixture of C8-C18 chains wherein about 70 mol % are C12-C14 chains. Therefore, it is contemplated that any one or more naturally derived C8-C18 groups may include a distribution of compounds of varying chain lengths, as is understood by the skilled person. It is to be understood that anywhere “coco” and / or “tallow” is used herein, it is contemplated that such a group may alternatively be an oleyl group or any other naturally derived C8-C18 group in other embodiments. 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 this disclosure, terminology such as cocoyl, oleyl, and tallowyl groups are used. This terminology may describe groups or chains. Moreover, the terminology could alternatively describe coco, oleic, and tallow groups or chains wherein, for example, cocoyl refers to a hydrocarbyl chain that was obtained from coconut oil whereas the terminology coco is generally used in the art to relate to the source of the material, e.g. an oil or an acid or an alcohol.

[0057] Also referring back, the subscripts m and n describe an average number of ethylene oxide and propylene oxide units / moles, respectively. Typically, m+n is from 3 to 15, 4 to 14, 5 to 13, 6 to 12, 7 to 11, 8 to 10, or 9 to 10. Alternatively, m+n may be 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15. In various embodiments, m itself is any one of the values above such that n may be zero. In other embodiments, n itself is any one of the values above such that m may be zero. In various embodiments, m is from 3 to 8, 3 to 7, 3 to 6, 3 to 5, or 3 to 4, and n may be zero or any value above. In other embodiments, n is from 3 to 8, 3 to 7, 3 to 6, 3 to 5, or 3 to 4, and m may be zero or any value above. 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] In various embodiments, the phosphate ester includes or is a mixture or combination of phosphate monoester and a phosphate diester wherein the phosphate monoester has the following structure (Ia) and the phosphate diester has the following structure (Ib)wherein each substituent may be as described above. For example, in one embodiment, each R′ has the formula R—O—[(CH2CH2O)m], R is a tallow or cocoyl group, and m is from 3 to 6.In other embodiments, the phosphate ester can be formed using a vegetable based C16-C18 and / or C18-unsaturated alcohol, e.g. a palm oil derivative. In other embodiments, an oleic chain e.g. an 9Z)-9-octadecen-1-yl chain can be utilized.

[0060] In various embodiments, the phosphate ester comprises a mixture of a phosphate monoester and a phosphate diester such that the monoester is present in a mole ratio of greater than 1:1 to the diester. In other words, the phosphate monoester is present in a number of moles that is greater than the number of moles of the phosphate diester. Alternatively, this ratio is of from about 0.6:1 to about 20:1 such that the phosphate monoester may be present in an amount less than, equal to, or more than the phosphate diester. 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. It is contemplated that each of the aforementioned ratios need not be limited to the particular chemistry set forth above and may be used in other embodiments with different R group chemistry.

[0061] In one embodiment, at least one R of the phosphate ester is a C16-C18 group. In another embodiment, at least one R of the phosphate ester is a cocoyl group or an oleyl group or a tallowyl group. In another embodiment, m+n is 3 to 6. In another embodiment, m is 3 to 6 and n is zero. Alternatively, n is 3 to 6 and m is zero.Amine

[0062] Referring back to the amine, the amine has the following structure (II)

[0063] Typically, the amine is either a secondary or a tertiary amine, depending on substituents. In various embodiments, the amine may be alternatively described as a secondary amine, a tertiary amine, a di-amine or as an ethoxylated amine. For example, each of (or at least one of) R1, R2, and R3 may be independently a naturally derived C8-C18 group. Alternatively, each of R1 and R3 may be independently a naturally derived C8-C18 group and R2 may be H. Alternatively, each of R1 and R3 may be independently a naturally derived C8-C18 group and R2 may be CH2CH2CH2NH2. Alternatively, R1 may be a naturally derived C8-C18 group and each of R2 and R3 may be (CH2CH2O)xH, wherein x is from 1 to 3. In still other embodiments, the amine may be described as an unsymmetric amine and / or a functionalized amine.

[0064] In various embodiments, the amine can be described as follows wherein:

[0065] at least two of R1, R2, and R3 are independently a naturally derived C8-C18 group and R2 is optionally H; or

[0066] at least one of R1, R2, and R3 is independently a naturally derived C8-C18 group and one or two of R1, R2, and R3 is CH3 or 2-ethylhexyl, or

[0067] R1 a naturally derived C8-C18 group and R3 is H or CH3 or (CH2CH2O)xH, wherein x is from 1 to 3 and R2 is CH2CH2CH2NR42 wherein R4 is H or CH3 or (CH2CH2O)yH, wherein y is from 1 to 3; or

[0068] R1 is a naturally derived C8-C18 group and each of R2 and R3 is (CH2CH2O)xH, wherein x is from 1 to 3.Tertiary Amine

[0069] In various embodiments, each of R1, R2, and R3 is independently a naturally derived C8-C18 group. This group may be any of those described above. In one embodiment, each of (or one or more of) R1, R2, and R3 is a C16-C18 group. In another embodiment, at least one of (or one or more of) R1, R2, and R3 is an cocoyl group or a tallowyl group. Alternatively, one or more may be cocoyl, one or more may be tallowyl, or one two may be tallowyl and the other cocoyl or one or two may be cocoyl and the other tallowyl. Alternatively, all may be tallowyl or all may be cocoyl.

[0070] In other embodiments, at least two of R1, R2, and R3 are independently a naturally derived C8-C18 group and R2 is optionally H. Relative to a tertiary amine, R2 is not H and may be any group described above or herein.

[0071] In various embodiments, the amine is chosen from dimethyl cocoamine (C8-C18N(CH3)2), methyl di-cocoamine ((C8-C18)2NCH3), and combinations thereof. In one embodiment, the amine is dimethyl cocoamine (C8-C18N(CH3)2). In another embodiment, the amine is methyl di-cocoamine ((C8-C18)2NCH3).

[0072] In another embodiment, at least one of R1, R2, and R3 is independently a naturally derived C8-C18 group and one or two of R1, R2, and R3 is 2-ethylhexyl. In another embodiment, the amine is 2-ethylhexyl(tallowyl)methylamine wherein R1 is the naturally derived C8-C18 group, R2 is CH3, and R3 is 2-ethylhexyl.Secondary Amine

[0073] In other embodiments, each of R1 and R3 is independently a naturally derived C8-C18 group, which may be any as described above, and R2 is H. In one embodiment, each of R1 and R3 is a C16-C18 group. In another embodiment, at least one of R1 and R3 is an cocoyl group or a tallowyl group. Alternatively, one or both may be cocoyl, one or both may be tallowyl, or one may be tallowyl and the other cocoyl.

[0074] In other embodiments, at least two of R1, R2, and R3 are independently a naturally derived C8-C18 group and R2 is optionally H. Relative to a secondary amine, R2 is H.Di-Amine

[0075] In still other embodiments, each of R1 and R3 is independently a naturally derived C8-C18 group, which may be any as described above, and R2 is CH2CH2CH2NH2. In one embodiment, each of R1 and R3 is a C16-C18 group. In another embodiment, at least one of R1 and R3 is an cocoyl group or a tallowyl group. Alternatively, one or both may be cocoyl, one or both may be tallowyl, or one may be tallowyl and the other cocoyl.Ethoxylated Amine

[0076] In other embodiments, R1 is a naturally derived C8-C18 group, which may be any as described above, and each of R2 and R3 is (CH2CH2O)xH, wherein x is from 1 to 3. Alternatively, x may be 1, 2, or 3 or may be 1 to 2 or 2 to 3. In one embodiment, R1 is a C16-C18 group. In another embodiment, R1 is an cocoyl group or a tallowyl group.Additional Amines

[0077] In various embodiments, at least one of R1, R2, and R3 is independently a naturally derived C8-C18 group and one or two of R1, R2, and R3 is CH3 or 2-ethylhexyl. Any one or more of the aforementioned naturally derived groups may be utilized. In various embodiments, one of R1, R2, and R3 is CH3 and the other two of R1, R2, and R3 is the naturally derived C8-C18 group. In other embodiments, two of R1, R2, and R3 is CH3 and the other one of R1, R2, and R3 is the naturally derived C8-C18 group.

[0078] In other embodiments, R1 is a naturally derived C8-C18 group and R3 is H or CH3 or (CH2CH2O)xH, wherein x is from 1 to 3 and R2 is CH2CH2CH2NR42 wherein R4 is H or CH3 or (CH2CH2O)yH, wherein y is from 1 to 3.

[0079] In one embodiment, R1 is a naturally derived C8-C18 group and R3 is H.

[0080] In another embodiment, R1 is a naturally derived C8-C18 group and R3 is CH3.

[0081] In another embodiment, R1 is a naturally derived C8-C18 group and R3 (CH2CH2O)xH, wherein x is from 1 to 3, e.g. 1, 2, or 3 or any range thereof.

[0082] In other embodiments, R2 is CH2CH2CH2NR42 wherein R4 is H.

[0083] Alternatively, R2 is CH3.

[0084] Alternatively, R2 is (CH2CH2O)yH, wherein y is from 1 to 3, e.g. 1, 2, or 3 or any range thereof.

[0085] In still other embodiments, R1 is a naturally derived C8-C18 group and each of R2 and R3 is (CH2CH2O)xH, wherein x is from 1 to 3, e.g. 1, 2, or 3 or any range thereof.

[0086] In still other embodiments, one of R1, R2, and R3 is a naturally derived C12-C14 group and another of R1, R2, and R3 is a naturally derived C16-C18 group.

[0087] Alternatively, at least one of R1, R2, and R3 is a cocoyl group or a tallowyl group.

[0088] Alternatively, each of R1 and R3 is independently a cocoyl group or a tallowyl group and R2 is H.

[0089] Alternatively, the amine is chosen from: N-tallow-1,3-diaminopropane (C8-C18N(H)(CH2CH2CH2NH2), N.N.N′-trimethyl-N′-tallow-1,3-diaminopropane (C8-C18N(CH3)(CH2CH2CH2N(CH3)2, tris(2-hydroxyethyl)-N-tallowalkyl-1,3-diaminopropane ((C8-C18N(CH2CH2OH) (CH2CH2CH2N(CH2CH2OH)2); and combinations thereof.

[0090] Alternatively, the amine is N.N.N′-trimethyl-N′-tallow-1,3-diaminopropane (C8-C18N(CH3)(CH2CH2CH2N(CH3)2.

[0091] Alternatively, the amine is tris(2-hydroxyethyl)-N-tallowalkyl-1,3-diaminopropane ((C5-C18N(CH2CH2OH)(CH2CH2CH2N (CH2CH2OH)2).

[0092] Alternatively, R1 is a cocoyl group or a tallowyl group and each of R2 and R3 is (CH2CH2O)x, wherein x is from 1 to 3.

[0093] Alternatively, R1 is a naturally derived C8-C18 group and R3 is H.

[0094] Alternatively, R1 is a naturally derived C8-C18 group and R3 is CH3.

[0095] Alternatively, R1 is a naturally derived C8-C18 group and R3 is (CH2CH2O)xH, wherein x is from 1 to 3.

[0096] Alternatively, R2 is CH2CH2CH2NR42 wherein R4 is H.

[0097] Alternatively, R2 is CH2CH2CH2NR42, wherein R4 is CH3

[0098] Alternatively, R2 is CH2CH2CH2NR42, wherein R4 is (CH2CH2O)yH, wherein y is from 1 to 3.

[0099] Alternatively, R1 is a cocoyl group or a tallowyl group.

[0100] Alternatively, at least one of R1, R2, and R3 is independently a naturally derived C8-C18 group and one or two of R1, R2, and R3 is 2-ethylhexyl. For example, the amine may be 2-ethylhexyl(tallowyl)methylamine.

[0101] It is also contemplated that any one or more of the aforementioned embodiments may be combined together relative to one or more of R1, R2, and R3 independently.

[0102] It is contemplated that other amines may be used, for example, fatty esters of triethanolamine. A non-limiting example of such an ester compound is fatty acids, tallow, compounded with triethanolamine, e.g. a mixture of tallow esters of triethanol amine (i.e. mono-, di- and triesters). This can also be described as mono-, di- and triesters of a tertiary hydroxyl amine and a fatty acid.Additives

[0103] The composition may include, or be free of, one or more additives that is not the phosphate ester salt 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. In various embodiments, the composition includes from about 5 to about 25, about 5 to about 18, or about 7 to about 15, mass % of one or more additives. 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.

[0104] In various embodiments, the composition comprises phosphorus in varying amounts, e.g. up to 0.12, 0.11, 0.10, 0.09, 0.08, 0.07, 0.06, or 0.05 mass % of phosphorus, expressed as the proportion of the mass of atoms of phosphorus to the total mass of the composition. In other embodiments, the composition includes little to no sulfur, for example up to about 0.4, 0.3, 0.2, 0.1, 0.09, 0.08, 0.07, 0.06, or 0.05 mass % sulfur, expressed as the proportion of the mass of atoms of sulfur to the total mass of the composition. In various embodiments, the composition comprises sulphated ash in varying amounts, if at all, e.g. up to 0.12, 0.11, 0.10, 0.09, 0.08, 0.07, 0.06, or 0.05 mass % of sulphated ash based on the total mass of the composition. In various embodiments, the aforementioned values describe the phosphate amine itself or the phosphate amine in solution with a base stock. However, in many lubricant formulations the addition of other additives may cause the sulphate ash levels to be higher than the above values. 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.

[0105] In various embodiments, the composition includes an ashless dispersant in an amount of from about 0.1 to about 20, e.g. about 1 to about 8, mass %. In other embodiments, the composition includes a metal detergent in an amount of from about 0.1 to about 15, e.g. about 0.2 to about 9, mass %. In other embodiments, the composition includes a friction modifier in an amount of about 0.1 to about 5, e.g. about 0.1 to about 1.5, mass %. In other embodiments, the composition includes an antioxidant in an amount of from about 0.01 to about 5, e.g. about 0.01 to about 3, mass %. In other embodiments, the composition includes a pour point depressant in an amount of from about 0.01 to about 5, e.g. about 0.01 to about 1.5, mass %. In other embodiments, the composition includes an anti-foaming agent in an amount of from about 0.001 to about 5, e.g. about 0.001 to about 0.15, mass %. In other embodiments, the composition includes an antiwear agent in an amount of from about 0.01 to about 5, e.g. about 0.1 to about 2, mass %. In other embodiments, the composition includes a viscosity modifier in an amount of from about 0.01 to about 6, e.g. about 0.01 to about 4, mass %. 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.

[0106] In various embodiments, dispersants include, for example, derivatives of long chain hydrocarbon-substituted carboxylic acids, examples being derivatives of high molecular weight hydrocarbyl-substituted succinic acid. A noteworthy group of dispersants is constituted by hydrocarbon-substituted succinimides, made, for example, by reacting acids (or derivatives) with a nitrogen-containing compound, advantageously a polyalkylene polyamine, such as a polyethylene polyamine. Particularly typical are the reaction products of polyalkylene polyamines with alkenyl succinic anhydrides.

[0107] In other embodiments, the composition includes, or is free of, one or more anti-wear agents that is not the phosphate ester amine salt of this disclosure. For example, such anti-wear agents may include sulfur or phosphorous or both and may be capable of depositing polysulfide films on the surfaces involved. Noteworthy are dihydrocarbyl dithiophosphate metal salts wherein the metal may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper. In various embodiments, zinc dihydrocarbyl dithiophosphate metal salts may be prepared in accordance with known techniques by first forming a dihydrocarbyl dithiophosphoric acid (DDPA), usually by reaction of one or more alcohols or a phenol with P2S5 and then neutralizing the formed DDPA with a metal compound. For example, a dithiophosphoric acid may be made by reacting mixtures of primary and secondary alcohols. Alternatively, multiple dithiophosphoric acids can be prepared where the hydrocarbyl groups on one are entirely secondary in character and the hydrocarbyl groups on the others are entirely primary in character. To make the metal salt, any basic or neutral metal compound could be used but the oxides, hydroxides and carbonates are most generally employed. Commercial additives frequently include an excess of metal due to the use of an excess of the basic metal compound in the neutralization reaction. The typical dihydrocarbyl dithiophosphate metal salts are zinc dihydrocarbyl dithiophosphates (ZDDP) which are oil-soluble salts of dihydrocarbyl dithiophosphoric acids. In various embodiments, the zinc dihydrocarbyl dithiophosphate comprises a zinc dialkyl dithiophosphate. In various embodiments, the composition includes an amount of dihydrocarbyl dithiophosphate metal salt that introduces from zero to about 0.10 mass % of phosphorus into the composition. Typically, the composition is free of 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.Physical Properties

[0108] In various embodiments, the composition has a coefficient of friction as determined using ASTM D4172 that is at least about 20, 25, 30, 35, 40, 45, or greater, % less than that of a comparative composition that comprises zinc dialkyl dithiophosphate (ZDDP) in a comparative amount but is free of the phosphate ester amine salt. 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 phosphate ester amine salt 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 a content and type of base 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.

[0109] In various embodiments, the composition has a 4-ball wear preventative performance as determined using ASTM D4172 that has an average wear scar diameter that is at least about 10, 15, 20, 25, 30, 35, 40, 45, or greater % smaller than that of a comparative composition that comprises zinc dialkyl dithiophosphate (ZDDP) in a comparative amount, but is free of the phosphate ester amine salt. In other words, when the composition of this disclosure is compared to a comparative composition that includes ZDDP, the instant composition has 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 phosphate ester amine salt 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 a content and type of base 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.

[0110] The composition is not limited to any particular total base number (TBN). However, in various embodiments, the composition has a TBN 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, both whole and fractional, including and between those described above, are hereby expressly contemplated for use herein.

[0111] 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 0WX, 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 0WX, In various embodiments in the form of an SAE 5WX or SAE 0WX, 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.

[0112] The composition is not limited in its use and may be used to lubricate mechanical engine components, particularly in internal combustion engines, e.g. spark-ignited or compression-ignited two- or four-stroke reciprocating engines. The engines may be conventional gasoline or diesel engines designed to be powered by gasoline or petroleum diesel, respectively; alternatively, the engines may be specifically modified to be powered by an alcohol-based fuel or biodiesel fuel. In various embodiments, the composition is a crankcase lubricant.

[0113] In other embodiments, the composition is used in the lubrication of a compression-ignited internal combustion engine (diesel engine), especially a compression-ignited internal combustion engine which is fueled at least in part with a biodiesel fuel. Such engines include passenger car diesel engines and heavy duty diesel engines, for example engines found in road trucks. In various embodiments, the composition is used in the lubrication of a passenger car compression-ignited internal combustion engine (e.g. a light duty diesel engine), which is fueled at least in part with a biodiesel fuel, e.g. an engine which employs a late post-injection of fuel into the cylinder. In various embodiments, the composition is used in the lubrication of a crankcase of the aforementioned engines.Method of Forming the Composition

[0114] 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 phosphate ester amine salt, and combining the oil and the salt 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 salt, and / or with the combination of the oil and the salt, to form the composition. The method may include batch or continuous steps.Method of Forming the Phosphate Ester Amine Salt

[0115] The method of forming the phosphate ester amine salt 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 phosphate ester amine salt. Alternatively, the phosphate ester amine salt may be formed entirely independently from the method of forming the composition. In such an embodiment, the phosphate ester amine salt may be provided in an already formed state.

[0116] In various embodiments, the reaction to form the phosphate ester amine salt may generally proceed as follows wherein ultimate charge balance is understood by those of skill in the art:

[0117] Typically, the skilled person determines the base number (BN) of the amine and the acid number (AN) of the phosphate ester independently. For example, the amine can have two base numbers if it is a diamine. The same is true for the phosphate ester. For example, the phosphate monoester has a certain acid number while the phosphate diester has a different acid number. When forming the salt, the skilled person can neutralize about 95 mol % of the phosphate monoester with the amine based on the measured BN and AN values, wherein the extent of the reaction is determined potentiometrically. The skilled person may choose to not neutralize the phosphate diester because it is typically more difficult. Moreover, relative to the amine, the skilled person can choose to react one or both of the amine moieties with the phosphate monoester. Therefore, the terminology “salt” has a broad definition and neutralization can mean different things, each as understood by the skilled person. Relative to this disclosure, the terminology “phosphate ester amine salt” may include compounds generated by any one or more of the aforementioned methods, again as is understood by the skilled person. In various embodiments, the phosphate ester amine salt may be formed as described in WO 2018 / 017449, which is expressly incorporated herein by reference in its entirety in various non-limiting embodiments.EXAMPLES

[0118] The following examples, illustrating embodiments of this disclosure, are intended to illustrate and not to limit the scope of the embodiments described herein. Unless otherwise noted, all solvents, substrates, and reagents are purchased or otherwise obtained from various commercial suppliers and utilized as received (i.e., without further purification) or as in a form used conventionally in the art.General Procedure For Formation Of Salts

[0119] Various phosphate ester amine salts were synthesized using the same or similar procedure as described hereafter. A phosphatized naturally derived C16-C18 fatty alkoxylated alcohol, with ethylene oxide as the source of alkoxylation, having an average alkoxylation degree of 4, a pyrophosphate content less than 1%, mono to diester ratio in the range of 1-1.5, and a phosphorus content of 4.8% (referred to as ‘P1’ hereinafter), was used as a phosphate ester source. A 2-liter four-necked round-bottomed flask, equipped with an overhead stirrer (400 rpm), a thermometer, a nitrogen inlet, a distillation setup, and a dosing funnel, was charged with 727.63 grams of phosphate ester P1 (acid value 85.9 mg KOH / g, first equivalent point). The temperature of the reaction mixture was raised to 75° C., after which, under a stream of nitrogen, 0.95 equivalents (247.47 grams) of amine AM1 (amine value 4.276 mmole / g) was dosed over a period of 1 hour. During dosing, the temperature was kept between 75 and 80° C. Next, the temperature was brought to 100° C., and the mixture was allowed to react for an additional 4 hours. Under a reduced pressure of 100 mbar, for 1 hour, water from the phosphate ester was distilled off. The product was collected as an oil.

[0120] The procedure described above is common to all of the phosphate ester amine salts in the Examples below. Those skilled in the art will recognize that adjustments in stoichiometry, reaction time, and reaction temperature may be required to achieve the desired product(s) with varying starting materials. Various phosphate ester amine salts were synthesized using the same or similar procedures as described above, selecting components from the lists reported in Table 1 and Table 2 in the combinations reported in Table 3.TABLE 1PhosphateEstersP1Phosphatized naturally derived C16-C18fatty alkoxylated alcohol, sourceof alkoxylation is ethylene oxide,with average alkoxylation degree of 4,with a pyrophosphate content less than 1%, monoto diester ratio in the range of 1-1.5,and a phosphorous content of 4.8%P2Phosphatized naturally derived C16-C18fatty alkoxylated alcohol, sourceof alkoxylation is ethylene oxide,with average alkoxylation degree of 4,with a pyrophosphate content from 25% to 35%,mono to diester ratio in the range of0.5-1, and a phosphorous content of 5.6%P3Phosphatized naturally derived C16-C18fatty alkoxylated alcohol, source ofalkoxylation is propylene oxide, with averagealkoxylation degree of 4, with a pyrophosphatecontent less than 1%, mono to diester ratioin the range of 1-1.5, and aphosphorous content of 4.7%TABLE 2AmineAM1CocoalkyldimetylamineAM2DicocoamineAM3Bis (2-hydroxyethyl) Tallow AlkylamineAM4OleyldimethylamineAM5Tris (2-hydroxyethyl) N-tallow AlkyldiaminopropaneAM6DicocomethylamineAM72-Ethylhexyl(tallow)methylamineAM8Bis (2-hydroxyethyl) Oleyl AmineAM9OleyldimethylamineTABLE 3ExamplePhosphateAmineEx1P1AM1Ex2P1AM2Ex3P1AM3Ex4P1AM4Ex5P1AM5Ex6P1AM6Ex7P1AM7Ex8P1AM8Ex9P1AM10Ex10P2AM2Ex11P2AM3Ex12P2AM4Ex13P3AM2Ex14P3AM3Ex15P3AM4Evaluation of Physical Properties of Lubricant CompositionsThe resulting phosphate ester amine salts were then added at a treat rate of 0.5% w / w to a base oil selected from Group II, Group III, and Group IV base stocks. The antiwear and friction-reducing performances were benchmarked against a commercial amine phosphate derived from C11-C14 branched alkylamines and mono- of dihexyl phosphates, with a phosphorus content of 4.8% (referred to as ‘AP’ hereinafter), and a primary zinc dialkyldithiophosphate with a phosphorus content of 9.5% (referred to as ‘ZDDP’ hereinafter).The prepared lubricant compositions were tested for antiwear properties using a High Frequency Reciprocating Rig (HFRR) to evaluate the anti-wear properties of fluid lubricants under reciprocating contact conditions. The protocol employed was as follows:Load: 1000 g

[0124] Duration: 60 minutes

[0125] Frequency: 20 Hz

[0126] Temperature: Isothermal at 120° C.

[0127] Standard steel ball on AISI 52100 steel

[0128] Friction was constantly monitored, and the reported value is the average over the duration of the experiment. Wear 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.

[0129] The results in group II base oil are reported in Table 4 and shown in the FIGURE hereinafter. The data indicates that the prepared phosphate ester salts exhibit better performance in terms of wear scar diameter compared to the commercial amine phosphate and the primary ZDDP, as well as a better friction level in selected examples.TABLE 4Wear ScarPhosphorous level at 0.5diameterCoefficientmass % treat rate parts perExamplePhosphateAmine(μm)of Frictionmillion)Ex1P1AM12260.08178Ex2P1AM22590.08143Ex3P1AM32350.09159Ex4P1AM42270.06185Ex5P1AM52290.08217Ex6P1AM62130.07150Ex7P1AM72000.09152Ex8P1AM82180.09154Base oil——4350.22—AP——2930.11240ZDDP——3230.12475

[0130] Comparative results for selected combinations of phosphate ester sources with amines is reported in Table 5.TABLE 5ExamplePhosphateAmineWear Scar Diameter (μm)Ex2P1AM2259Ex3P1AM3235Ex4P1AM4227Ex10P2AM2304Ex11P2AM3236Ex12P2AM4240Ex13P3AM2255Ex14P3AM3290Ex15P3AM4214

[0131] The comparative results in group II, group III and group IV base oil are shown in Table 6 hereinafter.TABLE 6Phos-Group IIGroup IIIGroup IVExamplephateAmineWSDCoFWSDCoFWSDCoFEx1P1AM12260.082270.1262190.1Ex2P1AM22590.084990.3544720.39Ex3P1AM32350.092450.1222950.127Ex4P1AM42270.062300.1232750.113Ex6P1AM62130.072360.1012360.097Ex7P!AM72000.09————Ex9P1AM9——2210.069——

[0132] WSD refers to Wear Scar Diameter.

[0133] CoF refers to Coefficient of Friction.

[0134] The ASTM D4172-20 Standard Test Method for Wear Preventive Characteristics of Lubricating Fluid (Four-Ball Method) was used to evaluate the anti-wear properties of fluid lubricants in sliding contact. Friction was constantly monitored, and the reported value is the average over the duration of the experiment (60 min). Wear was measured at the end of the test using optical microscopy, and the reported value is the average of the wear scar diameters on the three lower balls.

[0135] The results in group II base oil are shown in Table 7 hereinafter. The data indicates that the proposed new phosphate esters exhibit better performance in terms of wear scar diameter compared to the commercial amine phosphate and the primary ZDDP, as well as a considerably improved friction level.TABLE 7ExampleWSD (mm)CoFEx10.3220.06Ex20.3320.08Ex30.3580.05Ex40.3680.08Ex50.3930.07Ex60.3780.09Ex80.3750.06Base oil0.790.12AP0.3670.11ZDDP0.5450.13

[0136] As a whole, the data above show the capability of the amine phosphate ester salts 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 containing either known ZDDP or amine phosphate salts anti-wear additives at comparative treat rates. These results are unexpected over what is known in the art because of the comparative low phosphorous content of these salt products and their resultant lubricant formulations. It is well known in the art that the wear prevention capability of amine phosphate salts (and other phosphorous containing anti-wear additives) is related to the formation of protective phosphate glasses on metal surfaces. Obtaining such superior wear protection at the comparative low levels is thus unexpected. Obtaining such significant coefficient of friction benefits simultaneously is a further unanticipated benefit. Indeed, the independent friction performance of some embodiments rivals that of some of the best known and best performing ashless organic friction modifiers that are currently employed in the lubricant industry. This competitive friction performance comes with the additional benefit of very good wear prevention capability.

[0137] 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

1. A lubricant composition that is ashless, metal free, and sulfur free and that comprises:(1) an oil of lubricating viscosity; and(2) about 0.05 to about 3 wt % actives of a phosphate ester amine salt that is the reaction product of:a phosphate ester; andan amine;wherein the phosphate ester has the following structure (I)whereinR′ has the formula R—O(CH2CH2O)m(CH2CH2CH2O)n], where R is a naturally derived C8-C18 group and the sum of m+n is from 3 to 15; andR″ is H or independently a second R′; andwherein the amine has the following structure (II)whereinat least two of R1, R2, and R3 are independently a naturally derived C8-C18 group and R2 is optionally H; orat least one of R1, R2, and R3 is independently a naturally derived C8-C18 group and one or two of R1, R2, and R3 is CH3 or 2-ethylhexyl, orR1 a naturally derived C8-C18 group and R3 is H or CH3 or (CH2CH2O)xH, wherein x is from 1 to 3 and R2 is CH2CH2CH2NR42 wherein R4 is H or CH3 or (CH2CH2O)yH, wherein y is from 1 to 3; orR1 is a naturally derived C8-C18 group and each of R2 and R3 is (CH2CH2O)xH, wherein x is from 1 to 3.

2. The lubricant composition of claim 1 wherein the phosphate ester comprises a mixture of a phosphate monoester and a phosphate diester each according to structure (I) and such that the monoester is present in a mole ratio of greater than about 1:1 to the diester.

3. The lubricant composition of claim 1 wherein the phosphate ester comprises a mixture of a phosphate monoester and a phosphate diester each according to structure (I) and such that the monoester is present in a mole ratio of from about 0.6:1 to about 20:1 to the diester.

4. The lubricant composition of claim 1 wherein the phosphate ester comprises a mixture of a phosphate monoester to a phosphate diester each according to structure (I) and at least one R of one or both of the phosphate monoester and phosphate diester is a C16-C18 group.

5. The lubricant composition of claim 1 wherein m+n is from 3 to 6.

6. The lubricant composition of claim 1 wherein one of R1, R2, and R3 is a naturally derived C12-C14 group and another of R1, R2, and R3 is a naturally derived C16-C18 group.

7. The lubricant composition of claim 1 wherein the amine is chosen from dimethyl cocoamine, methyl di-cocoamine, and combinations thereof.

8. The lubricant composition of claim 1 wherein at least one of R1, R2, and R3 is a cocoyl group or a tallowyl group.

9. The lubricant composition of claim 1 wherein each of R1 and R3 is independently a cocoyl group or a tallowyl group and R2 is H.

10. The lubricant composition of claim 1 wherein the amine is chosen from:N-tallow-1,3-diaminopropane;N.N.N′-trimethyl-N′-tallow-1,3-diaminopropane;tris(2-hydroxyethyl)-N-tallowalkyl-1,3-diaminopropane; andcombinations thereof.

11. The lubricant composition of claim 1 wherein the amine is N.N.N′-trimethyl-N′-tallow-1,3-diaminopropane.

12. The lubricant composition of claim 1 wherein the amine is tris(2-hydroxyethyl)-N-tallowalkyl-1,3-diaminopropane.

13. The lubricant composition of claim 1 wherein R1 is a cocoyl group or a tallowyl group and each of R2 and R3 is (CH2CH2O)x, wherein x is independently from 1 to 3.

14. The lubricant composition of claim 1 wherein R1 a naturally derived C5-C18 group and R3 is H.

15. The lubricant composition of claim 1 wherein R1 a naturally derived C5-C18 group and R3 is CH3 or 2-ethylhexyl.

16. The lubricant composition of claim 1 wherein R1 a naturally derived C8-C18 group and R3 is (CH2CH2O)xH, wherein x is from 1 to 3.

17. The lubricant composition of claim 14 wherein R2 is CH2CH2CH2NR42, wherein R4 is CH3 18. The lubricant composition of claim 14 wherein R2 is CH2CH2CH2NR42, where each R4 is (CH2CH2O)yH and y is from 1 to 3.

19. The lubricant composition of claim 14 wherein R1 is a cocoyl group or a tallowyl group.

20. The lubricant composition of claim 1:exhibits a coefficient of friction as determined using ASTM D4172 that is at least 20% less than that of a comparative composition that comprises zinc dialkyl dithiophosphate in a comparative amount but is free of the phosphate ester amine salt; andexhibits a 4-ball wear preventative performance as determined using ASTM D4172 that has an average wear scar diameter that is at least 10% smaller than that of a comparative composition that comprises zinc dialkyl dithiophosphate in a comparative amount but is free of the phosphate ester amine salt.

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