NON-METALLIC PHOSPHORUS ANTIWEAR ADDITIVES

BACKGROUND OF THE DISCLOSURE

1. Field of the Disclosure

[0001] The present disclosure relates generally a lubricating composition, for example, of an engine. The present disclosure relates more particularly to a lubricating composition including one or more non-metallic phosphorus antiwear additives.

2. Technical Background

[0002] Lubricating oils are used in many systems for a variety of purposes. For example, lubricating oils are used to lubricate the moving parts in systems such as gears, motors, engines (e.g., automotive and aircraft engines), turbines, compressors, and manufacturing systems. A lubricating oil is typically circulated through the system passing over or through the components and parts that it lubricates.

[0003] Additives are typically added to lubricating oils to improve their properties and/or maintain their properties with age. Such additives may include active materials that interact with surfaces of the system or with substances or contaminants in the liquid. Common additives include, for example, dispersants, detergents, viscosity index improvers, pour point depressants, corrosion and/or rust inhibitors, antioxidants, friction modifiers, antifoams, and antiwears, and are typically formulated to provide a desired balance of properties to the lubricating oil. For example, antiwear additives are commonly added to lubricating oils to reduce, or even prevent, wear. Generally, under pressure, antiwear additives form a protective layer on a surface. This protective layer separates contact surfaces from one another, thereby reducing wear on those surfaces.

[0004] Zinc dihydrocarbyl dithiophosphates (ZDDPs) have been used as antiwear additives in lubricant compositions for decades. A disadvantage of these additives is that, when used to lubricate internal combustion engines, they give rise to ash that contributes to exhaust emission equipment degradation (e.g., filters, traps and catalysts). It is therefore desirable to reduce the amount of ash-forming additives used for lubricating internal combustion engines. It is also desirable to reduce the amount of zinc and/or sulfur in the exhaust emissions from internal combustion engines.

[0005] Attempts have therefore been made to provide antiwear additives and/or friction modifiers which contain neither zinc nor sulfur, or at least contain them in reduced amounts. One such ashless antiwear additive is tri-o-cresyl phosphate (tris(2-methylphenyl) phosphate; also known as TCP orTOCP). TCP, however, is toxic and its use presents safety concerns. [0006] Therefore, there remains a need for high performance ashless antiwear additives that overcome the health and safety drawbacks of TCP.

SUMMARY OF THE DISCLOSURE

[0007] In one aspect, the present disclosure provides a lubricating composition including: a base oil present in a total amount of at least 70 wt%; and one or more antiwear compounds present in a total amount in the range of 0.01 wt% to 5 wt%, having the formula (I): wherein each of Ri, R2, and R3 is independently selected from phenyl substituted with one, two or three substituents each selected from C1-C3 alkoxy and NO2.

[0008] And in certain desirable embodiments, the lubricating compositions of the disclosure are substantially free (e.g., no more than 0.05%, no more than 0.01% or even no more than 0.005%) of tri(2-methylphenyl)phosphate.

[0009] In another aspect, the disclosure provides a method of providing a lubricating composition having favorable antiwear properties. In such a method, an effective amount of the one or more antiwear compounds of formula (I) is included in the lubricating composition.

[0010] In another aspect, the disclosure provides a method of lubricating a surface, the method including contacting the surface with a lubricating composition of the disclosure.

[0011] In another aspect, the disclosure provides use of a lubricating composition as described herein for lubricating a surface.

[0012] In another aspect, the disclosure provides a method of reducing wear of a surface, the method including lubricating an interface between the surface and a contacting surface with a lubricating composition of the disclosure.

[0013] Additional aspects of the disclosure will be evident from the disclosure herein.

BRIEF DESCRIPTION OF THE DRAWINGS

[0014] The accompanying drawings are included to provide a further understanding of the methods and devices of the disclosure, and are incorporated in and constitute a part of this specification. The drawings are not necessarily to scale, and sizes of various elements may be distorted for clarity. The drawings illustrate one or more embodiment(s) of the disclosure, and together with the description serve to explain the principles and operation of the disclosure.

[0015] Figure 1 is graph illustrating the friction coefficients of different antiwear compounds of the disclosure and controls in High Frequency Reciprocating Rig (HFRR) test. m-TCP as used herein is tris(3-methylphenyl) phosphate. p-TCP as used herein is tris(4- methylphenyl) phosphate. TMPP and TNPP compounds are as described herein.

[0016] Figure 2 is graph illustrating average wear scar diameter from 4-Ball Wear Test of different antiwear compounds of the disclosure and controls. m-TCP, p-TCP, TMPP and TNPP compounds are as described herein.

[0017] Figure 3 is graph illustrating the total wear volume at the end of Cameron Plint test of different antiwear compounds of the disclosure and controls. m-TCP, p-TCP, TMPP and TNPP compounds are as described herein.

DETAILED DESCRIPTION

[0018] The particulars shown herein are by way of example and for purposes of illustrative discussion of certain embodiments of the present invention only and are presented in the cause of providing what is believed to be the most useful and readily understood description of the principles and conceptual aspects of various embodiments of the invention. In this regard, no attempt is made to show structural details of the invention in more detail than is necessary for the fundamental understanding of the invention, the description taken with the drawings and/or examples making apparent to those skilled in the art how the several forms of the invention may be embodied in practice. Thus, before the disclosed compositions and methods are described, it is to be understood that the aspects described herein are not limited to specific embodiments, apparatus, or configurations, and as such can, of course, vary. It is to be understood that the embodiments of the invention disclosed herein are illustrative of the principles of the present invention. Other modifications that may be employed are within the scope of the invention. Thus, by way of example, but not of limitation, alternative configurations of the present invention may be utilized in accordance with the teachings herein. In addition, the terminology used herein is for the purpose of describing particular aspects only and, unless specifically defined herein, is not intended to be limiting. Accordingly, the present invention is not limited to that precisely as shown and described.

[0019] As described above, the present inventors have noted that certain antiwear additives such as ZDDP give rise to ash, which contributes to particulate matter in the exhaust emissions from the internal combustion engines. In certain embodiments, the phosphorous antiwear compounds of the disclosure can provide comparable or even better wear protection performance as compared to ZDDP, and in some cases, as compared to TCP. For example, in certain embodiments, the compounds of the disclosure performed better in the Cameron Plint test (for purposes of this disclosure, performed as described in the Examples) than TCP or ZDDP at the same phosphorus treat rate.

[0020] Accordingly, one aspect of the disclosure is a lubricating composition. The lubricating composition includes a base oil and one or more antiwear compounds of formula

(I)·

[0021] The base oil comprises one or more base stocks. Many different base stocks are known, including, but not limited to, synthetic oils, natural oils, or mixtures thereof. Base stock may also be used in refined or in unrefined state (i.e. , with or without at least one purification step). Natural oil includes, but is not limited to, vegetable oil, paraffinic oil, naphthenic oils, paraffinic-naphthenic oil, petroleum oil, treated (e.g., solvent, acid, or distillate derived), paraffinic, naphthenic, or asphaltic oil, and oils derived from coal or shale. Synthetic oil includes, but is not limited to, hydrocarbon oil and halo-substituted hydrocarbon oil (such as polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1 -hexenes), poly(l-octenes), poly(l-decenes), dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl) benzenes, biphenyls, terphenyls, alkylated polyphenyls, alkylated diphenyl ethers, alkylated diphenyl sulfides, etc.), polyalphaolefins (PAOs), the linear or branched C10-C18 alkanes, the linear or branched haloalkanes, polyhaloalkanes, perhaloalkanes, cycloalkanes, alkyl-and/or halo-substituted cycloalkanes, aryl hydrocarbons, lower alkylaryl hydrocarbons, and haloaryl hydrocarbons.

[0022] Base stock categories have been defined by the American Petroleum Institute (API Publication 1509) providing a set of guidelines for all lubricant base oils. These are shown in Table 1. In certain embodiments, the lubricating composition is a Group I, II, II, IV, or V base oil as defined by the American Petroleum Institute (API Publication 1509).

Table 1 - Base Oil Stocks API Guidelines

[0023] Group I base stocks are generally derived from mineral oils manufactured by solvent extraction and solvent dewaxing, or solvent extraction and catalytic dewaxing. Group II and/or Group III base stocks (such as hydrocracked and hydroprocessed base oils as well as synthetic oils such as hydrocarbon oils, polyalphaolefins, alkyl aromatics, and synthetic esters) are typically manufactured by known processes comprising catalytic hydrogenation and/or catalytic hydrocracking, and catalytic hydroisomerisation. Group III oil base stock tend to be highly paraffinic with saturates higher than 90%, a viscosity index over 125, low aromatic content (less than 3%), and an aniline point of at least 118. PAOs are typically derived from C ₆ , Cs, Cio, C12, C _M , and C16 olefins or mixtures thereof and have a viscosity index greater than 135. PAOs can be manufactured by catalytic oligomerisation (polymerisation to low molecular weight products) of linear a-olefin (otherwise known as LAO) monomers. This leads to the presence of two classes of materials, PAOs and HVI- PAOs (high viscosity index PAOs), with PAOs being formed in the presence of a catalyst such as AICI3 or BF3, and HVI-PAOs being formed using a Friedel-Crafts catalyst or a reduced chromium catalyst.

[0024] An example of suitable Group I base stock includes, but is not limited to, AP/E core 150, available from ExxonMobil. Some examples of suitable Group II base stock include, but are not limited to, EHC 50 and EHC 110, available from ExxonMobil. Some examples of suitable Group III base stock include, but are not limited to, Yubase 4 and Yubase 6 available for example, from SK Lubricants. An example of suitable Group V base stock includes, but is not limited to, Priolube 3970, available from Croda International pic.

[0025] Esters also form a useful base stock (classified as Group V), including synthetic esters, as do GTL (gas-to-liquid) materials, particularly those derived from a hydrocarbon source. For example, the esters of dibasic acids with monoalcohols, or the polyol esters of monocarboxyilic acid may be useful in the emulsions of the disclosure. Such esters should typically have a viscosity of less than 10,000 cP at -35°C, in accordance with ASTM D5293. In certain embodiments, the base stock will comprise one or more of esters and one or more of natural oils (such as paraffin oil).

[0026] In certain embodiments, base stocks may be obtained from petrochemical sources, for example as the higher boiling fractions isolated during the refining of crude oil or as the products of chemical reactions of feedstocks from petrochemical sources. In certain embodiments, base oil stocks may be prepared by polymerisation, oligomerisation, condensation, alkylation, acylation, etc. of smaller molecules into larger or more complex molecules. Suitable base stocks may be derived from gas-to-liquids materials, coal-to- liquids materials, biomass-to-liquids materials and combinations thereof. Gas-to-liquids (also referred to as GTL materials) may be obtained by one or more process steps of synthesis, combination, transformation, rearrangement, degradation and combinations of two or more thereof applied to gaseous carbon-containing compounds. GTL derived base stocks and base oils may be obtained from the Fischer-Tropsch synthesis process in which synthesis gas comprising a mixture of hydrogen and carbon monoxide is catalytically converted to hydrocarbons, usually waxy hydrocarbons that are generally converted to lower-boiling materials hydroisomerization and/or dewaxing. Biomass-to-liquids (also referred to as BTL materials) may be manufactured from compounds of plant origin for example by hydrogenation of carboxylic acids or triglycerides to produce linear paraffins, followed by hydroisomerization to produced branched paraffins. Coal-to-liquids materials may be made by gasifying coal to make synthesis gas which is then converted to hydrocarbons.

[0027] In certain embodiments, the base oil has a lubricating viscosity, such as kinematic viscosity at 100 °C in the range of 2 to 50 cSt, e.g., in the range of 2 to 25 cSt, or 2 to 20 cSt, or 2 to 15 cSt, or 2 to 10 cSt, or 2 to 5 cSt, or 3 to 50 cSt, or 3 to 25 cSt, or 3 to 20 cSt, or 3 to 15 cSt, or 3 to 10 cSt, or 3 to 5 cSt, or 3.5 to 25 cSt, or 3.5 to 20 cSt, or 3.5 to 10 cSt, or 3.5 to 5 cSt, or 10 to 20 cSt, or 10 to 25 cSt, or 10 to 50 cSt.

[0028] As noted above, the base oil is present in the lubricating compositions of the disclosure in a total amount of at least 70 percent by weight, based on the total weight of the composition. In certain embodiments, the base oil is present in a total amount of or at least about 80 wt%, or at least about 85 wt%, or at least about 90 wt%, or at least about 95 wt%, or even at least about 98 wt% of the composition. In certain embodiments, the base oil is present in a total amount in the range of 70 to 99 wt%, e.g., in the range of 70 to 95 wt%, or 70 to 90 wt%, or 70 to 80 wt%. In certain embodiments, the base oil is present in an amount of at least 80 wt%, e.g., in the range of 80 to 99 wt%, or 80 to 95 wt%, or 80 to 90 wt%, or 80 to 85 wt%. In certain embodiments, the base oil is present in an amount of at least 85 wt%, e.g., in the range of 85 to 99 wt%, or 85 to 95 wt%, or 85 to 90 wt%. In certain embodiments, the base oil is present in an amount of at least 90 wt%, e.g., in the range of 90 to 99 wt%, or 90 to 95 wt%, or 95 to 99 wt%.

[0029] The lubricating compositions of the disclosure also include one or more antiwear compounds of formula (I): wherein each of Ri, R2, and R3 is independently selected from phenyl substituted with one, two or three substituents each selected from C1-C3 alkoxy and NO2

[0030] In certain embodiments as otherwise described herein, the one or more antiwear compounds included in the lubricating composition are those in which each of Ri, R2, and R3 is independently selected from phenyl substituted with one, two or three substituents each selected from C1-C2 alkoxy and NO2. [0031] In certain embodiments as otherwise described herein, the one or more antiwear compounds included in the lubricating composition are those in which each of Ri, R2, and R3 is independently selected from phenyl substituted with one, two or three C ₁ -C ₃ alkoxy substituents. For example, in certain such embodiments, each of Ri, R ₂ and R ₃ is phenyl substituted with one C ₁ -C ₃ alkoxy substituent, e.g., C ₁ -C ₂ alkoxy substituent. In certain embodiments as otherwise described herein, the one or more antiwear compounds included in the lubricating composition are those in which each of Ri, R ₂ , and R ₃ is a methoxyphenyl.

[0032] In certain embodiments as otherwise described herein, the one or more antiwear compounds included in the lubricating composition are those in which each of Ri, R ₂ , and R ₃ is independently selected from phenyl substituted with NO ₂ . In certain embodiments as otherwise described herein, the one or more antiwear compounds included in the lubricating composition are those in which each of Ri, R ₂ , and R ₃ is a mononitrophenyl.

[0033] In certain embodiments as otherwise described herein, the one or more antiwear compounds included in the lubricating composition are those in which each of Ri, R ₂ , and R ₃ is independently selected from 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2- ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, 2-nitrophenyl, 3-nitrophenyl, and 4- nitrophenyl. For example, in certain embodiments as otherwise described herein, the one or more antiwear compounds included in the lubricating composition are those in which each of Ri, R ₂ , and R ₃ is independently selected from 2-methoxyphenyl, 3-methoxyphenyl, 4- methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, 2-nitrophenyl, 3- nitrophenyl, and 4-nitrophenyl.

[0034] In certain embodiments as otherwise described herein, the one or more antiwear compounds included in the lubricating composition are those in which each of Ri, R ₂ , and R ₃ is independently selected from 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2- nitrophenyl, 3-nitrophenyl, and 4-nitrophenyl. In certain embodiments as otherwise described herein, the one or more antiwear compounds included in the lubricating composition are those in which each of Ri, R ₂ , and R ₃ is independently selected from 2- methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-nitrophenyl, 3-nitrophenyl, and 4- nitrophenyl.

[0035] In certain embodiments as otherwise described herein, the one or more antiwear compounds included in the lubricating composition are those in which each of Ri, R ₂ , and R ₃ is independently selected from 2-methoxyphenyl, 3-methoxyphenyl, and 4-methoxyphenyl.

In certain embodiments as otherwise described herein, the one or more antiwear compounds included in the lubricating composition are those in which each of Ri, R ₂ , and R ₃ is independently selected from 2-nitrophenyl, 3-nitrophenyl, and 4-nitrophenyl. [0036] The antiwear compounds as otherwise described herein, in certain embodiments, are those wherein each of Ri, R2, and R3 are the same moiety (e.g., each of Ri, R2, and R3 are 4-methoxyphenyl). However, in other embodiments, each of Ri, R2 and R3 need not be the same; the person of ordinary skill in the art will appreciate that the use of a mixture of phenols can be used in the synthesis of the antiwear compounds to provide a mixture of compounds having a distribution of Ri, R2 and R3 groups.

[0037] Particular examples of antiwear compounds of formula (I) suitable for use in various embodiments of the lubricating compositions described herein include, but are not

[0038] In certain embodiments of the lubricating compositions as otherwise described herein, the one or more antiwear compounds of formula (I) include at least 50 wt%, at least 75 wt%, or even at least 90 wt% of one of the compounds listed above.

[0039] In certain embodiments of the lubricating compositions as otherwise described herein, the antiwear compound of formula (I) is tris(4-methoxyphenyl) phosphate.

[0040] In certain embodiments of the lubricating compositions as otherwise described herein, the antiwear compound of formula (I) is tris(2-nitrophenyl) phosphate, tris(3- nitrophenyl) phosphate, tris(4-nitrophenyl) phosphate, or a combination thereof.

[0041] In certain embodiments of the lubricating compositions as otherwise described herein, the antiwear compound of formula (I) is tris(4-nitrophenyl) phosphate.

[0042] The compounds of formula (I) can be made by conventional methods, for example, by the reaction of phosphorus oxychloride with appropriate phenol(s) or naphthol(s).

[0043] As noted above, the one or more antiwear compounds of formula (I) can be present in the lubricating composition in a total amount in the range of 0.01 to 5 percent by weight, based on the total weight of the composition. For example, in certain embodiments, the one or more antiwear compounds of formula (I) are present in a total amount in the range of 0.01 to 4 wt%, 0.01 to 3 wt%, or 0.01 to 2 wt%, or 0.01 to 1 wt%. In certain embodiments, the one or more antiwear compounds of formula (I) are present in a total amount in the range of 0.1 to 5 wt%, e.g., 0.1 to 4 wt%, or 0.1 to 3 wt%, or 0.1 to 2 wt%, or 0.1 to 1 wt%. In certain embodiments, the one or more antiwear compounds of formula (I) are present in a total amount in the range of 0.5 to 5 wt%, e.g., 0.5 to 4 wt%, or 0.5 to 3 wt%, or 0.5 to 2 wt%. In certain embodiments, the one or more antiwear compounds of formula (I) are present in a total amount in the range of 1 to 5 wt%, e.g., 1 to 4 wt%, or 1 to 3 wt%. The person of ordinary skill in the art will select an amount that provides the desired degree of antiwear performance.

[0044] Phosphorus content is another way to measure the amount of the antiwear compound(s) present in the lubricating composition. This measurement allows for the comparison of the performance of different phosphorus-containing antiwear compounds to be compared to one another on a phosphorus basis. Accordingly, in certain embodiments as otherwise described herein, the one or more antiwear compounds of formula (I) are present in the lubricating composition at a concentration of 100 to 2000 ppm by weight of phosphorus, e.g., or 100 to 1500 ppm by weight of phosphorus, or 100 to 1000 ppm by weight of phosphorus, or 200 to 2000 ppm by weight of phosphorus, or 200 to 1500 ppm by weight of phosphorus, or 200 to 1000 ppm by weight of phosphorus, or 200 to 800 ppm by weight of phosphorus, or 200 to 600 ppm by weight of phosphorus.

[0045] The lubricant composition may further comprise at least one antiwear additive in addition to the antiwear compound of formula (I). Such other antiwear additives may be ash- producing additives or ashless additives. Examples of such other antiwear additives include non-phosphorus containing additives such as for example, sulfurized olefins, and/or phosphorus-containing antiwear additives. Examples of suitable phosphorus-containing antiwear additives include trilauryl phosphite, triphenylphosphorothionate (e.g. Irgalube TPPT), monohydrocarbyl dihydrogen phosphites, dihydrocarbyl hydrogen phosphites, trihydrocarbyl phosphites, and mixtures thereof, for example, dibutyl phosphite, dihexyl phosphite, dicyclohexyl phosphite, diisodecyl phosphite, di-n-octylphosphite, Irgafos® OPH, diphenyl isodecyl phosphite, diphenyl phosphite, di-n-octyl phosphite, dioleyl hydrogen phosphite, dimethylphenyl phosphite, ethyl hexyl diphenyl phosphite, phenyl diisodecyl phosphite, triisodecyl phosphite, triisoocytyl phosphite, triphenyl phosphite, tris(dipropyleneglycol)phosphite, tris(nonylphenyl)phosphites, tris(2,4-di-t- butylphenyl)phosphite, tris(5-norbomene-2-methyl)phosphite, tris(tridecyl)phosphite; also di- and tri-phosphites, such as bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-t- butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, distearyl pentaerythritol diphosphites, heptakis(dipropyleneglycol)triphosphite, tetraphenyl dipropyleneglycol diphosphite, tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene diphosphite; also poly(dipropyleneglycol)phenyl phosphite, poly 4, 4'isopropylidenediphenol-Ci ₂ -Ci ₅ alcohol phosphite (Weston 439), Alkyl (Cio) bisphenol A phosphite (Doverphos® 675, Dover), Alkyl (C12-C15) bisphenol A phosphite (Doverphos 613), tris(dipropyleneglycol)phosphite, phenyl neopentylene glycol phosphite, 2,4,6-tri-t-butylphenyl-2-butyl-2-ethyl-1,3 propanediol phosphite; 2,2-methylenebis(4,6-di-tert-butylphenyl)2-ethylhexyl phosphite, monohydrocarbyl dihydrogen phosphates, dihydrocarbyl hydrogen phosphates, and trihydrocarbyl phosphates, such as tributyl phosphate, triphenyl phosphate, and tritolyl phosphate, dithiophosphates (such as Irgalube® 62 and Irgalube 353), trithiophosphates, trilauryl trithiophosphite; phosphonites, Irgafos 12 (Ciba, CA # [80410-33-9]), diphosphonites, phosphorothionates such as tris(nonylphenyl)phosphorothionate (such as Irgalube 211)and tris(butylphenyl)phosphorothionate (such as Irgalube 232), amine phosphates (such as Irgalube 349). Examples of suitable ash-forming, phosphorus-containing antiwear additives include dihydrocarbyl dithiophosphate metal salts (such as, e.g., alkali and alkaline earth metals, aluminum, lead, tin, molybdenum, manganese, nickel, copper and zinc). Suitable dihydrocarbyl dithiophosphate zinc salts (ZDDPs) may have hydrocarbyl groups independently having 1 to 18 carbon atoms, suitably 2 to 13 carbon atoms or 3 to 18 carbon atoms, more suitably 2 to 12 carbon atoms or 3 to 13 carbon atoms, for example 3 to 8 carbon atoms. Examples of suitable hydrocarbyl groups include alkyl, cycloalkyl and alkaryl groups which may contain ether or ester linkages and also which may contain substituent groups for example, halogen or nitro groups. The hydrocarbyl groups may be alkyl groups which are linear and/or branched and suitably may have from 3 to 8 carbon atoms. In certain embodiments, ZDDPs have hydrocarbyl groups which are a mixture of secondary alkyl groups and primary alkyl groups for example, 90 mol. % secondary alkyl groups and 10 mol. % primary alkyl groups.

[0046] In certain embodiments, the one or more antiwear compounds of formula (I) will reduce the amount of additional antiwear additives that might be required to achieve a desired amount of antiwear properties for the lubricant composition. The additional antiwear additives may be present in the lubricating composition at a concentration of 10 to 1000 ppm by weight of phosphorus, e.g., 100 to 1000 ppm by weight of phosphorus, for example 200 to 1000 ppm by weight of phosphorus, or 200 to 800 ppm by weight of phosphorus, or 200 to 600 ppm by weight of phosphorus.

[0047] However, in certain embodiments, substantially no (e.g., no more than 0.05%, no more than 0.01% or even no more than 0.005%) metal-containing antiwear additive (e.g., none of those described above) is present in the lubricating composition. And in certain embodiments, substantially no (e.g., no more than 0.05%, no more than 0.01% or even no more than 0.005%) antiwear additive other than the antiwear additives of formula (I) (e.g., none of the antiwear additives described above) is present in the lubricating composition.

[0048] The lubricant compositions of the disclosure as otherwise described herein can also include a variety other additives. Examples of such other additives include friction modifiers, dispersants (metallic and non-metallic), dispersant viscosity modifiers, detergents (metallic and non-metallic), viscosity index improvers, viscosity modifiers, pour point depressants, rust inhibitors, corrosion inhibitors, antioxidants (sometimes also called oxidation inhibitors), anti-foams (sometimes also called anti-foaming agents), seal swell agents (sometimes also called seal compatibility agents), extreme pressure additives (metallic, non-metallic, phosphorus containing, non-phosphorus containing, sulfur containing and non-sulfur containing), surfactants, demulsifiers, anti-seizure agents, wax modifiers, lubricity agents, anti-staining agents, chromophoric agents, and metal deactivators. [0049] In certain embodiments as otherwise described herein, the lubricant composition may further include one or more friction modifiers. Such other friction modifiers may be ash- producing additives or ashless additives. Examples of such other friction modifiers include fatty acid derivatives including for example, other fatty acid esters, amides, amines, and ethoxylated amines. Examples of suitable ester friction modifiers include esters of glycerol for example, mono-, di-, and tri-oleates, mono-palmitates and mono-myristates. A particularly suitable fatty acid ester friction modifier is glycerol monooleate. Examples of such other friction modifiers may also include molybdenum compounds for example, organo molybdenum compounds, molybdenum dialkyldithiocarbamates, molybdenum dialkylthiophosphates, molybdenum disulfide, tri-molybdenum cluster dialkyldithiocarbamates, non-sulfur molybdenum compounds and the like. Suitable molybdenum-containing compounds are described for example, in European Patent Publication No. EP-1533362-A1 for example in paragraphs [0101] to [0117] Friction modifiers may also include a combination of an alkoxylated hydrocarbyl amine and a polyol partial ester of a saturated or unsaturated fatty acid or a mixture of such esters, for example as described in International Patent Publication No. WO 93/21288.

[0050] Friction modifiers may be present in the lubricating composition, for example, at a concentration of 0.01 to 5 % by weight based on the total composition, e.g., range of 0.01 to 1.5 wt%.

[0051] Molybdenum containing friction modifiers may be present in the lubricating composition, for example, at a concentration of 10 to 1000 ppm by weight molybdenum, more suitably in the range of 400 to 600 ppm by weight.

[0052] In certain embodiments as otherwise described herein, the lubricant composition may further include one or more dispersants. Dispersants (also called dispersant additives) help hold solid and liquid contaminants for example resulting from oxidation of the lubricant composition during use, in suspension and thus reduce sludge flocculation, precipitation and/or deposition for example on lubricated surfaces. They generally comprise long-chain hydrocarbons, to promote oil-solubility, and a polar head capable of associating with material to be dispersed. Examples of suitable dispersants include oil soluble polymeric hydrocarbyl backbones each having one or more functional groups which are capable of associating with particles to be dispersed. The functional groups may be amine, alcohol, amine- alcohol, amide or ester groups. The functional groups may be attached to the hydrocarbyl backbone through bridging groups. More than one dispersant may be present in the lubricant composition. [0053] Examples of suitable ashless dispersants include oil soluble salts, esters, amino- esters, amides, imides and oxazolines of long chain hydrocarbon-substituted mono- and polycarboxyl ic acids or anhydrides thereof; thiocarboxylate derivatives of long chain hydrocarbons; long chain aliphatic hydrocarbons having polyamine moieties attached directly thereto; Mannich condensation products formed by condensing a long chain substituted phenol with formaldehyde and polyalkylene polyamine; Koch reaction products and the like. Examples of suitable dispersants include derivatives of long chain hydrocarbyl- substituted carboxylic acids, for example in which the hydrocarbyl group has a number average molecular weight of up to 20000, for example 300 to 20000, 500 to 10000, 700 to 5000 or less than 15000. Examples of suitable dispersants include hydrocarbyl-substituted succinic acid compounds, for example succinimide, succinate esters or succinate ester amides and in particular, polyisobutenyl succinimide dispersants. The dispersants may be borated or non-borated. one suitable dispersant is ADX 222.

[0054] Additionally or alternatively, dispersancy may be provided by polymeric compounds capable of providing viscosity index improving properties and dispersancy. Such compounds are generally known as dispersant viscosity improver additives or multifunctional viscosity improvers. Examples of suitable dispersant viscosity modifiers may be prepared by chemically attaching functional moieties (for example amines, alcohols and amides) to polymers which tend to have number average molecular weights of at least 15000, for example in the range 20000 to 600000 (for example as determined by gel permeation chromatography or light scattering methods). Examples of suitable dispersant viscosity modifiers and methods of making them are described in International Patent Publication Nos. WO 99/21902, WO 2003/099890 and W02006/099250. More than one dispersant viscosity modifier may be present in the lubricant composition.

[0055] In certain embodiments as otherwise described herein, the lubricant composition may further comprise one or more detergents. Detergents (also called detergent additives) may help reduce high temperature deposit formation for example on pistons in internal combustion engines, including for example high-temperature varnish and lacquer deposits, by helping to keep finely divided solids in suspension in the lubricant composition.

Detergents may also have acid-neutralizing properties. Ashless (that is non-metal containing detergents) may be present. Metal-containing detergent comprises at least one metal salt of at least one organic acid, which is called soap or surfactant. Detergents may be overbased in which the detergent comprises an excess of metal in relation to the stoichiometric amount required to neutralize the organic acid. The excess metal is usually in the form of a colloidal dispersion of metal carbonate and/or hydroxide. Examples of suitable metals include Group I and Group II metals, more suitably calcium, magnesium and combinations thereof, especially calcium. More than one metal may be present.

[0056] Examples of suitable organic acids include sulfonic acids, phenols (sulfurized or preferably sulfurized and including for example, phenols with more than one hydroxyl group, phenols with fused aromatic rings, phenols which have been modified for example alkylene bridged phenols, and Mannich base-condensed phenols and saligenin-type phenols, produced for example by reaction of phenol and an aldehyde under basic conditions) and sulfurized derivatives thereof, and carboxylic acids including for example, aromatic carboxylic acids (for example hydrocarbyl-substituted salicylic acids and sulfurized derivatives thereof, for example hydrocarbyl substituted salicylic acid and derivatives thereof). More than one type of organic acid may be present. Additionally or alternatively, non-metallic detergents may be present. Suitable non-metallic detergents are described for example in US7622431. More than one detergent may be present in the lubricant composition.

[0057] In certain embodiments as otherwise described herein, the lubricant composition may further comprise one or more viscosity index improvers. Viscosity index improvers (also called viscosity modifiers, viscosity improvers or VI improvers) impart high and low temperature operability to a lubricant composition and facilitate it remaining shear stable at elevated temperatures whilst also exhibiting acceptable viscosity and fluidity at low temperatures.

[0058] Examples of suitable viscosity modifiers include high molecular weight hydrocarbon polymers (for example polyisobutylene, copolymers of ethylene and propylene and higher alpha-olefins); polyesters (for example polymethacrylates); hydrogenated poly(styrene-co- butadiene or isoprene) polymers and modifications (for example star polymers); and esterified poly(styrene-co-maleic anhydride) polymers. Oil-soluble viscosity modifying polymers generally have number average molecular weights of at least 15000 to 1000000, preferably 20000 to 600000 as determined by gel permeation chromatography or light scattering methods. Viscosity modifiers may have additional functions as multifunction viscosity modifiers. More than one viscosity index improver may be present.

[0059] In certain embodiments as otherwise described herein, the lubricant composition may further comprise one or more pour point depressants. Pour point depressants (also called lube oil improvers or lube oil flow improvers), lower the minimum temperature at which the lubricant will flow and can be poured. Examples of suitable pour point depressants include Cs to Cie dialkyl fumarate/vinyl acetate copolymers, methacrylates, polyacrylates, polyarylamides, polymethacrylates, polyalkyl methacrylates, vinyl fumarates, styrene esters, condensation products of haloparaffxn waxes and aromatic compounds, vinyl carboxylate polymers, terpolymers of dialkyfumarates, vinyl esters of fatty acids and allyl vinyl ethers, wax naphthalene and the like. More than one pour point depressant may be present.

[0060] In certain embodiments as otherwise described herein, the lubricant composition may further comprise one or more rust inhibitors and/or corrosion inhibitors. Rust inhibitors generally protect lubricated metal surfaces against chemical attack by water or other contaminants. Examples of suitable rust inhibitors include non-ionic polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols, polyoxyalkylene polyols, anionic alky sulfonic acids, zinc dithiophosphates, metal phenolates, basic metal sulfonates, fatty acids and amines. More than one rust inhibitor may be present.

[0061] Corrosion inhibitors (also called anti-corrosive agents) reduce the degradation of metallic parts contacted with the lubricant composition. Examples of corrosion inhibitors include phosphosulfurized hydrocarbons and the products obtained by the reaction of phosphosulfurized hydrocarbon with an alkaline earth metal oxide or hydroxide, non- ionic polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols, thiadiazoles, triazoles and anionic alkyl sulfonic acids. Examples of suitable epoxidized ester corrosion inhibitors are described in U.S. Patent Publication No. US2006/0090393. More than one corrosion inhibitor may be present.

[0062] In certain embodiments as otherwise described herein, the lubricant composition may further comprise one or more antioxidants. Antioxidants (sometimes also called oxidation inhibitors) reduce the tendency of oils to deteriorate in use. Evidence of such deterioration might include for example the production of varnish-like deposits on metal surfaces, the formation of sludge and viscosity increase. Examples of suitable antioxidants include alkylated diphenylamines, N-alkylated phenylenediamines, phenyl-a-naphthylamine, alkylated phenyl-a-naphthylamines, dimethylquinolines, trimethyldihydroquinolines and oligomeric compositions derived therefrom, hindered phenolics (including ashless (metal- free) phenolic compounds and neutral and basic metal salts of certain phenolic compounds), aromatic amines (including alkylated and non-alkylated aromatic amines), sulfurized alkyl phenols and alkali and alkaline earth metal salts thereof, alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylidenebisphenols, thiopropionates, metallic dithiocarbamates, 1,3,4-dimercaptothiadiazole and derivatives, oil soluble copper compounds (for example, copper dihydrocarbyl thio- or thio-phosphate, copper salts of a synthetic or natural carboxylic acids, for example a Cs to Cis fatty acid, an unsaturated acid or a branched carboxylic acid, for example basic, neutral or acidic Cu' and/or Cu" salts derived from alkenyl succinic acids or anhydrides), alkaline earth metal salts of alkylphenolthioesters, suitably having Cs to C12 alkyl side chains, calcium nonylphenol sulfide, barium t-octylphenyl sulfide, dioctylphenylamine, phosphosulfized or sulfurized hydrocarbons, oil soluble phenates, oil soluble sulfurized phenates, calcium dodecylphenol sulfide, phosphosulfurized hydrocarbons, sulfurized hydrocarbons, phosphorus esters, low sulfur peroxide decomposers and the like. More than one antioxidant may be present, and more than one type of antioxidant may be present.

[0063] In certain embodiments as otherwise described herein, the lubricant composition may further comprise one or more anti-foams. Anti-foams (sometimes also called anti foaming agents) retard the formation of stable foams. Examples of suitable anti-foam agents include silicones, organic polymers, siloxanes (including poly siloxanes and (poly) dimethyl siloxanes, phenyl methyl siloxanes), acrylates and the like. More than one anti-foam may be present.

[0064] In certain embodiments as otherwise described herein, the lubricant composition may further comprise one or more seal swell agents. Seal swell agents (sometimes also called seal compatibility agents or elastomer compatibility aids) help to swell elastomeric seals for example by causing a reaction in the fluid or a physical change in the elastomer. Examples of suitable seal swell agents include long chain organic acids, organic phosphates, aromatic esters, aromatic hydrocarbons, esters (for example butylbenzyl phthalate) and polybutenyl succinic anhydride. More than one seal swell agent may be present.

[0065] In certain embodiments as otherwise described herein, other additives may be present in the lubricant composition of the disclosure including, but not limited to, extreme pressure additives (including metallic, non- metallic, phosphorus containing, non-phosphorus containing, sulfur containing and non-sulfur containing extreme pressure additives), surfactants, demulsifiers, anti-seizure agents, wax modifiers, lubricity agents, anti-staining agents, chromophoric agents and metal deactivators.

[0066] In certain embodiments, some additives may exhibit more than one function.

[0067] Representative suitable amounts of additives (if present) in the lubricant composition of the disclosure as otherwise described herein are provided in Table 2. The concentrations expressed in Table 2 are by weight of lubricating composition and are independent of any solvent or diluent. More than one of each type of additive may be present. Within each type of additive, more than one class of that type of additive may be present. More than one additive of each class of additive may be present. And these values are merely representative; in certain embodiments, the amounts may fall outside these representative ranges. Additives may suitably be supplied by manufacturers and suppliers in solvent or diluents. Table 2.

Additives Example embodiments % by weight

Dispersant 0.1 - 10%; or 0.1 - 8%; or 0.1 - 5%

Detergent 0.01 - 6%; or 0.01 - 4%; or 0.01 - 3%

Viscosity Index Improver 0.01 - 15%; or 1 - 15%; or 1 - 4% Pour point depressant 0.01 - 3%; or 0.01 - 1.5%; or 0.01 - 0.5%

Corrosion and/or rust inhibitors 0.01 - 3%; or 0.01 - 1.5%; or 0.01 - 0.5%

Antioxidants 0.5 - 5% Friction modifier 0.01 - 3%; or 0.01 - 1.5%; or 0.01 - 1% Seal Swell Agents 0.1 - 10%; or 0.1 - 8%; or 0.1 - 4%

0.001 - 0.1%; or 0.001 - 0.05%; or 0.001 - 0.01%

Antifoams (e.g., 1 - 10 ppm Si for silicon-based antifoams)

[0068] In certain embodiments as otherwise described herein, the lubricant composition of the present disclosure is a multi-grade lubricating composition according to the API classification xW-y where x is 0, 5, 10, 15 or 20 and y is 20, 30, 40, 50 or 60 as defined by SAE J3002004, for example 5W-20, 5W-30, 0W- 20. Lubricant compositions of the disclosure may have, for example, an HTHS viscosity at 150 °C of at least 2.6cP as measured according to ASTM D4683, CEC L-36-A-90, or ASTM D5481. In certain embodiments, the lubricant composition may have an HTHS viscosity at 150 °C of from 1 to less than 2.6cP, for example 1.5 cP, 1 8cP, or 2 cP, as measured according to ASTM D4683.

[0069] In another aspect, the disclosure provides a method of providing a lubricating composition having favorable antiwear properties. In such a method, an effective amount of the one or more antiwear compounds of formula (I) is included in the lubricating composition. The lubricating composition can be as otherwise described herein. Such lubricating compositions can be provided, for example, by combining the one or more antiwear compounds of formula (I) to a base oil. Other additives, e.g., as disclosed herein, can also be combined with the base oil.

[0070] As noted above, an antiwear compound of formula (I) is used as an antiwear additive in a lubricant composition. Thus, another aspect of the present disclosure provides a method of lubricating a surface, the method including contacting the surface with a lubricating composition of the disclosure.

[0071] In an additional aspect, the disclosure provides a method of reducing wear on a surface, the method including lubricating an interface between the surface and a contacting surface with a lubricating composition of the disclosure. The surface can be, for example, the surface of an engine, a motor, a turbine, or a transmission.

[0072] The compositions of the disclosure can, in many embodiments, provide improved antiwear performance as compared to conventional antiwear compounds. For example, in certain embodiments, use of the compound(s) of the formula (I) can provide for improved wear performance over conventional antiwear compounds. For example, in certain embodiments of the compositions and methods as described herein, a lubricating composition of the disclosure provides a wear volume as measured via the Cameron Plint method that is at least about 10% less than (e.g., at least 15% less than, or at least 20% less than, or at least 30% less than, or even at least 50% less than) the wear volume of a lubricating composition that is identical but for replacing the compound(s) of formula (I) with an equivalent amount based on phosphorus treat rate of TCP. In certain embodiments of the compositions and methods as described herein, a lubricating composition of the disclosure provides a wear volume as measured via the Cameron Plint method that is at least about 10% less than (e.g., at least 15% less than, or at least 20% less than, or at least 30% less than, or even at least 50% less than) the wear volume of a lubricating composition that is identical but for replacing the compound(s) of formula (I) with an equivalent amount based on phosphorus treat rate of ZDDP. In certain embodiments of the compositions and methods as described herein, a lubricating composition of the disclosure provides a wear rate as measured via the Cameron Plint method that is at least about 10% less than (e.g., at least 15% less than, or at least 20% less than, or at least 30% less than, or even at least 50% less than) the wear rate of a lubricating composition that is identical but for replacing the compound(s) of formula (I) with an equivalent amount based on phosphorus treat rate of TCP. In certain embodiments of the compositions and methods as described herein, a lubricating composition of the disclosure provides a wear rate as measured via the Cameron Plint method that is at least about 10% less than (e.g., at least 15% less than, or at least 20% less than, or at least 30% less than, or even at least 50% less than) the wear rate of a lubricating composition that is identical but for replacing the compound(s) of formula (I) with an equivalent amount based on phosphorus treat rate of ZDDP. Similarly, in certain aspects, the lubricating compositions of the disclosure can provide improved friction properties as compared to compositions including conventional antiwear agents such as ZDDP.

[0073] The lubricant compositions and methods described herein can be useful in lubrication of many different types of mechanical systems. For example, in certain embodiments, the lubricant compositions can be used for lubricating an engine, motor, turbine, or transmission, e.g., by introducing a lubricating composition of the disclosure to the engine, motor, turbine or transmission. In certain embodiments, a lubricating composition of the disclosure is an engine oil, for example, for use in a vehicle engine (e.g., a gasoline engine or a diesel engine). In certain embodiments, a lubricant composition of the disclosure may be used to lubricate an internal combustion engine, for example as a crankcase lubricant. The engine may be a spark-ignition, internal combustion engine, or a compression-ignition, internal combustion engine. The internal combustion engine may be a spark-ignition internal combustion engine used in automotive or aviation applications. The internal combustion engine may be a two-stroke compression-ignition engine and the at least one long chain fatty acid ester may be used as an anti-wear additive and/or friction modifier in a system oil lubricant composition and/or a cylinder oil lubricant composition used to lubricate the engine. The two-stroke compression-ignition engine may be used in marine applications. The lubricant composition of the disclosure may be used to lubricate the engine, for example to lubricate the crankcase of the engine. In certain embodiments, a lubricant composition of the disclosure may be a power transmission fluid for example useful as an automatic transmission fluid, a fluid in a clutch (for example a dual clutch), or a gear lubricant.

[0074] In other embodiments, a lubricant composition of the disclosure can be provided as a functional fluid, for example a metalworking fluid that may be used to lubricate metals during machining, rolling and the like.

[0075] In certain embodiments, a lubricant composition of the disclosure may be suitable for use in turbine lubrication.

[0076] In certain embodiments, a lubricant composition of the disclosure may be suitable for use in aviation lubricant applications.

[0077] In certain embodiments, a lubricant composition of the disclosure may be used to lubricate a solid surface, including for example metallic surfaces and non-metallic surfaces. Suitable metallic surfaces include surfaces of ferrous based materials, for example cast iron and steels; surfaces of aluminum-based solids, for example aluminum-silicon alloys; surfaces of metal matrix compositions; surfaces of copper and copper alloys; surfaces of lead and lead alloys; surfaces of zinc and zinc alloys; and surfaces of chromium-plated materials. Suitable non-metallic surfaces include surfaces of ceramic materials; surfaces of polymer materials; surfaces of carbon-based materials; and surfaces of glass. Other surfaces which may be lubricated include surfaces of coated materials for example surfaces of hybrid materials for example metallic materials coated with non-metallic materials and non-metallic materials coated with metallic materials; surfaces of diamond-like carbon coated materials and SUMEBore materials for example as described in Sultzer technical review 4/2009 pages 11-13.

[0078] In certain embodiments, a lubricant composition of the disclosure may be used to lubricate a surface at any typical temperature which might be encountered in a lubricating environment, for example at a temperature such as may be encountered in an internal combustion engine, for example a temperature in the range of ambient to 250 °C, e.g. 50 to 220 °C, or 50 to 200 °C, or 90 to 200 °C, or 90 to 120 °C. Typically ambient temperature may be 20 °C, but may be less than 20°C, for example 0°C, -5°C, -10°C, etc.

[0079] It will be apparent to those skilled in the art that various modifications and variations can be made to the processes and devices described here without departing from the scope of the disclosure. Thus, it is intended that the present disclosure cover such modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.

[0080] Certain aspects of the disclosure are now explained further via the following non limiting examples.

[0081] Example 1

[0082] Several antiwear compounds of formula (I) of the disclosure at a concentration of 400 ppm by weight of phosphorus were blended in base stock with a standard additive package. The standard additive package did not contain any other antiwear compounds. The negative control of the tests was the base stock with a standard additive package but without the antiwear compounds of formula (I) or ZDDP. The positive control was the base stock with a standard additive package and ZDDP (400 ppm by weight of phosphorus).

[0083] A High Frequency Reciprocating Rig (HFRR) friction test is usually used to assess lubricity of diesel fuels (according to ASTM D6079-97). It may also be used to assess friction coefficients between sliding solid surfaces in the presence of lubricant compositions with various friction modifiers over a temperature range. The friction coefficient was measured when a needle was reciprocated on a metal disk. The test was run at 400 g load, 40-140 °C (20 °C intervals) for 35 minutes, and the results are shown in Figure 1. Most of the antiwear compounds of formula (I) of the disclosure showed lower the friction coefficient compared to ZDDP. All three TMPP compounds offered consistent and low friction coefficient across the whole temperature regime.

[0084] A 4-Ball Wear test according to ASTM D 4172 evaluated the antiwear property of the compounds of the disclosure during sliding contact. . In this test, one ball bearing was rotated above a cradle of three others in the presence of a lubricant. Wear scar size reflects wear preventative properties of the tested fluids. The test was run at 15 kg, 75 °C, for 1 hour, and the results are shown in Figure 2. 4-TMPP gave comparable result to ZDDP and lowered the wear scar diameter as compared to the negative control group.

[0085] The Cameron Plint High Frequency Friction wear test was used to simulate reciprocating boundary friction and produce wear at higher temperatures (180°C). The apparatus was set up in a pin on plate configuration. The pin was reciprocated along the plate at a frequency of 2 Hz, stroke length of 2.3 mm and with an applied pressure of 300 N. The lubricating composition was fed into the contact area at a rate of 0.8 mL/hr. Standard steel B01 Flat Plate and EN31 Roller plint components were used in these tests.

[0086] The results from 6.8 hour tests are shown in Figure 3 and in Table 3 below.

Table 3

[0087] The antiwear compounds of the disclosure, 4-TMPP, 3-TNPP and 4-TNPP, showed low wear volume, less than 50% of the negative control, and lower than ZDDP at the same concentration. 2-TMPP and 3-TMPP were omitted from the graph because they had high wear volume, higher than the baseline utilized.

[0088] Direct comparison between ZDDP and 4-TMPP was performed in engine camshaft wear test. Nissan KA24E (IVA) engine was used. The results are provided in Table 4.

Here, the lubricating composition having 4-TMPP exhibited 60% reduction of camshaft nose wear compared to the lubricating composition having ZDDP, even at roughly 2/3 of the phosphorus concentration. Similarly, camshaft lobe wear and camshaft follower scuffing was reduced by 66% and 57%, respectively, when the lubricating composition having 4- TMPP was used compared to the lubricating composition having ZDDP. Table 4

[0089] The particulars shown herein are by way of example and for purposes of illustrative discussion of certain embodiments of the present invention only and are presented in the cause of providing what is believed to be the most useful and readily understood description of the principles and conceptual aspects of various embodiments of the invention. In this regard, no attempt is made to show structural details of the invention in more detail than is necessary for the fundamental understanding of the invention, the description taken with the drawings and/or examples making apparent to those skilled in the art how the several forms of the invention may be embodied in practice. Thus, before the disclosed processes and devices are described, it is to be understood that the aspects described herein are not limited to specific embodiments, apparatus, or configurations, and as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and, unless specifically defined herein, is not intended to be limiting.

[0090] The terms “a,” “an,” “the” and similar referents used in the context of describing the invention (especially in the context of the following embodiments and claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context.

[0091] All methods described herein can be performed in any suitable order of steps unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention otherwise claimed. No language in the specification should be construed as indicating any non-claimed element essential to the practice of the invention.

[0092] Unless the context clearly requires otherwise, throughout the description and the claims, the words ‘comprise’, ‘comprising’, and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of “including, but not limited to”. Words using the singular or plural number also include the plural and singular number, respectively. Additionally, the words “herein,” “above,” and “below” and words of similar import, when used in this application, shall refer to this application as a whole and not to any particular portions of the application. [0093] As will be understood by one of ordinary skill in the art, each embodiment disclosed herein can comprise, consist essentially of or consist of its particular stated element, step, ingredient or component. As used herein, the transition term “comprise” or “comprises” means includes, but is not limited to, and allows for the inclusion of unspecified elements, steps, ingredients, or components, even in major amounts. The transitional phrase “consisting of” excludes any element, step, ingredient or component not specified. The transition phrase “consisting essentially of” limits the scope of the embodiment to the specified elements, steps, ingredients or components and to those that do not materially affect the embodiment.

[0094] All percentages, ratios and proportions herein are by weight, unless otherwise specified.

[0095] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

[0096] Groupings of alternative elements or embodiments of the invention disclosed herein are not to be construed as limitations. Each group member may be referred to and claimed individually or in any combination with other members of the group or other elements found herein. It is anticipated that one or more members of a group may be included in, or deleted from, a group for reasons of convenience and/or patentability. When any such inclusion or deletion occurs, the specification is deemed to contain the group as modified thus fulfilling the written description of all Markush groups used in the appended claims.

[0097] Some embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Of course, variations on these described embodiments will become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventor expects skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context. [0098] Various exemplary embodiments of the disclosure include, but are not limited to the enumerated embodiments listed below, which can be combined in any number and in any combination that is not technically or logically inconsistent.

[0099] Embodiment 1 provides a lubricating composition comprising: a base oil present in a total amount of at least 70 wt%; and one or more antiwear compounds present in a total amount in the range of 0.01 wt% to 5 wt%, having the formula: wherein each of Ri, R2, and R3 is independently selected from phenyl substituted with one, two or three substituents each selected from C1-C3 alkoxy and NO2.

[0100] Embodiment 2 provides the lubricating composition of embodiment 1, wherein the lubricating composition is substantially free (e.g., no more than 0.05%, no more than 0.01% or even no more than 0.005%) of tris(2-methylphenyl) phosphate.

[0101] Embodiment 3 provides the lubricating composition of embodiment 1 or embodiment 2, wherein each of Ri, R2, and R3 is independently selected from phenyl substituted with one, two or three substituents each selected from C1-C2 alkoxy and NO2.

[0102] Embodiment 4 provides the lubricating composition of embodiment 1 or embodiment 2, wherein each of Ri, R2, and R3 is independently selected from phenyl substituted with one, two or three NO2.

[0103] Embodiment 5 provides the lubricating composition of embodiment 1 or embodiment 2, wherein each of Ri, R2, and R3 is independently selected from nitrophenyl.

[0104] Embodiment 6 provides the lubricating composition of embodiment 1 or embodiment 2, wherein each of Ri, R2, and R3 is independently selected from phenyl substituted with one, two or three substituents each selected from C1-C3 alkoxy.

[0105] Embodiment 7 provides the lubricating composition of embodiment 1 or embodiment 2, wherein each of Ri, R2, and R3 is independently selected from phenyl substituted with one, two or three substituents each selected from C1-C2 alkoxy.

[0106] Embodiment 8 provides the lubricating composition of embodiment 1 or embodiment 2, wherein each of Ri, R2, and R3 is independently selected from methoxyphenyl. [0107] Embodiment 9 provides the lubricating composition of embodiment 1 or embodiment 2, wherein each of Ri, R2, and R3 is independently selected from 2- methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4- ethoxyphenyl, 2-nitrophenyl, 3-nitrophenyl, and 4-nitrophenyl.

[0108] Embodiment 10 provides the lubricating composition of embodiment 1 or embodiment 2, wherein each of Ri, R2, and R3 is independently selected from 3- methoxyphenyl, 4-methoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, 3-nitrophenyl, and 4- nitrophenyl.

[0109] Embodiment 11 provides the lubricating composition of embodiment 1 or embodiment 2, wherein each of Ri, R2, and R3 is independently selected from 2- methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-nitrophenyl, 3-nitrophenyl, and 4- nitrophenyl.

[0110] Embodiment 12 provides the lubricating composition of embodiment 1 or embodiment 2, wherein each of Ri, R2, and R3 is independently selected from 3- methoxyphenyl, 4-methoxyphenyl, 3-nitrophenyl, and 4-nitrophenyl.

[0111] Embodiment 13 provides the lubricating composition of embodiment 1 or embodiment 2, wherein each of Ri, R2, and R3 is independently selected from 2- methoxyphenyl, 3-methoxyphenyl, and 4-methoxyphenyl.

[0112] Embodiment 14 provides the lubricating composition of embodiment 1 or embodiment 2, wherein each of Ri, R2, and R3 is independently selected from 2-nitrophenyl, 3-nitrophenyl, and 4-nitrophenyl.

[0113] Embodiment 15 provides the lubricating composition of any of embodiments 1-14, wherein each of Ri, R2, and R3 are the same moiety.

[0114] Embodiment 16 provides the lubricating composition of any of embodiments 1-15, wherein at least one of the antiwear compounds is tris(2-methoxyphenyl) phosphate (e.g., wherein the one or more antiwear compounds of formula (I) include at least 50 wt%, at least 75 wt%, or even at least 90 wt% tris(2-methoxyphenyl) phosphate).

[0115] Embodiment 17 provides the lubricating composition of any of embodiments 1-16, wherein at least one of the antiwear compounds is tris(3-methoxyphenyl) phosphate (e.g., wherein the one or more antiwear compounds of formula (I) include at least 50 wt%, at least 75 wt%, or even at least 90 wt% tris(3-methoxyphenyl) phosphate).

[0116] Embodiment 18 provides the lubricating composition of any of embodiments 1-17, wherein at least one of the antiwear compounds is tris(4-methoxyphenyl) phosphate (e.g., wherein the one or more antiwear compounds of formula (I) include at least 50 wt%, at least 75 wt%, or even at least 90 wt% tris(4-methoxyphenyl) phosphate).

[0117] Embodiment 19 provides the lubricating composition of any of embodiments 1-18, wherein at least one of the antiwear compounds is tris(2-nitrophenyl) phosphate (e.g., wherein the one or more antiwear compounds of formula (I) include at least 50 wt%, at least 75 wt%, or even at least 90 wt% tris(2-nitrophenyl) phosphate).

[0118] Embodiment 20 provides the lubricating composition of any of embodiments 1-19, wherein at least one of the antiwear compounds is tris(3-nitrophenyl) phosphate (e.g., wherein the one or more antiwear compounds of formula (I) include at least 50 wt%, at least 75 wt%, or even at least 90 wt% tris(3-nitrophenyl) phosphate).

[0119] Embodiment 21 provides the lubricating composition of any of embodiments 1-20, wherein at least one of the antiwear compounds is tris(4-nitrophenyl) phosphate (e.g., wherein the one or more antiwear compounds of formula (I) include at least 50 wt%, at least 75 wt%, or even at least 90 wt% tris(4-nitrophenyl) phosphate).

[0120] Embodiment 22 provides the lubricating composition of any of embodiments 1-21, wherein the one or more antiwear compounds are present in a total amount in the range of 0.01 to 4 wt%, or 0.01 to 3 wt%, or 0.01 to 2 wt%, or 0.01 to 1 wt%.

[0121] Embodiment 23 provides the lubricating composition of any of embodiments 1-21, wherein the one or more antiwear compounds are present in a total amount in the range of 0.1 to 5 wt%, e.g., 0.1 to 4 wt%, or 0.1 to 3 wt%, or 0.1 to 2 wt%, or 0.1 to 1 wt%.

[0122] Embodiment 24 provides the lubricating composition of any of embodiments 1-21, wherein the one or more antiwear compounds are present in a total amount in the range of 0.5 to 5 wt%, e.g., 0.5 to 4 wt%, or 0.5 to 3 wt%, or 0.5 to 2 wt%.

[0123] Embodiment 25 provides the lubricating composition of any of embodiments 1-21, wherein the one or more antiwear compounds are present in a total amount in the range of 1 to 5 wt%, e.g., 1 to 4 wt%, or 1 to 3 wt%.

[0124] Embodiment 26 provides the lubricating composition of any of embodiments 1-21, wherein the one or more antiwear compounds of formula (I) are present in the lubricating composition at a concentration of 100 to 2000 ppm by weight of phosphorus, e.g., or 100 to 1500 ppm by weight of phosphorus, or 100 to 1000 ppm by weight of phosphorus, or 200 to 2000 ppm by weight of phosphorus, or 200 to 1500 ppm by weight of phosphorus, or 200 to 1000 ppm by weight of phosphorus, or 200 to 800 ppm by weight of phosphorus, or 200 to 600 ppm by weight of phosphorus. [0125] Embodiment 27 provides the lubricating composition according to any of embodiments 1-26, wherein substantially no (e.g., no more than 0.05%, no more than 0.01% or even no more than 0.005%) metal-containing antiwear additive is present in the lubricating composition.

[0126] Embodiment 28 provides the lubricating composition according to any of embodiments 1-26, wherein substantially no (e.g., no more than 0.05%, no more than 0.01% or even no more than 0.005%) antiwear additive other than the antiwear additives of formula (I) is present in the lubricating composition.

[0127] Embodiment 29 provides the lubricating composition of any of embodiments 1-28, wherein the base oil comprises one or more base stocks selected from Group I, Group II, Group III, Group IV and Group V base stocks, and mixtures thereof.

[0128] Embodiment 30 provides the lubricating composition of any of embodiments 1-29, wherein the base oil is present in an amount in the range of 70 to 99 wt%, e.g., in the range of 70 to 95 wt%, or 70 to 90 wt%, or 70 to 80 wt%.

[0129] Embodiment 31 provides the lubricating composition of any of embodiments 1-29, wherein the base oil is present in an amount of at least 80 wt%, e.g., in the range of 80 to 99 wt%, or 80 to 95 wt%, or 80 to 90 wt%, or 80 to 85 wt%.

[0130] Embodiment 32 provides the lubricating composition of any of embodiments 1-29, wherein the base oil is present in an amount of at least 85 wt%, e.g., in the range of 85 to 99 wt%, or 85 to 95 wt%, or 85 to 90 wt%.

[0131] Embodiment 33 provides the lubricating composition of any of embodiments 1-29, wherein the base oil is present in an amount of at least 90 wt%, e.g., in the range of 90 to 99 wt%, or 90 to 95 wt%, or 95 to 99 wt%.

[0132] Embodiment 34 provides the lubricating composition of any of embodiments 1-33, further comprising one or more of friction modifiers, dispersants (e.g., metallic and non- metallic), dispersant viscosity modifiers, detergents (e.g., metallic and non-metallic), viscosity index improvers, viscosity modifiers, pour point depressants, rust inhibitors, corrosion inhibitors, antioxidants, anti-foams, seal swell agents, extreme pressure additives (e.g., metallic, non-metallic, phosphorus containing, non-phosphorus containing, sulfur containing, and non-sulfur containing), surfactants, demulsifiers, anti-seizure agents, wax modifiers, lubricity agents, anti-staining agents, chromophoric agents, metal deactivators, and any combination thereof.

[0133] Embodiment 35 provides a method of lubricating a surface, the method comprising contacting the surface with a lubricating composition of any of embodiments 1-34. [0134] Embodiment 36 provides a method of reducing wear on a surface, the method including lubricating an interface between the surface and a contacting surface with a lubricating composition of any of embodiments 1-35.

[0135] Embodiment 37 provides the method of embodiment 35 or embodiment 36, wherein the surface is a surface of an engine, a motor, a turbine, or a transmission (e.g., a transmission in fluid connection with a motor, such as an electric motor).

[0136] Embodiment 38 provides use of a lubricating composition of any of embodiments 1- 34 for lubricating a surface.

[0137] Embodiment 39 provides use of a lubricating composition of any of embodiments 1- 34 for reducing wear on a surface.

[0138] Embodiment 40 provides the use of embodiment 39 to lubricate an interface between the surface and a contacting surface.

[0139] Embodiment 41 provides the use of one or more antiwear compounds having the formula: wherein each of Ri, R ₂ , and R ₃ is independently selected from phenyl substituted with one, two or three substituents each selected from C ₁ -C ₃ alkoxy and NO _2, for lubricating a surface, or for reducing wear on a surface.

[0140] Embodiment 42 provides the use of embodiment 41 , wherein the or more antiwear compounds are as further described in any of embodiments 2-35.

[0141] Embodiment 43 provides the use of any of embodiments 38-42, wherein the surface is a surface of an engine, a motor, a turbine, or a transmission (e.g., a transmission in fluid connection with a motor, such as an electric motor).

[0142] Numerous references have been made to patents and printed publications throughout this specification. Each of the cited references and printed publications are individually incorporated herein by reference in their entirety.

[0143] In closing, it is to be understood that the embodiments of the invention disclosed herein are illustrative of the principles of the present invention. Other modifications that may be employed are within the scope of the invention. Thus, by way of example, but not of limitation, alternative configurations of the present invention may be utilized in accordance with the teachings herein. Accordingly, the present invention is not limited to that precisely as shown and described.