LUBRICATING OIL COMPOSITIONS

Description

PRIORITY

This application claims priority to Great Britian patent application GB 2416467.5, filed Nov. 8, 2024.

FIELD OF THE INVENTION

This disclosure relates to the use of additives in lubricant compositions providing good oxidation, wear, and anti-corrosion properties, particularly for spark or compression ignited engine applications.

BACKGROUND OF THE INVENTION

The present invention relates to internal combustion engine lubricating oil compositions, which exhibit improved oxidation, wear and anti-corrosion characteristics. More specifically, the present invention relates to automotive crankcase lubricating oil compositions for use in gasoline (spark-ignited) and diesel (compression-ignited) internal combustion engines, such compositions being referred to as crankcase lubricants; and to the use of additives in such lubricating oil compositions for reducing corrosion and wear in use of such engines while improving the anti-oxidation performance of an engine lubricated with the lubricating oil composition.

The emphasis on fuel economy has been increased in recent years. One approach to improve the fuel economy of vehicles is to design new lubricant oils that reduce friction while maintaining a good film thickness for durability and wear protection while also preventing soot-induced viscosity increase. In an attempt to improve fuel economy, the use and stipulation of low viscosity grades by Original Equipment Manufacturers (OEM) is becoming increasingly widespread. One of the challenges for the provision of engine and/or drive train transmission oils having these reduced viscosity grades is maintaining cleanliness. Such oils must be able to reduce sludge, provide good soot handling, and provide wear protection, whilst providing desired fuel economy benefits. These targets should be achieved while maintaining low levels of sulphated ash and phosphorus, as well as ensuring seal compatibility. There is a need to provide new engine oils having low viscosity grades that meet these requirements.

U.S. Pat. No. 6,074,993 discloses a lubricating oil composition exhibiting improved fuel economy and wet clutch friction properties. The composition comprises: (a) an oil of lubricating viscosity; (b) at least one calcium or magnesium overbased detergent; (c) an oil soluble dimeric molybdenum compound; (d) an oil soluble organic trinuclear molybdenum compound; (e) at least one zinc dihydrocarbyldithiophosphate compound, wherein the composition has a TBN of at least 3.6 from the calcium or magnesium overbased detergent, a NOACK volatility of about 15 wt. % or less, molybdenum in an amount up to about 350 ppm from the trinuclear molybdenum compound, molybdenum in an amount up to 2,000 ppm from the dimeric molybdenum compound, and phosphorus in an amount up to about 0.1 wt. % from a zinc dihydrocarbyldithiophosphate compound.

U.S. Pat. No. 6,300,291 discloses lubricating oil composition exhibiting improved low temperature anti-wear performance and improved fuel economy and fuel economy retention properties. The composition comprises: (a) an oil of lubricating viscosity; (b) at least one calcium detergent; (c) at least one oil soluble molybdenum compound; (d) at least one nitrogen containing friction modifier; and (e) at least one zinc dihydrocarbyldithiophosphate compound, wherein the composition has a NOACK volatility of about 15.5 wt. % or less and contains from about 0.058 to 0.58 wt. % calcium from the calcium detergent, molybdenum in an amount up to about 350 ppm from a molybdenum compound, and phosphorus in an amount up to about 0.1 wt. % from a zinc dihydrocarbyldithiophosphate compound.

Pat. Pub. US2002/0137636 discloses a molybdenum-free lubricating oil composition exhibiting improved fuel economy and fuel economy retention properties. The composition comprises: (a) a major amount of base stock selected from the group consisting of one or more Group IV or Group V oils and mixtures thereof, and mixtures containing one or more Group III oils and at least one Group IV and/or Group V oils, the base stock having a NOACK volatility of 12% or less; and; (b) at least one calcium detergent; and (c) 0.2 to 2.0 wt. % of an organic friction modifier, wherein the composition has aNOACK volatility of about 12 wt. % or less and contains from about 0.058 to 0.58 wt. % calcium from the calcium detergent.

Pat. Pub. US2024/0141250A1 discloses a lubricating oil composition comprising or resulting from the admixing of: a) 50 to 99 wt % of one or more base oils; b) 0.1 to 15 wt % of one or more functionalized olefin copolymer having an M_n of from 10,000 to 35,000 g/mol; c) 0.1 to 20 wt % of one or more detergents wherein the detergent comprises at least one calcium detergent having a TBN of more than 100 mg KOH/g; at least one calcium detergent having a TBN of 100 mg KOH/g or less; and at least one magnesium detergent, where the difference in the TBN's for the Ca detergents is at least 100 mg KOH/g; d) 0.01 to 40 wt % of one or more dispersants wherein the dispersants comprise at least one borated dispersant and at least one non-borated dispersant; e) 0.01 to 20 of wt % sulfurized fatty acid ester; f) 0.01 to 5 wt % of one or more amine or phenol based antioxidants; and g) 0.001 to 15 wt % of molybdenum-containing compound.

Other references of interest include U.S. Pat. Nos. 5,895,779, 6,143,701, and 9,963,656 and Pat. Pub. No. US20070132274A1.

It has now surprisingly been found that the described combinations comprising amine functionalized olefin copolymer dispersant, alkaline earth metal salicylate and/or sulfonate detergents in combination with molybdenum-containing compounds, antioxidants and sulfurized fatty acid esters can be used in a lubricant composition, such as in internal combustion engines, to provide excellent viscosity, oxidation, wear and anti-corrosion properties, especially while maintaining sulfated ash, total base number, and soot properties for spark or compression ignited engine applications.

SUMMARY OF THE INVENTION

This disclosure relates to a lubricating oil composition comprising or resulting from the admixing of, based upon the total weight of the lubricating composition:

• • a) from 50 to 99 wt % of a base oil composition comprising one or more Group III base oils, one or more Group III+ base oils, one or more Group IV base oils, or a combination thereof;
  • b) from 0.1 to 15 wt % of a functionalized olefin copolymer having an M_n in the range of from about 10,000 g/mol to about 35,000 g/mol;
  • c) 0.1 to 20 wt % of a detergent composition comprising:
    • i) at least one first calcium detergent having a first TBN of greater than 100 mg KOH/g;
    • ii) at least one second calcium detergent having a second TBN of less than or equal to 100 mg KOH/g; and
    • iii) at least one magnesium detergent;
    • wherein the first TBN minus the second TBN is greater than or equal to 100 mg KOH/g;
  • d) from 0.01 to 40 wt % of a dispersant composition comprising:
    • i) at least one borated dispersant; and
    • ii) at least one non-borated dispersant;
  • e) a friction modifier composition comprising:
    • i) from 0.01 to 20 wt % of a sulfurized fatty acid ester; and
    • ii) from 0.01 to 10 wt % of a molybdenum-containing compound; and
  • f) from 0.01 to 10 wt % of an amine-based antioxidant, a phenol-based antioxidant, or a combination thereof;
  • wherein
    • the lubricating oil composition comprises molybdenum in an amount in the range of from 250 to 1,000 ppm by weight, according to ASTM D5185; and
    • the weight % of each component is based on the total weight of the lubricating oil composition.

In some embodiments, the lubricating oil composition is classified as OW-16, OW-20, OW-30, 5W-16, 5W-20, or 5W-30, according to SAE J300.

In some embodiments, the lubricating oil composition has a fuel economy of greater than 0.82%, greater than or equal to 0.83%, according to CEC L-101-09.

In some embodiments, the lubricating oil composition has:

• • i) a cold cranking simulator (CCS) test value at −35° C. of less than or equal to 6,600 cP, less than or equal to 6,200 cP, or less than or equal to 4,500 cP, according to ASTM D5293;
  • ii) a kinematic viscosity at 100° C. (KV₁₀₀) of less than or equal to 12.5 cSt, according to ASTM D445-19a; and
  • iii) a high temperature high shear (HTHS) viscosity at 150° C. of greater than or equal to 2.3 mPa·s, according to CEC-L-36 (ASTM D4683-20).
  • iv) a pour point of less than or equal to −40° C., according to ASTM D97;
  • v) a viscosity index in the range for from 150 to 175, according to ASTM D2270;
  • vi) a Noack volatility less than or equal to 15 wt %, according to CEC L-40-A-93; or
  • vii) a combination thereof.

In some embodiments, the lubricating oil composition has:

• • i) a phosphorus content in the range of from 300 to 1,000 ppm, from 400 to 900 ppm, from 500 to 800 ppm by weight, according to EN 14107;
  • ii) a sulfur content of less than 0.3 wt %, according to ASTM D5185;
  • iii) a sulfated ash content of less than 1.0 wt %, less than 0.9 wt %, less than 0.8 wt %, less than 0.7 wt %, or less than 0.6 wt %, according to ASTM D874; or
  • iv) a combination thereof.

While the disclosed process and composition are susceptible to various modifications and alternative forms, the drawings illustrate specific embodiments herein described in detail by way of example. It should be understood, however, that the description herein of specific embodiments is not intended to limit the invention to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The claimed subject matter may be understood by reference to the following description taken in conjunction with the accompanying drawings, in which like reference numerals identify like elements, and in which FIG. 1 is a graph comparing measured fuel economy for comparative and inventive blends disclosed herein.

While the disclosed process and system are susceptible to various modifications and alternative forms, the drawings illustrate specific embodiments and/or aspects herein described in detail by way of example. It should be understood, however, that the description herein of a specific embodiment is not intended to limit the invention to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.

DETAILED DESCRIPTION OF THE INVENTION

Illustrative embodiments of the subject matter claimed below will now be disclosed. In the interest of clarity, some features of some actual implementations may not be described in this specification. It will be appreciated that in the development of any such actual embodiments, numerous implementation-specific decisions must be made to achieve the developer's specific goals, such as compliance with system-related and business-related constraints, which will vary from one implementation to another. Moreover, it will be appreciated that such a development effort, even if complex and time-consuming, would be a routine undertaking for those of ordinary skill in the art having the benefit of this disclosure.

The words and phrases used herein should be understood and interpreted to have a meaning consistent with the understanding of those words and phrases by those skilled in the relevant art. No special definition of a term or phrase, i.e., a definition that is different from the ordinary and customary meaning as understood by those skilled in the art, is intended to be implied by consistent usage of the term or phrase herein. To the extent that a term or phrase is intended to have a special meaning, i.e., a meaning other than the broadest meaning understood by skilled artisans, such a special or clarifying definition will be expressly set forth in the specification in a definitional manner that provides the special or clarifying definition for the term or phrase.

For example, the following discussion contains a non-exhaustive list of definitions of several specific terms used in this disclosure (other terms may be defined or clarified in a definitional manner elsewhere herein). These definitions are intended to clarify the meanings of the terms used herein. It is believed that the terms are used in a manner consistent with their ordinary meaning, but the definitions are nonetheless specified here for clarity.

Definitions

As used herein, “A.I.”, “a.i.”, or “ai” is active ingredient.

As used herein, “absent” as it relates to components included within the lubricating oil compositions described herein and the claims thereto means that the particular component is present at 0 wt %, based upon the weight of the lubricating oil composition, or if present in the lubricating oil composition the component is present at levels that do not impact the lubricating oil composition properties, such as less than 10 ppm, or less than 1 ppm or less than 0.001 ppm.

As used herein, “active ingredient” (also referred to as “a.i.” or “A.I.”) refers to additive material that is neither diluent nor solvent.

As used herein, “aliphatic hydrocarbyl fatty acid ester” (also referred to as “fatty acid ester”) means an ester obtainable by converting the monocarboxylic acid functional group of the corresponding aliphatic hydrocarbyl fatty acid into an ester group. Suitably, the monocarboxylic acid functional group of the aliphatic hydrocarbyl fatty acid is converted to a hydrocarbyl ester such as, but not limited to, a C₁ to C₃₀ aliphatic hydrocarbyl ester or an alkyl ester, such as a C₁ to C₆ alkyl ester or a methyl ester. Alternatively, or additionally, the monocarboxylic acid functional group of the aliphatic hydrocarbyl fatty acid may be in the form of the natural glycerol ester. Accordingly, the term “aliphatic hydrocarbyl fatty acid ester” embraces aliphatic hydrocarbyl fatty acid glycerol ester(s) and aliphatic hydrocarbyl fatty acid C₁ to C₃₀ aliphatic hydrocarbyl ester(s), (e.g. aliphatic hydrocarbyl fatty acid alkyl ester(s), such as, but not limited to, aliphatic hydrocarbyl fatty acid C₁ to C₆ alkyl ester(s), especially aliphatic hydrocarbyl fatty acid methyl ester(s), also referred to as “fatty acid methyl ester(s)”). Suitably, the term “aliphatic hydrocarbyl fatty acid ester” embraces aliphatic (C₇ to C₂₉) hydrocarbyl, aliphatic (C₉ to C₂₇) hydrocarbyl, aliphatic (C₁₁ to C₂₃) hydrocarbyl fatty acid glycerol ester(s) and aliphatic (C₇ to C₂₉) hydrocarbyl, aliphatic (C₉ to C₂₇) hydrocarbyl, or aliphatic (C₁₁ to C₂₃) hydrocarbyl fatty acid C₁ to C₃₀ aliphatic hydrocarbyl ester(s). Suitably, to permit functionalization, such as sulfurization, of the aliphatic hydrocarbyl fatty acid ester(s) a proportion of the aliphatic hydrocarbyl chain(s) of the fatty acid ester(s) is unsaturated and includes at least one carbon to carbon double bond.

As used herein, “aliphatic hydrocarbyl fatty acid” (also referred to as “fatty acid”) means a monocarboxylic acid having an aliphatic C₇ to C₂₉, a C₉ to C₂₇, or a C₁₁ to C₂₃ hydrocarbyl chain. Such compounds may be referred to herein as a C₇ to C₂₉ aliphatic, a C₉ to C₂₇ aliphatic, or a C₁₁ to C₂₃ aliphatic, hydrocarbyl monocarboxylic acid(s) or hydrocarbyl fatty acid(s) (wherein C_x to C_y designates the total number of carbon atoms in the aliphatic hydrocarbyl chain of the fatty acid, the fatty acid itself due to the presence of the carboxyl carbon atom includes a total of C_x+1 to C_y+1 carbon atoms). In some embodiments, the aliphatic hydrocarbyl fatty acid, inclusive of the carboxyl carbon atom, has an even number of carbon atoms. The aliphatic hydrocarbyl chain of the fatty acid may be saturated or unsaturated (i.e. includes at least one carbon to carbon double bond). In some embodiments, the aliphatic hydrocarbyl chain is unsaturated and includes at least one carbon to carbon double bond—such fatty acids may be obtained from natural sources (e.g. derived from animal or vegetable oils) and/or by reduction of the corresponding saturated fatty acid. It will be appreciated that a proportion of the aliphatic hydrocarbyl chain(s) of the corresponding aliphatic hydrocarbyl fatty acid ester(s) is unsaturated (i.e. includes at least one carbon to carbon double bond) to permit reaction with other agents, such as sulfur, to form the corresponding functionalized, such as sulfurized, aliphatic hydrocarbyl fatty acid ester(s).

As used herein, “alkenyl” means a radical of carbon and hydrogen (such as a C₂ to C₃₀ radical, such as a C₂ to C₁₂ radical) having at least one double bond. Alkenyl groups in a compound are typically bonded to the compound directly via a carbon atom. Unless otherwise specified, alkenyl groups may be linear (i.e. unbranched) or branched, be cyclic, acyclic or part cyclic/acyclic.

As used herein, “alkyl substituted phenyl” is a phenyl group where a hydrogen atom has been replaced by an alkyl group, such as a C₁ to C₂₀ alkyl group, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, hexyl, heptyl, octyl, dimethyl hexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl and/or triacontyl.

As used herein, “alkyl” means a radical of carbon and hydrogen (such as a C₁ to C₃₀, such as a C₁ to C₁₂ group). Alkyl groups in a compound are typically bonded to the compound directly via a carbon atom. Unless otherwise specified, alkyl groups may be linear (i.e. unbranched) or branched, be cyclic, acyclic or part cyclic/acyclic. In some embodiments, the alkyl group comprises a linear or branched acyclic alkyl group. Representative examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, hexyl, heptyl, octyl, dimethyl hexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl and triacontyl.

As used herein, “alkylene” means a C₁ to C₂₀ or a C₁ to C₁₀ bivalent saturated aliphatic radical which may be linear or branched. Representative examples of alkylene include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, 1-methyl ethylene, 1-ethyl ethylene, 1-ethyl-2-methyl ethylene, 1,1-dimethyl ethylene and 1-ethyl propylene.

As used herein, “alkynyl” means a C₂ to C₃₀ (such as a C₂ to C₁₂) radical which includes at least one carbon to carbon triple bond.

As used herein, “aryl” means a group containing at least one aromatic ring, such a cyclopentadiene, phenyl, naphthyl, anthracenyl, and the like. Aryl groups are typically C₅ to C₄₀ (such as Cs to C₁₈, such as C₆ to C₁₄) aryl groups, optionally substituted by one or more hydrocarbyl groups, heteroatoms, or heteroatom containing groups (such as halo, hydroxyl, alkoxy and amino groups). In some embodiments, aryl groups include phenyl and naphthyl groups and substituted derivatives thereof, especially phenyl, and alkyl substituted derivatives of phenyl.

As used herein, “ash-containing” in relation to an additive means the additive includes a metal.

As used herein, “ashless” in relation to an additive means the additive does not include a metal.

As used herein, “base oil” (also referred to as “basestock,” “lubricating oil basestock,” or “oil of lubricating viscosity”) means a single oil or a blend of oils, and is typically a large liquid constituent of a lubricating composition, also referred to as a lubricant, into which additives and optional additional oils are blended, for example, to produce a lubricating composition, such as a final lubricant composition, a concentrate, or other lubricating composition.

As used herein, “CEC” is the Coordinating European Council, which develops and maintains standardized test methods for evaluating the quality and performance of fuels, lubricants, and related products in the automotive and industrial sectors.

As used herein, “comprising” is to be interpreted as specifying the presence of the stated features, integers, steps, or components as referred to, but does not preclude the presence or addition of one or more features, integers, steps, or components, or groups thereof. Moreover, each of the terms “by”, “comprising,” “comprises”, “comprised of” “including,” “includes,” “included,” “involving,” “involves,” “involved,” and “such as” are used in their open, non-limiting sense and may be used interchangeably. Further, the term “comprising” is intended to include examples and aspects encompassed by the terms “consisting essentially of” and “consisting of.” Similarly, the term “consisting essentially of” is intended to include examples encompassed by the term “consisting of.”

As used herein, “consisting essentially of” excludes additional material elements, but allows the inclusions of non-material elements that do not substantially change the nature of the invention.

As used herein, “consisting of” is closed and excludes all additional elements.

As used herein, “conversion” is used to denote the percentage of a component fed which disappears across a reactor.

As used herein, “effective amount” in respect of an additive means an amount of such an additive in a lubricating oil composition so that the additive provides the desired technical effect.

As used herein, “effective minor amount” in respect of an additive means an amount of such an additive of less than 50 wt % of the lubricating oil composition so that the additive provides the desired technical effect.

As used herein, “group” and “radical” are used interchangeably herein.

As used herein, “halogen” or “halo” means a group 17 atom or a radical of group 17 atom, such as fluoro, chloro, bromo and iodo.

As used herein, “hydrocarbon” means a compound of hydrogen and carbon atoms. A “heteroatom” is an atom other than carbon or hydrogen. When referred to as “hydrocarbons,” particularly as “refined hydrocarbons,” the hydrocarbons may also contain one or more heteroatoms or heteroatom containing groups (such as halo, especially chloro and fluoro, amino, alkoxyl, mercapto, alkylmercapto, nitro, nitroso, sulfoxy, etc.) in minor amounts (e.g., where the heteroatom(s) do not substantially alter the hydrocarbon properties of the hydrocarbon compound).

As used herein, “hydrocarbyl” means a radical that contains hydrogen and carbon atoms. In some embodiments, the group consists essentially of or consists only of hydrogen and carbon atoms, unless specified otherwise. In some embodiments, the hydrocarbyl group comprises an aliphatic hydrocarbyl group. The term “hydrocarbyl” includes “alkyl,” “alkenyl,” “alkynyl,” and “aryl” as defined herein. Hydrocarbyl groups may contain one or more atoms/groups other than carbon and hydrogen provided they do not affect the essentially hydrocarbyl nature of the hydrocarbyl group. Those skilled in the art will be aware of such atoms/groups (e.g., halo, especially chloro and fluoro, amino, alkoxyl, mercapto, alkylmercapto, nitro, nitroso, sulfoxy, etc.).

As used herein, “LOC” means lubricating oil composition.

As used herein, “major amount” means more than 50 wt % of a composition, such as more than 60 wt % of a composition, such as more than 70 wt % of a composition, such as from 80 to 99.009 wt % of a composition, such as from 80 to 99.9 from 80 to 99.009 wt % of a composition, of a composition based upon the weight of the composition.

As used herein, “metal content” of a lubricating oil composition or of an additive component, for example magnesium content, molybdenum-content or total metal content (i.e. the sum of all individual metal contents), is measured by ASTM D5185.

As used herein, “minor amount” means 50 wt % or less of a composition; such as 40 wt % or less of a composition; such as 30 wt % or less of a composition, such as from 20 to 0.001 wt %, such as from 20 to 0.1 wt %, based upon the weight of the composition.

As used herein, “M_n” is number average molecular weight and is reported in g/mol.

As used herein, “oil-soluble” and “oil-dispersible,” or cognate terms, used herein do not necessarily indicate that the compounds or additives are soluble, dissolvable, miscible, or are capable of being suspended in the oil in all proportions. These do mean, however, that they are, for example, soluble or stably dispersible in oil to an extent sufficient to exert their intended effect in the environment in which the oil is employed. Moreover, the additional incorporation of other additives may also permit incorporation of higher levels of a particular additive, if desired.

As used herein, “olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For purposes of this specification and the claims appended thereto, when a polymer or copolymer is referred to as comprising an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an “ethylene” content of 35 wt % to 55 wt %, it is understood that the mer unit in the copolymer is derived from ethylene in the polymerization reaction and said derived units are present at 35 wt % to 55 wt %, based upon the weight of the copolymer. A “polymer” has two or more of the same or different mer units. A “homopolymer” is a polymer having mer units that are the same. A “copolymer” is a polymer having two or more mer units that are different from each other. A “terpolymer” is a polymer having three mer units that are different from each other. Accordingly, the definition of copolymer, as used herein, includes terpolymers and the like. “Different” as used to refer to mer units indicates that the mer units differ from each other by at least one atom or are different isomerically. An “ethylene polymer” or “ethylene copolymer” is a polymer or copolymer comprising at least 50 mole % ethylene derived units, a “propylene polymer” or “propylene copolymer” is a polymer or copolymer comprising at least 50 mole % propylene derived units, and so on.

As used herein, “PIB” is polyisobutylene.

As used herein, “PIBSA” is polyisobutylene succinic anhydride.

As used herein, “PIBSA-PAM is polyisobutylene succinic anhydride-polyamine.

As used herein, “ppm” means parts per million by wt, based on the total weight of the lubricating oil composition, unless otherwise indicated.

As used herein, “substituted” means that a hydrogen atom has been replaced with hydrocarbon group, a heteroatom or a heteroatom containing group. An alkyl substituted derivative means a hydrogen atom has been replaced with an alkyl group.

As used herein, “sulfated ash content” is measured by ASTM D874.

As used herein, “sulfur content” is measured according to ASTM D5185 for full lubricating oil formulations (i.e., lower concentrations of measured element) and ASTM D4951 for additive package or concentrate (i.e., lower concentrations of measured element).

As used herein, “sulfurized aliphatic hydrocarbyl fatty acid ester” (also referred to as “sulfurized fatty acid”) means a compound obtained by sulfurizing an aliphatic hydrocarbyl fatty acid ester as defined herein, and includes “sulfurized aliphatic hydrocarbyl fatty acid methyl esters” (also referred to as “sulfurized fatty acid methyl esters”).

As used herein, “Total Acid Number” also referred to as “TAN” means total acid number as measured by ASTM D664.

As used herein, “Total Base Number” also referred to as “TBN” in relation to an additive component or of a lubricating oil composition (i.e. unused lubricating oil composition) means total base number as measured by ASTM D2896.

As used herein, “wt %” means weight percent of a component, based upon the weight of the composition, unless otherwise indicated, and is alternately referred to as weight percent (“weight %”, “wt %” or “% w/w”).

For purposes herein, the new numbering scheme for the Periodic Table of the Elements is used as set out in CHEMICAL AND ENGINEERING NEWS, 63(5), 27 (1985), i.e., alkali metals are Group 1 metals (e.g. Li, Na, K, etc.) and alkaline earth metals are Group 2 metals (e.g., Mg, Ca, Ba, etc.)

Unless otherwise indicated, all percentages reported are wt % on an active ingredient basis, i.e., without regard to carrier or diluent oil, unless otherwise stated.

Also, it will be understood that various components used, essential as well as optimal and customary, may react under conditions of formulation, storage or use and that the invention also provides the product obtainable or obtained as a result of any such reaction.

Lubricating Oil Compositions

The lubricating oil compositions disclosed herein comprise components that may or may not remain the same chemically before and after mixing with an oleaginous carrier (such as a base oil) and/or other additives. This disclosure encompasses compositions which comprise the components before mixing, or after mixing, or both before and after mixing.

This disclosure relates to lubricating oil compositions (also referred to as “lubricant compositions,” “lubricating compositions,” “lubricant oil compositions,” or “LOC's) comprising or resulting from the admixing of:

• • a) from 50 to 99 wt %, from 30 to 95 wt %, from 50 to 90 wt %, from 60 to 95 wt %, or from 70 to 85 wt % of a base oil composition comprising one or more Group III base oils, one or more Group III+ base oils, one or more Group IV base oils, or a combination thereof;
  • b) from 0.1 to 15 wt %, from 0.15 to 10 wt %, from 0.2 to 5 wt %, from 0.25 to 4 wt %, or from 0.5 to 3 wt % of a functionalized olefin copolymer having an M_n in the range of from about 10,000 g/mol to about 35,000 g/mol;
  • c) from 0.1 to 20 wt %, from 0.15 to 10 wt %, from 0.20 wt % to 5 wt %, or from 0.25 to 2 wt % of a detergent composition comprising:
    • i) at least one first calcium detergent having a first TBN of greater than 100 mg KOH/g, greater than 200 mg KOH/g, greater than 250 mg KOH/g, greater than 300 mg KOH/g, or greater than 350 mg KOH/g;
    • ii) at least one second calcium detergent having a second TBN of less than or equal to 150 mg KOH/g, less than or equal to 100 mg KOH/g, less than or equal to 80 mg KOH/g, or less than or equal to 30 mg KOH/g; and
    • iii) at least one magnesium detergent having a TBN of greater than 100 mg KOH/g, greater than 200 mg KOH/g, greater than 250 mg KOH/g, greater than 300 mg KOH/g, greater than 350 mg KOH/g, greater than 499 mg KOH/g, or greater than 450 mg KOH/g;
    • wherein the first TBN minus the second TBN is greater than or equal to 100 mg KOH/g, greater than or equal to 150 mg KOH/g, or greater than or equal to 200 mg KOH/g;
  • d) from 0.01 to 40 wt %, from 0.1 to 15 wt %, from 1 to 12 wt %, or from 2 to 10 wt % of a dispersant composition comprising:
    • i) at least one borated dispersant; and
    • ii) at least one non-borated dispersant; (not including component b) when present);
  • e) a friction modifier composition comprising:
    • i) from 0.01 to 20 wt %, from 0.1 to 5 wt %, 0.2 to 4 wt %, 0.3 to 3 wt %, 0.4 to 2 wt %, or 0.4 to 1 wt % of a sulfurized fatty acid ester;
    • ii) from 0.01 to 10 wt %, from 0.025 to 5 wt %, from 0.05 to 4 wt %, from 0.05 to 3 wt %, or from 0.05 to 1 wt % of a molybdenum-containing compound; and
  • f) from 0.01 to 10 wt %, from 0.5 to 5 wt %, from 1 to 4 wt %, or from 1.5 to 3 wt % of an amine-based antioxidant, a phenol-based antioxidant, or a combination thereof;
  • wherein
    • the lubricating oil composition comprises molybdenum in an amount in the range of from 250 to 1,000 ppm, from 350 to 900 ppm, from 400 to 800 ppm, from 450 to 700 ppm, or from 500 to 600 ppm by weight, according to ASTM D5185; and
    • the weight % of each component is based on the total weight of the lubricating oil composition.

In some embodiments, the lubricating oil composition is classified as OW-16, OW-20, OW-30, 5W-16, 5W-20, or 5W-30, according to SAE J300.

In some embodiments, the lubricating oil composition has a fuel economy of greater than 0.82%, greater than or equal to 0.83%, according to CEC L-101-09.

In some embodiments, the lubricating oil composition has:

• • i) a cold cranking simulator (CCS) test value at −35° C. of less than or equal to 6,600 cP, less than or equal to 6,200 cP, or less than or equal to 4,500 cP, according to ASTM D5293;
  • ii) a kinematic viscosity at 100° C. (KV₁₀₀) of less than or equal to 12.5 cSt, less than or equal to 9.3 cSt, or less than or equal to 8.2 cSt, according to ASTM D445-19a; and
  • iii) a high temperature high shear (HTHS) viscosity at 150° C. of greater than or equal to 2.3 mPa·s, greater than or equal to 2.6 mPa·s, or greater than or equal to 2.9 mPa·s, according to CEC-L-36 (ASTM D4683-20).
  • iv) a pour point of less than or equal to −40° C. or than or equal to −45° C. 2.3, according to ASTM D97;
  • v) a viscosity index in the range for from 150 to 175, from 150 to 165, or from 160 to 175, according to ASTM D2270;
  • vi) a Noack volatility less than or equal to 15 wt %, according to CEC L-40-A-93; or
  • vii) a combination thereof.

In some embodiments, the lubricating oil composition has:

• • i) a phosphorus content in the range of from 300 to 1,000 ppm, from 400 to 900 ppm, from 500 to 800 ppm by weight, according to EN 14107;
  • ii) a sulfur content of less than 0.3 wt %, according to ASTM D5185;
  • iii) a sulfated ash content of less than 1.0 wt %, less than 0.9 wt %, less than 0.8 wt %, less than 0.7 wt %, or less than 0.6 wt %, according to ASTM D874; or
  • iv) a combination thereof.

In some embodiments, the lubricating oil composition comprises or results from the admixing of:

• • A) from 50 to 99 wt %, from 30 to 95 wt %, from 50 to 90 wt %, from 60 to 95 wt %, or from 70 to 85 wt % of one or more base oils;
  • B) from 0.1 to 15 wt %, from 0.15 to 10 wt %, from 0.2 to 5 wt %, from 0.25 to 4 wt %, or from 0.5 to 3 wt % of a functionalized olefin copolymer having an M_n in the range of from about 10,000 g/mol to about 35,000 g/mol;
  • C) from 0.1 to 20 wt %, from 0.15 to 10 wt %, from 0.20 wt % to 5 wt %, or from 0.25 to 2 wt % of one or more detergents, wherein the one or more detergents comprises:
    • i) at least one first calcium detergent having a first TBN of greater than 100 mg KOH/g;
    • ii) at least one second calcium detergent having a second TBN of less than or equal to 100 mg KOH/g; and
    • iii) at least one magnesium detergent;
    • wherein the first TBN minus the second TBN is greater than or equal to 100 mg KOH/g;
  • D) from 0.01 to 40 wt %, from 0.1 to 15 wt %, from 1 to 12 wt %, or from 2 to 10 wt % of one or more dispersants, wherein the one or more dispersants comprise:
    • i) at least one borated dispersant; and
    • ii) at least one non-borated dispersant; (not including component b) when present);
  • E) a friction modifier composition comprising:
    • E-1) 0.01 to 20 wt %, from 0.1 to 5 wt %, from 0.2 to 4 wt %, from 0.3 to 3 wt %, from 0.4 to 2 wt %, or from 0.4 to 1 wt % of a sulfurized fatty acid ester;
    • E-3) from 0.01 to 10 wt %, from 0.025 to 5 wt %, from 0.05 to 4 wt %, from 0.05 to 3 wt %, or from 0.05 to 1 wt % of a molybdenum-containing compound; and
    • E-2) optionally, from 0.01 to 5 wt %, from 0.1 to 4 wt %, or from 0.25 to 3 wt %, based on total weight of the lubricating composition, of one or more friction modifiers other than the sulfurized fatty acid ester of E-1 and Mo containing compound of E-3, (such as but not limited to blends of friction modifiers);
  • F) from 0.01 to 10 wt %, from 0.5 to 5 wt %, from 1 to 4 wt %, or from 1.5 to 3 wt % of an amine-based antioxidant, a phenol-based antioxidant, or a combination thereof;
  • G) optionally, from 0.01 to 5 wt %, from 0.01 to 3 wt %, or from 0.1 to 1.5 wt % of one or more pour point depressants (such as but not limited to blends of pour point depressants);
  • H) optionally, from 0.001 to 5 wt %, from 0.01 to 3 wt %, or from 0.1 to 1.5 wt % of one or more anti-foam agents (such as blends of anti-foam agents);
  • I) optionally, from 0.001 to 10 wt %, from 0.01 to 6 wt %, from 0.01 to 5 wt %, from 0.1 to 4 wt %, from 0.1 to 2 wt %, or from 0.1 to 1 wt % of one or more viscosity modifiers (such as but not limited to blends of viscosity modifiers);
  • J) optionally, from 0.01 to 5 wt %, from 0.1 to 3 wt %, or from 0.1 to 1.5 wt % of one or more corrosion inhibitors and/or antirust agents (such as but not limited to blends of corrosion inhibitors and/or antirust agents);
  • K) optionally, from 0.001 to 10 wt %, from 0.1 to 5 wt %, from 0.15 to 3 wt %, or from 0.15 to 1.5 wt % of one or more anti-wear agents (such as but not limited to blends of anti-wear agents); and/or
  • O) optionally, from 0.001 to 15 wt %, from 0.15 to 10 wt %, from 0.20 wt % to 5.0 wt %, or from 0.25 to 2.0 wt % of one or more C₈ to C₃₆ alpha olefins;
  • wherein
    • the lubricating oil composition comprises molybdenum in an amount in the range of from 250 to 1,000 ppm, from 350 to 900 ppm, from 400 to 800 ppm, from 450 to 700 ppm, or from 500 to 600 ppm by weight, according to ASTM D5185; and
    • the weight % of each component is based on the total weight of the lubricating oil composition.

In some embodiments, the lubricating oil composition is classified as OW-16, OW-20, OW-30, 5W-16, 5W-20, or 5W-30, according to SAE J300.

In some embodiments, the lubricating oil composition has a fuel economy of greater than 0.82%, greater than or equal to 0.83%, according to CEC L-101-09.

In some embodiments, the lubricating oil composition has:

• • i) a cold cranking simulator (CCS) test value at −35° C. of less than or equal to 6,600 cP, less than or equal to 6,200 cP, or less than or equal to 4,500 cP, according to ASTM D5293;
  • ii) a kinematic viscosity at 100° C. (KV₁₀₀) of less than or equal to 12.5 cSt, less than or equal to 9.3 cSt, or less than or equal to 8.2 cSt, according to ASTM D445-19a;
  • iii) a high temperature high shear (HTHS) viscosity at 150° C. of greater than or equal to 2.3 mPa·s, greater than or equal to 2.6 mPa·s, or greater than or equal to 2.9 mPa·s, according to CEC-L-36 (ASTM D4683-20);
  • iv) a pour point of less than or equal to −40° C. or than or equal to −45° C. 2.3, according to ASTM D97;
  • v) a viscosity index in the range for from 150 to 175, from 150 to 165, or from 160 to 175, according to ASTM D2270;
  • vi) a Noack volatility less than or equal to 15 wt %, according to CEC L-40-A-93; or
  • vii) a combination thereof.

In some embodiments, the lubricating oil composition has:

• • i) a phosphorus content in the range of from 300 to 1,000 ppm, from 400 to 900 ppm, from 500 to 800 ppm by weight, according to EN 14107;
  • ii) a sulfur content of less than 0.3 wt %, according to ASTM D5185;
  • iii) a sulfated ash content of less than 1.0 wt %, less than 0.9 wt %, less than 0.8 wt %, less than 0.7 wt %, or less than 0.6 wt %, ASTM D874; or
  • iv) a combination thereof.

For purposes of this disclosure and the claims thereto, component B (functionalized olefin copolymer having an M_n of from 10,000 to about 35,000 g/mol) is not added in the elements C, D, F, G, H, I, J, O, E-3, and/or K above for determining weight percentages, even though they may show similar properties, e.g., element B (functionalized olefin copolymer having an M_n of from 10,000 to about 35,000 g/mol) may impact dispersant function positively, but is not added into element D for determining weight percent of dispersant.

Likewise, for purposes of this disclosure and the claims thereto, component E-1 (sulfurized fatty acid ester) is not added in the elements C, E-2, F, G, H, I, J, and/or K above for determining weight percentages, even though they may show similar properties, e.g., element E-1 may impact friction modification positively, but is not added into element E-2 for determining weight percent of friction modifier.

Likewise, for purposes of this disclosure and the claims thereto, component E-3 (molybdenum-containing compound) is not added in the elements C, E-2, F, G, H, I, J, and/or K above for determining weight percentages, even though they may show similar properties, e.g., element E-3 may impact friction modification positively, but is not added into element E-2 for determining weight percent of friction modifier.

In some embodiments, all of elements G, H, I, J, O, and K are present in addition to the elements A, B, C, D, E-3, E-2, F, and E-1 as described above.

Typically, the lubricating compositions may contain low levels of sulfur. In some embodiments, the lubricating composition contains less than or equal to 0.4, less than or equal to 0.3, or less than or equal to 0.2, or in the range of from 0.1 to 0.4, from 0.01 to less than 0.4, from 0.1 to less than 0.3, or from 0.15 to less than 0.2 wt % sulfur, expressed as atoms of sulfur, based on the total weight of the lubricating composition, as measured by ASTM D2622.

In some embodiments, the lubricating oil compositions and concentrates described herein are absent added components containing copper, such as: 1) copper compounds described in EP-A-24146 that are substantially free of phosphorus; 2) the oil-soluble copper salt of a synthetic or natural carboxylic acid; 3) oil-soluble copper dithiocarbamates of the general formula (RR′NCSS)_nCu, where n is 1 or 2 and R and R′ are the same or different hydrocarbyl radicals containing 1 to 18 carbon atoms or 2 to 12 carbon atoms, such as alkyl, alkenyl, aryl, aralkyl, alkaryl and cycloalkyl radicals; 4) copper and sulphur containing compounds such as copper mercaptides, disulphides and thioxanthates; and 5) copper sulphonates, phenates, and acetylacetonates.

In some embodiments, the lubricating oil compositions and concentrates described herein are absent added components containing copper, such as: added dihydrocarbyl dithiophosphate metal salt where the metal is copper.

In some embodiments, the lubricating oil compositions and concentrates described herein are absent added components containing copper as described in EP 0 280 580 A2 at page 3, line 30-47, including EP-A-241146 as referenced therein.

In some embodiments, the lubricating oil compositions and concentrates described herein do not comprise 5 to 500 parts per million by weight (ppm) of added copper present in oil-soluble form. (The term “added copper” is intended to exclude copper present in the oil as a result of accumulation of copper in the oil during use, e.g. by wear or corrosion of copper-containing components.)

In some embodiments, the kinematic viscosity at 100° C. (“KV₁₀₀”) of the lubricating oil composition is in the range of from 2 to 30 cSt, from 5 to 20 cSt, or from 6 to 17 cSt as determined according to ASTM D445-19a. Alternately, the lubricating oil composition has a KV₁₀₀ in the range of from 6.1 to less than 16.3 cSt, form 6.9 to less than 16.3 cSt, from 9.3 to less than 16.3 cSt, or from 9.3 to less than 12.5 cSt. Alternately, the lubricating oil composition has a KV₁₀₀ in the range of from 6.9 to less than 9.3 cSt.

In some embodiments, the lubricating oil composition has a total base number (TBN) in the range of from 1 to 30 mg KOH/g, from 5 to 15 mg KOH/g, from 4 to 15 mg KOH/g, from 5 to 14 mg KOH/g, or from 7 to 14 mg KOH/g, as determined by ASTM D2896. Alternately, in other embodiments, the lubricating oil composition has a total base number greater than or equal to 7 mg KOH/g, in the range of from 7 to 15 mg KOH/g, or from 7 to 12 mg KOH/g (as determined by ASTM D2896).

In some embodiments, the lubricating oil composition comprises a Group III basestock, such as greater than or equal to 10 wt %, greater than or equal to 30 wt %, or greater than or equal to 50 wt % of Group III basestock, based upon the weight of the lubrication oil composition.

In some embodiments, the lubricating oil composition comprises a Group III+ basestock, such as greater than or equal to 50 wt %, greater than or equal to 60 wt %, or greater than or equal to 70 wt % of Group III+ basestock, based upon the weight of the lubrication oil composition.

In some embodiments, the lubricating oil composition comprises a gas-to-liquids (GTL) basestock, such as greater than or equal to 50 wt %, greater than or equal to 60 wt %, greater than or equal to 70 wt %, or greater than or equal to 80 wt %, of GTL basestock, based upon the weight of the lubrication oil composition.

In some embodiments, the lubricating oil composition comprises a Group IV basestock, such as greater than or equal to 10 wt %, greater than or equal to 30 wt %, or greater than or equal to 50 wt % of Group IV basestock, based upon the weight of the lubrication oil composition.

In some embodiments, the lubricating oil composition comprises Group III+ basestock having a VI of greater than or equal to 140, such as greater than or equal to 50 wt %, greater than or equal to 60%, or greater than or equal to 70 wt % Group III+ basestock having a VI of greater than or equal to 140, based upon the weight of the lubrication oil composition. In some embodiments, the lubricating oil composition has a KV₁₀₀ of less than or equal to 12.5 cSt, less than or equal to 11.5 cSt, less than or equal to 10.5 cSt, or less than or equal to 9.5 cSt.

In some embodiments, Group III basestock, Group III+ basestock having a VI less than 140, Group IV basestock having a VI greater than 160, or a combination thereof are absent from the LOC.

In some embodiments, the lubricating oil compositions described herein are absent added additives comprising copper.

In some embodiments, the lubricating oil disclosed herein meets criteria to be designated as OW-16, OW-20, OW-30, 5W-16, 5W-20, 5W-30, according to SAE J300.

In some embodiments, the lubricating oil disclosed herein has a cold cranking simulator (CCS) test value at −35° C. of less than or equal to 6,600 cP, less than or equal to 6,200 cP, or less than or equal to 4,500 cP, according to ASTM D5293.

In some embodiments, the lubricating oil disclosed herein has a kinematic viscosity at 100° C. (KV100) of less than or equal to 12.5 cSt, less than or equal to 9.3 cSt, or less than or equal to 8.2 cSt, according to ASTM D445-19a.

In some embodiments, the lubricating oil disclosed herein has a high temperature high shear (HTHS) viscosity at 150° C. of greater than or equal to 2.3 mPa·s, greater than or equal to 2.6 mPa·s, or greater than or equal to 2.9 mPa·s, according to CEC-L-36 (ASTM D4683-20).

In some embodiments, the lubricating oil disclosed herein has a pour point of less than or equal to −40° C. or than or equal to −45° C. 2.3, according to ASTM D97.

In some embodiments, the lubricating oil disclosed herein has a viscosity index in the range for from 150 to 175, from 150 to 165, or from 160 to 175, according to ASTM D2270.

In some embodiments, the lubricating oil disclosed herein has a Noack volatility less than or equal to 15 wt %, according to CEC L-40-A-93.

In some embodiments, the lubricating oil disclosed herein has a combination of one or more physical properties as shown in Table 1 below.

TABLE 1
Oil Grade	0W-16	0W-20	0W-30	5W-16	5W-20	5W-30

Max CCS (cP@−35° C.)	4,500	4,500	6,200	6,600	6,600	6,600
KV100 (mm2/s)	7.0-8.2	8.2-9.3	9.3-12.5	7.0-8.2	8.2-9.3	9.3-12.5
HTHS (mPa · s@150° C.)	2.3-2.7	2.6-2.9	2.9-3.3	2.3-2.6	2.6-2.9	2.9-3.3
Pour Point (° C., range)	−45 to −48	−45 to −48	−45 to −48	−40 to −45	−40 to −45	−40 to −45
VI (range)	160-175	160-175	160-175	150-165	150-165	150-165
Noack Vol. (%@250° C.,	≤15	≤15	≤15	≤15	≤15	≤15
range)

In some embodiments, the lubricating oil disclosed herein has a phosphorus content in the range of from 300 to 1,000 ppm, from 400 to 900 ppm, from 500 to 800 ppm by weight, according to EN 14107.

In some embodiments, the lubricating oil disclosed herein has a molybdenum content in the range of from 250 to 1,000 ppm, from 350 to 900 ppm, from 400 to 800 ppm, from 450 to 700 ppm, or from 500 to 600 ppm by weight, according to ASTM D5185.

In some embodiments, the lubricating oil disclosed herein has a sulfur content of less than 0.3 wt %, according to ASTM D5185.

In some embodiments, the lubricating oil disclosed herein has a sulfated ash content of less than 1.0 wt %, less than 0.9 wt %, less than 0.8 wt %, less than 0.7 wt %, or less than 0.6 wt %, ASTM D874.

In some embodiments, the lubricating oil disclosed herein has a combination of one or more chemical properties as shown in Table 2 below.

TABLE 2
Oil Grade	0W-16	0W-20	0W-30	5W-16	5W-20	5W-30

Max CCS (cP@−35° C.)	4,500	4,500	6,200	6,600	6,600	6,600
KV100 (mm2/s)	7.0-8.2	8.2-9.3	9.3-12.5	7.0-8.2	8.2-9.3	9.3-12.5
HTHS (mPa · s@150° C.)	2.3-2.7	2.6-2.9	2.9-3.3	2.3-2.6	2.6-2.9	2.9-3.3
Pour Point (° C., range)	−45 to −48	−45 to −48	−45 to −48	−40 to −45	−40 to −45	−40 to −45
VI (range)	160-175	160-175	160-175	150-165	150-165	150-165
Noack Vol. (%@250° C., range)	≤15	≤15	≤15	≤15	≤15	≤15
Phosphorous (ppm)	300-1,000	300-1,000	300-1,000	300-1,000	300-1,000	300-1,000
Molybdenum (ppm)	250-1,000	250-1,000	250-1,000	250-1,000	250-1,000	250-1,000
Sulfur (ppm)	2,000	2,000	2,000	2,000	2,000	2,000
Sulfated Ash (wt %)	0.6-1.0	0.6-1.0	0.6-1.0	0.6-1.0	0.6-1.0	0.6-1.0

Concentrates

In some embodiments, compositions disclosed herein comprise a concentrate. A concentrate, also referred to as an additive package or addpack, is a composition typically having less than 50 wt %, less than 40 wt %, less than 30 wt %, less than 25 wt %, or less than 20 wt % basestock or base oil, based on the weight of the concentrate. In some embodiments, the concentrate is blended with one or more basestocks to form a lubricating oil product.

In some embodiments, a concentrate composition herein comprises or results from admixing:

• • (i) from 1 to less than 50 wt %, from 5 to 45 wt %, from 7 to 40 wt %, from 10 to 35 wt %, or from 10 to 25 wt % of a base oil composition comprising one or more Group III base oils, one or more Group III+ base oils, one or more Group IV base oils, or a combination thereof;
  • (ii) from 0.2 to 30 wt %, from 0.30 to 20 wt %, from 0.40 to 10 wt %, from 0.50 to 8.0 wt %, or from 1.0 to 6.0 wt % of a functionalized olefin copolymer having an M_n in the range of from about 10,000 g/mol to about 35,000 g/mol;
  • (iii) from 0.20 to 40 wt %, from 0.30 to 20 wt %, from 0.40 wt % to 10 wt %, or from 0.50 wt % to 4.0 wt % of one or more detergents, wherein the detergent comprises:
    • 1) at least one first calcium detergent having a first TBN of more than 100 mg KOH/g;
    • 2) at least one second calcium detergent having a second TBN of 100 mg KOH/g or less; and
    • 3) at least one magnesium detergent, where the difference between the first TBN and the second TBN is greater than or equal to 100 mg KOH/g;
  • (iv) from 0.02 to 80 wt %, from 0.20 to 30 wt %, from 2.0 to 24 wt %, or from 4.0 to 20 wt % of one or more dispersants (such as but not limited to PIBSA-PAM), wherein the dispersants comprise at least one borated dispersant and at least one non-borated dispersant (not including component ii); and
  • (v) a friction modifier composition comprising:
    • from 0.02 to 40 wt %, from 0.20 to 10 wt %, 0.40 to 8 wt %, 0.60 to 6.0 wt %, 0.80 to 4.0 wt %, or 0.80 to 2.0 wt % of a sulfurized fatty acid ester; and
    • from 0.02 to 20 wt %, from 0.05 to 10.0 wt %, from 0.10 to 8.0 wt %, from 0.10 to 6.0 wt %, or from 0.10 to 2.0 wt % of a molybdenum-containing compound; and
  • (vi) from 0.02 to 20 wt %, from 1.0 to 10.0 wt %, from 2.0 to 8.0 wt %, or from 3.0 to 6.0 wt % of an amine or phenol based antioxidant; and
  • (vii) optional additional components, such as friction modifiers (other than the sulfurized fatty acid ester friction modifier), anti-oxidants, pour point depressants, anti-foam agents, viscosity modifiers, corrosion inhibitors, anti-wear agents, extreme pressure additives, demulsifiers, seal compatibility agents, additive diluent base oils, C₈ to C₃₆ alpha olefins, etc.;
  • wherein
    • the concentrate composition comprises molybdenum in an amount in the range of from 500 to 2,000 ppm, from 700 to 1,800 ppm, from 800 to 1,600 ppm, from 900 to 1,400 ppm, or from 1,000 to 1,200 ppm by weight, according to ASTM D4951; and
    • the wt % of each component is based on the total weight of the concentrate composition.

In some embodiments, the concentrate described herein, comprises one or more alpha-olefins, such as linear alpha-olefins (LAO), having 8 to 36 carbon atoms, 8 to 24 carbon atoms, 10 to 20 carbon atoms, 12 to 20 carbon atoms, or 14 to 18 carbon atoms. In some embodiments, the concentrate described herein, comprises mixtures of linear alpha-olefins, having 14 or more carbon atoms.

In some embodiments, the concentrate described herein, comprises from 0.002 to 30 wt %, from 0.30 to 20 wt %, from 0.40 to 10 wt %, or from 0.50 to 4.0 wt % of one or more C₈ to C₃₆ alpha olefins based upon the weight of the concentrate composition. In some embodiments, the concentrate described herein, may comprise from 0.002 to 30 wt %, from 0.30 to 20 wt %, from 0.40 to 10 wt %, or from 0.50 to 4.0 wt % of one, two, three, four, five or more C₈ to C₃₆ alpha olefins, based upon the weight of the concentrate composition.

In some embodiments, concentrates disclosed herein are added or are present in a lubricating oil composition at from of 0.5 to 35 wt %, from 5 to 30 wt %, from 7.5 to 25 wt %, from 10 to 22.5 wt %, or from 15 to 20 wt %, based upon the weight of the lubricating oil composition. In some embodiments, concentrates disclosed herein are added to a base oil composition comprising one or more Group III base oils, one or more Group III+ base oils, one or more Group IV base oils, or a combination thereof.

In some embodiments, the concentrates described herein are absent added additives comprising copper.

A. Base Oil

A base oil may be selected from vegetable, animal, mineral, and synthetic lubricating oils, and mixtures thereof. In some embodiments, the base oil viscosity is in the range of from light distillate mineral oils to heavy lubricating oils such as gas engine oil, mineral lubricating oil, motor vehicle oil, light duty diesel oil, and heavy duty diesel oil.

In some embodiments, the kinematic viscosity at 100° C. (“KV₁₀₀”) of the base oil is in the range of from 1 to 30 cSt, from 2 to 25 cSt, or from 5 to 20 cSt, as determined according to ASTM D445-19a. In some embodiments, the kinematic viscosity at 100° C. (“KV₁₀₀”) of the base oil is in the range of from 1.0 cSt to 10 cSt, from 1.5 cSt to 3.3 cSt, from 2.7 cSt to 8.1 cSt, from 3.0 cSt to 7.2 cSt, or from 2.5 cSt to 6.5 cSt. Optionally, the high temperature high shear (HTHS) viscosity at 150° C. of the base oil ranges from 0.5 to 20 cP, such as 1 to 10 cP, such as 2 to 5 cP as determined according to CEC-L-36 (ASTM D4683-20).

In some embodiments, when one or more lubricating oil basestocks are used to make a concentrate, the one or more lubricating oil basestocks are present in a concentrate-forming amount to give a concentrate containing, from 5 wt % to 80 wt %, from 10 wt % to 70 wt %, or from 5 wt % to 50 wt % of active 15 ingredient (i.e., ingredients other than lubricating oil basestock(s)), based upon the weight of the concentrate.

Common oils useful as base oils include animal and vegetable oils (e.g. castor and lard oil), liquid petroleum oils, and hydrorefined and/or solvent-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils derived from coal or shale are also useful base oils. Basestocks may be manufactured using a variety of different processes including, but not limited to, distillation, solvent refining, hydrogen processing, oligomerization, esterification, and re-refining.

Synthetic lubricating oils useful herein as base oils include hydrocarbon oils such as homopolymerized and copolymerized olefins, referred to as polyalphaolefins or PAO's or group IV base oils (according to the API EOLCS 1509 definition (American Petroleum Institute Publication 1509, see section E.1.3, 19^th edition, January 2021, www.API.org)). Examples of PAO's useful as base oils include: poly(ethylene), copolymers of ethylene and propylene, polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1-hexenes), poly(1-octenes), poly(1-decenes), homo- or co-polymers of C₈ to C₂₀ alkenes, homo- or co-polymers of C₈, and/or C₁₀, and/or C₁₂ alkenes, C₈/C₁₀ copolymers, C₈/C₁₀/C₁₂ copolymers, and C₁₀/C₁₂ copolymers, and the derivatives, analogues and homologues thereof.

In some embodiments, the base oil comprises polyalphaolefins comprising oligomers of linear olefins having from 6 to 14 carbon atoms, from 8 to 12 carbon atoms, or 10 carbon atoms and having a kinematic viscosity at 100° C. (KV₁₀₀) of 10 or more (as measured by ASTM D445-19a); and has a viscosity index (“VI”), as determined by ASTM D-2270, of greater than or equal to 100, greater than or equal to 110, greater than or equal to 120, greater than or equal to 130, or greater than or equal to 140; and/or has a pour point of less than or equal to −5° C. (as determined by ASTM D 97), less than or equal to −10° C., or less than or equal to −20.

In some embodiments, polyalphaolefin oligomers useful in the present disclosure comprise C₂₀ to C₁₅₀₀ paraffins, C₄₀ to C₁₀₀₀ paraffins, C₅₀ to C₇₅₀ paraffins, or C₅₀ to C₅₀₀ paraffins. In some embodiments, the PAO oligomers are dimers, trimers, tetramers, pentamers, etc. of C₈ to C₁₄ alpha-olefins, C₆ to C₁₂ alpha-olefins, or C₈ to C₁₂ alpha-olefins. Suitable olefins include 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene and 1-dodecene. In some embodiments, the olefin is 1-decene, and the PAO is a mixture of dimers, trimers, tetramers and pentamers (and higher) of 1-decene. Useful PAO's are described more particularly in, for example, U.S. Pat. Nos. 5,171,908, 5,783,531, and in SYNTHETIC LUBRICANTS AND HIGH-PERFORMANCE FUNCTIONAL FLUIDS 1-52 (Leslie R. Rudnick & Ronald L. Shubkin, ed. Marcel Dekker, Inc. 1999).

In some embodiments, PAO's useful in the present disclosure have a number average molecular weight in the range of from 100 to 21,000 g/mol, from 200 to 10,000 g/mol, from 200 to 7,000 g/mol, from, from 200 to 2,000 g/mol, or from 200 to 500 g/mol. Useful PAO's are commercially available as SpectraSyn™ Hi-Vis, SpectraSyn™ Low-Vis, SpectraSyn™ plus, SpectraSyn™ Elite PAO's (ExxonMobil Chemical Company, Houston Texas) and Durasyn™ PAO's from Ineos Oligomers USA LLC.

Synthetic lubricating oils useful as base oils also include hydrocarbon oils such as homopolymerized and copolymerized: 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.

Another suitable class of synthetic lubricating oils useful as base oils comprises the esters of dicarboxylic acids (e.g., a phthalic acid, a succinic acid, an alkyl succinic acid, an alkenyl succinic acid, a maleic acid, an azelaic acid, a suberic acid, a sebasic acid, a fumaric acid, an adipic acid, a linoleic acid dimer, a malonic acid, an alkylmalonic acid, an alkenyl malonic acid, or a combination thereof) reacted with a variety of alcohols (e.g., a butyl alcohol, a hexyl alcohol, a dodecyl alcohol, a 2-ethylhexyl alcohol, an ethylene glycol, a diethylene glycol monoether, a propylene glycol, or a combination thereof). Specific examples of these esters include, but are not limited to 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.

Esters useful as synthetic oils herein also include those made from C₈ to C₁₂ monocarboxylic acids and polyols, and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol. Useful ester base oils are commercially available as Esterex™ Esters (ExxonMobil Chemical Company, Houston Texas).

Silicon-base oils such as the polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxysilicone oils and silicate oils comprise another useful class of synthetic lubricants useful herein; such oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexyl)silicate, tetra-(p-tert-butyl-phenyl) silicate, hexa-(4-methyl-2-ethylhexyl)disiloxane, poly(methyl)siloxanes and poly(methylphenyl)siloxanes.

Other synthetic lubricating oils useful herein include liquid esters of phosphorous-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.

Unrefined, refined, and re-refined oils can be used in the lubricating compositions of the present disclosure. 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 an ester oil obtained directly from an esterification process and used without further treatment is considered an 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 used by those in the art. Re-refined oils are oils obtained by processes similar to those used to obtain refined oils where the refining processes are applied to previously refined oils which have been previously used in service. Such re-refined oils are also referred to as reclaimed or reprocessed oils and often are additionally processed for removal of spent additive and oil breakdown products. In some embodiments, a re-refined base oil is substantially free from materials introduced through manufacturing, contamination or previous use.

Other examples of useful base oils are gas-to-liquid (“GTL”) base oils, i.e. the base oil is an oil derived from hydrocarbons made from synthesis gas (“syn 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. For further information on useful GTL base oils and blends thereof, please see U.S. Pat. No. 10,913,916 (column 4, line 62 to column 5, line 60) and U.S. Pat. No. 10,781,397 (column 14, line 54 to column 15, line 5, and column 16, line 44 to column 17, line 55).

In particular, oils from renewable sources, i.e., based in part on carbon and energy captured from the environment, such as biological sources, are useful herein.

The various base oils are often categorized as Group I, II, III, IV, or V according to the API EOLCS 1509 definition (American Petroleum Institute Publication 1509, see section E.1.3, 19^th edition, January 2021, www.API.org).

Group I basestocks are typically derived from solvent refining of crude oil. Group I basestocks have a viscosity index of between about 80 to 120 and contain greater than about 0.03% sulfur and/or less than about 90% saturated hydrocarbons. Group I basestocks have a KV₄₀ in the range of from 10 to 150 cSt and a KV₁₀₀ in the range of from 2 to 15 cSt. Group I basestocks are less expensive than other basestocks and have good solvency for additives. Compared to other basestocks, Group I basestocks have lower oxidation stability, higher sulfur content, and limited high temperature performance.

Group II basestocks are typically derived from hydrocracked mineral oils. Group II basestocks have a viscosity index of between about 80 to 120 and contain less than or equal to about 0.03% sulfur and/or greater than or equal to about 90% saturated hydrocarbons. Group II basestocks have a KV₄₀ in the range of from 10 to 150 cSt and a KV₁₀₀ in the range of from 2 to 15 cSt. Group II basestocks have better oxidation stability, low sulfur content, and better thermal stability than Group I. However, Group II basestocks are more expensive and have less solvency for additives compared to Group I basestocks.

Group II+ basestocks are typically derived from hydrocracked mineral oils. Group II+ basestocks have a viscosity index of between about 110 to 120 and contain less than or equal to about 0.03% sulfur and/or greater than or equal to about 90% saturated hydrocarbons. Group II+ basestocks have a KV₄₀ in the range of from 10 to 150 cSt and a KV₁₀₀ in the range of from 2 to 15 cSt. Group II+ basestocks have better oxidation stability and better thermal stability than Group II. However, Group II+ basestocks are more expensive the Group II basestocks.

Group III basestocks are typically derived from severely hydrocracked and hydroisomerized mineral oils. Group III basestocks have a viscosity index greater than or equal to about 120 and contain less than or equal to about 0.03% sulfur and greater than about 90% saturated hydrocarbons. Group III basestocks have a KV₄₀ in the range of from 10 to 150 cSt and a KV₁₀₀ in the range of from 2 to 15 cSt. Group III basestocks have better oxidation stability and lower volatility than Group II. However, Group III basestocks are more expensive the Group II basestocks.

Group III+ basestocks are typically derived from high quality, severely hydrocracked and hydroisomerized mineral oils. Group III+ basestocks have a viscosity index greater than or equal to about 130 and contain less than or equal to about 0.03% sulfur and greater than about 90% saturated hydrocarbons. Group III basestocks have a KV₄₀ in the range of from 10 to 150 cSt and a KV₁₀₀ in the range of from 2 to 15 cSt. Group III+ basestocks have high VI, excellent oxidation stability, low volatility, superior thermal stability, high purity, enhanced low temperature properties, and good compatibility with additives. However, Group III+ basestocks are more expensive the Group III basestocks. A Group III+ basestock is a group III basestock having a VI of 130 or more.

Gas-to-liquids basestocks are typically classified as Group III and often as Group III+ because of their superior performance characteristics. GTL basestocks are produced through the Fischer-Tropsch process, which converts natural gas into liquid hydrocarbons. GTL basestocks have a viscosity index in the range of from about 140 to about 160 and are highly pure with very low levels of sulfur and aromatics, often comparable to synthetic Group IV base stocks. GTL basestocks have a KV₄₀ in the range of from 20 to 100 cSt and a KV₁₀₀ in the range of from 4 to 12 cSt. Group III basestocks have better oxidation stability and lower volatility than Group II. However, Group III basestocks are more expensive the Group II basestocks.

Group IV basestocks include polyalphaolefins (PAO). Group IV basestocks are derived from synthetic oils made from polymerization of alpha-olefins. Group IV basestocks have a viscosity index in the range of from 140 to 170 and typically contain less than or equal to about 10 ppmw sulfur and typically greater than about 99% or nearly 100% saturated hydrocarbons. Group III basestocks have a KV₄₀ in the range of from 32 to 150 cSt and a KV₁₀₀ in the range of from 5 to 15 cSt. Group IV basestocks have superior oxidation stability, excellent thermal stability, and low temperature fluidity. However, Group IV basestocks are more expensive the Groups I-III basestocks.

Group V basestocks are basestocks not included in Groups I-IV. Group V basestocks include but are not limited to polyalkylene glycols (PAGs), esters, polyisobutylenes (PIBs), alkylated aromatics, silicones, phosphate esters, or combinations thereof. (Viscosity index measured by ASTM D2270, saturates is measured by ASTM D2007, and sulfur is measured by ASTM D2622, ASTM D4294, ASTM D4927, and ASTM D3120).

Base oils for use in the formulated lubricating compositions useful in the present disclosure are any one, two, three, or more of the variety of oils described herein. In some embodiments, base oils for use in the formulated lubricating compositions useful in the present disclosure are those described as API Group I, Group II, Group III (including Group III+), Group IV, and Group V oils and mixtures thereof. In some embodiments, base oils for use in the formulated lubricating compositions useful in the present disclosure are those described as API Group II, Group III, Group IV, and Group V oils and mixtures thereof. In some embodiments, base oils for use in the formulated lubricating compositions useful in the present disclosure are those described as the Group III, Group III+, IV and Group V base oils due to their exceptional volatility, stability, viscometric and cleanliness features. Minor quantities of Group I basestock, such as the amount used to dilute additives for blending into formulated lube oil products, can be tolerated but are typically kept to a minimum, e.g., amounts only associated with their use as diluent/carrier oil for additives used on an “as-received” basis. In regard to the Group II stocks, it is more useful that the Group II basestock be in the higher quality range associated with that stock, i.e. a Group II stock having a viscosity index in the range from 100 to 120.

The base oil useful herein may be selected from any of the synthetic, natural, or re-refined oils (such as those typically used as crankcase lubricating oils for spark-ignited and compression-ignited engines). Mixtures of synthetic and/or natural and/or re-refined base oils may be used if desired. Multi-modal mixtures (such as bi- or tri-modal mixtures) of Group I, II, III, IV, and/or V basestocks may be used if desired.

In some embodiments, the base oil or base oil blend used herein conveniently has a kinematic viscosity at 100° C. (KV₁₀₀, as measured according to ASTM D 445-19a, and reported in units of centistoke (cSt) or it its equivalent, mm²/s), of from about 2 to about 40 cSt, from 3 to 30 cSt, from 4 to 20 cSt, from 5 to 10 cSt. In some embodiments, the base oil or base oil blend has a kinematic viscosity at 100° C. in the range of from 2 to 20 cSt, from 2.5 to 2 cSt, or from 2.5 cSt to cSt.

In some embodiments, the base oil or base oil blend has a saturated hydrocarbon content of greater than or equal to 65 wt %, greater than or equal to 75 wt %, greater than or equal to 85 wt %, or greater than or equal to 90 wt % as determined by ASTM D 2007.

In some embodiments, the base oil or base oil blend has a sulfur content of less than 1 wt %, less than 0.6 wt %, less than 0.4 wt %, or less than 0.3 wt %, based on the total weight of the lubricating composition, according to ASTM D5185.

In embodiments, the volatility of the base oil or base oil blend, as measured by the Noack test (ASTM D5800, procedure B), is less than or equal to 30 wt %, less than or equal to 25 wt %, less than or equal to 20 wt %, less than or equal to 16 wt %, less than or equal to 12 wt %, or less than or equal to 10 wt %, based on the total weight of the lubricating composition.

In embodiments, the viscosity index (VI) of the base oil is greater than or equal to 95, greater than or equal to 110, greater than or equal to 120, greater than or equal to 125, greater than or equal to 130 to 240, or greater than or equal to 105 to 140 (as determined by ASTM D2270).

In some embodiments, the base oil is provided in a major amount, in combination with a minor amount of one or more additive components as described hereinafter, constituting a lubricant. In some embodiments, the base oil is provided in a minor amount, in combination minor amounts of additive components wherein the total amount of combined additive components as described hereinafter constitutes a major portion of the mixture of base oil and additives, constituting a concentrate. This preparation may be accomplished by adding the additives directly to the oil or by adding the one or more additives in the form of a concentrate thereof to disperse or dissolve the additive(s). Additives may be added to the oil by any method known to those skilled in the art, either before, at the same time as, or after addition of other additives.

In some embodiments, the base oil or blend of base oils constitutes the major component of an engine oil lubricant composition. In some embodiments the base oil or blend of base oils is present in the lubricating oil composition an amount in the range of from about 50 to about 99 wt %, from about 70 to about 95 wt %, or from 80 to about 95 wt %, based on the total weight of the lubricating oil composition.

In some embodiments, the one or more base oils are present in the lubricating composition in an amount greater than or equal to 32 wt %, greater than or equal to 55 wt %, greater than or equal to 60 wt %, or greater than or equal to 65 wt %, based on the total weight of the lubricating composition. In some embodiments, the one or more base oils are present in the lubricating composition at an amount less than or equal to 98 wt %, less than or equal to 95 wt %, less than or equal to 90 wt %, based upon the weight of the lubricating composition. In some embodiments, the one or more base oils are present in the lubricating composition in a range of from 1 to 99 wt %, from 50 to 97 wt %, from 60 to 95 wt %, or from 70 to 95 wt %, based upon the weight of the lubricating composition.

The base oils and blends thereof described above are also useful for making concentrates as well as for making lubricants therefrom. Concentrates constitute a convenient means of handling additives before their use, as well as facilitating solution or dispersion of additives in lubricants. When preparing a lubricant that contains more than one type of additive (sometime referred to as “additive components”), each additive may be incorporated separately, each in the form of a concentrate. In many instances, however, it is convenient to provide a so-called additive “package” (also referred to as an “addpack”) comprising one or more additives/co-additives, such as described hereinafter, in a single concentrate.

In some embodiments, the one or more base oils are present in a concentrate composition in an amount less than or equal to 50 wt %, less than or equal to 40 wt %, less than or equal to 30 wt %, or less than or equal to 20 wt %, based on the total weight of the concentrate composition. In some embodiments, the one or more base oils are present in the concentrate composition at an amount in the range of from 0.1 to 49 wt %, from 5 to 40 wt %, from 10 to 30 wt %, or from 15 to 25 wt %, based upon the weight of the concentrate composition.

In some embodiments, the lubricating composition of the present disclosure is a multigrade oil identified by the viscometric descriptors: SAE 0W-X, wherein X represents any one of 16, 20, 30, or 40; SAE 5W-X, wherein X represents any one of 16, 20, 30, 40, or 50; SAE 10W-X, wherein X represents any one of 20, 30, 40, 50, or 60; SAE 15W-X, wherein X represents any one of 30, 40, 50, or 60; 20W-X, wherein X represents any one of 40, 50, or 60; or 60; or 25W-X, wherein X represents any one of 40, 50, or 60. The characteristics of the different viscometric grades can be found in the SAE J300 classification. In some embodiments, the lubricating composition is in the form of an SAE 0W-X, wherein X represents any one of 16, 20, 30, or 40; SAE 5W-X, wherein X represents any one of 16, 20, 30, 40, or 50.

The lubricating composition according to the present disclosure may further comprise one or more additives such as detergents, friction modifiers (other than the sulfurized fatty acid ester friction modifier and Mo containing compound), pour point depressants, anti-foam agents, viscosity modifiers, dispersants, corrosion inhibitors, anti-wear agents, extreme pressure additives, demulsifiers, seal compatibility agents, additive diluent base oils, etc. Specific examples of such additives are described in for example Kirk-Othmer Encyclopedia of Chemical Technology, third edition, volume 14, pages 477-526, and several are discussed in further detail below.

B. Functionalized Olefin Copolymer

Functionalized olefin copolymers used in the formulations of the lubricating compositions herein may be ashless or ash-forming in nature. In some embodiments, the functionalized olefin copolymer is ashless.

In some embodiments, functionalized olefin copolymers useful herein contain a polar group attached to a relatively high molecular weight hydrocarbon chain. In some embodiments, the polar group comprises nitrogen, oxygen, phosphorus, or a combination thereof. Typical hydrocarbons or copolymers employed in the formation of the functionalized olefin copolymers of the present disclosure include copolymers, interpolymers, or lower molecular weight hydrocarbons. One family of such polymers comprises polymers of ethylene and/or at least one C₃ to C₂₈ alpha-olefin having the formula H₂C═CHR¹ wherein R¹ is straight or branched chain alkyl radical comprising from 1 to 26, from 1 to 18, from 1 to 8, or from 1 to 2 carbon atoms and wherein the polymer contains carbon-to-carbon unsaturation. In further embodiments, the carbon-to-carbon unsaturation comprises a high degree of terminal ethenylidene unsaturation.

In some embodiments, the functionalized olefin copolymer of the present disclosure has a number average molecular weight (g/mol) of greater than or equal to 10,000 g/mol, greater than or equal to 15,000 g/mol, or in the range of from 10,000 to 30,000 g/mol, from 15,000 to 28,000 g/mol, from 20,000 to 25,000 g/mol, or from 22,000 to 25,000 g/mol.

In some embodiments, the olefin copolymer has a narrow molecular weight distribution (MWD), also referred to as polydispersity index (PDI), as determined by the ratio of weight average molecular weight (M_w) to number average molecular weight (M_n), of less than or equal to 3, less than or equal to 2.5, less than or equal to 2.2, less than or equal to 2.0, or in the range of from 1.0 to 3.0, from 1.5 to 2.5, from 1.5 to 2.1, from 1.5 to 2.0, or from 1.6 to 1.8.

In some embodiments, functionalized copolymers are copolymer-substituted succinic acid and copolymer-substituted succinic anhydride derivatives. In some embodiments, succinimides, succinate esters, or succinate ester amides are prepared by the reaction of a copolymer-substituted succinic acid or anhydride compound, with at least one equivalent of a polyhydroxy or polyamino compound (such as an alkylene amine).

Succinimides useful herein can be formed by the condensation reaction between: 1) copolymer substituted succinic anhydrides, such as, but not limited to, ethylene-propylene copolymer succinic anhydride (EP Copolymer-SA); and 2) polyamine (PAM).

A non-exhaustive list of suitable polyamines includes: polyalkylene polyamines, hydroxy-substituted polyamines, polyoxyalkylene polyamines, and combinations thereof.

A non-exhaustive list of suitable polyalkylene polyamines includes tetraethylene pentamine, pentaethylene hexamine, tetraethylenepentamine (TEPA), pentaethylenehaxamine (PEHA), and other polyamines having an average of 5, 6, 7, 8, or 9 nitrogen atoms per molecule). Mixtures where the average number of nitrogen atoms per polyamine molecule is greater than 7 are commonly called heavy polyamines or H-PAMs and may be commercially available under trade names such as HPA™ and HPA-X™ from DowChemical, E-100™ from Huntsman Chemical, et al.

A non-exhaustive list of suitable polyalkylene polyamines includes hydroxy-substituted polyamines include N-hydroxyalkyl-alkylene polyamines such as N-(2-hydroxyethyl)ethylene diamine, N-(2-hydroxyethyl)piperazine, and/or N-hydroxyalkylated alkylene diamines of the type described, for example, in U.S. Pat. No. 4,873,009.

A non-exhaustive list of suitable polyoxyalkylene polyamines includes polyoxyethylene and/or polyoxypropylene diamines and triamines (as well as co-oligomers thereof) having an average M_n from about 200 to about 5000 g/mol. Products of this type are commercially available under the tradename Jeffamine™. Representative examples of useful succinimides are shown in U.S. Pat. Nos. 3,087,936; 3,172,892; 3,219,666; 3,272,746; 3,322,670; 3,652,616; 3,948,800; 6,821,307; and Canada Patent No. 1,094,044.

Succinate esters useful herein include those formed by the condensation reaction between EP copolymer substituted succinic anhydrides (EP Copolymer-SA) and alcohols or polyols. For example, the condensation product of an EP copolymer substituted with succinic anhydride and pentaerythritol is useful herein.

Succinate ester amides useful herein can be formed by a condensation reaction between copolymer-substituted succinic anhydrides and alkanol amines. A non-exhaustive list of suitable alkanol amines includes ethoxylated polyalkylpolyamines, propoxylated polyalkylpolyamines, polyalkenylpolyamines (such as but not limited to polyethylene polyamines and or propoxylated hexamethylenediamine), or a combination thereof. Representative examples are shown in U.S. Pat. No. 4,426,305.

Copolymer-substituted succinic anhydride esters of hydrocarbyl bridged aryloxy alcohols are also useful herein.

The above (copolymer)alkenylsuccinic derivatives can be post-reacted with various reagents such as sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid.

The above functionalized olefin copolymers, can also be post reacted with boron compounds such as boric acid, borate esters or highly borated dispersants, to form borated copolymers generally having from about 0.1 to about 5 moles of boron per mole of copolymer reaction product. The boron-containing copolymer may be present in an amount to deliver boron to the lubricating oil composition in an amount in the range of from 15 ppm to 2000 ppm, 25 ppm to 1000 ppm, 40 ppm to 600 ppm, or 80 ppm to 350 ppm.

In some embodiments, the functionalized copolymer is an amine functionalized ethylene-propylene copolymer. Typically the functionalized ethylene-propylene copolymer is prepared by reacting an ethylene-propylene copolymer with maleic anhydride to form an intermediate product and thereafter reacting the intermediate product with an amine. A non-exhaustive list of suitable amines includes N-phenyl-diamine (such as N-phenyl-1,4-phenylenediamine, N-phenyl-p-phenylenediamine (a.k.a. 4-amino-diphenylamine, ADPA), N-phenyl-1,3-phenylenediamine, N-phenyl-1,2-phenylenediamine), nitroaniline (such as 3-nitroaniline), N-phenylethane-diamine (such as N1-phenylethane-1,2-diamine), N-aminophenylacetamide (such as N-(4-aminophenyl)acetamide), morpholinopropanamine (such as 3-morpholinopropan-1-amine), aminoethylpiperazine (such as 1-(2-aminoethyl)piperazine), or a combination thereof.

The functionalized olefin polymer may be present in the lubricating oil composition in an amount in less than or equal to 0.1 wt %, less than or equal to 0.01 wt %, or less than or equal to 0.001 wt %, based on the weight of the lubricating oil composition. In some embodiments, the lubricating oil composition according to the present disclosure are absent or substantially absent a functionalized olefin copolymer having an M_n of from 10,000 to about 35,000 g/mol that may function as dispersants herein.

C. Detergents

The lubricating composition may comprise one or more metal detergents (such as blends of metal detergents) also referred to as a “detergent additive.” In some embodiments, metal detergents function both as detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life. In some embodiments, detergents comprise a polar head with a long hydrophobic tail, with the polar head comprising a metal salt of an acidic organic compound. In some embodiments, the salts contain a substantially stoichiometric amount of the metal in which case they are usually described as normal or neutral salts. In some embodiments, normal or neutral salts have a total base number (“TBN” as measured by ASTM D2896) of less than or equal to 150 mg KOH/g or in the range of from 0 to 80 mg KOH/g or from 5 to 30 mg KOH/g. A large amount of a metal base may be incorporated by reacting excess metal compound (e.g., an oxide or hydroxide) with an acidic gas (e.g., carbon dioxide). Such detergents, sometimes referred to as overbased, may have a TBN of greater than 100 mg KOH/g, greater than or equal to 200 mg KOH/g, greater than or equal to 250 mg KOH/g, greater than or equal to mg KOH/g, 350 mg KOH/g, greater than or equal to 400 mg KOH/g, or in the range of from 200 to 800 mg KOH/g, from 225 to 700 mg KOH/g, from 250 to 650 mg KOH/g, from 300 to 600 mg KOH/g, or from 150 to 650 mg KOH/g.

Suitable detergents include, but are not limited to, oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, naphthenates, other oil-soluble carboxylates of a metal, or a combination thereof. In some embodiments, oil-soluble carboxylates of a metal comprise an alkali metals (Group 1 metals, e.g., Li, Na, K, Rb) or alkaline earth metals (Group 2 metals, e.g., Be, Mg, Ca, Sr, Ba), or a combination thereof. In some embodiments, the metal is selected from sodium, potassium, lithium, calcium, or a combination thereof. In some embodiments, the metal is selected from Ca, Mg, or a combination thereof.

In some embodiments, the detergent additive(s) herein comprise calcium and/or magnesium metal salts. In some embodiments, the calcium salt comprises a calcium carboxylate, a calcium salicylate, a calcium sulfonate, a calcium phenate, or a combination thereof. In some embodiments, the magnesium salt comprises a magnesium carboxylate, a magnesium salicylate, a magnesium sulfonate, a magnesium phenate, or a combination thereof. In some embodiments, the detergents additives are selected from magnesium salicylate, calcium salicylate, magnesium sulfonate, calcium sulfonate, magnesium phenate, calcium phenate, or a combination thereof. In some embodiments, hybrid detergents comprise two, three, four, or more of these detergents.

In some embodiments, hybrid detergents are formed with mixed surfactant systems including phenate and/or sulfonate components, such as but not limited to phenate/salicylates, sulfonate/phenates, sulfonate/salicylates, sulfonates/phenates/salicylates, as described in U.S. Pat. Nos. 6,429,178; 6,429,179; 6,153,565; and 6,281,179. Where a hybrid sulfonate/phenate detergent is employed, the amount of a hybrid detergent would be considered equivalent to amounts of distinct phenate and sulfonate detergents introducing like amounts of phenate and sulfonate soaps, respectively.

In some embodiments, an overbased metal-containing detergent comprises a sodium salt, a calcium salt, a magnesium salt, or a combination thereof of the phenates, sulfur-containing phenates, sulfonates, salixarates and salicylates. In some embodiments, overbased phenates and salicylates typically have a total base number in the range of from 180 to 650 mg KOH/g or from 200 to 450 mg KOH/g. Overbased sulfonates typically have a total base number in the range of from 250 to 600 mg KOH/g or from 300 to 500 mg KOH/g. In some embodiments, the sulfonate detergent may be predominantly a linear alkylbenzene sulfonate detergent having a metal ratio of at least 8 as is described in paragraphs [0026] to [0037] of US Patent Publication 2005/065045 (and granted as U.S. Pat. No. 7,407,919).

The overbased detergent may be present in the lubricating oil composition in an amount in the range of from 0 wt % to 15 wt %, from 0.1 wt % to 10 wt %, from 0.2 wt % to 8 wt %, or from 0.2 wt % to 3 wt %, based upon the weight of the lubricating composition. In some embodiments, for a light duty or heavy duty diesel engine, the detergent is present in the lubricating oil composition in an amount in the range of from 2 wt % to 3 wt %, based upon the weight of the lubricating composition. In some embodiments, for a passenger car engine, the detergent may be present in the lubricating oil composition in an amount in the range of from 0.2 wt % to 1 wt %, based upon the weight of the lubricating composition.

In some embodiments, detergent additive(s) herein comprise one or more magnesium sulfonate detergents. The magnesium detergent may be a neutral salt or an overbased salt. In some embodiments, the magnesium detergent is an overbased magnesium sulfonate having TBN in the range of from 80 to 650 mg KOH/g (ASTM D2896), from 200 to 500 mg KOH/g, or from 240 to 450 mg KOH/g.

In some embodiments, detergent additive(s) herein comprise one or more magnesium salicylate detergents. In some embodiments, the magnesium detergent is a magnesium salicylate having TBN in the range of from 30 to 650 mg KOH/g (ASTM D2896), from 50 to 500 mg KOH/g, from 200 to 500 mg KOH/g, from 240 to 450 mg KOH/g, or less than or equal to 150 mg KOH/g or less than or equal to 100 mg KOH/g.

Alternately, the detergent additive(s) is a combination of magnesium salicylate and magnesium sulfonate.

In some embodiments, the magnesium detergents provides the lubricating composition thereof with magnesium atoms in the range of from 200 to 4000 ppm, from 200 to 2000 ppm, from 300 to 1500, or from 450 to 1200 ppm (ASTM D5185).

The detergent composition may comprise (or consist of) a combination of one or more magnesium sulfonate detergents and one or more calcium salicylate detergents.

In some embodiments, the combination of one or more magnesium sulfonate detergents and one or more calcium salicylate detergents provides the lubricating composition thereof with: 1) magnesium atoms in the range of from 200 to 4000 ppm, from 200 to 2000 ppm, from 300 to 1500 ppm, or from 450 1200 ppm (ASTM D5185); and 2) calcium atoms in an amount greater than or equal to 500 ppm, greater than or equal to 750, greater than or equal to 900 ppm, or in the range of from 500 to 4000 ppm, from 750 to 3000 ppm, or from 900 to 2000 ppm (ASTM D5185).

In some embodiments, the detergent comprises one or more calcium detergents such as calcium carboxylate, calcium salicylate, calcium sulfonate, phenate detergent, or a combination thereof.

In some embodiments, the calcium detergent has a TBN of from 30 to 700 mg KOH/g (ASTM D2896), such as 50 to 650 mg KOH/g, such as 200 to 500 mg KOH/g, such as 240 to 450 mg KOH/g or alternately of 150 mg KOH/g or less, such as 100 mg KOH/g or less, or 200 mg KOH/g or more, or 300 mg KOH/g or more, or 350 mg KOH/g or more.

In some embodiments, the calcium detergent is a calcium salicylate, sulfonate or phenate having TBN of from 30 to 700 mg KOH/g, 30 to 650 mg KOH/g (ASTM D2896), such as 50 to 650 mg KOH/g, such as 200 to 500 mg KOH/g, such as 240 to 450 mg KOH/g or alternately of 150 mg KOH/g or less, such as 100 mg KOH/g or less, or 200 mg KOH/g or more, or 300 mg KOH/g or more, or 350 mg KOH/g or more.

In some embodiments, the calcium detergent is present in the lubricating oil composition in amount sufficient to provide calcium atoms in an amount greater than or equal to 500 ppm, greater than or equal to 750, or greater than or equal to 900 ppm (ASTM D5185). If present, any calcium detergent is suitably present in amount sufficient to provide atomic calcium to the lubricating oil composition (ASTM D5185) in an amount less than or equal to 4000 ppm, less than or equal to 3000, or less than or equal to 2000 ppm. If present, any calcium detergent is suitably present in amount sufficient to provide atomic calcium to the lubricating oil composition (ASTM D5185) in an amount in the range of from 500 to 4000 ppm, from 750 to 3000 ppm, from 900 to 2000 ppm.

In some embodiments, the total atomic amount of metal from detergent in the lubrication composition is less than or equal to 5000 ppm, less than or equal to 4000 ppm, or less than or equal to 2000 ppm (ASTM D5185). In some embodiments, the total atomic amount of metal from detergent in the lubrication composition is greater than or equal to 500 ppm, greater than or equal to 800 ppm, or greater than or equal to 1000 ppm (ASTM D5185). In some embodiments, the total atomic amount of metal from detergent in the lubrication composition is in the range of from 500 to 5000 ppm, from 500 to 3000 ppm, or from 500 to 2000 ppm (ASTM D5185).

In some embodiments, sulfonate detergents are prepared from sulfonic acids, which can be obtained by the sulfonation of alkyl substituted aromatic hydrocarbons, such as those obtained from the fractionation of petroleum or by the alkylation of aromatic hydrocarbons. In some embodiments, sulfonate detergents are obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl or their halogen derivatives such as chlorobenzene, chlorotoluene, chloronaphthalene, or a combination thereof. The alkylation may be carried out in the presence of a catalyst with alkylating agents having from about 3 to more than 70 carbon atoms. In some embodiments, the alkaryl sulfonates contain from about 9 to about 80 or more carbon atoms or from about 16 to about 60 carbon atoms per alkyl substituted aromatic moiety. In some embodiments, the oil soluble sulfonates or alkaryl sulfonic acids are neutralized with oxides, hydroxides, alkoxides, carbonates, carboxylate, sulfides, hydrosulfides, nitrates, borates and ethers of the metal. The amount of metal compound is chosen having regard to the desired TBN of the final product. In some embodiments, the amount of metal compound ranges from about 100 to 220 wt % or is 125 wt %) wherein 100 wt % is the stoichiometric amount of the metal compound.

In some embodiments, metal salts of phenols and sulfurized phenols are prepared by reaction with an appropriate metal compound such as an oxide or hydroxide, and neutral or overbased products may be obtained by methods well known in the art. Sulfurized phenols may be prepared by reacting a phenol with sulfur or a sulfur containing compound such as hydrogen sulfide, sulfur monohalide, or sulfur dihalide, to form products, which are generally mixtures of compounds in which 2 or more phenols are bridged by sulfur containing bridges.

In some embodiments, carboxylate detergents, such as salicylates, can be prepared by reacting an aromatic carboxylic acid, such as a C_5-100, C_9-30, or C_14-24 alkyl-substituted hydroxy-benzoic acid, with an appropriate metal compound, such as an oxide or hydroxide, and neutral or overbased products may be obtained by methods well known in the art. The aromatic moiety of the aromatic carboxylic acid can contain heteroatoms, such as nitrogen and oxygen. In some embodiments, the moiety contains only carbon atoms. In some embodiments, the moiety contains six or more carbon atoms. In some embodiments, the moiety comprises benzene. In some embodiments, an aromatic carboxylic acid contains one or more aromatic moieties, such as one or more benzene rings, either fused or connected via alkylene bridges.

In some embodiments, substituents in oil-soluble salicylic acids are alkyl substituents. In some embodiments, alkyl-substituted salicylic acids comprise alkyl groups containing from 5 to 100, from 9 to 30, or from 14 to 20 carbon atoms. In some embodiments, the alkyl-substituted salicylic acids comprise more than one alkyl group, and the average number of carbon atoms in all of the alkyl groups is at least 9 to ensure adequate oil solubility.

In some embodiments, the ratio of atomic detergent metal to atomic molybdenum in the lubricating oil composition is less than or equal to 3:1 or less than or equal to 2:1.

In some embodiments, metal organic and/or inorganic base salts are minimized in order to suppress sulfated ash content of a lubricating oil composition. In some embodiments, salicylate detergents are used in order to maintain a low sulfur level, and the lubricating composition herein may comprise one or more salicylate detergents. In some embodiments, salicylate detergents are present in or added to the lubricating oil composition in an amount in the range of from 0.05 to 20.0 wt %, from 1.0 to 10.0 wt %, or from 2.0 to 5.0 wt %, based on the total weight of the lubricating oil composition.

In some embodiments, the total sulfated ash content of the lubricating oil composition herein is less than or equal to 2.0 wt %, less than or equal to 1.0 wt % or less than or equal to 0.8 wt %, based on the total weight of the lubricating oil composition as determined by ASTM D874.

In some embodiments, each of the detergents, independently, have a TBN (total base number) value in the range of from 10 to 700 mg KOH/g, from 10 to 500 mg KOH/g, from 100 to 650, from 10 to 500 mg KOH/g, from 30 to 350 mg KOH/g, or from 50 to 300 mg KOH/g, as measured by ISO 3771.

In some embodiments, the detergent comprises, based on the total weight of the LOC:

• • 1) from 0.1 to 19.8 wt %, from 0.25 to 9.0 wt %, or from 0.25 to 5 wt % of at least one first calcium detergent (such as calcium salicylate detergent, calcium sulfonate detergent, or a combination thereof) having a first TBN of greater than 100 mg KOH/g, greater than or equal to 200 mg KOH/g, greater than or equal to 250 mg KOH/g, greater than or equal to 300 mg KOH/g, or greater than or equal to 350 mg KOH/g or more;
  • 2) from 0.1 to 9.8 wt %; from 0.25 to 8.0 wt %, or from 0.5 to 5 wt % of at least one second calcium detergent (such as calcium salicylate detergent, calcium sulfonate detergent, or a combination thereof) having a second TBN of less than or equal to 100 mg KOH/g, less than or equal to 90 mg KOH/g, less than or equal to 80 mg KOH/g, or less than or equal to 70 mg KOH/g; and
  • 3) from 0.1 to 19.8 wt %, from 0.25 to 9.0 wt %, or from 0.25 to 5 wt % of at least one magnesium detergent (such as magnesium salicylate detergent, magnesium sulfonate detergent, or a combination thereof) having a TBN of greater than or equal to 100 mg KOH/g, greater than or equal to 200 mg KOH/g, greater than or equal to 250 mg KOH/g, greater than or equal to 300 mg KOH/g, greater than or equal to 350 mg KOH/g, greater than or equal to 400 mg KOH/g, or greater than or equal to 450 mg KOH/g;
  • where the difference between the first TBN and the second TBN is greater than or equal to 100 mg KOH/g, greater than or equal to 150 mg KOH/g, or greater than or equal to 200 mg KOH/g.

In some embodiments, the detergent comprises, based on the total weight of the LOC:

• • 1) from 0.1 to 19.8 wt %, from 0.25 to 9.0 wt %, or from 0.25 to 5 wt % of at least one first calcium salicylate detergent having a first TBN of greater than 100 mg KOH/g, greater than or equal to 200 mg KOH/g, greater than or equal to 250 mg KOH/g, greater than or equal to 300 mg KOH/g, or greater than or equal to 350 mg KOH/g or more;
  • 2) from 0.1 to 9.8 wt %; from 0.25 to 8.0 wt %, or from 0.5 to 5 wt % of at least one second calcium salicylate detergent having a second TBN of less than or equal to 100 mg KOH/g, less than or equal to 90 mg KOH/g, less than or equal to 80 mg KOH/g, or less than or equal to 70 mg KOH/g; and
  • 3) from 0.1 to 19.8 wt %, from 0.25 to 9.0 wt %, or from 0.25 to 5 wt % of at least one magnesium sulfonate detergent having a TBN of greater than or equal to 100 mg KOH/g, greater than or equal to 200 mg KOH/g, greater than or equal to 250 mg KOH/g, greater than or equal to 300 mg KOH/g, greater than or equal to 350 mg KOH/g, greater than or equal to 400 mg KOH/g, or greater than or equal to 450 mg KOH/g;
  • where the difference between the first TBN and the second TBN is greater than or equal to 100 mg KOH/g, greater than or equal to 150 mg KOH/g, or greater than or equal to 200 mg KOH/g.

In some embodiments, lubricating oil compositions formulated for use in light duty and or heavy duty diesel engines comprise detergents in an amount in the range of from about 0.5 to about 10 wt %, from about 2.5 to about 7.5 wt %, or from about 4 to about 6.5 wt %, based on the total weight of the lubricating oil composition.

In some embodiments, lubricating oil compositions formulated for use in automotive engines comprise detergents in an amount in the range of from about 0.5 to about 10 wt %, from about 2.5 to about 7.5 wt %, or from about 4 to about 6.5 wt %, based on the total weight of the lubricating oil composition.

D. Dispersants

During engine operation, oil-insoluble oxidation byproducts are produced. Dispersants help keep these byproducts in solution, thus diminishing their deposition on metal surfaces. Dispersants used in the formulation of the lubricating oil compositions herein may be ashless or ash-forming in nature. In some embodiments, the dispersant is ashless. So called ashless dispersants are organic materials that form substantially no ash upon combustion. For example, non-metal-containing or borated metal-free dispersants are considered ashless. In contrast, metal-containing detergents tend form ash upon combustion.

In some embodiments, dispersants useful herein contain a polar group attached to a relatively high molecular weight hydrocarbon chain. In some embodiments, the polar group contains at least one element of nitrogen, oxygen, or phosphorus. In some embodiments, the hydrocarbon chains contain 50 to 400 carbon atoms.

Dispersants of (Poly)Alkenylsuccinic Derivatives

A particularly useful class of dispersants includes the (poly)alkenylsuccinic derivatives, typically produced by the reaction of a long chain hydrocarbyl substituted succinic compound, usually a hydrocarbyl substituted succinic anhydride, with a polyhydroxy or polyamino compound. The long chain hydrocarbyl group constituting the oleophilic portion of the molecule which confers solubility in the oil, is often a polyisobutylene group (typically the long chain hydrocarbyl group, such as a polyisobutylene group, has an M_n of 400 to 3000 g/mol, such as 450 to 2500 g/mol). Many examples of this type of dispersant are well known commercially and in the literature. Exemplary U.S. patents describing such dispersants include U.S. Pat. Nos. 3,172,892; 3,2145,707; 3,219,666; 3,316,177; 3,341,542; 3,444,170; 3,454,607; 3,541,012; 3,630,904; 3,632,511; 3,787,374 and 4,234,435. Other types of dispersant are described in U.S. Pat. Nos. 3,036,003; 3,200,107; 3,254,025; 3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,413,347; 3,697,574; 3,725,277; 3,725,480; 3,726,882; 4,454,059; 3,329,658; 3,449,250; 3,519,565; 3,666,730; 3,687,849; 3,702,300; 4,100,082; 5,705,458. A further description of dispersants useful herein may be found, for example, in European Patent Application No. 0 471 071 and European Patent Application No. 0 451 380, to which reference is made for this purpose.

Hydrocarbyl-substituted succinic acid and hydrocarbyl-substituted succinic anhydride derivatives are useful dispersants. In particular, succinimide, succinate esters, or succinate ester amides prepared by the reaction of a hydrocarbon-substituted succinic acid or anhydride compound having greater than or equal to 25 carbon atoms or in the range of from 28 to 400 carbon atoms, in the hydrocarbon substituent, with at least one equivalent of with a polyhydroxy or polyamino compound (such as an alkylene amine) are particularly useful herein. Hydrocarbyl-substituted succinic acid and hydrocarbyl-substituted succinic anhydride derivatives may have a number average molecular weight greater than or equal to 400 g/mol, greater than or equal to 900 g/mol, greater than or equal to 1500 g/mol, or in the range of from 400 and 4000 g/mol, from 800 to 3000, from 2000 and 2800 g/mol, from about 2100 to 2500 g/mol, or from about 2200 to about 2400 g/mol.

Succinimides, which are particularly useful herein, are formed by the condensation reaction between: 1) hydrocarbyl substituted succinic anhydrides, such as polyisobutylene succinic anhydride (PIBSA); and 2) polyamine (PAM). Examples of suitable polyamines include: polyalkylene polyamines, hydroxy-substituted polyamines, polyoxyalkylene polyamines, and combinations thereof. Examples of polyalkylene polyamines include tetraethylene pentamine, pentaethylene hexamine, tetraethylenepentamine (TEPA), pentaethylenehaxamine (PEHA), and other polyamines having an average of 5, 6, 7, 8, or 9 nitrogen atoms per molecule). Mixtures where the average number of nitrogen atoms per polyamine molecule is greater than 7 are commonly called heavy polyamines or H-PAMs and may be commercially available under trade names such as HPA™ and HPA-X™ from Dow Chemical, E-100™ from Huntsman Chemical, et al. Examples of hydroxy-substituted polyamines include N-hydroxyalkyl-alkylene polyamines such as N-(2-hydroxyethyl)ethylene diamine, N-(2-hydroxyethyl)piperazine, and/or N-hydroxyalkylated alkylene diamines of the type described, for example, in U.S. Pat. No. 4,873,009. Examples of polyoxyalkylene polyamines include polyoxyethylene and/or polyoxypropylene diamines and triamines (as well as co-oligomers thereof) having an average M_n from about 200 to about 5000 g/mol. Products of this type are commercially available under the tradename Jeffamine™. Representative examples of useful succinimides are shown in U.S. Pat. Nos. 3,087,936; 3,172,892; 3,219,666; 3,272,746; 3,322,670; 3,652,616; 3,948,800; 6,821,307; and Canada Patent No. 1,094,044.

Succinate esters useful as dispersants include those formed by the condensation reaction between hydrocarbyl substituted succinic anhydrides and alcohols or polyols. For example, the condensation product of a hydrocarbyl substituted succinic anhydride and pentaerythritol is a useful dispersant.

Succinate ester amides useful herein are formed by a condensation reaction between hydrocarbyl substituted succinic anhydrides and alkanol amines. Suitable alkanol amines include ethoxylated polyalkylpolyamines, propoxylated polyalkylpolyamines, and polyalkenylpolyamines such as polyethylene polyamines and/or propoxylated hexamethylenediamine. Representative examples are shown in U.S. Pat. No. 4,426,305.

Hydrocarbyl substituted succinic anhydrides (such as PIBSA) esters of hydrocarbyl bridged aryloxy alcohols are also useful as dispersants herein. For information on such dispersants, please see U.S. Pat. No. 7,485,603, particularly, column 2, line 65 to column 6, line 22 and column 23, line 40 to column 26, line 46. In particular PIBSA esters of methylene-bridged naphthyloxy ethanol (i.e., 2-hydroxyethyl-1-naphthol ether (or hydroxy-terminated ethylene oxide oligomer ether of naphthol) are useful herein.

In some embodiments, the molecular weight of the hydrocarbyl substituted succinic anhydrides used in the preceding paragraphs is in the range of from 350 to 4000 g/mol, from 400 to 3000 g/mol, from 450 to 2800 g/mol, or from 800 to 2500 g/mol. The above (poly)alkenylsuccinic derivatives can be post-reacted with various reagents such as sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid.

The above (poly)alkenylsuccinic derivatives and/or functionalized olefin polymers, can also be post reacted with boron compounds such as boric acid, borate esters or highly borated dispersants, to form borated dispersants generally having from about 0.1 to about 5 moles of boron per mole of dispersant reaction product.

Dispersants useful herein include borated succinimides, including those derivatives from mono-succinimides, bis-succinimides, and/or mixtures of mono- and bis-succinimides, wherein the hydrocarbyl succinimide is derived from a hydrocarbylene group such as polyisobutylene having a M_n in the range of from about 300 to about 5000 g/mol, from about 500 to about 3000 g/mol, from about 1000 to about 2000 g/mol, or a mixture of such hydrocarbylene groups, often with high terminal vinylic groups.

In some embodiments, the boron-containing dispersant may be present in the lubricating oil composition in an amount in the range of from 0.01 wt % to 20 wt %, from 0.1 wt % to 15 wt %, from 0.1 wt % to 10 wt %, from 0.5 wt % to 8 wt %, from 1.0 wt % to 6.5 wt %, or from 0.5 wt % to 2.2 wt %, based on the weight of the lubricating oil composition.

In some embodiments, the boron-containing dispersant may be present in the lubricating oil composition in an amount to deliver boron to the lubricating oil composition in an amount in the range of from 15 ppm to 2000 ppm, from 25 ppm to 1000 ppm, from 40 ppm to 600 ppm, or from 80 ppm to 350 ppm.

In some embodiments, the borated dispersant may be used in combination with non-borated dispersant and may be the same or different compound as the non-borated dispersant. In some embodiments, the lubricating composition includes one or more boron-containing dispersants and one or more non-borated dispersants, wherein the total amount of dispersant in the lubricating oil composition is in the range of from 0.01 wt % to 20 wt %, from 0.1 wt % to 15 wt %, from 0.1 wt % to 10 wt %, from 0.5 wt % to 8 wt %, from 1.0 wt % to 6.5 wt %, or from 0.5 wt % to 2.2 wt %, based on the weight of the lubricating oil composition. In some embodiments, the ratio of borated dispersant to non-boronated dispersant is in the range of from 1:10 to 10:1 (weight:weight), from 1:5 to 3:1, or from 1:3 to 2:1.

Dispersants of Mannich Bases

Mannich base dispersants useful herein are typically made from the reaction of an amine component, a hydroxy aromatic compound (substituted or unsubstituted, such as alkyl substituted), such as alkylphenols, and an aldehyde, such as formaldehyde. See U.S. Pat. Nos. 4,767,551 and 10,899,986. Process aids and catalysts, such as oleic acid and sulfonic acids, can also be part of the reaction mixture. Representative examples are shown in U.S. Pat. Nos. 3,697,574; 3,703,536; 3,704,308; 3,751,365; 3,756,953; 3,798,165; 3,803,039; 4,231,759, 9,938,479; 7,491,248; 10,899,986, and WO 2001/42399.

Dispersants of Polymethacrylate or Polyacrylate Derivatives

Polymethacrylate or polyacrylate derivatives are another class of dispersants useful herein. These dispersants are typically prepared by reacting a nitrogen containing monomer and a methacrylic or acrylic acid esters containing 5-25 carbon atoms in the ester group. Representative examples are shown in U.S. Pat. Nos. 2,100,993, and 6,323,164. Polymethacrylate and polyacrylate dispersants are typically lower molecular weights.

The lubricating composition of the disclosure typically comprises dispersant at 0.1 wt % to 20 wt % of the composition, such as 0.2 to 15 wt %, such as 0.25 to 10 wt %, such as 0.3 to 5 wt %, such as 1.0 wt % to 3.0 wt % of the lubricating oil composition. Alternately the dispersant may be present at 0.1 wt % to 5 wt %, or 0.01 wt % to 4 wt %, or 0.05 wt % to 2 wt % of the lubricating composition.

For further information on dispersants useful herein, please see U.S. Pat. No. 10,829,712 column 13, line 36 to column 16, line 67; and U.S. Pat. No. 7,485,603, column 2, line 65 to column 6, line 22, column 8, line 25 to column 14, line 53, and column 23, line 40 to column 26, line 46.

E. Friction Modifiers (Components E-1, E-2, and E-3)

A friction modifier is any material or materials that can alter the coefficient of friction of a surface lubricated by any lubricant or fluid containing such material(s). Friction modifiers, also known as friction reducers, lubricity agents, or oiliness agents, and other such agents that change the ability of base oils, formulated lubricating oil compositions, or functional fluids, to modify the coefficient of friction of a lubricated surface may be effectively used in combination with the base oils or lubricating oil compositions of the present disclosure if desired. Friction modifiers that lower the coefficient of friction are particularly advantageous in combination with the base oils and lubricating compositions of this disclosure. E-3 components may be selected from Mo-containing compounds described herein below.

In some embodiments, friction modifiers include organometallic compounds or materials, or mixtures thereof. In some embodiments, organometallic compounds or materials, comprise tungsten compounds, molybdenum compounds, or a combination thereof. In some embodiments, nonlimiting examples of tungsten and/or a molybdenum compounds comprise a molybdenum amine, a molybdenum diamine, an organotungstenate, a molybdenum dithiocarbamate, a molybdenum dithiophosphate, a molybdenum amine complex, a molybdenum carboxylate, or a combination thereof. In some embodiments, molybdenum-containing compounds (E-3) include molybdenum dithiocarbamates, trinuclear molybdenum compounds (such as described in WO 98/26030), sulfides of molybdenum, and molybdenum dithiophosphate.

Other known E-3 friction modifiers comprise oil-soluble organo-molybdenum compounds. Such organo-molybdenum friction modifiers may also provide antioxidant and anti-wear credits to a lubricating oil composition. In some embodiments, such oil-soluble organo-molybdenum compounds include, but are not limited to, a dithiocarbamate, a dithiophosphate, a dithiophosphinate, a xanthate, a thioxanthate, a sulfide, or a combination thereof. In some embodiments, E-3 friction modifiers comprise a molybdenum dithiocarbamate, a dialkyldithiophosphate, an alkyl xanthate, an alkylthioxanthate, or a combination thereof.

In some embodiments, the molybdenum compound comprises an acidic molybdenum compound. These compounds will react with a basic nitrogen compound as measured by ASTM test D-664 or D-2896 titration procedure and are typically hexavalent. In some embodiments, the acidic molybdenum compound comprises a molybdic acid, an ammonium molybdate, a sodium molybdate, a potassium molybdate, other alkali metal molybdates (e.g., hydrogen sodium molybdate), other molybdenum salts (e.g., MoOCl₄, MoO₂Br₂, Mo₂O₃Cl₆, molybdenum trioxide), or a combination thereof.

In some embodiments, a molybdenum compound suitable for use as a E-3 friction modifier comprises one or more organo-molybdenum compounds of the formulas:

• • wherein R″ is an organo group selected from the group consisting of alkyl, aryl, aralkyl and alkoxyalkyl. In some embodiments R″ has from 1 to 30 carbon atoms or from 2 to 12 carbon atoms. In some embodiments R″ is an alkyl having from 2 to 12 carbon atoms. In some embodiments the E-3 friction modifier comprises one or more dialkyldithiocarbamates of molybdenum.

In some embodiments, the one or more organo-molybdenum compounds useful in the lubricating oil compositions of this disclosure are trinuclear molybdenum compounds. In some embodiments, the trinuclear molybdenum compounds comprise one or more compounds described by the formula Mo₃S_kL_nQ_z, wherein: each L is an independently selected ligand having organo groups with a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil, n is from 1 to 4; k varies from 4 to 7; Q is selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers; and z ranges from 0 to 5 and includes non-stoichiometric values. In some embodiments, the ligand organo groups comprise carbon atoms in an amount greater than or equal to 21, greater than or equal to 25, greater than or equal to 30, or greater than or equal to 35.

In some embodiments, lubricating oil compositions useful in all aspects of the present disclosure contain molybdenum in an amount greater than or equal to 250 ppm, greater than or equal to 300 ppm, greater than or equal to 350 ppm, or greater than or equal to 400 ppm, or greater than or equal to 450 ppm. In some embodiments, lubricating oil compositions useful in all aspects of the present disclosure contain molybdenum in an amount less than or equal to 1,000 ppm, less than or equal to 900 ppm, less than or equal to 800 ppm, less than or equal to 700 ppm, or less than or equal to 600 ppm. In some embodiments, lubricating oil compositions useful in all aspects of the present disclosure contain molybdenum in an amount in the range of from 250 to 1,000 ppm, from 300 to 900 ppm, from 350 to 800 ppm, from 400 to 700 ppm, or from 450 to 600 ppm (measured as atoms of molybdenum).

For more information or useful friction modifiers containing Mo, please see U.S. Pat. No. 10,829,712 (column 8, line 58 to column 11, line 31).

Molybdenum-containing compounds useful as E-3 include: molybdenum dithiocarbamates, dialkyldithiophosphates, alkyl xanthates and alkylthioxanthates, where the alkyl groups are C₁ to C₃₀ linear, branched, cyclic alkyl groups, such as C_{2 to 15} alkyl groups, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, cyclobutyl, pentyl, isopentyl, hexyl, isohexyl, cyclohexyl, phenyl, alkyl substituted phenyl, octyl, isooctyl, cyclooctyl, nononyl, decyl, isodecyl, undecyl, dodecyl, and isomers thereof.

Ashless friction modifiers may be present in the lubricating oil compositions of the present disclosure and are known generally and include esters formed by reacting carboxylic acids and anhydrides with alkanols and amine-based friction modifiers. Other useful friction modifiers generally include a polar terminal group (e.g. carboxyl or hydroxyl) covalently bonded to an oleophilic hydrocarbon chain. Esters of carboxylic acids and anhydrides with alkanols are described in U.S. Pat. No. 4,702,850. Examples of other conventional organic friction modifiers are described by M. Belzer in the “Journal of Tribology” (1992), Vol. 114, pp. 675-682 and M. Belzer and S. Jahanmir in “Lubrication Science” (1988), Vol. 1, pp. 3-26. In some embodiments, the total amount of organic ashless friction modifier in a lubricating oil composition according to the present disclosure is less than or equal to 5 wt %, less than or equal to 2 wt %, or less than or equal to 0.5 wt %, based on the total weight of the lubricating oil composition.

Illustrative friction modifiers useful in the lubricating compositions described herein include, for example, alkoxylated fatty acid esters, alkanolamides, polyol fatty acid esters, borated glycerol fatty acid esters, fatty alcohol ethers, sulfurized fatty acid esters, and mixtures thereof.

Illustrative alkoxylated fatty acid esters include, for example, polyoxyethylene stearate, fatty acid polyglycol ester, and the like. These can include polyoxypropylene stearate, polyoxybutylene stearate, polyoxyethylene isosterate, polyoxypropylene isostearate, polyoxyethylene palmitate, and the like.

Illustrative alkanolamides include, for example, lauric acid diethylalkanolamide, palmic acid diethylalkanolamide, and the like. These can include oleic acid diethyalkanolamide, stearic acid diethylalkanolamide, oleic acid diethylalkanolamide, polyethoxylated hydrocarbylamides, polypropoxylated hydrocarbylamides, and the like.

Illustrative polyol fatty acid esters include, for example, glycerol mono-oleate, saturated mono-, di-, and tri-glyceride esters, glycerol mono-stearate, and the like. These can include polyol esters, hydroxyl-containing polyol esters, and the like.

Illustrative borated glycerol fatty acid esters include, for example, borated glycerol mono-oleate, borated saturated mono-, di-, and tri-glyceride esters, borated glycerol mono-sterate, and the like. In addition to glycerol polyols, these can include trimethylolpropane, pentaerythritol, sorbitan, and the like. These esters can be polyol monocarboxylate esters, polyol dicarboxylate esters, and on occasion polyoltricarboxylate esters. In some embodiments, the esters can be selected from the glycerol mono-oleates, glycerol dioleates, glycerol trioleates, glycerol monostearates, glycerol distearates, and glycerol tristearates and the corresponding glycerol monopalmitates, glycerol dipalmitates, and glycerol tripalmitates, and the respective isostearates, linoleates, or combinations thereof. Ethoxylated, propoxylated, butoxylated fatty acid esters of polyols, especially using glycerol as underlying polyol are useful herein.

Illustrative fatty alcohol ethers include, for example, stearyl ether, myristyl ether, and the like. Alcohols, including those that have carbon numbers from C₃ to C₅₀, can be ethoxylated, propoxylated, or butoxylated to form the corresponding fatty alkyl ethers. In some embodiments, the underlying alcohol portion is stearyl, myristyl, C₁₁-C₁₃ hydrocarbon, oleyl, isosteryl, and the like.

Illustrative sulfurized fatty acid esters useful as component E-1, include sulfurized fatty acid methyl esters, such as sulfurized fatty acid ester derived from any suitable fatty acid ester, such as those derived from a vegetable oil (e.g. glycerol ester or trans-esterification product), such as, but not limited to, one or more of palm oil, corn oil, grapeseed oil, coconut oil, cottonseed oil, wheatgerm oil, soya oil, safflower oil, olive oil, peanut oil, rapeseed oil and sunflower oil, or an animal oil (e.g. glycerol ester or trans-esterification product) such as tallow oil or lard oil. The sulfurized fatty acid ester may be derived from one or more of palm oil, rapeseed oil, soya oil, tallow oil, lard oil, or a trans-esterified product thereof. In some embodiments, the sulfurized fatty acid ester is derived from a vegetable oil, especially one or more of palm oil, soya oil, rapeseed oil, or a trans-esterified product thereof. The sulfurized fatty acid ester suitably comprises substantially only sulfurized fatty acid ester and no other sulfurized carboxylic acid ester. For further descriptions of fatty acid esters, such as fatty acid methyl esters, please see U.S. Pat. No. 11,136,523, especially Col 8, line 1-56, Col 12, line 56 to Col 16, line 60, which is incorporated by reference herein.

In some embodiments, one or more oil-soluble or oil-dispersible sulfurized fatty acid ester(s), such as sulfurized fatty acid methyl ester(s), are present as an additive in an amount providing the lubricating oil composition with sulfur in an amount greater than or equal to 0.02 wt %, greater than or equal to 0.05 wt %, or greater than or equal to 0.08 wt %, based on the total weight of the lubricating oil composition. In some embodiments, the one or more sulfurized fatty acid ester(s) provides the lubricating oil composition with sulfur in an amount less than or equal to 0.30 wt %, less than or equal to 0.25 wt %, or less than or equal to 0.20 wt %, based on the total weight of the lubricating oil composition. In some embodiments, the one or more sulfurized fatty acid ester(s) provides the lubricating oil composition with sulfur in an amount in the range of from 0.02 wt % to 0.30 wt %, from 0.05 wt % to 0.30 wt %, or from 0.05 to 0.20 wt %, based on the total weight of the lubricating oil composition.

In some embodiments, friction modifiers are present in the lubricating oil composition in an amount in the range of from 0.01 wt % to 5 wt %, from about 0.1 wt % to about 2.5 wt %, from about 0.1 wt % to about 1.5 wt %, or from about 0.1 wt % to about 1 wt %. Concentrations of molybdenum-containing materials are often described in terms of Mo metal concentration. In some embodiments, Mo is present in the lubricating oil composition in an amount in the range of from 250 to 1,000 ppm, from 300 to 900 ppm, from 350 to 800 ppm, from 400 to 700 ppm, or from 450 to 600 ppm (measured as atoms of molybdenum). Friction modifiers of all types may be used alone or in mixtures with the materials of this disclosure. Often mixtures of two or more friction modifiers, or mixtures of friction modifier(s) with alternate surface active material(s), are also desirable. For example, combinations of Mo containing compounds with polyol fatty acid esters, such as glycerol mono-oleate are useful herein.

Compositions according to the present disclosure may contain sulfurized fatty acid ester that are described as friction modifiers herein. These sulfurized fatty acid ester additives are not included as friction modifiers for purposes of determining the amount of friction modifiers (E-2) in a lubricating oil composition or concentrate herein.

Likewise, compositions according to the present disclosure may comprise one or more molybdenum-containing compounds that can act as friction modifiers providing a specific amount of molybdenum atoms to the lubricating oil composition. These molybdenum compounds are not included as friction modifiers for purposes of determining the amount of friction modifiers in a lubricating oil composition or concentrate herein.

F. Antioxidants (Component F)

Antioxidants retard the oxidative degradation of base oils during service. Such degradation may result in deposits on metal surfaces, the presence of sludge, or a viscosity increase in a lubricant. A wide variety of oxidation inhibitors that are useful in lubricating oil compositions. See Lubricants and Related Products, Klamann, Wiley VCH, 1984; U.S. Pat. Nos. 4,798,684; and 5,084,197, for example.

Useful antioxidants include hindered phenols (i.e., phenol based antioxidants useful in component E). These phenolic antioxidants may be ashless (metal-free) phenolic compounds or neutral or basic metal salts of certain phenolic compounds. Typical phenolic antioxidant compounds are the hindered phenolics which contain a sterically hindered hydroxyl group, and these include those derivatives of dihydroxy aryl compounds in which the hydroxyl groups are in the o- or p-position to each other. Typical phenolic antioxidants include the hindered phenols substituted with C₆₊ alkyl groups and the alkylene coupled derivatives of these hindered phenols. Examples of phenolic materials of this type 2-t-butyl-4-heptyl phenol; 2-t-butyl-4-octyl phenol; 2-t-butyl-4-dodecyl phenol; 2,6-di-t-butyl-4-heptyl phenol; 2,6-di-t-butyl-4-dodecyl phenol; 2-methyl-6-t-butyl-4-heptyl phenol; and 2-methyl-6-t-butyl-4-dodecyl phenol. Other useful hindered mono-phenolic antioxidants may include, for example, hindered 2,6-di-alkyl-phenolic proprionic ester derivatives. Bis-phenolic antioxidants may also be advantageously used herein. Examples of ortho-coupled phenols include: 2,2′-bis(4-heptyl-6-t-butyl-phenol); 2,2′-bis(4-octyl-6-t-butyl-phenol); and 2,2′-bis(4-dodecyl-6-t-butyl-phenol). Para-coupled bisphenols include for example 4,4′-bis(2,6-di-t-butyl phenol) and 4,4′-methylene-bis(2,6-di-t-butyl phenol).

Effective amounts of one or more catalytic antioxidants may also be used. The catalytic antioxidants comprise an effective amount of a) one or more oil soluble polymetal organic compounds; and, effective amounts of b) one or more substituted N,N′-diaryl-o-phenylenediamine compounds or c) one or more hindered phenol compounds; or a combination of both b) and c). Catalytic antioxidants useful herein are more fully described in U.S. Pat. No. 8,048,833.

Non-phenolic oxidation inhibitors which may be used include aromatic amine antioxidants (amine based antioxidants useful in component E) and these may be used either as such or in combination with phenolics. Typical examples of non-phenolic antioxidants include: alkylated and non-alkylated aromatic amines such as aromatic monoamines of the formula R⁸R⁹R¹⁰N, where R⁸ is an aliphatic, aromatic or substituted aromatic group, R⁹ is an aromatic or a substituted aromatic group, and R¹⁰ is H, alkyl, aryl or R¹¹S(O)_XR¹² where R¹¹ is an alkylene, alkenylene, or aralkylene group, R¹² is an alkyl group, or an alkenyl, aryl, or alkaryl group, and x is 0, 1 or 2. The aliphatic group R⁸ may contain from 1 to about 20 or 6 to 12 carbon atoms. The aliphatic group is typically a saturated aliphatic group. In some embodiments, both R⁸ and R⁹ are aromatic or substituted aromatic groups, and the aromatic group may be a fused ring aromatic group such as naphthyl. In some embodiments, aromatic groups R⁸ and R⁹ may be joined together with other groups such as S.

In some embodiments, aromatic amines antioxidants have alkyl substituent groups of at least about 6 carbon atoms. Nonlimiting examples of aliphatic groups include hexyl, heptyl, octyl, nonyl, decyl, or a combination thereof. In some embodiments, the aliphatic groups will not contain less than or equal to 14 carbon atoms. The general types of amine antioxidants useful in the present compositions include but are not limited to diphenylamines, phenyl naphthylamines, phenothiazines, imidodibenzyls, diphenyl phenylene diamines, or combinations thereof. Polymeric amine antioxidants can also be used. Particular examples of aromatic amine antioxidants useful in the present disclosure include: p,p′-dioctyldiphenylamine; t-octylphenyl-alpha-naphthylamine; phenyl-alphanaphthylamine; p-octylphenyl-alpha-naphthylamine; or mixtures thereof. The antioxidant in component E) may be solely (consist of or consist essentially of) amine based antioxidants, such as aromatic amine antioxidants. The antioxidant in component E) may be solely (consist of or consist essentially of) phenyl amine (such as diphenyl amine) based antioxidants. The antioxidant in component E) may exclude phenol-based antioxidants.

Sulfur containing anti-oxidants are also useful herein. In particular, one or more oil-soluble or oil-dispersible sulfur containing anti-oxidant(s) can be used as an antioxidant additive. For example, sulfurized alkyl phenols and alkali or alkaline earth metal salts thereof also are useful antioxidants herein. In some embodiments, the lubricating oil composition of the present disclosure includes one or more sulfur containing anti-oxidant(s) in an amount sufficient to provide the lubricating oil composition with from 0.02 to 0.2, from 0.02 to 0.15, from 0.02 to 0.1, or from 0.04 to 0.1 wt % sulfur based on the total weight of the lubricating oil composition. Optionally the oil-soluble or oil-dispersible sulfur containing anti-oxidant(s) are selected from sulfurized C₄ to C₂₅ olefin(s), sulfurized aliphatic (C₇ to C₂₉) hydrocarbyl fatty acid ester(s), ashless sulfurized phenolic anti-oxidant(s), sulfur containing organo-molybdenum compound(s), and combinations thereof. For further information, on sulfurized materials useful as anti-oxidants herein, please see U.S. Pat. No. 10,731,101 (column 15, line 55 to column 22, line 12).

Antioxidants useful herein include hindered phenols, arylamines. These antioxidants may be used individually by type or in combination with one another.

In some embodiments, antioxidants include, but are not limited to: Irganox™ L67, Irganox™ L135, ETHANOX™ 4702, Lanxess Additin™ RC 7110; ETHANOX™ 4782J; Irganox™ 1135, Irganox™ 5057, or a combination thereof.

In some embodiments, antioxidant additives are present in the lubricating oil composition in an amount in the range of from about 0.01 to 5 wt %, from about 0.01 to 3 wt %, from 0.01 to 1.5 wt %, or from 0.01 to less than 1 wt %, based upon the weight of the lubricating oil composition.

Compositions according to the present disclosure may contain an additive having a different enumerated function that also has secondary effects as an antioxidant (for example, phosphorus-containing anti-wear agents (such as ZDDP) may also have antioxidant effects). These additives are not included as antioxidants for purposes of determining the amount of antioxidant in a lubricating oil composition or concentrate herein. However, amine based antioxidants and phenol based antioxidant are included as as antioxidants for purposes of determining the amount of antioxidant in a lubricating oil composition or concentrate herein. The antioxidant may consist of or consist essentially of amine-based antioxidants and/or phenol based antioxidant. The antioxidant may exclude antioxidants that are not amine based antioxidant and/or phenol based antioxidant.

G. Pour Point Depressants

Conventional pour point depressants (also known as lube oil flow improvers) may be added to the compositions of the present disclosure if desired. These pour point depressant may be added to lubricating compositions of the present disclosure to lower the minimum temperature at which the fluid will flow or can be poured. Examples of suitable pour point depressants include polymethacrylates, polyacrylates, polyarylamides, condensation products of haloparaffin waxes and aromatic compounds, vinyl carboxylate polymers, copolymers of dialkyl fumarate and vinyl acetates (such as copolymers of C₈-C₁₈dialkyl fumarate/vinyl acetate), terpolymers of dialkylfumarates, vinyl esters of fatty acids and allyl vinyl ethers. U.S. Pat. Nos. 1,815,022; 2,015,748; 2,191,498; 2,387,501; 2,655,479; 2,666,746; 2,721,877; 2,721,878; and 3,250,715 describe useful pour point depressants and/or the preparation thereof. Such additives may be used in an amount of about 0.01 to 5 wt % or about 0.01 to 1.5 wt %.

H. Anti-Foam Agents

Anti-foam agents may advantageously be added to lubricant compositions described herein. These agents prevent or retard the formation of stable foams. Silicones and organic polymers are typical anti-foam agents. For example, polysiloxanes, such as silicon oil or polydimethyl siloxane, provide antifoam properties.

In some embodiments, anti-foam agents are commercially available and may be used in minor amounts such less than or equal to 5 wt %, less than or equal to 3 wt %, less than or equal to 1 wt %, or less than or equal to 0.1 wt %, based on the weight of the lubricating oil composition. In some embodiments, anti-foam agents are present in the lubricating oil composition in an amount in the range of from 0.1 ppm to 5 wt %, from 0.5 ppm to 3 wt %, or from 10 ppm to 1 wt % to 10 ppm, based on the weight of the lubricating oil composition.

In some embodiments, the lubricating oil composition comprises an anti-foam agent comprising polyalkyl siloxane, such as a polydialkyl siloxane, wherein the alkyl is a C₁-C₁₀ alkyl group. In some embodiments, the anti-foam agent comprises a polydimethylsiloxane (PDMS), also known as a silicone oil. In some embodiments, the siloxane is a poly(R³)siloxane, wherein R³ is one or more same or different linear branched or cyclic hydrocarbyls, such as alkyls or aryls, typically having 1 to 20 carbon atoms. In some embodiments, the lubricating oil composition comprises a polymeric siloxane compound according to Formula 1 below wherein R¹ and R² are independently are independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl, phenyl, naphthyl, alkyl substituted phenyl, or isomers thereof (such as methyl, phenyl) and n is from 2 to 1000, such as 50 to 450 alternately such as 40 to 100.

Additionally or alternatively, it may be that the lubricating oil composition comprises an organo modified siloxane (OMS), such as a siloxane modified with an organo group such as a polyether (e.g. ethylene-propyleneoxide copolymer), long chain hydrocarbyl (e.g. C₁₁-C₁₀₀ alkyl), or aryl (e.g. C₆-C₁₄ aryl). It may be that, for example, the lubricating oil composition comprises an organo modified siloxane compound according to Formula 1, wherein n is from 2 to 1000, such as 50 to 450 (alternately such as 40 to 100), and wherein R¹ and R² are the same or different, optionally wherein each of R¹ and R² is, independently an organo group, such as an organo group selected from polyether (e.g. ethylene-propyleneoxide copolymer), long chain hydrocarbyl (e.g. C₁₁-C₁₀₀ alkyl), or aryl (e.g. C₆-C₁₄ aryl). In some embodiments, one of R¹ and R² is CH₃.

In some embodiments, the siloxane according to Formula 1 is incorporated into the lubricating oil composition in an amount sufficient so as to provide a Si content in the lubricating oil composition in an amount in the range of from about 0.1 to less than about 30 ppm, from about 0.1 to about 25 ppm, from about 0.1 to about 20 ppm, from about 0.1 to about 15 ppm, from about 0.1 to about 10 ppm, or from about 3 to about 10 ppm.

In an embodiment, silicone antifoam agents useful herein are available from Dow Corning Corporation and Union Carbide Corporation, such as Dow Corning FS-1265 (1000 centistokes), Dow Corning DC-200, and Union Carbide UC-L45. Silicone anti-foamants useful herein are polydimethylsiloxane, phenyl-methyl polysiloxane, linear, cyclic or branched siloxanes, silicone polymers and copolymers, and organo-silicone copolymers. Also, a siloxane polyether copolymer antifoamant available from OSI Specialties, Inc. of Farmington Hills, Mich. and may be substituted or included. One such material is sold as SILWET-L-7220.

Acrylate polymer antifoam agent can also be used herein. Typical acrylate anti-foamants include polyacrylate antifoamant available from Monsanto Polymer Products Co. known as PC-1244. In some embodiments, an acrylate polymer antifoam agent useful herein is PX™3841 (i.e., an alkyl acrylate polymer), commercially available from Dorf Ketl, also referred to as Mobilad™C₄₀₂.

In embodiments, a combination of silicone anti-foamant and acrylate anti-foamant can be used, such as at a weight ratio of the silicone anti-foamant to the acrylate anti-foamant of from about 5:1 to about 1:5, see for example US 2021/0189283A1.

I. Viscosity Modifiers

Viscosity modifiers (also referred to as viscosity index improvers or viscosity improvers) can be included in the lubricating compositions described herein. Viscosity modifiers provide lubricants with high and low temperature operability. These additives impart shear stability at elevated temperatures and acceptable viscosity at low temperatures. Suitable viscosity modifiers include high molecular weight hydrocarbons, polyesters, and viscosity modifier dispersants that can function as both a viscosity modifier and a dispersant. In some embodiments, molecular weights of these polymers are in the range of from about 10,000 to 1,500,000 g/mol, from about 20,000 to 1,200,000 g/mol, or from about 50,000 and 1,000,000 g/mol.

Examples of suitable viscosity modifiers are linear or star-shaped polymers and copolymers of methacrylate, butadiene, olefins, styrene, or alkylated styrenes. Polyisobutylene is a commonly used viscosity modifier. Another suitable viscosity modifier is polymethacrylate (copolymers of various chain length alkyl methacrylates, for example), some formulations of which also serve as pour point depressants. Other suitable viscosity modifiers include copolymers of ethylene and propylene, hydrogenated styrene-diene block copolymer, hydrogenated block copolymers of styrene and isoprene, hydrogenated block copolymers of styrene and isobutylene, and polyacrylates (copolymers of various chain length acrylates, for example). Specific examples include styrene-isoprene or styrene-butadiene based polymers of 50,000 to 200,000 g/mol molecular weight.

Copolymers useful as viscosity modifiers include those commercially available from Chevron Oronite Company LLC under the trade designation “PARATONE™” (such as “PARATONE™ 8921,” PARATONE™ 68231,” and “PARATONE™ 8941”); from Afton Chemical Corporation under the trade designation “HiTEC™” (such as HiTEC™ 5850B, and HiTEC™5777); and from The Lubrizol Corporation under the trade designation “Lubrizol™ 7067C”. Hydrogenated polyisoprene star polymers useful as viscosity modifiers herein include those commercially available from Infineum International Limited, e.g., under the trade designation “Infineum SV200” and “Infineum SV600”. Hydrogenated diene-styrene block copolymers useful as viscosity modifiers herein are commercially available from Infineum International Limited, e.g., under the trade designation “Infineum SV 50”.

Polymers useful as viscosity modifiers herein include polymethacrylate or polyacrylate polymers, such as linear polymethacrylate or polyacrylate polymers, such as those available from Evnoik Industries under the trade designation “Viscoplex™” (e.g., Viscoplex™ 6-954) or star polymers which are available from Lubrizol Corporation under the trade designation Asteric™ (e.g., Lubrizol™ 87708 and Lubrizol 87725).

Vinyl aromatic-containing polymers useful as viscosity modifiers herein may be derived from vinyl aromatic hydrocarbon monomers, such as styrenic monomers, such as styrene. Illustrative vinyl aromatic-containing copolymers useful herein may be represented by the following general formula: A-B wherein A is a polymeric block derived predominantly from vinyl aromatic hydrocarbon monomer (such as styrene), and B is a polymeric block derived predominantly from conjugated diene monomer (such as isoprene).

In some embodiments, the viscosity modifiers are used in the lubricating oil composition in an amount in the range of from about 0.01 to about 10 wt %, from about 0.1 to about 7 wt %, from about 0.1 to about 4 wt %, from about 0.2 to about 2 wt %, from about 0.2 to about 1 wt %, or from about 0.2 to about 0.5 wt %, based on the total weight of the lubricating oil composition.

Viscosity modifiers are typically added as concentrates, in large amounts of diluent oil. The “as delivered” viscosity modifier typically contains from 20 wt % to 75 wt % of an active polymer for polymethacrylate or polyacrylate polymers, or from 8 wt % to 20 wt % of an active polymer for olefin copolymers, hydrogenated polyisoprene star polymers, or hydrogenated diene-styrene block copolymers, in the “as delivered” polymer concentrate.

J. Corrosion Inhibitors/Antirust Agents (Component J)

Corrosion inhibitors may be used to reduce the corrosion of metals and are often alternatively referred to as metal deactivators or metal passivators. Some corrosion inhibitors may alternatively be characterized as antioxidants.

Suitable corrosion inhibitors may include nitrogen and/or sulfur containing heterocyclic compounds such as triazoles (e.g., benzotriazoles), substituted thiadiazoles, imidazoles, thiazoles, tetrazoles, hydroxyquinolines, oxazolines, imidazolines, thiophenes, indoles, indazoles, quinolines, benzoxazines, dithiols, oxazoles, oxatriazoles, pyridines, piperazines, triazines and derivatives of any one or more thereof. A particular corrosion inhibitor is a benzotriazole represented by the structure:

• • wherein R⁸ is absent (hydrogen) or is a C₁ to C₂₀ hydrocarbyl or substituted hydrocarbyl group which may be linear or branched, saturated or unsaturated. It may contain ring structures that are alkyl or aromatic in nature and/or contain heteroatoms such as N, O, or S. Examples of suitable compounds may include benzotriazole, alkyl-substituted benzotriazoles (e.g., tolyltriazole, ethylbenzotriazole, hexylbenzotriazole, octylbenzotriazole, etc.), aryl substituted benzotriazole, alkylaryl- or arylalkyl-substituted benzotriazoles, and the like, as well as combinations thereof. For instance, the triazole may comprise or be a benzotriazole and/or an alkylbenzotriazole in which the alkyl group contains from 1 to about 20 carbon atoms or from 1 to about 8 carbon atoms. Non-limiting examples of such corrosion inhibitors may comprise or be benzotriazole, tolyltriazole, and/or optionally substituted benzotriazoles such as Irgamet™ 39, which is commercially available from BASF of Ludwigshafen, Germany. In some embodiments, the corrosion inhibitor may comprise or be benzotriazole and/or tolyltriazole.

Additionally or alternatively, the corrosion inhibitor may include a substituted thiadiazoles represented by the structure:

• • wherein R¹⁵ and R¹⁶ are independently hydrogen or a hydrocarbon group, which group may be aliphatic or aromatic, including cyclic, alicyclic, aralkyl, aryl and alkaryl, and wherein each w is independently selected from 1, 2, 3, 4, 5, or 6, independently selected from 2, 3, or 4, or is 2. These substituted thiadiazoles are derived from the 2,5-dimercapto-1,3,4-thiadiazole (DMTD) molecule. Many derivatives of DMTD have been described in the art, and any such compounds may be included in the fluid used in the present disclosure. For example, U.S. Pat. Nos. 2,719,125, 2,719,126, and 3,087,937 describe the preparation of various 2, 5-bis-(hydrocarbon dithio)-1,3,4-thiadiazoles.

Further additionally or alternatively, the corrosion inhibitor may include one or more other derivatives of DMTD, such as a carboxylic ester in which R″ and R¹⁶ may be joined to the sulfide sulfur atom through a carbonyl group. Preparation of these thioester containing DMTD derivatives is described, for example, in U.S. Pat. No. 2,760,933. DMTD derivatives produced by condensation of DMTD with alpha-halogenated aliphatic carboxylic acids having at least 10 carbon atoms are described, for example, in U.S. Pat. No. 2,836,564. This process produces DMTD derivatives wherein R¹⁵ and R¹⁶ are HOOC—CH(R¹⁹)— (R¹⁹ being a hydrocarbyl group). DMTD derivatives further produced by amidation or esterification of these terminal carboxylic acid groups may also be useful.

The preparation of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazoles is described, for example, in U.S. Pat. No. 3,663,561.

A class of DMTD derivatives may include mixtures of a 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazole and a 2,5-bis-hydrocarbyldithio-1,3,4-thiadiazole. Such mixtures may be sold under the tradename HiTEC® 4313 and are commercially available from Afton Chemical Company.

The preparation of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazoles is described, for example, in U.S. Pat. No. 3,663,561.

A class of DMTD derivatives may include mixtures of a 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazole and a 2,5-bis-hydrocarbyldithio-1,3,4-thiadiazole. Such mixtures may be sold under the tradename HiTEC™ 4313 and are commercially available from Afton Chemical Company.

Still further additionally or alternatively, the corrosion inhibitor may include a trifunctional borate having the structure, B(OR⁴⁶)₃, in which each R⁴⁶ may be the same or different. As the borate may typically be desirably compatible with the non-aqueous medium of the composition, each R⁴⁶ may in particular comprise or be a hydrocarbyl C₁-C₈ moiety. For compositions in which the non-aqueous medium comprises or is a lubricating oil basestock, for example, better compatibility can typically be achieved when the hydrocarbyl moieties are each at least C₄. Non-limiting examples of such corrosion inhibitors thus include, but are not limited to, triethylborate, tripropylborates such as triisopropylborate, tributylborates such as tri-tert-butylborate, tripentylborates, trihexylborates, trioctylborates such as tri-(2-ethylhexyl)borate, monohexyl dibutylborate, and the like, as well as combinations thereof.

When used, a corrosion inhibitor may comprise a substituted thiadiazole, a substituted benzotriazole, a substituted triazole, a trisubstituted borate, or a combination thereof.

When desired, corrosion inhibitors can be used in any effective amount, but, when used, may typically be used in amounts from about 0.001 wt % to 5.0 wt %, based on the weight of the composition, e.g., from 0.005 wt % to 3.0 wt % or from 0.01 wt % to 1.0 wt %. In some embodiments, such additives are used in the lubricating oil composition in an amount in the range of from about 0.01 to 5 wt % or from about 0.01 to 1.5 wt %, based upon the weight of the lubricating oil composition.

In some embodiments, 3,4-oxypyridinone-containing compositions may contain substantially no (e.g., 0, or less than 0.001 wt %, 0.0005 wt % or less, not intentionally added, and/or absolutely no) triazoles, benzotriazoles, substituted thiadiazoles, imidazoles, thiazoles, tetrazoles, hydroxyquinolines, oxazolines, imidazolines, thiophenes, indoles, indazoles, quinolines, benzoxazines, dithiols, oxazoles, oxatriazoles, pyridines, piperazines, triazines, derivatives thereof, combinations thereof, or all corrosion inhibitors.

K. Anti-wear Agents (Component K)

Anti-wear agents described herein exclude compounds represented by the formula (I) in section G above. Compositions according to the present disclosure may contain an additive having a different enumerated function that also has secondary effects as an anti-wear (for example, organo-molybdenum friction modifiers (such as molybdenum dithiocarbamates, dialkyldithiophosphates, alkyl xanthates and alkylthioxanthates) may also have anti-wear effects). These additives are not included as anti-wear additives for purposes of determining the amount of anti-wear additives in a lubricating oil composition or concentrate herein.

The lubricating oil composition of the present disclosure can contain one or more anti-wear 10 agents that can reduce friction and excessive wear. Any anti-wear agent known by a person of ordinary skill in the art may be used in the lubricating oil composition. Non-limiting examples of suitable anti-wear agents include zinc dithiophosphate, metal (e.g., Pb, Sb, Mo and the like) salts of dithiophosphates, metal (e.g., Zn, Pb, Sb, Mo and the like) salts of dithiocarbamates, metal (e.g., Zn, Pb, Sb and the like) salts of fatty acids, boron compounds, phosphate esters, phosphite esters, amine salts of phosphoric acid esters or thiophosphoric acid esters, reaction products of dicyclopentadiene and thiophosphoric acids and combinations thereof. The amount of the anti-wear agent may vary from about 0.01 wt % to about 5 wt %, from about 0.05 wt % to about 3 wt %, or from about 0.1 wt % to about 1 wt %, based on the total weight of the lubricating oil composition.

In embodiments, the anti-wear agent is or comprises a dihydrocarbyl dithiophosphate metal salt, such as zinc dialkyl dithiophosphate compounds. The metal of the dihydrocarbyl dithiophosphate metal salt may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper. In some embodiments, the metal is zinc. In other embodiments, the alkyl group of the dihydrocarbyl dithiophosphate metal salt has from about 3 to about 22 carbon atoms, from about 3 to about 18 carbon atoms, from about 3 to about 12 carbon atoms, or from about 3 to about 8 carbon atoms. In further embodiments, the alkyl group is linear or branched.

In embodiments, the lubricating oil compositions described herein are absent added dihydrocarbyl dithiophosphate metal salt where the metal is copper.

Useful anti-wear agents also include substituted or unsubstituted thiophosphoric acids, and salts thereof include zinc-containing compounds such as zinc dithiophosphate compounds selected from zinc dialkyl-, diaryl- and/or alkylaryl-dithiophosphates.

A metal alkylthiophosphate and more particularly a metal dialkyl dithiophosphate in which the metal constituent is zinc, or zinc dialkyl dithiophosphate (ZDDP) can be a useful component of the lubricating compositions of this disclosure. ZDDP can be derived from primary alcohols, secondary alcohols or mixtures thereof. ZDDP compounds generally are of the formula Zn[SP(S)(OR¹)(OR²)]₂ where R¹ and R² are C₁-C₁₈ alkyl groups or C₂-C₁₂ alkyl groups. These alkyl groups may be straight chain or branched. Alcohols used in the ZDDP can be 2-propanol, butanol, secondary butanol, pentanols, hexanols such as 4-methyl-2-pentanol, n-hexanol, n-octanol, 2-ethyl hexanol, alkylated phenols, and the like. Mixtures of secondary alcohols or of primary and secondary alcohol can be used. Alkyl aryl groups may also be used. Useful zinc dithiophosphates include secondary zinc dithiophosphates such as those available from The Lubrizol Corporation under the trade designations “LZ 677A”, “LZ 1095” and “LZ 1371”, from Chevron Oronite under the trade designation “OLOA 262” and from Afton Chemical under the trade designation “HITEC™ 7169”.

The ZDDP is typically used in amounts of from about 0.4 weight percent to about 1.2 wt %, from about 0.5 wt % to about 1.0 wt %, or from about 0.6 wt % t to about 0.8 wt %, based on the total weight of the lubricating oil composition, although more or less can often be used advantageously. In some embodiments, the ZDDP is a secondary ZDDP and is present in an in the lubricating oil composition in an amount in the range of from about 0.6 to 1.0 wt %, based on the total weight of the lubricating oil composition.

In embodiments, the zinc compound can be a zinc dithiocarbamate complex, such as the zinc dithiocarbamates represented by the formula:

• • where each R₁ is independently a linear, cyclic, or branched, saturated or unsaturated, aliphatic hydrocarbon moiety having from 1 to about 10 carbon atoms, n is 0, 1, or 2, L is a ligand that saturates the coordination sphere of zinc, and x is 0, 1, 2, 3, or 4. In some embodiments, the ligand, L, is selected from the group consisting of water, hydroxide, ammonia, amino, amido, alkylthiolate, halide, and combinations thereof.

The ZDDP and or the zinc carbamates are typically used in the lubricating oil composition in an amount in the range of from about 0.4 wt % to about 1.2 wt %, from about 0.5 wt % to about 1.0 wt %, or from about 0.6 wt % to about 0.8 wt %, based on the total weight of the lubricating oil composition, although more or less can often be used advantageously.

Anti-wear additives useful herein also include boron-containing compounds, such as borate esters, borated fatty amines, borated epoxides, alkali metal (or mixed alkali metal or alkaline earth metal) borates and borated overbased metal salts.

L. Demulsifiers

Demulsifiers useful herein include those described in 10,829,712 (Col 20, ln 34-40). Typically, a small amount of a demulsifying component may be used herein. In some embodiments, the demulsifying component is described in EP 330,522. It is obtained by reacting an alkylene oxide with an adduct obtained by reacting a bis-epoxide with a polyhydric alcohol. Such additives may be used in an amount of about 0.001 to 5 wt % or about 0.01 to 2 wt %.

M. Seal Compatibility Agents

Optional additives include seal compatibility agents such as organic phosphates, aromatic esters, aromatic hydrocarbons, esters (butylbenzyl phthalate, for example), and polybutenyl succinic anhydride. Such additives may be used in an amount of about 0.001 to 5 wt % or about 0.01 to 2 wt %.

N. Extreme Pressure Agents.

The lubricating oil composition of the present disclosure can contain one or more extreme pressure agents that can prevent sliding metal surfaces from seizing under conditions of extreme pressure. Any extreme pressure agent known by a person of ordinary skill in the art may be used in the lubricating oil composition. Generally, the extreme pressure agent is a compound that can combine chemically with a metal to form a surface film that prevents the welding of asperities in opposing metal surfaces under high loads. Non-limiting examples of suitable extreme pressure agents include sulfurized animal or vegetable fats or oils, sulfurized animal or vegetable fatty acid esters, fully or partially esterified esters of trivalent or pentavalent acids of phosphorus, sulfurized olefins, dihydrocarbyl polysulfides, sulfurized Diels-Alder adducts, sulfurized dicyclopentadiene, sulfurized or co-sulfurized mixtures of fatty acid esters and monounsaturated olefins, co-sulfurized blends of fatty acid, fatty acid ester and alpha-olefin, functionally-substituted dihydrocarbyl polysulfides, thia-aldehydes, thia-ketones, epithio compounds, sulfur-containing acetal derivatives, co-sulfurized blends of terpene and acyclic olefins, and poly sulfide olefin products, amine salts of phosphoric acid esters or thiophosphoric acid esters and combinations thereof. The amount of the extreme pressure agent may vary from about 0.01 wt % to about 5 wt %, from about 0.05 wt % to about 3 wt %, or from about 0.1 wt % to about 1 wt %, based on the total weight of the lubricating oil composition.

O. Alpha-Olefins

In some embodiments, the LOC comprises one or more alpha-olefins, such as linear alpha-olefins (LAO) having from 8 to 36 carbon atoms, from 8 to 24 carbon atoms, from 10 to 20 carbon atoms, from 12 to 20 carbon atoms, or from 14 to 18 carbon atoms. In some embodiments, the base oil comprises mixtures of linear alpha-olefins, having from 8 to 24 carbon atoms, from 10 to 20 carbon atoms, from 12 to 20 carbon atoms, or from 14 to 18 carbon atoms. In embodiments, the base oil comprises mixtures of linear alpha-olefins, having 14 or more carbon atoms.

In some embodiments, the LOC may comprise from 0.001 to 15 wt %, from 0.15 to 10 wt %, from 0.20 wt % to 5 wt %, or from 0.25 to 2 wt %, based upon the weight of the lubricating composition, of one or more C₈ to C₃₆ alpha olefins. In embodiments, the LOC may comprise from 0.001 to 15 wt %, (in particular 0.15 to 10 wt %, alternately 0.20 wt % to 5 wt %, alternately 0.25 to 2 wt %) based upon the weight of the lubricating composition, of one, two, three, four, five or more C₈ to C₃₆ alpha olefins, such linear alpha olefins having from 8 to 24 carbon atoms, from 10 to 20 carbon atoms, from 12 to 20 carbon atoms, or from 14 to 18 carbon atoms.

When lubricating oil compositions contain one or more of the additives discussed above, the additive(s) are typically blended into the composition in an amount sufficient for it to perform its intended function. Typical amounts of such additives useful in the present disclosure, especially for use in crankcase lubricants, are shown the Tables below.

It is noted that many of the additives are shipped from the additive manufacturer as a concentrate, containing one or more additives together, with a certain amount of base oil or other diluents. Accordingly, the weight amounts in the Tables below, as well as other amounts mentioned herein, are directed to the amount of active ingredient (that is the non-diluent portion of the ingredient). The weight percent (wt %) indicated below is based on the total weight of the lubricating oil composition.

Typical Amounts of Optional Lubricating Oil Components in LOC

ADDITIVE FORMULATIONS	A (wt %)	B (wt %)	C (wt %)
Dispersant (borated and non-borated)	0.1-40	1-20	4 to 15
Detergents	0.1-20	0.2-15	2 to 10
Functionalized olefin copolymer	0.1-15	0.2-10	0.3-5
Amine and or phenol based Antioxidant	0.01-7	0.10-5	1 to 5
Sulfurized fatty acid ester	0.01-20	0.1 to 10	0.5-5
Molybdenum-containing compound	0.01-10	0.1 to 7	0.1 to 5
Antifoaming Agent	0.001-5	0.001-0.2	0.001-0.1
Friction Modifier	0-5	0-1.5	0.1 to 5
Viscosity Modifier	0.01-25	1-20	5-15
LAO	0.1 to 10	0.1 to 5	0.1 to 2.5
Optional additional additives	0-20	0.1-10	0.1-5
one or more Group III base oils,	Balance	Balance	Balance
one or more Group III+ base oils,
one or more Group IV base oils,
or a combination thereof (50 to 99 wt %)

ADDITIVE FORMULATIONS	D (wt %)	E (wt %)	F (wt %)
Dispersant borated	0.1-10	0.5-8	0.5-5
Dispersant non-borated	0.1 to 30	0.5 to 20	1 to 15
Detergent Ca high TBN	0.1-19.8	0.25-9	0.25 to 5
Detergent Mg, high TBN	0.1-19.8	0.5-8	0.5 to 5
Detergent Ca low TBN	0.1-9.8	0.5-8	0.5 to 5
Functionalized olefin copolymer	0.1-15	0.2-10	0.3-5
Amine-and/or phenol-based antioxidant	0.01-7	0.10-5	1 to 5
Sulfurized fatty acid ester	0.01-20	0.1 to 10	0.5-5
Molybdenum-containing compound	0.01-10	0.1 to 7	0.1 to 5
Antifoaming Agent	0.001-5	0.001-0.2	0.001-0.1
Friction Modifier	0-5	0-1.5	0.1 to 5
Viscosity Modifier	0.01-25	1-20	5-15
LAO	0.1 to 10	0.1 to 5	0.1 to 2.5
Optional additional additives	0-20	0.1-10	0.1-10
GTL Basestock (50 to 99 wt %)	Balance	Balance	Balance

In some embodiments, the lubricating oil compositions described herein, such as those it the Tables 1 and 2 above, have a KV₁₀₀ in the range of from 9.3 to less than 12.5 cSt and an HTHS₁₅₀ greater than or equal to 2.9 cP.

The foregoing additives are typically commercially available materials. These additives may be added independently but are usually pre-combined in packages which can be obtained from suppliers of lubricant oil additives. Additive packages with a variety of ingredients, proportions and characteristics are available and selection of the appropriate package will take the use of the ultimate composition into account.

Fuels

This disclosure also relates to a method of lubricating an automotive internal combustion engine during operation of the engine comprising:

• • (i) providing to a crankcase of the automotive internal combustion engine a lubricating composition of described herein;
  • (ii) providing a hydrocarbon fuel in the automotive internal combustion engine; and
  • (iii) combusting the fuel in the automotive internal combustion engine, such as a spark-ignited or compression-ignited two- or four-stroke reciprocating engine, such as a diesel engine or passenger car engine (such as a spark-ignited combustion engine).

This disclosure also relates to a fuel composition comprising the lubricating oil compositions described herein and a hydrocarbon fuel, wherein the fuel may be derived from petroleum and/or biological sources (“biofuel” or “renewable fuel”). In some embodiments, the fuel comprises from 0.1 to 100 wt % renewable fuel, from 1 to 75 wt % renewable fuel, from 5 to 50 wt % renewable fuel, based upon the total weight of the from 1 to 50 wt % renewable fuel and the petroleum derived fuel.

In some embodiments, this disclosure relates to a fuel composition comprising the lubricating oil composition described herein and a hydrocarbon fuel, optionally the hydrocarbon fuel is derived from petroleum sources and or renewable (such as biological) sources.

The renewable fuel component is typically produced from vegetable oil (such as palm oil, rapeseed oil, soybean oil, jatropha oil), microbial oil (such as algae oil), animal fats (such as cooking oil, animal fat, and/or fish fat) and or biogas. Renewable fuel refers to biofuel produced from biological resources formed through contemporary biological processes. In an embodiment, the renewable fuel component is produced by means of a hydrotreatment process. Hydrotreatment involves various reactions where molecular hydrogen reacts with other components, or the components undergo molecular conversions in the presence of molecular hydrogen and a solid catalyst. The reactions include, but are not limited to, hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrification, hydrodemetallization, hydrocracking, and isomerization. The renewable fuel component may have different distillation ranges which provide the desired properties to the component, depending on the intended use.

Uses

The lubricating compositions of the disclosure 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, by adding the lubricant thereto. Typically, they are crankcase lubricants such as passenger car motor oils, light duty diesel engine lubricants, or heavy duty diesel engine lubricants.

In particular, the lubricating compositions of the present disclosure are suitably used in the lubrication of the crankcase of a compression-ignited (or spark assisted compression ignited) internal combustion engine, such as a light duty diesel engine, a heavy duty diesel engine, or an automotive diesel engine.

In particular, the lubricating compositions of the present disclosure are suitably used in the lubrication of the crankcase of a spark-ignited turbo charged internal combustion engine.

CERTAIN EMBODIMENTS

In a first set of embodiments, this disclosure relates to:

• • Embodiment 1. A lubricating oil composition comprising or resulting from the admixing of:
  • a) from 50 to 99 wt %, from 55 to 95 wt %, from 60 to 90 wt %, or from 70 to 85 wt % of a base oil composition comprising one or more Group III base oils, one or more Group III+ base oils, one or more Group IV base oils, or a combination thereof;
  • b) from 0.1 to 15 wt %, from 0.15 to 10 wt %, from 0.20 to 5.0 wt %, from 0.25 to 4.0 wt %, or from 0.50 to 3.0 wt % of a functionalized olefin copolymer having an M_n in the range of from about 10,000 g/mol to about 35,000 g/mol;
  • c) from 0.10 to 20 wt %, from 0.15 to 10 wt %, from 0.20 wt % to 5.0 wt %, or from 0.25 to 2.0 wt % of a detergent composition comprising:
    • i) at least one first calcium detergent having a first TBN of greater than 100 mg KOH/g, greater than 200 mg KOH/g, greater than 250 mg KOH/g, greater than 300 mg KOH/g, or greater than 350 mg KOH/g;
    • ii) at least one second calcium detergent having a second TBN of less than or equal to 150 mg KOH/g, less than or equal to 100 mg KOH/g, less than or equal to 80 mg KOH/g, or less than or equal to 30 mg KOH/g; and
    • iii) at least one magnesium detergent having a TBN of greater than 100 mg KOH/g, greater than 200 mg KOH/g, greater than 250 mg KOH/g, greater than 300 mg KOH/g, greater than 350 mg KOH/g, greater than 499 mg KOH/g, or greater than 450 mg KOH/g;
    • wherein the first TBN minus the second TBN is greater than or equal to 100 mg KOH/g, greater than or equal to 150 mg KOH/g, or greater than or equal to 200 mg KOH/g;
  • d) from 0.01 to 40 wt %, from 0.10 to 15 wt %, from 1.0 to 12 wt %, or from 2.0 to 10 wt % of a dispersant composition comprising:
    • i) at least one borated dispersant; and
    • ii) at least one non-borated dispersant; (not including component b) when present);
  • e) a friction modifier composition comprising:
    • i) from 0.01 to 20 wt %, from 0.10 to 5.0 wt %, 0.20 to 4.0 wt %, 0.30 to 3.0 wt %, 0.40 to 2.0 wt %, or 0.40 to 1.0 wt % of a sulfurized fatty acid ester;
    • ii) from 0.01 to 10 wt %, from 0.025 to 5.0 wt %, from 0.05 to 4.0 wt %, from 0.05 to 3.0 wt %, or from 0.05 to 1.0 wt % of a molybdenum-containing compound; and
  • f) from 0.01 to 10 wt %, from 0.50 to 5.0 wt %, from 1.0 to 4.0 wt %, or from 1.5 to 3.0 wt % of an amine-based antioxidant, a phenol-based antioxidant, or a combination thereof;
  • wherein
    • the lubricating oil composition has a molybdenum content in the range of from 250 to 1,000 ppm, from 350 to 900 ppm, from 400 to 800 ppm, from 450 to 700 ppm, or from 500 to 600 ppm by weight, according to ASTM D5185; and
    • the wt % of each component is based on the total weight of the lubricating oil composition.
  • Embodiment 2. The lubricating oil composition of Embodiment 1, wherein the lubricating oil composition is classified as OW-16, OW-20, OW-30, 5W-16, 5W-20, or 5W-30, according to SAE J300.
  • Embodiment 3. The lubricating oil composition of Embodiment 1 or Embodiment 2, wherein the lubricating oil composition has a fuel economy of greater than 0.82% or greater than or equal to 0.83%, according to OM471 Fuel Economy test.
  • Embodiment 4. The lubricating oil composition of any one of Embodiments 1 through 3, wherein the lubricating oil further has one or more of:
    • i) a cold cranking simulator (CCS) test value at −35° C. of less than or equal to 6,600 cP, less than or equal to 6,200 cP, or less than or equal to 4,500 cP, according to ASTM D5293;
    • ii) a kinematic viscosity at 100° C. (KV₁₀₀) of less than or equal to 12.5 cSt, less than or equal to 9.3 cSt, or less than or equal to 8.2 cSt, according to ASTM D445-19a;
    • iii) a high temperature high shear (HTHS) viscosity at 150° C. of greater than or equal to 2.3 mPa·s, greater than or equal to 2.6 mPa·s, or greater than or equal to 2.9 mPa·s, according to CEC-L-36 (ASTM D4683-20);
    • iv) a pour point of less than or equal to −40° C. or than or equal to −45° C. 2.3, according to ASTM D97;
    • v) a viscosity index in the range for from 150 to 175, from 150 to 165, or from 160 to 175, according to ASTM D2270;
    • vi) a Noack volatility less than or equal to 15 wt %, according to CEC L-40-A-93; or
    • vii) a combination thereof.
  • Embodiment 5. The lubricating oil composition of any one of Embodiments 1 through 4, wherein the lubricating oil further has one or more of:
    • i) a phosphorus content in the range of from 300 to 1,000 ppm, from 400 to 900 ppm, from 500 to 800 ppm by weight, according to ASTM D5185;
    • ii) a sulfur content of less than 0.3 wt %, according to ASTM D5185;
    • iii) a sulfated ash content of less than 1.0 wt %, less than 0.9 wt %, less than 0.8 wt %, less than 0.7 wt %, or less than 0.6 wt %, ASTM D874; or
    • iv) a combination thereof
  • Embodiment 6. The lubricating oil composition of any one of Embodiments 1 through 5, wherein the friction modifier composition further comprises from 0.01 to 5 wt % of one or more friction modifiers other than the sulfurized fatty acid ester and the molybdenum-containing compound, wherein the weight % of each component is based on the total weight of the lubricating oil composition.
  • Embodiment 7. The lubricating oil composition of any one of Embodiments 1 through 6, wherein the lubricating oil composition further comprises one or more of:
    • a) from 0.001 to 10 wt % of one or more anti-wear agents;
    • b) from 0.01 to 5 wt % of one or more pour point depressants;
    • c) from 0.001 to 5 wt % of one or more anti-foam agents;
    • d) from 0.001 to 10 wt % of one or more viscosity modifiers; and
    • e) from 0.01 to 5 wt % of one or more corrosion inhibitors and/or antirust agents;
    • wherein the weight % of each component is based on the total weight of the lubricating oil composition.
  • Embodiment 8. The lubricating oil composition of any one of Embodiments 1 through 7, wherein the lubricating oil composition further comprises one or more of:
    • a) from 0.001 to 15 wt % of one or more C₈ to C₃₆ linear alpha olefins;
    • b) from 0.001 to 15 wt % of one or more polyisobutylene succinic anhydrides;
    • c) from 0.001 to 15 wt % of one or more zinc dialkyl dithiophosphates (ZDDP) which are optionally derived from primary alcohols, secondary alcohols or mixtures thereof;
    • d) from 0.001 to 15 wt % of pour point depressant, selected from the group consisting of copolymers of dialkyl fumarate and vinyl acetate;
    • e) from 0.01 to 10 wt % of one or more viscosity modifiers selected from polyacrylate, polymethacrylate, ethylene propylene copolymers, hydrogenated styrene-diene block copolymers, hydrogenated block copolymers of styrene and isoprene, hydrogenated block copolymers of styrene and isobutylene, hydrogenated polyisoprene star polymers and polyacrylates; and
    • f) from 0.001 to 15 wt % of hydrogenated styrene-diene block copolymer;
    • wherein the weight % of each component is based on the total weight of the lubricating oil composition.
  • Embodiment 9. The lubricating oil composition of any one of Embodiments 1 through 8, wherein:
    • a) the at least one borated dispersant comprises one or more borated PIBSA-PAM dispersants; and
    • b) the at least one non-borated dispersant comprises one or more non-borated PIBSA-PAM dispersants.
  • Embodiment 10. The lubricating oil composition of any one of Embodiments 1 through 9, wherein:
    • a) the at least one first calcium detergent comprises a first Ca alkyl salicylate and the first TBN is greater than or equal to 200 mg KOH/g;
    • b) the at least one second calcium detergent comprises a second Ca alkyl salicylate and the second TBN is less than or equal to 100 mg KOH/g; and
    • c) the at least one magnesium detergent comprises a Mg sulfonate detergent having a TBN greater than or equal to 250 mg KOH/g;
    • wherein the first TBN minus the second TBN is greater than or equal to 200 mg KOH/g.
  • Embodiment 11. The lubricating oil composition of any one of Embodiments 1 through 10, wherein:
    • a) the at least one first calcium detergent comprises a first Ca alkyl salicylate and the first TBN is greater than 100 mg KOH/g;
    • b) the at least one second calcium detergent comprises a second Ca alkyl salicylate and the second TBN is less than or equal to 100 mg KOH/g; and
    • c) the at least one magnesium detergent comprises a Mg sulfonate detergent having a TBN greater than or equal to 250 mg KOH/g;
    • wherein the first TBN minus the second TBN is greater than or equal to 250 mg KOH/g.
  • Embodiment 12. The lubricating oil composition of any one of Embodiments 1 through 11, wherein the sulfurized fatty acid ester comprises one or more sulfurized fatty acid methyl esters; wherein in further embodiments, the one or more sulfurized fatty acid methyl esters comprise a sulfurized lard oil fatty acid methyl ester, a sulfurized palm oil fatty acid methyl ester, a sulfurized rapeseed oil fatty acid methyl ester, or a combination thereof.
  • Embodiment 13. The lubricating oil composition of any one of Embodiments 1 through 12, wherein the sulfurized fatty acid ester is derived from a sulfurized plant oil, a sulfurized animal oil, or a combination thereof; wherein in further embodiments:
    • a) the plant oil is selected from a corn oil, a grapeseed oil, a coconut oil, a cottonseed oil, a wheatgerm oil, a soya oil, a safflower oil, a olive oil, a peanut oil, a rapeseed oil, a sunflower oil, or a combination thereof; and
    • b) the animal oil is selected from a tallow oil, a lard oil, or a combination thereof.
  • Embodiment 14. The lubricating oil composition of any one of Embodiments 1 through 13, wherein the lubricating oil composition comprises from 0.1 to 15 wt %, from 0.15 to 10 wt %, from 0.2 to 5 wt %, from 0.25 to 4 wt %, or from 0.5 to 3 wt % of the functionalized copolymer.
  • Embodiment 15. The lubricating oil composition of any one of Embodiments 1 through 14, wherein the lubricating oil composition is a diesel engine oil, a light duty diesel engine oil, or a heavy-duty diesel engine oil.
  • Embodiment 16. The lubricating oil composition of any one of Embodiments 1 through 15, wherein the lubricating oil composition has a sulfur content of less than or equal to 0.3 wt % or less, based upon the weight of the lubricating oil composition.
  • Embodiment 17. The lubricating oil composition of any one of Embodiments 1 through 16, wherein the lubricating oil composition is absent added copper.
  • Embodiment 18. A method of lubricating an automotive internal combustion engine (such as a diesel engine) during operation of the engine, the method comprising:
    • (i) providing the lubricating composition of any one of Embodiments 1 through 17 to a crankcase of the automotive internal combustion engine;
    • (ii) providing a hydrocarbon fuel in the automotive internal combustion engine; and
    • (iii) combusting the fuel in the automotive internal combustion engine.
  • Embodiment 19. A fuel composition comprising the composition of any one of Embodiments 1 through 17 and a hydrocarbon fuel derived from petroleum sources, renewable sources, or a combination thereof.
  • Embodiment 20. The fuel composition of Embodiment 19, wherein at least a portion of the fuel is derived from biological sources and a portion of the fuel is derived from petroleum sources.
  • Embodiment 21. The fuel composition of Embodiment 19 or 20, wherein the lubricating oil composition is absent added copper.
  • Embodiment 22. A concentrate composition comprising or resulting from the admixing of:
    • a) from 1 to less than 50 wt %, from 5 to 45 wt %, from 7 to 40 wt %, from 10 to 35 wt %, or from 10 to 25 wt % of a base oil composition comprising one or more Group I, Group II, Group III base oils, one or more Group III+ base oils, one or more Group IV base oils, or a combination thereof;
    • b) from 0.2 to 30 wt %, from 0.30 to 20 wt %, from 0.40 to 10 wt %, from 0.50 to 8.0 wt %, or from 1.0 to 6.0 wt % of a functionalized olefin copolymer having an M_n in the range of from about 10,000 g/mol to about 35,000 g/mol;
    • c) from 0.20 to 40 wt %, from 0.30 to 20 wt %, from 0.40 wt % to 10 wt %, or from 0.50 wt % to 4.0 wt % of one or more detergents, wherein the detergent comprises:
      • i) at least one first calcium detergent having a first TBN of greater than 100 mg KOH/g, greater than 200 mg KOH/g, greater than 250 mg KOH/g, greater than 300 mg KOH/g, or greater than 350 mg KOH/g;
      • ii) at least one second calcium detergent having a second TBN of less than or equal to 150 mg KOH/g, less than or equal to 100 mg KOH/g, less than or equal to 80 mg KOH/g, or less than or equal to 30 mg KOH/g; and
      • iii) at least one magnesium detergent having a TBN of greater than 100 mg KOH/g, greater than 200 mg KOH/g, greater than 250 mg KOH/g, greater than 300 mg KOH/g, greater than 350 mg KOH/g, greater than 499 mg KOH/g, or greater than 450 mg KOH/g;
      • wherein the first TBN minus the second TBN is greater than or equal to 100 mg KOH/g, greater than or equal to 150 mg KOH/g, or greater than or equal to 200 mg KOH/g;
    • d) from 0.02 to 80 wt %, from 0.20 to 30 wt %, from 2.0 to 24 wt %, or from 4.0 to 20 wt % of one or more dispersants, wherein the dispersants comprise:
      • i) at least one borated dispersant; and
      • ii) at least one non-borated dispersant;
    • e) from 0.02 to 40 wt %, from 0.20 to 10 wt %, 0.40 to 8 wt %, 0.60 to 6.0 wt %, 0.80 to 4.0 wt %, or 0.80 to 2.0 wt % of a sulfurized fatty acid ester;
    • f) from 0.02 to 20 wt %, from 0.05 to 10.0 wt %, from 0.10 to 8.0 wt %, from 0.10 to 6.0 wt %, or from 0.10 to 2.0 wt % of a molybdenum-containing compound; and
    • g) from 0.02 to 20 wt %, from 1.0 to 10.0 wt %, from 2.0 to 8.0 wt %, or from 3.0 to 6.0 wt % of an amine-based antioxidant, a phenol-based antioxidant, or a combination thereof;
    • wherein
      • the concentrate composition has a molybdenum content in the range of from 500 to 2,000 ppm, from 700 to 1,800 ppm, from 800 to 1,600 ppm, from 900 to 1,400 ppm, or from 1,000 to 1,200 ppm by weight, according to ASTM D4951; and
      • the wt % of each component is based on the total weight of the concentrate composition.
  • Embodiment 23. The concentrate of Embodiment 22, wherein the concentrate is absent added copper.
  • Embodiment 24. A method for preparing a lubricating oil composition comprising combining:
  • a) from 50 to 99 wt %, from 30 to 95 wt %, from 50 to 90 wt %, from 60 to 95 wt %, or from 70 to 85 wt % of a base oil composition comprising one or more Group III base oils, one or more Group III+ base oils, one or more Group IV base oils, or a combination thereof;
  • b) from 0.1 to 15 wt %, from 0.15 to 10 wt %, from 0.2 to 5 wt %, from 0.25 to 4 wt %, or from 0.5 to 3 wt % of a functionalized olefin copolymer having an M_n in the range of from about 10,000 g/mol to about 35,000 g/mol;
  • c) from 0.1 to 20 wt %, from 0.15 to 10 wt %, from 0.20 wt % to 5 wt %, or from 0.25 to 2 wt % of a detergent composition comprising:
    • i) at least one first calcium detergent having a first TBN of greater than 100 mg KOH/g, greater than 200 mg KOH/g, greater than 250 mg KOH/g, greater than 300 mg KOH/g, or greater than 350 mg KOH/g;
    • ii) at least one second calcium detergent having a second TBN of less than or equal to 150 mg KOH/g, less than or equal to 100 mg KOH/g, less than or equal to 80 mg KOH/g, or less than or equal to 30 mg KOH/g; and
    • iii) at least one magnesium detergent having a TBN of greater than 100 mg KOH/g, greater than 200 mg KOH/g, greater than 250 mg KOH/g, greater than 300 mg KOH/g, greater than 350 mg KOH/g, greater than 499 mg KOH/g, or greater than 450 mg KOH/g;
    • wherein the first TBN minus the second TBN is greater than or equal to 100 mg KOH/g, greater than or equal to 150 mg KOH/g, or greater than or equal to 200 mg KOH/g;
  • d) from 0.01 to 40 wt %, from 0.1 to 15 wt %, from 1 to 12 wt %, or from 2 to 10 wt % of a dispersant composition comprising:
    • i) at least one borated dispersant; and
    • ii) at least one non-borated dispersant; (not including component b) when present);
  • e) a friction modifier composition comprising:
    • i) from 0.01 to 20 wt %, from 0.1 to 5 wt %, 0.2 to 4 wt %, 0.3 to 3 wt %, 0.4 to 2 wt %, or 0.4 to 1 wt % of a sulfurized fatty acid ester;
    • ii) from 0.01 to 10 wt %, from 0.025 to 5 wt %, from 0.05 to 4 wt %, from 0.05 to 3 wt %, or from 0.05 to 1 wt % of a molybdenum-containing compound; and
  • f) from 0.01 to 10 wt %, from 0.5 to 5 wt %, from 1 to 4 wt %, or from 1.5 to 3 wt % of an amine-based antioxidant, a phenol-based antioxidant, or a combination thereof;
  • wherein
    • the lubricating oil composition has a molybdenum content in the range of from 250 to 1,000 ppm, from 350 to 900 ppm, from 400 to 800 ppm, from 450 to 700 ppm, or from 500 to 600 ppm by weight, according to ASTM D5185; and
    • the wt % of each component is based on the total weight of the lubricating oil composition.
  • Embodiment 25. The method for preparing a lubricating oil composition of Embodiment 24, wherein the lubricating oil composition is classified as OW-16, OW-20, OW-30, 5W-16, 5W-20, or 5W-30, according to SAE J300.
  • Embodiment 26. The method for preparing a lubricating oil composition of Embodiment 24 or 25, wherein the lubricating oil composition has a fuel economy of greater than 0.82% or greater than or equal to 0.83%, according to OM471 Fuel Economy test.
  • Embodiment 27. The method for preparing a lubricating oil composition of any one of Embodiments 24 through 26, wherein the lubricating oil composition has:
  • i) a cold cranking simulator (CCS) test value at −35° C. of less than or equal to 6,600 P, less than or equal to 6,200 cP, or less than or equal to 4,500 cP, according to ASTM D5293;
  • ii) a kinematic viscosity at 100° C. (KV₁₀₀) of less than or equal to 12.5 cSt, less than or equal to 9.3 cSt, or less than or equal to 8.2 cSt, according to ASTM D445-19a;
  • iii) a high temperature high shear (HTHS) viscosity at 150° C. of greater than or equal to 2.3 mPa·s, greater than or equal to 2.6 mPa·s, or greater than or equal to 2.9 mPa·s, according to CEC-L-36 (ASTM D4683-20);
  • iv) a pour point of less than or equal to −40° C. or than or equal to −45° C. 2.3, according to ASTM D97;
  • v) a viscosity index in the range for from 150 to 175, from 150 to 165, or from 160 to 175, according to ASTM D2270;
  • vi) a Noack volatility less than or equal to 15 wt %, according to CEC L-40-A-93; or
  • vii) a combination thereof.
  • Embodiment 28. The method for preparing a lubricating oil composition of any one of Embodiments 24 through 27, wherein the lubricating oil composition has:
  • i) a phosphorus content in the range of from 300 to 1,000 ppm, from 400 to 900 ppm, from 500 to 800 ppm by weight, according to ASTM D5185;
  • ii) a sulfur content of less than 0.3 wt %, according to ASTM D5185;
  • iii) a sulfated ash content of less than 1.0 wt %, less than 0.9 wt %, less than 0.8 wt %, less than 0.7 wt %, or less than 0.6 wt %, ASTM D874; or
  • iv) a combination thereof.
  • Embodiment 29. The method for preparing a lubricating oil composition of Embodiments 24 through 28, wherein the lubricating oil composition is absent added copper.

This invention also relates to:

• • 1. A lubricating oil composition comprising or resulting from the admixing of:
    • a) from 50 to 99 wt % of a base oil composition comprising one or more Group III base oils, one or more Group III+ base oils, one or more Group IV base oils, or a combination thereof;
    • b) from 0.1 to 15 wt % of a functionalized olefin copolymer having an M_n in the range of from about 10,000 g/mol to about 35,000 g/mol;
    • c) 0.1 to 20 wt % of a detergent composition comprising:
      • i) at least one first calcium detergent having a first TBN of greater than 100 mg KOH/g;
      • ii) at least one second calcium detergent having a second TBN of less than or equal to 100 mg KOH/g; and
      • iii) at least one magnesium detergent;
      • wherein the first TBN minus the second TBN is greater than or equal to 100 mg KOH/g;
    • d) from 0.01 to 40 wt % of a dispersant composition comprising:
      • i) at least one borated dispersant; and
      • ii) at least one non-borated dispersant;
    • e) a friction modifier composition comprising:
      • i) from 0.01 to 20 wt % of a sulfurized fatty acid ester; and
      • ii) from 0.01 to 10 wt % of a molybdenum-containing compound; and
    • f) from 0.01 to 10 wt % of an amine-based antioxidant, a phenol-based antioxidant, or a combination thereof;
    • wherein
      • the lubricating oil composition comprises molybdenum in an amount in the range of from 250 to 1,000 ppm, according to ASTM D5185; and
      • the weight % of each component is based on the total weight of the lubricating oil composition.
  • 2. The lubricating oil composition of paragraph 1, wherein the lubricating oil composition is classified as OW-16, OW-20, OW-30, 5W-16, 5W-20, or 5W-30, according to SAE J300.
  • 3. The lubricating oil composition of paragraph 1 or 2, wherein the lubricating oil composition has a fuel economy of greater than 0.82%, according to OM471 Fuel Economy test.
  • 4. The lubricating oil composition of any one of the preceding paragraphs 1 to 3, wherein the lubricating oil composition has:
    • i) a cold cranking simulator (CCS) test value at −35° C. of less than or equal to 6,600 cP, according to ASTM D5293;
    • ii) a kinematic viscosity at 100° C. (KV₁₀₀) of less than or equal to 12.5 cSt, according to ASTM D445-19a; and
    • iii) a high temperature high shear (HTHS) viscosity at 150° C. of greater than or equal to 2.3 mPa·s, according to CEC-L-36 (ASTM D4683-20);
    • iv) a pour point of less than or equal to −40° C., according to ASTM D97;
    • v) a viscosity index in the range of from 150 to 175, according to ASTM D2270;
    • vi) a Noack volatility less than or equal to 15 wt %, according to CEC L-40-A-93; or
    • vii) a combination thereof.
  • 5. The lubricating oil composition of any one of the preceding paragraphs 1 to 4, wherein the lubricating oil composition has:
    • i) a phosphorus content in the range of from 300 to 1,000 ppm, from 400 to 900 ppm, from 500 to 800 ppm by weight, according to EN 14107;
    • ii) a sulfur content of less than 0.3 wt %, according to ASTM D5185;
    • iii) a sulfated ash content of less than 1.0 wt %, according to ASTM D874; or
    • iv) a combination thereof.
  • 6. The lubricating oil composition of any one of the preceding paragraphs 1 to 5, wherein the friction modifier composition further comprises from 0.01 to 5 wt % of one or more friction modifiers other than the sulfurized fatty acid ester and the molybdenum-containing compound, wherein the weight % of each component is based on the total weight of the lubricating oil composition.
  • 7. The lubricating oil composition of any one of the preceding paragraphs 1 to 6, wherein the lubricating oil composition further comprises one or more of:
    • a) from 0.001 to 10 wt % of one or more anti-wear agents;
    • b) from 0.01 to 5 wt % of one or more pour point depressants;
    • c) from 0.001 to 5 wt % of one or more anti-foam agents;
    • d) from 0.001 to 10 wt % of one or more viscosity modifiers; and
    • e) from 0.01 to 5 wt % of one or more corrosion inhibitors and/or antirust agents;
    • wherein the weight % of each component is based on the total weight of the lubricating oil composition.
  • 8. The lubricating oil composition of any one of the preceding paragraphs 1 to 7, wherein the lubricating oil composition further comprises one or more of:
    • a) from 0.001 to 15 wt % of one or more C₈ to C₃₆ linear alpha olefins;
    • b) from 0.001 to 15 wt % of one or more polyisobutylene succinic anhydrides;
    • c) from 0.001 to 15 wt % of one or more zinc dialkyl dithiophosphates (ZDDP) which are optionally derived from primary alcohols, secondary alcohols or mixtures thereof;
    • d) from 0.001 to 15 wt % of pour point depressant, selected from the group consisting of copolymers of dialkyl fumarate and vinyl acetate;
    • e) from 0.01 to 10 wt % of one or more viscosity modifiers selected from polyacrylate, polymethacrylate, ethylene propylene copolymers, hydrogenated styrene-diene block copolymers, hydrogenated block copolymers of styrene and isoprene, hydrogenated block copolymers of styrene and isobutylene, hydrogenated polyisoprene star polymers and polyacrylates; and
    • f) from 0.001 to 15 wt % of hydrogenated styrene-diene block copolymer;
    • wherein the weight % of each component is based on the total weight of the lubricating oil composition.
  • 9. The lubricating oil composition of any one of the preceding paragraphs 1 to 8, wherein:
    • a) the at least one borated dispersant comprises one or more borated PIBSA-PAM dispersants; and
    • b) the at least one non-borated dispersant comprises one or more non-borated PIBSA-PAM dispersants.
  • 10. The lubricating oil composition of any one of the preceding paragraphs 1 to 9, wherein:
    • a) the at least one first calcium detergent comprises a first Ca alkyl salicylate and the first TBN is greater than or equal to 200 mg KOH/g;
    • b) the at least one second calcium detergent comprises a second Ca alkyl salicylate and the second TBN is less than or equal to 100 mg KOH/g; and
    • c) the at least one magnesium detergent comprises a Mg sulfonate detergent having a TBN greater than or equal to 250 mg KOH/g;
    • wherein the first TBN minus the second TBN is greater than or equal to 200 mg KOH/g.
  • 11. The lubricating oil composition of any one of the preceding paragraphs 1 to 10, wherein:
    • a) the at least one first calcium detergent comprises a first Ca alkyl salicylate and the first TBN is greater than 100 mg KOH/g;
    • b) the at least one second calcium detergent comprises a second Ca alkyl salicylate and the second TBN is less than or equal to 100 mg KOH/g; and
    • c) the at least one magnesium detergent comprises a Mg sulfonate detergent having a TBN greater than or equal to 250 mg KOH/g;
    • wherein the first TBN minus the second TBN is greater than or equal to 250 mg KOH/g.
  • 12. The lubricating oil composition of any one of the preceding paragraphs 1 to 11, wherein the sulfurized fatty acid ester comprises one or more sulfurized fatty acid methyl esters.
  • 13. The lubricating oil composition of any one of the preceding paragraphs 1 to 12, wherein the sulfurized fatty acid ester is derived from a sulfurized plant oil, a sulfurized animal oil, or a combination thereof.
  • 14. The lubricating oil composition of any one of the preceding paragraphs 1 to 13, wherein the lubricating oil composition is a diesel engine oil, a light duty diesel engine oil, or a heavy-duty diesel engine oil.
  • 15. The lubricating oil composition of any one of the preceding paragraphs 1 to 14, wherein the lubricating oil composition is absent added copper.

EXAMPLES

The following examples are included to demonstrate embodiments of the disclosure. It should be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventor to function well in the practice of the invention, and thus can be considered to constitute preferred modes for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the invention.

Test Methods

All molecular weights are number average unless otherwise noted.

As used herein, M_n is number average molecular weight, M_w is weight average molecular weight, and M_z is z average molecular weight. Molecular weight distribution (MWD), also referred to as polydispersity index (PDI), is defined to be M_w divided by M_n. Unless otherwise noted, all molecular weight units (e.g., M_w, M_n, M_z) are reported in g/mol. Molecular weights (M_w, M_n, M_z) and molecular weight distribution (M_w/M_n) are determined by Gel Permeation Chromatography using polystyrene standards (Acquity™ APC Polystyrene High MW Calibration Kit, 266-1,760,000 Da) using an Agilent Acuity P-SM-FTN and P-15m high temperature GPC-SEC (gel permeation/size exclusion chromatograph) equipped with an on-line differential refractive index (DRI) detector and a PDA UV detector for 215,254 and 304 wavelengths using Empower™ 3, version 7.41.00.00, software.

Boron content is measured according to ASTM D5185 for full lubricating oil formulations (i.e., lower concentrations of measured element) and ASTM D4951 for additive package or concentrate (i.e., lower concentrations of measured element).

Calcium content is measured according to ASTM D5185 for full lubricating oil formulations (i.e., lower concentrations of measured element) and ASTM D4951 for additive package or concentrate (i.e., lower concentrations of measured element).

Cold cranking simulator (CCS) test values are measured according to ASTM D5293.

Fuel economy is measured according to Daimler Trucks in-house OM471 Fuel Economy test.

High temperature high shear (HTHS) viscosity at 150° C. is measured according to CEC-L-36 (ASTM D4683-20).

KV₁₀₀ is kinematic viscosity measured at 100° C. according to ASTM D445-19a and is reported in cSt.

KV₄₀ is kinematic viscosity measured at 40° C. according to ASTM D445-19a and is reported in cSt.

Magnesium content is measured according to ASTM D5185 for full lubricating oil formulations (i.e., lower concentrations of measured element) and ASTM D4951 for additive package or concentrate (i.e., lower concentrations of measured element).

Molybdenum content is measured according to ASTM D5185 for full lubricating oil formulations (i.e., lower concentrations of measured element) and ASTM D4951 for additive package or concentrate (i.e., lower concentrations of measured element).

Noack volatility is measured according to CEC L-40-A-93.

Phosphorus content is measured according to ASTM D5185 for full lubricating oil formulations (i.e., lower concentrations of measured element) and ASTM D4951 for additive package or concentrate (i.e., lower concentrations of measured element).

Pour point is measured according to ASTM D97.

Sulfated ash (“SASH”) content is measured by ASTM D874.

Sulfur content is measured according to ASTM D5185 for full lubricating oil formulations (i.e., lower concentrations of measured element) and ASTM D4951 for additive package or concentrate (i.e., lower concentrations of measured element).

Total Base Number (TBN) is determined according to ASTM D2896 and reported in units of mg KOH/g.

Viscosity index is measured according to ASTM D2270.

Zinc content is measured according to ASTM D5185 for full lubricating oil formulations (i.e., lower concentrations of measured element) and ASTM D4951 for additive package or concentrate (i.e., lower concentrations of measured element).

Starting Materials

Blend components used in the examples are shown in Table 3 below.

TABLE 3
Component	Material	Description
Dispersant 1	B-PIBSA-PAM-950	Borated PIBSA-PAM dispersant (950 Mn PIB) in ~50%
		oil)
Dispersant 2	PIBSA-PAM 1000 Mn	PIBSA-TEPA HR 1000 g/mol Mn
Dispersant 3	PIBSA-PAM 2200 Mn	PIBSA-PAM dispersant (2200 Mn PIB) in ~43% oil;
		ai ~55; diluted to KV100 of 600 cSt
		(±20 cSt); ~43.2% “mineral oil”; ~26.4 TBN
Functionalized	Amine Functionalized	amine functionalized ethylene propylene copolymer
OCP	EP Copolymer	(~23,000 Mn, in ~65% oil)
Detergent 1	Ca Salicylate-350	Ca salicylate/PDMS Blend TBN 350 in ~43 wt %
	TBN	oil/antifoamant
Detergent 2	Ca salicylate-64 TBN	Ca alkyl salicylate (TBN ~64, in ~60 wt % oil)
Detergent 3	Mg sulfonate-400	Mg sulfonate detergent (400 TBN, n ~43 wt % oil)
	TBN
Anti-wear	ZDDP	Zinc dialkyldithiophosphate derived from mix of primary
agent		and secondary alcohols
Friction	Mo Friction modifier	Trimeric MoDTC AO/FM (ai ~45)
modifier 1 (E-3)
Antioxidant	DPA antioxidant	Diphenyl amine antioxidant
Friction	Sulfurized FAME	Sulfurized lard oil and/or palm oil fatty acid methyl ester ai
modifier 2 (E-1)		100% (supplied by Dover Chemical Corp.)
LAO	Linear alpha olefin	blend of C14-C18 linear alpha olefins
PIBSA	PIBSA	PIBSA (Mn 950, ai ~72)
Anti-foam	Anti-foamant	PDMS silicone anti-foamant
agent
Diluent		Group III basestock diluent having a KV100 of around 4
		cSt
Pour point	PPD	C8-C18 dialkylfumarate/vinyl acetate copolymer in ~43%
depressant		diluent
Viscosity	VM	11 m % Infineum SV260 (Hydrogenated styrene-diene
modifier		copolymer) in 89.3 m % oil
Basestock 1	YUBASE ™ 6 base oil	Group III Basestock 6 cSt (available from SK Lubricants)
Basestock 2	DURASYN41 base oil	Polyalphaolefin (PAO) base oil classified as Group IV
		having a viscosity of around 4 cSt at 100° C. (available from
		Ineos)
Basestock 3	YUBASE4PLUS ™	hydrocracked, hydroisomerized mineral base oil, classified
	base oil	as Group III+ having a viscosity of around cSt at 100° C.
		(available from SK Lubricants)

Blend Compositions

Lubricating oil composition blends were prepared using the starting materials described in Table 4.

• • Comparative Example 1 is a baseline blend having a viscosity grade of 5W-20 and an Mo content of 200 ppm.
  • Comparative Example 2 is the same as comparative Example 1 except for a higher content of Mo-containing friction modifier (E-3). Comparative Example 2 has a viscosity grade of 5W-20 and an Mo content of 500 ppm.
  • Comparative Example 3 is the same as comparative Example 1 except for a change in the basestock blend to produce a reduced summer viscosity grade of 5W-16. Comparative Example 3 has a Mo content of 200 ppm.
  • Comparative Example 4 is the same as comparative Example 1 except for a change in the basestock blend to produce a reduced winter viscosity grade of OW-20. Comparative Example 3 has a Mo content of 200 ppm.
  • Inventive Example 5 is the same as comparative Example 3 except for a change in the basestock blend to produce a reduced viscosity grade of OW-16. Inventive Example 5 has a Mo content of 500 ppm.

TABLE 4
					Ex. 5
			Ex. 3	Ex. 4	Added
		Ex. 2	Reduced	Reduced	Mo +
	Ex. 1	Added	Summer	Winter	Red.
Component	Base	Mo	Vis.	Vis.	Vis.

Friction modifier	0.364	0.909	0.364	0.364	0.909
1 (E-3)
Friction modifier	0.655	0.655	0.655	0.655	0.655
2 (E-1)
Viscosity modifier	4.000	4.000	1.585	4.870	—
Basestock 1	—	5.000	3.264	5.000	—
Basestock 2	20.000	—	—	—	15.000
Basestock 3	57.565	72.890	77.586	73.435	66.890
Oil Total	100.000	100.000	100.000	100.000	100.000
SAE Grade	5W-20	5W-20	5W-16	0W-20	0W-16
Formulations contained same amounts of dispersant (Dispersant 1:Dispersant 2:Dispersant 3 ratio of ~1:3:6) Detergent (Detergent 1:Detergent 2:Detergent 3 ratio of ~1:3.4:4.5), anti-foam agent, PIBSA, Diluent, LAO, anti-wear agent, anti-oxidant (~2 m %), Functionalized OCP (~1.2 m %) and pour point depressant.

Experimental Results

The lubricating oil compositions of Examples 1-5 were tested according to the test methods described above to determine physical properties as shown in Table 5 below.

TABLE 5
					Ex. 5
			Ex. 3	Ex. 4	Added
		Ex. 2	Reduced	Reduced	Mo +
Physical	Ex. 1	Added	Summer	Winter	Red.
Properties	Base	Mo	Vis.	Vis.	Vis.

HTHS150 (cP)	2.6	2.6	2.5	2.5	2.5
KV100 (cSt)	7.9	7.9	7.2	7.8	6.8
CCS @−30° C. (cP)	3457	3501	3284	2815	2811
CCS @−35° C. (cP)	6360	6763	6292	5166	5209

The lubricating oil compositions of Examples 1-5 were tested according to the test methods described above to determine chemical properties as shown in Table 6 below.

TABLE 6
					Ex. 5
			Ex. 3	Ex. 4	Added
		Ex. 2	Reduced	Reduced	Mo +
Chemical	Ex. 1	Added	Summer	Winter	Red.
Properties	Base	Mo	Vis.	Vis.	Vis.

Mo content (ppm)	200	500	200	200	500
P content (ppm)	620	620	620	620	620
S content (ppm)	2650	3100	3650	6650	3100
Sulfated Ash	0.69	0.69	0.69	0.69	0.69
content (wt %)

The lubricating oil compositions of Examples 1-5 were tested according to the test methods described above to determine fuel economy as shown in Table 7 below and FIG. 1. In isolation, reducing viscosity (e.g., 5W-xx→0W-xx, xW-20→xW-16) and increasing molybdenum content each resulted in moderate improvements in fuel economy. However, surprisingly the combination of reducing viscosity and increasing the amount of Mo-containing friction modifier produced an unexpected improvement in fuel economy that exceeded the sum of the fuel economy increases produced individually by either reducing viscosity or increasing the amount of Mo-containing friction modifier.

• • Comparative Example 4 (reduced winter grade viscosity) shows that moving from 5W-20 to OW-20 (Comparative Example 1 vs comparative Example 4) had little to no impact on fuel economy (“FE”). This would be expected since FE testing is run in a fully fired engine operating at high temperatures such that winter viscosity is not relevant to performance. Therefore, 0W-16 at 200 ppm Mo would be expected to provide similar performance to comparative Example 3.
  • Comparative Example 2 shows a FE increase of 12.7% over comparative Example 1 resulting from additional Mo-containing friction modifier. Comparative Example 3 shows a FE increase of 15.5% over comparative Example 1 resulting from decreasing viscosity. Therefore, the sum of these individual changes was 28.2%. Inventive Example 5 shows a FE increase of 32.4% over comparative Example 1 resulting from additional Mo-containing friction modifier and decreasing viscosity, which exceeds the expected 28.2%.

TABLE 7
					Ex. 5
			Ex. 3	Ex. 4	Added
		Ex. 2	Reduced	Reduced	Mo +
	Ex. 1	Added	Summer	Winter	Red.
Performance	Base	Mo	Vis.	Vis.	Vis.
Fuel Economy	0.71	0.79	0.82	0.69	0.94
(%)

For the sake of brevity, only certain ranges are explicitly disclosed herein. However, in addition to recited ranges, any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited. Additionally, within a range includes every point or individual value between its end points even though not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited. All documents and references cited herein, including testing procedures, publications, patents, journal articles, etc., are herein fully incorporated by reference for all jurisdictions in which such incorporation is permitted and to the extent such disclosure is consistent with the description of the present invention.

Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the processes, machines, means, processes, and/or steps described in the specification. As one of the ordinary skill in the art will readily appreciate from the disclosure of the present invention, processes, machines, means, processes, and/or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein, may be utilized according to the present invention. Accordingly, the appended claims are intended to include within their scope such processes, machines, means, processes, and/or steps.