Lubricant compositions containing low MONO-alkyl-substituted diphenylamine antioxidant for use in soot control applications

Abstract

This disclosure relates to the use of di(alkyl substituted phenyl)amine antioxidants as additives in lubricant compositions to reduce oil viscosity, particularly in the presence of high soot concentrations, in engine crankcase applications, especially in compression ignited engine and or spark ignited engine applications, where the antioxidant comprises from 0 to 15 mass% mono-alkyl substituted diphenylamine antioxidants, and 85 to 100 mass% di(alkyl substituted phenyl)amines based upon the weight of the mono- and di-(alkyl substituted phenyl) amines, preferably where unsubstituted phenyl amines are minimized, tri- alkyl substituted phenyl amines are minimized, and ortho substituted di-alkyl substituted phenyl amines are minimized.

Description

LUBRICANT COMPOSITIONS CONTAINING LOW MONO-ALKYL-SUBSTITUTED DIPHENYLAMINE ANTIOXIDANT FOR USE IN SOOT CONTROL APPLICATIONSFIELD OF THE INVENTION

[0001] This disclosure relates to the use of difalkyl-substituted phenyl)amine antioxidants as additives in lubricant oil compositions having good oxidation and soot dispersancy properties in internal combustion engine applications, especially in compression ignited engine and or spark ignited engine applications, where monofalkyl-substituted phenyl)amine antioxidants minimized or absent in the lubricating oil composition, and preferably where unsubstituted phenyl amines, and / or tri-alkyl substituted phenyl amines, and / or ortho substituted di-alkyl substituted phenyl amines, and / or tetra-alkyl substituted phenyl amines are minimized.BACKGROUND OF THE INVENTION

[0002] The present invention relates to lubricating oil compositions which exhibit improved soot control characteristics. More specifically, the present invention relates to lubricating oil compositions for use in internal combustion engines, such as gasoline, diesel, natural gas, hydrogen, methanol, ammonia, and or ethanol internal combustion engines (including spark ignited, compression ignited, and spark assisted compression ignited engines), such compositions optionally referred to as crankcase lubricants; and to the use of additives in such lubricating oil compositions for soot control in use of such engines and / or improving the viscometric performance of an engine lubricated with the lubricating oil composition.

[0003] Oxidation is a concern for in-service lubricating oils as it can cause thickening of the oil, sludge, varnish, acid number increase and corrosion. These outcomes are generally detrimental to proper operation of automotive engines and limit useful life of the lubricating oil and or an engine. With continually evolving engine designs, operating conditions and oil performance expectations, oxidation continues to be an important ongoing technical challenge.

[0004] One way to slow down oxidation in engines is to introduce antioxidants to lubricating oils. Additionally, antioxidants can also extend drain intervals, maintain viscosity, reduce deposit, reduce foam formation, protect against corrosion as well as protect lubricating oil against high temperature.

[0005] There are many antioxidants that have varying degrees of effectiveness. Commercial lubricants are usually formulated with one or more antioxidants to protect the fluid under a wide range of conditions (e.g., temperature, time, air mixtures, pressure, etc.).

[0006] Isomer mixtures of alkylated diphenylamines (such as mixture of di(nonyl-phenyl)amine and (nonyl- phenyl)(phenyl)amine), such as Irganox™ L67, are commonly used as antioxidants in organic fluids such as engine oils, gear oils, hydraulic fluids, compressor oils, turbine oils, and grease. However, these antioxidant isomer blends contribute to soot handling (soot agglomeration causes viscosity increase) and / or viscometric problems (such as kinematic viscosity increase overtime), and thus there is a desire to improve the kinematic viscosity increase over time of di (alkylp henyl)ami nes in organic fluids such as engine oils, gear oils, hydraulic fluids, compressor oils, turbine oils, and grease.

[0007] Diphenylamine antioxidants, such as octylated / butylated diphenylamines (which are typically high in monosubstituted octylated / butylated diphenylamine) are commonly used in engine oil formulations, but have known issues in lubricating oil compositions (e.g., do not blend into engine oils easily as they are solid at typical blending temperatures) and / or are not stable in engine oils at treat rates commonly used in modernlubricating oils.

[0008] It has now surprisingly been found that compositions of di(alkylphenyl)amine (such as di(Cs 9 alkylphenyl)amine) having low amounts of mono(alkyl substituted phenyl)amine can be used in an additive package and or a lubricating oil composition, such as in internal combustion engines, to provide improved soot control and viscometric properties, such as reduced viscosity growth, enhanced dynamic viscosity, improved wear and / or better retained fuel economy as more viscous oils increase fuel consumption.SUMMARY OF THE INVENTION

[0009] This disclosure relates to lubricating oil additives that maintain or improve oxidation performance and / or improve kinematic viscosity growth and or dynamic viscosity in lubricating oils.

[0010] This disclosure also relates a method to reduce oil viscosity, particularly in the presence of high soot concentrations (sooted viscosity), in an internal combustion engine comprising lubricating an internal combustion engine with a lubricating oil composition comprising:1 ) 50 mass% or more of one or more base oils;2) diphenylamine antioxidant comprising: at least 85 mass% of di(Cs 9 substituted phenyl)amine; from 0 to 15 mass% (such as 1 to 10 mass%, such as 0 to 8 mass%, such as 0 to 5 mass%) of mono(Cs-9 substituted phenyl)amine; and optionally from 0 to 2 mass% unsubstituted diphenyl amine, based upon the weight of the unsubstituted, mono- and di-phenylamines (preferably at least 85 mass% of di(Cs 9 substituted phenyl)amine, from 0 to 15 mass% (such as 1 to 10 mass%, such as 0 to 8 mass%, such as 0 to 5 mass%) of mono(Cs-9 substituted phenyl)amine, and from 0 to 2 mass % (such as 0 to 1 .0 mass%, such as 0 to 0.5 mass%, such as 0 to 0.2 mass%, such as 0 to less than 0.1 mass%, such as 0 to 0.01 mass%) of unsubstituted diphenyl amine, based upon the weight of the mono-, di-, and unsubstituted phenylamines);3) detergent;4) dispersant; and5) optional styrenic block copolymer viscosity modifier, wherein the lubricating oil composition, when containing 12 mass% carbon black (based upon the weight of the lubricating oil composition, has a dynamic viscosity (Pas) at a shear rate of 1 .3(1 / s) at least 10 % lower (such as at least 15% lower, such as at least 20% lower, such as at least 25% lower) than the dynamic viscosity at a shear rate of 1.3(1 / s) of the same lubricating oil composition except that the Cs-9 diphenylamine antioxidant has been replaced with the same amount of diphenylamine antioxidant having:1) about 68 mass% di-Cg-alkyl diphenylamine,2) about 29 mass% of mono-Cg-alkyl diphenylamine, and3) about 3 mass% of tri-Cg-alkyl diphenylamine, based on the weight of 1), 2) and 3), as determined by Ultra-Performance Liquid Chromatography as described in the Experimental section below (hereinafter “UPLC”); and / or wherein the lubricating oil composition, when containing 12 mass% carbon black (based upon the weight of the lubricating oil composition, has a dynamic viscosity (Pas) at a shear rate of 4.3(1 / s) at least 5 % lower (such as at least 10% lower, such as at least 13% lower) than the dynamic viscosity at a shear rate of 4.3(1 / s) of the same lubricating oil composition except that the Cs-9 diphenylamine antioxidant has beenreplaced with the same amount of diphenylamine antioxidant having:1) about 68 mass% di-Cg-alkyl diphenylamine,2) about 29 mass% of mono-Cg-alkyl diphenylamine, and3) about 3 mass% of tri-Cg-alkyl diphenylamine, based on the weight of 1), 2) and 3), as determined by UPLC in the Experimental section; and or wherein the lubricating oil composition, when containing 12 mass% carbon black (based upon the weight of the lubricating oil composition, has a dynamic viscosity (Pas) at a shear rate of 8.3(1 / s) at least 5 % lower (such as at least 10% lower, such as at least 15% lower, such as at least 17% lower) than the dynamic viscosity at a shear rate of 8.3(1 / s) of the same lubricating oil composition except that the Cs-g diphenylamine antioxidant has been replaced with the same amount of diphenylamine antioxidant having:1) about 68 mass% di-Cg-alkyl diphenylamine,2) about 29 mass% of mono-Cg-alkyl diphenylamine, and3) about 3 mass% of tri-Cg-alkyl diphenylamine, based on the weight of 1), 2) and 3), as determined by UPLC in the Experimental section below.

[0011] In any embodiment described herein, the diphenylamine antioxidant comprises 0 to 2 mass%, such as 0 to 1 mass% (such as less than 0.5 mass%, such as less than 0.25 mass%, such as less than 0.1 mass%, such as less than 0.05 mass%, such as less than 0.01 mass%) of unsubstituted diphenyl amine, based upon the weight of the mono (Cs-g substituted phenyl)amines, the di-(Cs-g substituted phenyl)amines, and any unsubstituted diphenylamine.

[0012] In any embodiment described herein, unsubstituted diphenylamine diphenyl amine antioxidant is present in the diphenylamine antioxidant at less than 2 mass% (such as from 0.0010 to less than 1 mass%, such as 0.050 to less than 0.5 mass%, such as 0.010 to less than 0.25 mass%, such as present at less than 0.1 mass%, such as present at less than 0.05 mass%, such as present at less than 0.01 mass%, such as 0.010 to less than 0.1 mass%), based upon the weight of the mono (Cs-g substituted phenyl)amines, the di- (Cs-g substituted phenyl)amines, any tri-(Cs-g substituted phenyl)amines, and the unsubstituted diphenylamine in the diphenylamine antioxidant.

[0013] In any embodiment described herein, the diphenyl amine antioxidant comprises less than 2 mass%, such as less than 1 mass% (such as less than 0.5 mass%, such as less than 0.25 mass%, such as less than 0.1 mass%, such as less than 0.05 mass%, such as less than 0.01 mass%) of unsubstituted diphenyl amine, based upon the weight of the mono (Cs-g substituted phenyl)amines, the di-(Cs-g substituted phenyl)amines, the tri-(Cs-g substituted phenyl)amines, and any unsubstituted diphenylamine.

[0014] In any embodiment described herein, the diphenyl amine antioxidant comprises less than 2 mass%, such as 0.0010 to 2 mass%, (0.01 to less than 1 mass%, such as less than 0.5 mass%, such as less than 0.25 mass%, such as less than 0.1 mass%, such as less than 0.05 mass%, such as less than 0.01 mass%) of unsubstituted diphenyl amine, based upon the weight of the mono (Cs-g substituted phenyl)amines, the di- (Cs-g substituted phenyl)amines, any tri-(Cs-g substituted phenyl)amines, any tetra-(Cs-g substituted phenyl)amines, and any unsubstituted diphenylamine.

[0015] In embodiments, the di-(Cs-g substituted phenyl)amines may be di-(Cs substituted phenyl)amines, or di-(Cg substituted phenyl)amines and or di-(Cs and Cg substituted phenyl)amines.

[0016] In embodiments, the mono-(C8-9 substituted phenyl)amines may be mono-(Cs substituted phenyl)amines, or di-(Cg substituted phenyl)amines and or mono-(Cs and C9 substituted phenyl)amines.

[0017] In embodiments, the tri-(Ce-9 substituted phenyl)amines may be tri-(Cs substituted phenyl)amines, or tri-(Cg substituted phenyl)amines and or tri-(Ce and C9 substituted phenyl)amines.

[0018] In embodiments, the tetra-(Ce-9 substituted phenyl)amines may be tetra-(Ce substituted phenyl)amines, or tetra-(Cg substituted phenyl)amines and or tetra-(Ce and C9 substituted phenyl)amines.

[0019] In embodiments, the mono-, di-, tri-, and / or tetra-(Cs-9 substituted phenyl)amines may each independently be mono-, di-, tri-, and / or tetra-(Cs substituted phenyl)amines, or mono-, di-, tri-, amd / or tetra- (C9 substituted phenyl)amines, or mono-, di-, tri-, and / or tetra(Cs and C9 substituted phenyl)amines.

[0020] Unless otherwise indicated, for purposes of this invention and the claims thereto when sooted rheology (dynamic viscosity tested on a blend containing carbon black) is determined on lubricating oil composition, carbon black having an iodine number of 253 mg / g by ASTM D1510, an oil absorption number (OAN) of 192 cc / 100g by ASTM D2414, a 325 mesh residue of less than 10 ppm by ASTM D1514, and a tint of 87 % by ASTM D3265 (such as Vulcan™ XC72R) shall be used.

[0021] This invention further relates to a lubricating oil composition comprising or resulting from the admixing of:(i) at least 50 mass% of one or more base oils, based upon the weight of the lubricating oil composition;(ii) one or more dispersants;(iii) one or more detergents; and(iv) diphenyl amine antioxidant composition comprising: a) from 0 to less than 10 mass% mono-Cs-g-alkyl substituted diphenyl amine represented by the Formula (III) where n is 1 , w is 0, and z is 0, b) 90 mass% or more of di-Cs g-alkyl substituted diphenyl amine represented by Formula (III), where n is 1 , w is 0, and z is 1 , c) from 0 to less than 10 mass% tri-Cs-g-alkyl substituted diphenyl amine represented by Formula (III), where w + n + z = 3, d) 1 mass% or less (preferably 0.001 to less than 0.1 mass%, preferably 0.010 to less than 0.1 mass%) of unsubstituted diphenyl amines represented by Formula (III) where n is 0, w is 0, and z is 0, based upon the total weight of the diphenyl amines of a), b), c) and d) present in the lubricating oil composition, where Formula (III)Formula (III) where each Rais independently a linear Cs-9 alkyl or branched Cs-9 alkyl group, n is 1 or 0, z is 0 or 1 , and w is 0 or 1 , where the branched Cs-9 alkyl group may be singly, doubly or triply branched at one, two, three, four or more carbons, and may be symmetrically branched or asymmetrically branched.

[0022] This invention further relates to a lubricating oil composition comprising or resulting from the admixing of:(i) at least 50 mass% of one or more base oils, based upon the weight of the lubricating oil composition;(ii) one or more dispersants;(iii) one or more detergents; and(iv) diphenyl amine antioxidant composition comprising: a) from 0 to less than 15 mass% (such as from 1 to 15 mass%) mono-Cs-g-alkyl substituted diphenyl amine represented by the Formula (X) where n is 1 and w, v, and z are 0, b) 85 mass% or more of di-Cs g-alkyl substituted diphenyl amine represented by Formula (X), where n is 1 , z is 1 , w is 0, and v is 0, c) from 0 to less than 10 mass% (such as 0.1 to less than 10 mass%) tri-Cs-g-alkyl substituted diphenyl amine represented by Formula (X), where n + z + w + v = 3, d) from 0 to less than 10 mass% (such as 0.1 to less than 10 mass%) tetra-Cs -g-alkyl substituted diphenyl amine represented by Formula (X), where n + z + w + v = 4, e) 2 mass% or less (such as 1 mass% or less, such as less than 0.5 mass%, such as less than 0.25 mass%, such as less than 0.1 mass%, such as less than 0.05 mass%, such as less than 0.01 mass%, such as such as from 0.010 to less than 0.1 ) of unsubstituted diphenyl amine represented by Formula (X) where v is 0, n is 0, w is 0, and z is 0, based upon the total weight of the diphenyl amines of a), b), c), d) and e) present in the lubricating oil composition, where Formula (X) is:Formula (X) where each Rais independently a linear Cs-g alkyl or branched Cs-g alkyl group, n is 1 or 0, z is 0 or 1 , v is 0 or 1, and w is 0 or 1 , where the branched Cs-g alkyl group may be singly, doubly or triply branched at one, two, three, four or more carbons, and may be symmetrically branched or asymmetrically branched.Preferably tetra-Cs g-alkyl substituted diphenyl amines are unobserved by the UPLC method in the Experimental section below.

[0023] This invention further relates to a method to reduce sooted viscosity in an internal combustion engine comprising lubricating an internal combustion engine with a lubricating oil composition comprising:1 ) 50 mass% or more of one or more base oils;2) diphenylamine antioxidant comprising: at least 85 mass% of di (Cs g substituted phenyl)amine and from 0 to 15 mass% (such as 1 to 10 mass%, such as 0.001 to 8 mass%, such as 0 to 5 mass%, such as from 0.001 to less than 0.0 mass%) of mono(Cs-g substituted phenyl)amine, based upon the weight of the mono- and di-phenylamine, and optionally wherein unsubstituted diphenyl amine is present at 2 mass % or less (such as 1 mass% or less, such as less than 0.5 mass%, such as less than 0.25mass%, such as less than 0.1 mass%, such as less than 0.05 mass%, such as less than 0.01 mass%), based upon the weight of the mono-diphenylamine, di-phenylamine and optional unsubstituted diphenyl amine;3) detergent;4) dispersant; and5) optional styrenic block copolymer viscosity modifier, wherein the the lubricating oil composition has a dynamic viscosity (Pas) at 1.3(1 / s) at least 10 % lower (such as at least 15% lower, such as at least 20% lower, such as at least 25% lower) than the dynamic viscosity at 1.3(1 / s) of the same lubricating oil composition except that the Cs-9 diphenylamine antioxidant has been replaced with the same amount of diphenylamine antioxidant having:1) about 68 mass% di-Cg-alkyl diphenylamine,2) about 29 mass% of mono-Cg-alkyl diphenylamine, and3) about 3 mass% of tri-Cg-alkyl diphenylamine, based on the weight of 1), 2) and 3), as determined by Ultra-Performance Liquid Chromatography as described in the Examples.

[0024] This invention further relates to the use of a diphenylamine antioxidant to reduce sooted viscosity in engine crankcase lubricant compositions, particularly in the presence of high soot concentrations, the diphenylamine antioxidant comprising: at least 85 mass% of di(Cs 9 substituted phenyl)amine and from 0 to 15 mass% (such as 1 to 10 mass%, such as 0 to 8 mass%, such as 0 to 5 mass%) of mono(Cs-9 substituted phenyl)amine, based upon the weight of the mono- and di-phenylamine; and preferably to the use of the aforementioned embodiments of the diphenylamine antioxidant.

[0025] All comparative formulations of diphenylamine antioxidant having. 1) about 68 mass% di-Cg-alkyl diphenylamine, 2) about 29 mass% of mono-Cg-alkyl diphenylamine, and 3) about 3 mass% of tri-Cg-alkyl diphenylamine, based on the weight of 1), 2) and 3), as determined by Ultra-Performance Liquid Chromatography as described in the Experimental section below contain less than 0.1 mass% unsubstituted diphenylamine and tetra-Cs 9-alkyl substituted diphenylamines are not observed as determined by the UPLC method described in the Experimental section.

[0026] Further, the Cs-9 alkyl diphenylamine compositions (and concentrates and lubricating oils comprising such) disclosed herein are free of any added tetra-Cs 9-alkyl substituted diphenylamines. Also, tetra-Cs 9- alkyl substituted diphenylamines are not observed in the inventive Cs-9 alkyl diphenylamine compositions disclosed herein as determined by the UPLC method described in the Experimental section.

[0027] In any composition described herein (such as a lubricating oil composition or a concentrate composition), unsubstituted diphenylamine diphenyl amine is present in the composition at less than 1 mass% (such as from 0.0010 to less than 1 mass%, such as 0.050 to less than 0.5 mass%, such 0.010 to less than 0.25 mass%, such as present at less than 0.1 mass%, such as present at less than 0.05 mass%, such as present at less than 0.01 mass%), based upon the weight of the composition (such as a lubricating oil composition or a concentrate composition).BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 (Fig. 1) is a graph of measured dynamic viscosity (Pas) at shear rate of 1 .3 1 / s for oils from Example 1 (DPA = diphenylamine).

[0029] Figure 2 (Fig.2) is a graph of measured dynamic viscosity (Pas) at shear rate of 1 .3 1 / s for oils from Example 2 (DPA = diphenylamine).

[0030] Figure 3 (Fig.3) is a graph of low shear viscosity (shear rate = 1.3 1 / s) as a function of monosubstituted diphenylamine content from Example 1 (DPA = diphenylamine).

[0031] Figure 4 (Fig.4) is a graph of low shear viscosity (shear rate = 1.3 1 / s) as a function of monosubstituted diphenylamine content from Example 2 (DPA = diphenylamine).

[0032] Figure 5 (Fig.2) is a graph of dynamic viscosity as a function of Shear Rate for styrenated DPAs (Oils G and H) compared to Oil B (Example 1).

[0033] Figure 6 (Fig.6) is a graph of dynamic viscosity as a function of Shear Rate for octylated DPAs (Oils E and F) compared to Oil C (Example 1).

[0034] Figure 7 (Fig.7) is a graph of dynamic viscosity as a function of Shear Rate for nonylated DPAs (Oils B, C and D, Example 1).

[0035] Figure 8 (Fig.8) is a graph of dynamic viscosity as a function of Shear Rate for styrenated DPAs (Oils M and N) compared to Oil J (Example 2).

[0036] Figure 9 (Fig.9) is a graph of dynamic viscosity as a function of Shear Rate for nonylated DPAs (Oils J, K and L, Example 2).

[0037] Figure 10 (Fig. 10) is a graph of liquid viscosity as a function of soot content during the ISB Viscosity Test (Oils 1 and 2).DEFINITIONS

[0038] For purposes of this specification and all claims to this invention, the following words and expressions, if and when used, have the meanings ascribed below.

[0039] 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), / .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.).

[0040] The term "comprising" or any cognate word specifies the presence of stated features, steps, or integers or components, but does not preclude the presence or addition of one or more other features, steps, integers, components or groups thereof. The expressions "consists of" or "consists essentially of" or cognates may be embraced within “comprises” or cognates, wherein "consists essentially of' permits inclusion of substances not materially affecting the characteristics of the composition to which it applies.

[0041] The term "LOC" means lubricating oil composition.

[0042] The term "major amount" means more than 50 mass% of a composition, such as more than 60 mass% of a composition, such as more than 70 mass% of a composition, such as from 80 to 99.009 mass% of a composition, such as from 80 to 99.9 from 80 to 99.009 mass% of a composition, of a composition based upon the mass of the composition.

[0043] The term "minor amount" means 50 mass% or less of a composition; such as 40 mass% or less of a composition; such as 30 mass% or less of a composition, such as from 20 to 0.001 mass%, such as from 20 to 0.1 mass%, based upon the mass of the composition.

[0044] The term "mass%" means mass percent of a component, based upon the mass of the composition as measured in grams, unless otherwise indicated, and is alternately referred to as weight percent("weight %", "mass%", or "% w / w").

[0045] The term "active ingredient" (also referred to as "ai", "a.i.", or "A.I.") refers to additive material that is neither diluent nor solvent. Unless otherwise indicated, amounts herein are described as active ingredient.

[0046] The terms "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.

[0047] The terms "group" and "radical" are used interchangeably herein.

[0048] The term "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).

[0049] The term "hydrocarbyl" means a radical that contains hydrogen and carbon atoms. Preferably, the group consists essentially of, more preferably consists only of, hydrogen and carbon atoms, unless specified otherwise. Preferably, 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.).

[0050] The term "alkyl" means a radical of carbon and hydrogen (such as a Ci to C30, such as a Ci 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 ( / .e., unbranched) or branched, be cyclic, acyclic, or part cyclic / acyclic. Preferably, 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.

[0051] The term "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 ( / .e., unbranched) or branched, be cyclic, acyclic or part cyclic / acyclic.

[0052] The term "alkylene" means a Ci to C20, preferably a Ci 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.

[0053] An "olefin", alternatively referred to as "alkene", is a linear, branched, or cyclic compound of carbonand 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 "isoprene" content of 55 mass% to 95 mass%, it is understood that the mer unit in the copolymer is derived from isoprene in the polymerization reaction and said derived units are present at 55 mass% to 95 mass%, 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. "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 "isoprene polymer" or "isoprene copolymer" is a polymer or copolymer comprising at least 50 mol % isoprene derived units, a "butadiene polymer" or "butadiene copolymer" is a polymer or copolymer comprising at least 50 mol % butadiene derived units, and so on. Likewise, when a polymer is referred to as a "partially or fully saturated polymer comprising C4-5 olefins", the C4-5 olefin(s) present in such polymer or copolymer are the polymerized form of the olefin(s), and the polymer has been partially or fully saturated (such as by hydrogenation) after polymerization of the monomers.

[0054] The term "alkynyl" means a C2 to C30 (such as a C2 to C12) radical, which includes at least one carbon-to-carbon triple bond.

[0055] The term "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 C5 to Cis, such as Ce to Ci 4) aryl groups, optionally substituted by one or more hydrocarbyl groups, heteroatoms, or heteroatomcontaining groups (such as halo, hydroxyl, alkoxy and amino groups). Preferred aryl groups include phenyl and naphthyl groups and substituted derivatives thereof, especially phenyl, and alkyl substituted derivatives of phenyl.

[0056] The term "styrenated" means containing at least one styrene group. A styrenated diphenylamine is a diphenylamine that has been reacted with styrene such that styrene group(s) is / are attached to one or both phenyl rings of the diphenylamine.

[0057] The term "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. An "alkyl substituted phenyl" is a phenyl group where a hydrogen atom has been replaced by an alkyl group, such as a Ci to C20 alkyl group, such as methyl, ethyl, n-propyl, isopropyl, 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. A "substituted phenyl" is a phenyl group where a hydrogen atom has been replaced by hydrocarbon group, a heteroatom, or a heteroatom-containing group (such an alkyl group, such as a Ci to C20 alkyl group, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tertbutyl, 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).

[0058] The term "antioxidant" or equivalent term (e.g., "oxidation stabilizer" or "oxidation inhibitor") refers to a composition with the capability of controlling (reducing) oxidation, and consequently preventingcomponents in a lubricating oil composition from breakdown and causing thickening (increasing viscosity) of the LOG. Based on the mechanism of action, antioxidants are categorized as primary antioxidants (radical scavengers), secondary antioxidants (peroxide decomposers), and metal deactivators (complex-forming or chelating agents).

[0059] A "hindered phenol" is a phenol with one or more bulky functional groups (i.e. functional groups having at least 4 non-hydrogen atoms, such as substituted or unsubstituted C4 to C40 alkyl groups.) Common hindered phenols include butylated hydroxy toluene and substituted butylated hydroxy toluenes.

[0060] The term "halogen" or "halo" means a group 17 atom or a radical of group 17 atom, such as fluoro, chloro, bromo, and iodo.

[0061] The term "ashless" in relation to an additive means the composition does not include a metal.

[0062] The term "ash-containing" in relation to an additive means the composition includes a metal.

[0063] The term "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.

[0064] The term "effective minor amount" in respect of an additive means an amount of such an additive of less than 50 mass% of the lubricating oil composition so that the additive provides the desired technical effect.

[0065] The term "effective major amount" in respect of an additive means an amount of such an additive of 50 mass% or more of the lubricating oil composition so that the additive provides the desired technical effect.

[0066] The term "ppm" means parts per million by mass, based on the total mass of the lubricating oil composition, unless otherwise indicated.

[0067] The term "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.

[0068] The term "aliphatic hydrocarbyl fatty acid" means a monocarboxylic acid having an aliphatic C7 to C29, preferably a C9 to C27, most preferably a C11 to C23 hydrocarbyl chain. Such compounds may be referred to herein as aliphatic (C7 to C29), more preferably (Cg to C27), most preferably (C11 to C23), hydrocarbyl monocarboxylic acid(s) or hydrocarbyl fatty acid(s) (wherein Cxto Cydesignates 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 Cx+ito Cy+icarbon atoms). Preferably, 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); preferably, 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).

[0069] The term "aliphatic hydrocarbyl faty 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, preferably a Ci to C30 aliphatic hydrocarbyl ester, such as an alkyl ester, preferably a Ci to Ce alkyl ester, especially 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 Ci to C30 aliphatic hydrocarbyl ester(s), [e.g., aliphatic hydrocarbyl fatty acid alkyl ester(s), more preferably aliphatic hydrocarbyl fatty acid Ci to Ce alkyl ester(s), especially aliphatic hydrocarbyl fatty acid methyl ester(s)]. Suitably, the term “aliphatic hydrocarbyl fatty acid ester” embraces aliphatic (C7 to C29) hydrocarbyl, more preferably aliphatic (Cg to C27) hydrocarbyl, most preferably aliphatic (C11 to C23) hydrocarbyl fatty acid glycerol ester(s) and aliphatic (C7 to C29) hydrocarbyl, more preferably aliphatic (C9 to C27) hydrocarbyl, most preferably aliphatic (C11 to C23) hydrocarbyl fatty acid Ci 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.

[0070] The term "sulfurized aliphatic hydrocarbyl faty acid ester" means a compound obtained by sulfurizing an aliphatic hydrocarbyl fatty acid ester as defined herein.

[0071] The term "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 mass%, 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. When the term “absent” is used in relation to monomer reactants and / or to repeat units in (co)polymers described herein, it means present at 0 mass%, based upon the weight of all (co)monomers in the (co)polymer, or, if present at all, at levels so low that they do not substantially impact the physical properties of the (co)polymer, such as at 0.2 mass% or less, or at 0.1 mass% or less.

[0072] The term "absent or present at less than 0.3 mass%" as it relates to components included within the lubricating oil compositions described herein and the claims thereto means that the particular component is absent as defined above, or is present at any of the following amounts: less than 0.3 mass%, 0.29 mass% or less, 0.28 mass% or less, 0.27 mass% or less, 0.26 mass% or less, 0.25 mass% or less, 0.24 mass% or less, 0.23 mass% or less, 0.22 mass% or less, 0.21 mass% or less, 0.20 mass% or less, 0.19 mass% or less, 0.18 mass% or less, 0.17 mass% or less, 0.16 mass% or less, 0.15 mass% or less, 0.14 mass% or less, 0.13 mass% or less, 0.12 mass% or less, 0.11 mass% or less, 0.10 mass% or less, 0.09 mass% or less, 0.08 mass% or less, 0.07 mass% or less, 0.06 mass% or less, 0.05 mass%, or less 0.04 mass% or less, 0.03 mass% or less, 0.02 mass% or less, 0.01 mass% or less. If any of the lesser amounts are referred to (for example a component is "present at 0.19 mass% or less"), each of the lesser amounts above are included therein.

[0073] The term "absent or present at less than 0.2 mass%" as it relates to components included withinthe lubricating oil compositions described herein and the claims thereto means that the particular component is absent as defined above, or is present at any of the following amounts: 0.19 mass% or less, 0.18 mass% or less, 0.17 mass% or less, 0.16 mass% or less, 0.15 mass% or less, 0.14 mass% or less, 0.13 mass% or less, 0.12 mass% or less, 0.11 mass% or less, 0.10 mass% or less, 0.09 mass% or less, 0.08 mass% or less, 0.07 mass% or less, 0.06 mass% or less, 0.05 mass% or less, 0.04 mass% or less, 0.03 mass% or less, 0.02 mass% or less, 0.01 mass% or less. If any of the lesser amounts are referred to (for example a component is "present at 0.19 mass% or less"), each of the lesser amounts above are included therein.

[0074] As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, and Mz is z average molecular weight. Molecular weight distribution (MWD), also referred to as polydispersity index (PDI), is defined to be Mw divided by Mn. Unless otherwise noted, all molecular weight units (e.g., Mw, Mn, Mz) are reported in g / mol.

[0075] Total Base Number also referred to as "TBN", in relation to an additive component or of a lubricating oil composition ( / .e., unused lubricating oil composition) means total base number as measured by ASTM D2896 and reported in units of mgKOH / g.

[0076] Total Acid Number ("TAN") is determined by ASTM D664.

[0077] Phosphorus, Boron, Calcium, Zinc, Molybdenum, Sodium, Silicon, and Magnesium content are measured by ASTM D5185.

[0078] Sulfur content in oil formulations is measured by ASTM D5185.

[0079] Sulfated ash ("SASH") content is measured by ASTM D874.

[0080] Kinematic viscosity (KV100, KV40, etc.) is determined pursuant to ASTM D445-19a and reported in units of cSt, unless otherwise specified.

[0081] Viscosity index is determined according to ASTM D2270.

[0082] Saponification number is determined by ASTM D94, and reported in units of mgKOH / g.

[0083] Unless otherwise indicated, all percentages reported are mass% on an active ingredient basis, i.e., without regard to carrier or diluent oil, unless otherwise indicated.

[0084] 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 disclosure also provides the product obtainable or obtained as a result of any such reaction.

[0085] Further, it is understood that any upper and lower quantity, range and ratio limits set forth herein may be independently combined.

[0086] Also, it will be understood that the preferred features of each aspect of the present disclosure are regarded as preferred features of every other aspect of the present disclosure. Accordingly, preferred and more preferred features of one aspect of the present disclosure may be independently combined with other preferred and / or more preferred features of the same aspect or different aspects of the present disclosure.DETAILED DESCRIPTION OF THE INVENTION

[0087] The features of the disclosure relating, where appropriate, to each and all aspects of the disclosure, will now be described in more detail as follows.

[0088] The lubricating oil compositions of the disclosure 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 otheradditives. This disclosure encompasses compositions which comprise the components before mixing, or after mixing, or both before and after mixing.

[0089] For purposes of this invention and the claims thereto "mono-Cg-alkyl substituted diphenyl amine", also referred to as "(Cg-alkyl substituted phenyl)(phenyl)amine" or "(nonylphenyl)(phenyl)amine", means a nitrogen atom bound to: 1) hydrogen, 2) an unsubstituted phenyl group, and 3) a phenyl group substituted with one C9 alkyl group.

[0090] "mono-Cs-alkyl substituted diphenylamine", also referred to as "(Cs-alkyl substituted phenyl)(phenyl)amine", means a nitrogen atom bound to: 1) hydrogen, 2) an unsubstituted phenyl group, and 3) a phenyl group substituted with one Cs alkyl group.

[0091] "mono-Cs-g-alkyl substituted diphenylamine" means a nitrogen atom bound to: 1) hydrogen, 2) an unsubstituted phenyl group, and 3) a phenyl group substituted with one Cs or C9 alkyl group.

[0092] For purposes of this invention and the claims thereto "di-Cs-alkyl substituted diphenylamine", also referred to as "di(Cs-alkyl substituted phenyl) amine", means a nitrogen atom bound to: 1) hydrogen, and 2) two phenyl groups each independently substituted with one Cs alkyl group, each of which is independently linear or branched.

[0093] For purposes of this invention and the claims thereto "di-Cg-alkyl substituted diphenyl amine", also referred to as "di(Cg-alkyl substituted phenyl) amine", means a nitrogen atom bound to: 1) hydrogen, and 2) two phenyl groups each independently substituted with one C9 alkyl group, each of which is independently linear or branched.

[0094] For purposes of this invention and the claims thereto "di-Cs-g-alkyl substituted diphenyl amine", also referred to as "di(Cs 9-alkyl substituted phenyl) amine", means a nitrogen atom bound to: 1) hydrogen, and 2) two phenyl groups each independently substituted with one C9 or Cs alkyl group, each of which is independently linear or branched.

[0095] For purposes of this invention and the claims thereto "tri-Cs-alkyl substituted diphenylamine", also referred to as "di(Cs-alkyl substituted phenyl) (Cs-alkyl substituted phenyl) amine, means a nitrogen atom bound to 1) hydrogen, 2) a phenyl group independently substituted with two Cs alkyl groups, each of which is independently linear or branched, and 3) a phenyl group substituted with one Cs alkyl group.

[0096] For purposes of this invention and the claims thereto "tri-Cg-alkyl substituted diphenylamine", also referred to as "di(Cg-alkyl substituted phenyl) (Cg-alkyl substituted phenyl) amine, means a nitrogen atom bound to 1) hydrogen, 2) a phenyl group independently substituted with two C9 alkyl groups, each of which is independently linear or branched, and 3) a phenyl group substituted with one C9 alkyl group.

[0097] For purposes of this invention and the claims thereto "tri-Cs-g-alkyl substituted diphenylamine", also referred to as "di(Cs g-alkyl substituted phenyl) (Cs-g-alkyl substituted phenyl) amine, means a nitrogen atom bound to 1) hydrogen, 2) a phenyl group independently substituted with two Cs-9 alkyl groups, each of which is independently linear or branched, and 3) a phenyl group substituted with one Cs-9 alkyl group.

[0098] For purposes of this invention and the claims thereto "tetra-Cs-alkyl substituted diphenylamine" means a nitrogen atom bound to 1) hydrogen, 2) a phenyl group independently substituted with two Cs alkyl groups, each of which is independently linear or branched, and 3) a phenyl group substituted with two Cs alkyl groups, each of which is independently linear or branched.

[0099] For purposes of this invention and the claims thereto "tetra-Cg-alkyl substituted diphenylamine" means a nitrogen atom bound to 1) hydrogen, 2) a phenyl group independently substituted with two C9 alkyl groups, each of which is independently linear or branched, and 3) a phenyl group substituted with two C9 alkyl groups, each of which is independently linear or branched.

[0100] For purposes of this invention and the claims thereto "tetra-Cs-9-alkyl substituted diphenylamine" means a nitrogen atom bound to 1) hydrogen, 2) a phenyl group independently substituted with two Cs-9 alkyl groups, each of which is independently linear or branched, and 3) a phenyl group substituted with two Cs-9 alkyl groups, each of which is independently linear or branched. For purposes of this invention and the claims thereto "diphenylamine antioxidant" means antioxidant comprising a nitrogen atom bound to 1) hydrogen, 2) two phenyl groups each of which may independently be substituted with one or more C9 or Cs alkyl groups.

[0101] For purposes of this invention and the claims thereto "unsubstituted diphenylamine", means a nitrogen atom bound to 1 ) hydrogen, 2) two unsubstituted phenyl groups.

[0102] For purposes of this invention and the claims thereto "diphenyl amine antioxidant" also referred to as "aminic antioxidant" means antioxidant comprising a nitrogen atom bound to 1) hydrogen, 2) two phenyl groups each of which may independently be substituted with one or more Cs-9 alkyl groups.Polar Diluents

[0103] Polar diluents are useful for solubilizing Cs diphenylamine compositions, alone or as blends with additional Cs-gdiphenylamines.

[0104] For purposes of this invention and claims thereto, when hydrogen-bond acceptor groups are described as being 2, 3, 4, 5, or 6 atoms (such as carbon atoms) apart, the hydrogen acceptor is not included in that count. For example, in ethoxylated lauryl alcohol (2-(dodecyloxy)ethan-1-ol), the two hydrogen-bond acceptor groups (-OH and -O-) are considered two atoms apart (specifically two carbon atoms apart).

[0105] Likewise, in the C8-C10 tri-methylol propane ester formula below (n is 0, 1 or 2), the ester groups are considered three atoms apart (specifically 3 carbon atoms apart).

[0106] While in a (dipropylene glycol) dibenzoate formula below, the ester groups are considered two atoms apart (specifically 2 carbon atoms apart) from the "-O-" ether group.

[0107] Likewise, in the dioctyl terephthalate formula below, the ester groups are considered four atoms apart

[0108] Likewise, in the trioctyl mellitate formula below, the three ester groups are considered 2, 3, and 4 four atoms apart (specifically 2, 3 and 4 carbon atoms apart) depending on which positions the ester groups occupy (e.g., ortho, meta, or para to each other).

[0109] In embodiments, the polar diluent(s) comprise two or more available hydrogen-bond acceptor groups. An available hydrogen acceptor group is defined to be a group containing a moiety (such as an oxygen containing group, such as an ester, ether or alcohol group) capable of participating in a hydrogen bond with the positively charged hydrogen atom from the amine functionality of the di (Cs-alkyl substituted phenyl) amine. Sterically hindered groups (such as a sterically hindered oxygen containing group, such as a sterically hindered ester, sterically hindered ether or sterically hindered alcohol group) that are not capable of participating in a hydrogen bond with the positively charged hydrogen atom from the amine functionality of the di(Cs-alkyl substituted phenyl) amine are not considered available. In particular, in embodiments, the polar diluent comprises two or more hydrogen-bond acceptor groups that are 2, 3, 4, 5, or 6 atoms apart where the hydrogen-bond acceptor groups do not have one or more adjacent quaternary sp3 carbons. For example, in the homopolymethylmethacrylate formula below (z is the number of repeat units, such as 2 to 10,000) the ester group is bound to an adjacent quaternary sp3 carbon (identified by the arrow) and thus is considered sterically hindered.

[0110] In embodiments, the polar diluent has an aniline point of 25°C or less, such as about 20 °C or less, such as about 15 °C or less, such as about 10 °C or less, such 5 °C or less, such as 0 °C or less.

[0111] In embodiments, the polar diluent has at 2, 3, 4 or 5 available hydrogen-bond acceptor groups (such as more ester, ether or alcohol groups) that are 2, 3, 4, 5, or 6 carbon atoms (such as 2, 3, or 4 carbon atoms) apart.

[0112] In embodiments, the polar diluent(s) are one or more diluent(s) selected from the group consisting of: i) di- and tri-esters derived from propylene glycol (such as difpropylene glycol)dibenzoate), ii) Cs-16 alkyl triesters derived from trimethylolpropane (such as Cs-Cio tri-methylol propane ester), ill) ethoxylated C10-24 alcohols (such as ethoxylated C12-18 alcohols, such as ethoxylated lauryl alcohol), and iv) phthalates, terephthalates, isophthalates, trimellitates and pyromellitates (such as Ce to C24 dialkyl terephthalates, such as Cs to C16 dialkyl terephthalates, such as dioctyl terephthalate, such as Ce to C24 dialkyl isophthalates, Ce to C24 dialkyl phthalates, and Ce to C24 trialkyl trimellitate, and Ce to C24 tetraalkyl pyromellitate).Lubricating Oil Compositions

[0113] This disclosure relates to lubricating oil compositions (also referred to as "LOG", "lubricant compositions", "lubricating compositions", or "lubricant oil compositions") comprising or resulting from the admixing of:(a) from 1 to 99 mass% (alternately 30 to 95 mass%, alternately 50 to 90 mass%, alternately 60 to 95 mass%, alternately 70 to 85 mass%) of one or more base oils, based upon the weight of the lubricating composition;(b) from 0.01 to 20 mass% (in particular 0.1 to 12 mass%, alternately 0.1 to 8 mass%), based on total weight of the lubricating composition, of one or more dispersants (such as blends of dispersants);(c) from 0.10 to 20 mass% (in particular 0.15 to 10 mass%, alternately 0.20 mass% to 5 mass%, alternately 0.25 to 2 mass%), based upon the weight of the composition, of one or more detergents; and(d) from 0.01 to 20 mass% (in particular 0.10 to 15 mass%, alternately 0.15 to 10 mass%, alternately 0.20 mass% to 5 mass%, alternately 0.25 to 2 mass%, alternately 0.5 to 1 mass%), based upon the weight of the lubricating oil composition, of antioxidant comprising:1) one or more diphenyl amine antioxidants represented by Formula (III) where w is 0, n is 1 and z is 1 ;2) unsubstituted diphenylamine represented by Formula (III), where w, n and z are zero present at 2 mass% or less (such as less than 1 mass%, such as less than 0.1 mass%, such as 0.001 to less than 0.01 mass%) of unsubstituted diphenylamine represented by Formula (III), where w, n and z are zero, based upon the weight of the lubricating oil composition; and3) mono-substituted diphenyl amine antioxidants represented by Formula (III) (such as Formula (III), where n is 1 , w is 0, and z is 0, present at present at 2 mass% or less, such as less than 1 mass% (such as 0.001 to less than 0.3 mass% such as 0.005 to less than 0.1 mass%, such as 0.01 to 0.05 mass%), based upon the weight of the lubricating oil composition: where Formula (III) iswhere each Rais independently a linear Cs-9 alkyl or branched Cs-9 alkyl group, n is 1 or 0, z is 0 or 1 , and w is 0 or 1 , where the branched Cs-9 alkyl group may be singly, doubly or triply branched at one, two, three, four or more carbons, and may be symmetrically branched or asymmetrically branched, where the lubricating oil composition, when containing 12 mass% carbon black (based upon the weight of the lubricating oil composition) may preferably exhibit: a dynamic viscosity (Pas) at a shear rate of 1 .3(1 / s) at least 10 % lower (such as at least 15% lower, such as at least 20% lower, such as at least 25% lower) than the dynamic viscosity at a shear rate of 1.3(1 / s) of the same lubricating oil composition except that the Cs-9 diphenylamine antioxidant has been replaced with the same amount of diphenylamine antioxidant having: 1) about 68 mass% di-Cg-alkyl diphenylamine, 2) about 29 mass% of mono-Cg-alkyl diphenylamine, and 3) about 3 mass% of tri- Cg-alkyl diphenylamine, based on the weight of 1), 2) and 3), as determined by UPLC in the Experimental section; and / or wherein the lubricating oil composition, when containing 12 mass% carbon black (based upon the weight of the lubricating oil composition), has a dynamic viscosity (Pas) at a shear rate of 4.3(1 / s) at least 5 % lower (such as at least 10% lower, such as at least 13% lower) than the dynamic viscosity at a shear rate of 4.3(1 / s) of the same lubricating oil composition except that the Cs-9 diphenylamine antioxidant has been replaced with the same amount of diphenylamine antioxidant having: 1) about 68 mass% di-Cg- alkyl diphenylamine, 2) about 29 mass% of mono-Cg-alkyl diphenylamine, and 3) about 3 mass% of tri-Cg- alkyl diphenylamine, based on the weight of 1 ), 2) and 3), as determined by UPLC in the Experimental section; and or wherein the lubricating oil composition, when containing 12 mass% carbon black (based upon the weight of the lubricating oil composition), has a dynamic viscosity (Pas) at a shear rate of 8.3(1 / s) at least 5 % lower (such as at least 10% lower, such as at least 15% lower, such as at least 17% lower) than the dynamic viscosity at a shear rate of 8.3(1 / s) of the same lubricating oil composition except that the Cs-9 diphenylamine antioxidant has been replaced with the same amount of diphenylamine antioxidant having: 1) about 68 mass% di-Cg-alkyl diphenylamine, 2) about 29 mass% of mono-Cg-alkyl diphenylamine, and 3) about 3 mass% of tri- Cg-alkyl diphenylamine, based on the weight of 1), 2) and 3), as determined by UPLC in the Experimental section.

[0114] This disclosure also relates to lubricating oil compositions comprising or resulting from the admixing of:A) from 1 to 99 mass% (alternately 30 to 95 mass%, alternately 50 to 90 mass%, alternately 60 to 95 mass%, alternately 70 to 85 mass%) based upon the weight of the lubricating oil composition, of one or more base oils;B) from 0.01 to 20 mass% (in particular 0.1 O to 15 mass%, alternately, 0.15 to 10 mass%, alternately 0.20 mass% to 5 mass%, alternately 0.25 to 2.5 mass%, alternately 0.5 to 1 mass%, alternately at least 3 mass%, alternately 3 to 20 mass%), based upon the weight of the lubricating oil composition, of diphenyl amine antioxidant comprising (or consisting essentially of, or consisting of): i) one or more di-Cs-9-alkyl substituted diphenyl amine represented by Formula (III) below, where n is 1, w is 0, and z is 1 , and ii) unsubstituted diphenyl amine represented by the Formula (III), where n is 0, w is 0, and z is 0, present at less than 2 mass% (such as less than 1 mass%, such as less than 0.1 mass%, such as less than 0.01 mass% such as from 0.0010 to less than 0.10 mass%, such as from 0.0010 to 0.010 mass%),based upon the weight of the lubricating oil composition, and ill) mono- Cs-9-alkyl substituted diphenyl amines represented by the Formula (III), where n is 1 , w is 0, and z is 0, present at 0.0010 to 4 mass%, such as 0.0010 to 3 mass%, such as 0.0010 to less than 1 mass% (such as from 0.0010 to less than 0.3 mass%, such as less than 0.1 mass%, such as less than 0.01 mass%, such as less than 0.001 mass%, such as less than 0.0005 mass%), based upon the weight of the lubricating oil composition, and iv) tri- Cs-9-alkyl substituted diphenyl amines represented by the Formula (III), where n is 1 , w is 1 , and z is 1, present at less than 1 mass%, such as at less than 0.3 mass% (such as less than 0.1 mass%, such as less than 0.01 mass%, such as less than 0.001 mass%, such as less than 0.0005 mass%), based upon the weight of the lubricating oil composition, where Formula (III) is:where each Rais independently a linear Cs-9 alkyl or branched Cs-9 alkyl group, n is 1 , z is 0 or 1, and w is 0 or 1 ;C) from 0.10 to 20 mass% (in particular, 0.15 to 10 mass%, alternately 0.20 mass% to 5 mass%, alternately 0.25 to 2 mass%), based upon the weight of the lubricating oil composition, of one or more detergents, preferably carboxylate detergents (such as blends of detergents);D) optionally, from 0.01 to 5 mass% (in particular 0.1 to 4 mass%, alternately 0.25 to 3 mass%, alternately 0.045-0.15 mass%), based on total weight of the lubricating oil composition, of one or more friction modifiers (such as blends of friction modifiers);F) optionally, from 0.01 to 5 mass% (in particular, 0.01 to 3 mass%, alternately 0.1 to 1 .5 mass%), based on total weight of the lubricating oil composition, of one or more pour point depressants (such as blends of pour point depressants);G) optionally, from 0.001 to 3 mass% (in particular, 0.01 to 2 mass%, alternately 0.1 to 1 .5 mass%), based on total weight of the lubricating oil composition, of one or more anti-foam agents (such as blends of antifoam agents);H) optionally, from 0.001 to 10 mass% (in particular, 0.01 to 6 mass%, alternately 0.01 to 5 mass%, alternately 0.1 to 4 mass%, alternately 0.1 to 2 mass%, alternately 0.1 to 1 mass%), based on total weight of the lubricating oil composition, of one or more viscosity modifiers (such as blends of viscosity modifiers);I) optionally, from 0.01 to 20 mass% (in particular, 0.1 to 12 mass%, alternately 0.1 to 8 mass%), based on total weight of the lubricating oil composition, of one or more dispersants (such as blends of dispersants);J) optionally, from 0.01 to 5 mass% (in particular, 0.1 to 3 mass%, alternately 0.1 to 1.5 mass%), based on total weight of the lubricating oil composition, of one or more inhibitors and / or anti-rust agents (such as blends of inhibitors and / or anti-rust agents);K) from 0.001 to 10 mass% (in particular, 0.01 to 5 mass%, alternately 0.1 to 3 mass%, alternately 0. to 1 .5 mass%), based on total weight of the lubricating oil composition, of one or more antiwear agents (such as blends of antiwear agents, such as ZDDP);M) optionally, from 0.01 to 5 mass% (in particular, 0.05 to 2 mass%, alternately 0.1 to 1 mass%), based on total weight of the lubricating oil composition, of one or more seal compatibility agents, such as seal swell agents, and / orO) optionally, from 0.01 to 5 mass% (in particular, 0.1 to 3 mass%, alternately 0.1 to 1.5 mass%), based on total weight of the lubricating oil composition, of one or more unsaturated Ci2-Ceo hydrocarbons (such as C12-C24 linear alpha-olefins (LAOs), oligomers / polymers of polyisobutylenes, and / or blends thereof).

[0115] All elements A through O are as described more fully herein.For purposes of this disclosure, component B) antioxidants are not added in the elements C, D, F, G, H, I, J, K, M, and / or O above for determining weight percentages, even though they may show similar properties, e.g., element B) antioxidants may impact wear positively, but is not added into element K) for determining weight percent of anti-wear agents.

[0116] In embodiments, element D (friction modifier(s), such as one or more friction modifiers, such as one or more glycerol-based friction modifiers, such as glycerol mono-oleate) is present, in addition to the base oil and diphenyl amine antioxidant(s), at from 0.01 to 5 mass% (in particular 0.1 to 4 mass%, alternately 0.25 to 3 mass%, alternately 0.045-0.15 mass%), based on total weight of the lubricating oil composition.

[0117] This invention further relates to a lubricating oil composition comprising an antioxidant composition comprising or made by admixing:1) phenylamine antioxidant comprising one or more di-Cs g-alkyl substituted diphenyl amine as represented by Formula (III) above, where n is 1 , z is 1 and w is 0, and2) optionally, one or more additional antioxidants (such as diphenyl amines other than 1) above, hindered phenol, sulfurized fatty acid esters, molybdenum containing compounds, ashless dithiocarbamates, and the like), where unsubstituted and or alkyl substituted diphenylamine(s) represented by Formula (III), where n is 0, w is 0 and z is 1 or 0, are absent or present at less than 0.30 mass%, such as less than 0.2 mass%, such as less than 0.1 mass%, based upon the weight of the lubricating oil composition.

[0118] This invention further relates to a lubricating oil composition wherein di-Cg-alkyl substituted diphenyl amine represented by Formula (III), where w is 0, n is 1, and z is 1, is present in the lubricating oil composition at 0.5 mass% or more, 1 .0 mass% or more, or 2.0 mass% or more, or 3.0 mass% or more, based upon the mass of the lubricating composition and mono-Cg-alkyl substituted diphenyl amine represented by Formula (III), where w is 0, n is 1 , and z is 0, is present in the lubricating oil composition at 0.3 mass% or less, or at 0.1 mass% or less, based upon the mass of the lubricating composition.

[0119] This invention further relates to lubricating oil compositions as described above comprising element B (aminic antioxidant, such as antioxidant comprising 90 mass% or more of bis(nonylphenyl)amine and or bis(octylphenyl)amine and 10 mass% or less of (nonylphenyl)(phenyl)amine and or (octylphenyl)(phenyl)amine based on the weight of the bis(nonylphenyl)amine, bis(octylphenyl)amine,(octylphenyl)(phenyl)amine, and (nonylphenyl)(phenyl)amine) in combination with, or resulting from the admixing with, one or more additives selected from the group consisting of: element D (such as glycerol-based friction modifiers and or organomolybdenum-based friction modifiers); element C (such as calcium and or magnesium sulfonate-based detergents and or calcium and or magnesium salicylate based detergents, such as detergents providing high levels of Mg to the lubricating oil composition); element K (such as zinc-based antiwear agents, such as ZDDPs derived from primary alcohols); element I (such as dispersants, such as PIBSA-PAM, derived from a polymer, such as PIB, having an Mn of 1600 g / mol or less); and element A (such as refined and or renewable Group II base oil(s), refined and or renewable Group III base oil(s), Group IV base oil(s)), and combinations thereof, and variants thereof).

[0120] The invention also includes lubricating oil composition comprising element B aminic antioxidant and element A base oil, selected from Group I, II III, IV and or V base oils, such as base oils selected from the group of Group I base oils, Group II base oils, Group III vase oils, renewable oils (plant and / or microbe-based oils, such as group II and or Group III renewable oils), re-refined oils, and combinations thereof, and variants thereof.

[0121] Common commercially available di(nonylphenyl) aminic antioxidants typically comprise a large (typically greater than 10 mass%, based on the weight of total mass% of the mono-, di- and tri-nonyl substituted diphenyl aminic components in the di(nonylphenyl) aminic antioxidant) amount of (nonylphenyl)(phenyl)amine. As used herein, these are referred to as “baseline aminic antioxidants” and are typically compositions of about 68 mass% bis(nonylphenyl)amine, about 29 mass% of mono(nonylphenyl) amine, and about 3 mass% of tri(nonylphenyl) amine based on the total mass% of the mono-, di- and trisubstituted (nonylphenyl) aminic components. It has been found that aminic antioxidants that comprise larger amounts of bis(nonylphenyl)amine are preferred and in fact may act synergistically with other lubricant oil additives. As used herein, these may also be referred to as “enhanced aminic antioxidants (as defined above)” and are typically a composition of several components, most preferably 90 (or 91 , or 92, or 93, or 94, or 95, or 96, or 97, or 98, or 99, or 99.3) mass% or more of bis(nonylphenyl)amine, and 10 (or 9, or 8, or 7, or 6, or 5, or 4, or 3 or 2, or 1) mass% or less of (nonylphenyl)(phenyl)amine, and 0 to 0.01 mass%, such as 0.001 to 0.01 mass% unsubstituted phenylamine, based on the total mass% of the unsubstituted, mono- and disubstituted (nonylphenyl) aminic components. Enhanced aminic antioxidants can be obtained by any means such as by distilling or otherwise separating out the bis(nonylphenyl)amine component from the other baseline aminic antioxidant components, or through direct organic synthesis. The lubricating oil composition comprising baseline aminic antioxidant used for comparison purposes herein is Comparative Formulation A [where Comparative Formulation A is the same lubricating oil composition except that the diphenyl amine antioxidant has been replaced with the same amount of diphenyl amine antioxidant having: 1) about 68 mass% di-Cg-alkyl diphenyl amine, 2) about 29 mass% of mono-Cg-alkyl diphenyl amine, and 3) about 3 mass% of tri-Cg-alkyl diphenyl amine, based on the weight of 1), 2) and 3), as determined by UPLC, as described in the Experimental section below. While the benefits and synergies available with the enhanced aminic antioxidants are illustrated by comparison with the Component 2 in the Experimental section below, itis expected that the same advantages will be shown when compared to other Cg-alkyl diphenyl amine antioxidant compositions containing amounts, such as more than 10 (or 20, or 25, or 30, or 40, or 50) mass%, of mono-Cg-alkyl diphenyl amine, as determined by UPLC in the Experimental section.

[0122] Glycerol-based friction modifiers useful herein in combination with the enhanced aminic antioxidant(s) are described further herein, and in any embodiment include compounds such as glycerol monooleates, saturated mono-, di-, and tri-glyceride esters, glycerol monostearates, and polyols. In a preferred embodiment the glycerol-based friction modifier comprises glycerol mono-oleate.

[0123] Organomolybdenum-based friction modifiers useful herein in combination with the enhanced aminic antioxidant(s) are described further herein, and in any embodiment include compounds such as organomolybdenum compounds of dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, sulfides, and the like, and mixtures thereof. Desirable organomolybdenum-based friction modifiers include molybdenum dithiocarbamates, dialkyldithiophosphates, alkyl xanthates and alkylthioxanthates. In a more preferred embodiment, the organomolybdenum-based friction modifiers are selected from dimeric molybdenum dialkyldithiocarbamates and trimeric molybdenum dialkyldithiocarbamates, and most preferably dimeric dialkyldithiocarbamate (where the alkyls are selected from Ce to Ci 4 alkyl groups, and may be combinations of C to C14 and Ce to C12 alkyls, such as hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, or isomers thereof).

[0124] Sulfonate-based detergents useful herein in combination with the enhanced aminic antioxidant(s) are described further herein, and in any embodiment include overbased calcium and / or magnesium sulfonate salts. Useful sulfonate based detergents include those having TBN's of greater than 100 such as 200 to 600, such as 300 to 500 mgKOH / g (as determined by ASTM D2896).

[0125] Magnesium based detergents, useful for providing high Mg content (such as 400 to 10,000 ppm) to the lubricating oil(s) comprising enhanced aminic antioxidant(s) include magnesium sulfonates, phenates, carboxylates (such as salicylates) as described below. Preferred magnesium based detergents useful herein in combination with the enhanced aminic antioxidant(s) include those having TBN's of greater than 100, such as 200 to 600, such as 300 to 500 mgKOH / g (as determined by ASTM D2896).

[0126] Calcium based detergents, useful for providing high Ca content (such as 400 to 20,000 ppm) to the lubricating oil(s) comprising enhanced aminic antioxidant(s) include calcium carboxylates (such as salicylates) and calcium sulfonates as described below. Preferred calcium based detergents include those having TBN's of greater than 50, such as 50 to 650, such as 100 to 600, such as 200 to 500 mgKOH / g (as determined by ASTM D2896).

[0127] Zinc-based antiwear agents useful in combination with enhanced aminic antioxidant(s) are described further herein, and in any embodiment include compounds such as zinc dialkyldithiophosphate, where the alkyl groups are derived from one or more primary alcohols, one or more secondary alcohols or combinations of primary and secondary alcohols. Typically, the alcohols are mono-alcohols represented by the formula R- alkyl, where the alkyls are selected from C4 to C30 alkyl groups, and may be combinations of alkyl groups selected from butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl or isomers thereof). In embodiments useful primary alcohols for use in preparing zinc-based antiwear agents, such as zinc dialkyldithiophosphates, include C4 toCao primary alcohols, such as linear or branched alcohols having a CH2OH group, such butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, and icosanol or isomers and mixtures thereof.

[0128] Low Mn dispersants (such as less than 1600 g / mol) useful herein in combination with the enhanced aminic antioxidant(s) are described below. Preferred Low Mn dispersants include dispersants PIBSA-PAMs derived from polyisobutylene (PIB) having an Mn of from 400 to less than 1600g / mol. PIBSA-PAM's are PIB's that are treated with an acid or anhydride (such as succinic acid or succinic anhydride) to form a PIB- succinate, then combined with a polyamine to form a PIBSA-PAM as further described below.

[0129] In embodiments, the lubricating oil composition may further comprising zinc dialkyldithiophosphate.

[0130] In embodiments, the lubricating oil composition may further comprise hindered phenolic antioxidant.

[0131] In embodiments, the lubricating oil composition may further comprises a molybdenum containing compound such as a dimeric and or trimeric molybdenum containing compound providing 50 to 1000 ppm Mo to the lubricating oil composition.

[0132] In embodiments, the lubricating oil composition may further comprises additional antioxidant comprising oil-soluble or oil-dispersible sulfur-containing antioxidant(s), sulfurized aliphatic (C7 to C29) hydrocarbyl fatty acid ester(s), sulfur-containing organo-molybdenum compound(s), and combinations thereof.

[0133] In embodiments, the lubricating oil composition may further comprise ethoxylated alcohol.

[0134] In embodiments, the lubricating oil composition the detergent in the lubricating oil composition comprises carboxylate detergent, such as salicylate detergent, such as alkaline earth metal salicylate detergent, such as calcium or magnesium salicylate detergent, optionally having a TBN of 100 or less and or optionally providing from 1 to 30 mmol soap, such as 5 to 25 mmol / kg soap to the lubricating oil composition.

[0135] Generally, the total base number of the lubricating composition may range from 1 to 30, such as 4 to 15 mgKOH / g, such as 5 to 15 mgKOH / g, such as 5 to 12 mgKOH / g, such as 7 to 12 mgKOH / g, such as 8 to 11 mgKOH / g, as measured by ASTM D2896.

[0136] The lubricating compositions of the present disclosure may contain low levels of phosphorus, namely not greater than 1600, preferably not greater than 1200, more preferably not greater than 800, such as 1 to 1600, such as 50 to 1200, such as 100 to 800 parts per million (ppm) by mass of phosphorus, expressed as atoms of phosphorus, based on the total mass of the lubricating compositions, as measured by ASTM D5185.

[0137] Suitably, the lubricant composition may have a phosphorus level of 1200 ppm or less, alternately 1000 ppm or less, alternately 800ppm or less, as measured by ASTM D5185.

[0138] The lubricating compositions of the present disclosure may contain a ratio of atoms of Magnesium to atoms of Calcium based on the total mass of the lubricating compositions, as measured by ASTM D5185, of at least to 0.5, preferably at least 0.6, more preferably at least 0.65.

[0139] Typically, the lubricating compositions may contain low levels of sulfur. Preferably, the lubricating composition contains up to 0.4, more preferably up to 0.3, most preferably up to 0.2, such as 0.1 to 0.4 mass% sulfur, based on the total mass of the lubricating oil composition, as measured by ASTM D5185.

[0140] Typically, the lubricating compositions may contain low levels of sulfated ash, such as 1.2 % or less, such as 1 .0 mass% or less, preferably 0.9 mass or less %, preferably 0.8 mass% or less, alternately 0.0001to 0.5 mass% or less sulfated ash, based on the total mass of the lubricating composition, as measured by ASTM D874-13a (2018).

[0141] Generally, the kinematic viscosity at 100° C ("KV100") of the lubricating composition may range from 2 to 30 cSt, such as 2 to 20 cSt, such as 5 to 15 cSt as determined according to ASTM D 445-19a).

[0142] In embodiments, the kinematic viscosity at 100° C ("KV100") of the lubricating composition may range from 1 to 30 cSt, alternately 3 to 20, alternately 3 to 17 cSt, alternately 3.5 to 16.3 cSt alternately 9.3 to less than 12.5 cSt, alternately 12.5 to less than 16.3 cSt, as determined according to ASTM D 445-19a).

[0143] Preferably, the lubricating composition of the present disclosure may be a multigrade oil identified by the viscometric descriptor SAE 40W-X, SAE 30W-X, SAE 25W-X, SAE 20W-X, SAE 15W-X, SAE 10W-X, SAE 5W-X or SAE 0W-X, where X represents any one of 8, 12, 16, 20, 30, 40, and 50; the characteristics of the different viscometric grades can be found in the SAE J300 classification. Alternately, the lubricating composition may be the form of viscosity grade SAE 15W-X, SAE 10W-X, SAE 5W-X or SAE 0W-X, such as in the form of SAE 15W-X or SAE 10W-X, wherein X represents any one of 8, 12, 16, 20, 30, 40, and 50. Alternately, the lubricating composition of the present disclosure may be a multigrade oil identified by the viscometric descriptor SAE 10W-30, 15W-40, 5W-30, 5W-40, 10W-40, 5W-50. (See standard SAE J300 published January 2015 by SAE International, formerly known as Society of Automotive Engineers).

[0144] Optionally, the lubricating oil composition containing diphenyl amine antioxidants described herein may be absent phenolic antioxidant.

[0145] In embodiments, the lubricating oil composition may comprise 1 to 500 ppm of boron, such as 25 to 400 ppm of boron, such as 50 to 300 ppm boron, such as 50 to 200 ppm boron.

[0146] In embodiments, the lubricating oil composition may comprise less than 75 ppm boron, alternately less than 60 ppm boron, alternately from 1 to 70 ppm boron. Alternately, the lubricating oil composition may be absent boron.

[0147] In embodiments, the lubricating oil composition may comprise acylated polymers, such as polyisobutylene succinic acid (PIBSA), optionally having an Mn of 500 to 50,000 g / mol, such as 600 to 5,000 g / mol, such as 700 to 3000 g / mol, such as 700 to 2000 g / mol, such as 700 to 1500 g / mol such as 800 to 1400 g / mol, such as 800 to less than 1000 g / mol. In embodiments, the lubricating oil composition may comprise acylated polymers, such as polyisobutylene succinic acid, having an Mn of 500 to 1600 g / mol, such as 700 to 1200 g / mol. In embodiments, the lubricating oil composition comprises more than 0.1 mass% (such as 0.1 to 10 mass%, such as 0.5 to 8 mass%), functionalized (such as aminated) polybutene (such as polyisobutylene), such as PIBSA-PAM.

[0148] In embodiments, the lubricating oil composition may comprise 20 mass% or less (such as 15 mass% or less, such as 10 mass% or less, such as 5 mass% or less, such as 3 mass% or less, such as 1 mass% or less) of block copolymer (such as styrenic block copolymer), such as linear block copolymer, radial (aka "star") block copolymer, random block copolymer, and / or tapered block copolymer. In embodiments, the lubricating oil composition may be substantially free of or may be absent block copolymer, such as block, radial, random, and / or tapered block copolymer.

[0149] In embodiments, the lubricating oil composition may comprise 20 mass% or less (such as 15 mass% or less, such as 10 mass% or less, such as 5 mass% or less, such as 3 mass% or less, such as 1 mass% orless) styrenic copolymer, such as block, radial, random, and / or tapered styrenic block copolymer. In embodiments, the lubricating oil composition may be substantially free or absent styrenic copolymer, such as block, star, random, and / or tapered styrenic block copolymer.

[0150] Alternately, the lubricating oil composition may comprise styrenic block copolymer viscosity modifier such as 0.1 to 10 mass%, such as 0.5 to 5 mass%, such as 1 to 3 mass% of styrenic block copolymer viscosity modifier, based upon the weight of the lubricating oil composition. Optionally, the sytrenic block copolymer comprises hydrogenated styrene-isoprene butadiene block copolymer is optionally combined with one or more Cs-20 dialkyl fumarate / vinyl acetate copolymers. Optionally the dialkyl fumarate / vinyl acetate copolymers (such as one or more Cs to C20 dialkyl fumarate / vinyl acetate copolymers, such as one or more Os to C18 dialkyl fumarate / vinyl acetate copolymers, such as one or more C12 to Cis dialkyl fumarate / vinyl acetate copolymers) has a pour point (ASTM D97) of -10°C or less (such as -15°C or less, such as -20°C or less, such as -25 °C or less, such as -30 °C or less).

[0151] In another advantageous form, the lubricating oil composition of the instant disclosure further optionally includes one or more functionalized polymers at from 0.2 to 2.0 mass%, or 0.4 to 1.8 mass%, or 0.6 to 1 .6 mass%, or 0.8 to 1 .4 mass%, or 1 .0 to 1 .2 mass% of the composition comprising an amide, imide, and / or ester functionalized partially or fully saturated polymer comprising C4-5 olefins having: i) an Mw / Mn of less than 2, or less than 1.8, or less than 1.6, ii) a Functionality Distribution (Fd) value of 3.5 or less, or 3.2 or less, or 3.0 or less, or 2.5 or less, iii) optionally, an Average Functionality Value (Fv) of 1.4 to 20 FG grafts / polymer chain, such as 1 .4 to 15 FG grafts / polymer chain, such as 3 to 12.5 FG grafts / polymer chain, such as 4 to 10 FG grafts / polymer chain , such as 5 to 10 FG grafts / polymer chain, such as 6 to 10 FG grafts / polymer chain; and iv) an Mn of 10,000 g / mol or more, or 15,000 g / mol or more, or 20,000 g / mol or more, or 25,000 g / mol or more (GPC-PS) of the polymer prior to functionalization, provided that, if the polymer prior to functionalization is a copolymer of isoprene and butadiene, then the Mn of the copolymer is greater than 25,000 g / mol, or 30,000 g / mol or more, or 35,000 g / mol or more, or 40,000 g / mol or more (GPC-PS). (Functionality Distribution (Fd), Average Functionality Value (Fv), and GPC-PS are determined as set out in United States Patent Application USSN 18 / 480,571, filed October 4, 2023 (US 20240141156 A1), which is incorporated by reference herein.)

[0152] The functionalized polymer of the lubricating oil composition of the instant disclosure may include at least 50 %, or at least 60%, or at least 70% of 1 ,4-insertions of monomer. Furthermore, the functionalized polymer of the lubricating oil composition of the instant disclosure may include a partially or fully saturated homopolyisoprene containing one or more pendant amine groups and having an Mn of 25,000 to 100,000 g / mol, or 35,000 to 90,000 g / mol, or 45,000 to 80,000 g / mol, or 55,000 to 75,000 g / mol (GPC-PS) and at least 50%, or at least 60%, or at least 70% of 1 ,4-insertions prior to functionalization.

[0153] The functionalized polymer of the lubricating oil composition of the instant disclosure may be absent of styrene repeat units, or absent of butadiene repeat units, or is not a homo-polyisobutylene, or is not a copolymer of isoprene and butadiene.

[0154] In embodiments, the lubricating oil composition may have a total saponification number (SAP) of 25 (such as 28, such as 30, such as 32) mgKOH / g or more, as determined by ASTM 94.

[0155] In embodiments, the lubricating compositions of the present disclosure may be a heavy-duty dieseloil (e.g., for use in an engine for a heavy-duty diesel vehicle, i.e., a heavy-duty diesel vehicle having a gross vehicle weight rating of 10,000 pounds or more.)

[0156] In embodiments, the lubricating compositions of the present disclosure may be a passenger car motor oil. In embodiments, the lubricating compositions of the present disclosure may be a passenger car diesel oil.

[0157] In embodiments, the lubricating composition of the present disclosure may be a lubricating composition comprising: an oil of lubricating viscosity having greater than 50 mass% of Group I, II, III, IV, and / or V oil (such as a Group III base oil, a Group IV base oil, a Group V base oil, or mixtures thereof); a first PIB succinimide dispersant derived from an 1800 to 2500 Mn PIB; a second PIB succinimide dispersant derived from a PIB with an Mn less than 1600, where at least one of the first PIB succinimide dispersant(s) and the second PIB succinimide dispersant is boron-free (optionally, at least one of the first PIB succinimide dispersant(s) and the second PIB succinimide dispersant is borated); optionally an amide, imide, and / or ester functionalized partially or fully saturated polymer comprising C4-5 olefins as described in United States serial number USSN 18 / 480,571 , filed October 4, 2023 published as US 20240141156 A1 (sometimes referred to as a dispersant or a dispersant viscosity modifier); an alkaline earth metal salicylate detergent; an alkaline earth metal sulfonate detergent present in an amount to deliver 0.1 mass% to 1.2 mass% of alkaline earth metal soap to the lubricating composition; and a phosphorus anti wear agent present in an amount to deliver 300 to 900 ppm phosphorous to the lubricating composition, the lubricating composition having a total sulfated ash of between 0.3 to 1.1 mass%.

[0158] In embodiments, the lubricating oil compositions of the present disclosure comprise: an oil of lubricating viscosity having greater than 50 mass% of Group I, II, III, IV, and / or V oil (such as refined and or renewable Group II base oil, refined and or renewable Group III base oil, Group IV base oil, Group V base oil, or mixtures thereof) and a lower Mn dispersant (such as PIB succinimide dispersant derived from a PIB having an Mn of less than 1600 g / mol, such as 600 to less than 1600 g / mol, such as 650 to 1500 g / mol, such as 700 to 1400 g / mol, such as 800 to 1300 g / mol, such as 850 to 1200 g / mol, such as 900 to 1150 g / mol, such as 900 to 1000 g / mol). The lower molecular weight dispersant (such as lower molecular weight PIBSA- PAM dispersant) may be present in the lubricating composition in an amount of from 0.5 to 10 mass%, or from 0.8 to 6 mass%, or from 1 .0 to 5 mass%, or from 1 .5 to 5 mass% or from 1 .5 to 4.0 mass% or from 1 .5 to 4.8 mass%, or at 2 mass% or more, such as 2 to 5 mass%, based upon the weight of the lubricating oil composition.

[0159] The lubricating compositions disclosed herein may have a kinematic viscosity as measured by ASTM D-445 at 100° C of 3 cSt (mm2 / s), or more, such as from 3 to 26.1 cSt, such as from 4.0 to less than 6.1 cSt, such as from 5.0 to less than 7.1 cSt, such as from 6.9 to less than 9.3 cSt, such as 9.3 to less than 12.5 cSt, such as 12.5 to less than 16.3 cSt, such as 16.3 to less than 21.9 cSt, such as 21.9 to 26.1 cSt.

[0160] The lubricating composition disclosed herein, may have a high temperature high shear viscosity (HTHS) as measured by ASTM D4683 at 150° C of 4.0 mPa-s or more, or 3.7 mPa-s or more, or 3.5 mPa-s, or more, or 2.9 mPa-s or more, or 2.6 mPa-s or more, or 2.3 mPa-s or more, or 2.0 mPa-s or more, or 1.7 mPa-s or more.

[0161] The lubricating composition disclosed herein may have a SAE viscosity grade of 0W-Y, wherein Ymay be 12, 16, or 20. In one embodiment, the lubricating composition has an SAE viscosity grade of OW-12. Concentrates

[0162] A concentrate, also referred to as an additive package, adpak, or addpack, is a composition having less than 50 mass% (such as less than 40 mass%, such as less than 30 mass%, such as less than 25 mass%, such as less than 20 mass%) base oil and lubricant composition additives (such as described herein) which is typically then further blended with additional base oil to form a lubricating oil product.

[0163] This disclosure relates to concentrate compositions comprising or resulting from the admixing of: (i) from 1 to less than 50 mass% (alternately 5 to 45 mass%, alternately 7 to 40 mass%, alternately 10 to 35 mass%, alternately 10 to 25 mass%), based upon the weight of the composition, of one or more base oil(s); (ii) from 0.1 O to 20 mass% (in particular 0.15 to 10 mass%, alternately 0.20 mass% to 5 mass%, alternately 0.25 to 2 mass%), based upon the weight of the composition, of one or more detergent(s), such as carboxylate detergents, such as calcium salicylate; (iii) from 0.10 to 20 mass% (in particular 0.15 to 10 mass%, alternately 0.20 mass% to 5 mass%, alternately 0.25 to 2 mass%), based upon the weight of the composition, of one or more dispersant(s) (such as PIBSA-PAM); and (iv) from 0.010 to 20 mass% (in particular 0.10 to 15 mass%, alternately 0.15 to 10 mass%, alternately 0.20 mass% to 5 mass%, alternately 0.25 to 2 mass%), based upon the weight of the concentrate, of diphenyl amine antioxidant comprising: 1) one or more di-Cs-9-alkyl substituted diphenyl amine represented by Formula (III), where n is 1 , z is 1 and w is 0), 2) from 0 to 2 mass% (such as 0 to 1 .0 mass%, to 0 to 0.5 mass%, such as 0 to 0.1 mass %, such as 0 to less than 0.1 mass %, such as from 0.0010 to less than 0.01 mass%) of unsubstituted diphenyl amine represented by Formula (III), where n is 0, z is 0 and w is 0), and 3) from 0 to 1.5 mass% (such as 0 to 1 mass%, such as 0.001 to 0.5 mass%, such as 0.005 to less than 0.3 mass%, such as 0.001 to 0.1 mass%) of mono-C8-9-alkyl substituted diphenyl amine represented by Formula (III), where n is 1 , z is 0 and w is 0), based upon the weight of the concentrate:where: the branched Cs g-alkyl may be singly, doubly or triply branched at one, two, three, four or more carbons, and may be symmetrically branched or asymmetrically branched; each Rais independently a linear Cs g-alkyl or branchedCs g-alkyl group, n is 0 or 1 , z is 0 or 1, and w is 0 or 1 ;(v) optional additional components, antioxidants (other than (iv) above), pour point depressants, anti-foam agents, viscosity modifiers, corrosion inhibitors, antiwear agents, extreme pressure additives, demulsifiers, seal compatibility agents, additive diluent base oils, friction modifier(s) (such as, organic FM, such as organic ester, such as fatty acid ester), etc. Optionally, the concentrate comprises 0 to less than 0.3 mass% of tetra substituted diphenyl amines, based upon the weight of the concentrate.

[0164] In embodiments, the concentrate composition may optionally be absent solvent (such as aliphatic or aromatic solvent) and / or absent functionalized base oil.

[0165] This disclosure also relates to concentrate compositions comprising or resulting from the admixing of:A) from 1 to less than 50 mass% (alternately 5 to 45 mass%, alternately 7 to 40 mass%, alternately 10 to 35 mass%, alternately 10 to 25 mass%), based upon the weight of the concentrate composition, of one or more base oil(s);B) from 0.10 to 35 mass% (in particular, 0.15 to 20 mass%, alternately 0.20 mass% to 5 mass%, alternately 0.25 to 3 mass%), based upon the weight of the concentrate composition, of one or more di -Cs-9- alkyl substituted diphenyl amine represented by Formula (III), where n is 1 , w is 0, and z is 1 , and optionally hindered phenol antioxidants, where: mono-C8-9-alkyl substituted diphenyl amine represented by Formula (III) where z is 0, w is 0 and n is 1 , are absent or present at less than 0.30 mass% (such as less than 0.1 mass%, such as from 0.0010 to less than 0.1 mass%), tri-Cs-9-alkyl substituted diphenyl amine represented by Formula (III) where z is 1 , w is 1 and n is 1 , are absent or present at less than 0.30 mass% (such as less than 0.1 mass%, such as from 0.0010 to less than 0.1 mass%), tetra-Cs-9-alkyl substituted diphenyl amine represented by Formula (III) where z is 1 , w is 1 and n is 2 (where each Raof Ra(nj may be the same or different), are absent or present at less than 0.30 mass% (such as less than 0.1 mass%), and unsubstituted diphenyl amine represented by Formula (III) where z is 0, w is 0 and n is 1 , are absent or present at less than 0.30 mass% (such as less than 0.1 mass%, such as from 0.0010 to less than 0.1 mass%), based upon the weight of the concentrate;C) from 0.1 to 20 mass% (in particular 0.5 to 10 mass%, alternately 2 to 6 mass%), based on total weight of the concentrate composition, of one or more detergent(s) (such as blends of detergents);D) optionally, from 0.01 to 5 mass% (in particular, 0.1 to 4 mass%, alternately 0.25 to 3 mass%, alternately 0.25 to .075 mass%), based on total weight of the concentrate composition, of one or more friction modifier(s) (such as organic friction modifiers, such as glycerol monoeoleate);E) optionally, from 0.01 to 20 mass% (in particular, 0.01 to 15 mass%, alternately 0.1 to 10 mass%), based on total weight of the concentrate composition, of one or more antioxidant(s) (such as blends of antioxidants), other than B) above;F) optionally, from 0.01 to 5 mass% (in particular, 0.01 to 3 mass%, alternately 0.1 to 1 .5 mass%), based on total weight of the concentrate composition, of one or more pour point depressants (such as blends of pour point depressants);G) optionally, from 0.001 to 3 mass% (in particular, 0.01 to 2 mass%, alternately 0.02 to 1 mass%), based on total weight of the concentrate composition, of one or more anti-foam agents (such as blends of anti-foam agents);I) optionally, from 0.01 to 40 mass% (in particular, 0.1 to 30 mass%, alternately 1 to 20 mass%), based on total weight of the concentrate composition, of one or more dispersants (such as blends of dispersants);K) optionally, from 0.001 to 10 mass% (in particular, 0.1 to 8 mass%, alternately 1 to 5 mass%alternately 0.25 to .075 mass%), based on total weight of the lubricating composition, of one or more antiwear agents (such as blends of antiwear agents, such as ZDDP).

[0166] Concentrates may be present in the lubricating oil composition at from of 0.5 mass% to 35 mass%, such as 5 mass% to 30 mass%, such as 7.5 mass% to 25 mass%, such as 10 to 22.5 mass%, such as 15 to 20 mass%, based upon the mass of the lubricating oil composition.

[0167] Optionally, the concentrate may be absent functionalized oil.

[0168] In embodiments, the concentrate composition may optionally be absent solvent (such as aliphatic or aromatic solvent) and / or absent functionalized base oil.

[0169] Optionally, the concentrate may be absent phenolic antioxidant.

[0170] In embodiments, the concentrate may comprise less than 20 mass% (such as less than 15 mass%, such as less than 10 mass%, such as less than 5 mass%, such as less than 3 mass%, such as less than 1 mass%), functionalized (such as aminated) polybutene (such as polyisobutylene), such as PIBSA-PAM. In embodiments, the concentrate comprises is substantially free or absent, functionalized (such as aminated) polybutene (such as polyisobutylene), such as PIBSA-PAM.

[0171] In embodiments, the concentrate may comprise acylated polymers, such as polyisobutylene succinic acid, optionally, having an Mn of 500 to 50,000 g / mol, such as 600 to 5,000 g / mol, such as 700 to 3000 g / mol. In embodiments, the concentrate may comprise acylated polymers, such as polyisobutylene succinic acid, having an Mn of 500 1600 g / mol, such as 700 to 1200 g / mol.

[0172] In embodiments, the concentrate may comprise 20 mass% or less (such as 15 mass%, such as 10 mass%, such as 5 mass%, such as 3 mass%, such as 1 mass% or less) block copolymer, such as styrenic block copolymer, star block copolymer, random block copolymer, and / or tapered block copolymer.

[0173] In embodiments, the concentrate may be substantially free of or absent block copolymer, such as block, star, random, and / or tapered block copolymer.

[0174] In embodiments, the concentrate may comprise 20 mass% or less (such as 15 mass% or less, such as 10 mass% or less, such as 5 mass% or less, such as 3 mass% or less, such as 1 mass% or less) styrenic copolymer, such as block, star, random, and / or tapered styrenic block copolymer).

[0175] In embodiments, the concentrate may be substantially free of or absent styrenic copolymer, such as block, star, random, and / or tapered sytrenic block copolymer).

[0176] In embodiments, the concentrate may comprise less than 20 mass% (such as less than 15 mass%, such as 10 mass%, such as less than 5 mass%, such as less than 3 mass%, such as less than 1 mass%) of functionalized diluent, such as functionalized oil.

[0177] In embodiments, the concentrate may substantially free of or absent functionalized diluent, such as functionalized oil.

[0178] In embodiments, the concentrate may comprise less than 0.5 mass% (such as less than 0.4 mass%, such as less than 0.3 mass%, such as less than 0.2 mass%, such as less than 0.1 mass%, such as 0 mass%, based upon the weight of the concentrate, of secondary hydrocarbyl amine compounds and tertiary hydrocarbyl amine compounds.

[0179] In embodiments, the concentrate may have a kinematic viscosity at 100° C of less than 1000 cSt, such as less than 500 cSt, such as less than 200 cSt.

[0180] Concentrates are typically combined with base oils to form lubricating oil compositions, where the concentrate typically is present at rates of 1 to 50 mass% (such as 2.5 to 40 mass%, such as 5 to 30 mass%, such as 8 to 25 mass%, such as 10 to 20 mass%), based upon the weight of the lubricating oil composition. The invention also includes concentrates comprising: 1) Cs-9 aminic antioxidant (such as antioxidant comprising 90 mass% or more of bis(C8-9phenyl)amine and 10 mass% or less of (C8-9phenyl)(phenyl)amine based on the weight of the bis(nonylphenyl)amine and (C8-9phenyl)(phenyl)amine), and 2) base oil selected from one or more refined, re-refined and or renewable Group I base oils, refined and or renewable Group II base oils, refined re-refined and or renewable Group III base oils or combinations thereof (such as combinations of Group III base oil(s) and renewable base oil(s); and or combinations of Group III base oil(s) and Group II base oils, and or combinations of Group I base oil(s) and Group II base oils). A useful petroleum derived base oil / renewable base oil combination herein is available commercially as Nexbase4PLUS™ (which can be described as being a combination of a renewable Group III oil combined with a refined Group III oil).

[0181] This invention also relates to booster packages comprising the enhanced aminic antioxidants described herein and or other additives useful in combination with a concentrate or lubricating oil composition containing the enhanced aminic antioxidants described herein. Booster packages are typically compositions containing a few (such as 1 , 2, 3, or 4) components (such as detergents, dispersants, ZDDP's, molybdenum components (such as MoDTC dimers and or trimers, etc.), antioxidants (such as the enhanced diphenylamine antioxidants described herein), that are added to a concentrate by a manufacturer or distributor immediately before providing the concentrate to a customer who will then use the concentrate to form a lubricating composition. Booster packages can also be proved separately for a customer to add to a concentrate or lubricating oil composition. The invention also includes booster packages comprising: 1) enhanced aminic antioxidant described herein (such as antioxidant comprising 85 mass% or more (such as 90 mass% or more) of bis(C8-9phenyl)amine and 10 mass% or less (such as 10 mass% or less) of (C8-9phenyl)(phenyl)amine and less than 2 mass%(such as less than 1 mass%, such as less than 0.1 mass%) of unsubstituted diphenylamine, based on the weight of the unsubstituted phenylamine, bis(Cs gphenyl)amine, and (Cs- 9phenyl)(phenyl)amine), and one or more of the components listed in Q above, such as one, two, three, four, five, six or more of:1) glycerol-based friction modifiers, such as glycerol mono-oleate;2) sulfonate-based detergents, such as magnesium and or calcium sulfonate detergents;3) organomolybdenum-based friction modifiers, such as molybdenum dithiocarbamate dimers and or trimers;4) magnesium-based detergents providing 400 ppm or more of Mg to the composition, such as magnesium salicylate and or sulfonate detergents;5) carboxylate based detergents, such as such as magnesium and or calcium salicylate detergents; and6) zinc-based antiwear agents, such as zinc dialkyldithiophosphates where the alkyl group is derived from primary alcohols; and7) dispersants (such as PIBSA-PAM) derived from a polymer (such as polyisobutylene) having an Mn of 1600 g / mol or less.A. Base Oil

[0182] The base oil (also referred to as "base stock", "lubricating oil basestock", or "oil of lubricating viscosity") useful herein may be 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.

[0183] A base oil may be selected from vegetable, animal, mineral, and synthetic lubricating oils, and mixtures thereof. It may range in viscosity from light distillate mineral oils to heavy lubricating oils, such as those for gas engine oil, mineral lubricating oil, motor vehicle oil, and heavy-duty diesel oil. Generally, the kinematic viscosity at 100° C ("KV100") of the base oil ranges from 1 to 30, such as 2 to 25 cSt, such as 5 to 20 cSt, as determined according to ASTM D445-19a, in particular, 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. Generally, 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 ASTM D4683-20.

[0184] Typically, when lubricating oil basestock(s) is used to make a concentrate, it may advantageously be present in a concentrate-forming amount to give a concentrate containing, from 5 mass% to 80 mass%, from 10 mass% to 70 mass%, or from 5 mass% to 50 mass% of active ingredient, based upon the weight of the concentrate.

[0185] 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. Base stocks may be manufactured using a variety of different processes including, but not limited to, distillation, solvent refining, hydrogen processing, oligomerization, esterification, and re-refining.

[0186] 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, 22nd edition, October 2023, www.API.org)]. Examples of PAO's useful as base oils include: poly(ethylenes), copolymers of ethylene and propylene, polybutylenes, polypropylenes, propyleneisobutylene copolymers, chlorinated polybutylenes, poly(1 -hexenes), poly(1 -octenes), poly(1 -decenes), homo- or co-polymers of Cs to C20 alkenes, homo- or co-polymers of Cs, and / or C10, and / or C12 alkenes, Cs / Cio copolymers, C8 / C10 / C12 copolymers, and C10 / C12 copolymers, and the derivatives, analogues and homologues thereof.

[0187] In another embodiment, the base oil may comprise polyalphaolefins comprising oligomers of linear olefins having 6 to 14 carbon atoms, more preferably 8 to 12 carbon atoms, more preferably 10 carbon atoms having a Kinematic viscosity at 100° C of 10 cSt or more (as measured by ASTM D445); and preferably having a viscosity index ("VI"), as determined by ASTM D2270, of 100 or more, preferably 110 or more, more preferably 120 or more, more preferably 130 or more, more preferably 140 or more; and / or having a pour point of -5° C or less (as determined by ASTM D97), more preferably -10° C or less, more preferably -20° C or less.

[0188] In another embodiment polyalphaolefin oligomers useful in the present disclosure may comprise C20 to C1500 paraffins, preferably C40 to C1000 paraffins, preferably C50 to C750 paraffins, preferably C50 to C500 paraffins. The PAO oligomers are dimers, trimers, tetramers, pentamers, etc., of C5 to C14 alpha-olefins in one embodiment, and Ce to Ci 2 alpha-olefins in another embodiment, and Cs to C12 alpha-olefins in another embodiment. Suitable olefins include 1 -pentene, 1 -hexene, 1 -heptene, 1 -octene, 1 -nonene, 1 -decene, 1- undecene, and 1 -dodecene. In one embodiment, the olefin is a combination of 1 -octene, 1 -decene, and 1 - dodecene, or alternately may be substantially 1 -decene, and the PAO is a mixture of dimers, trimers, tetramers, and pentamers (and higher) thereof. Useful PAO's are described more particularly in, for example, US Patent Nos. 5,171 ,908 and 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).

[0189] PAO's useful in the present disclosure typically possess a number average molecular weight of from 100 to 21 ,000 g / mol in one embodiment, and from 200 to 10,000 g / mol in another embodiment, and from 200 to 7,000 g / mol in yet another embodiment, and from 200 to 2,000 g / mol in yet another embodiment, and from 200 to 500 g / mol in yet another embodiment. Desirable 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.

[0190] 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.

[0191] Additional classes of synthetic lubricating oils useful as base oils herein are described at Paragraph

[0226] to

[0231] of US 20240141156 A1 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 hydrogen 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 US Patent No. 10,913,916 (col 4, In 62 to col 5, In 60) and US Patent No. 10,781 ,397 (col 14, In 54 to col 15, In 5, and col 16, In 44 to col 17, In 55).

[0192] In particular, oils from renewable sources, i.e., based in part on carbon and energy captured from the environment, such as biological sources (biomass), are useful herein. The renewable source may be (or is derived from vegetable oil (such as palm oil, coconut oil, rapeseed oil, soybean oil, jatropha oil, coconut, corn oil), microbial oil (such as algae oil), animal fats (such as cooking oil, animal fat, and / or fish fat). Renewable oils may be combined with refined oils (e.g., oils derived from petroleum, coal or other nonrenewable, i.e., not replaceable within 100 years, resources) for use herein. A useful base oil combination may comprise a refined Group III oil blended with one or more oils derived from renewable materials, such as a mixture of SynNova™ 4 and Nexbase™3043. A useful base oil containing renewable material is Nexbase™ 4Plus (KV100 ~ 4 cSt).

[0193] Renewable oil, also referred to as renewable base oil, refers to oil produced from renewable sources, i.e., based in parton carbon and / or energy captured from the environment, such as from biological resources(e.g. , biomass) Renewable oils may have greater than 90 % saturates, sulfurcontentof less than 0.3 mass%, and viscosity index properties falling in API Groups II and or III, and thus for purposes of this invention and claims renewable oils can be Group II or Group III base oils (API EOLCS 1509 definition (American Petroleum Institute Publication 1509, see section E.1.3, 22nd edition, October 2023, www.API.org).

[0194] Re-refined oils (also referred to as re-refined base oil or "RRBO") 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. A re-refined base oil is preferably substantially free from materials introduced through manufacturing, contamination, or previous use. The base oils used herein preferably comprise re-refined base oils.

[0195] The various base oils useful herein 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, 19th edition, January 2021 , www.API.org).

[0196] 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 desirable embodiments, base oils for use in the formulated lubricating compositions useful in the present disclosure are those described as API Group I (including Group l+), Group II (including Group II+), Group III (including Group III+), Group IV, and Group V oils and mixtures thereof, preferably API Group II, Group III, Group IV, and Group V oils and mixtures thereof. The base oil may be a 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 often more useful that the Group II base stock 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.

[0197] 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 base stocks may be used if desired.

[0198] The base oil or base oil blend used herein conveniently has a kinematic viscosity at 100°C (KV100, as measured according to ASTM D445-19a, and reported in units of centistoke (cSt) or it its equivalent, mm2 / s), of about 2 to about 40 cSt, alternately of 3 to 30 cSt, alternately 4 to 20 cSt at 100°C, alternately 5 to 10 cSt, alternately the base oil or base oil blend may have a kinematic viscosity at 100°C of 2 to 20 cSt, of 2.5 to 2 cSt, and preferably of about 2.5 cSt to about 9 cSt.

[0199] The base oil or base oil blend preferably has a saturate content of at least 65 mass%, more preferably at least 75 mass%, such as at least 85 mass%, such as at least than 90 mass% as determined by ASTM D2007.

[0200] Preferably, the base oil or base oil blend will have a sulfur content of less than 1 mass%, preferablyless than 0.6 mass%, most preferably less than 0.4 mass%, such as less than 0.3 mass%, based on the total mass of the lubricating composition, as measured by ASTM D5185.

[0201] 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 mass%, such as less than or equal to 25 mass%, such as less than or equal to 20 mass%, such as less than or equal to 16 mass%, such as less than or equal to 12 mass%, such as less than or equal to 10 mass%, based on the total mass of the lubricating composition.

[0202] In embodiments, the viscosity index (VI) of the base oil is at least 95, preferably at least 110, more preferably at least 120, even more preferably at least 125, most preferably from about 130 to 240, in particular from about 105 to 140 (as determined by ASTM D2270).

[0203] The base oil may be provided in a major amount, in combination with a minor amount of one or more additive components as described hereinafter, constituting a lubricant. 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.

[0204] The base oil may be provided in a minor amount, in combination with minor amounts of one or more additive components as described hereinafter, constituting an additive 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 solution, slurry or suspension thereof to disperse or dissolve the additive(s) in the oil. 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.

[0205] The base oil typically constitutes the major component of an engine oil lubricant composition of the present disclosure and typically is present in an amount ranging from about 50 to about 99 mass%, preferably from about 70 to about 95 mass%, and more preferably from about 80 to about 95 mass%, based on the total weight of the composition.

[0206] Typically, one or more base oils are present in the lubricating composition in an amount of 32 mass% or more, alternately 55 mass% or more, alternately 60 mass% or more, alternately 65 mass% or more, based on the total weight of the lubricating composition. Typically, one or more base oils are present in the lubricating composition at an amount of 98 mass% or less, more preferably 95 mass% or less, even more preferably 90 mass% or less. Alternately, one or more base oils are present in the lubricating composition at from 1 to 99 mass%, alternately 50 to 97 mass%, alternately to 60 to 95 mass%, alternately 70 to 95 mass%, based upon the weight of the lubricating composition.

[0207] 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.

[0208] Typically, one or more base oils are present in the concentrate composition in an amount of 50 mass%or less, alternately 40 mass% or less, alternately 30 mass% or less, alternately 20 mass% or less, based on the total weight of the concentrate composition. Typically, one or more base oils are present in the concentrate composition at an amount of 0.1 to 49 mass%, alternately 5 to 40 mass%, alternately to 10 to 30 mass%, alternately 15 to 25 mass%, based upon the weight of the concentrate composition.B. Antioxidants

[0209] The present invention relates to antioxidants that disrupt oxidation and increase the useful life of lubricating oils. More particularly, the present invention may describe antioxidant compositions comprising a plurality of antioxidative lubricant additives. In embodiments, the antioxidant comprises diphenylamine antioxidant and optionally one or more additional antioxidants and / or optionally one or more carboxylate detergents, where mono-Cs g-alkyl substituted diphenylamines are absent or present at less than 15 mass% (such as less than 10 mass%, such as less than 5 mass%, such as less than 3 mass%) and, optionally, unsubstituted diphenylamine is present at 0.01 mass% or less, based upon the weight of the diphenylamine antioxidant, to provide enhanced oxidative performance. Primary antioxidants, optional additional antioxidants and detergents compatible with the present invention are described herein.

[0210] The antioxidant composition useful herein typically comprises a primary antioxidant and one or more optional additional antioxidants. Preferred primary antioxidants of the present invention typically comprise diphenylamine anti-oxidants comprising at least 85 mass% (such as 90 mass% or more, such as 95 mass% or more, such as 99 mass% or more, such as 100 mass%) of di-Cs-9-alkyl substituted diphenylamine and 15 mass% or less, (such as 10 mass% or less, such as 5 mass% or less, such as 1 mass% or less, such as 0 mass%) of mono-Cs g-alkyl substituted diphenylamine are present, based upon the weight of the mono- and di- Cs-g-alkyl substituted diphenylamines.

[0211] The primary antioxidants employed in the lubricating oil of the present invention are typically represented by Formula (III):where each Rais independently a linear Cs-9 alkyl or branched Cs-9 alkyl group, n is 0 or 1 , z is 0 or 1 and w is 0 or 1 , where the at least 85% of the primary antioxidant is n is 1 , z is 1 and w is 0, based upon the weight of compounds represented by Formula (III). Examples of branched Cs-9 alkyl groups (C9H18 and or CsH alkyl groups) useful herein include, isononyl, methyloctyl, ethylheptyl, dimethylheptyl, propylhexyl, trimethylhexyl, methylethylhexyl, tetramethylpentyl, dimethylethylpentyl, diethylpentyl, butylpentyl, isooctyl, methylheptyl, dimethylhexyl, ethylhexyl, trimethylpentyl, methylethylpentyl, dimethylethylbutyl, diethylbutyl, methylpropylbutyl, and the like.

[0212] In embodiments, Racomprises branched alkyl groups, such as 2,4,4-trimethylpentyl.

[0213] In embodiments the diphenyl antioxidants employed in the lubricating oil of the present invention comprise less than a) 10 mass% N-phenyl-4-(2,4,4-trimethylpentan-2-yl)aniline, b) more than 80 mass% ofbis(4-(2,4,4-trimethylpentan-2-yl)phenyl)amine, and c) less than 10 mass% of tri 2,4-bis(2,4,4- trimethyl pentan-2-yl)-N-(4-(2,4,4-trimethylpentan-2-yl)p henyl)anili ne, based upon the weight of a), b) and c).

[0214] In embodiments, the diphenylamine antioxidant composition may comprise less than 15 mass%, or 14 mass% or less, or 13 mass% or less, or 12 mass% or less, or 11 mass% or less, or 10 mass% or less, 9 mass% or less, or 8 mass% or less, or 7 mass% or less, or 6 mass% or less, or 5 mass% or less, or 4 mass% or less, 3 mass% or less, or 2 mass% or less, or 1 mass% or less, or 0.5 mass% or less, or 0.1 mass% or less, or 0 mass%) of mono-Cs-9-alkyl substituted diphenylamines represented by Formula (III), where w is 0, n is 1 and z is 0), based upon the weight of the diphenylamine antioxidant composition.

[0215] In embodiments, the diphenylamine antioxidant composition may comprise 0.0010 mass% to less than 0.5 mass%, or 0.4 mass% or less, or 0.3 mass% or less, or 0.2 mass% or less, or 0.1 mass% or less, or 0.01 mass% or less, 0.001 mass% or less, or 0 mass%) of unsubstituted diphenylamines represented by Formula (III), where w is 0, n is 0 and z is 0), or Formula (X), where w is 0, n is 0, v is 0 and z is 0, based upon the weight of the diphenylamine antioxidant composition.

[0216] In embodiments, the diphenylamine antioxidant composition may comprise more than 85 mass%, or 86 mass% or more, or 87 mass% or more, or 88 mass% or more, or 89 mass% or more, or 90 mass% or more, or 91 mass% or more, or 92 mass% or more, or 93 mass% or more, or 94 mass% or more, or 95 mass% or more, or 96 mass% or more, or 97 mass% or more, or 98 mass% or more, or 99 mass% or more, or 99.5 mass% or more, or 99.9 mass% or more, or 100 mass% of di-Cs g-alkyl substituted diphenylamines represented by Formula (III), where n is 1 , w is 0, and z is 1 , based upon the weight of the diphenylamine antioxidant composition. This invention further relates to an antioxidant composition comprising an antioxidant composition comprising or made by admixing:1) phenylamine antioxidant comprising one or more di-Cs g-alkyl substituted diphenylamine as represented by Formula (III) where n is 1 , z is 1 and w is 0, and2) optionally, one or more additional antioxidants (such as diphenylamines other than 1) above, hindered phenol, sulfurized fatty acid esters, molybdenum containing compounds, ashless dithiocarbamates, and the like), where, alkyl substituted diphenylamine(s) and or unsubstituted diphenylamine represented by Formula (III) where n is 0, w is 0 and z is 1 or 0, are absent or present at less than 15 mass%, such as less than 0.1 mass%, such as less than 0.01 mass%, based upon the weight of diphenylamine antioxidant composition.

[0217] In embodiments, the di-Cs g-alkyl substituted diphenylamine (such as represented by Formula (III) where n is 1 and z is 1 and w is 0), has: i) more than 90% (such as 95% or more, such as 99% or more, such a 100%) of the alkyl groups in the para position (i.e., para to the bond to the phenylamine);(ii) optionally less than 10%, such 5% or less, such as 0%, of the alkyl groups in an ortho position (i.e., ortho to the bond to the phenylamine); and iii) optionally less than 10%, such 5% or less, such as 0%, of the alkyl groups in a meta position (i.e., meta to the bond to the phenylamine), based upon the weight of the di-Cs g-alkyl substituted diphenylamine.

[0218] In embodiments, the di-Cs 9-alkyl substituted diphenyl amine such as represented by Formula (III) where n is 1 , z is 1 and w is 0), comprises less than 5 mass% (or less than 4 mass%, or less than 3 mass%, or less than 2 mass%, or less than 1 mass%, or 0 mass%) of the isomers shown below, where each R is independently a linear Cs-9 alkyl or branched Cs-9 alkyl group:based upon the weight of di-Cs 9-alkyl substituted diphenyl amine represented by Formula (III) where n is 1 , z is 1 and w is 0.

[0219] In general, the diphenylamine isomers can be separated by well-known techniques such as distillation (such as thin film evaporation and or flash distillation), dialysis, recrystallization, chromatography, and the like. The isomer content may be determined by mass spectrometry as described in the Experimental Section.

[0220] The di-Cs -9-alkyl substituted diphenylamines described herein are typically synthesized by reaction of nonene (branched or linear) and or diisobutylene with diphenyl amine in the presence of Lewis acid catalyst. Further, di-Cs 9-alkyl substituted diphenylamines may also be synthesized by a reaction of nonyl (branched or linear) and or para-octyl phenol with ammonia in the presence of hydrogen transfer catalyst and hydrogen (see for example, see US 5,449,829 which exemplifies such synthesis using a Pd / C catalyst).

[0221] The primary antioxidant, such as the Cs 9-alkyl substituted diphenylamine compositions described herein, may be present at about 0.01 mass% to about 20 mass% of the lubricating oil composition, such as from about 0.05 mass% to about 15 mass%, 0.1 mass% to about 10 mass%, 0.5 mass% to about 8 mass%, or 1 mass% to about 5 mass%.

[0222] When present in a concentrate, the primary antioxidant, such as the Cs 9-alkyl substituted diphenylamine compositions described herein, may be present at about 0.01 mass% to about 40 mass% of the concentrate, such as from about 0.020 mass% to about 30 mass%, such as from about 0.025 mass% to about 20 mass%, such as from about 0.05 mass% to about 15 mass%, 0.1 mass% to about 10 mass%, 0.5 mass% to about 8 mass%, or 1 mass% to about 5 mass%.Additional Antioxidants

[0223] The present invention may employ one or more additional antioxidants in combination with the primary antioxidants. The additional antioxidants may be present at about 0.01 mass% to about 20 mass% of the lubricating oil composition, such as from about 0.05 mass% to about 15 mass%, 0.1 mass% to about 10 mass%, 0.5 mass% to about 8 mass%, or 1 mass% to about 5 mass%.

[0224] When present in a concentrate, the additional antioxidant may be present at about 0.01 mass% to about 30 mass% of the concentrate, such as from about 0.025 mass% to about 20 mass%, such as from about 0.05 mass% to about 15 mass%, 0.1 mass% to about 10 mass%, 0.5 mass% to about 8 mass%, or 1 mass% to about 5 mass%.

[0225] A number of additional antioxidants are compatible with the present invention. Examples of additional antioxidants include hindered phenols, molybdenum succinimides, and dithiocarbamates (such Zn or Mo-dialkyldithiocarbamates). These oil-soluble components are generally known.

[0226] A preferred additional antioxidant employed in the lubricating oil of the present invention may be a hindered phenol, such as a sterically hindered phenol. The 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 Ce+alkyl groups and the alkylene coupled derivatives of these hindered phenols. Examples of phenolic materials of this type include 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, such as C? Cg-(branched)-alkyl 3-(3,5-di-tert-butyl-4- hydroxyphenyl)propanoate) available as IRGANOX™ L135. 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).

[0227] Particularly useful hindered phenol antioxidants often contains a secondary butyl and / or a tertiary butyl group as a sterically hindering group. The phenol group is often further substituted with a hydrocarbyl group and / or a bridging group linking to a second aromatic group. Suitable hindered phenols include, but are not limited to, 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4- ethyl-2,6-di-tert-butylphenol, 4- propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert- butylphenol, 4-dodecyl-2,6-di-tert-butylphenol, 4- alkylester-2,6-di-tert-butylphenol, such as C? Cg-(branched)-alkyl 3-(3,5-di-tert-butyl-4- hydroxyphenyl)propanoate).

[0228] A preferred hindered phenol may be represented by the formula:

[0229] 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 US Patent No. 8,048,833.

[0230] Non-phenolic oxidation inhibitors, which may be used include aromatic amine antioxidants (other than those represented by Formula (III) above) 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 RsRgRioN, where Rs is an aliphatic, aromatic orsubstituted aromatic group, R9 is an aromatic or a substituted aromatic group, and Rw is H, alkyl, aryl or RnS(0)xRi2 where Rn 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 Rs may contain from 1 to about 20 carbon atoms, and preferably contains from about 6 to 12 carbon atoms. The aliphatic group is typically a saturated aliphatic group. Preferably, both Rs and R9 are aromatic or substituted aromatic groups, and the aromatic group may be a fused ring aromatic group such as naphthyl. Aromatic groups Rs and R9 may be joined together with other groups such as S.

[0231] Typical aromatic amines antioxidants have alkyl substituent groups of at least about 6 carbon atoms. Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl, and decyl. Generally, the aliphatic groups will not contain more than about 14 carbon atoms. The general types of amine antioxidants useful in the present compositions include phenyl naphthylamines, phenothiazines, imidodibenzyls and diphenyl phenylene diamines. Mixtures of two or more aromatic amines are also useful. Polymeric amine antioxidants can also be used.

[0232] Sulfur-containing antioxidants are also useful herein. In particular, one or more oil-soluble or oil- dispersible sulfur-containing antioxidant(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. Suitably, the lubricating oil composition(s) of the present disclosure may include the one or more sulfur-containing antioxidant(s) in an amount to provide the lubricating oil composition with from 0.02 to 0.2, preferably from 0.02 to 0.15, even more preferably 0.02 to 0.1 , even more preferably 0.04 to 0.1 , mass% sulfur based on the total mass of the lubricating oil composition. Optionally the oil-soluble or oil-dispersible sulfur-containing antioxidant(s) are selected from sulfurized C4 to C25 olefin(s), sulfurized aliphatic (C7 to C29) hydrocarbyl fatty acid ester(s), ashless sulfurized phenolic antioxidant(s), sulfur-containing organo-molybdenum compound(s), and combinations thereof. For further information, on sulfurized materials useful as antioxidants herein, please see US Patent No. 10,731 ,101 (col 15, In 55 to col 22, In 12).

[0233] An additional antioxidant employed in the lubricating oil of the present invention may be a molybdenum succinimide. The mono and polysuccinimides that can be used to prepare the molybdenum succinimide complexes described herein are disclosed in numerous references and are well known in the art. Certain fundamental types of succinimides and the related materials encompassed by the term of art "succinimide" are taught in U.S. Pat. No's. 3,219,666; 3,172,892; and 3,272,746, the disclosures of which are hereby incorporated by reference. The term "succinimide" is understood in the art to include many of the amide, imide, and amidine species which may also be formed. The predominant product however is a succinimide and this term has been generally accepted as meaning the product of a reaction of an alkenyl substituted succinic acid or anhydride with a nitrogen-containing compound.

[0234] Suitable dithiocarbamates include, but are not limited to, dithiocarbamates wherein the metal is zinc, copper or molybdenum, ashless thiocarbamates or dithiocarbamates (i.e., essentially metal free) such as methylenebis(dialkyldithiocarbamate), ethylenebis(dialkyldithiocarbamate), and isobutyl disulfide-2, 2'- bis(dialkyldithiocarbamate) where the alkyl groups of the dialkyldithiocarbamate can preferably have from 1 to 6 carbon atoms. Examples of preferred ashless dithiocarbamates are methylenebis(dibutyldithiocarbamate), ethylenebis(dibutylthiocarbamate) and isobutyl disulfide-2, 2'-bis(dibutyldithiocarbamate).

[0235] The additional antioxidant employed in the lubricating oil of the present invention may be a sterically hindered phenol described in US 9,512,380, such as those shown at columns 82 to 100.

[0236] Antioxidant additives may be used in an amount of about 0.01 to 10 (alternately 0.01 to 5, alternately 0.01 to 3) mass%, alternately about 0.03 to 5 mass%, alternately 0.05 to less than 3 mass%, based upon the weight of the lubricating composition.

[0237] 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.

[0238] The lubricating composition according to the present disclosure may further comprise one or more additives such as detergents, friction modifiers, 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, pp. 477-526, and several are discussed in further detail below.C. Detergents

[0239] The lubricating composition may comprise one or more metal detergents (such as blends of metal detergents) also referred to as a "detergent additive." Metal detergents typically 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. Detergents generally comprise a polar head with a long hydrophobic tail, with the polar head comprising a metal salt of an acidic organic compound. The salts may contain a substantially stoichiometric amount of the metal in which case they are usually described as normal or neutral salts, and would typically have a total base number ("TBN" as measured by ASTM D2896) of up to 150 mgKOH / g, such as from 0 to 80 (or 5-30) mgKOH / 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 100 mgKOH / g or more (such as more than 150 mgKOH / g, such as 200 mgKOH / g or more), and typically will have a TBN of 250 mgKOH / g or more, such as 300 mgKOH / g or more, such as from 200 to 800 mgKOH / g, 225 to 700 mgKOH / g, 250 to 650 mgKOH / g, or 300 to 600 mgKOH / g, such as 150 to 650 mgKOH / g.

[0240] Suitable detergents include, oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, naphthenates and other oil-soluble carboxylates of a metal, particularly the 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), particularly, sodium, potassium, lithium, calcium, and magnesium, such as calcium and / or magnesium. Furthermore, the detergent may comprise a hybrid detergent comprising any combination of sodium, potassium, lithium, calcium, or magnesium salts of sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and naphthenates or other oil-soluble carboxylates of a Group 1 and / or 2 metal.

[0241] Sulfonate detergents are particularly useful in the blends described herein. In particular overbased calcium sulfonate, magnesium sulfonate, combinations of magnesium and calcium sulfonate detergents, and hybrid detergents comprising at least one sulfonate based detergent are useful in the blends described herein.

[0242] Preferably, the detergent additive(s) useful in the present disclosure comprises calcium and / or magnesium metal salts. The detergent may be one or more calcium and / or magnesium carboxylate (e.g., salicylate), sulfonate, or phenate detergents. More preferably, the detergent additives are selected from magnesium salicylate, calcium salicylate, magnesium sulfonate, calcium sulfonate, magnesium phenate, calcium phenate, and hybrid detergents comprising two, three, four, or more of more of these detergents and / or combinations thereof.

[0243] Magnesium based detergents are useful in the blends described herein. In particular, magnesium carboxylate (e.g., salicylate), sulfonate, or phenate detergents are useful in the blends described herein, such as magnesium salicylate, magnesium sulfonate, magnesium phenate, combinations of magnesium salicylate and magnesium sulfonate, and hybrid detergents comprising at least one magnesium based detergent as described below.

[0244] The overbased metal-containing detergent may be sodium salts, calcium salts, magnesium salts, or mixtures thereof of the phenates, sulfur-containing phenates, sulfonates, salixarates, and salicylates. Overbased phenates and salicylates typically have a total base number of 180 to 650 mgKOH / g, such as 200 to 450 TBN mgKOH / g. Overbased sulfonates typically have a total base number of 250 to 600 mgKOH / g, or 300 to 500 mgKOH / g. In 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 Application Publication No. 2005 / 065045 (and granted as US Patent No. 7,407,919). The overbased detergent may be present at 0 mass% to 15 mass%, or 0.1 mass% to 10 mass%, or 0.2 mass% to 8 mass%, or 0.2 mass% to 3 mass%, based upon of the lubricating composition. For example, in a heavy-duty diesel engine, the detergent may be present at 2 mass% to 3 mass% of the lubricating composition. For a passenger car engine, the detergent may be present at 0.2 mass% to 1 mass% of the lubricating composition.

[0245] The detergent additive(s) may comprise one or more magnesium sulfonate detergents. The magnesium detergent may be a neutral salt or an overbased salt. Suitably the magnesium detergent is an overbased magnesium sulfonate having a TBN of from 80 to 650 mgKOH / g (ASTM D2896), such as 200 to 500 mgKOH / g, such as 240 to 450 mgKOH / g.

[0246] Alternately, may comprise one or more magnesium salicylate detergents, preferably the detergent additive(s) is a magnesium salicylate. Suitably the magnesium detergent is a magnesium salicylate having TBN of from 30 to 650 mgKOH / g (ASTM D2896), such as 50 to 500 mgKOH / g, such as 200 to 500 mgKOH / g, such as 240 to 450 mgKOH / g or alternately of 150 mgKOH / g or less, such as 100 mgKOH / g or less.

[0247] Alternately, the detergent additive(s) is a combination of magnesium salicylate and magnesium sulfonate.

[0248] The magnesium detergent typically provides the lubricating composition thereof with from 200 to 5000 ppm of magnesium atoms, suitably 200-4000 ppm, from 200-2000 ppm, from 300 to 1500 or from 450- 1200 ppm of magnesium atoms (ASTM D5185). In embodiments, the magnesium-based detergent providinghigh amounts of Mg to compositions described herein, provides at least 400 ppm (such as 400 ppm to 20,000 ppm, such as 450 to 10,000 ppm, such as 500 ppm to 8000ppm, such as 600 ppm or more, such as 700 ppm or more, such as 800 ppm or more, such as 1000 ppm or more, such as 1200 ppm or more, such as 2000 ppm or more, such as 3000 ppm or more, such as 4000 ppm or more, such as 5000 ppm or more) of magnesium atoms (ASTM D5185) to the composition (booster pack, concentrate, lubricating oil composition, etc. described herein). The detergent may comprise one or more magnesium detergents such as magnesium carboxylate (e.g., salicylate), sulfonate, or phenate detergent. The detergent may comprise one or more magnesium sulfonates.

[0249] Suitably the magnesium detergent, such as a magnesium salicylate, sulfonate, or phenate, has a TBN of from 30 to 700 mgKOH / g (ASTM D2896), such as 50 to 650 mgKOH / g, such as 200 to 500 mgKOH / g, such as 240 to 450 mgKOH / g or alternately of 150 mgKOH / g or less, such as 100 mgKOH / g or less, or 200 mgKOH / g or more, or 300 mgKOH / g or more, or 350 mgKOH / g or more.

[0250] The detergent composition may comprise (or consist of) a combination of one or more magnesium sulfonate detergents and one or more calcium salicylate detergents. The combination of one or more magnesium sulfonate detergents and one or more calcium salicylate detergents preferably provides the lubricating composition thereof with: 1) from 200-4000 ppm of magnesium atoms, suitably from 200-2000 ppm, from 300 to 1500 ppm or from 450-1200 ppm of magnesium atoms (ASTM D5185), and 2) at least 500 ppm, preferably at least 750 ppm, more preferably at least 900 ppm of atomic calcium, such as from 500- 4000 ppm, preferably from 750-3000 ppm, more preferably from 900-2000 ppm atomic calcium atoms (ASTM D5185).

[0251] The detergent may comprise one or more calcium detergents such as calcium carboxylate (e.g., salicylate), sulfonate, or phenate detergent. The detergent may comprise one or more calcium salicylates.

[0252] Suitably, the calcium detergent is a calcium salicylate, sulfonate, or phenate having a TBN of from 30 to 700 mgKOH / g, 30 to 650 mgKOH / g (ASTM D2896), such as 50 to 650 mgKOH / g, such as 200 to 500 mgKOH / g, such as 240 to 450 mgKOH / g or alternately of 150 mgKOH / g or less, such as 100 mgKOH / g or less, or 200 mgKOH / g or more, or 300 mgKOH / g or more, or 350 mgKOH / g or more.

[0253] Suitably, the calcium detergent is a calcium carboxylate (salicylate) detergent having a TBN of from 30 to 700 mgKOH / g, 30 to 650 mgKOH / g (ASTM D2896), such as 50 to 650 mgKOH / g, such as 200 to 500 mgKOH / g, such as 240 to 450 mgKOH / g or alternately of 150 mgKOH / g or less, such as 100 mgKOH / g or less, or 200 mgKOH / g or more, or 300 mgKOH / g or more, or 350 mgKOH / g or more.

[0254] Calcium detergent is typically present in amount sufficient to provide at least 500 ppm, preferably at least 750 more preferably at least 900 ppm atomic calcium and no more than 4000 ppm, preferably no more than 3000 ppm, more preferably no more than 2000 ppm atomic calcium to the lubricating oil composition (ASTM D5185). If present, any calcium detergent is suitably present in amount sufficient to provide at from 500-4000 ppm, preferably from 750-3000 ppm more preferably from 900-2000 ppm atomic calcium to the lubricating oil composition (ASTM D5185).

[0255] In embodiments, the calcium salicylate-based detergent provides at least 400 ppm (such as 400 ppm to 20,000 ppm, such as 450 to 10,000 ppm, such as 500 ppm to 8000ppm, such as 600 ppm or more, such as 700 ppm or more, such as 800 ppm or more, such as 1000 ppm or more, such as 1200 ppm or more,such as 2000 ppm or more, such as 2100 ppm or more, such as 3000 ppm or more, such as 4000 ppm or more, such as 5000 ppm or more) of calcium atoms (ASTM D5185) to the composition (booster pack, concentrate, lubricating oil composition, etc.).

[0256] Preferred substituents in oil-soluble salicylic acids are alkyl substituents. In alkyl - substituted salicylic acids, the alkyl groups advantageously contain 5 to 100, preferably 9 to 30, especially 14 to 20, carbon atoms. Where there is more than one alkyl group, the average number of carbon atoms in all of the alkyl groups is preferably at least 9 to ensure adequate oil solubility.

[0257] In preferred embodiments, the composition of the present invention may include one or more alkali or alkaline earth metals carboxylate (such as barium, sodium potassium, lithium, calcium, and / or magnesium salicylate) detergents. Such carboxylate detergents (such as salicylate detergents) may be present at about 0.01 mass% to about 10 mass% of the lubricating oil composition, such as from about 0.05 mass% to about 8 mass%, 0.1 mass% to about 5 mass%, 0.5 mass% to about 4 mass%, or 1 mass% to about 3 mass%. Carboxylate detergents include aromatic carboxylates (e.g., salicylates, naphthenates), aliphatic carboxylates (e.g., stearates), and the like. The carboxylate detergents may be overbased (as measured by ASTM D2896), for example, low overbased (TBN from 15 to 30), medium overbased (TBN from 31 to 170), high overbased (TBN from 171 to 400) and high high overbased (TBN > 400) carboxylate detergents. One or more overbased carboxylate detergents (e.g., low overbased and medium overbased) may be used.

[0258] Sulfonate and carboxylate detergents may be prepared as described at Paragraph

[0374] to

[0376] of US 20240141156 A1.

[0259] In embodiments, the ratio of atomic detergent metal to atomic molybdenum in the lubricating oil composition may be less than 3:1 , such as less than 2:1.

[0260] Further, as metal organic and inorganic base salts, which are used as detergents can contribute to the sulfated ash content of a lubricating oil composition, in embodiments of the present disclosure, the amounts of such additives are minimized. In order to maintain a low sulfur level, salicylate detergents can be used and the lubricating composition herein may comprise one or more salicylate detergents (said detergents are preferably used in amounts in the range of 0.05 to 20.0 mass%, more preferably from 1 .0 to 10.0 mass% and most preferably in the range of from 2.0 to 5.0 mass%, based on the total weight of the lubricating composition).

[0261] The total sulfated ash content of the lubricating composition herein is typically not greater than 2.0 mass%, alternately at a level of not greater than 1 .0 mass% and alternately at a level of not greater than 0.8 mass%, based on the total weight of the lubricating composition as determined by ASTM D874.

[0262] Furthermore, it is useful that each of the detergents, independently, have a TBN (total base number) value in the range of from 10 to 700 mgKOH / g, 10 to 500 mgKOH / g, alternately in the range of from 100 to 650, alternately in the range of from 10 to 500 mgKOH / g, alternately in the range of from 30 to 350 mgKOH / g, and alternately in the range of from 50 to 300 mgKOH / g, as measured by ASTM D2896.

[0263] The sulfonate detergents (such as Ca and / or Mg sulfonate detergents) may be present in an amount to deliver 0.1 mass% to 1.5 mass%, or 0.15 to 1.2 mass%, or 0.2 mass% to 0.9 mass% sulfonate soap to the lubricant composition.

[0264] The salicylate detergents (such as Ca and / or Mg salicylate detergents) are present in an amount todeliver 0.3 mass% to 1 .4 mass%, or 0.35 mass% to 1 .2 mass%, or 0.4 mass% to 1 .0 mass% salicylate soap to the lubricant composition.

[0265] The sulfonate soap may be present in an amount 0.2 mass% to 0.8 mass% of the lubricant composition, and the salicylate soap may be present in an amount 0.3 mass% to 1 .0 mass% of the lubricant composition.

[0266] The total of all alkaline earth metal detergent soap may be present in an amount 0.6 mass% to 2.1 mass%, or 0.7 mass% to 1 .4 mass% of the lubricant composition.

[0267] Typically, lubricating compositions formulated for use in heavy-duty diesel engines comprise detergents at from about 0.1 to about 10 mass%, alternately from about 0.5 to about 7.5 mass%, alternately from about 1 to about 6.5 mass%, based on the lubricating composition.

[0268] Typically, lubricating compositions formulated for use in a passenger-car engines comprise detergents at from about 0.1 to about 10 mass%, alternately from about 0.5 to about 7.5 mass%, alternately from about 1 to about 6.5 mass%, based on the lubricating composition.

[0269] Typically, lubricating compositions formulated for use in a drive train (e.g., transmissions) comprise detergents at from about 0.1 to about 10 mass%, alternately from about 0.5 to about 7.5 mass%, alternately from about 2 to about 6.5 mass%, based on the lubricating composition.D. Friction Modifiers

[0270] 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, or lubricity agents or oiliness agents, and other such agents that change the ability of base oils, formulated lubricating 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 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.

[0271] Illustrative friction modifiers may include, for example, organometallic compounds or materials, or mixtures thereof. Illustrative organometallic friction modifiers useful in the lubricating oil formulations of this disclosure include, for example, tungsten and / or molybdenum compounds, such as molybdenum amine, molybdenum diamine, an organotungstenate, a molybdenum dithiocarbamate, molybdenum dithiophosphates, molybdenum amine complexes, molybdenum carboxylates, and the like, and mixtures thereof. Examples of useful molybdenum-containing compounds may conveniently include molybdenum dithiocarbamates, trinuclear molybdenum compounds, for example, as described in PCT Publication No. WO 98 / 26030, sulfides of molybdenum and molybdenum dithiophosphate.

[0272] Other known 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. Examples of such oil-soluble organo-molybdenum compounds include dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, sulfides, and the like, and mixtures thereof. Particularly preferred are molybdenum dithiocarbamates, dialkyldithiophosphates, alkyl xanthates and alkylthioxanthates.

[0273] Additionally, the molybdenum compound may be an acidic molybdenum compound. Thesecompounds will react with a basic nitrogen compound as measured by ASTM test D664 or D2896 titration procedure and are typically hexavalent. Included are molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, e.g., hydrogen sodium molybdate, MoOCw, MoC B^, MO2O3C16, molybdenum trioxide or similar acidic molybdenum compounds.

[0274] Useful molybdenum compounds include those described at paragraphs [0393[ to

[0394] of US 20240141156 A1. Lubricating oil compositions useful in all aspects of the present disclosure preferably contain at least 10 ppm, at least 30 ppm, at least 40 ppm and more preferably at least 50 ppm molybdenum. Suitably, lubricating oil compositions useful in all aspects of the present disclosure contain no more than 1000 ppm, no more than 750 ppm, or no more than 500 ppm of molybdenum. Lubricating oil compositions useful in all aspects of the present disclosure preferably contain from 10 to 1000, such as 30 to 750 or 40 to 500, ppm of molybdenum (measured as atoms of molybdenum).

[0275] Organomolybdenum-based friction modifiers useful herein, such as in compositions and lubricating oils, include those described in this Section D and may in any embodiment include compounds such as organomolybdenum compounds of dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, sulfides, and the like, and mixtures thereof. Desirable organomolybdenum-based friction modifiers include molybdenum dithiocarbamates, dialkyldithiophosphates, alkyl xanthates and alkylthioxanthates. In a more preferred embodiment, the organomolybdenum-based friction modifiers are selected from dimeric molybdenum dialkyldithiocarbamates and trimeric molybdenum dialkyldithiocarbamates, and most preferably dimeric dialkyldithiocarbamate (where the alkyl groups are independently selected from C 6 to C14 alkyl groups, and may be selected from C10-C14 and C6-C12 alkyl groups, such as hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, or isomers thereof).

[0276] For more information on useful friction modifiers containing Mo, please see US Patent No. 10,829,712 (col 8, In 58 to col 11 , In 31).

[0277] 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 US Patent 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. Typically, the total amount of organic ashless friction modifier in a lubricant according to the present disclosure does not exceed 5 mass%, based on the total mass of the lubricating oil composition and preferably does not exceed 2 mass% and more preferably does not exceed 0.5 mass%.

[0278] 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, and mixtures thereof as described in paragraphs

[0399] -

[0403] of US 20240141156 A1.

[0279] Ashless friction modifiers, such as glycerol-based friction modifiers useful herein, such as incompositions and lubricating oils, include those described in this Section D and may in any embodiment include glycerol-based friction modifiers such as glycerol monooleates, saturated mono-, di-, and tri-glyceride esters, glycerol monostearates, and polyols. In a preferred embodiment the glycerol-based friction modifier is glycerol mono-oleate. Useful concentrations of friction modifiers may range from 0.01 mass% to 5 mass%, or about 001 mass% to about 2.5 mass%, or about 0.05 mass% to about 1 .5 mass%, or about 0.051 mass% to about 1 mass%. Concentrations of molybdenum-containing materials are often described in terms of Mo metal concentration. Advantageous concentrations of Mo may range from 25 ppm to 700 ppm or more, and often with a preferred range of 50-200 ppm. 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.F. Pour Point Depressants

[0280] 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 depressants 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, and terpolymers of dialkylfumarates, vinyl esters of fatty acids and allyl vinyl ethers. Particularly useful PPD’s include dialkyl fumarate / vinyl acetate copolymers (such as one or more Cs to C20 dialkyl fumarate / vinyl acetate copolymers, such as one or more C12 to Cie dialkyl fumarate / vinyl acetate copolymers). US Patent 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 mass%, preferably about 0.01 to 1 .5 mass%, based upon the weight of the lubricating composition.G. Anti-Foam Agents

[0281] Anti-foam agents may advantageously be added to lubricant compositions described herein. These agents prevent or retard the formation of stable foams. Silicones, fluoro-silicones, and / organic polymers are typical anti-foam agents. For example, polysiloxanes, such as silicon oil or polydimethyl siloxane, provide anti-foam properties.

[0282] Anti-foam agents are commercially available (such as polydimethylsiloxane (PDMS) and others described in paragraphs

[0416] -

[0423] of US 20240141156 A1) and may be used in minor amounts such as 5 mass% or less, 3 mass% or less, 1 mass% or less, 0.1 mass% or less, such as from 5 to mass% to 0.1 ppm such as from 3 mass% to 0.5 ppm, such as from 1 mass% to 10 ppm, such as from 1 ppm to 1 mass% based upon the weight of the lubricating composition.

[0283] In embodiments, silicone anti-foam 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 include polydimethylsiloxane, phenylmethyl polysiloxane, linear, cyclic or branched siloxanes, silicone polymers and copolymers, and / organo- silicone copolymers.H. Viscosity Modifiers

[0284] 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 (also referred to as a dispersant viscosity modifiers or DVMs) that can function as both a viscosity modifier and a dispersant. Typical molecular weights of the viscosity modifier polymers are between about 10,000 to 1 ,500,000 g / mol, more typically about 20,000 to 1 ,200,000 g / mol, and even more typically between about 50,000 and 1 ,000,000 g / mol.

[0285] Examples of suitable viscosity modifiers are linear or radial (star-shaped) polymers and copolymers of methacrylate, butadiene, olefins (such as isobutylene, butadiene, and the like), 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 block copolymers of styrene and isoprene, 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.

[0286] 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 radial (star) polymers useful as viscosity modifiers herein include those commercially available from Infineum International Limited, e.g., under the trade series designations "SV200™" and "SV600™". Hydrogenated diene-styrene block copolymers useful as viscosity modifiers herein are commercially available from Infineum International Limited, e.g., under the trade designation "SV 50™".

[0287] 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).

[0288] 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).

[0289] Vinyl aromatic-containing polymers useful as viscosity modifiers may have a Kinematic viscosity at 100° C of 20 cSt or less, such as 15 cSt or less, such as 12 cSt or less, but may be diluted (such as in GroupI, II, and / or III basestock) to higher Kinematic viscosities at 100° C, such as to 40 cSt or more, such as 100 cSt or more, such as 1000 cSt or more, such as 1000 to 2000 cSt. ) .

[0290] Dispersant viscosity modifiers (also described as dispersants above) useful herein include the amide, imide, and / or ester functionalized partially or fully saturated polymers comprising C4-5 olefins as described in United States application USSN 18 / 480,571, filed October 4, 2023, which is herein incorporated by reference in its entirety. Preferred DVM's include polymers referred to as “functionalized polymers” described in USSN 18 / 480,571 , and preferably are a functionalized hydrogenated polyisoprene family of polymers for use in lubricating oil compositions, which are disclosed in commonly owned United States Application 18 / 480,571 , filed October 4, 2023 which claims priority to and the benefit of U.S. Provisional Application No. 63 / 379,006, filed October 11 , 2022, which is herein incorporated by reference in its entirety. In an advantageous form, the lubricating oil composition described herein further optionally includes one or more functionalized polymers described in USSN 18 / 480,571 as dispersant viscosity modifiers at from 0.2 to 2.0 mass%, or 0.4 to 1 .8 mass%, or 0.6 to 1 .6 mass%, or 0.8 to 1 .4 mass%, or 1 .0 to 1 .2 mass% of the lubricating oil composition, where the functionalized polymers comprises an amide, imide, and / or ester functionalized partially or fully saturated polymer comprising C4-5 olefins having: i) an Mw / Mn of less than 2, or less than 1.8, or less than 1.6; ii) a Functionality Distribution (Fd) value of 3.5 or less, or 3.2 or less, or 3.0 or less, or 2.5 or less; iii) an Average Functionality Value (Fv) of 1 .4 to 20 FG g rafts / poly mer chain, such as 1 .4 to 15 FG grafts / polymer chain, such as 3 to 12.5 FG grafts / polymer chain, such as 4 to 10 FG grafts / polymer chain , such as 5 to 10 FG grafts / polymer chain, such as 6 to 10 FG grafts / polymer chain; and iv) an Mn of 10,000 g / mol or more, or 15,000 g / mol or more, or 20,000 g / mol or more, or 25,000 g / mol or more (GPC-PS) of the polymer prior to functionalization, optionally provided that, if the polymer prior to functionalization is a copolymer of isoprene and butadiene, then the Mn of the copolymer is greater than 25,000 g / mol, or 30,000 g / mol or more, or 35,000 g / mol or more, or 40,000 g / mol or more (GPC-PS). (GPC-PS is performed as set out in United States Patent Application USSN 18 / 480,571 , filed October 4, 2023). For the functionalized polymer described in 18 / 480,571 useful herein, Average Functionality [also referred to as Average Functionality Value (Fv)] and Functionality Distribution (Fd) value are determined by Gel Permeation Chromatography using polystyrene standards as described in the Experimental section of US Patent Application USSN 18 / 480,571, filed October 4, 2023, "FG" means functional group. The functionalized polymers described in 18 / 480,571 useful herein may include at least 50 %, or at least 60%, or at least 70% of 1 ,4-insertions of monomer, such as isoprene monomer. Furthermore, the functionalized polymers described in 18 / 480,571 useful herein may include a partially or fully saturated homopolyisoprene containing one or more pendant amine groups and having an Mn of 25,000 to 100,000 g / mol, or 35,000 to 90,000 g / mol, or 45,000 to 80,000 g / mol, or 55,000 to 75,000 g / mol (GPC-PS) and at least 50%, or at least 60%, or at least 70% of 1 ,4-insertions prior to functionalization. The functionalized polymers described in 18 / 480,571 useful herein may be absent of styrene repeat units, or absent of butadiene repeat units, or is not a homo-polyisobutylene, or is not a copolymer of isoprene and butadiene. For purposes of this invention and the claims thereto, the dispersant viscosity modifiers of amide, imide, and / or ester functionalized partially or fully saturated polymers comprising C4-5 olefins as described in United States application USSN 18 / 480,571 , filed October 4, 2023, are included with dispersants for weight % determinations.

[0291] Other useful DVM's include functionalized olefin copolymers (such as amine functionalized ethylene propylene copolymers).

[0292] Typically, the viscosity modifiers may be used in an amount of about 0.01 to about 10 mass%, such as about 0.1 to about 7 mass%, such as 0.1 to about 4 mass%, such as about 0.2 to about 2 mass%, such as about 0.2 to about 1 mass%, and such as about 0.2 to about 0.5 mass%, based on the total weight of the formulated lubricant composition.

[0293] Viscosity modifiers are typically added as concentrates, in large amounts of diluent oil. The "as delivered" viscosity modifier typically contains from 20 mass% to 75 mass% of an active polymer for polymethacrylate or polyacrylate polymers, or from 8 mass% to 20 mass% of an active polymer for olefin copolymers, hydrogenated polyisoprene star polymers, or hydrogenated diene-styrene block copolymers, in the "as delivered" polymer concentrate.I. Dispersants

[0294] 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 compositions herein may be ashless or ash-forming in nature. Preferably, 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 to form ash upon combustion.

[0295] Dispersants useful herein typically contain a polar group attached to a relatively high molecular weight hydrocarbon chain. The polar group typically contains at least one element of nitrogen, oxygen, or phosphorus. Typical hydrocarbon chains contain 40 to 500, such as 50 to 400 carbon atoms. When used in context of functionalized polymers operating as dispersants, the molecular weights are typically reported in terms of the base polymer prior to modification. For example, PI BSA-PAM dispersant molecular weights are typically reported for the base polymer prior to functionalization with the acylating agent (maleic acid or anhydride) and functional group (such as polyamine).Dispersants of (Polv)alkenylsuccinic derivatives

[0296] 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 Mn 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 US Patents describing such dispersants include US Patent 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 dispersants are described in US Patent 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 Applications Nos. 0 471 071 and 0 451 380, to which reference is made for this purpose.

[0297] Hydrocarbyl-substituted succinic acid and hydrocarbyl-substituted succinic anhydride derivatives areuseful dispersants. In particular, succinimide, succinate esters, or succinate ester amides prepared by the reaction of a hydrocarbon-substituted succinic acid or anhydride compound (typically having at least 25 carbon atoms, such as 28 to 400 carbon atoms, in the hydrocarbon substituent), with at least one equivalent of 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 of at least 400 g / mol, such as at least 900 g / mol, such as at least 1500 g / mol, such as from 400 to 4000 g / mol, such as from 800 to 3000, such as from 2000 to 2800 g / mol, such from about 2100 to 2500 g / mol, and such as from about 2200 to about 2400 g / mol.

[0298] 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: polyhydrocarbyl polyamines, polyalkylene polyamines, hydroxy-substituted polyamines, polyoxyalkylene polyamines, and combinations thereof. Examples of polyamines include tetraethylene pentamine, pentaethylene hexamine, tetraethylenepentamine (TEPA), pentaethylenehaxamine (PEHA), N-phenyl-p-phenylenediamine (ADPA), 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. 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 US Patent 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 Mn 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 US Patent Nos. 3,087,936; 3,172,892; 3,219,666; 3,272,746; 3,322,670; 3,652,616; 3,948,800; and 6,821 ,307; and CA Patent No. 1 ,094,044.

[0299] The dispersants may comprise one or more, optionally borated, higher molecular weight (Mn 1600 g / mol or more, such as 1800 to 3000 g / mol) succinimides and one or more, optionally borated, lower molecular weight (Mn less than 1600 g / mol) succinimides, where the higher molecular weight may be 1600 to 3000 g / mol, such as 1700 to 2800 g / mol, such as 1800 to 2500 g / mol, such as 1850 to 2300 g / mol; and the lower molecular weight may be 600 to less than 1600 g / mol, such as 650 to 1500 g / mol, such as 700 to 1400 g / mol, such as 800 to 1300 g / mol, such as 850 to 1200 g / mol such as 900 to 1150 g / mol, such as 900 to 1000 g / mol. The higher molecular weight succinimide dispersant may be present in the lubricating composition in an amount of from 0.5 to 10 mass%, or from 0.8 to 6 mass%, or from 1 .0 to 5 mass%, or from 1 .5 to 5 mass%, or from 1 .5 to 4.0 mass%; and the lower molecular weight succinimides dispersant may be present in the lubricating composition in an amount of from 1 to 5 mass%, or from 1.5 to 4.8 mass%, or from 1.8 to 4.6 mass%, or from 1.9 to 4.6 mass%, or at 2 mass% or more, such as 2 to 5 mass%. The lower molecular weight succinimides may differ from the higher molecular weight succinimides, by 500 g / mol or more, such as by 750 g / mol or more, such as by 1000 g / mol or more, such as by 1200 g / mol or more, such as by 500 to 3000 g / mol, such as by 750 to 2000 g / mol, such as by 1000 to 1500 g / mol.

[0300] 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.

[0301] 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 US Patent No. 4,426,305.

[0302] 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 US Patent No. 7,485,603, particularly, col 2, In 65 to col 6, In 22 and col 23, In 40 to col 26, In 46. In particular, PIBSA esters of methylene-bridged naphthyloxy ethanol ( / .e., 2-hydroxyethyl-1 -naphthol ether (or hydroxyterminated ethylene oxide oligomer ether of naphthol) are useful herein.

[0303] The molecular weight of the hydrocarbyl-substituted succinic anhydrides used in the preceding paragraphs will typically range from 350 to 4000 g / mol, such as 400 to 3000 g / mol, such as 450 to 2800 g / mol, such as 800 to 2500 g / mol, such as 800 to 1200 g / mol, such as 800 to 1000 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.

[0304] The dispersants may be present in the lubricant in an amount 0.1 mass% to 20 mass% of the composition, such as 0.2 to 15 mass%, such as 0.25 to 10 mass%, such as 0.3 to 5 mass%, such as 1.0 mass% to 3.0 mass%, of the lubricating oil composition.

[0305] The above (poly)alkenylsuccinic derivatives, 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.

[0306] Dispersants useful herein include borated succinimides, including those derivatives from monosuccinimides, bis-succinimides, and / or mixtures of mono- and bis-succinimides, wherein the hydrocarbyl succinimide is derived from a hydrocarbylene group such as polyisobutylene having an Mn of from about 300 to about 5000 g / mol, or from about 500 to about 3000 g / mol, or about 800 to about 2000 g / mol, or about 1000 to about 2000 g / mol, or a mixture of such hydrocarbylene groups, often with high terminal vinylic groups.

[0307] The boron-containing dispersant may be present at 0.01 mass% to 20 mass%, or 0.1 mass% to 15 mass%, or 0.1 mass% to 10 mass%, or 0.5 mass% to 8 mass%, or 1 .0 mass% to 6.5 mass%, or 0.5 mass% to 2.2 mass% of the lubricating composition.

[0308] The boron-containing dispersant may be present in an amount to deliver boron to the composition at 15 ppm to 2000 ppm, or 25 ppm to 1000 ppm, or 40 ppm to 600 ppm, or 80 ppm to 350 ppm.

[0309] 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 one embodiment, the lubricating composition may include one or more boron-containing dispersants and one or more non-borated dispersants, wherein the total amount of dispersant may be 0.01 mass% to 20 mass%, or 0.1 mass% to 15 mass%, or 0.1 mass% to 10 mass%, or 0.5 mass% to 8 mass%, or 1.0 mass% to 6.5 mass%, or 0.5 mass% to 2.2 mass% of thelubricating composition and wherein the ratio of borated dispersant to non-boroated dispersant may be 1 :10 to 10:1 (weightweight) or 1 :5 to 3:1 or 1 :3 to 2:1.

[0310] The borated dispersant may be used in combination with non-borated dispersant and may be a different compound as the non-borated dispersant. In one embodiment, the lubricating composition may include one or more boron-containing dispersants derived from polyisobutylene having an Mn lower (such as 1200 g / mol or less, such as 1100 g / mol or less, such as 1000 g / mol or less such as 900 g / mol or less) than the Mn of polyiosobutylene (such as 1300 g / mol or more, such as 1500 g / mol or more, such as 2000 g / mol or more, such as 2500 g / mol or more, such as 3000 g / mol or more) used to prepare one or more non-borated dispersants, wherein the total amount of dispersant may be 0.01 mass% to 20 mass%, or 0.1 mass% to 15 mass%, or 0.1 mass% to 10 mass%, or 0.5 mass% to 8 mass%, or 1 .0 mass% to 6.5 mass%, or 0.5 mass% to 2.2 mass% of the lubricating composition and wherein the ratio of borated dispersant to non-borated dispersant may be 1 :10 to 10:1 (weightweight) or 1 :5 to 3:1 or 1 :3 to 2:1.

[0311] The dispersant may comprise one or more borated or unborated poly(alkenyl)succinimides, where the polyalkyenyl is derived from polyisobutylene and the imide is derived from a polyamine ("PIBSA-PAM").

[0312] The dispersant may comprise one or more PIBSA-PAMs, where the PIB is derived from polyisobutylene having an Mn of from 600 to 5000, such as from 700 to 4000, such as from 800 to 3000, such as from 900 to 2500 g / mol, such as 600 to less than 1600 g / mol and the polyamine is derived from hydrocarbyl-substituted polyamines, such as tetraethylene pentamine, pentaethylene hexamine, tetraethylenepentamine (TEPA), pentaethylenehaxamine (PEHA), N-phenyl-p-phenylenediamine (ADPA), and other polyamines having an average of 5, 6, 7, 8, or 9 nitrogen atoms per molecule. The dispersant may be borated, typically at levels of up to 4 mass% such as from 1 to 3 mass%. For purposes of this invention and the claims thereto, when a polyisobutylene polymer (PIB) derived dispersant (such as PIBSA-PAM) is referred to as having a specific Mn, that Mn refers to the Mn of the PIB that the PIB derived dispersant (such as PIBSA-PAM) was derived from. Unless otherwise indicated, the Mn of polyisobutylene is determined by Gel Permeation Chromatography-Size Exclusion Chromatography, equipped with a differential refractive index (DRI) detector and three Mixed D PL gel columns (300mm x7.5mm) containing 5 pm particle size gel, calibrated using polystyrene standards correlated to PIB samples of known molecular weight.

[0313] The dispersant may comprise one or more borated and one or more non-borated PIBSA-PAM's.

[0314] In embodiments, the dispersant may be one or more optionally borated lower Mn dispersant (such as PIBSA-PAM dispersant derived from a PIB having an Mn of less than 1600 g / mol, such as 600 to less than 1600 g / mol, such as 650 to 1500 g / mol, such as 700 to 1400 g / mol, such as 800 to 1300 g / mol, such as 850 to 1200 g / mol, such as 900 to 1150 g / mol, such as 900 to 1000 g / mol, where the PAM may optionally be TEPA, PEHA, and or ADPA). The optionally borated lower molecular weight dispersant(s) may be present in a lubricating oil composition in an amount of from 0.5 to 10 mass%, or from 0.8 to 6 mass%, or from 1.0 to 5 mass%, or from 1 .5 to 5 mass% or from 1 .5 to 4.0 mass% or from 1 .5 to 4.8 mass%, or at 2 mass% or more, such as 2 to 5 mass%, based upon the weight of the lubricating oil composition. The dispersant may comprise one or more borated PIBSA-PAM's derived from a PIB having an Mn of 700 to 1800 g / mol (such as 800 to 1500 g / mol) and one or more non-borated PIBSA-PAM's derived from a PIB having an Mn of more than 1800 to 5000 g / mol (such as 2000 to 3000 g / mol). The dispersant may comprise one or more non-borated PIBSA-PAM's derived from a PIB having an Mn of 700 to 1800 g / mol (such as 800 to 1500 g / mol) and one or more borated PIBSA-PAM's derived from a PIB having an Mn of more than 1800 to 5000 g / mol (such as 2000 to 3000 g / mol).

[0315] The dispersant may comprise PIBSA derived from a PIB having an Mn of 700 to 5000 g / mol (such as 800 to 3000 g / mol) and one or more borated or non-borated PIBSA-PAM's derived from a PIB having an Mn of 700 to 5000 g / mol.

[0316] The dispersant may comprise PIBSA derived from a PIB having an Mn of 700 to 5000 g / mol (such as 800 to 3000 g / mol) and one or more borated PIBSA-PAM's derived from a PIB having an Mn of 700 to 1800 g / mol (such as 800 to 1500 g / mol) and one or more non-borated PIBSA-PAM's derived from a PIB having an Mn of more than 1800 to 5000 g / mol (such as 2000 to 3000 g / mol). The dispersant may comprise PIBSA derived from a PIB having an Mn of 700 to 5000 g / mol (such as 800 to 3000 g / mol) one or more non- borated PIBSA-PAM's derived from a PIB having an Mn of 700 to 1800 g / mol (such as 800 to 1500 g / mol) and one or more borated PIBSA-PAM's derived from a PIB having an Mn of more than 1800 to 5000 g / mol (such as 2000 to 3000 g / mol).

[0317] The dispersant may comprise one or more borated or non-borated PIBSA-PAM's and one or more PIBSA-esters of hydrocarbyl bridged aryloxy alcohols.

[0318] The dispersant may comprise one or more borated and one or more non-borated PIBSA-PAM's.

[0319] The dispersant may comprise one or more, optionally borated, higher molecular weight (Mn 1600 g / mol or more, such as 1800 to 3000 g / mol) PIBSA-PAM's and one or more, optionally borated, lower molecular weight (Mn less than 1600 g / mol) PIBSA-PAM's, where the higher molecular weight may be 1600 to 3000 g / mol, such as 1700 to 2800 g / mol, such as 1800 to 2500 g / mol, such as 1850 to 2300 g / mol; and the lower molecular weight may be 600 to less than 1600 g / mol, such as 650 to 1500 g / mol, such as 700 to 1400 g / mol, such as 800 to 1300 g / mol, such as 850 to 1200 g / mol, such as 900 to 1150 g / mol, such as 900 to 100 g / mol. The higher molecular weight PIBSA-PAM dispersant may be present in the lubricating composition in an amount of from 0.5 to 10 mass%, or from 0.8 to 6 mass%, or from 1 .0 to 5 mass%, or from 1 .5 to 5 mass% or from 1 .5 to 4.0 mass%; and the lower molecular weight PIBSA-PAM dispersant may be present in the lubricating composition in an amount of from 1 to 5 mass%, or from 1.5 to 4.8 mass%, or from 1 .8 to 4.6 mass%, or from 1 .9 to 4.6 mass%, or at 2 mass% or more, such as 2 to 5 mass%.Dispersants of Mannich Bases

[0320] 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 US Patent 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 US Patent 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; and 10,899,986, and PCT Publication No. WO 01 / 42399.Dispersants of Polymethacrylate or Polyacrylate Derivatives

[0321] 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 USPatent Nos. 2,100,993, and 6,323,164. Polymethacrylate and polyacrylate dispersants are typically lower molecular weights.Functionalized Polymer Dispersants

[0322] Dispersants useful herein include the amide, imide, and / or ester functionalized partially or fully saturated polymers comprising C4-5 olefins as described in United States application USSN 18 / 480,571 , filed October 4, 2023 (US 20240141156 A1), which is herein incorporated by reference in its entirety. Preferred dispersants include polymers referred to as “functionalized polymers” described in USSN 18 / 480,571 , filed Oct 4, 2023 US 20240141156 A1 , and preferably are a functionalized hydrogenated polyisoprene family of polymers for use in lubricating oil compositions disclosed in United States Application 18 / 480,571 , filed October 4, 2023 US 20240141156 A1 .

[0323] In an advantageous form, the lubricating oil composition described herein further optionally includes one or more functionalized polymers described in USSN 18 / 480,571 at from 0.1 to 5.0 mass%, or 0.2 to 2.0 mass%, or 0.4 to 1 .8 mass%, or 0.6 to 1 .6 mass%, or 0.8 to 1 .4 mass%, or 1 .0 to 1 .2 mass% of the lubricating oil composition, where the functionalized polymers comprises an amide, imide, and / or ester functionalized partially or fully saturated polymer comprising C4-5 olefins having: i) an Mw / Mn of less than 2, or less than 1 .8, or less than 1 .6; ii) a Functionality Distribution (Fd) value of 3.5 or less, or 3.2 or less, or 3.0 or less, or 2.5 or less; iii) an Average Functionality Value (Fv) of 1.4 to 20 FG grafts / polymer chain, such as 1.4 to 15 FG grafts / polymer chain, such as 3 to 12.5 FG grafts / polymer chain, such as 4 to 10 FG grafts / polymer chain , such as 5 to 10 FG grafts / polymer chain, such as 6 to 10 FG grafts / polymer chain; and iv) an Mn of 10,000 g / mol or more, or 15,000 g / mol or more, or 20,000 g / mol or more, or 25,000 g / mol or more (GPC-PS) of the polymer prior to functionalization, optionally provided that, if the polymer prior to functionalization is a copolymer of isoprene and butadiene, then the Mn of the copolymer is greater than 25,000 g / mol, or 30,000 g / mol or more, or 35,000 g / mol or more, or 40,000 g / mol or more (GPC-PS). (GPC-PS is performed as set out in United States Patent Application USSN 18 / 480,571 , filed October 4, 2023). For the functionalized polymer described in 18 / 480,571 useful herein, Average Functionality [also referred to as Average Functionality Value (Fv)] and Functionality Distribution (Fd) value are determined by Gel Permeation Chromatography using polystyrene standards as described in the Experimental section of US Patent Application USSN 18 / 480,571 , filed October 4, 2023, "FG" means functional group. The functionalized polymers described in 18 / 480,571 useful herein may include at least 50 %, or at least 60%, or at least 70% of 1 ,4-insertions of monomer, such as isoprene monomer. Furthermore, the functionalized polymers described in 18 / 480,571 useful herein may include a partially or fully saturated homopolyisoprene containing one or more pendant amine groups and having an Mn of 25,000 to 100,000 g / mol, or 35,000 to 90,000 g / mol, or 45,000 to 80,000 g / mol, or 55,000 to 75,000 g / mol (GPC-PS) and at least 50%, or at least 60%, or at least 70% of 1 ,4-insertions prior to functionalization. The functionalized polymers described in 18 / 480,571 useful herein may be absent of styrene repeat units, or absent of butadiene repeat units, or are not a homopolyisobutylene, or are not a copolymer of isoprene and butadiene.

[0324] The lubricating composition of the disclosure typically comprises dispersant at 0.1 mass% to 20 mass% of the composition, such as 0.2 to 15 mass%, such as 0.25 to 10 mass%, such as 0.3 to 5 mass%, such as 2.0 mass% to 4.0 mass% of the lubricating oil composition. Alternately the dispersant may be present at 0.1mass% to 5 mass%, or 0.01 mass% to 4 mass% of the lubricating composition.

[0325] For further information on dispersants useful herein, please see US Patent No. 10,829,712, col 13, In 36 to col 16, In 67 and US Patent No. 7,485,603, col 2, In 65 to col 6, In 22, col 8, In 25 to col 14, In 53, and col 23, In 40 to col 26, In 46.

[0326] Compositions according to the present disclosure may contain an additive having a different enumerated function that also has secondary effects as a dispersant. These additives are not included as dispersants for purposes of determining the amount of dispersant in a lubricating oil composition or concentrate herein.J. Corrosion Inhibitors / Anti-rust Agents

[0327] 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 include those disclosed at paragraphs

[0460] -

[0472] of US 20240141156 A1.Non-limiting examples of useful corrosion inhibitors may comprise or be benzotriazole, triazoles such as tolyltriazole, and / or optionally, substituted benzotriazoles, such as Irgamet™ 30 and Irgamet™ 39, which are commercially available from BASF of Ludwigshafen, Germany. A preferred corrosion inhibitor may comprise or be benzotriazole and / or tolyltriazole. A preferred corrosion inhibitor may comprise or be 1 H-1 , 2, 4-tri azole- 1-methanamine, N,N-bis(2-ethylhexyl) and or 1 H-benzotriazole-1-methanamine, N,N-bis(2-ethylhexyl)-4- methyl).

[0328] Compositions according to the present disclosure may contain an additive having a different enumerated function that also has secondary effects as a corrosion inhibitor (for example, Component B, may also have corrosion inhibitor effects). These additives are not included as corrosion inhibitor for purposes of determining the amount of corrosion inhibitor in a lubricating oil composition or concentrate herein.K. Anti -wear Agents

[0329] The lubricating oil composition of the present disclosure can contain one or more anti-wear 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 mass% to about 5 mass%, from about 0.05 mass% to about 3 mass%, or from about 0.1 mass% to about 1 mass%, based on the total weight of the lubricating oil composition.

[0330] 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 dihydrocarbyldithiophosphate 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.

[0331] 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.

[0332] A metal alkylthiophosphate and more particularly a metal dialkyl dithio phosphate in which the metal constituent is zinc, or zinc dialkyl dithio phosphate (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)(ORi)(OR2)]2 where Ri and R2 are C1-C18 alkyl groups, preferably 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.

[0333] Zinc-based antiwear agents useful in compositions described herein, and in any embodiment, include compounds such as zinc dialkyldithiophosphate, where the alkyl groups are derived from one or more primary alcohols, one or more secondary alcohols or combinations of primary and secondary alcohols. Typically, the alcohols are mono-alcohols represented by the formula R-alkyl, where the alkyls are selected from C4 to C30 alkyl groups, and may be combinations of alkyl groups selected from butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, triacontyl or isomers thereof). Useful ZDDP's include one or more ZDDP's (such as ZDDP's derived from desirable alcohols or combination of alcohols, such as primary and or secondary alcohols, such as isooctanol and / or 4-methyl-pentan-2-ol and / or 2-butanol) to the compositions herein can improve fuel economy, while maintaining good viscosity control.

[0334] 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".

[0335] The anti-wear additives, such as ZDDP and / or the zinc carbamates, are typically used in amounts of from about 0.4 mass% to about 1 .2 mass%, preferably from about 0.5 mass% to about 1 .0 mass%, and more preferably from about 0.6 mass% to about 0.8 mass%, based on the total weight of the lubricating composition, although more or less can often be used advantageously. Preferably, the anti-wear additive is ZDDP, preferably a secondary ZDDP, and is present in an amount of from about 0.6 to 1.0 mass% of the total weight of the lubricating composition.

[0336] 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.

[0337] Compositions according to the present disclosure may contain an additive having a different enumerated function that also has secondary effects as an anti-wear agent (for example, Component Bdescribed above, may also have anti-wear effects). These additives are not included as anti-wear agents for purposes of determining the amount of anti-wear agents in a lubricating oil composition or concentrate herein.L. Demulsifiers

[0338] Demulsifiers useful herein include those described in US Patent No. 10,829,712 (col 20, In 34-40). Typically, a small amount of a demulsifying component may be used herein. A preferred demulsifying component is described in European Patent No. 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 mass%, preferably about 0.01 to 2 mass%.M. Seal Compatibility Agents

[0339] Other 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 mass%, preferably about 0.01 to 2 mass%. In embodiments the seal compatibility agents are sea swell agents, such as PIBSA (polyisobutenyl succinic anhydride).N. Extreme Pressure Agents

[0340] 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, cosulfurized blends of fatty acid, fatty acid ester and alpha-olefin, functionally substituted dihydrocarbyl polysulfides, thia-aldehydes, thia-ketones, epithio compounds, sulfur-containing acetal derivatives, cosulfurized 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 mass% to about 5 mass%, from about 0.05 mass% to about 3 mass%, or from about 0.1 mass% to about 1 mass%, based on the total weight of the lubricating oil composition.O. Non-basestock Unsaturated Hydrocarbons

[0341] The lubricating oil composition of the present disclosure can contain one or more unsaturated hydrocarbons. These unsaturated hydrocarbons are distinct from any baseoils (lubricating oil basestocks of Group I, II, III, IV and / or V) and / or viscosity modifiers that may be present in the compositions and always have at least one (and typically only one, in the case of linear alpha-olefins, or LAOs) unsaturation per molecule. Without being bound by theory, the unsaturation(s) may provide an antioxidation functionality and / or a sulfur-trapping functionality that may supplement and / or replace one or more antioxidant additives and / or one or more corrosion inhibitor additives, but unsaturated hydrocarbons (LAOs) will typically not provide the only antioxidant nor the only corrosion inhibition functionality in lubrication oil compositions. Non-limiting examples of unsaturated hydrocarbons can include one or more unsaturated C12-C60 hydrocarbons (such as C12-C48 hydrocarbons, C12-C36 hydrocarbons, C12-C30 hydrocarbons, or C12-C24 hydrocarbons). When only one unsaturation is present, the unsaturated hydrocarbons may be termed linear alpha-olefins (LAOs). Other non-limiting examples of unsaturated hydrocarbons can include oligomers / polymers of polyisobutylenes that have retained (or been post-polymerization modified to exhibit) a (near-) terminal unsaturation, and / or blends thereof. When present, unsaturated hydrocarbons (LAOs) may be present from 0.01 to 5 mass% (in particular, 0.1 to 3 mass%, alternately 0.1 to 1.5 mass%), based on total weight of the lubricating oil composition.

[0342] 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 in the Table below.

[0343] 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 table 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 (mass%) indicated below is based on the total weight of the lubricating oil composition.Typical Amounts of Lubricating Oil Components

[0344] Typical Amounts of Lubricating Oil Components in LOG (Continued)| ADDITIVE FORMULATIONS | D (mass%) | E (mass%) | F (mass%) |Typical Amounts of Lubricating Oil Components in LOC (Continued)

[0346] 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

[0347] This disclosure also relates to a method of lubricating an internal combustion engine during operation of the engine comprising:(i) Providing the lubricating composition described herein to a crankcase of the internal combustion engine;(ii) providing fuel, such as a hydrocarbon fuel, ammonia fuel, hydrogen fuel, in the automotive internal combustion engine; and(iii) combusting the fuel in the internal combustion engine, such as a diesel engine or passenger car engine (such as a spark-ignited internal combustion engine).

[0348] 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 embodiments, the fuel comprises from 0.1 to 100 mass% renewable fuel, alternately from 1 to 75 mass% renewable fuel, alternately from 5 to 50 mass% renewable fuel, based upon the total mass of the from 1 to 50 mass% renewable fuel and the petroleum derived fuel.

[0349] The renewable fuel component is typically produced from vegetable oil (such as palm oil, coconut 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

[0350] 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 or light and heavy-duty diesel engine lubricants, but can be powertrain or other lubricants used in power transmission.

[0351] In particular, the lubricating compositions of the present disclosure are suitably used in the lubrication of the crankcase of a compression-ignited, internal combustion engine, such as a heavy-duty diesel engine, a light duty diesel engine marine engines, standing engines and the like.

[0352] 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.

[0353] In embodiments, the lubricating oils of this disclosure are used in spark-assisted high compression internal combustion engines.

[0354] In embodiments, the lubricating compositions of the present disclosure are suitably used in the lubrication of the crankcase of an engine for a heavy-duty diesel vehicle ( / .e., a heavy-duty diesel vehicle having a gross vehicle weight rating of 10,000 pounds or more.)

[0355] In embodiments, the lubricating compositions of the present disclosure are suitably used in the lubrication of the crankcase of a passenger car diesel engine.

[0356] In particular, lubricating oil formulations of this disclosure are particularly useful in compression- ignited internal combustion engines, i.e., heavy-duty diesel engines, employing low viscosity oils, such as API FA-4 and future oil categories, in which wear protection of the valve train becomes challenging.

[0357] In particular, lubricating oil formulations of this disclosure are particularly useful in powertrainlubrication, such as in electric and or hybrid vehicles.

[0358] The lubricating oils described herein are also useful for lubricating an internal combustion engine (such as an automotive internal combustion engine) during operation of the engine comprising:(i) providing a lubricating composition described herein to a crankcase of the internal combustion enginesuch as an automotive crankcase;(ii) providing a hydrocarbon fuel and or biofuel to the internal combustion engine; and(iii) combusting the fuel in the internal combustion engine.

[0359] In particular, the lubricating compositions of the present disclosure are suitably used in the lubrication of the oil sump of an internal combustion engine, such as a gasoline engine, a diesel engine (such as an automotive internal combustion engine, a spark-ignited internal combustion engine, a spark assisted, compression-ignited internal combustion engine, a compression-ignited internal combustion engine, such as a heavy-duty diesel engine), where the oil sump temperature is greater than 100°C, such as 110°C or more, such as 120°C or more.

[0360] This disclosure further relates to:1 . A method to reduce sooted viscosity in an internal combustion engine comprising lubricating an internal combustion engine with a lubricating oil composition comprising:1 ) 50 mass% or more of one or more base oils;2) diphenylamine antioxidant comprising: at least 85 mass% of di(Cs 9 substituted phenyl)amine and from 0 to 15 mass% (such as 1 to 10 mass%, such as 1 .5 to 8 mass%, such as 2 to 5 mass%, such as from 0.001 to less than 0.1 mass%) of mono(Cs-9 substituted phenyl)amine, and less than 0.1 mass%, such as 0.010 to less than 0.10 mass%, such as 0.0010 to 0.010 mass% of unsubstituted phenylamine based upon the weight of the unsubstituted, mono substituted- and di-substituted phenylamines;3) detergent;4) dispersant; and5) optional styrenic block copolymer viscosity modifier, wherein the lubricating oil composition, when containing 12 mass% carbon black (based upon the weight of the lubricating oil composition), has a dynamic viscosity (Pas) at a shear rate of 1.3(1 / s) at least 10 % lower (such as at least 15% lower, such as at least 20% lower, such as at least 25% lower) than the dynamic viscosity at a shear rate of 1 .3(1 / s) of the same lubricating oil composition except that the Cs-9 diphenylamine antioxidant has been replaced with the same amount of diphenylamine antioxidant having:1) about 68 mass% di-Cg-alkyl diphenylamine,2) about 29 mass% of mono-Cg-alkyl diphenylamine, and3) about 3 mass% of tri-Cg-alkyl diphenylamine, based on the weight of 1), 2) and 3), as determined by UPLC in the Experimental section.2. The method of paragraph 1 , wherein the lubricating oil composition, when containing 12 mass% carbon black (based upon the weight of the lubricating oil composition), has a dynamic viscosity (Pas) at a shear rate of 4.3(1 / s) at least 5 % lower (such as at least 10% lower, such as at least 13% lower) than the dynamic viscosity at a shear rate of 4.3(1 / s) of the same lubricating oil composition except that the Cs-9 diphenylamine antioxidant has been replaced with the same amount of diphenylamine antioxidant having:1) about 68 mass% di-Cg-alkyl diphenylamine,2) about 29 mass% of mono-Cg-alkyl diphenylamine, and3) about 3 mass% of tri-Cg-alkyl diphenylamine, based on the weight of 1), 2) and 3), as determined by UPLC in the Experimental section.3. The method of paragraph 1 or 2, wherein the lubricating oil composition, when containing 12 mass% carbon black (based upon the weight of the lubricating oil composition), has a dynamic viscosity (Pas) at a shear rate of 8.3(1 / s) at least 5 % lower (such as at least 10% lower, such as at least 15% lower, such as at least 17% lower) than the dynamic viscosity at a shear rate of 8.3(1 / s) of the same lubricating oil composition except that the Cs-g diphenylamine antioxidant has been replaced with the same amount of diphenylamine antioxidant having:1) about 68 mass% di-Cg-alkyl diphenylamine,2) about 29 mass% of mono-Cg-alkyl diphenylamine, and3) about 3 mass% of tri-Cg-alkyl diphenylamine, based on the weight of 1), 2) and 3), as determined by UPLC in the Experimental section.4. The method of paragraph 1 , 2, or 3, wherein the lubricating oil composition comprises styrenic block copolymer viscosity modifier.5. The method of paragraph 1 , 2, or 3, wherein the lubricating oil composition comprises 0.1 to 10 mass%, such as 0.5 to 5 mass%, such as 1 to 3 mass% of styrenic block copolymer viscosity modifier, based upon the weight of the lubricating oil composition.6. The method of paragraph 5, wherein the sytrenic block copolymer comprises hydrogenated styreneisoprene butadiene block copolymer is optionally combined with one or more Cs-2o dialkyl fumarate / vinyl acetate copolymers.7. The method of paragraph 6, wherein the dialkyl fumarate / vinyl acetate copolymers (such as one or more Cs to C20 dialkyl fumarate / vinyl acetate copolymers, such as one or more Cs to Cie dialkyl fumarate / vinyl acetate copolymers, such as one or more C12 to Cie dialkyl fumarate / vinyl acetate copolymers) has a pour point (ASTM D97) of -10°C or less (such as -15°C or less, such as -20°C or less, such as -25 °C or less, such as -30 °C or less).8. The method of any of paragraphs 1 to 7, wherein the detergent comprises calcium and or magnesium salicylate and or sulfonate detergents.9. The method of any of paragraphs 1 to 7, wherein the detergent comprises calcium salicylate and or magnesium sulfonate detergents.10.The method of any of paragraphs 1 to 9, wherein the lubricating oil composition comprises boron containing compounds, such as borated dispersant, such as borated PIBSA-PAM.11 .The method of any of paragraphs 1 to 10, wherein the lubricating oil composition comprises dispersant derived from poyisobutylene having a number average molecular weight of 1600 g / mol or less, such as 1000 g / mol or less.12.The method of any of paragraphs 1 to 11 , wherein the lubricating oil composition comprises dispersant derived from poyisobutylene having a number average molecular weight of 2000 g / mol or more.13.The method of any of paragraphs 1 to 12, wherein the diphenylamine antioxidant comprises: at least 85mass% of di(Cs 9 substituted phenyl)amine and from 0 to 15 mass% (such as 1 to 10 mass%, such as 0.5 to 8 mass%, such as 2 to 5 mass%) of mono(Cg substituted phenyl)amine, based upon the weight of the mono- and di-phenylamines.14.The method of any of paragraphs 1 to 13, wherein the diphenylamine antioxidant comprises: at least 85 mass% of di(Cs substituted phenyl)amine and from 0 to 15 mass% (such as 0.1 to 10 mass%, such as 0.5 to 8 mass%, such as 1 to 5 mass%) of mono(Cs substituted phenyl)amine, based upon the weight of the mono- and di-phenylamines.15.The method of any of paragraphs 1 to 14, wherein the diphenylamine antioxidant comprising: at least 85 mass% of di(Cg substituted phenyl)amine, from 0 to 15 mass% (such as 1 to 10 mass%, such as 0 to 8 mass%, such as 0 to 5 mass%) of mono(Cg substituted phenyl)amine and from 0 to 0.1 mass% (such as 0.01 to less than 0.1 mass%, such as 0.001 to to 0.01 mass %) unsubstituted phenylamine, based upon the weight of the mono- and di-phenylamines.16.The method of any of paragraphs 1 to 15, wherein the lubricating oil composition comprises one or more molybdenum containing compounds, such as dinuclear or trinuclear molybdenum containing compounds, such as molybdenum dithiocarbamate dimer and or trimer.17.The method of any of paragraphs 1 to 16, wherein the lubricating oil composition comprises polyisobutylene and or polyisobutylenesuccinate.18.The method of any of paragraphs 1 to 17, wherein the lubricating oil composition comprises at least 1200 ppm Ca (such as at least 1300 ppm Ca, such as at least 1400 ppm Ca) and or at least 800 ppm Mg (such as at least 900 ppm Mg, such as at least 1000 ppm Mg).19.The method of any of paragraphs 1 to 18, wherein the lubricating oil composition, when containing 12 mass% carbon black (based upon the weight of the lubricating oil composition), has a dynamic viscosity (Pas) at a shear rate of 1 .3(1 / s) at least 10 % lower (such as at least 15% lower, such as at least 20% lower, such as at least 25% lower) than the dynamic viscosity at a shear rate of 1.3(1 / s) of the same lubricating oil composition except that the Cs-g diphenylamine antioxidant has been replaced with the same amount of diphenylamine antioxidant having: 1) about 68 mass% di-Cg-alkyl diphenylamine, 2) about 29 mass% of mono-Cg-alkyl diphenylamine, and 3) about 3 mass% of tri-Cg-alkyl diphenylamine, based on the weight of 1), 2) and 3), as determined by UPLC in the Experimental section; and a dynamic viscosity (Pas), when containing 12 mass% carbon black (based upon the weight of the lubricating oil composition), at a shear rate of 4.3(1 / s) at least 5 % lower (such as at least 10% lower, such as at least 13% lower) than the dynamic viscosity at a shear rate of 4.3(1 / s) of the same lubricating oil composition except that the Cs-g diphenylamine antioxidant has been replaced with the same amount of diphenylamine antioxidant having: 1) about 68 mass% di-Cg-alkyl diphenylamine, 2) about 29 mass% of mono-Cg-alkyl diphenylamine, and 3) about 3 mass% of tri- Cg-alkyl diphenylamine, based on the weight of 1), 2) and 3), as determined by UPLC in the Experimental section; and a dynamic viscosity (Pas), when containing 12 mass% carbon black (based upon the weight of the lubricating oil composition), at a shear rate of 8.3(1 / s) at least 5 % lower (such as at least 10% lower, such as at least 15% lower, such as at least 17% lower) than the dynamic viscosity at a shear rate of 8.3(1 / s) of the same lubricating oil composition except that the Cs-g diphenylamine antioxidant has been replaced with the sameamount of diphenylamine antioxidant having: 1) about 68 mass% di-Cg-alkyl diphenylamine, 2) about 29 mass% of mono-Cg-alkyl diphenylamine, and 3) about 3 mass% of tri-Cg-alkyl diphenylamine, based on the weight of 1), 2) and 3), as determined by UPLC in the Experimental section.20.The method of any of paragraphs 1 to 19, wherein the Cs-9 diphenylamine antioxidant is provided to a concentrate used to prepare the lubricating oil composition in molten form.21. The method of any of paragraphs 1 to 18, wherein the Cs-9 diphenylamine antioxidant is provided to a concentrate used to prepare the lubricating oil composition as a blend of Cs-9 diphenylamine antioxidant with polar diluent, such as Cs-Cio tri-methylol propane ester.22.The method of any of paragraphs 1 to 21 wherein the Cs-9 diphenylamine antioxidant comprises Cs diphenylamine antioxidant, C9 diphenylamine antioxidant, or Cs&9 diphenylamine antioxidant.23.The method of any of paragraphs 1 to 21 wherein the Cs-9 diphenylamine antioxidant is Cs diphenylamine antioxidant, C9 diphenylamine antioxidant or Cs&9 diphenylamine antioxidant.24.The method of any of paragraphs 1 to 21 wherein the dispersant comprises one or more amide, imide, and / or ester functionalized partially or fully saturated polymers comprising C4-5 olefins having: i) an Mw / Mn of less than 2, or less than 1 .8, or less than 1 .6; ii) a Functionality Distribution (Fd) value of 3.5 or less, or 3.2 or less, or 3.0 or less, or 2.5 or less; iii) an Average Functionality Value (Fv) of 1 .4 to 20 FG grafts / polymer chain, such as 1 .4 to 15 FG grafts / polymer chain, such as 3 to 12.5 FG grafts / polymer chain, such as 4 to 10 FG grafts / polymer chain , such as 5 to 10 FG grafts / polymer chain, such as 6 to 10 FG grafts / polymer chain; and iv) an Mn of 10,000 g / mol or more, or 15,000 g / mol or more, or 20,000 g / mol or more, or 25,000 g / mol or more (GPC-PS) of the polymer prior to functionalization, optionally provided that, if the polymer prior to functionalization is a copolymer of isoprene and butadiene, then the Mn of the copolymer is greater than 25,000 g / mol, or 30,000 g / mol or more, or 35,000 g / mol or more, or 40,000 g / mol or more (GPC-PS).

[0361] The following non-limiting examples are provided to illustrate the disclosure.Experimental

[0362] All molecular weights are number average molecular weights (Mn) reported in g / mol, as determined by gel permeation chromatography using polystyrene standards, unless otherwise noted. "A.I.", "a.i.", and "ai" are mass% active ingredient, unless otherwise indicated.Testing Procedures

[0363] Total Base Number also referred to as "TBN", in relation to an additive componentor of a lubricating oil composition ( / .e., unused lubricating oil composition) means total base number as measured by ASTM D2896 and reported in units of mgKOH / g.

[0364] KV100 is Kinematic viscosity measured at 100°C according to ASTM D445-19a.

[0365] Aniline point is determined according ASTM 611, Method A.

[0366] ICP is Inductively Coupled Plasmas Atomic Emission Spectroscopy (ICP-AES) and measures elemental composition of oils according to ASTM D5185.

[0367] The relative amounts of mono-, di- and tri alkylated diphenylamine are determined using UltraPerformance Liquid Chromatography (UPLC) with UV and mass spectrometer detectors using the conditions detailed in Table A. The mass spectrometer chromatograms were used to confirm identity of the mono-, di- and tri-alkyl substituted diphenylamines. The UV spectrometer chromatograms were used toestablish the relative % of each alkyl-substituted diphenylamine by comparing the area under the curve for each constituent. For the purposes of the examples below the area under the curve absorbance is equated to mass%.

[0368] The relative amounts of mono-, di- and tri styrenated diphenylamine are determined using Ultra- Performance Liquid Chromatography (UPLC) with UV and mass spectrometer detectors using the conditions detailed in Table B. The mass spectrometer chromatograms were used to confirm identity of mono-, di- and tri substituted styrenated diphenylamines (i.e., the diphenylamine is substituted with styrene), and the UV spectrometer chromatograms were used to establish the relative % of styrenated diphenylamine by comparing the area under the curve for each constituent. For the purposes of the examples below the area under the curve absorbance is equated to mass%.Table A. UPLC method to analyse alkylated diphenylamines.Table B: UPLC method to analyse styrenated diphenylamines.

[0369] Sooted Rheology experiments were performed where dynamic viscosity was measured on samples containing a suspension of 12 wt.% carbon black (Vulcan™ XC72R) prepared by adding 44.0 g of each oil to a 100 ml beaker containing 6.0 g of Vulcan XC72R carbon black. The dynamic viscosity of the suspension was measured on a Haake RS600 Rheometer, controlled by Haake RheoWin Job Manager software (ver. 4.30.0028), using the conditions in Table below. The dynamic viscosity of the sample on the final shear sweep was used to compare the soot dispersancy of the different diphenylamine components. Viscosities (q, Pa-s) were taken at approximate shear rates of 1.3, 4.3 and 8.3 (1 / s, ±0.1) as indicated in Tables 3 and 4 below. The dynamic viscosity decreases as the shear rate increases. It is desirable for the suspension to maintain a consistently low viscosity during the shear sweep.Sooted Rheology MethodISB Viscosity

[0370] The ISB Soot Viscosity Test was developed to replace the Mack T11 test (ASTM D7156) which is being phased out. Table 6 shows results of an inventive formulation and a comparative formulation. These oils were prepared and tested in the ISB Soot Viscosity test run in a Cummins ISB diesel engine. (ASTM WK92615). The ISB Soot Viscosity test evaluates the ability of the oil to control viscosity increase from soot agglomeration as soot levels in the oil increase during use. The test is run for 156 hours or until oil viscosity increases to the point of engine failure. Every 12 hours an oil sample is taken to measure soot content and kinematic viscosity at 100 °C up to 156 hours maximum. The kinematic viscosity increases as soot content increases. It is desirable to maintain as low a viscosity increase as possible.

[0371] All measured quantities (weights, temperatures) are within ± 1 %.MaterialsComponent Chart

[0372] Component 1 is a distilled version of Component 2, containing a higher concentration of mono-Cg- alkyl diphenylamine, and lower concentration of di-Cg-alkyl substituted diphenylamine and no tri-Cg-alkyl substituted diphenylamine, as shown in Table C below (isomer content determined by UPLC as per Table A in the Testing Procedures section).

[0373] Component 2 is Cg-alkyl diphenylamine and contains isomers of: mono-Cg-alkyl substituted diphenylamine, tri-Cg-alkyl substituted diphenylamine, and di-Cg-alkyl substituted diphenylamine as shown in the table below (isomer content determined by UPLC). Cg-alkyl diphenylamine is a known debit for soot handling and is the most commonly used commerical aminic antioxidant in engine oils. Any benefit or debit the other substituted diphenylamines listed below have towards soot handling would be demonstrated by a difference in performance compared to Component 2.

[0374] Component 3 is a distilled version of Component 2, containing a lower concentration of mono-Cg- alkyl diphenylamine, and higher concentration of tri-Cg-alkyl substituted diphenylamine, and higher proportion of di-Cg-alkyl substituted diphenylamine as shown in Table C below (isomer content determined by UPLC as per Table A in the Testing Procedures section).

[0375] Component 4 is Cs-alkyl diphenylamine and contains isomers of: mono-Cs-alkyl substituted diphenylamine, tri-Cs-alkyl substituted diphenylamine, and di-Cs-alkyl substituted diphenylamine as shown in Table C below (isomer content determined by UPLC as per Table A in the Testing Procedures section).

[0376] Component 5 is a styrenated diphenylamine and contains isomers of: mono-substituted diphenylamine, tri-substituted diphenylamine, and di-substituted diphenylamine as shown in Table C below (isomer content determined by UPLC as per Table B in the Testing Procedures section).

[0377] Component 6 is a distilled version of Component 5, containing a lower concentration of monosubstituted diphenylamine and a higher proportion of tri-substituted and di-substituted diphenylamine as shown in Table C below (isomer content determined by UPLC as per Table B in the Testing Procedures section).Table C: Mono, Di, Tri-substituted content of components determined by UPLC* based upon the combined weight of the mono-, di-, and tri-substituted isomers.** based upon the combined weight of unsubstituted diphenylamine and mono-, di-, and- tri-substituted isomers. Tetra-substituted isomers were not observed.ExamplesFinished Oil Blending Methods

[0378] Oil A, Oil B, Oil C, Inventive Oil D, Oil G and Oil H in Example 1 were blended by combining H-SD block copol and Group III base oil, then blending in a concentrated additive package and Mo-friction modifier. Each diphenylamine component was then added at the final stage.

[0379] Inventive Oil E was blended by combining H-SD block copol and Group III base oil. Component 4 was combined with 50% TMP ester as a pre-blend and blended with the concentrated additive package and Mo-friction modifier at the base oil / viscosity addition in the final stage.

[0380] Inventive Oil F was blended by combining LOFI and H-SD block copol in Group III base oil. Component 4 was heated until liquid and then added to the blend along with a concentrated additive package and Mo-friction modifer at the final stage.

[0381] Oil I, Oil J, Oil K and Inventive Oil L, Oil M and Oil N in Example 2 were blended by adding Group III base oil, then blending in a concentrated additive package and Mo-friction modifier. Each diphenylamine component was then added at the final stage.

[0382] Oil 1 and Oil 2 in Example 3 were blended by combining LOFI and OCP Viscosity Modifier in Group II base oil, then blending in a concentrated additive package and each diphenylamine component at the final stage.

[0383] The formulated oils are shown in Tables 1 and 2 below.Example 1

[0384] Components 1 -6 were each blended into oils as described above to form Oils B-H respectively. Oil A contained none of the diphenylamine components described and acted as the reference oil for the sooted rheology test. The compositions of the oils are shown in Table 1 .Detergent, ZDDP, PIBSA, PIB, anti-foamant, Mo-friction modifier and Group I diluent oil.

[0385] A suspension of 12.0 wt% carbon black (Vulcan XC72R) in the oil was prepared by weighing 44 g of the oil and adding to a 100 ml beaker containing 6 g of Vulcan XC72R carbon black. The suspension was mixed via overhead stirring (200-400 rpm) at 90°C for 16 h, followed by 100°C for 1 h under an air atmosphere.

[0386] The dynamic viscosites of the oils were measured on a Haake rheometer according to the method described above. Each sample was run in duplicate and the average viscosity value at increasing shear rate taken on the final shear sweep. Selected average viscosities and shear rates (1.3, 4.3, 8.3 1 / s) of the samples are summarized in Table 3 and plotted in Figure 1. Final sweep of shear rate and viscosity data for the Oils in Example 1 are also plotted in Figures 5-7.Example 2

[0387] Components 1 , 2, 3, 5 and 6 were blended into an oil as described above to form Oils l-N, all of which contained no H-SD block copolymer. Oil I contained none of the components described and acted as the reference oil for the sooted rheology test. These were prepared and tested in the sooted rheology testusing identical conditions to Oils A-H in Example 1. The composition of the oils are shown in Table 2.AAeach concentrated additive package had the same amount of Ca Salicylate Detergent, Mg Sulfonate Detergent, ZDDP, PIBSA, PIB, anti-foamant, Mo-friction modifier and Group I diluent oil.

[0388] The dynamic viscosites of the oils were measured on a Haake rheometer according to the method described above. Each sample was run in duplicate and the average viscosity value at increasing shear rate taken on the final shear sweep. Selected average viscosities and shear rates (1.3, 4.3, 8.3 1 / s) of the samples are summarized in Table 4 and plotted in Figure 2. Final sweep of shear rate and viscosity data for the Oils in Example 1 are also plotted in Figures 8-9.Sooted Viscosity Results

[0389] The viscosity of the sooted oils was approximately 10OOx larger than the starting viscosity of the fresh oils (conversion of Pas to cP / cSt units). It can therefore be assumed any small differences in starting viscosity of the oils did not effect the performance of the oils in the sooted viscosity test.

[0390] Alkyl and aromatic substituted diphenylamines are a debit for sooted viscosity, as shown by the increase in viscosity of Oils B-H compared to reference Oil A and Oils J-N compared to reference Oil I.

[0391] The results from Example 1 show a surprising improvement in sooted viscosity control for the oil in the sooted rheology test described, as the concentration of mono-nonyl Cg-alkyl diphenylamine is reduced from 50% to 30% to 0.1 % (Oils B-D). This is demonstrated in Table 3, Figure 1 and Figure 7. This is alsoseen in Example 2, where the oils contained no H-SD block copolymer (Table 4, Figure 2 and Figure 9).

[0392] Example 1 also shows the effect can be extended to Cs-alkyl diphenylamines, which also have low amounts of mono-alkylated dipehanylamine, both when diluted in polar diluent ( such as TMP ester) and as a neat component (Oils E and F). Both show an improvement over Cg-alkyl diphenylamines with higher mono content (Oils B and C) as shown in Table 2, Figure 1 and Figure 6.

[0393] In Examples 1 and 2, replacing alkylated diphenylamine with styrenated diphenylamine resulted in worse sooted viscosity control of the oil. The performance of the styrenated diphenylamine was improved by lowering the concentration of mono-substituted diphenylamine in the component, but the sooted rheology performance was still worse than the alkylated diphenylamines tested. This is visualised in Figures 1 , 2, 5 and 8.

[0394] It can be inferred that reducing mono-substituted diphenylamine content results in improved sooted viscosity control in the sooted rheology test described above, both with and without H-SD block copolymer. The relationship between sooted viscosity control and mono-substituted diphenylamine content at low shear rate (1.3 1 / s) in this test is visualised in Figures 3 and 4.

[0395] It can also be inferred from the data that styrenated diphenylamines have worse sooted viscosity control than alkylated diphenylamines in this test, both with and without H-SD block copolymer.

[0396] The inventive oils (Oils D, E, F and L) containing Components 3, 4 and 5 having low concentrations of mono-alkylated diphenylamine in formulated oils show a surprising improvement in sooted viscosity control over conventional aminic antioxidants (which are typically nonylated-diphenylamines that contain higher concentrations of mono-alkylated diphenylamine).Table 3: Measured Dynamic Viscosity Values (Pas) at Three Shear Rates (1 / s) for oils from Example 1 (DPA = diphenylamine)diphenylamine)Example 3

[0397] Component 2 and Component 4 were each blended into the oils as described in finished oil blending methods to form Comparative Oil 1 and Inventive Oil 2, respectively. The formulations for these oils are shown in Table 5 below. Table 5AAeach concentrated additive package had the same amount of Ca Sulfonate detergent, Mg Sulfonate detergent, ZDDP, PIBSA, PIB, anti-foamant, S-FAME, LOFI and Group I diluent oil.

[0398] Oils 1 and 2 were tested in ISB Viscosity Test as described in the Test Methods section above. The viscosity at 100°C at various soot concentrations (+- 0.1 %) are shown in Table 6.

[0399] The results show a surprising improvement in soot viscosity control in the ISB test, when Component2 (Cg-alkyl diphenylamine) is replaced by Component 4 (Cs-alkyl diphenylamine with lower levels of monooctyl diphenylamine) at 50% Al in TMP ester at equal treat rate. The antioxidant replacement improved the performance of the oil, allowing the oil to pass the limits of the test where previously it had failed. These engine test results support the findings of the sooted rheology test method, where replacing Cg-alkyl diphenylamine with a Cs-alkyl diphenylamine antioxidant with lower levels of mono-alkyl diphenylamine improved sooted rheology control.Table 6: Measured viscosity values (cSt) at various soot content (%) during the ISB Viscosity Test.

[0400] All documents described herein are incorporated by reference herein, including any priority documents and / or testing procedures, to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and the specific embodiments, while forms of the invention have been illustrated and described, various modifications can be made without departing from the spirit and scope of the invention. Accordingly, it is not intended that the invention be limited thereby. The term "comprising" is considered synonymous with the term "including." Likewise, whenever a composition, an element, or a group of elements is preceded with the transitional phrase "comprising", it is understood that we also contemplate the same composition or group of elements with transitional phrases "consisting essentially of", "consisting of', "selected from the group of consisting of", or "is" preceding the recitation of the composition, element, or elements and vice versa.

Claims

Claims1 . A method to reduce sooted viscosity in an internal combustion engine comprising lubricating an internal combustion engine with a lubricating oil composition comprising:1 ) 50 mass% or more of one or more base oils;2) diphenylamine antioxidant comprising: at least 85 mass% of di(Cs 9 substituted phenyl)amine and from 0 to 15 mass% (such as 1 to 10 mass%, such as 0 to 8 mass%, such as 0 to 5 mass%) of mono(C8-9 substituted phenyl)amine, and from 0 to 2 mass% of unsubstituted diphenylamine, based upon the weight of the unsubstituted, mono substituted- and disubstituted-diphenylamines;3) detergent;4) dispersant; and5) optional styrenic block copolymer viscosity modifier, wherein the lubricating oil composition, when containing 12 mass% carbon black (based upon the weight of the lubricating oil composition), has a dynamic viscosity (Pas) at a shear rate of 1.3(1 / s) at least 10 % lower (such as at least 15% lower, such as at least 20% lower, such as at least 25% lower) than the dynamic viscosity at a shear rate of 1 .3(1 / s) of the same lubricating oil composition except that the Cs-9 diphenylamine antioxidant has been replaced with the same amount of diphenylamine antioxidant having:1) about 68 mass% di-Cg-alkyl diphenylamine,2) about 29 mass% of mono-Cg-alkyl diphenylamine, and3) about 3 mass% of tri-Cg-alkyl diphenylamine, based on the weight of 1), 2) and 3), as determined by UPLC in the Experimental section.

2. The method of claim 1 , wherein the lubricating oil composition, when containing 12 mass% carbon black (based upon the weight of the lubricating oil composition) has a dynamic viscosity (Pas) at a shear rate of 4.3(1 / s) at least 5 % lower (such as at least 10% lower, such as at least 13% lower) than the dynamic viscosity at a shear rate of 4.3(1 / s) of the same lubricating oil composition except that the Cs-9 diphenylamine antioxidant has been replaced with the same amount of diphenylamine antioxidant having:1) about 68 mass% di-Cg-alkyl diphenylamine,2) about 29 mass% of mono-Cg-alkyl diphenylamine, and3) about 3 mass% of tri-Cg-alkyl diphenylamine, based on the weight of 1), 2) and 3), as determined by UPLC in the Experimental section.

3. The method of claim 1 , wherein the lubricating oil composition, when containing 12 mass% carbon black (based upon the weight of the lubricating oil composition, has a dynamic viscosity (Pas) at a shear rate of 8.3(1 / s) at least 5 % lower (such as at least 10% lower, such as at least 15% lower, such as at least 17% lower) than the dynamic viscosity at a shear rate of 8.3(1 / s) of the same lubricating oil composition except that the Cs-9 diphenylamine antioxidant has been replaced with the same amount of diphenylamine antioxidant having:1) about 68 mass% di-Cg-alkyl diphenylamine,2) about 29 mass% of mono-Cg-alkyl diphenylamine, and3) about 3 mass% of tri-Cg-alkyl diphenylamine, based on the weight of 1), 2) and 3), as determined by UPLC in the Experimental section.

4. The method of claim 1 , wherein the lubricating oil composition comprises styrenic block copolymer viscosity modifier.

5. The method of claim 1 , wherein the lubricating oil composition comprises 0.1 to 10 mass% of styrenic block copolymer viscosity modifier, based upon the weight of the lubricating oil composition.

6. The method of claim 5, wherein the sytrenic block copolymer comprises hydrogenated styreneisoprene butadiene block copolymer is optionally combined with one or more Cs-20 dialkyl fumarate / vinyl acetate copolymers.

7. The method of claim 6, wherein the dialkyl fumarate / vinyl acetate copolymers have a pour point (ASTM D97) of -10°C or less.

8. The method claim 1 , wherein the detergent comprises calcium and or magnesium salicylate and or sulfonate detergents.

9. The method of claim 1 , wherein the detergent comprises calcium salicylate and or magnesium sulfonate detergents.

10. The method of claim 1 , wherein the lubricating oil composition comprises boron containing compounds.11 . The method claim 1 , wherein the lubricating oil composition comprises dispersant derived from poyisobutylene having a number average molecular weight of 1600 g / mol or less.

12. The method of claim 1 , wherein the lubricating oil composition comprises dispersant derived from poyisobutylene having a number average molecular weight of 2000 g / mol or more.

13. The method of claim 1 , wherein the diphenylamine antioxidant comprises: at least 85 mass% of di (Cs 9 substituted phenyl)amine and from 0 to 15 mass% (such as 1 to 10 mass%, such as 0 to 8 mass%, such as 0 to 5 mass%) of mono(Cg substituted phenyl)amine, based upon the weight of the mono- and diphenylamines.

14. The method of claim 1 , wherein the diphenylamine antioxidant comprises: at least 85 mass% of di(Cs substituted phenyl)amine, from 0 to 15 mass% of mono(Cs substituted phenyl)amine, and less than 0.1 mass% of unsubstituted phenylamine, based upon the weight of the unsubstituted, mono substituted- and disubstituted-diphenyl amines.

15. The method of claim 1 , wherein the diphenylamine antioxidant comprising: at least 85 mass% of di (Cg substituted phenyl)amine and from 0 to 15 mass% of mono(Cg substituted phenyl)amine, based upon the weight of the unsubstituted, mono substituted- and disubstituted-diphenylamines.

16. The method of claim 1 , wherein the lubricating oil composition comprises one or more molybdenum containing compounds.

17. The method of claim 1 , wherein the lubricating oil composition comprises polyisobutylene and or polyisobutylenesuccinate.

18. The method of claim 1 , wherein the lubricating oil composition comprises at least 1200 ppm Ca and or at least 800 ppm Mg, based upon the weight of the lubricating oil composition.

19. The method of claim 1 , wherein the lubricating oil composition has a dynamic viscosity (Pas) at a shear rate of 1 .3(1 / s) at least 10 % lower than the dynamic viscosity at a shear rate of 1 .3(1 / s) of the same lubricating oil composition except that the Cs-g diphenylamine antioxidant has been replaced with the sameamount of diphenylamine antioxidant having:1) about 68 mass% di-Cg-alkyl diphenylamine,2) about 29 mass% of mono-Cg-alkyl diphenylamine, and3) about 3 mass% of tri-Cg-alkyl diphenylamine, based on the weight of 1), 2) and 3), as determined by UPLC in the Experimental section; and a dynamic viscosity (Pas) at a shear rate of 4.3(1 / s) at least 5 % lower than the dynamic viscosity at a shear rate of 4.3(1 / s) of the same lubricating oil composition except that the Cs-g diphenylamine antioxidant has been replaced with the same amount of diphenylamine antioxidant having:1) about 68 mass% di-Cg-alkyl diphenylamine,2) about 29 mass% of mono-Cg-alkyl diphenylamine, and3) about 3 mass% of tri-Cg-alkyl diphenylamine, based on the weight of 1), 2) and 3), as determined by UPLC in the Experimental section; and a dynamic viscosity (Pas) at a shear rate of 8.3(1 / s) at least 5 % lower than the dynamic viscosity at a shear rate of 8.3(1 / s) of the same lubricating oil composition except that the Cs-g diphenylamine antioxidant has been replaced with the same amount of diphenylamine antioxidant having:1) about 68 mass% di-Cg-alkyl diphenylamine,2) about 29 mass% of mono-Cg-alkyl diphenylamine, and3) about 3 mass% of tri-Cg-alkyl diphenylamine, based on the weight of 1), 2) and 3), as determined by UPLC in the Experimental section.

20. The method of claim 1 , wherein the Cs-g diphenylamine antioxidant is provided to a concentrate used to prepare the lubricating oil composition in molten form.21 . The method of claim 1 , wherein the Cs-g diphenylamine antioxidant is provided to a concentrate used to prepare the lubricating oil composition as a blend of Cs-g diphenylamine antioxidant with polar diluent, optionally Cs-Cio tri-methylol propane ester.

22. The method of claim 1 , wherein the dispersant comprises one or more amide, imide, and / or ester functionalized partially or fully saturated polymers comprising C4-5 olefins having: i) an Mw / Mn of less than 2, ; ii) a Functionality Distribution (Fd) value of 3.5 or less; iii) an Average Functionality Value (Fv) of 1 .4 to 20 FG grafts / polymer chain; and iv) an Mn of 10,000 g / mol or more, (GPC-PS) of the polymer prior to functionalization, optionally provided that, if the polymer prior to functionalization is a copolymer of isoprene and butadiene, then the Mn of the copolymer is greater than 25,000 g / mol, (GPC-PS).

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