Lubricant Compositions Containing Phenolic Antioxidants and Alkyl Alcohols For Use in Internal Combustion Engines

Abstract

This disclosure relates to an antioxidant composition, comprising: 1) C10 to C36 linear, branched or cyclic alcohol, 2) hindered phenolic antioxidant, 3) optionally molybdenum containing compound, and 4) optionally, diphenylamine compound, and the use thereof as antioxidant in lubricant compositions having good oxidation properties in internal combustion engine applications, especially in compression ignited engine and or spark ignited engine applications.

Description

PRIORITY

[0001] This application claims priority to and the benefit of U.S. Ser. No. 63 / 713,949, filed on Oct. 30, 2024.FIELD OF THE INVENTION

[0002] This disclosure relates to the use of hindered phenolic antioxidants in combination with C10-C36 alcohols (preferably with optional molybdenum containing compounds) as additives in lubricant oil compositions having good oxidation properties in internal combustion engine applications, especially in compression ignited engine and or spark ignited applications.BACKGROUND OF THE INVENTION

[0003] The present invention relates to lubricating oil compositions which exhibit improved oxidation 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) using a fuel optionally comprising a portion of or all bio-fuel such as biodiesel, such compositions optionally referred to as crankcase lubricants; and to the use of additives in such lubricating oil compositions for reducing oxidation in use of such engines and / or improving the viscometric performance of an engine lubricated with the lubricating oil composition.

[0004] 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, fuel choices, and oil performance expectations, oxidation continues to be an important ongoing technical challenge.

[0005] A method 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.

[0006] 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.).

[0007] C9 alkyl substituted diphenylamine antioxidants are commonly used in engine oil formulations, however there is a desire to replace C9 alkyl substituted diphenylamine antioxidant. Other antioxidants, such as hindered phenol based antioxidants, are available for use, but tend to be expensive and less effective than C9 alkyl substituted diphenylamine antioxidant, particularly for viscosity control.

[0008] US 2020 / 299603 discloses the use of an alcohol of formula R—OH, in which R is a linear or branched saturated alkyl group with 10 to 36 carbon atoms, in a lubricant composition having good cold start properties to improve the cleanliness of a 4-stroke vehicle engine.

[0009] WO 2024 / 091494 discloses a lubricating composition containing saturated primary monohydric alcohol and a dispersant, among other things, where the saturated primary monohydric alcohol provides a metal-free, ashless additive that aids in oxidation and deposit control as well as the resulting undesirable viscosity increase. Example 2 illustrates a finished oil blend comprising dodecanol and C9 substituted diphenylamine antioxidant.

[0010] WO2024 / 091553 discloses a lubricating composition containing a branched diol and a dispersant, where the alcohol provides a metal-free, ashless additive that aids in oxidation and deposit control as well as in addressing the resulting undesirable viscosity increase.

[0011] U.S. Pat. No. 9,650,587 (WO 2012 / 062020) discloses compositions containing limited solubility antioxidants combined with a compatibilizer for use in additive packages or lubricating oil compositions.

[0012] US 2023 / 0250353 discloses the use of diester materials to increase oxidation resistance of lubricating oil compositions.

[0013] US2024 / 0141156 discloses functionalized polymers comprising amide, imide, and / or ester functionalized partially or fully saturated polymer comprising C4-5 olefins having: i) an Mw / Mn of less than 2, ii) a Functionality Distribution (Fd) value of 3.5 or less, and iii) an Mn of 10,000 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 (GPC-PS).

[0014] Other references of interest include: GB 1,112,784; CN101319155A; CN103865615A; EP1981955B9; EP2055763A1; EP2155657 B1; EP2548940B1; EP4118170A1; EP4118171A1; EP0630881A1; EP0398215A1; JP2016193994A; US20110030269A1; US 2017 / 0081609; US 2017 / 066991; US 2020 / 299603; U.S. Pat. Nos. 3,452,056; 3,505,223; 3,533,992; 3,004,916A; U.S. Pat. Nos. 4,822,839A; 5,236,610; 5,269,961; 5,449,829; 6,383,992B1; U.S. Pat. No. 7,928,045B2; U.S. Pat. Nos. 9,315,760; 7,960,322; 7,145,038; 8,999,903; 9,512,380; 9,315,760; 11,499,117; 11,518,732; WO2012 / 173774A1; WO 2018 / 156304; WO 2020 / 194125; WO2020 / 239963A1; WO 2023 / 133090 A1, WO 2023 / 209038A1, WO2024 / 156810A1, WO2024 / 158648A1, and US2024 / 0240099A1.

[0015] It has now surprisingly been found that compositions comprising certain hindered phenols in combination with C10 or higher alcohols (optionally combined with molybdenum containing compounds and or diphenylamine compounds) can be used in an additive package and or a lubricating oil composition, such as in internal combustion engines to provide stability, improved viscometric control, such as providing reduced kinematic viscosity growth and / or enhanced oxidation performance.SUMMARY OF THE INVENTION

[0016] This disclosure relates to lubricating oil compositions and or concentrates that maintain or improve oxidation performance and have improved kinematic viscosity growth in lubricating oils. More particularly, the present invention relates to an antioxidant composition, comprising: 1) hindered phenolic antioxidant, 2) C10 to C36 linear, branched or cyclic alcohol (such as branched or linear alcohol), 3) optionally, a molybdenum containing compound, 4) optionally, hydrocarbyl substituted diphenylamine compound, 5) optionally, salicylate detergent, and 6) optionally, 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, ii) a Functionality Distribution (Fd) value of 3.5 or less (GPC-PS), and iii) an Mn of 10,000 g / mol or more (GPC-PS) of the polymer prior to functionalization, and optionally, 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); preferably, where when a lubricating oil composition comprises the antioxidant composition, the growth of kinematic viscosity of the lubricating oil composition, as determined by the Daimler Truck Oxidation Test at 168 hours, is less than 150%, preferably 100% or less, such as 80% or less, such as 50% or less (as described in the Experimental section below), and or the oxidation, as determined by the Nitration-Oxidation Test 1 at 144 hours, as described in the Experimental section below, is 70 A / cm or less, such as 60 A / cm or less, such as 50 A / cm or less, such as 45 A / cm or less.

[0017] This disclosure also relates to antioxidant and or concentrate compositions, often useful in passenger car motor oil applications, comprising: 1) hindered phenolic antioxidant, 2) C10 to C36 linear, branched or cyclic alcohol (such as branched or linear alcohol), 3) optionally, a molybdenum containing compound, 4) optionally, hydrocarbyl substituted diphenylamine compound, and 5) optionally, salicylate detergent, and 6) optionally, 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, ii) a Functionality Distribution (Fd) value of 3.5 or less (GPC-PS), and iii) an Mn of 10,000 g / mol or more (GPC-PS) of the polymer prior to functionalization, and optionally, 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) preferably; where when lubricating oil composition comprises the antioxidant composition and or the concentrate, the oxidation of the lubricating oil composition, as determined by the CEC-L109 Oxidation test at 216 hours (as described in the Experimental section below), is less than 130 A / cm, preferably 100 or less A / cm, such as 50 A / cm or less, such as 40 A / cm or less, such as 30 A / cm or less, such as 20 A / cm or less, and the percent viscosity increase as determined by the CEC-L109 Oxidation test at 216 hours (as described in the Experimental section below) is 100% or less, such as 90% or less, such 60% or less, such 50% or less.

[0018] More particularly, the present invention relates to an antioxidant composition, comprising: 1) hindered phenolic antioxidant, 2) C8 to C36 linear, branched or cyclic alcohol (such as branched or linear alcohol), 3) optionally, a molybdenum containing compound, 4) optionally, hydrocarbyl substituted diphenylamine compound, and 5) optionally, salicylate detergent, and 6) optionally, 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, ii) a Functionality Distribution (Fd) value of 3.5 or less (GPC-PS), and iii) an Mn of 10,000 g / mol or more (GPC-PS) of the polymer prior to functionalization, and optionally, 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); preferably, where when lubricating oil composition comprises the antioxidant composition, the oxidation at 216 hours of the lubricating oil composition, as determined by the CEC-L109 test, is less than 130 A / cm, preferably 100 or less, such as 50 or less, and the percent viscosity increase as determined by the CEC-L109 test at 216 hours is less than 10%, such as less than 50%.

[0019] This invention further relates to a concentrate comprising: 1) less than 50 mass % base oil (such as 40 mass % or less, such as 30 mass % or less, such as 20 mass % or less, such as 10 mass % or less of base oil, based upon the weight of the concentrate), 2) hindered phenolic antioxidant, 3) C8 to C36 linear, branched or cyclic alcohol (such as C10 to C24 branched and / or linear alcohol, such as C12 to C18 branched and / or linear alcohol, C12 to C18 linear alcohol, such as C12 linear alcohol), 4) optionally, a molybdenum containing compound, 5) optionally, hydrocarbyl substituted diphenylamine compound (such as di(C8 to C9-hydrocarbyl-phenyl)amine, such as di(nonylphenyl)amine and or di(octylphenyl)amine), and 6) optionally, 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, ii) a Functionality Distribution (Fd) value of 3.5 or less (GPC-PS), and iii) an Mn of 10,000 g / mol or more (GPC-PS) of the polymer prior to functionalization, and optionally, 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);

[0020] where when lubricating oil composition comprises the concentrate composition, the growth of kinematic viscosity of the lubricating oil composition, as determined by the Daimler Truck Oxidation Test at 168 hours, described in the Experimental section below, is less than 150%, preferably 100% or less, such as 80% or less, such as 50% or less and or the oxidation, as determined by the Nitration Oxidation test described in the Experimental section below, is 70 A / cm or less, such as 60 A / cm or less, such as 50 A / cm or less, such as 45 A / cm or less.

[0021] The present invention further relates to a lubricating oil composition, comprising: 1) hindered phenolic antioxidant, 2) C8 to C36 linear, branched or cyclic alcohol (such as branched or linear alcohol), and 3) molybdenum containing compound, where preferably the growth of kinematic viscosity of the lubricating oil composition, as determined by the Daimler Truck Oxidation Test at 168 hours, as described in the Experimental section below, is less than 150%, preferably 100% or less, such as 80% or less, such as 50% or less and or the oxidation, as determined by the Nitration-Oxidation test described in the Experimental section below, is 70 A / cm or less, such as 60 A / cm or less, such as 50 A / cm or less, such as 45 A / cm or less, such as 40 A / cm or less, such as 36 A / cm or less.

[0022] The present invention relates to a lubricating oil composition comprising: 1) hindered phenolic antioxidant, 2) C8 to C36 linear, branched or cyclic alcohol (such as branched or linear alcohol), 3) molybdenum containing compound, and 4) optional hydrocarbyl substituted diphenylamine compound, preferably where the growth of kinematic viscosity of the lubricating oil composition, as determined by the Daimler Truck Oxidation Test at 168 hours, as described in the Experimental section below, is less than 150%, preferably 100% or less, such as 80% or less, such as 50% or less and or the oxidation, as determined by the Nitration-Oxidation test described in the Experimental section below, is 70 A / cm or less, such as 60 A / cm or less, such as 50 A / cm or less, such as 45 A / cm or less.

[0023] The present invention relates to a lubricating oil composition, comprising: 1) hindered phenolic antioxidant, 2) C8 to C36 linear, branched or cyclic alcohol (such as branched or linear alcohol), 3) molybdenum containing compound, and 4) hydrocarbyl substituted diphenylamine compound, preferably where the growth of kinematic viscosity of the lubricating oil composition, as determined by the Daimler Oxidation Test at 168 hours, is less than 150%, preferably 100% or less, such as 80% or less, such as 50% or less and or the oxidation, as determined by the Nitration-Oxidation test described in the Experimental section below, is 70 A / cm or less, such as 60 A / cm or less, such as 50 A / cm or less, such as 45 A / cm or less.

[0024] The present invention relates to a lubricating oil composition, comprising:

[0025] 1) hindered phenolic antioxidant,

[0026] 2) C8 to C36 linear, branched or cyclic alcohol (such as branched or linear alcohol),

[0027] 3) molybdenum containing compound,

[0028] 4) 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, ii) a Functionality Distribution (Fd) value of 3.5 or less (GPC-PS), and iii) an Mn of 10,000 g / mol or more (GPC-PS) of the polymer prior to functionalization, and optionally, 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), and

[0029] 5) optionally, hydrocarbyl substituted diphenylamine compound, preferably where the growth of kinematic viscosity of the lubricating oil composition, as determined by the Daimler Truck Oxidation Test at 168 hours, is less than 150%, preferably 100% or less, such as 80% or less, such as 50% or less and or the oxidation, as determined by the Nitration-Oxidation test described in the Experimental section below, is 70 A / cm or less, such as 60 A / cm or less, such as 50 A / cm or less, such as 45 A / cm or less.

[0030] This disclosure further relates to lubricating oil compositions comprising:

[0031] 1) hindered phenolic antioxidant,

[0032] 2) C8 to C36 linear, branched or cyclic alcohol,

[0033] 3) a combination of molybdenum containing compound(s) and hydrocarbyl substituted diphenylamine compound(s); and

[0034] 4) 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, ii) a Functionality Distribution (Fd) value of 3.5 or less (GPC-PS), preferably where the oxidation, as determined by the Nitration-Oxidation test described in the Experimental section below, is 70 A / cm or less, such as 60 A / cm or less, such as 50 A / cm or less, such as 45 A / cm or less.

[0035] The present invention relates to a lubricating oil composition, comprising:

[0036] 1) hindered phenolic antioxidant,

[0037] 2) C8 to C36 linear, branched or cyclic alcohol (such as branched or linear alcohol),

[0038] 3) molybdenum containing compound,

[0039] 4) optionally an amide, imide, and / or ester functionalized partially or fully saturated polymer comprising C4-C5 olefins having: i) an Mw / Mn of less than 2, ii) a Functionality Distribution (Fd) value of 3.5 or less (GPC-PS), and iii) an Mn of 10,000 g / mol or more (GPC-PS) of the polymer prior to functionalization, and optionally, 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), and

[0040] 5) optionally, hydrocarbyl substituted diphenylamine compound, preferably where the oxidation, as determined by the Nitration-Oxidation test described in the Experimental section below, is 70 A / cm or less, such as 60 A / cm or less, such as 50 A / cm or less, such as 45 A / cm or less.

[0041] This invention further relates to lubricating oil compositions comprising or resulting from the admixing of at least 50 mass % of one or more base oils, based upon the weight of the lubricating oil composition; and an antioxidant composition and / or a concentrate composition described herein.

[0042] This invention further relates to lubricating oil compositions, concentrates, and or anti-oxidant compositions wherein hydrocarbyl substituted diphenylamine compound is absent.

[0043] This invention further relates to lubricating oil compositions, concentrates, and or anti-oxidant compositions wherein hydrocarbyl substituted diphenylamine compound is absent or present at less than 0.3 mass % (such as less than 0.2 mass %, such as less than 0.1 mass %).

[0044] In embodiments, the antioxidant composition and or the concentrate, and or the lubricating oil composition(s) described herein is / are absent aminic antioxidant, such as absent phenyl amine antioxidant, such as absent alkyl substituted diphenyl amine antioxidant, such as absent alkyl substituted diphenyl amine antioxidant, such as absent C8 alkyl substituted diphenyl amine antioxidant, absent C9 alkyl substituted diphenyl amine antioxidant and or absent C8-C9 alkyl substituted diphenyl amine antioxidant.

[0045] (For the amide, imide, and / or ester functionalized partially or fully saturated polymer comprising C4-5 olefins polymers described and or used herein, Average Functionality [also referred to as Average Functionality Value (Fv)], Functionality Distribution (Fd) value and number average molecular weight (Mn) are determined by Gel Permeation Chromatography using polystyrene standards as described in the Experimental section of U.S. patent application Ser. No. 18 / 480,571, filed Oct. 4, 2023.)

[0046] According to another aspect of the present invention, there is provided the use of the lubricating oil composition described above for lubrication of an engine.BRIEF DESCRIPTION OF THE DRAWINGS

[0047] FIG. 1 (FIG. 1) is a graph of the Daimler Oxidation Test results for Examples A through F (168 hours).

[0048] FIG. 2 (FIG. 2) is a graph of the Nitration-Oxidation Test results for Examples A through F (144 hours).

[0049] FIG. 3 (FIG. 3) is a graph of CEC-L-109 test results for LOC Blends 1A to 1G.

[0050] FIG. 4 (FIG. 4) is a graph of CEC-L-109 test results for LOC Blends 2A to 2G.

[0051] FIG. 5 (FIG. 5) is a graph of CEC-L-109 test results for LOC Blends 3A to 3G.

[0052] FIG. 6 (FIG. 6) is a graph of CEC-L-109 test results for LOC Blends 4A to 4G.DEFINITIONS

[0053] 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.

[0054] For purposes herein, the new numbering scheme for the Periodic Table of the Elements is used as set out in CHEMICAL AND ENGINEERING NEWS, 63(5), 27 (1985), i.e., Alkali metals are group 1 metals (e.g., Li, Na, K, etc.) and Alkaline earth metals are group 2 metals (e.g., Mg, Ca, Ba, etc.).

[0055] 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.

[0056] The term “LOC” means lubricating oil composition.

[0057] 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.

[0058] 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.

[0059] 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”).

[0060] 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.

[0061] 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.

[0062] The terms “group” and “radical” are used interchangeably herein.

[0063] 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).

[0064] 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.).

[0065] The term “alkyl” means a radical of carbon and hydrogen (such as a C1 to C30, such as a C1 to C12 group). Alkyl groups in a compound are typically bonded to the compound directly via a carbon atom. Unless otherwise specified, alkyl groups may be linear (i.e., unbranched) or branched, be cyclic, acyclic, or part cyclic / acyclic. 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.

[0066] 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 (i.e., unbranched) or branched, be cyclic, acyclic or part cyclic / acyclic.

[0067] The term “alkylene” means a C1 to C20, preferably a C1 to C10, bivalent saturated aliphatic radical, which may be linear or branched. Representative examples of alkylene include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, 1-methyl ethylene, 1-ethyl ethylene, 1-ethyl-2-methyl ethylene, 1,1-dimethyl ethylene and 1-ethyl propylene.

[0068] An “olefin”, alternatively referred to as “alkene”, is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For purposes of this specification and the claims appended thereto, when a polymer or copolymer is referred to as comprising an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an “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.

[0069] 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.

[0070] 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 C18, such as C6 to C14) aryl groups, optionally substituted by one or more hydrocarbyl groups, heteroatoms, or heteroatom-containing groups (such as halo, hydroxyl, alkoxy and amino groups). Preferred aryl groups include phenyl and naphthyl groups and substituted derivatives thereof, especially phenyl, and alkyl substituted derivatives of phenyl.

[0071] 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 C1 to C20 alkyl group, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, hexyl, heptyl, octyl, dimethyl hexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl and / or triacontyl. 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 C1 to C20 alkyl group, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, hexyl, heptyl, octyl, dimethyl hexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl and / or triacontyl).

[0072] An alkaryl group is an aryl group that has been substituted with one or more alkyl groups (where the alkyl group may be a substituted or unsubstituted alkyl group).

[0073] An aralkyl is an alkyl group that has been substituted with one or more aryl groups (where the aryl group may be a substituted or unsubstituted aryl group). A substituent group derived from styrene can be an aralkyl group when the substituent is incorporated through the ethylene moiety of the styrene.

[0074] 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 preventing components in a lubricating oil composition from breakdown and causing thickening (increasing viscosity) of the lubricating oil composition. 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).

[0075] 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 (3,5 di-t-butyl, 4-hydroxy toluene) and substituted butylated hydroxy toluenes. Commercial examples include Irganox™ L135 or Songnox™ L115.

[0076] A hindered phenolic antioxidant is a hindered phenol that functions as an antioxidant, preferably as a primary antioxidant (radical scavenger).

[0077] The term “halogen” or “halo” means a group 17 atom or a radical of group 17 atom, such as fluoro, chloro, bromo, and iodo.

[0078] The term “ashless” in relation to an additive means the composition does not include a metal.

[0079] The term “ash-containing” in relation to an additive means the composition includes a metal.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] The term “ppm” means parts per million by mass, based on the total mass of the lubricating oil composition, unless otherwise indicated.

[0084] 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.

[0085] 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. The term “absent” as it relates to components included within the concentrate compositions described herein and the claims thereto means that the particular component is present at 0 mass %, based upon the weight of the concentrate composition, or if present in the concentrate composition the component is present at levels that do not impact the concentrate properties, such as less than 10 ppm, or less than 1 ppm or less than 0.001 ppm. The term “absent” as it relates to components included within the antioxidant compositions described herein and the claims thereto means that the particular component is present at 0 mass %, based upon the weight of the antioxidant composition, or if present in the antioxidant composition the component is present at levels that do not impact the antioxidant 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. The term “absent” means that a particular material is present at 0 mass %, based upon the weight of the composition, or if present in the composition the material is present at levels that do not impact the composition properties, such as less than 10 ppm, or less than 1 ppm or less than 0.001 ppm.

[0086] 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 %0, 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.

[0087] The term “absent or present at less than 0.2 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: 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.

[0088] The term “absent or present at less than 0.1 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: 0.095 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.

[0089] 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.

[0090] Total Base Number also referred to as “TBN”, in relation to an additive component or of a lubricating oil composition (i.e., unused lubricating oil composition) means total base number as measured by ASTM D2896 and reported in units of mgKOH / g. “High TBN” is considered to be greater than or equal to 200 KOH / g, or greater than 300 mgKOH / g, or 300 to 500 mgKOH / g. “Low TBN” is considered less than 200 KOH / g, or less than 100 KOH / g.

[0091] Total Acid Number (“TAN”) is determined by ASTM D664.

[0092] Phosphorus, Boron, Calcium, Zinc, Molybdenum, Sodium, Silicon, and Magnesium content are measured by ASTM D5185.

[0093] Sulfur content in oil formulations is measured by ASTM D5185.

[0094] Sulfated ash (“SASH”) content is measured by ASTM D874.

[0095] Kinematic viscosity (KV100, KV40, etc.) is determined pursuant to ASTM D445-19a and reported in units of cSt, unless otherwise specified.

[0096] Viscosity index is determined according to ASTM D2270.

[0097] Saponification number is determined by ASTM D94 and reported in units of mgKOH / g.

[0098] For purposes of this invention and the claims thereto, when a composition (including, but not limited to antioxidant compositions, concentrate packages, lubricating oil compositions) comprising one or more polar diluents and one or more diphenylamine antioxidants (such as aralkyl substituted diphenylamine antioxidants) is described as “stable at X ° C. for Y hours” or “clear after Y hours at X ° C.”, it means that the composition comprising the polar diluent(s) and the diphenylamine antioxidant(s) is observed to be clear (meaning having no crystallization, precipitation or cloudiness) after X hours of being held at Y ° C. temperature in a clear glass container with no agitation.

[0099] For purposes of this invention and the claims thereto, for the amide, imide, and / or ester functionalized partially or fully saturated polymer comprising C4_s olefins polymers described and or used herein, Average Functionality [also referred to as Average Functionality Value (Fv)], Functionality Distribution (Fd) value and number average molecular weight (Mn) are determined by Gel Permeation Chromatography using polystyrene standards as described in the Experimental section of U.S. patent application Ser. No. 18 / 480,571, filed Oct. 4, 2023.)

[0100] Unless otherwise indicated, all percentages reported are mass % on an active ingredient basis, i.e., without regard to carrier or diluent oil.

[0101] 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.

[0102] Further, it is understood that any upper and lower quantity, range and ratio limits set forth herein may be independently combined.

[0103] 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

[0104] 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.

[0105] 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 other additives. This disclosure encompasses compositions which comprise the components before mixing, or after mixing, or both before and after mixing.

[0106] The antioxidant 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 other additives. This disclosure encompasses compositions which comprise the components before mixing, or after mixing, or both before and after mixing.

[0107] The concentrate 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 other additives. This disclosure encompasses compositions which comprise the components before mixing, or after mixing, or both before and after mixing.

[0108] The booster pack 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 other additives. This disclosure encompasses compositions which comprise the components before mixing, or after mixing, or both before and after mixing.

[0109] The compositions disclosed herein are useful in booster backs, concentrates and lubricating oil compositions, among other things.Antioxidant Compositions

[0110] This invention relates to antioxidant compositions comprising:

[0111] 1) from 0 to less than 50 mass % of one or more base oils (such as 0.01 to 40 mass %, such as 30 mass % or less, such as 20 mass % or less, such as 10 mass % or less) of base oil, based upon the weight of the antioxidant composition),

[0112] 2) from 0.1 to 99.9 mass %, such as 0.1 to 90.0 mass % (such as 0.1 to 80 mass % such as 0.2 to 60 mass %, such as 0.5 to 50 mass %) of one or more hindered phenolic antioxidants,

[0113] 3) from 0.1 to 99.9 mass %, such as 0.25 to 90.0 mass % (such as such as 0.5 to 80 mass %, such as 1 to 60 mass %, such as 1.5 mass % to 50 mass %) of one or more C8 to C36 linear, branched or cyclic alcohols (such as C10 to C24 branched and / or linear alcohols, such as C12 to C18 branched and / or linear alcohols, such as C12 to C18 linear alcohols, such as C12 linear alcohol),

[0114] 4) optionally, from 0.01 to 10 mass, such as 0.1 to 8 mass %, such as 0.5 to 5 mass % of one or more molybdenum containing compounds (such as molybdenum dithiocarbamate (MoDTC) dimer and or trimer),

[0115] 5) optionally, from 0.01 to 10 mass, such as 0.1 to 8 mass %, such as 0.1 to 5 mass %, 0.2 to 3.5 mass %, such as 0.25 mass % to 3.0 mass %, such as 0.25 mass % to 2.8 mass %) of one or more hydrocarbyl substituted diphenylamine compounds (such as di(C8 to C9-hydrocarbyl-phenyl)amine, such as di(nonylphenyl)amine and or di(octylphenyl)amine, such as styryl substituted diphenylamine and or alpha methyl styryl diphenylamine), and

[0116] 6) optionally, from 0.3 to 20 mass %, (such as 0.3 to 14 mass %, such as 0.4 mass % to 12 mass %, such as 0.5 mass % to 10 mass %) of 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, ii) a Functionality Distribution (Fd) value of 3.5 or less (GPC-PS), and iii) an Mn of 10,000 g / mol or more (GPC-PS) of the polymer prior to functionalization, and optionally, 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), where when a lubricating oil composition comprises the antioxidant composition 1) the growth of kinematic viscosity of the lubricating oil composition, as determined by the Daimler Truck Oxidation Test at 168 hours, described in the Experimental section below, is less than 150%, preferably 100% or less, such as 80% or less, such as 50% or less and or the oxidation, as determined by the Nitration Oxidation test described in the Experimental section below, is 70 A / cm or less, such as 60 A / cm or less, such as 50 A / cm or less, such as 45 A / cm or less; and or 2) the oxidation at 216 hours of the lubricating oil composition, as determined by the CED-L109 test at 216 hours, is less than 130 A / cm, preferably 100 or less, such as 50 or less, and the percent viscosity increase as determined by the CED-L109 test at 216 hours is less than 10%, such as less than 50%.

[0117] In embodiments, an antioxidant composition may be obtained by combining:

[0118] 1) from 0.1 than 50 mass % of one or more base oils (such as 0.01 to 40 mass %, such as 30 mass % or less, such as 20 mass % or less, such as 10 mass % or less) of base oil, based upon the weight of the antioxidant composition),

[0119] 2) from 0.1 to 99.9 mass %, such as 0.1 to 90.0 mass % (such as 0.1 to 80 mass % such as 0.2 to 60 mass %, such as 0.5 to 50 mass %) of one or more hindered phenolic antioxidants,

[0120] 3) from 0.1 to 99.9 mass %, such as 0.25 to 90.0 mass % (such as such as 0.5 to 80 mass %, such as 1 to 60 mass %, such as 1.5 mass % to 50 mass %) of one or more C8 to C36 linear, branched or cyclic alcohols (such as C10 to C24 branched and / or linear alcohols, such as C12 to C18 branched and / or linear alcohols, such as C12 to C18 linear alcohols, such as C12 linear alcohol),

[0121] 4) optionally, from 0.01 to 10 mass, such as 0.1 to 8 mass %, such as 0.5 to 5 mass % of one or more molybdenum containing compounds (such as molybdenum dithiocarbamate (MoDTC) dimer and or trimer), 5) optionally, from 0.1 to 10.0 mass % such as 0.1 to 8 mass %, such as 0.1 to 5 mass %, 0.2 to 3.5 mass %, such as 0.25 mass % to 3.0 mass %, such as 0.25 mass % to 2.8 mass %) of one or more hydrocarbyl substituted diphenylamine compounds (such as di(C8 to C9-hydrocarbyl-phenyl)amine, such as di(nonylphenyl)amine and or di(octylphenyl)amine).

[0122] In embodiments, an antioxidant composition may be obtained by combining:

[0123] 1) less than 50 mass % of one or more base oils (such as 40 mass % or less, such as 30 mass % or less, such as 20 mass % or less, such as 10 mass % or less of base oil) based upon the weight of the antioxidant composition),

[0124] 2) from 0.1 to 10.0 mass % (such as 0.2 mass % to 3.5 mass %, such as 0.3 mass % to 3.0 mass %) of one or more hindered phenolic antioxidants,

[0125] 3) from 0.1 to 4.0 mass % (such as 0.2 mass % to 3.5 mass %, such as 0.3 mass % to 3.0 mass %) of on or more C10 to C36 linear, branched or cyclic alcohols (such as C10 to C24 branched and / or linear alcohols, such as C12 to C18 branched and / or linear alcohols, such as C12 to C18 linear alcohols, such as C12 linear alcohol), and

[0126] 4) from 0.02 to 0.55 mass % (such as 0.03 mass % to 0.50 mass %, such as 0.04 mass % to 0.45 mass %) of one or more molybdenum containing compounds (such as molybdenum dithiocarbamate (MoDTC) dimer and or trimer).

[0127] The antioxidant compositions described herein may be used as lubricant additives, as lubricant additive packages (such as all or part of a concentrate), and as booster packs for lubricant additives and additive packages, among other things. Booster packages are typically a combination of lubricant additives provided separately for use with a concentrate and are typically combined with a concentrate before or at the same time that the concentrate is formulated into a lubricating oil composition or before the concentrate is provided to a customer.

[0128] In embodiments, the antioxidant composition(s) described herein is / are absent aminic antioxidant, such as absent phenyl amine antioxidant, such as absent alkyl substituted diphenyl amine antioxidant, such as absent alkyl substituted diphenyl amine antioxidant, such as absent C8 alkyl substituted diphenyl amine antioxidant, absent C9 alkyl substituted diphenyl amine antioxidant and or absent C8-C9 alkyl substituted diphenyl amine antioxidant.

[0129] Alternately, the antioxidant composition(s) described herein further comprise one or more diphenyl amine antioxidant compositions described in U.S. patent application Ser. No. 63 / 593,559, filed Oct. 27, 2023, and entitled Lubricant Compositions Containing High C9 Disubstituted Diphenylamine Antioxidant Content.

[0130] Alternately, the antioxidant composition(s) described herein further comprise diphenyl amine antioxidant compositions described in European Patent Office Patent Application and EP serial number European Patent Application 23218548.8, filed Dec. 20, 2023, entitled Lubricant Compositions Containing C8 Disubstituted Diphenylamine Antioxidant.

[0131] In embodiments, the antioxidant composition comprises less than 0.1 mass %, based upon the mass of the antioxidant composition, (such as 0 mass %) of aminic antioxidant (such as diphenyl amine antioxidant) as described in Component E below as Additional Antioxidants.

[0132] Alternately, the antioxidant composition(s) described herein comprise one or more additional antioxidants as described in Component E below as Additional Antioxidants.

[0133] In embodiments, the antioxidant composition comprises one or more additional antioxidants, such as aminic antioxidant (such as diphenyl amine antioxidant), as described in Component E below as Additional Antioxidants.

[0134] In embodiments, the antioxidant composition further comprises diphenyl amine antioxidant comprising 1) di(C9-alkyl substituted diphenyl) amine, and 2) from 0 to less than 10 mass % of mono-C9-alkyl substituted diphenyl amine, based upon the weight of any unsubstituted diphenylamine, the mono-phenyl amines and di-phenyl amines present in the antioxidant composition (as determined by UPLC as described in the Experimental section of US2025 / 0136889A1).

[0135] In embodiments, the antioxidant composition further comprises diphenyl amine antioxidant comprising 90 mass % or more of di(C9-alkyl substituted diphenyl) amines, from 0 to less than 10 mass % of mono-C9-alkyl substituted diphenyl amine, and from 0 to less than 10 mass % of tri-C9-alkyl substituted diphenyl amine, based upon the weight of any unsubstituted diphenylamine, and the mono-, di-, and tri-phenyl amines present in the antioxidant composition (as determined by UPLC as described in the Experimental section of US2025 / 0136889A1).

[0136] In embodiments, the antioxidant composition further comprises diphenyl amine antioxidant comprising: 1) 85 mass % or more of di(C9-alkyl substituted diphenyl) amines, 2) from 0 to less than 15 mass % of mono-C9-alkyl substituted diphenyl amine and tri-C9-alkyl substituted diphenyl amine, and 3) less than 0.1 mass % of unsubstituted diphenylamine, based upon the weight of unsubstituted diphenylamine, and mono-, di-, and tri-phenyl amines present in the antioxidant composition (as determined by UPLC as described in the Experimental section of US2025 / 0136889A1).

[0137] In embodiments, the antioxidant composition further comprises diphenyl amine antioxidant comprising: a) diphenylamine antioxidant comprising: 1) di(C8-alkyl substituted phenyl) amine, and 2) less than 15 mass % of mono-C8-alkyl substituted diphenylamine (based upon the weight of any unsubstituted diphenylamine, mono-C8-alkyl substituted phenylamines, di-C8-alkyl substituted phenylamines, and any tri-C8-alkyl substituted phenylamines present in the antioxidant composition, as determined by UPLC as described in the Experimental section of US2025 / 0136889A1); and b) polar diluent having an aniline point of 25° C. or less, and at least 2 available hydrogen-bond acceptor groups (such as ester, ether or alcohol groups) that are 2, 3, 4, 5, or 6 atoms apart, wherein the composition comprising the polar diluent of b) combined with the diphenylamine antioxidant of a) is clear after 96 hours at 20° C. in a clear glass container without agitation.

[0138] In embodiments, the antioxidant composition further comprises diphenyl amine antioxidant comprising: a) diphenylamine antioxidant comprising: 1) di(C8-alkyl substituted phenyl) amine, and 2) less than 15 mass % of mono-C8-alkyl substituted diphenylamine (based upon the weight of any unsubstituted diphenylamine, and the mono-C8-alkyl substituted phenylamines, di-C8-alkyl substituted phenylamines, and any tri-C8-alkyl substituted phenylamines present in the antioxidant composition, as determined by UPLC as described in the Experimental section of US2025 / 0136889A1); and b) polar diluent having an aniline point of 25° C. or less, and at least 2 available hydrogen-bond acceptor groups (such as ester, ether or alcohol groups) that are 2, 3, 4, 5, or 6 atoms apart, wherein the composition comprising the polar diluent of b) combined with the diphenylamine antioxidant of a) is clear after 96 hours at 20° C. in a clear glass container without agitation; and c) salicylate detergent, optionally wherein the antioxidant composition is combined with the detergent at a temperature of 70° C. or more, or 75° C. or more, or 80° C. or more.

[0139] Further, the alkyl substituted diphenylamine compositions described herein are free of added tetra-C9-alkyl substituted diphenylamines. Also, tetra-C9-alkyl substituted diphenylamines are not observed in the alkyl substituted diphenylamine compositions disclosed herein as determined by the UPLC method described in the Experimental section of US2025 / 0136889A1).

[0140] In embodiments, the antioxidant composition(s) described herein further comprise aralkyl substituted diphenylamine antioxidant compositions described in European Patent Office Patent Application number 23218539.7, filed Dec. 20, 2023, entitled Lubricant Compositions Containing Aralkyl Substituted Diphenylamine Antioxidant.

[0141] In embodiments, the antioxidant composition(s) described herein further comprise diphenyl amine antioxidant compositions described in European Patent Office Patent Application number 23218550.4, filed Dec. 20, 2023, entitled Lubricant Compositions Containing Mono-aralky and Di-aralkylSubstituted Diphenylamine Antioxidants.

[0142] In embodiments, the antioxidant composition(s) described herein may comprise from 0 to 20 mass % (such as 0.1 to 10 mass %) of one, two, three or more of:

[0143] a) aralkyl substituted diphenylamine as described in Component E below as Additional Antioxidants;

[0144] b) stable antioxidant compositions comprising: i) diphenylamine antioxidant comprising: aralkyl substituted diphenylamine; and ii) polar diluent having an aniline point of 0° C. or less, and at least 2 available hydrogen-bond acceptor groups that are 2, 3, 4, 5, or 6 atoms apart, as described in Component E below as Additional Antioxidants; and

[0145] c) a stable antioxidant composition comprising a homogeneous diphenylamine antioxidant fluid comprising di-aralkyl substituted diphenylamine and at least 45 mass % mono-aralkyl substituted diphenylamine, based upon the weight of any unsubstituted diphenylamine, and the mono- and di-substituted diphenylamines, as determined by UPLC as described in the Experimental section of US2025 / 0136889A1, as described in Component E below as Additional Antioxidants.

[0146] In embodiments, the antioxidant composition(s) described herein comprise 0.01 to 20 mass % such as 0.1 to 10 mass %, based upon the mass of the antioxidant composition, of one, two, three or more additional antioxidants as described in Component E below as Additional Antioxidants.

[0147] In embodiments, the antioxidant composition(s) described herein comprise less than 0.1 mass %, based upon the mass of the antioxidant composition, (such as 0 mass %) of one, two, three or more additional antioxidants as described in Component E below as Additional Antioxidants.Concentrate Compositions

[0148] This disclosure also relates to concentrate compositions comprising or resulting from the admixing of:

[0149] A) from 0.1 to less than 50 mass % (alternately 5 to 45 mass %, alternately 7 to 40 mass %, alternately 10 to 35 mass %, alternately 1 to 25 mass %), based upon the weight of the concentrate composition, of one or more base oil(s);

[0150] B) from 0.10 to 45 mass % (in particular, from 0.10 to 35 mass %, alternately 0.010 to 30 mass %, alternately 0.15 to 20 mass %, alternately 0.20 mass % to 5 mass %, alternately 0.25 to 4 mass %) based upon the weight of the concentrate composition of one or more C10 to C36 linear, branched or cyclic alcohols (such as C10 to C24 branched and / or linear alcohols, such as C12 to C18 branched and / or linear alcohols, such as C12 to C18 linear alcohols, such as C12 linear alcohol) as described herein,

[0151] C) from 0.1 to 40 mass % (in particular, 0.25 to 30 mass %, alternately 0.4 to 20 mass %, alternately 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, such as salicylate and or sulfonate detergent, such as calcium and or magnesium salicylate and or sulfonate detergent, such as calcium salicylate and magnesium sulfonate detergent, such as calcium and magnesium salicylate detergent, such as magnesium sulfonate detergent, such as calcium salicylate detergent);

[0152] D) optionally, from 0.01 to 10 mass % (in particular, 0.1 to 5 mass %, alternately 0.1 to 4 mass %, alternately 0.25 to 3 mass %, alternately 0.25 to 0.75 mass %), based on total weight of the concentrate composition, of one or more friction modifier(s) (such as molybdenum compounds, such as molybdenum dithiocarbamate dimer and or molybdenum dithiocarbamate trimer);

[0153] E) from 0.01 to 45 mass % (in particular, 0.01 to 35 mass %, alternately 0.01 to 30 mass %, alternately 0.1 to 20 mass %), based on total weight of the concentrate composition, of one or more antioxidant(s) comprising hindered phenolic antioxidants (such as hindered 2,6-di-alkyl-phenolic proprionic ester derivatives, such as C7-C9-(branched)-alkyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate);

[0154] 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);

[0155] 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);

[0156] I) optionally, from 0.01 to 60 mass % (in particular, in particular 0.15 to 50 mass %, from 0.1 to 40 mass %, alternately 1 to 30 mass %, alternately 5 to 20 mass %), based on total weight of the concentrate composition, of one or more dispersants, such as blends of dispersants (for purposes of this disclosure and the claims thereto, amide, imide, and / or ester functionalized partially or fully saturated polymer comprising C4-C5 olefins having: i) an Mw / Mn of less than 2, ii) a Functionality Distribution (Fd) value of 3.5 or less (GPC-PS), described and or used herein (and as described in US patent application U.S. Ser. No. 18 / 480,571, filed Oct. 4, 2023) shall be considered dispersants for this element I), even though they may also occasionally be referred herein to as a dispersant viscosity modifiers, DVM's);

[0157] K) optionally, from 0.001 to 10 mass % (in particular, 0.1 to 8 mass %, alternately 1 to 5 mass % alternately 0.25 to 0.75 mass %), based on total weight of the concentrate composition, of one or more anti-wear agents (such as blends of anti-wear agents, such as ZDDP).

[0158] For purposes of this disclosure and the claims thereto, the amide, imide, and / or ester functionalized partially or fully saturated polymer comprising C4-5 olefins polymers described and or used herein (and described in US patent application U.S. Ser. No. 18 / 480,571, filed Oct. 4, 2023), shall be added to Element I for determining weight percent of dispersants, even though they be referred to as Dispersant Viscosity Modifiers.

[0159] Concentrates may be present in a lubricating oil composition at from of 0.5 mass % to 40 mass %, such as 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.

[0160] Optionally, the concentrate may be absent of aminic antioxidant.

[0161] In embodiments, the concentrate composition(s) described herein is / are absent aminic antioxidant, such as absent phenyl amine antioxidant, absent alkyl substituted diphenyl amine antioxidant, absent C8 alkyl substituted diphenyl amine antioxidant, absent C9 alkyl substituted diphenyl amine antioxidant, and or absent C8-C9 alkyl substituted diphenyl amine antioxidant.

[0162] In embodiments, the concentrate composition(s) described herein may further comprise diphenyl amine antioxidant compositions described in U.S. Patent Application No. 63 / 593,559 filed in the United States Patent Office on Oct. 27, 2023 entitled Lubricant Compositions Containing High C9 Disubstituted Diphenylamine Antioxidant Content, published as US2025 / 0136889A1.

[0163] In embodiments, the concentrate composition(s) described herein may further comprise diphenyl amine antioxidant compositions described in WO2025 / 088375.

[0164] In embodiments, the concentrate composition(s) described herein further comprise diphenyl amine antioxidant compositions described in European Patent Office Patent Application and EP serial number European Patent Application 23218548.8, filed Dec. 20, 2023, entitled Lubricant Compositions Containing C8 Disubstituted Diphenylamine Antioxidant.

[0165] In embodiments, the concentrate composition comprises less than 0.1 mass %, based upon the mass of the concentrate composition, (such as 0 mass %) of aminic antioxidant (such as diphenyl amine antioxidant) as described in Component E below as Additional Antioxidants.

[0166] Alternately, the concentrate composition(s) described herein comprise one or more additional antioxidants as described in Component E below as Additional Antioxidants.

[0167] In embodiments, the concentrate composition comprises one or more additional antioxidants, such as aminic antioxidant (such as diphenyl amine antioxidant), as described in Component E below as Additional Antioxidants.

[0168] In embodiments, the concentrate composition further comprises diphenyl amine antioxidant comprising 1) di(C9-alkyl substituted diphenyl) amine, and 2) from 0 to less than 10 mass % of mono-C9-alkyl substituted diphenyl amine, based upon the weight of any unsubstituted diphenylamine, and the mono- and di-phenyl amines present in the concentrate composition (as determined by UPLC as described in the Experimental section of US2025 / 0136889A1).

[0169] In embodiments, the concentrate composition further comprises diphenyl amine antioxidant comprising 90 mass % or more of di(C9-alkyl substituted diphenyl) amines, from 0 to less than 10 mass % of mono-C9-alkyl substituted diphenyl amine, and from 0 to less than 10 mass % of tri-C9-alkyl substituted diphenyl amine, based upon the weight of any unsubstituted diphenylamine, and the mono-, di-, and tri-phenyl amines present in the concentrate composition (as determined by UPLC as described in the Experimental section of US2025 / 0136889A1).

[0170] In embodiments, the concentrate composition further comprises diphenyl amine antioxidant comprising: 1) 85 mass % or more of di(C9-alkyl substituted diphenyl) amines, 2) from 0 to less than 15 mass % of mono-C9-alkyl substituted diphenyl amine and tri-C9-alkyl substituted diphenyl amine, and 3) less than 0.1 mass % of unsubstituted diphenylamine, based upon the weight of unsubstituted diphenylamine, and mono-, di-, and tri-phenyl amines present in the concentrate composition (as determined by UPLC as described in the Experimental section of US2025 / 0136889A1).

[0171] In embodiments, the concentrate composition further comprises diphenyl amine antioxidant comprising: a) diphenylamine antioxidant comprising: 1) di(C8-alkyl substituted phenyl) amine and 2) less than 15 mass % of mono-C8-alkyl substituted diphenylamine (based upon the weight of any unsubstituted diphenylamine, and the mono-C8-alkyl substituted phenylamines, di-C8-alkyl substituted phenylamines, and any tri-C8-alkyl substituted phenylamines present in the antioxidant composition, as determined by UPLC as described in the Experimental section of US2025 / 0136889A1); and b) polar diluent having an aniline point of 25° C. or less, and at least 2 available hydrogen-bond acceptor groups (such as ester, ether or alcohol groups) that are 2, 3, 4, 5, or 6 atoms apart, wherein the composition comprising the polar diluent of b) combined with the diphenylamine antioxidant of a) is clear after 96 hours at 20° C. in a clear glass container without agitation.

[0172] In embodiments, the concentrate composition further comprises diphenyl amine antioxidant comprising: a) diphenylamine antioxidant comprising: 1) di(C8-alkyl substituted phenyl) amine and 2) less than 15 mass % of mono-C8-alkyl substituted diphenylamine (based upon the weight of any unsubstituted diphenylamine, and the mono-C8-alkyl substituted phenylamines, di-C8-alkyl substituted phenylamines, and any tri-C8-alkyl substituted phenylamines present in the antioxidant composition (as determined by UPLC as described in the Experimental section of US2025 / 0136889A1); and b) polar diluent having an aniline point of 25° C. or less, and at least 2 available hydrogen-bond acceptor groups (such as ester, ether or alcohol groups) that are 2, 3, 4, 5, or 6 atoms apart, wherein the composition comprising the polar diluent of b) combined with the diphenylamine antioxidant of a) is clear after 96 hours at 20° C. in a clear glass container without agitation; and c) salicylate detergent, optionally wherein the antioxidant composition is combined with the detergent at a temperature of 70° C. or more, or 75° C. or more, or 80° C. or more.

[0173] In embodiments, the concentrate composition(s) described herein further comprise Aralkyl Substituted Diphenylamine Antioxidants described in European Patent Office Patent Application number 23218539.7, filed Dec. 20, 2023 entitled Lubricant Compositions Containing Aralkyl Substituted Diphenylamine Antioxidant.

[0174] In embodiments, the concentrate composition(s) described herein further comprise diphenyl amine concentrate compositions described in European Patent Office Patent Application number 23218550.4, filed Dec. 20, 2023 entitled Lubricant Compositions Containing Mono-aralky and Di-aralkyl Substituted Diphenylamine Antioxidants.

[0175] In embodiments, the concentrate composition(s) described herein may comprise from 0 to 20 mass % (such as 0.1 to 10 mass %) of one, two, three or more of:

[0176] a) aralkyl substituted diphenylamine as described in Component E below as Additional Antioxidants;

[0177] b) stable antioxidant compositions comprising: i) diphenylamine antioxidant comprising: aralkyl substituted diphenylamine; and ii) polar diluent having an aniline point of 0° C. or less, and at least 2 available hydrogen-bond acceptor groups that are 2, 3, 4, 5, or 6 atoms apart, as described in Component E below as Additional Antioxidants; and

[0178] c) a stable antioxidant composition comprising a homogeneous diphenylamine antioxidant fluid comprising di-aralkyl substituted diphenylamine and at least 45 mass % mono-aralkyl substituted diphenylamine, based upon the weight of any unsubstituted diphenylamine, and the mono- and di-substituted diphenylamines, as described in Component E below as Additional Antioxidants.

[0179] In embodiments, the concentrate composition(s) described herein comprise 0.01 to 20 mass % such as 0.1 to 10 mass %, based upon the mass of the concentrate composition, of one, two, three or more additional antioxidants as described in Component E below as Additional Antioxidants.

[0180] In embodiments, the concentrate composition(s) described herein comprise less than 0.1 mass %, based upon the mass of the concentrate composition, (such as 0 mass %) of one, two, three or more additional antioxidants as described in Component E below as Additional Antioxidants.

[0181] In embodiments, the concentrate composition is absent aminic antioxidant, such as absent phenyl amine antioxidant, such as absent alkyl substituted diphenyl amine antioxidant, such as absent alkyl substituted diphenyl amine antioxidant, such as absent C8-C9 alkyl substituted diphenyl amine antioxidant.

[0182] 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 maleated) polybutene (such as polyisobutylene), such as polyisobutylene succinic anhydride (“PIBSA”) typically resulting from the treatment of polyisobutylene with maleic acid or maleic anhydride.

[0183] 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.

[0184] In embodiments, the concentrate comprises: a) from 0.01 to 60 mass %, such as 0.1 to 20 mass %, such as 0.15 to 50 mass %, such as 0.1 to 40 mass %, such as 1 to 30 mass %, such as 1 to 15 mass %, 2 to 10 mass %, 5 to 9 mass % of functionalized (such as aminated) polybutene (such as polyisobutylene), such as PIBSA-PAM, and b) 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 (GPC-PS), and iii) an Mn of 10,000 g / mol or more (GPC-PS) of the polymer prior to functionalization, and optionally, 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), are present. In embodiments, component a), such as PIBSA-PAM, and component b), such as amide, imide, and / or ester functionalized polymers or copolymers of isoprene, are present in the concentrate at a ratio of 0.5:1 to 10:1, such as 2.5:1 to 6:1.

[0185] In embodiments, the concentrate comprises: a) from 0.1 to 20 mass %, such as 1 to 15 mass % of functionalized (such as aminated) polybutene (such as polyisobutylene), such as PIBSA-PAM; and b) from 0.1 to 20 mass %, such as 1 to 15 mass % of 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 (GPC-PS), and iii) an Mn of 10,000 g / mol or more (GPC-PS) of the polymer prior to functionalization, and optionally, 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), are present. In embodiments, component a), such as PIBSA-PAM, and component b), such as amide, imide, and / or ester functionalized polymers or copolymers of isoprene, are present in the concentrate at a ratio of 0.5 to 10:1, such as 2.5 to 6.

[0186] 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 to 1600 g / mol, such as 700 to 1200 g / mol.

[0187] 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) of block copolymer, such as block, star, random, and / or tapered block copolymer.

[0188] In embodiments, the concentrate may be substantially free of or absent block copolymer, such as block, star, random, and / or tapered block copolymer.

[0189] 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) of styrenic copolymer, such as block, star, random, and / or tapered styrenic block copolymer).

[0190] In embodiments, the concentrate may be substantially free of or absent styrenic copolymer, such as block, star, random, and / or tapered sytrenic block copolymer).

[0191] 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.

[0192] In embodiments, the concentrate may substantially free of or absent functionalized diluent, such as functionalized oil. Optionally, the concentrate may be absent functionalized oil.

[0193] In embodiments, the concentrate composition may optionally be absent solvent (such as aliphatic or aromatic solvent) and / or absent functionalized base oil.

[0194] 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.

[0195] In embodiments, the concentrate composition comprises (such as comprises 0.1 to 10 mass %, based upon the weight of the concentrate composition) diphenyl amine antioxidant comprising: 1) di(C9-alkyl substituted diphenyl) amine and 2) from 0 to less than 10 mass % of mono-C9-alkyl substituted diphenyl amine, based upon the weight of any unsubstituted diphenylamine, and the mono- and di-phenyl amines present in the concentrate composition (as determined by UPLC as described in the Experimental section of US2025 / 0136889A1).

[0196] In embodiments, the concentrate composition comprises (such as comprises 0.1 to 10 mass %, based upon the weight of the concentrate composition) diphenyl amine antioxidant comprising: 90 mass % or more of di(C9-alkyl substituted diphenyl) amines, from 0 to less than 10 mass % of mono-C9-alkyl substituted diphenyl amine, and from 0 to less than 10 mass % of tri-C9-alkyl substituted diphenyl amine, based upon the weight of any unsubstituted diphenylamine, and the mono-, di-, and tri-phenyl amines present in the concentrate composition (as determined by UPLC as described in the Experimental section of US2025 / 0136889A1).Lubricating Oil Compositions

[0197] This invention further relates to lubricating oil compositions (also referred to as “LOC”, “lubricant compositions”, “lubricating compositions”, or “lubricant oil compositions”) comprising, and or resulting from the admixing of at least:

[0198] (i) at least 50 mass % of one or more base oils, based upon the weight of the lubricating oil composition; and

[0199] (ii) an antioxidant composition and or a concentrate as described herein.

[0200] This disclosure relates to lubricating oil compositions comprising or resulting from the admixing of:

[0201] (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; and

[0202] (b) from 0.01 to 20 mass % (in particular 0.1 to 12 mass %, alternately 0.1 to 10 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) (for purposes of this disclosure and the claims thereto, amide, imide, and / or ester functionalized partially or fully saturated polymer comprising C4-C5 olefins having: i) an Mw / Mn of less than 2, ii) a Functionality Distribution (Fd) value of 3.5 or less (GPC-PS), as described and or used herein (and as described in US patent application U.S. Ser. No. 18 / 480,571, filed Oct. 4, 2023) shall be considered dispersants, even though they may also be referred herein to as a dispersant viscosity modifiers, DVM's); and

[0203] (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

[0204] (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 4 mass %, alternately 0.5 to 3 mass %, 0.5 to 2 mass %, 0.5 to 1.5 mass %), based upon the weight of the lubricating oil composition, of one or more C10 to C36 linear, branched or cyclic alcohols (such as C10 to C24 branched and / or linear alcohols, such as C12 to C18 branched and / or linear alcohols, such as C12 to C18 linear alcohols, such as C12 linear alcohol) as described herein; and,

[0205] (e) from 0.01 to 30 mass % (in particular, 0.05 to 20 mass %, alternately 0.1 to 15 mass %, alternately 0.1 to 10 mass %), based on total weight of the concentrate composition, of one or more antioxidant(s) comprising hindered phenolic antioxidants (such as hindered 2,6-di-alkyl-phenolic proprionic ester derivatives, such as C7-C9-(branched)-alkyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate), and

[0206] (f) optionally, from 0.01 to 10 mass % (in particular, 0.1 to 5 mass %, alternately 0.1 to 4 mass %, alternately 0.25 to 3 mass %, alternately 0.25 to 0.75 mass %), based on total weight of the concentrate composition, of one or more friction modifier(s) (such as molybdenum compounds, such as molybdenum dithiocarbamate dimer and or molybdenum dithiocarbamate trimer).

[0207] This disclosure also relates to lubricating oil compositions comprising or resulting from the admixing of:

[0208] 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;

[0209] B) 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 2.5 mass %, alternately 0.5 to 1 mass %), based upon the weight of the lubricating oil composition, of one or more C10 to C36 linear, branched or cyclic alcohols (such as C10 to C24 branched and / or linear alcohols, such as C12 to C18 branched and / or linear alcohols, such as C12 to C18 linear alcohols, such as C12 linear alcohol) as described herein,

[0210] 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);

[0211] 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, such as molybdenum compounds, such as molybdenum dithiocarbamate dimer and or molybdenum dithiocarbamate trimer);

[0212] E) from 0.01 to 30 mass % (in particular, 0.01 to 20 mass %, alternately 0.01 to 15 mass %, alternately 0.1 to 10 mass %), based on total weight of the lubricating oil composition, of one or more antioxidant(s) comprising hindered phenolic antioxidants (such as hindered 2,6-di-alkyl-phenolic proprionic ester derivatives, such as C7-C9-(branched)-alkyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate);

[0213] 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);

[0214] 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 anti-foam agents);

[0215] 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);

[0216] 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 such as blends of borated and non-borated dispersants);

[0217] 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);

[0218] 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 anti-wear agents (such as blends of anti-wear agents, such as ZDDP);

[0219] 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 / or

[0220] O) 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 C12-C60 hydrocarbons (such as C12-C24 linear alpha-olefins (LAOs), oligomers / polymers of polyisobutylenes, and / or blends thereof).

[0221] For purposes of this disclosure and the claims thereto, the amide, imide, and / or ester functionalized partially or fully saturated polymer comprising C4-5 olefins polymers described and or used herein (and described in US patent application U.S. Ser. No. 18 / 480,571, filed Oct. 4, 2023), shall be added to Element I for determining weight percent of dispersants, even though they may show similar properties to Element H's, e.g., may modify viscosity.

[0222] For purposes of this disclosure, molybdenum compounds are considered friction modifiers, Component D, and are not added in the elements C, 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 D) may impact wear positively, but is not added into element K) for determining weight percent of anti-wear agents.

[0223] In embodiments, all of elements D, F, G, H, I, J, K, M, and O are present in addition to the base oil, detergent, C10 to C36 linear, branched or cyclic alcohols, and antioxidant(s) comprising hindered phenolic antioxidants described herein.

[0224] In embodiments, elements D, F, G, H, I, and J are present in addition to the base oil, detergent, C10 to C36 linear, branched or cyclic alcohols, and antioxidant(s) comprising hindered phenolic antioxidants described herein.

[0225] In embodiments, elements I, F, and G are present in addition to the base oil, detergent, C10 to C36 linear, branched or cyclic alcohols, and antioxidant(s) comprising hindered phenolic antioxidants described herein.

[0226] In embodiments, element K is present in addition to the base oil, detergent, C10 to C36 linear, branched or cyclic alcohols, and antioxidant(s) comprising hindered phenolic antioxidants described herein.

[0227] In embodiments, the lubricating oil composition may further comprising zinc dialkyldithiophosphate.

[0228] In embodiments, the lubricating oil composition comprises hindered phenolic antioxidant, C10 to C36 linear, branched or cyclic alcohols, and molybdenum containing compound such as a dimeric and or trimeric molybdenum containing compound, optionally providing 10 to 1600 ppm, such as 20 to 1000 ppm Mo to the lubricating oil composition.

[0229] In embodiments, the lubricating oil composition(s) described herein is / are absent aminic antioxidant, such as absent phenyl amine antioxidant, such as absent alkyl substituted diphenyl amine antioxidant, such as absent alkyl substituted diphenyl amine antioxidant, such as absent C8 alkyl substituted diphenyl amine antioxidant, absent C9 alkyl substituted diphenyl amine antioxidant and or absent C8-C9 alkyl substituted diphenyl amine antioxidant.

[0230] Alternately, the lubricating oil composition(s) described herein further comprise diphenyl amine antioxidant compositions described in U.S. Patent Application Ser. No. 63 / 593,559 filed in the United States Patent Office on Oct. 27, 2023 entitled Lubricant Compositions Containing High C9 Disubstituted Diphenylamine Antioxidant Content.

[0231] Alternately, the lubricating oil composition(s) described herein further comprise diphenyl amine antioxidant compositions described in European Patent Office Patent Application number 23218548.8 filed Dec. 20, 2023 entitled Lubricant Compositions Containing C8 Disubstituted Diphenylamine Antioxidant.

[0232] In embodiments, the lubricating oil composition comprises less than 0.1 mass %, based upon the mass of the lubricating oil composition, (such as 0 mass %) of aminic antioxidant (such as diphenyl amine antioxidant) as described in Component E below as Additional Antioxidants.

[0233] Alternately, the lubricating oil composition(s) described herein comprise one or more additional antioxidants as described in Component E below as Additional Antioxidants.

[0234] Alternately, the lubricating oil composition comprises one or more additional antioxidants, such as aminic antioxidant (such as diphenyl amine antioxidant), as described in Component E below as Additional Antioxidants.

[0235] Alternately, the lubricating oil composition further comprises diphenyl amine antioxidant comprising 1) di(C9-alkyl substituted diphenyl) amine, and 2) from 0 to less than 10 mass % of mono-C9-alkyl substituted diphenyl amine, based upon the weight of any unsubstituted diphenylamine, and the mono- and di-phenyl amines present in the lubricating oil composition (as determined by UPLC as described in the Experimental section of US2025 / 0136889A1).

[0236] Alternately, the lubricating oil composition further comprises diphenyl amine antioxidant comprising 90 mass % or more of di(C9-alkyl substituted diphenyl) amines, from 0 to less than 10 mass % of mono-C9-alkyl substituted diphenyl amine, and from 0 to less than 10 mass % of tri-C9-alkyl substituted diphenyl amine, based upon the weight of any unsubstituted diphenylamine, and the mono-, di-, and tri-phenyl amines present in the lubricating oil composition (as determined by UPLC as described in the Experimental section of US2025 / 0136889A1).

[0237] Alternately, the lubricating oil composition further comprises diphenyl amine antioxidant comprising: 1) 85 mass % or more of di(C9-alkyl substituted diphenyl) amines, 2) from 0 to less than 15 mass % of mono-C9-alkyl substituted diphenyl amine and tri-C9-alkyl substituted diphenyl amine, and 3) less than 0.1 mass % of unsubstituted diphenylamine, based upon the weight of unsubstituted diphenylamine, and mono-, di-, and tri-phenyl amines present in the lubricating oil composition (as determined by UPLC as described in the Experimental section of US2025 / 0136889A1).

[0238] Alternately, the lubricating oil composition comprises (such as 0.1 to 15 mass %, such as 0.5 to 10 mass %, based upon the weight of the lubricating oil composition) diphenyl amine antioxidant comprising: 1) di(C9-alkyl substituted diphenyl) amine and 2) from 0 to less than 15 mass % (such as less than 10 mass %) of mono-C9-alkyl substituted diphenyl amine, based upon the weight of any unsubstituted diphenylamine, and the mono- and di-phenyl amines present in the lubricating oil composition (as determined by UPLC as described in the Experimental section of US2025 / 0136889A1).

[0239] Alternately, the lubricating oil composition comprises (such as 0.1 to 15 mass %, such as 0.5 to 10 mass %, based upon the weight of the lubricating oil composition) diphenyl amine antioxidant comprising: 90 mass % or more of di(C9-alkyl substituted diphenyl) amines, from 0 to less than 10 mass % of mono-C9-alkyl substituted diphenyl amine, and from 0 to less than 10 mass % of tri-C9-alkyl substituted diphenyl amine, based upon the weight of any unsubstituted diphenylamine, and the mono-, di-, and tri-phenyl amines present in the lubricating oil composition (as determined by UPLC as described in the Experimental section of US2025 / 0136889A1).

[0240] In embodiments, the lubricating oil composition further comprises diphenyl amine antioxidant comprising: a) diphenylamine antioxidant comprising: 1) di(C8-alkyl substituted phenyl) amine and 2) less than 15 mass % of mono-C8-alkyl substituted diphenylamine (based upon the weight of mono-C8-alkyl substituted phenylamines, di-C8-alkyl substituted phenylamines, and any tri-C8-alkyl substituted phenylamines present in the antioxidant composition); and b) polar diluent having an aniline point of 25° C. or less, and at least 2 available hydrogen-bond acceptor groups (such as ester, ether or alcohol groups) that are 2, 3, 4, 5, or 6 atoms apart, wherein the composition comprising the polar diluent of b) combined with the diphenylamine antioxidant of a) is clear after 96 hours at 20° C. in a clear glass container without agitation.

[0241] In embodiments, the lubricating oil composition further comprises diphenyl amine antioxidant comprising: a) diphenylamine antioxidant comprising: 1) di(C8-alkyl substituted phenyl) amine and 2) less than 15 mass % of mono-C8-alkyl substituted diphenylamine (based upon the weight of any unsubstituted diphenylamine, and the mono-C8-alkyl substituted phenylamines, di-C8-alkyl substituted phenylamines, and any tri-C8-alkyl substituted phenylamines present in the antioxidant composition, (as determined by UPLC as described in the Experimental section of US2025 / 0136889A1); and b) polar diluent having an aniline point of 25° C. or less, and at least 2 available hydrogen-bond acceptor groups (such as ester, ether or alcohol groups) that are 2, 3, 4, 5, or 6 atoms apart, wherein the composition comprising the polar diluent of b) combined with the diphenylamine antioxidant of a) is clear after 96 hours at 20° C. in a clear glass container without agitation.

[0242] In embodiments, the lubricating oil composition further comprises diphenyl amine antioxidant comprising: a) diphenylamine antioxidant comprising: 1) di(C8-alkyl substituted phenyl) amine and 2) less than 15 mass % of mono-C8-alkyl substituted diphenylamine (based upon the weight of any unsubstituted diphenylamine, and mono-C8-alkyl substituted phenylamines, di-C8-alkyl substituted phenylamines, and any tri-C8-alkyl substituted phenylamines present in the antioxidant composition, (as determined by UPLC as described in the Experimental section of US2025 / 0136889A1); and b) polar diluent having an aniline point of 25° C. or less, and at least 2 available hydrogen-bond acceptor groups (such as ester, ether or alcohol groups) that are 2, 3, 4, 5, or 6 atoms apart, wherein the composition comprising the polar diluent of b) combined with the diphenylamine antioxidant of a) is clear after 96 hours at 20° C. in a clear glass container without agitation; and c) salicylate detergent, optionally wherein the antioxidant composition is combined with the detergent at a temperature of 70° C. or more, or 75° C. or more, or 80° C. or more.

[0243] In embodiments, the lubricating oil composition comprises less than 0.1 mass %, based upon the mass of the lubricating oil composition, (such as 0 mass %) of additional antioxidants as described in Component E below as Additional Antioxidants.

[0244] In embodiments, the lubricating oil composition comprises less than 0.1 mass %, based upon the mass of the lubricating oil composition, (such as 0 mass %) of aminic antioxidant (such as diphenyl amine antioxidant).

[0245] Alternately, the lubricating oil composition comprises additional antioxidants, such as aminic antioxidant (such as diphenyl amine antioxidant), as described in Component E below as Additional Antioxidants.

[0246] In embodiments, the lubricating oil composition(s) described herein further comprise compositions described in European Patent Office Patent Application number 23218539.7, filed Dec. 20, 2023 entitled Lubricant Compositions Containing Aralkyl Substituted Diphenylamine Antioxidant.

[0247] In embodiments, the lubricating oil composition(s) described herein further comprise diphenyl amine compositions described in European Patent Office Patent Application number 23218550.4, filed Dec. 20, 2023 entitled Lubricant Compositions Containing Mono-aralky and Di-aralkyl Substituted Diphenylamine Antioxidants.

[0248] In embodiments, the lubricating oil composition(s) described herein may comprise from 0 to 20 mass % (such as 0.1 to 10 mass %) of one, two, three or more of:

[0249] a) aralkyl substituted diphenylamine as described in Component E below as Additional Antioxidants;

[0250] b) stable antioxidant compositions comprising: i) diphenylamine antioxidant comprising: aralkyl substituted diphenylamine; and ii) polar diluent having an aniline point of 0° C. or less, and at least 2 available hydrogen-bond acceptor groups that are 2, 3, 4, 5, or 6 atoms apart, as described in Component E below as Additional Antioxidants, and

[0251] c) a stable antioxidant composition comprising a homogeneous diphenylamine antioxidant fluid comprising di-aralkyl substituted diphenylamine and at least 45 mass % mono-aralkyl substituted diphenylamine, based upon the weight of any unsubstituted diphenylamine, and the mono- and di-substituted diphenylamines (as determined by UPLC as described in the Experimental section of US2025 / 0136889A1), as described in Component E below as Additional Antioxidants.

[0252] In embodiments, the lubricating oil composition(s) described herein comprise 0.01 to 20 mass % such as 0.1 to 10 mass %, based upon the mass of the lubricating oil composition, of one, two, three or more additional antioxidants as described in Component E below as Additional Antioxidants.

[0253] In embodiments, the lubricating oil composition(s) described herein comprise less than 0.1 mass %, based upon the mass of the lubricating oil composition, (such as 0 mass %) of one, two, three or more additional antioxidants as described in Component E below as Additional Antioxidants.

[0254] In embodiments, the lubricating oil composition comprises hindered phenolic antioxidant, a molybdenum containing compound such as a dimeric and or trimeric molybdenum containing compound, optionally providing 10 to 1000 ppm Mo to the lubricating oil composition, and one or more additional antioxidants as described in Component E below as Additional Antioxidants (such as one or more diphenyl amine).

[0255] In embodiments, the detergent in the lubricating oil composition comprises one or more carboxylate detergent, such as one or more salicylate detergent, such as one or more alkaline earth metal salicylate detergent, such as calcium and or magnesium salicylate detergent, optionally said detergent having a TBN of up to 700 mgKOH / g, such as 50 to 500 mgKOH / g, such as 100 to 450 mgKOH / g. In embodiments detergents having a TBN of 100 or more (such as 200 mgKOH / g or more) can be used in combination with detergents having a TBN of less than 100 mgKOH / g.

[0256] In embodiments, the detergent in the lubricating oil composition comprises one or more carboxylate detergent, such as one or more salicylate detergents, such as one or more alkaline earth metal salicylate detergent, such as calcium and or magnesium salicylate detergent, said detergent providing from 1 to 500 mmol / kg soap, such as 5 to 400 mmol / kg soap to the lubricating oil composition.

[0257] In embodiments, the detergent in the lubricating oil composition comprises one or more carboxylate detergent, such as one or more salicylate detergent, such as one or more alkaline earth metal salicylate detergent, such as calcium and or magnesium salicylate detergent, said detergent having: 1) having a TBN of 50 to 700 mgKOH / g, such as 60 to 400 mgKOH / g (such as a combination of detergent having a TBN over 100 mgKOH / g and a second detergent having a TBN less than 100 mgKOH / g) and 2) from 1 to 500 mmol soap, such as 5 to 400 mmol soap to the lubricating oil composition.

[0258] 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.

[0259] 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.

[0260] Suitably, the lubricant composition may have a phosphorus level of 1200 ppm or less, alternately 1000 ppm or less, alternately 800 ppm or less, as measured by ASTM D5185.

[0261] 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.

[0262] 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.

[0263] 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 0.0001 to 0.5 mass % or less sulfated ash, based on the total mass of the lubricating composition, as measured by ASTM D874-13a (2018).

[0264] 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).

[0265] 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).

[0266] 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 OW-X, where X represents any one of 8, 12, 16, 20, 30, 40, and 50. Preferably, the lubricating composition of the present disclosure may be a multigrade oil identified by the viscometric descriptor SAE 25W-X, SAE 20W-X, SAE 15W-X, SAE 10W-X, SAE 5W-X or SAE OW-X, where X represents any one of 8, 12, 16, 20, 30, 40, and 50. Alternately, the lubricating composition may be the form of viscosity grade SAE 15W-X, SAE 10W-X, SAE 5W-X or SAE OW-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 April 2021 by SAE International, formerly known as Society of Automotive Engineers). In embodiments, the lubricating composition disclosed herein may have a SAE viscometric descriptor of OW-Y, wherein Y may be 12, 16, 20, or 30. In embodiments, the lubricating composition has an SAE viscometric descriptor of OW-12.

[0267] 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.

[0268] 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.

[0269] In embodiments, the lubricating oil composition may comprise 0 to 600 ppm molybdenum, alternately from 20 to 200 ppm molybdenum, alternately from 35 to 100 ppm molybdenum. Alternately, the lubricating oil composition may be absent molybdenum.

[0270] 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.

[0271] 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 block, radial (aka “star”), random, 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.

[0272] 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) 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.

[0273] 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 5 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 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; and iii) 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). (GPC-PS is determined as set out in U.S. patent application Ser. No. 18 / 480,571, filed Oct. 4, 2023).

[0274] The functionalized polymer may include at least 50%, or at least 60%, or at least 70% of 1,4-insertions of monomer. Furthermore, the functionalized polymer 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.

[0275] 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.

[0276] In embodiments, the lubricating compositions of the present disclosure may be a heavy-duty diesel oil (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.)

[0277] In embodiments, the lubricating compositions of the present disclosure may be a passenger car motor oil.

[0278] In embodiments, the lubricating compositions of the present disclosure may be a passenger car diesel oil.

[0279] In embodiments, the lubricating composition of the present disclosure may be a lubricating composition comprising: an oil of lubricating viscosity having 50 mass % or more of one or more 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 1800, such as 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); one or more molybdenum compounds (such as molybdenum dithiocarbamate dimer and or molybdenum dithiocarbamate trimer); one or more hindered phenolic antioxidants (such as hindered 2,6-di-alkyl-phenolic proprionic ester derivatives, such as C7-C9-(branched)-alkyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate); one or more C10 to C36 linear, branched or cyclic alcohols (such as C10 to C24 branched and / or linear alcohols, such as C12 to C18 branched and / or linear alcohols, such as C12 to C18 linear alcohols, such as C12 linear alcohol); optionally a dispersant viscosity modifier such as an amide, imide, and / or ester functionalized partially or fully saturated polymer comprising C4-5 olefins as described in U.S. Ser. No. 18 / 480,571, filed Oct. 4, 2023; an alkaline earth metal salicylate detergent; an alkaline earth metal sulfonate detergent present in an amount to deliver preferably 0.1 mass % to 1.2 mass % of alkaline earth metal soap to the lubricating composition; a phosphorus anti wear agent present in an amount to deliver 300 to 900 ppm phosphorous to the lubricating composition, the lubricating composition preferably having a total sulfated ash of between 0.3 to 1.1 mass %.

[0280] 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. 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.

[0281] The internal combustion engines that may be lubricated with the compositions described herein may be engines designed for moving vehicles (such as automobiles, trucks, generators, marine engines, etc.), stationary engines, such as heavy duty internal combustion engines or standing generators comprising internal combustion engines.

[0282] The internal combustion engines that may be lubricated with the compositions described herein may be passenger car engines, diesel engines, hydrogen engines, ammonia engines, natural gas engines, gasoline engines, marine engines, and or motorcycle engines.

[0283] In embodiments, the lubricating compositions disclosed herein may be used in heavy-duty engines (e.g., heavy-duty vehicles having a gross vehicle weight rating of 10,000 pounds or more).

[0284] In embodiments, the lubricating compositions disclosed herein may be used in light-duty engines (e.g., light-duty vehicles having a gross vehicle weight rating of less than 10,000 pounds).

[0285] In embodiments, the lubricating compositions disclosed herein may be used as passenger car motor oils.A. Base Oil

[0286] 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.

[0287] 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.

[0288] 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 %, from 5 mass % to 50 mass %, or from 5 mass % to less than 50 mass % of active ingredient, based upon the weight of the concentrate.

[0289] 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.

[0290] 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, 19th edition, January 2021, www.API.org)]. Examples of PAO's useful as base oils include: poly(ethylenes), copolymers of ethylene and propylene, polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1-hexenes), poly(1-octenes), poly(1-decenes), homo- or co-polymers of C8 to C20 alkenes, homo- or co-polymers of C8, and / or C10, and / or C12 alkenes, C8 / C10 copolymers, C8 / C10 / C12 copolymers, and C10 / C12 copolymers, and the derivatives, analogues and homologues thereof.

[0291] 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.

[0292] 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 C6 to C12 alpha-olefins in another embodiment, and C5 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, U.S. Pat. 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).

[0293] 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.

[0294] 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.

[0295] Another suitable class of synthetic lubricating oils useful as base oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) reacted with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.

[0296] Esters useful as synthetic oils herein also include those made from C5 to C12 monocarboxylic acids and polyols, and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol.

[0297] Desirable ester base oils are commercially available as Esterex™ Esters (ExxonMobil Chemical Company, Houston, Texas).

[0298] Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxysilicone oils and silicate oils comprise another useful class of synthetic lubricants useful herein; such oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl)silicate, tetra-(p-tert-butyl-phenyl) silicate, hexa-(4-methyl-2-ethylhexyl)disiloxane, poly(methyl)siloxanes, and poly(methylphenyl)-siloxanes.

[0299] Other synthetic lubricating oils useful herein include liquid esters of phosphorous-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.

[0300] Unrefined, refined, and re-refined oils can be used in the lubricating compositions of the present disclosure. Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from distillation, or an ester oil obtained directly from an esterification process and used without further treatment is considered an unrefined oil. Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration, and percolation are used by those in the art. Re-refined oils are oils obtained by processes similar to those used to obtain refined oils where the refining processes are applied to previously refined oils which have been previously used in service. Such re-refined oils are also referred to as reclaimed or reprocessed oils and often are additionally processed for removal of spent additive and oil breakdown products. A re-refined base oil is preferably substantially free from materials introduced through manufacturing, contamination, or previous use.

[0301] Other examples of useful base oils are gas-to-liquid (“GTL”) base oils, i.e., the base oil is an oil derived from hydrocarbons made from synthesis gas (“syn gas”) containing H2 and CO using a Fischer-Tropsch catalyst. These hydrocarbons typically require further processing in order to be useful as a base oil. For example, they may, by methods known in the art, be hydroisomerized; hydrocracked and hydroisomerized; dewaxed; or hydroisomerized and dewaxed. For further information on useful GTL base oils and blends thereof, please see U.S. Pat. No. 10,913,916 (col 4, ln 62 to col 5, ln 60) and U.S. Pat. No. 10,781,397 (col 14, ln 54 to col 15, ln 5, and col 16, ln 44 to col 17, ln 55).

[0302] In particular, oils from renewable sources, i.e., based in part on carbon and energy captured from the environment, such as biological sources, are useful herein.

[0303] The various base oils are often categorized as Group I, II, III, IV, or V according to the API EOLCS 1509 definition (American Petroleum Institute Publication 1509, see section E.1.3, 19th edition, January 2021, www.API.org). Generally speaking, Group I base stocks have a viscosity index of between about 80 to 120 and contain greater than about 0.03% sulfur and / or less than about 90% saturates. Group II base stocks have a viscosity index of between about 80 to 120 and contain less than or equal to about 0.03% sulfur and greater than or equal to about 90% saturates. Group III base stocks have a viscosity index greater than about 120 and contain less than or equal to about 0.03% sulfur and greater than about 90% saturates. Group IV base stocks include polyalphaolefins (PAO). Group V base stocks include base stocks not included in Groups I-IV. (Viscosity index measured by ASTM D 2270, saturates is measured by ASTM D2007, and sulfur is measured by ASTM D5185, D2622, ASTM D4294, ASTM D4927, and ASTM D3120).

[0304] 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 I+), 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.

[0305] The base oil useful herein may be selected from any of the synthetic, renewable, 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.

[0306] 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.

[0307] 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.

[0308] Preferably, the base oil or base oil blend will have a sulfur content of less than 1 mass %, preferably less 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.

[0309] 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.

[0310] 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).

[0311] 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.

[0312] 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.

[0313] 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.

[0314] 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.

[0315] The base oils and blends thereof described above are also useful for making concentrates as well as for making lubricants therefrom.

[0316] 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.

[0317] 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. Linear, Branched or Cyclic Alcohols

[0318] The lubricating compositions, concentrates and or booster packs of the present invention also contain one or more alcohols, which may contain one hydroxyl group (mono-hydric), contain two hydroxyl groups (diol or dihydric) or contain three or more hydroxyl groups (multi-hydric or multi-ol). Suitable alcohols are described below.

[0319] In embodiments, the alcohol comprises one or more C10 to C36 linear, branched or cyclic alcohols (such as C10 to C24 branched and / or linear alcohols, such as C12 to C18 branched and / or linear alcohols, such as C12 to C18 linear alcohols, such as C12 linear alcohol).

[0320] In embodiments, the lubricating composition of the present invention comprises a saturated monohydric alcohol, such as a linear or branched primary alcohol (a primary alcohol is an alcohol containing a —CH2OH group). Primary monohydric linear or branched alcohols suitable for use in the lubricating composition may contain 8 to 34 carbon atoms, for example, 10 to 32, or 10 to 30, or 12 to 26, or 12 to 16, or at least 12 carbons, at least 14 carbons, and in some embodiments, up to 32 carbons, up to 30 carbons, up to 24 carbons, up to 22 carbons, or up to 18 carbons. Mixtures of alcohols may also be used herein. In embodiments, the alcohol mixture comprises at least 50 wt %, or at least 60 wt %, or at least 80 wt %, or at least 90 wt % of saturated linear or branched monohydric alcohols comprising at least 10 aliphatic carbon atoms, or at least 12 aliphatic carbon atoms. In embodiments, the alcohol mixture used comprises no more than 5.0 wt % of C6 and lower linear alcohols, or no more than 2 wt % or no more than 1 wt % of of C6 and lower linear alcohols. In embodiments, the alcohol mixture is substantially free of C6 and lower linear, branched, and or cyclic alcohols. In some embodiments, a mixture of linear and branched alcohols may be employed.

[0321] Alcohols useful herein may be represented by the formula (I), (II), or (III), preferably formula (I).wherein R1 is methyl or a linear or branched C8 to C34 alkyl group (such as octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl and triacontyl) and R2 is a linear or branched C8 to C34 alkyl group (such as octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl and triacontyl) and X is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30, such as 10, 11, or 12.

[0323] In embodiments, the alcohol comprises an alcohol represented by Formula I where R1 is methyl or a C8 to C34 alkyl group (such as octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl and triacontyl) and R2 is a C8 to C34 alkyl group (such as octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl and triacontyl). Examples of alcohols of represented by Formula I include 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol, 2-octyldodecanol, 2-decyltetradecanol, 2-dodecylhexadecanol, or any combination thereof. These types of alcohols are commercially available from Sasol and marketed as ISOFOL® alcohols. In some embodiments, the alcohol includes 2-hexyldecanol, 2-decyltetradecanol, or any combination thereof. In some embodiments, the alcohol includes 2-hexyldecanol. In some embodiments, the alcohol includes 2-decyltetradecanol. In some embodiments, the lubricating composition is substantially free of or free of 2-ethylhexanol and / or 2-butyloctanol.

[0324] In embodiments, the alcohol comprises an alcohol represented by Formula II, where x is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30, such as 10, 11, 12. In embodiments, the alcohol comprises decanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol heptadecanol, octadecanol, nonadecanol, cicosanol, or mixtures thereof. Alternately in some embodiments, the alcohol comprises linear primary alcohols such as decanol, docecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, or mixtures thereof.

[0325] Other exemplary primary alcohols include commercially available mixtures of alcohols. These include oxoalcohols which may comprise, for example, various mixtures of alcohols having from 8-24 carbon atoms. Of the various commercial alcohols useful herein, one 12 to 18 aliphatic carbon atoms. The alcohols in the mixture may include one or more of, for example, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, and octadecyl alcohol. Several suitable sources of these alcohol mixtures are the technical grade alcohols sold under the name NEODOL® alcohols (Shell Oil Company, Houston, Tex.) and under the name ALFOL® alcohols (Sasol, Westlake, La.), and fatty alcohols derived from animal and vegetable fats and sold commercially by, for example, Henkel, Sasol, and Emery.

[0326] In embodiments, the alcohol comprises alcohol with an isoalkyl group. (An isoalkyl group is a group of atoms resulting from the removal of a hydrogen atom from a methyl group situated at the end of the straight chain segment of an isoalkane.) Particularly useful alcohols with an isoalkyl group are those where the methyl group is attached to the penultimate carbon atom of the main chain. For example, the alcohol having an isoalkyl group may be represented by Formula III where x is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18, such as 8, 9, 10, 11, 12, 13, or 14, such as isodecanol, isododecanol, isotridecanol, isotetradecanol, isopentadecanol, isohexadecanol, isoheptadecanol, isooctadecanol, isononadecanol, isoeicosanol.

[0327] In some embodiments, the lubricating composition may include mixtures of alcohols of Formula I, or Formula II, or Formula III.

[0328] Examples of alcohols which may be used in the present invention are summarized in the table below, where the alcohols have the formula of Formula IV (shown above):R1R2x =C2C40β-branched2-EHLFormula IC4C60β-branchedIsofol 12Formula IC6C80β-branchedIsofol 16Formula IC8C100β-branchedIsofol 20Formula IC10C120β-branchedIsofol 24Formula IC10-C11C12-C130β-branchedIsofol 2426SFormula IC12C140β-branchedIsofol 28Formula IC14C160β-branchedIsofol 32Formula ICH3H3linear1-hexanolFormula IICH3H5linear1-octanolFormula IICH3H7linear1-decanolFormula IICH3H9linear1-dodecanolFormula IICH3H11linear1-tetradecanolFormula IICH3H15linearStearylFormula IIalcoholCH3H19linearBehenylFormula IIalcoholCH3CH36IsoalkylIsodecylFormula IIIalcoholCH3CH38IsoalkylIsododecylFormula IIIalcoholCH3CH39IsoalkylIsotridecylFormula IIIalcoholCH3CH314IsoalkylIsostearylFormula IIIalcohol

[0329] The alcohols useful herein, such as one or more C8 to C36 linear, branched or cyclic alcohols (such as C10 to C24 branched and / or linear alcohols, such as C12 to C18 branched and / or linear alcohols, such as C12 to C18 linear alcohols, such as C12 linear alcohol) may be present in the concentrate, booster pack, or lubricating oil composition at from 0.10 to 20 mass % (in particular, from 0.5 to 15 mass %, alternately 1.0 to 10 mass %, alternately 1.5 to 8 mass %, alternately 1 mass % to 6 mass %, alternately 2 to 4 mass %), based upon the weight of the concentrate, booster pack, or lubricating oil composition, as the case may be.C. Detergents

[0330] 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 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.

[0331] 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.

[0332] Preferably, the detergent additive(s) useful in the present disclosure comprises calcium and / or magnesium metal salts. The detergent may be a calcium and / or magnesium carboxylate (e.g., salicylates), sulfonate, or phenate detergent. 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.

[0333] The metal-containing detergent may also include “hybrid” detergents formed with mixed surfactant systems including phenate and / or sulfonate components, e.g., phenate / salicylates, sulfonate / phenates, sulfonate / salicylates, sulfonates / phenates / salicylates, as described, for example, in U.S. Pat. Nos. 6,429,178; 6,429,179; 6,153,565; and 6,281,179. Where, for example, a hybrid sulfonate / phenate detergent is employed, the hybrid detergent would be considered equivalent to amounts of distinct phenate and sulfonate detergents introducing like amounts of phenate and sulfonate soaps, respectively.

[0334] 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 U.S. Pat. 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.

[0335] 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.

[0336] Alternately, 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.

[0337] Alternately, the detergent additive(s) is a combination of magnesium salicylate and magnesium sulfonate.

[0338] The magnesium detergent provides the lubricating composition thereof with from 200-4000 ppm of magnesium atoms, suitably from 200-2000 ppm, from 300 to 1500 or from 450-1200 ppm of magnesium atoms (ASTM D5185).

[0339] The detergent composition may comprise (or consist of) a combination of one or more magnesium sulfonate detergents and one or more calcium salicylate detergents.

[0340] The combination of one or more magnesium sulfonate detergents and one or more calcium salicylate detergents 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 (ASTM D5185).

[0341] 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.

[0342] Suitably the calcium detergent 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.

[0343] 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.

[0344] 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 to the lubricating oil composition (ASTM D5185). If present, any calcium detergent is suitably present in amount sufficient to provide 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).

[0345] Suitably the total atomic amount of metal from detergent in the lubrication composition according to all aspects of the disclosure is no more than 5000 ppm, preferably no more than 4000 μm and more preferably no more than 2000 ppm (ASTM D5185). The total amount of atomic metal from detergent in the lubrication oil composition according to all aspects of the disclosure is suitably at least 500 ppm, preferably at least 800 ppm and more preferably at least 1000 ppm (ASTM D5185). The total amount of atomic metal from detergent in the lubrication oil composition according to all aspects of the disclosure is suitably from 500 to 5000 ppm, preferably from 500 to 3000 ppm and more preferably from 500 to 2000 ppm (ASTM D5185).

[0346] Sulfonate detergents may be prepared from sulfonic acids which are typically obtained by the sulfonation of alkyl substituted aromatic hydrocarbons, such as those obtained from the fractionation of petroleum or by the alkylation of aromatic hydrocarbons. Examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl, or their halogen derivatives such as chlorobenzene, chlorotoluene, and chloronaphthalene. The alkylation may be carried out in the presence of a catalyst with alkylating agents having from about 3 to more than 70 carbon atoms. The alkaryl sulfonates usually contain from about 9 to about 80 or more carbon atoms, preferably from about 16 to about 60 carbon atoms per alkyl substituted aromatic moiety. The oil soluble sulfonates or alkaryl sulfonic acids may be neutralized with oxides, hydroxides, alkoxides, carbonates, carboxylate, sulfides, hydrosulfides, nitrates, borates and ethers of the metal. The amount of metal compound is chosen having regard to the desired TBN of the final product, but typically ranges from about 100 to 220 mass % (preferably at least 125 mass %) of that stoichiometrically required.

[0347] Metal salts of phenols and sulfurized phenols are prepared by reaction with an appropriate metal compound such as an oxide or hydroxide and neutral or overbased products may be obtained by methods well known in the art. Sulfurized phenols may be prepared by reacting a phenol with sulfur or a sulfur-containing compound such as hydrogen sulfide, sulfur monohalide, or sulfur dihalide, to form products which are generally mixtures of compounds in which 2 or more phenols are bridged by sulfur-containing bridges.

[0348] Carboxylate detergents, e.g., salicylates, can be prepared by reacting an aromatic carboxylic acid (such as a C5-100, C9-30, C10-30, C10-26, C14-24, C10-20, alkyl-substituted hydroxy-benzoic acid) with an appropriate metal compound such as an oxide or hydroxide and neutral or overbased products may be obtained by methods well known in the art. The aromatic moiety of the aromatic carboxylic acid can contain heteroatoms, such as nitrogen and oxygen. Preferably, the moiety contains only carbon atoms; more preferably the moiety contains six or more carbon atoms; for example, benzene is a preferred moiety. The aromatic carboxylic acid may contain one or more aromatic moieties, such as one or more benzene rings, either fused or connected via alkylene bridges.

[0349] 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.

[0350] 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.

[0351] 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.

[0352] 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).

[0353] 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.

[0354] 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.

[0355] 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.

[0356] The salicylate detergents (such as Ca and / or Mg salicylate detergents) are present in an amount to deliver 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.

[0357] 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.

[0358] 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.

[0359] 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.

[0360] 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.

[0361] 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.

[0362] In embodiments, salicylate detergent(s) (such as Mg salicylate, Ca salicylate, or Ca salicylate and Mg salicylate) are present in the antioxidant, concentrate, finished oil and or booster packs described herein.D. Friction Modifiers

[0363] 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.

[0364] 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.

[0365] 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.

[0366] Additionally, the molybdenum compound may be an acidic molybdenum compound. These compounds 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, MoOC14, MoO2Br2, Mo2O3C16, molybdenum trioxide or similar acidic molybdenum compounds.

[0367] Among the molybdenum compounds useful in the compositions of this disclosure are organo-molybdenum compounds represented by the formula: Mo(R″OCS2)4 and / or Mo(R″SCS2)4, wherein R″ is an organo group selected from the group consisting of alkyl, aryl, aralkyl and alkoxyalkyl, generally of from 1 to 30 carbon atoms, and preferably 2 to 12 carbon atoms and most preferably alkyl of 2 to 12 carbon atoms. Especially preferred are the dialkyldithiocarbamates of molybdenum.

[0368] Another group of organo-molybdenum compounds useful in the lubricating compositions of this disclosure are trinuclear molybdenum compounds, especially those represented by the formula Mo3SkLnQz and mixtures thereof wherein the L groups are independently selected ligands having organo groups with a sufficient number of carbon atoms such as to render the compound soluble or dispersible in the oil (preferably each L is an independently selected ligand having one or more organo groups with a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil, optionally the organo groups have at least 21 carbon atoms in total), n is from 1 to 4 (such as 1, 2, 3, or 4), k varies from 4 to 7 (such as 4, 5, 6, or 7), Q is selected from the group consisting essentially of, or consisting of, neutral electron-donating compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 (such as 0, 1, 2, 3, 4, or 5) and includes non-stoichiometric values. At least 21 carbon atoms should be present among all the ligand / organo groups, such as at least 25, at least 30, or at least 35 carbon atoms.

[0369] 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).

[0370] Concentrate 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, Concentrate compositions useful in all aspects of the present disclosure contain up to 1800 ppm, such as up to 1600 ppm, up to 1000 ppm, up to 750 ppm, up to 500 ppm of molybdenum. Concentrate compositions useful in all aspects of the present disclosure preferably contain from 10 to 1000 ppm, such as 30 to 750 ppm or 40 to 500 ppm of molybdenum (measured as atoms of molybdenum).

[0371] Booster 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, booster compositions useful in all aspects of the present disclosure contain up to 1800 ppm, such as up to 1600 ppm, up to 1000 ppm, up to 750 ppm, up to 500 ppm of molybdenum.

[0372] Lubricating oil compositions useful in all aspects of the present disclosure preferably contain from 10 to 1500 ppm, 10 to 1000 ppm, 30 to 750 ppm or 40 to 500 ppm of molybdenum (measured as atoms of molybdenum).

[0373] For more information on useful friction modifiers containing Mo, please see U.S. Pat. No. 10,829,712 (col 8, ln 58 to col 11, ln 31).

[0374] Ashless friction modifiers may be present in the lubricating oil compositions of the present disclosure and are known generally and include esters formed by reacting carboxylic acids and anhydrides with alkanols and amine-based friction modifiers. Other useful friction modifiers generally include a polar terminal group (e.g., carboxyl or hydroxyl) covalently bonded to an oleophilic hydrocarbon chain. Esters of carboxylic acids and anhydrides with alkanols are described in U.S. Pat. No. 4,702,850. Examples of other conventional organic friction modifiers are described by M. Belzer in the “Journal of Tribology” (1992), Vol. 114, pp. 675-682 and M. Belzer and S. Jahanmir in “Lubrication Science” (1988), Vol. 1, pp. 3-26. 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 %.

[0375] 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.

[0376] Illustrative alkoxylated fatty acid esters include, for example, polyoxyethylene stearate, fatty acid polyglycol ester, and the like. These can include polyoxypropylene stearate, polyoxybutylene stearate, polyoxyethylene isosterate, polyoxypropylene isostearate, polyoxyethylene palmitate, and the like.

[0377] Illustrative alkanolamides include, for example, lauric acid diethylalkanolamide, palmic acid diethylalkanolamide, and the like. These can include oleic acid diethyalkanolamide, stearic acid diethylalkanolamide, oleic acid diethylalkanolamide, polyethoxylated hydrocarbylamides, polypropoxylated hydrocarbylamides, and the like.

[0378] Illustrative polyol fatty acid esters include, for example, glycerol monooleate, saturated mono-, di-, and tri-glyceride esters, glycerol monostearate, and the like. These can include polyol esters, hydroxyl-containing polyol esters, and the like.

[0379] Illustrative borated glycerol fatty acid esters include, for example, borated glycerol monooleate, borated saturated mono-, di-, and tri-glyceride esters, borated glycerol monosterate, and the like. In addition to glycerol polyols, these can include trimethylolpropane, pentaerythritol, sorbitan, and the like. These esters can be polyol monocarboxylate esters, polyol dicarboxylate esters, and on occasion polyoltricarboxylate esters. Preferred can be the glycerol monooleates, glycerol di-oleates, glycerol tri-oleates, glycerol mono-oleates, glycerol di-stearates, and glycerol tri-stearates and the corresponding glycerol mono-palmitates, glycerol di-palmitates, and glycerol tri-palmitates, and the respective isostearates, linoleates, and the like. Ethoxylated, propoxylated, and / or butoxylated fatty acid esters of polyols, especially using glycerol as underlying polyol are useful herein.

[0380] Illustrative fatty alcohol ethers include, for example, stearyl ether, myristyl ether, and the like. Alcohols, including those that have carbon numbers from C3 to C50, can be ethoxylated, propoxylated, or butoxylated to form the corresponding fatty alkyl ethers. The underlying alcohol portion can preferably be stearyl, myristyl, C11-C13 hydrocarbon, oleyl, isosteryl, and the like.

[0381] 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.E. Antioxidants

[0382] Antioxidant employed in the lubricating oil of the present invention comprise a hindered phenolic antioxidant, such as 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 C6+ 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 C7-C9-(branched)-alkyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate) available as IRGANOX™ L135, such as C7-C9-(branched)-alkyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate), where the C7-C9-(branched)-alkyl group may be one or more of 2-ethylpentyl, 2-ethylheptyl, 2-ethylhexyl, 2-ethylpentylm 3-methylhexyl, 4-methyloctyl, 6-methylheptyl, 2-ethylheptyl, 2-ethylhexyl, 2-ethylpentyl, 3-methylhexyl, 4-methyloctyl, and 6-methylheptyl. In embodiments, the hindered phenol may one, two, three, or more of 2-ethylpentyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propanoate), 2-ethylheptyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propanoate), 2-ethylhexyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propanoate, bis(2-ethylhexyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propanoate), 3-methylhexyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propanoate, 4-methyloctyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propanoate, 6-methylheptyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propanoate, 2-ethylheptyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propanoate; bis(2-ethylhexyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propanoate); 2-ethylpentyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propanoate; 3-methylhexyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propanoate; 4-methyloctyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propanoate; and 6-methylheptyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propanoate. 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).

[0383] Particularly useful hindered phenol antioxidants often contain 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 C7-C9-(branched)-alkyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propanoate).

[0384] Useful hindered phenol(s) are represented by the formula:where Ra is a C4 to C20 alkyl group (such as a C4 to C12 alkyl group, such as a C4 to C8 alkyl group, such as 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, and or icosyl), Rb is a C4 to C20 alkyl group (such as a C4 to C12 alkyl group, such as a C4 to C8 alkyl group, such as 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, and or icosyl), and each Rc is hydrogen, a thioether group, or a linear or branched C1 to C40 alkyl group (such as such as a C1 to C20 alkyl group, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, hexyl, heptyl, octyl, dimethyl hexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl and / or triacontyl).

[0386] A preferred hindered phenol is represented by the formula:

[0387] Useful hindered phenol(s) may also be represented by the formula:where Ra is a C4 to C20 alkyl group (such as a C4 to C12 alkyl group, such as a C4 to C8 alkyl group, such as 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, and or icosyl), Rb is a C4 to C20 alkyl group (such as a C4 to C12 alkyl group, such as a C4 to C8 alkyl group, such as 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, and or icosyl), and G is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, such as 0, 1, 2, 3, 4, or 5.

[0389] Another preferred hindered phenol useful herein is represented by the formula:2-((((2-((3-(3-(tert-butyl)-4-hydroxy-5-isopropylphenyl)propanoyl)oxy)ethyl)thio)methyl)thio)ethyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate.

[0391] The hindered phenol antioxidant employed in the lubricating oil of the present invention may be a sterically hindered phenol described in U.S. Pat. No. 9,512,380, such as those shown at columns 82 to 100.

[0392] The hindered phenolic antioxidant 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 %.

[0393] When present in a concentrate, the hindered phenolic antioxidant 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 %.

[0394] When present in a booster (such as an antioxidant composition described herein), the hindered phenolic antioxidant may be present at about 0.01 mass % to about 40 mass % of the booster, 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

[0395] The antioxidant composition useful herein comprises a hindered phenolic antioxidant and, optionally, one or more additional antioxidants. Preferred additional antioxidants of the present invention may comprise diphenylamine antioxidants.

[0396] In embodiments, the antioxidant comprises hindered phenolic antioxidant, one or more additional antioxidants (such as and one or more diphenylamine antioxidants) and / or optionally one or more carboxylate detergents.

[0397] 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 % of the lubricating oil composition.

[0398] When present in a concentrate, the additional antioxidants 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 %.

[0399] When present in an antioxidant composition described herein (such as a booster), the additional antioxidants may be present at about 0.01 mass % to about 40 mass % of the booster, 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 %.

[0400] Additional antioxidants of the present invention may comprise diphenylamine compositions, such as hydrocarbyl substituted diphenylamine antioxidant, such as di(alkylphenyl)amine, where optionally the alkyl comprises C8 and or C9 linear, branched or cyclic alkyl. In embodiments, diphenylamine composition is present at 0.3 mass % or less, at at 0.2 mass % or less, or at 0.1 mass % or less, or at 0.05 mass % or less, or at 0.01 mass % or less, or at 0 mass %, based upon the weight of the lubricating oil composition.

[0401] Preferred additional antioxidants of the present invention may comprise diphenylamine compositions, wherein the diphenylamine composition comprises: alkyl or aralkyl substituted diphenyl amines represented by Formula (A):where n is 0 or 1, z is 0 or 1, and w is 0 or 1, and each Ra is independently a C8 to C9 linear, branched, or cyclic alkyl group or aralkyl represented by the Formula (1A):where Ph is a substituted or unsubstituted phenyl group, R1 is C1 to C20 (such as C1 to C12, such as C1) hydrocarbyl group, R2 is C1 to C20 (such as C1 to C12, such as C1) hydrocarbyl group (wherein R1 and R2 are preferably independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, docecyl, phenyl, naphthyl, alkyl substituted phenyl, (such as tolyl), or an isomer thereof (such as isooctyl, methylheptyl, dimethylhexyl, ethylhexyl, trimethylpentyl, methylethylpentyl, dimethylethylbutyl, diethylbutyl, methylpropylbutyl, and the like), and R1 and R2 may be bound to each other.In embodiments, the antioxidant composition useful as an additional additive may comprise aralkyl substituted diphenylamine represented by Formula A, where n is 1, at least one Ra is an aralkyl group represented by the Formula (1A) where Ph is a substituted or unsubstituted phenyl group, preferably unsubstituted phenyl, R1 is C1 to C20 hydrocarbyl group, R2 is C1 to C20 hydrocarbyl group, and wherein R1 and R2 are preferably independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, docecyl, phenyl, naphthyl, alkyl substituted phenyl, or an isomer thereof, and R1 and R2 may be bound to each other.

[0405] In embodiments, the aralkyl substituted diphenylamine is useful in a stable antioxidant composition, which may be used as an additional anti-oxidant, comprising: a) diphenylamine antioxidant comprising: aralkyl substituted diphenylamine represented by Formula (A) where at least one Ra is is represented by the Formula (IA); and b) polar diluent having an aniline point of 0° C. or less, and at least 2 available hydrogen-bond acceptor groups that are 2, 3, 4, 5, or 6 atoms apart, preferably comprising oxygen groups and not comprising sulfur groups, preferably comprising ester and or ether groups, wherein the composition comprising the polar diluent of b) combined with the diphenylamine antioxidant of a) is clear after 150 hours at 20° C. in a clear glass container without agitation. Preferably, 1) Ph is a substituted or unsubstituted phenyl group, preferably unsubstituted phenyl, R1 is C1 to C20 hydrocarbyl group, R2 is C1 to C20 hydrocarbyl group, and wherein R1 and R2 are preferably independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, docecyl, phenyl, naphthyl, alkyl substituted phenyl, or an isomer thereof, and R1 and R2 may be bound to each other; and 2) the polar diluent is selected from the group consisting of:

[0406] i) di- and tri-esters derived from propylene glycol,

[0407] ii) C8-16 alkyl triesters derived from tri-methylolpropane, and

[0408] iii) phthalates, terephthalates, isophthalates, trimellitates and pyromellitates, preferably the polar diluent(s) are one or more diluent(s) selected from the group consisting of: (di-propylene glycol) dibenzoate, C8-C10 tri-methylol propane ester, trioctyl trimellitate, and dioctylterephthalate.

[0409] The phrases “stable at X ° C. for Y hours” and “clear after Y hours at X ° C.” are defined in the DEFINITIONS section above.

[0410] The stable antioxidant composition useful as an additional anti-oxidant, may further comprising detergent (such as 1 to 98 mass %, based upon the weight of the composition), preferably: 1) carboxylate, preferably salicylate detergent, preferably calcium salicylate detergent, and or 2) sulfonate detergent, preferably magnesium sulfonate detergent.

[0411] Optionally, the stable antioxidant composition is combined with the detergent at a temperature of about 50° C. or more, alternately about 70° C. or more, prior to being combined with optional dispersants, friction modifiers; antioxidants, other than the antioxidants of i), pour point depressants, anti-foaming agents, viscosity modifiers, corrosion inhibitors, antirust agents, and / or anti-wear agents.

[0412] In embodiments, the diphenylamine antioxidants useful as additional antioxidants comprise at least 45% of the diphenylamine antioxidant where n is 1, z is 0 and w is 0, based upon the weight of compounds represented by Formula (1A), where Ph is phenyl, and R1 and R2 are methyl.

[0413] In embodiments, the diphenylamine antioxidants useful as additional antioxidants comprise more than a) 45 mass % mono(4-(2-phenylpropan-2-yl)phenyl)amine, b) less than 55 mass % of bis(4-(2-phenylpropan-2-yl)phenyl)amine, and c) less than 10 mass % of tri(4-(2-phenylpropan-2-yl)phenyl)amine, based upon the weight of a), b) and c).

[0414] In embodiments, the diphenylamine antioxidant composition useful as additional antioxidants may comprise less than 55 mass %, or 50 mass % or less, or 45 mass % or less, or 40 mass % or less, or 30 mass % or less, or 20 mass % or less, 15 mass % and more than 5 mass %, such as more than 10 mass % of di-aralkyl substituted diphenylamines represented by Formula (A), where w is 0, n is 1 and z is 1), based upon the weight of the diphenylamine antioxidant composition.

[0415] In embodiments, the diphenylamine antioxidant composition useful as additional antioxidants may comprise more than 45 mass %, or 50 mass % or more, or 55 mass % or more, or 60 mass % or more, or 70 mass % or more, or 80 mass % or more, or 90 mass % or more, or 92 mass % or more, or 93 mass % or more, or 94 mass % or more, or 45 to 95 mass % and not less than 45 mass % of mono-aralkyl substituted diphenylamines represented by Formula (1A), where n is 1, w is 0, and z is 0, based upon the weight of the diphenylamine antioxidant composition.

[0416] In embodiments, the antioxidant composition useful as additional antioxidants, may comprise from 0 to 20 mass % (such as 0.1 to 10 mass %) of diphenylamine compositions (based upon the weight of the additional antioxidant composition), comprising di-aralkyl substituted diphenylamine and at least 45 mass % mono-aralkyl substituted diphenylamine, based upon the weight of any unsubstituted diphenylamine, and the mono- and di-substituted diphenylamines.

[0417] In embodiments, the composition useful as additional antioxidant comprises at least 45 mass % mono-aralkyl substituted diphenylamine and di-aralkyl substituted diphenylamine, based upon the weight of any unsubstituted diphenylamine, and the mono- and di-substituted diphenylamines, may be used to prepare a stable antioxidant composition, which also may be used as an additional antioxidant, comprising a homogeneous diphenylamine antioxidant fluid comprising di-aralkyl substituted diphenylamine and at least 45 mass % mono-aralkyl substituted diphenylamine, based upon the weight of any unsubstituted diphenylamine, and the mono- and di-substituted diphenylamines, wherein the diphenylamine antioxidant fluid is clear after 90 days at 20° C. in a clear glass container without agitation.

[0418] Preferably, the stable antioxidant composition useful as additional antioxidant comprises:

[0419] a) from 45 to 95 mass % mono-aralkyl substituted diphenylamine represented by the Formula (A) where n is 1, w is 0, and z is 0;

[0420] b) 5 to 55 mass % of di-aralkyl substituted diphenylamine represented by Formula (A), where n is 1, w is 0, and z is 1;

[0421] c) from 0 to less than 10 mass % (such as from 0 to less than 5 mass %) tri-aralkyl substituted diphenylamine represented by Formula (A), where n is 1, w is 1 and z is 1; and

[0422] d) 1 mass % or less (such as 0.5 mass % or less, such as 0.1 mass % or less, such as 0.01 mass % or less) of unsubstituted diphenylamines represented by Formula (A) where n is 0, w is 0, and z is 0, based upon the total weight of the diphenylamines of a), b), c) and d) present in the composition (as determined by UPLC as described in the Experimental section of US2025 / 0136889A1).

[0423] Preferably, the stable antioxidant composition useful as additional antioxidant comprises less than 1 mass % (such as less than 0.5 mass %, such as less than 0.1, such as less than 0.01 mass %) of unsubstituted diphenylamines, such as those represented by Formula (A) above where n is 0, w is 0, and z is 0, based upon the composition of the diphenylamine.

[0424] Preferred mono and di-aralkyl combinations, useful herein include:such as 40 to 70% mono substituted.

[0426] In embodiments, C9 diphenylamine antioxidant useful as additional antioxidant comprises less than 10 mass %, such as 5 mass % or less, such as 2 mass % or less of diphenylamine represented by Formula (A) where z is 0, w is 0, n is 1, and Ra is a C9 linear or branched alkyl, and 90 mass % or more, such as 95 mass % or more, such as 98 mass % or more of diphenylamine where n is 1, z is 1, and w is 0, each Ra is independently a C9 linear or branched alkyl, based upon the weight of the diphenylamine.

[0427] In embodiments, C9 diphenylamine antioxidant useful as additional antioxidant is represented by Formula (A) where n is 1, z is 1, w is zero and each Ra group is branched C9 alkyl group.

[0428] Preferred additional antioxidants of the present invention may comprise diphenylamine compositions, wherein the diphenylamine composition comprises: 1) di(C9-alkyl substituted diphenyl) amine and 2) from 0 to less than 10 mass % of mono-C9-alkyl substituted diphenyl amine, based upon the weight of any unsubstituted diphenyl amine and the mono- and di-phenyl amines present in the diphenylamine composition.

[0429] Preferred additional antioxidants of the present invention may comprise diphenylamine compositions, wherein diphenylamine composition comprises: 90 mass % or more of di(C9-alkyl substituted diphenyl) amines, from 0 to less than 10 mass % of mono-C9-alkyl substituted diphenyl amine, and from 0 to less than 10 mass % of tri-C9-alkyl substituted diphenyl amine, based upon the weight of any unsubstituted diphenyl amine and the mono-, di-, and tri-phenyl amines present in the antioxidant composition.

[0430] Preferred additional antioxidants useful in the present invention may comprise a stable antioxidant composition comprising: a) diphenylamine antioxidant comprising: 1) di(C8-alkyl substituted phenyl) amine and 2) less than 15 mass % of mono-C8-alkyl substituted diphenylamine (based upon the weight of any unsubstituted diphenyl amine and the mono-C8-alkyl substituted phenylamines, di-C8-alkyl substituted phenylamines, and any tri-C8-alkyl substituted phenylamines present in the antioxidant composition); and b) polar diluent having an aniline point of 25° C. or less, and at least 2 available hydrogen-bond acceptor groups (such as ester, ether or alcohol groups) that are 2, 3, 4, 5, or 6 atoms apart, wherein the composition comprising the polar diluent of b) combined with the diphenylamine antioxidant of a) is clear after 96 hours at 20° C. in a clear glass container without agitation.

[0431] Preferred additional antioxidants useful in the present invention may comprise a stable antioxidant composition comprising: a) diphenylamine antioxidant comprising: 1) di(C8-alkyl substituted phenyl) amine and 2) less than 15 mass % of mono-C8-alkyl substituted diphenylamine (based upon the weight of mono-C8-alkyl substituted phenylamines, di-C8-alkyl substituted phenylamines, and any tri-C8-alkyl substituted phenylamines present in the antioxidant composition); and b) polar diluent having an aniline point of 25° C. or less, and at least 2 available hydrogen-bond acceptor groups (such as ester, ether or alcohol groups) that are 2, 3, 4, 5, or 6 atoms apart, wherein the composition comprising the polar diluent of b) combined with the diphenylamine antioxidant of a) is clear after 96 hours at 20° C. in a clear glass container without agitation; and the additional antioxidants composition further optionally comprises salicylate detergent, wherein optionally wherein the diphenylamine antioxidant composition of a) and b) is combined with the detergent at a temperature of 70° C. or more, or 75° C. or more, or 80° C. or more; and d) optionally wherein the diphenylamine antioxidant composition is heated to a temperature of at least 90° C. prior to addition to a concentrate or a lubricating oil composition.

[0432] In embodiments, the C8 alkyl diphenylamine antioxidant useful as additional antioxidant herein comprises:

[0433] a) from 0 to less than 10 mass % mono-C8-alkyl substituted diphenylamine represented by the Formula (A) where n is 1, w is 0, and z is 0;

[0434] b) 90 mass % or more of di-C8-alkyl substituted diphenylamine represented by Formula (A), where n is 1, w is 0, and z is 1;

[0435] c) from 0 to less than 10 mass % tri-C-alkyl substituted diphenylamine represented by Formula (A), where n is 1, w is 1, and z is 1;

[0436] d) 1 mass % or less (such as 0.5 mass % or less, such as 0.1 mass % or less, such as 0.01 mass % or less) of unsubstituted diphenylamines represented by Formula (A) where n is 0, w is 0, and z is 0, based upon the total weight of the diphenylamines of a), b), c) and d) present in the composition (as determined by UPLC as described in the Experimental section of US2025 / 0136889A1), where each Ra is independently a linear C8 alkyl group or branched C8 alkyl group, n is 1 or 0, z is 0 or 1, and w is 0 or 1, where the branched C8 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.

[0437] Preferred additional antioxidants useful in the present invention may comprise diphenylamine compositions described in the following, which are incorporated by reference herein:

[0438] 1) U.S. Patent Application Ser. No. 63 / 593,559, filed Oct. 27, 2023, and entitled: Lubricant Compositions Containing High C9 Disubstituted Diphenylamine Antioxidant Content;

[0439] 2) European Patent Application 23218539.7, filed Dec. 20, 2023, and entitled: Lubricant Compositions Containing Aralkyl Substituted Diphenylamine Antioxidant;

[0440] 3) European Patent Application 23218548.8, filed Dec. 20, 2023, and entitled: Lubricant Compositions Containing C8 Disubstituted Diphenylamine Antioxidant; and

[0441] 4) European Patent Application 23218550.4, filed Dec. 20, 2023, and entitled: Lubricant Compositions Containing Mono-aralky and Di-aralkyl Substituted Diphenylamine Antioxidants.

[0442] A number of additional antioxidants are compatible with the present invention. Examples of additional antioxidants include molybdenum succinimides, and dithiocarbamates (such Zn or Mo-dialkyldithiocarbamates). These oil-soluble components are generally known.

[0443] Effective amounts of one or more catalytic antioxidants may also be used as additional antioxidants. The catalytic antioxidants comprise an effective amount of a) one or more oil soluble polymetal organic compounds; and, effective amounts of b) one or more substituted N,N′-diaryl-o-phenylenediamine compounds or c) one or more hindered phenol compounds; or a combination of both b) and c). Catalytic antioxidants useful herein are more fully described in U.S. Pat. No. 8,048,833.

[0444] Non-phenolic oxidation inhibitors, which may be used include aromatic amine antioxidants (other than those represented by Formulas A 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 R8R9R10N, where R8 is an aliphatic, aromatic or substituted aromatic group, R9 is an aromatic or a substituted aromatic group, and R10 is H, alkyl, aryl or R11S(O)xR12 where R11 is an alkylene, alkenylene, or aralkylene group, R12 is an alkyl group, or an alkenyl, aryl, or alkaryl group, and x is 0, 1, or 2. The aliphatic group R8 may contain from 1 to about 20 carbon atoms, and preferably contains from about 6 to 12 carbon atoms. The aliphatic group is typically a saturated aliphatic group. Preferably, both R8 and R9 are aromatic or substituted aromatic groups, and the aromatic group may be a fused ring aromatic group such as naphthyl. Aromatic groups R8 and R9 may be joined together with other groups such as sulfur.

[0445] 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.

[0446] 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 U.S. Pat. No. 10,731,101 (col 15, ln 55 to col 22, In 12).

[0447] 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. Nos. 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.

[0448] 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).

[0449] 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.

[0450] 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.

[0451] 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.F. Pour Point Depressants

[0452] 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. U.S. Pat. Nos. 1,815,022; 2,015,748; 2,191,498; 2,387,501; 2,655,479; 2,666,746; 2,721,877; 2,721,878; and 3,250,715 describe useful pour point depressants and / or the preparation thereof. Such additives may be used in an amount of about 0.01 to 5 mass %, preferably about 0.01 to 1.5 mass %, based upon the weight of the lubricating composition.G. Anti-Foam Agents

[0453] 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.

[0454] Anti-foam agents are commercially available 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.

[0455] For example, it may be that the lubricating oil composition comprises an anti-foam agent comprising polyalkyl siloxane, such as a polydialkyl siloxane, for example, wherein the alkyl is a C1-C10 alkyl group, e.g., a polydimethylsiloxane (PDMS), also known as a silicone oil. Alternately, the siloxane is a poly(R3)siloxane, wherein R3 is one or more same or different linear branched or cyclic hydrocarbyls, such as alkyls or aryls, typically having 1 to 20 carbon atoms. It may be that, for example, the lubricating oil composition comprises a polymeric siloxane compound according to Formula 1 below wherein R1 and R2 are independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl, phenyl, naphthyl, alkyl substituted phenyl, or isomers thereof (such as methyl, phenyl) and n is from 2 to 1000, such as 50 to 450, alternately such as 40 to 100.

[0456] Additionally, or alternatively, it may be that the lubricating oil composition comprises an organo-modified siloxane (OMS), such as a siloxane modified with an organo group such as a polyether (e.g., ethylene-propyleneoxide copolymer), long chain hydrocarbyl (e.g., C11-C100 alkyl), or aryl (e.g., C6-C14 aryl). It may be that, for example, the lubricating oil composition comprises an organo-modified siloxane compound according to Formula 1, wherein n is from 2 to 2000, such as 50 to 450 (alternately such as 40 to 100), and wherein R1 and R2 are the same or different, optionally wherein each of R1 and R2 is, independently an organo group, such as an organo group selected from polyether (e.g., ethylene-propyleneoxide copolymer), long chain hydrocarbyl (e.g., C11-C100 alkyl), or aryl (e.g., C6-C14 aryl). Preferably, one of R1 and R2 is CH3.

[0457] Based on the total weight of the lubricant composition, the siloxane according to Formula 1 is incorporated so as to provide about 0.1 to less than about 30 ppm Si, or about 0.1 to about 25 ppm Si, or about 0.1 to about 20 ppm Si, or about 0.1 to about 15 ppm Si, or about 0.1 to about 10 ppm Si. More preferably, it is in the range of about 3-10 ppm Si.

[0458] 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, phenyl-methyl polysiloxane, linear, cyclic or branched siloxanes, silicone polymers and copolymers, and / organo-silicone copolymers. Also, a siloxane polyether copolymer Anti-foamant available from OSI Specialties, Inc. of Farmington Hills, Michigan and may be substituted or included. One such material is sold as SILWET-L-7220.

[0459] Acrylate polymer anti-foam agent can also be used herein. Typical acrylate anti-foamants include polyacrylate anti-foamant available from Monsanto Polymer Products Co. known as PC-1244. A preferred acrylate polymer anti-foam agent useful herein is PX™3841 (i.e., an alkyl acrylate polymer), commercially available from Dorf Ketl, also referred to as Mobilad™C402.

[0460] In embodiments, a combination of silicone anti-foamant and acrylate anti-foamant can be used, such as at a weight ratio of the silicone anti-foamant to the acrylate anti-foamant of from about 5:1 to about 1:5, see, for example, US Patent Application Publication No. 2021 / 0189283.H. Viscosity Modifiers

[0461] 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.

[0462] Examples of suitable viscosity modifiers are linear or radial (star-shaped) polymers and copolymers of methacrylate, butadiene, olefins, 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.

[0463] 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 designation “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™”.

[0464] 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).

[0465] 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).

[0466] 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 Group I, 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.).

[0467] Dispersant viscosity modifiers useful herein may include the amide, imide, and / or ester functionalized partially or fully saturated polymers comprising C4-5 olefins as described in U.S. application Ser. No. 18 / 480,571, filed Oct. 4, 2023, which is herein incorporated by reference in its entirety. Useful DVM's include polymers referred to as “functionalized polymers” described in U.S. Ser. No. 18 / 480,571, and preferably are functionalized hydrogenated polyisoprene polymers (optionally of higher molecular weights than amide, imide, and / or ester functionalized partially or fully saturated polymers comprising C4-5 olefins selected primarily for their dispersant properties). In an advantageous form, the lubricating oil composition described herein further optionally includes one or more functionalized polymers described in Ser. No. 18 / 480,571 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, and iii) 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 U.S. patent application Ser. No. 18 / 480,571, filed Oct. 4, 2023). For the functionalized polymer described in Ser. No. 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 U.S. patent application Ser. No. 18 / 480,571, filed Oct. 4, 2023. The functionalized polymers described in Ser. No. 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 Ser. No. 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 Ser. No. 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.

[0468] Other useful DVM's include functionalized olefin copolymers (such as amine functionalized ethylene propylene copolymers).

[0469] 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.

[0470] 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

[0471] 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.

[0472] 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 PIBSA-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 (Poly)Alkenylsuccinic Derivatives

[0473] 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 U.S. Pat. Nos. 3,172,892; 3,2145,707; 3,219,666; 3,316,177; 3,341,542; 3,444,170; 3,454,607; 3,541,012; 3,630,904; 3,632,511; 3,787,374 and 4,234,435. Other types of dispersants are described in U.S. Pat. Nos. 3,036,003; 3,200,107; 3,254,025; 3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,413,347; 3,697,574; 3,725,277; 3,725,480; 3,726,882; 4,454,059; 3,329,658; 3,449,250; 3,519,565; 3,666,730; 3,687,849; 3,702,300; 4,100,082; 5,705,458. A further description of dispersants useful herein may be found, for example, in European Patent Applications Nos. 0 471 071 and 0 451 380, to which reference is made for this purpose.

[0474] Hydrocarbyl-substituted succinic acid and hydrocarbyl-substituted succinic anhydride derivatives are useful dispersants. In particular, succinimide, succinate esters, or succinate ester amides prepared by the reaction of a hydrocarbon-substituted succinic acid or anhydride compound (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.

[0475] 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 U.S. Pat. No. 4,873,009. Examples of polyoxyalkylene polyamines include polyoxyethylene and / or polyoxypropylene diamines and triamines (as well as co-oligomers thereof) having an average 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 U.S. Pat. Nos. 3,087,936; 3,172,892; 3,219,666; 3,272,746; 3,322,670; 3,652,616; 3,948,800; and 6,821,307; and CA Patent No. 1,094,044.

[0476] 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.

[0477] 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.

[0478] Succinate ester amides useful herein are formed by a condensation reaction between hydrocarbyl-substituted succinic anhydrides and alkanol amines. Suitable alkanol amines include ethoxylated polyalkylpolyamines, propoxylated polyalkylpolyamines, and polyalkenylpolyamines such as polyethylene polyamines and / or propoxylated hexamethylenediamine. Representative examples are shown in U.S. Pat. No. 4,426,305.

[0479] Hydrocarbyl-substituted succinic anhydrides (such as PIBSA) esters of hydrocarbyl bridged aryloxy alcohols are also useful as dispersants herein. For information on such dispersants, please see U.S. Pat. No. 7,485,603, particularly, col 2, ln 65 to col 6, In 22 and col 23, ln 40 to col 26, ln 46. In particular, PIBSA esters of methylene-bridged naphthyloxy ethanol (i.e., 2-hydroxyethyl-1-naphthol ether (or hydroxy-terminated ethylene oxide oligomer ether of naphthol) are useful herein.

[0480] 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. The above (poly)alkenylsuccinic derivatives can be post-reacted with various reagents such as sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid.

[0481] 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.

[0482] 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.

[0483] Dispersants useful herein include borated succinimides, including those derivatives from mono-succinimides, bis-succinimides, and / or mixtures of mono- and bis-succinimides, wherein the hydrocarbyl succinimide is derived from a hydrocarbylene group such as polyisobutylene having an Mn of from about 300 to about 5000 g / mol, or from about 500 to about 3000 g / mol, or about 1000 to about 2000 g / mol, or a mixture of such hydrocarbylene groups, often with high terminal vinylic groups.

[0484] 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.

[0485] 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.

[0486] 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 the lubricating composition and wherein the ratio of borated dispersant to non-boronated dispersant may be 1:10 to 10:1 (weight:weight) or 1:5 to 3:1 or 1:3 to 2:1.

[0487] 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 polyisobutylene (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 (weight:weight) or 1:5 to 3:1 or 1:3 to 2:1.

[0488] 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”).

[0489] 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 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 %. The dispersant may comprise one or more borated and one or more non-borated PIBSA-PAM's. 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).

[0490] 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.

[0491] 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).

[0492] 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.

[0493] The dispersant may comprise one or more borated and one or more non-borated PIBSA-PAM's.

[0494] 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 11500 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 %.

[0495] Optionally the dispersant may be a multifunctional oil soluble molybdenum compound. A particularly preferred oil soluble molybdenum compound is an unsulfurized or sulfurized oxymolybdenum containing composition prepared by (i) reacting an acidic molybdenum compound and a basic nitrogen compound selected from the dispersant group consisting of succinimide, a carboxylic acid amide, a hydrocarbyl monoamine, a phosphoramide, a thiophosphoramide, a Mannich base, a dispersant viscosity index improver, or a mixture thereof in the presence of a polar promoter, to form an oxymolybdenum complex. More preferably the basic nitrogen compound is a succinimide. For further information on oil soluble molybdenum compounds useful herein, including oxymolybdenum succinimide dispersant combinations, see U.S. Pat. No. 8,623,798, column 16, line 22 to column 22, line 4 and U.S. Pat. No. 6,562,765, both to Chevron Oronite.Dispersants of Mannich Bases

[0496] Mannich base dispersants useful herein are typically made from the reaction of an amine component, a hydroxy aromatic compound (substituted or unsubstituted, such as alkyl substituted), such as alkylphenols, and an aldehyde, such as formaldehyde. See U.S. Pat. Nos. 4,767,551 and 10,899,986. Process aids and catalysts, such as oleic acid and sulfonic acids, can also be part of the reaction mixture. Representative examples are shown in U.S. Pat. Nos. 3,697,574; 3,703,536; 3,704,308; 3,751,365; 3,756,953; 3,798,165; 3,803,039; 4,231,759; 9,938,479; 7,491,248; and 10,899,986, and PCT Publication No. WO 01 / 42399.Dispersants of Polymethacrylate or Polyacrylate Derivatives

[0497] Polymethacrylate or polyacrylate derivatives are another class of dispersants useful herein. These dispersants are typically prepared by reacting a nitrogen-containing monomer and a methacrylic or acrylic acid esters containing 5-25 carbon atoms in the ester group. Representative examples are shown in U.S. Pat. Nos. 2,100,993, and 6,323,164. Polymethacrylate and polyacrylate dispersants are typically lower molecular weights.

[0498] 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 0.1 mass % to 5 mass %, or 0.01 mass % to 4 mass % of the lubricating composition.

[0499] For further information on dispersants useful herein, please see U.S. Pat. No. 10,829,712, col 13, ln 36 to col 16, ln 67 and U.S. Pat. No. 7,485,603, col 2, ln 65 to col 6, ln 22, col 8, ln 25 to col 14, In 53, and col 23, ln 40 to col 26, ln 46.Amide, Imide, and / or Ester Functionalized Saturated C4-5 Polymer

[0500] Dispersants useful herein include the amide, imide, and / or ester functionalized partially or fully saturated polymers comprising C4-5 olefins as described in U.S. application Ser. No. 18 / 480,571, filed Oct. 4, 2023, which is herein incorporated by reference in its entirety. Preferred functionalized polymers include polymers referred to as “functionalized polymers” and described in U.S. Ser. No. 18 / 480,571, and preferably are a functionalized hydrogenated polyisoprene family of polymers for use in lubricating oil compositions. In an advantageous form, the lubricating oil composition described herein further optionally includes one or more functionalized polymers described in Ser. No. 18 / 480,571 as dispersant 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, and iii) 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 U.S. patent application Ser. No. 18 / 480,571, filed Oct. 4, 2023). For the functionalized polymer described in Ser. No. 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 U.S. patent application Ser. No. 18 / 480,571, filed Oct. 4, 2023. The functionalized polymers described in Ser. No. 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 Ser. No. 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 Ser. No. 18 / 480,571 useful herein may be absent of styrene repeat units, or absent of butadiene repeat units, or are not a homo-polyisobutylene, or are not a copolymer of isoprene and butadiene.

[0501] Compositions according to the present disclosure may contain an additive having a different enumerated function that also has secondary effects as a dispersant. Unless otherwise indicated, 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

[0502] 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.

[0503] Suitable corrosion inhibitors may include nitrogen and / or sulfur-containing heterocyclic compounds such as triazoles (e.g., benzotriazoles), substituted thiadiazoles, imidazoles, thiazoles, tetrazoles, hydroxyquinolines, oxazolines, imidazolines, thiophenes, indoles, indazoles, quinolines, benzoxazines, dithiols, oxazoles, oxatriazoles, pyridines, piperazines, triazines and derivatives of any one or more thereof. A particular corrosion inhibitor is a benzotriazole represented by the structure:wherein R8 is absent (hydrogen) or is a C1 to C20 hydrocarbyl or substituted hydrocarbyl group which may be linear or branched, saturated or unsaturated. It may contain ring structures that are alkyl or aromatic in nature and / or contain heteroatoms such as N, O, or S. Examples of suitable compounds may include benzotriazole, alkyl-substituted benzotriazoles (e.g., tolyltriazole, ethylbenzotriazole, hexylbenzotriazole, octylbenzotriazole, etc.), aryl substituted benzotriazole, alkylaryl- or arylalkyl-substituted benzotriazoles, and the like, as well as combinations thereof. For instance, the triazole may comprise or be a benzotriazole and / or an alkylbenzotriazole in which the alkyl group contains from 1 to about 20 carbon atoms or from 1 to about 8 carbon atoms. Non-limiting examples of such corrosion inhibitors may comprise or be benzotriazole, 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.

[0505] Additionally, or alternatively, the corrosion inhibitor may include one or more substituted thiadiazoles represented by the structure:wherein R15 and R16 are independently hydrogen or a hydrocarbon group, which group may be aliphatic or aromatic, including cyclic, alicyclic, aralkyl, aryl and alkaryl, and wherein each w is independently 1, 2, 3, 4, 5, or 6 (preferably 2, 3, or 4, such as 2). These substituted thiadiazoles are derived from the 2,5-dimercapto-1,3,4-thiadiazole (DMTD) molecule. Many derivatives of DMTD have been described in the art, and any such compounds may be included in the fluid used in the present disclosure. For example, U.S. Pat. Nos. 2,719,125; 2,719,126; and 3,087,937; describe the preparation of various 2, 5-bis-(hydrocarbon dithio)-1,3,4-thiadiazoles.

[0507] Further, additionally or alternatively, the corrosion inhibitor may include one or more other derivatives of DMTD, such as a carboxylic ester in which R15 and R16 may be joined to the sulfide sulfur atom through a carbonyl group. Preparation of these thioester-containing DMTD derivatives is described, for example, in U.S. Pat. No. 2,760,933. DMTD derivatives produced by condensation of DMTD with alpha-halogenated aliphatic carboxylic acids having at least 10 carbon atoms are described, for example, in U.S. Pat. No. 2,836,564. This process produces DMTD derivatives wherein R15 and R16 are HOOC—CH(R19)—(R19 being a hydrocarbyl group). DMTD derivatives further produced by amidation or esterification of these terminal carboxylic acid groups may also be useful.

[0508] The preparation of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazoles is described, for example, in U.S. Pat. No. 3,663,561.

[0509] A class of DMTD derivatives may include mixtures of a 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazole and a 2,5-bis-hydrocarbyldithio-1,3,4-thiadiazole. Such mixtures may be sold under the tradename HiTEC™ 4313 and are commercially available from Afton Chemical Company.

[0510] The preparation of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazoles is described, for example, in U.S. Pat. No. 3,663,561.

[0511] Still further, additionally or alternatively, the corrosion inhibitor may include a trifunctional borate having the structure, B(OR46)3, in which each R46 may be the same or different. As the borate may typically be desirably compatible with the non-aqueous medium of the composition, each R46 may, in particular, comprise or be a hydrocarbyl C1-C8 moiety. For compositions in which the non-aqueous medium comprises or is a lubricating oil basestock, for example, better compatibility can typically be achieved when the hydrocarbyl moieties are each at least C4. Non-limiting examples of such corrosion inhibitors thus include, but are not limited to, triethylborate, tripropylborates such as triisopropylborate, tributylborates such as tri-tert-butylborate, tripentylborates, trihexylborates, trioctylborates such as tri-(2-ethylhexyl)borate, monohexyl dibutylborate, and the like, as well as combinations thereof.

[0512] When used, a corrosion inhibitor may comprise a substituted thiadiazole, a substituted benzotriazole, a substituted triazole, a trisubstituted borate, or a combination thereof.

[0513] When desired, corrosion inhibitors can be used in any effective amount, but, when used, may typically be used in amounts from about 0.001 mass % to 5.0 mass %, based on the weight of the composition, e.g., from 0.005 mass % to 3.0 mass % or from 0.01 mass % to 1.0 mass %. Alternately, 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.

[0514] In some embodiments, 3,4-oxypyridinone-containing compositions may contain substantially no (e.g., 0, or less than 0.001 mass %, 0.0005 mass % or less, not intentionally added, and / or absolutely no) triazoles, benzotriazoles, substituted thiadiazoles, imidazoles, thiazoles, tetrazoles, hydroxyquinolines, oxazolines, imidazolines, thiophenes, indoles, indazoles, quinolines, benzoxazines, dithiols, oxazoles, oxatriazoles, pyridines, piperazines, triazines, derivatives thereof, combinations thereof, or all corrosion inhibitors.

[0515] 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

[0516] 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.

[0517] In embodiments, the anti-wear agent is or comprises a dihydrocarbyl dithiophosphate metal salt, such as zinc dialkyl dithiophosphate compounds. The metal of the dihydrocarbyl dithiophosphate metal salt may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel, or copper. In some embodiments, the metal is zinc. In other embodiments, the alkyl group of the dihydrocarbyl dithiophosphate metal salt has from about 3 to about 22 carbon atoms, from about 3 to about 18 carbon atoms, from about 3 to about 12 carbon atoms, or from about 3 to about 8 carbon atoms. In further embodiments, the alkyl group is linear or branched.

[0518] 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.

[0519] 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)(OR1)(OR2)]2 where R1 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. Useful zinc dithiophosphates include secondary zinc dithiophosphates such as those available from The Lubrizol Corporation under the trade designations “LZ™ 677A”, “LZ™ 1095” and “L™Z 1371”, from Chevron Oronite under the trade designation “OLOA™ 262” and from Afton Chemical under the trade designation “HiTEC™ 7169”.

[0520] In embodiments, the zinc compound can be a zinc dithiocarbamate complex, such as the zinc dithiocarbamates represented by the formula:where each RI is independently a linear, cyclic, or branched, saturated or unsaturated, aliphatic hydrocarbon moiety having from 1 to about 10 carbon atoms, n is 0, 1, or 2, L is a ligand that saturates the coordination sphere of zinc, and x is 0, 1, 2, 3, or 4. In certain embodiments, the ligand, L, is selected from the group consisting of water, hydroxide, ammonia, amino, amido, alkylthiolate, halide, and combinations thereof.

[0522] 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.

[0523] 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.

[0524] 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 B described 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

[0525] Demulsifiers useful herein include those described in U.S. Pat. No. 10,829,712 (col 20, ln 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

[0526] 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

[0527] The lubricating oil composition of the present disclosure can contain one or more extreme pressure agents that can prevent sliding metal surfaces from seizing under conditions of extreme pressure. Any extreme pressure agent known by a person of ordinary skill in the art may be used in the lubricating oil composition. Generally, the extreme pressure agent is a compound that can combine chemically with a metal to form a surface film that prevents the welding of asperities in opposing metal surfaces under high loads. Non-limiting examples of suitable extreme pressure agents include sulfurized animal or vegetable fats or oils, sulfurized animal or vegetable fatty acid esters, fully or partially esterified esters of trivalent or pentavalent acids of phosphorus, sulfurized olefins, dihydrocarbyl polysulfides, sulfurized Diels-Alder adducts, sulfurized dicyclopentadiene, sulfurized or co-sulfurized mixtures of fatty acid esters and monounsaturated olefins, co-sulfurized blends of fatty acid, fatty acid ester and alpha-olefin, functionally substituted dihydrocarbyl polysulfides, thia-aldehydes, thia-ketones, epithio compounds, sulfur-containing acetal derivatives, co-sulfurized blends of terpene and acyclic olefins, and poly sulfide olefin products, amine salts of phosphoric acid esters or thiophosphoric acid esters, and combinations thereof. The amount of the extreme pressure agent may vary from about 0.01 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

[0528] The lubricating oil composition of the present disclosure can contain one or more unsaturated hydrocarbons. These unsaturated hydrocarbons are distinct from any base oils (lubricating oil base oils 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.

[0529] 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.

[0530] 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 ComponentsA (mass %B (mass %C (mass %Additive Formulationsa.i.)a.i.)a.i.)Dispersant0.1-200.1-20 1-8Detergents (such as Salicylate)0.1-200.1-20 0.2-9  C10 to C36 linear, branched or0.01-8 0.1-5  0.5-3  cyclic alcohol(s)Corrosion Inhibitor, anti-rust / optional0.05-7  0.1-1.5extreme pressure agentshindered phenol AO0.01-20 0.1-8  0.2 to 5Additional Antioxidant that is  0-100.01-5  0.1-4  not hindered phenol AO, such asdiphenyl aminePour Point Depressantoptional0-50.01-1.5 Anti-foaming Agentoptional0-50.001-0.15 Friction Modifier, such as Mooptional0.01-5  0.5-3.0containing compound, such asMoDTCAnti-wear Agentoptional0.01-5  0.1-3  Viscosity Modifieroptional0.01-10  0.25-3  Seal Swell Agentsoptional0-50-2Extreme Pressure Agentsoptional0-50-3Base oilBalanceBalanceBalance(such as 50to 95 m %)Typical Amounts of Lubricating Oil Components in LOC (Continued)ADDITIVE FORMULATIONSD (mass %)E (mass %)F (mass %)Dispersant (borated and non-borated)0.1-40  1-20  4 to 15Detergents0.1-200.2-15  2 to 10C10 to C36 linear, branched or cyclic alcohol(s)0.01-8 0.1-5 0.5-3Hindered phenolic AO0.1-150.5-5 0.2 to 5Amine based Antioxidant 0-70.01-5   1 to 5Molybdenum containing compound  0-100.1 to 70.5 to 5Antifoaming Agent0.001-5  0.001-0.2  0.001-0.1 Friction Modifier, other than the Mo 0-50.01-1.5 0.1 to 5containing compoundViscosity Modifier0.01-25   1-20  5-15Optional additional additives  0-200.1-100.1-5Base oil (50 to 99 mass %)BalanceBalanceBalanceTypical Amounts of Lubricating Oil Components in LOC (Continued)ADDITIVE FORMULATIONSG (mass %)H (mass %)I (mass %)Dispersant borated0.1-10  0.5-80.5-5Dispersant non-borated0.1 to 300.5 to 20  1 to 15Detergent Ca high TBN0.1-19.80.25-9 0.25 to 5 Detergent Mg, preferably high TBN (150 or0.1-19.80.5-80.5 to 5more)Detergent Ca low TBN (less than 150) 0-9.80.1-80.5 to 5C10 to C36 linear, branched or cyclic alcohol(s)0.01-8   0.1-50.5-3Hindered Phenolic AO0.1-15  0.2-50.3 to 3Amine (such as alkyl substituted0.01-7   0.10-5   1 to 5diphenylamine) a based antioxidantSulfurized antioxidant0-200.1 to 100.5-5Molybdenum containing compound0.01-10  0.05 to 7 0.1 to 5Antifoaming Agent0.001-5   0.001-0.2 0.001-0.1 Friction Modifier, other than the Mo0-5  0.01-1.50.1 to 5containing compoundViscosity Modifier0.01-25    1-20  5-15ZDDP0-20 0.1-10 0.1-10Optional additional additives0-20 0.1-10 0.1-10Base oil (50 to 99 mass %)BalanceBalanceBalanceThe 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.FuelsThis 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;

[0534] (ii) providing fuel, such as a hydrocarbon fuel, ammonia fuel, hydrogen fuel, in the automotive internal combustion engine; and

[0535] (iii) combusting the fuel in the internal combustion engine.

[0536] This disclosure also relates to a method of lubricating an internal combustion engine during operation of the engine comprising:

[0537] (ii) providing the lubricating composition as described herein to a crankcase of the internal combustion engine;

[0538] (ii) providing a hydrocarbon fuel to the internal combustion engine; and

[0539] (iii) combusting the fuel in the internal combustion engine (such as a spark-ignited or compression-ignited two- or four-stroke reciprocating engine, such as a diesel engine or passenger car engine).

[0540] 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.

[0541] The renewable fuel component is typically produced from vegetable oil (such as palm oil, rapeseed oil, soybean oil, jatropha oil), microbial oil (such as algae oil), animal fats (such as cooking oil, animal fat, and / or fish fat) and / or biogas. Renewable fuel refers to biofuel produced from biological resources formed through contemporary biological processes. In an embodiment, the renewable fuel component is produced by means of a hydrotreatment process. Hydrotreatment involves various reactions where molecular hydrogen reacts with other components, or the components undergo molecular conversions in the presence of molecular hydrogen and a solid catalyst. The reactions include, but are not limited to, hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrification, hydrodemetallization, hydrocracking, and isomerization. The renewable fuel component may have different distillation ranges, which provide the desired properties to the component, depending on the intended use.Uses

[0542] 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 heavy-duty diesel engine lubricants, but can be powertrain or other lubricants used in power transmission.

[0543] 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 or a light duty diesel engine.

[0544] 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.

[0545] In embodiments, the lubricating oils of this disclosure are used in spark-assisted high compression internal combustion engines.

[0546] 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 (i.e., a heavy-duty diesel vehicle having a gross vehicle weight rating of 10,000 pounds or more.)

[0547] In embodiments, the lubricating compositions of the present disclosure are suitably used in the lubrication of the crankcase of a passenger car diesel engine.

[0548] 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.

[0549] 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 the internal combustion engine; (ii) providing a hydrocarbon fuel and or biofuel to the internal combustion engine; and (iii) combusting the fuel in the internal combustion engine.

[0550] Also, the antioxidant compositions, concentrates and or lubricating oil compositions of the invention may be useful as lubricant components and as lubricating oil compositions for hydrogen engines and or ammonia engines (i.e., where hydrogen (or hydrogen combined with natural gas) and or ammonia fuels the engine).

[0551] The lubricating oil compositions described herein are also useful for lubricating a hydrogen or ammonia fueled internal combustion engine during operation of the engine comprising: (i) providing to an internal combustion engine, such as to a crankcase, a lubricating composition comprising: 1) C10 to C36 linear, branched or cyclic alcohol, 2) hindered phenolic antioxidant, and 3) optionally, molybdenum containing compound, as described herein; (ii) providing fuel comprising hydrogen and or ammonia to the internal combustion engine; and (iii) combusting the fuel in an internal combustion engine, such as a hydrogen or ammonia fueled engine.

[0552] 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.

[0553] In particular, the lubricating compositions of the present disclosure are suitably used in a method of reducing viscometric growth such as by 10% or more, (such as by 20% or more, such as by 30% or more, such as by 40% or more, 50% or more, such as by 60% or more, such as by 70% or more, such as by 80% or more, 90% or more, such as by 100% or more, such as by 150% or more, such as by 200% or more), as determined by the CEC-L-109-14 Oxidation Test for Engine Oils Operating in the Presence of Biodiesel Fuel at 216 hours, of a lubricating oil composition in an internal combustion engine, the method comprising: supplying a lubricating oil composition to the internal combustion engine, where the lubricating oil composition comprises the antioxidant composition, the concentrate composition, the lubricating oil composition or the booster pack as described herein, as compared to the same lubricating oil composition except that C10 to C36 linear, branched or cyclic alcohol is absent, alternately C10 to C36 linear, branched or cyclic alcohol and molybdenum compounds are absent, alternately C10 to C36 linear, branched or cyclic alcohol and diphenylamine antioxidants are absent, or alternately C10 to C36 linear, branched or cyclic alcohol, molybdenum compounds, and diphenylamine antioxidants are absent.

[0554] In particular, the lubricating compositions of the present disclosure are suitably used in a method of reducing viscometric growth (such as by 10% or more, such as by 20% or more, such as by 30% or more, such as by 40% or more, 50% or more, such as by 60% or more, such as by 70% or more, such as by 80% or more, 90% or more, such as by 100% or more, such as by 150% or more, such as by 200% or more), as determined by the Daimler Truck Oxidation Test at 168 hours, of a lubricating oil composition in an internal combustion engine, the method comprising: supplying a lubricating oil composition to the internal combustion engine, where the lubricating oil composition comprises the antioxidant composition, the concentrate composition, the lubricating oil composition or the booster pack as described herein, as compared to the same lubricating oil composition except that: C10 to C36 linear, branched or cyclic alcohol is absent, alternately C10 to C36 linear, branched or cyclic alcohol and molybdenum compounds are absent, alternately C10 to C36 linear, branched or cyclic alcohol and diphenylamine antioxidants are absent, or alternately C10 to C36 linear, branched or cyclic alcohol, molybdenum compounds, and diphenylamine antioxidants are absent.

[0555] In particular, the lubricating compositions of the present disclosure are suitably used in a method of maintaining and or reducing oxidation by 5% or more (such as by 10% or more, such as by 20% or more, such as by 30% or more, such as by 40% or more, 50% or more, such as by 60% or more, such as by 70% or more, such as by 80% or more, 90% or more, such as by 100% or more, such as by 150% or more, such as by 200% or more), as determined by the Nitration Oxidation Test at 144 hours, of a lubricating oil in an internal combustion engine, the method comprising: supplying a lubricating oil composition to the internal combustion engine, where the lubricating oil composition comprises the antioxidant composition, the concentrate composition, the lubricating oil composition or the booster pack of any of claims 1 to 33, as compared to the same lubricating oil composition except that: C10 to C36 linear, branched or cyclic alcohol is absent, alternately C10 to C36 linear, branched or cyclic alcohol and molybdenum compounds are absent, alternately C10 to C36 linear, branched or cyclic alcohol and diphenylamine antioxidants are absent, or alternately C10 to C36 linear, branched or cyclic alcohol, molybdenum compounds, and diphenylamine antioxidants are absent.

[0556] This invention further relates to:

[0557] 1. An antioxidant composition, comprising: 1) C10 to C36 linear, branched or cyclic alcohol, 2) hindered phenolic antioxidant, 3) optionally, molybdenum containing compound, and 4) optionally, diphenylamine composition.

[0558] 2. The antioxidant composition of paragraph 1, further 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, and ii) a Functionality Distribution (Fd) value of 3.5 or less.

[0559] 3. The antioxidant composition of paragraph 1 or 2, further comprising dispersant 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, ii) a Functionality Distribution (Fd) value of 3.5 or less, and iii) an Mn of 10,000 g / mol or more (GPC-PS) of the polymer prior to functionalization, and optionally, 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).

[0560] 4. The antioxidant composition of paragraph 1, 2 or 3 wherein the C10 to C36 linear, branched or cyclic alcohol comprises branched alcohol, linear alcohol, or a combination thereof.

[0561] 5. The antioxidant composition of paragraph 1, 2 or 3, wherein the C10 to C36 linear, branched or cyclic alcohol comprises one or more C10 to C24 alcohols.

[0562] 6. The antioxidant composition of paragraph 1, 2 or 3, wherein the C10 to C36 linear, branched or cyclic alcohol comprises of one or more C12 to C18 linear alcohols.

[0563] 7. The antioxidant composition of paragraph 1, 2 or 3, wherein the C10 to C36 linear, branched or cyclic alcohol comprises C12 linear, branched or cyclic alcohol.

[0564] 8. The antioxidant composition of paragraph 1, 2 or 3, wherein the hindered phenolic antioxidant is represented by the formula:where Ra is a C4 to C20 alkyl group (such as a C4 to C12 alkyl group, such as a C4 to C8 alkyl group), Rb is a C4 to C20 alkyl group (such as a C4 to C12 alkyl group, such as a C4 to C8 alkyl group, Rc is hydrogen, a thioether group, or a linear or branched C1 to C40 alkyl group (such as such as a C1 to C20 alkyl group), preferably Ra is a C4 to C8 alkyl group, Rb is a C4 to C8 alkyl group, and each Re is a linear or branched C1 to C20 alkyl group.

[0566] 9. The antioxidant composition of paragraph 1, 2 or 3, wherein the hindered phenolic antioxidant is represented by the formula:where Ra is a C4 to C20 alkyl group (such as a C4 to C12 alkyl group, such as a C4 to C8 alkyl group), Rb is a C4 to C20 alkyl group (such as a C4 to C12 alkyl group, such as a C4 to C8 alkyl group, Rc is hydrogen, a thioether group, or a linear or branched C1 to C40 alkyl group (such as such as a C1 to C20 alkyl group), preferably Ra is a C4 to C8 alkyl group, Rb is a C4 to C8 alkyl group, and G is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.

[0568] 10. The antioxidant composition of paragraph 1, 2 or 3, wherein the hindered phenolic antioxidant comprises C7-C9-(branched)-alkyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate or the hindered phenolic antioxidant is represented by the formula:where Ra and Rb are each a t-butyl alkyl group and G is 1.

[0570] 11. The antioxidant composition of claim 1, wherein: 1) the molybedenum compound comprises one or more organo-molybdenum compounds represented by the formula Mo(R″OCS2)4 or Mo(R″SCS2)4, wherein R″ is an organo group selected from the group consisting of alkyl, aryl, aralkyl and alkoxyalkyl or 2) the molybedenum compound comprises one or more trinuclear molybdenum compounds represented by the formula Mo3SkLnQz and mixtures thereof wherein each L is an independently selected ligand having one or more organo groups with a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil, optionally at least 21 carbon atoms, n is from 1 to 4, k is from 4 to 7, Q is selected from the group consisting of neutral electron-donating compounds, and z is from 0 to 5 and includes non-stoichiometric values.

[0571] 12. The antioxidant composition of any of paragraphs 1 to 11, wherein the molybdenum compound is present and comprises one or more dialkyldithiocarbamates of molybdenum.

[0572] 13. The antioxidant composition of any of paragraphs 1 to 12, wherein the molybdenum compound is present and provides from 10 to 250 ppm molybdenum to the antioxidant composition.

[0573] 14. The antioxidant composition of any of paragraphs 1 to 13, further comprising diphenylamine, preferably present at 0.3 mass % or less, or at 0.2 mass % or at less than 0.1 mass %, or is absent, based upon the weight of the antioxidant composition.

[0574] 15. The antioxidant composition of any of paragraphs 1 to 14, wherein the diphenylamine composition comprises hydrocarbyl substituted diphenylamine antioxidant.

[0575] 16. The antioxidant composition of any of paragraphs 1 to 15, wherein the diphenylamine composition comprises di(alkylphenyl)amine, where optionally the alkyl comprises C8 and or C9 linear, branched or cyclic alkyl.

[0576] 17. The antioxidant composition of any of paragraphs 1 to 16, wherein the diphenylamine composition comprises: 1) di(C9-alkyl substituted diphenyl) amine and 2) from 0 to less than 15 m % (such as 1 to 10 mass %) of mono-C9-alkyl substituted diphenyl amine, based upon the weight of any unsubstituted diphenyl amine and the mono- and di-phenyl amines present in the antioxidant composition (as determined by UPLC as described in the Experimental section of US2025 / 0136889A1).

[0577] 18. The antioxidant composition of any of paragraphs 1 to 16, wherein diphenylamine composition comprises: 1) 85 mass % or more (optionally 90 mass % or more) of di(C9-alkyl substituted diphenyl) amines, 2) from 0 to 15 mass % (optionally 0 to less than 10 mass %) of mono-C9-alkyl substituted diphenyl amines tri-C9-alkyl substituted diphenyl amines, and 3) less than 0.1 mass % of unsubstituted diphenylamine, based upon the weight of unsubstituted diphenyl amines and the mono-, di-, and tri-phenyl amines present in the antioxidant composition (as determined by UPLC as described in the Experimental section of US2025 / 0136889A1).

[0578] 19. The antioxidant composition of any of paragraphs 1 to 18, wherein diphenylamine composition is present and comprises: a stable antioxidant composition comprising:

[0579] a) diphenylamine antioxidant comprising: 1) di(C8-alkyl substituted phenyl) amine and 2) less than 15 mass % of mono-C8-alkyl substituted diphenylamine (based upon the weight of any unsubstituted diphenyl amine and the mono-C8-alkyl substituted phenylamines, di-C8-alkyl substituted phenylamines, and any tri-C8-alkyl substituted phenylamines present in the antioxidant composition); and

[0580] b) polar diluent having an aniline point of 25° C. or less, and at least 2 available hydrogen-bond acceptor groups (such as ester, ether or alcohol groups) that are 2, 3, 4, 5, or 6 atoms apart, wherein the composition comprising the polar diluent of b) combined with the diphenylamine antioxidant of a) is clear after 96 hours at 20° C. in a clear glass container without agitation.

[0581] 20. The antioxidant composition of any of paragraphs 1 to 19, wherein diphenylamine composition is present and comprises: a stable antioxidant composition comprising:

[0582] a) diphenylamine antioxidant comprising: 1) di(C8-alkyl substituted phenyl) amine and 2) less than 15 mass % of mono-C8-alkyl substituted diphenylamine (based upon the weight of any unsubstituted diphenyl amine and the mono-C8-alkyl substituted phenylamines, di-C8-alkyl substituted phenylamines, and any tri-C8-alkyl substituted phenylamines present in the antioxidant composition (as determined by UPLC as described in the Experimental section of US2025 / 0136889A1); and

[0583] b) polar diluent having an aniline point of 25° C. or less, and at least 2 available hydrogen-bond acceptor groups (such as ester, ether or alcohol groups) that are 2, 3, 4, 5, or 6 atoms apart, wherein the composition comprising the polar diluent of b) combined with the diphenylamine antioxidant of a) is clear after 96 hours at 20° C. in a clear glass container without agitation; and

[0584] c) salicylate detergent, optionally wherein the antioxidant composition is combined with the detergent at a temperature of 70° C. or more, or 75° C. or more, or 80° C. or more.

[0585] 21. The antioxidant composition of any of paragraphs 1 to 20, wherein diphenylamine composition is present and comprises: a stable antioxidant composition comprising:

[0586] a) diphenylamine antioxidant comprising: aralkyl substituted diphenylamine; and

[0587] b) polar diluent having an aniline point of 0° C. or less, and at least 2 available hydrogen-bond acceptor groups that are 2, 3, 4, 5, or 6 atoms apart, preferably comprising oxygen groups and not comprising sulfur groups, preferably comprising ester and or ether groups,

[0588] wherein the composition comprising the polar diluent of b) combined with the diphenylamine antioxidant of a) is clear after 150 hours at 20° C. in a clear glass container without agitation.

[0589] 22. The antioxidant composition of paragraph 21, wherein:

[0590] 1) the aralkyl group of the aralkyl substituted diphenylamine is represented by the formula (I):where Ph is a substituted or unsubstituted phenyl group, preferably unsubstituted phenyl, R1 is C1 to C20 hydrocarbyl group, R2 is C1 to C20 hydrocarbyl group, and wherein R1 and R2 are preferably independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, docecyl, phenyl, naphthyl, alkyl substituted phenyl, or an isomer thereof, and Rand R2 may be bound to each other; and

[0592] 2) the polar diluent selected from the group consisting of:

[0593] i) di- and tri-esters derived from propylene glycol,

[0594] ii) C8-16 alkyl triesters derived from tri-methylolpropane, and

[0595] iii) phthalates, terephthalates, isophthalates, trimellitates and pyromellitates, preferably the polar diluent(s) are one or more diluent(s) selected from the group consisting of: (di-propylene glycol) dibenzoate, C8-C10 Tri-methylol propane ester, trioctyl trimellitate, and dioctylterephthalate.

[0596] 23. The antioxidant composition of any of paragraphs 1 to 22, wherein diphenylamine composition is present and comprises: a stable antioxidant composition comprising a homogeneous diphenylamine antioxidant fluid comprising di-aralkyl substituted diphenylamine and at least 45 mass % mono-aralkyl substituted diphenylamine, based upon the weight of any unsubstituted diphenyl amine and the mono- and di-substituted diphenylamines (as determined by UPLC as described in the Experimental section of US2025 / 0136889A1), wherein the diphenylamine antioxidant fluid is clear after 90 days at 20° C. in a clear glass container without agitation.

[0597] 24. A concentrate composition comprising:

[0598] i) the antioxidant composition of any of paragraphs 1 to 23;

[0599] ii) from 1 to less than 50 mass % base oil, based upon the weight of stable concentrate;

[0600] iii) optionally one or more detergents, dispersants, friction modifiers; antioxidants, other than the antioxidants of i) above, pour point depressants, anti-foaming agents, viscosity modifiers, corrosion inhibitors, antirust agents, and / or anti-wear agents.

[0601] 25. The concentrate composition of paragraph 24, wherein the antioxidant composition is combined with detergent at a temperature of about 50° C. or more, alternately about 70° C. or more, prior to being combined with one or more optional dispersants, friction modifiers; antioxidants, other than the antioxidants of i), pour point depressants, anti-foaming agents, viscosity modifiers, corrosion inhibitors, antirust agents, anti-wear agents, and / or amide, imide, and / or ester functionalized partially or fully saturated polymer comprising C4-5 olefins.

[0602] 26. The concentrate composition of paragraph 24, wherein the concentrate further comprises: 1) one or more of magnesium salicylate detergent, magnesium sulfonate detergent, calcium salicylate detergent, and calcium sulfonate detergent, 2) optional zinc dialkyldithiophosphate, at least a portion of which is derived from primary alcohol, secondary alcohol, or a combination of primary and secondary alcohol, and 3) optional organic friction modifier, such as glycerol monooleate.

[0603] 27. The concentrate composition of paragraph 24, wherein the concentrate further comprises: 1) one or more of magnesium salicylate detergent and calcium salicylate detergent, 2) optional zinc dialkyldithiophosphate, at least a portion of which is derived from primary alcohol, secondary alcohol, or a combination of primary and secondary alcohol, and 3) optional organic friction modifier, such as glycerol monooleate.

[0604] 28. A lubricating oil composition comprising or resulting from the admixing of:

[0605] (i) at least 50 mass % of one or more base oils, preferably selected from one or more of API Group I, II, III, IV, and V base oils, where optionally Group V base oil is present at 20 mass % or less, based upon the weight of the lubricating oil composition;

[0606] (ii) the antioxidant composition and or concentrate composition of any paragraphs 1 to 27.

[0607] 29. The lubricating oil composition of paragraph 28, wherein the growth of kinematic viscosity of the lubricating oil composition, as determined by the Daimler Oxidation Test at 168 hours, is less than 150%, preferably 100% or less, such as 80% or less, such as 50% or less and or the Nitration-Oxidation, as determined by the Nitration-Oxidation test, is 70 A / cm or less, such as 60 A / cm or less, such as 50 A / cm or less, such as 45 A / cm or less.

[0608] 30. The lubricating oil composition of paragraph 28 comprising a molybdenum containing compound providing from 10 to 200 ppm Mo to the lubricating oil composition.

[0609] 31. A booster pack comprising: 1) the antioxidant composition and or a concentrate composition of any paragraphs 1 to 27; and 2) optionally, 1 to 99 mass % of detergent, based upon the mass of the booster pack.

[0610] 32. A booster pack comprising: 1) the antioxidant composition and or a concentrate composition of any paragraphs 1 to 27; and 2) optionally, 1 to 99 mass % of salicylate detergent, 3) optionally, 1 to 99 mass % of molybdenum compound, based upon the mass of the booster pack.

[0611] 33. The booster pack of paragraph 31, further comprising one, two, three, four, or more of the following components: i) optionally, one or more friction modifiers; ii) optionally, one or more antioxidants, other than diphenylamine compound antioxidants; iii) optionally, one or more pour point depressants; iv) optionally, one or more anti-foaming agents; v) optionally, one or more viscosity modifiers; vi) optionally, one or more base oils; vii) optionally, one or more inhibitors and / or antirust agents; and / or vii) optionally, one or more anti-wear agents.

[0612] 34. A method of lubricating an internal combustion engine during operation of the engine comprising:

[0613] (i) providing to an internal combustion engine the antioxidant composition, the concentrate composition, the lubricating oil composition or the booster pack of any of paragraphs 1 to 33;

[0614] (ii) providing a fuel in the internal combustion engine; and

[0615] (iii) combusting the fuel in the internal combustion engine.

[0616] 35. A method of reducing viscometric growth, as determined by the CEC-L-109-14 Oxidation Test for Engine Oils Operating in the Presence of Biodiesel Fuel over 216 hours, of a lubricating oil composition in an internal combustion engine, the method comprising: supplying a lubricating oil composition to the internal combustion engine, where the lubricating oil composition comprises the antioxidant composition, the concentrate composition, the lubricating oil composition or the booster pack of any of paragraphs 1 to 33, as compared to the same lubricating oil composition except that C10 to C36 linear, branched or cyclic alcohol is absent.

[0617] 36. A method of reducing viscometric growth, as determined by the Daimler Truck Oxidation Test at 168 hours, of a lubricating oil in an internal combustion engine, the method comprising: supplying a lubricating oil composition to the internal combustion engine, where the lubricating oil composition comprises the antioxidant composition, the concentrate composition, the lubricating oil composition or the booster pack of any of paragraphs 1 to 33, as compared to the same lubricating oil composition except that C10 to C36 linear, branched or cyclic alcohol is absent.

[0618] 37. A method of maintaining and or reducing oxidation as determined by the Nitration Oxidation Test at 144 hours of a lubricating oil in an internal combustion engine, the method comprising: supplying a lubricating oil composition to the internal combustion engine, where the lubricating oil composition comprises the antioxidant composition, the concentrate composition, the lubricating oil composition or the booster pack of any of paragraphs 1 to 33, as compared to the same lubricating oil composition except that C10 to C36 linear, branched or cyclic alcohol and molybdenum compounds are absent.

[0619] 38. The methods of paragraph 35, 36, or 37 wherein diphenylamine antioxidant is absent.

[0620] 39. A lubricating oil comprising:

[0621] i) one or more base oils;

[0622] ii) C10 to C36 linear, branched or cyclic alcohol;

[0623] iii) hindered phenolic antioxidant;

[0624] iv) molybdenum containing compound;

[0625] v) optionally, one or more detergents;

[0626] vi) optionally, one or more friction modifiers, other than the molybdenum compound;

[0627] vii) optionally, one or more antioxidants, other than hindered phenolic antioxidants;

[0628] viii) optionally, one or more pour point depressants;

[0629] ix) optionally, one or more anti-foaming agents;

[0630] x) optionally, one or more viscosity modifiers;

[0631] xi) optionally, one or more inhibitors and / or antirust agents; and / or

[0632] xi) optionally, one or more anti-wear agents.

[0633] The following non-limiting examples are provided to illustrate the disclosure.EXPERIMENTAL

[0634] 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

[0635] KV100 is Kinematic viscosity measured at 100° C. according to ASTM D445-19a.

[0636] The Daimler Truck Oxidation (DTOXID) Test is a blown air oxidation test used to test diesel and petroleum engine lubricating oils for their resistance to oxidation and thermal / oxidation mediated viscosity growth. The test can be carried out on the engine oil directly, or the engine oil can be pretreated with 5 mass %1 B100 biodiesel. A 250 g sample of the test sample with iron (III) acetylacetonate (100 ppm Fe) is heated at 156° C. for 168 hours with air bubbling through the heated sample at 10 L / h. Samples are taken at 72, 96, 120, 144, and 168 hours. The samples for the start of test, at the intermediary time points and at end of test were measured for kinematic viscosity at 100° C. (KV100) using ASTM 445 method and oxidation by Fourier Transform infrared spectroscopy analysis using DIN 51453 method.

[0637] Nitration-Oxidation Test was performed according to the procedure described U.S. Pat. No. 12,006,486 at column 33 and line 28-45 and to column 34, line 17-36 except that the test was run at 140° C. for 144 hours with a gas flow of 15 L / hr and the gas blend consisted of 800 ppm NO2 in air. Results are reported in absorbance (A / cm).

[0638] Pressure Differential Scanning Calorimetry (PDSC) oxidative stability test is performed according to CEC L-85-T-99 and is reported as oxidation induction time (OIT) in minutes.

[0639] CEC-L109 Oxidation (“L109”) at 216 hr (reported in units of absorbance per centimeter (A / cm) for oxidation and percentage (%) for percent viscosity increase “PVIS”) was determined using the CEC-L-109-14 Oxidation Test for Engine Oils Operating in the Presence of Biodiesel Fuel over 216 hours.

[0640] Content of unsubstituted diphenylamines, mono-substituted phenylamines, di-substituted phenylamines, and any tri-substituted phenylamines (such as mono-alkyl substituted phenylamines, di-alkyl substituted phenylamines, and any tri-alkyl substituted phenylamines) is determined by Ultra-Performance Liquid Chromatography (UPLC) as described in US2025 / 0136889 A1 (Ser. No. 18 / 924,430, filed Oct. 23, 2024.ComponentsComponentDescriptionF-H-PIF-H-PI is functionalized hydrogenated isoprene block copolymer producedaccording U.S. Ser. No. 18 / 480,571, filed Oct. 4, 2023. Mw (GPC-PS), Mn (GPC-PS), Functionality Distribution (Fd) for F-H-PI are determined according to theprocedures disclosed in U.S. Ser. No. 18 / 480,571, filed Oct. 4, 2023.Borated-PIBSA-Borated PIBSA-PAM in oil derived from PIB having an Mn less than 1000PAMg / molPIBSA-PAM 1PIBSA-PAM dispersant derived from PIB having an Mn less than 1000 g / molPIBSA-PAM 2PIBSA-PAM dispersant derived from PIB having an Mn of 2000 g / mol or morePIBSA-EsterPIBSA ester prepared in a manner similar to methods according toUS2009 / 0203559, such as Ex. 1Mg SalicylateMagnesium Salicylate Detergent in oilCa SalicylateCalcium Salicylate Detergent (200 to 400 TBN) in oilCa sulfonateCalcium sulfonate detergent in oilMg sulfonateMagnesium sulfonate detergent in oilZDDPZDDP (derived from primary and or secondary alcohols) in oilHindered phenol 1C7-C9-(branched)-alkyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propanoate)available as IRGANOX ™ L135C9-DPAdi(nonylphenyl)amine. available as Naugalube ™ 438.MoDTCmolybdenum dithiocarbamate trimerFVA copol -1C12-18 dialkylfumarate / vinyl acetate copolymer (~43% oil).FVA copol -2C8-18 dialkyl fumarate / vinyl acetate copolymer in oilPIBSAPolyisobutylene succinic anhydride derived from PIB having an Mn less than1000 g / molPIBpolyisobutyleneAnti-foamantPDMS silicone anti-foamant25 SSI high ethyleneHigh ethylene content ethylene-propylene olefin copolymer in oil, having acontent OCPshear stability index of 25.H-Star SBChydrogenated styrene-diene star block copolymer viscosity modifier (~94 m %oil)Gp II base oilGroup II base oildiluentGroup I base oilLOClubricating oil composition.Example 1

[0641] Three base blends were prepared then further modified to form three additional blends for each base blend having 2.5% of dodecanol, molybdenum containing compound, and one or more antioxidants (C9-DPA and or Hindered phenol 1). Each blend was then combined with C12-18 dialkylfumarate / vinyl acetate copolymer (~43% oil), 25 SSI high ethylene content OCP, and Group II base oil. The blends are shown in Table 1.TABLE 1ExampleConstituentABCDEFF-H-PI1.1561.1561.1561.1561.1561.156MoDTC000.1200.1200.1200.120C9-DPA00000.5000.500Hindered phenol 12.5002.5002.5002.5002.5002.500Dodecanol02.5000.0002.50002.500Group III Basestock81.77581.77581.66581.66581.15581.1554-7 cStDaimler Oxidation test(oxidation A / cm)144 hours73.379.660.872.345.855.7168 hours85.591.371.984.254.564.2Daimler Oxidation test(KV100 % Change avg)144 hours78.646.167.948.148.936.7168 hours254.377.6140.079.479.051.2Nitration Oxidation Test1 (A / cm)120 hours53.66520.126.221.125.6144 hours8592.930.940.533.336.4DSC induction time (min)74.984.540.342.65984.1*All blends have the same amount of PIBSA-PAM 1, borated PIBSA-PAM dispersant, PIBSA-PAM 2, Ca and Mg sulfonate, ZDDP, PIBSA, antifoamant, diluent, FVA-2, 25 SSI high ethylene content OCP, Gp II base oil.

[0642] The results demonstrated a significant improvement in KV100% for blends containing dodecanol compared to the ones without, showcasing the effectiveness of alcohols in providing viscosity control in systems without diphenylamine. Moreover, even in the presence of C9-DPA, the benefit of alcohol was evident. This improvement in performance also translated to PDSC results once more, where addition of dodecanol increased the induction time observed compared to the ones without.Example 2

[0643] A base blend was prepared for each of Tables 4, 5, 6, and 7, then further modified to form blends having varying amounts of dodecanol, molybdenum compound, antioxidants (C9-DPA and or Hindered phenol 1), etc. Each modified base blend was then combined with FVA copol-1, and H-Star SBC with the balance being made up of ~4 to ~6 cSt Group III base oil to form the lubricating oil compositions, LOC's, (shown in Tables 4, 5, 6, and 7).

[0644] Overall in all of the L-109 tests below C9-DPA outperforms hindered phenol in each of the formulations 1 to 4 to a greater or lesser extent. Reducing viscosity growth, in particular, is challenging in formulations with hindered phenol as the only primary antioxidant. There is a need for components that improve viscosity control in L-109 in formulations that are diphenylamine free.

[0645] Lubricating Oil Compositions LOC 1A to LOC 1 G exhibit very limited viscosity increase over the course of the L-109 test. Even in the absence of primary antioxidants, Kv100% increase is below 50%, which is the most stringent limit set by automotive manufacturers. In this case an additive to improve viscosity control is unnecessary.TABLE 4Blends 1A-1G Lubricating Oil Compositionsmass %LOC 1ALOC 1BLOC 1CLOC 1DLOC 1ELOC IFLOC 1GHindered phenol 11.01.01.02.03.0—docecanol1.02.0—————C9-DPA——————0.79FVA Copol0.30.30.30.30.30.30.3H-Star SBC16.516.516.516.516.516.516.5Group III base69.768.768.769.768.771.771.127oil 4-6 cStTotal100100100100100100100L109 Oxidation83.292.670.653.548.89229.3(A / cm)L109 PVIS (%)2311198.810.639.314.5*All blends have the same amount of borated PIBSA-PAM, PIBSA-PAM 2, Ca salicylate, ZDDP, PIBSA, antifoamant and diluent.

[0646] In the absence of primary antioxidant (LOC 2F) oxidation and viscosity control, in particular, are substantially higher than for LOC 1F. Addition of hindered phenol improved both oxidation control and consequently viscosity control (c.f. LOC 2F with LOC 2C, 2D, 2E). Significantly, dodecanol also exhibited concentration dependent viscosity control with hindered phenol (c.f. LOC 2A and 2B with LOC 2C).TABLE 5Blends 2A-2G Lubricating Oil Compositionsmass %LOC 2ALOC 2BLOC 2CLOC 2DLOC 2ELOC 2FLOC 2GHindered phenol 11.01.01.02.03.0—docecanol1.02.0—————C9-DPA——————0.5FVA Copol0.10.10.10.10.10.10.1H-SBC5.65.65.65.65.65.65.6Group III base79.578.580.579.578.581.581.1oil ~4 cStTotal100100100100100100100Mo ppm———————C9-DPA——————0.64L109 Oxidation11111092.56250.811345.6(A / cm)L109 PVIS (%)65.542.278.231.227.413625.7*All blends have the same amount of borated PIBSA-PAM, PIBSA-PAM 2, PIBSA-Ester, Ca salicylate, ZDDP, PIBSA, antifoamant, and diluent.

[0647] In Table 6 below, viscosity control is improved by 83 and 92% by addition of 1 and 2 mass % of dodecanol (LOC 3A and 3B) to LOC 3C respectively. However, at the higher dodecanol amount oxidation is marginally higher than LOC 3C at the end of the test. Even at 3 mass % hindered phenol (LOC 3E) viscosity control does not match that of LOC 3A with 1 mass % hindered phenol and 1 mass % dodecanol.TABLE 6Blends 3A-3G Lubricating Oil Compositionsmass %LOC 3ALOC 3BLOC 3CLOC 3DLOC 3ELOC 3FLOC 3GHindered1.01.01.02.03.0—phenol 1docecanol1.02.0————C9-DPA——————1.0FVA Copol0.20.20.20.20.20.20.2H-SBC7.67.67.67.67.67.67.6Gp III base76.575.577.576.575.578.577.5oil 4-6 cStTotal100100100100100100100Mo ppm75757575757575C9-DPA——————0.14L109107.8125.2115.591.679.9125.739.5Oxidation(A / cm)L109 PVIS82.273.5165101.287.827434.5(%)*All blends have the same amount of PIBSA-PAM 1, borated PIBSA-PAM, PIBSA-PAM 2, PIBSA-Ester, Mg and Ca salicylate, ZDDP, PIBSA, antifoamant, and diluent.

[0648] In Table 7 below, viscosity control was improved by 46% and 52% by addition of 1 and 2 mass % of dodecanol (LOC 4A and 4B) to LOC 4D respectively. At 2 mass % hindered phenol (LOC 4D) oxidation control was similar to LOC 4A.TABLE 7Blends 4A-4G Lubricating Oil Compositionsmass %LOC 4ALOC 4BLOC 4CLOC 4DLOC 4ELOC 4FLOC 4GHindered phenol 12.02.01.02.03.0—docecanol1.02.0—————C9-DPA——————1.25FVA Copol0.20.20.20.20.20.20.2H-Star SBC8.18.18.18.18.18.18.1Gp III+ base oil,76.4575.4578.577.4576.4579.4678.2~4 cStTotal100100100100100100100Mo ppm83838383838383C9-DPA0000000.153L109 Oxidation90.5101109.187.265.1119.330.2(A / cm)L109 PVIS (%)10599.325615199.340848.2*All blends have the same amount of PIBSA-PAM 1, borated PIBSA-PAM, PIBSA-PAM 2, PIBSA-Ester, Mg and Ca salicylate, ZDDP, PIBSA, antifoamant and diluent.

[0649] 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

1. An antioxidant composition, comprising:1) C10 to C36 linear, branched, or cyclic alcohol, or a combination thereof,2) hindered phenolic antioxidant,3) optionally, molybdenum containing compound, and4) optionally, diphenylamine composition.

2. The antioxidant composition of claim 1, further 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, and ii) a Functionality Distribution (Fd) value of 3.5 or less.

3. The antioxidant composition of claim 1, further comprising dispersant 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, ii) a Functionality Distribution (Fd) value of 3.5 or less, and iii) an Mn of 10,000 g / mol or more (GPC-PS) of the polymer prior to functionalization, and optionally, 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).

4. The antioxidant composition of claim 1, wherein the C10 to C36 linear, branched or cyclic alcohol comprises branched alcohol, linear alcohol, or a combination thereof.

5. The antioxidant composition of claim 1, wherein the C10 to C36 linear, branched or cyclic alcohol comprises one or more C10 to C24 alcohols, optionally C12 linear, branched or cyclic alcohol.

6. The antioxidant composition of claim 1, wherein the C10 to C36 linear, branched or cyclic alcohol comprises of one or more C12 to C18 linear alcohols.

7. The antioxidant composition of claim 1, wherein the C10 to C36 linear, branched or cyclic alcohol comprises C12 linear, branched or cyclic alcohol.

8. The antioxidant composition of claim 1, wherein the hindered phenolic antioxidant is represented by the formula:where Ra is a C4 to C20 alkyl group (preferably a C4 to C12 alkyl group, preferably a C4 to C8 alkyl group), Rb is a C4 to C20 alkyl group (optionally a C4 to C12 alkyl group, optionally, a C4 to C8 alkyl group, Rc is hydrogen, a thioether group, or a linear or branched C1 to C40 alkyl group (preferably a C1 to C20 alkyl group), preferably Ra is a C4 to C8 alkyl group, Rb is a C4 to C8 alkyl group, and each Re is a linear or branched C1 to C20 alkyl group.

9. The antioxidant composition of claim 1, wherein the hindered phenolic antioxidant is represented by the formula:where Ra is a C4 to C20 alkyl group (preferably a C4 to C12 alkyl group, preferably a C4 to C8 alkyl group), Rb is a C4 to C20 alkyl group (preferably a C4 to C12 alkyl group, preferably a C4 to C8 alkyl group, Rc is hydrogen, a thioether group, or a linear or branched C1 to C40 alkyl group (preferably a C1 to C20 alkyl group), preferably Ra is a C4 to C8 alkyl group, Rb is a C4 to C8 alkyl group, and G is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.

10. The antioxidant composition of claim 1, wherein the hindered phenolic antioxidant comprises C7-C9-(branched)-alkyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate or the hindered phenolic antioxidant is represented by the formula:where Ra and Rb are each a t-butyl alkyl group and G is 1.

11. The antioxidant composition of claim 1, wherein: 1) the molybedenum compound comprises one or more organo-molybdenum compounds represented by the formula Mo(R″OCS2)4 or Mo(R″SCS2)4, wherein R″ is an organo group selected from the group consisting of alkyl, aryl, aralkyl and alkoxyalkyl or 2) the molybedenum compound comprises one or more trinuclear molybdenum compounds represented by the formula Mo3SkLnQz and mixtures thereof wherein each L is an independently selected ligand having one or more organo groups with a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil, optionally at least 21 carbon atoms, n is from 1 to 4, k is from 4 to 7, Q is selected from the group consisting of neutral electron-donating compounds, and z is from 0 to 5 and includes non-stoichiometric values.

12. The antioxidant composition of claim 1, wherein the molybdenum compound comprises one or more dialkyldithiocarbamates of molybdenum.

13. The antioxidant composition of claim 1, wherein the molybdenum compound provides from 10 to 250 ppm molybdenum to the antioxidant composition.

14. The antioxidant composition of claim 1, further comprising diphenylamine antioxidant, optionally present at 0.3 mass % or less, based upon the weight of the antioxidant composition.

15. The antioxidant composition of claim 1, wherein the diphenylamine composition comprises hydrocarbyl substituted diphenylamine antioxidant.

16. The antioxidant composition of claim 1, wherein the diphenylamine composition comprises di(alkylphenyl)amine, where optionally the alkyl comprises C8 and or C9 linear, branched or cyclic alkyl.

17. The antioxidant composition of claim 1, wherein the diphenylamine composition comprises: 1) di(C9-alkyl substituted diphenyl) amine and 2) from 0 to less than 15 mass % of mono-C9-alkyl substituted diphenyl amine, based upon the weight of any unsubstituted diphenyl amines, mono-phenyl amines, and di-phenyl amines present in the antioxidant composition.

18. The antioxidant composition of claim 1, wherein diphenylamine composition comprises: 1) 85 mass % or more of di(C9-alkyl substituted diphenyl) amines; 2) from 0 to less than 15 mass % of mono-C9-alkyl substituted diphenyl amine and tri-C9-alkyl substituted diphenyl amine; and 3) less than 0.1 mass % of unsubstituted diphenylamine, based upon the weight of the unsubstituted diphenyl amines, mono-, di-, and tri-phenyl amines present in the antioxidant composition.

19. The antioxidant composition of claim 1, wherein diphenylamine composition comprises: a stable antioxidant composition comprising:a) diphenylamine antioxidant comprising: 1) di(C8-alkyl substituted phenyl) amine, 2) less than 15 mass % of mono-C8-alkyl substituted diphenylamine and tri-C8-alkyl substituted phenylamines, 3) less than 0.1 mass % unsubstituted diphenylamines, (based upon the weight of unsubstituted diphenyl amines, mono-C8-alkyl substituted phenylamines, di-C8-alkyl substituted phenylamines, and any tri-C8-alkyl substituted phenylamines present in the antioxidant composition); andb) polar diluent having an aniline point of 25° C. or less, and at least 2 available hydrogen-bond acceptor groups (preferably ester, ether or alcohol groups) that are 2, 3, 4, 5, or 6 atoms apart,wherein the composition comprising the polar diluent of b) combined with the diphenylamine antioxidant of a) is clear after 96 hours at 20° C. in a clear glass container without agitation.

20. The antioxidant composition of claim 1, wherein diphenylamine composition comprises: a stable antioxidant composition comprising:a) diphenylamine antioxidant comprising: 1) di(C8-alkyl substituted phenyl) amine and 2) less than 15 mass % of mono-C8-alkyl substituted diphenylamine (based upon the weight of mono-C8-alkyl substituted phenylamines, di-C8-alkyl substituted phenylamines, and any tri-C8-alkyl substituted phenylamines present in the antioxidant composition); andb) polar diluent having an aniline point of 25° C. or less, and at least 2 available hydrogen-bond acceptor groups (preferably ester, ether or alcohol groups) that are 2, 3, 4, 5, or 6 atoms apart,wherein the composition comprising the polar diluent of b) combined with the diphenylamine antioxidant of a) is clear after 96 hours at 20° C. in a clear glass container without agitation; andc) salicylate detergent, optionally wherein the antioxidant composition is combined with the detergent at a temperature of 70° C. or more, or 75° C. or more, or 80° C. or more.

21. The antioxidant composition of claim 1, wherein diphenylamine composition comprises: a stable antioxidant composition comprising:a) diphenylamine antioxidant comprising: aralkyl substituted diphenylamine; andb) polar diluent having an aniline point of 0° C. or less, and at least 2 available hydrogen-bond acceptor groups that are 2, 3, 4, 5, or 6 atoms apart, preferably comprising oxygen groups and not comprising sulfur groups, preferably comprising ester and or ether groups,wherein the composition comprising the polar diluent of b) combined with the diphenylamine antioxidant of a) is clear after 150 hours at 20° C. in a clear glass container without agitation.

22. The antioxidant composition of claim 21, wherein:1) the aralkyl group of the aralkyl substituted diphenylamine is represented by the formula (I):where Ph is a substituted or unsubstituted phenyl group, preferably unsubstituted phenyl, R1 is C1 to C20 hydrocarbyl group, R2 is C1 to C20 hydrocarbyl group, and wherein R1 and R2 are preferably independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, docecyl, phenyl, naphthyl, alkyl substituted phenyl, or an isomer thereof, and Rand R2 may be bound to each other; and2) the polar diluent selected from the group consisting of:i) di- and tri-esters derived from propylene glycol,ii) C8-16 alkyl triesters derived from tri-methylolpropane, andiii) phthalates, terephthalates, isophthalates, trimellitates and pyromellitates,preferably the polar diluent(s) are one or more diluent(s) selected from the group consisting of: (di-propylene glycol) dibenzoate, C8-C10 tri-methylol propane ester, trioctyl trimellitate, and dioctylterephthalate.

23. The antioxidant composition of claim 1, wherein diphenylamine composition comprises: a stable antioxidant composition comprising a homogeneous diphenylamine antioxidant fluid comprising di-aralkyl substituted diphenylamine and at least 45 mass % mono-aralkyl substituted diphenylamine, based upon the weight of unsubstituted diphenyl amines, mono-substituted diphenyl amines, and di-substituted diphenylamines, wherein the diphenylamine antioxidant fluid is clear after 90 days at 20° C. in a clear glass container without agitation.

24. A concentrate composition comprising:i) the antioxidant composition of claim 1;ii) from 1 to less than 50 mass % of base oil, based upon the weight of stable concentrate;iii) optionally one or more detergents, dispersants, friction modifiers; antioxidants, other than the antioxidants of i) above, pour point depressants, anti-foaming agents, viscosity modifiers, corrosion inhibitors, antirust agents, and / or anti-wear agents.

25. The concentrate composition of claim 24, wherein the antioxidant composition is combined with detergent at a temperature of about 50° C. or more, alternately about 70° C. or more, prior to being combined with one or more optional dispersants, friction modifiers; antioxidants, other than the antioxidants of i), pour point depressants, anti-foaming agents, viscosity modifiers, corrosion inhibitors, antirust agents, anti-wear agents, and / or amide, imide, and / or ester functionalized partially or fully saturated polymer comprising C4-5 olefins.

26. The concentrate composition of claim 24, wherein the concentrate further comprises:1) one or more of magnesium salicylate detergent, magnesium sulfonate detergent, calcium salicylate detergent, and calcium sulfonate detergent,2) optional zinc dialkyldithiophosphate, at least a portion of which is derived from primary alcohol, secondary alcohol, or a combination of primary and secondary alcohol, and3) optional organic friction modifier, preferably glycerol monooleate.

27. The concentrate composition of claim 24, wherein the concentrate further comprises:1) one or more of magnesium salicylate detergent and calcium salicylate detergent,2) optional zinc dialkyldithiophosphate, at least a portion of which is derived from primary alcohol, secondary alcohol, or a combination of primary and secondary alcohol, and3) optional organic friction modifier, preferably glycerol monooleate.

28. A lubricating oil composition comprising or resulting from the admixing of:(i) at least 50 mass % of one or more base oils, preferably selected from one or more of API Group I, II, III, IV, and V base oils, where optionally Group V base oil is present at 20 mass % or less, based upon the weight of the lubricating oil composition; and(ii) the antioxidant composition of claim 1.

29. The lubricating oil composition of claim 28, wherein the growth of kinematic viscosity of the lubricating oil composition, as determined by the Daimler Oxidation Test at 168 hours, is less than 150%, preferably 100% or less, preferably 80% or less, preferably 50% or less and or the Oxidation, as determined by the Nitration-Oxidation test, is 70 A / cm or less, preferably 60 A / cm or less, preferably 50 A / cm or less, preferably 45 A / cm or less.

30. The lubricating oil composition of claim 28 comprising a molybdenum containing compound providing from 10 to 200 ppm Mo to the lubricating oil composition.

31. A booster pack comprising:1) the antioxidant composition of claim 1; and2) optionally, 1 to 99 mass % of detergent, based upon the mass of the booster pack.

32. A booster pack comprising:1) the antioxidant composition of claim 1; and2) optionally, 1 to 99 mass % of salicylate detergent,3) optionally, 1 to 99 mass % of molybdenum compound, based upon the mass of the booster pack.

33. The booster pack of claim 31, further comprising one, two, three, four, or more of the following components.i) optionally, one or more friction modifiers;ii) optionally, one or more antioxidants, other than diphenylamine compound antioxidants;iii) optionally, one or more pour point depressants;iv) optionally, one or more anti-foaming agents;v) optionally, one or more viscosity modifiers;vi) optionally, one or more base oils;vii) optionally, one or more inhibitors and / or antirust agents; and / orvii) optionally, one or more anti-wear agents.

34. A method of lubricating an internal combustion engine during operation of the engine comprising:(i) providing to the internal combustion engine the lubricating oil composition of claim 28;(ii) providing a fuel in the internal combustion engine; and(iii) combusting the fuel in the internal combustion engine.

35. A method of reducing viscometric growth, as determined by the CEC-L-109-14 Oxidation Test for Engine Oils Operating in the Presence of Biodiesel Fuel over 216 hours, of a lubricating oil composition in an internal combustion engine, the method comprising: supplying a lubricating oil composition to the internal combustion engine, where the lubricating oil composition comprises the antioxidant composition of claim 1, as compared to the same lubricating oil composition except that C10 to C36 linear, branched or cyclic alcohol is absent.

36. A method of reducing viscometric growth, as determined by the Daimler Truck Oxidation Test at 168 hours, of a lubricating oil in an internal combustion engine, the method comprising: supplying a lubricating oil composition to the internal combustion engine, where the lubricating oil composition comprises the antioxidant composition, the concentrate composition, the lubricating oil composition of claim 1, as compared to the same lubricating oil composition except that C10 to C36 linear, branched or cyclic alcohol is absent.

37. A method of maintaining and or reducing oxidation as determined by the Nitration Oxidation Test at 144 hours of a lubricating oil in an internal combustion engine, the method comprising:supplying a lubricating oil composition to the internal combustion engine, where the lubricating oil composition comprises the lubricating oil composition of claim 1, as compared to the same lubricating oil composition except that C10 to C36 linear, branched or cyclic alcohol and molybdenum compounds are absent.

38. The method of claim 35 wherein diphenylamine antioxidant is absent.

39. The method of claim 36 wherein diphenylamine antioxidant is absent.

40. The method of claim 37 wherein diphenylamine antioxidant is absent.

41. A lubricating oil comprising:i) one or more base oils;ii) C10 to C36 linear, branched or cyclic alcohol;iii) hindered phenolic antioxidant;iv) molybdenum containing compound;v) optionally, one or more detergents;vi) optionally, one or more friction modifiers, other than the molybdenum compound;vii) optionally, one or more antioxidants, other than hindered phenolic antioxidants;viii) optionally, one or more pour point depressants;ix) optionally, one or more anti-foaming agents;x) optionally, one or more viscosity modifiers;xi) optionally, one or more inhibitors and / or antirust agents; and / orxi) optionally, one or more anti-wear agents.

Images