Lubricating oil compositions and use thereof for improving journal bearing wear in internal combustion engine

Abstract

To provide lubricating oil compositions for reducing wear of a journal bearing in an internal combustion engine.SOLUTION: A lubricant composition comprises or is obtained by mixing: (i) a base oil; (ii) an overbased calcium-based detergent at a treatment level capable of supplying 500 to 1300 mass ppm of calcium to the composition; and (iii) an overbased magnesium-based detergent at a treatment level capable of supplying 500 to 1300 mass ppm of magnesium to the composition, wherein the total combined mass of calcium and magnesium in the composition is in the range of 1000 ppm to 1800 ppm. The total sulfated ash of the composition is 1.0 mass% or less, the high-temperature high-shear viscosity at 150°C is 1.8 mPa*s or more and 2.9 mPa*s or less, and the total phosphorus level is 0.080 mass% or less. A method for reducing journal bearing wear in an internal combustion engine and a method for producing the lubricant composition are also provided.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and the benefit of U.S. Patent Application No. 63 / 588,238, filed October 5, 2023.

[0002] This disclosure relates to lubricating oil compositions, and more particularly, to lubricating oil compositions with improved journal bearing wear for use in internal combustion engines. [Background technology]

[0003] There is a continuing trend towards the adoption of increasingly lower viscosity Society of Automotive Engineers (SAE) grades in both factory fill oils and service fill oils in passenger vehicle (PVL) and commercial vehicle (CVL) applications. This is driven by the increasing desire for improved fuel economy (FE) due to regional emission requirements. Associated with this is the established use of industry-wide start / stop technology in both ICE and hybrid applications. However, the durability of the main journal bearings and connecting rod (big-end) journal bearings in internal combustion engines is often viewed as a fundamental issue when introducing these low viscosity fluids (<0W-20) because the journal bearings in these systems are non-ferrous materials (e.g., aluminum bimetallic, SnCu, and polymer coatings) that are less resilient to wear compared to ferrous or steel materials and react differently to traditional lubricant additive ingredients. Historically, bearing systems have been considered particularly susceptible to wear due to the nature of the contacts, the use of low viscosity fluids, and the introduction of start / stop technology. Traditionally, journal bearings, being hydrodynamically lubricated systems, have relied on lubricant viscosity to minimize contact between surfaces and control wear. In a low engine oil viscosity environment, increased start / stop events expose the system to more boundary lubrication, increasing stress on the contacts and resulting in greater levels of wear for journal bearings in internal combustion engines. Thus, there is a need for new engine oils, particularly for gasoline, diesel, natural gas, and hydrogen engines, with low viscosity grades that meet these requirements in terms of improved engine wear protection while maintaining desirable fuel economy benefits and reduced engine gas emissions. These needs are particularly pronounced with respect to passenger vehicle engines and the associated oils for lubricating the engines. More particularly, there is a need for low viscosity PVL engine oils that provide improved journal bearing wear resistance for internal combustion engines as well as improved fuel economy. The present invention relates to lubricating oil compositions having improved engine wear characteristics. More specifically, the present invention relates to crankcase lubricating oil compositions, such as those referred to as crankcase lubricants, for use in compression-ignited or spark-ignited internal combustion engines, as well as hydrogen and natural gas engines; and to the use of certain additives in such lubricating oil compositions to reduce journal bearing wear in internal combustion engines. It has now surprisingly been found by the inventors that certain combinations of base oils and mixtures of overbased calcium and magnesium detergents can be used in lubricant compositions for internal combustion engines to provide improved engine wear protection in the TE-92 Start / Stop test method, compared to lubricant compositions of comparable viscosity that do not contain the mixture of overbased calcium and magnesium detergents. Summary of the Invention

[0004] The present invention relates to a lubricating oil composition comprising or incorporating an oil of lubricating viscosity comprising a Group I base oil, a Group II base oil, a Group III base oil, a Group IV base oil, or a combination thereof, in an amount greater than 50 mass % of the composition; an overbased calcium-based detergent having a total base number (KOH / g) of 9 to 500 and a treat level capable of delivering 500 to 1300 mass ppm of calcium to the composition; and an overbased magnesium-based detergent having a total base number (KOH / g) of 9 to 500 and a treat level capable of delivering 500 to 1300 mass ppm of magnesium to the composition, wherein the combined total mass of calcium and magnesium in the composition is in the range of 1000 ppm to 1800 ppm; the lubricating oil composition has a total sulfated ash content of 1.0 mass % or less, and the lubricating oil composition has a total sulfated ash content of 1.0 mass % or less, and the total sulfated ash content meets ASTM and wherein the lubricating oil composition has a high temperature high shear viscosity (HTHS) at 150°C of between 1.8 mPa·s and 2.9 mPa·s, and a total phosphorus level of 0.080 wt.% or less, as measured in accordance with D4683-20; and wherein the lubricating oil composition provides a 5% to 60% reduction in journal bearing wear, as measured by maximum average wear in microns using the TE-92 Start / Stop Test Method, compared to a lubricating oil composition having an equivalent HTHS but not containing a mixture of an overbased calcium-based detergent and an overbased magnesium-based detergent at a combined loading of calcium and magnesium in the range of 1000 ppm to 1800 ppm in said composition.

[0005] According to another aspect of the present invention, there is provided a method for reducing journal bearing wear in an internal combustion engine, the method comprising the steps of supplying to an internal combustion engine a lubricating oil composition comprising, or incorporating, the following: an oil of lubricating viscosity comprising a Group I base oil, a Group II base oil, a Group III base oil, a Group IV base oil, or a combination thereof, in an amount greater than 50% by weight of the composition; an overbased calcium detergent having a total base number (KOH / g) of 9 to 500, inclusive, and a treat level to deliver 500 to 1300 ppm by weight of calcium to the composition; and an overbased magnesium detergent having a total base number (KOH / g) of 9 to 500, inclusive, and a treat level to deliver 500 to 1300 ppm by weight of magnesium to the composition, wherein the combined total weight of calcium and magnesium in the composition is in the range of 1000 ppm to 1800 ppm; and the lubricating oil composition has a total sulfated ash content of 1.0% by weight or less, and is in accordance with ASTM and wherein the lubricating oil composition has a high temperature high shear viscosity (HTHS) at 150°C, measured in accordance with D4683-20, of greater than or equal to 1.8 mPa·s and less than or equal to 2.9 mPa·s, a total phosphorus level of less than or equal to 0.080 wt%, and wherein the lubricating oil composition provides a 5% to 60% reduction in journal bearing wear, as measured by maximum average wear in microns using the TE-92 Start / Stop Test Method, compared to a lubricating oil composition having an equivalent HTHS but that does not contain a mixture of overbased calcium and overbased magnesium detergents at a combined loading of calcium and magnesium in said composition in the range of 1000 ppm to 1800 ppm.

[0006] According to yet a further aspect of the present invention, there is provided a method for producing a lubricating oil composition, the method comprising the steps of combining or blending: (i) an oil of lubricating viscosity comprising a Group I base oil, a Group II base oil, a Group III base oil, a Group IV base oil, or a combination thereof, in an amount greater than 50 mass % of the composition; (ii) an overbased calcium detergent having a total base number (KOH / g) of 9 to 500, inclusive, and a treat level capable of delivering 500 to 1300 ppm by mass of calcium to the composition; and (iii) an overbased magnesium detergent having a total base number (KOH / g) of 9 to 500, inclusive, and a treat level capable of delivering 500 to 1300 ppm by mass of magnesium to the composition; wherein the combined total mass of calcium and magnesium in the composition is in the range of 1000 ppm to 1800 ppm; and wherein the lubricating oil composition has a total sulfated ash content of 1.0 mass % or less, and is in accordance with ASTM and wherein the lubricating oil composition has a high temperature high shear viscosity (HTHS) at 150°C, measured in accordance with D4683-20, of greater than or equal to 1.8 mPa·s and less than or equal to 2.9 mPa·s, a total phosphorus level of less than or equal to 0.080 wt%, and wherein the lubricating oil composition provides a 5% to 60% reduction in journal bearing wear, as measured by maximum average wear in microns using the TE-92 Start / Stop Test Method, compared to a lubricating oil composition having an equivalent HTHS but that does not contain a mixture of overbased calcium and overbased magnesium detergents at a combined loading of calcium and magnesium in said composition in the range of 1000 ppm to 1800 ppm. [Brief description of the drawings]

[0007] [Figure 1] FIG. 1 is a cutaway perspective view of a typical internal combustion engine showing the locations of various bearings within the engine that require lubrication. [Diagram 2] 1A-1D are cross-sectional schematics of journal bearing shell materials for solid, bimetal, and trimaterial / metal bearings. [Diagram 3]1 is a bar graph of journal bearing wear as measured by maximum average wear in microns using the TE-92 Start / Stop test method for inventive and comparative lubricating oil compositions. [Figure 4] 2 is another bar graph of journal bearing wear as measured by maximum average wear in microns using the TE-92 Start / Stop test method for inventive and comparative lubricating oil compositions. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] definition For purposes of this specification and any claims to the invention, the following words and phrases shall have the following meanings if and when used. For purposes herein, the new numbering scheme of the Periodic Table of the Elements as described in CHEMICAL AND ENGINEERING NEWS, 1985, 63(5), 27 is used, i.e., the alkali metals are the Group 1 metals (e.g., Li, Na, K, etc.) and the alkaline earth metals are the Group 2 metals (e.g., Mg, Ca, Ba, etc.).

[0009] The term "comprising" or any synonym thereof denotes the presence of a stated feature, step, or integer or component, but does not exclude the presence or addition of one or more other features, steps, integers, components, or groups thereof. The expressions "consisting of," "consisting essentially of," or cognate terms may be included within "comprising" or its cognate terms, with "consisting essentially of" permitting the inclusion of substances that do not materially affect the characteristics of the composition to which it is applied. The term "LOC" refers to a lubricating oil composition. The term "major amount" means, based on the weight of the composition, more than 50% by weight of the composition, such as more than 60% by weight of the composition, such as more than 70% by weight of the composition, such as from 80 to 99.009% by weight of the composition, such as from 80 to 99.9% by weight of the composition, 80 to 99.009% by weight. The term "minor amount" means, based on the weight of the composition, 50% by weight or less of the composition; such as 40% by weight or less of the composition; such as 30% by weight or less of the composition, for example 20-0.001% by weight of the composition, for example 20-0.1% by weight. The term "% by weight" means the weight percent of a component based on the weight of the composition measured in grams, unless otherwise specified, and is interchangeable with weight percent ("% by weight," "wt%," or "% w / w"). The term "active ingredient" (also referred to as "ai" or "AI") refers to an additive material that is not a diluent or solvent. Unless otherwise specified, amounts herein are listed as active ingredients.

[0010] The terms "oil-soluble" and "oil-dispersible" or synonyms thereof as used herein do not necessarily indicate that a compound or additive is soluble, dissolvable, miscible, or capable of being suspended in oil in all proportions. However, these terms mean, for example, that the compound or additive is soluble or stably dispersible in oil to a degree sufficient to exert its intended effect in the environment in which the oil is employed. Furthermore, it is possible to incorporate higher levels of a particular additive, if desired, by incorporating additional additives. The terms "group" and "radical" are used interchangeably herein. The term "hydrocarbon" refers to a compound of hydrogen and carbon atoms. "Heteroatom" refers to an atom other than carbon or hydrogen. When referring to "hydrocarbons", particularly "refined hydrocarbons", the hydrocarbon may contain one or more heteroatoms or heteroatom-containing groups (e.g., halo, especially chloro and fluoro, amino, alkoxyl, mercapto, alkylmercapto, nitro, nitroso, sulfoxy, etc.) in small amounts (e.g., amounts in which the heteroatom(s) do not substantially alter the hydrocarbon character of the hydrocarbon compound). The term "hydrocarbyl" refers to a radical that contains hydrogen and carbon atoms. Preferably, the group consists essentially of hydrogen and carbon atoms, more preferably only of hydrogen and carbon atoms, unless otherwise specified. Preferably, the hydrocarbyl group comprises an aliphatic hydrocarbyl group. The term "hydrocarbyl" includes "alkyl", "alkenyl", "alkynyl", and "aryl" as defined herein. The hydrocarbyl group may contain one or more atoms / groups other than carbon and hydrogen, so long as they do not affect the essentially hydrocarbyl character of the hydrocarbyl group. Those skilled in the art will recognize such atoms / groups (e.g., halo, especially chloro and fluoro, amino, alkoxyl, mercapto, alkylmercapto, nitro, nitroso, sulfoxy, etc.).

[0011] The term "alkyl" refers to a radical of carbon and hydrogen (e.g., C1-C 30 , for example C1~C 12 The alkyl group in the compound is usually attached directly to the compound via a carbon atom. Unless otherwise specified, the alkyl group may be linear (i.e., unbranched) or branched, and may be cyclic, acyclic, or partially 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, dimethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, and triacontyl. The term "alkenyl" refers to a radical of carbon and hydrogen having at least one double bond (e.g., C2-C 30 Radicals, e.g. C2-C 12An alkenyl group in a compound is typically attached directly to the compound via a carbon atom. Unless otherwise specified, an alkenyl group can be straight-chained (i.e., unbranched) or branched, and can be cyclic, acyclic, or part cyclic / acyclic.

[0012] The term "alkylene" refers to any C1-C alkylene group that may be linear or branched. 20 , preferably C1 to C 10 Representative examples of alkylene include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, 1-methylethylene, 1-ethylethylene, 1-ethyl-2-methylethylene, 1,1-dimethylethylene, and 1-ethylpropylene. An "olefin", also known as an "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 appended claims, when a polymer or copolymer is said to contain 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 55-95% by weight, it is understood that the mer units in the copolymer are derived from isoprene in a polymerization reaction, and the derived units are present in an amount of 55-95% by weight based on the weight of the copolymer. A "polymer" has two or more of the same or different mer units. A "homopolymer" is a polymer having the same mer units. A "copolymer" is a polymer having two or more mer units that are different from each other. The term "different" when referring to mer units means that the mer units differ from each other at at least one atom or are isomeric. An "isoprene polymer" or "isoprene copolymer" is a polymer or copolymer that contains at least 50 mole percent isoprene-derived units, a "butadiene polymer" or "butadiene copolymer" is a polymer or copolymer that contains at least 50 mole percent butadiene-derived units, etc. Similarly, when a polymer is "C 4‐5When a term is used to refer to a "partially or completely saturated polymer containing olefins," the C 4‐5 The olefin(s) is the polymerized form of an olefin(s) which is partially or fully saturated (eg, by hydrogenation) after polymerization of the monomers.

[0013] The term "alkynyl" refers to a C-C alkyl group containing at least one carbon-carbon triple bond. 30 (For example, C2~C 12 ) radical. The term "aryl" refers to a group that contains at least one aromatic ring, such as cyclopentadiene, phenyl, naphthyl, anthracenyl, etc. Aryl groups typically have a C5-C alkyl group that may be optionally substituted with one or more hydrocarbyl groups, heteroatoms, or heteroatom-containing groups (e.g., halo, hydroxyl, alkoxy, and amino groups). 40 (For example, C5~C 18 For example, C6~C 14 ) aryl groups. Preferred aryl groups include phenyl and naphthyl groups, and the substituted derivatives thereof, particularly phenyl, and the alkyl substituted derivatives of phenyl. The term "substituted" means that a hydrogen atom is replaced with a hydrocarbon group, a heteroatom, or a heteroatom-containing group. Alkyl-substituted derivatives mean that a hydrogen atom is replaced with an alkyl group. "Alkyl-substituted phenyl" refers to a derivative in which a hydrogen atom is replaced with an alkyl group, e.g., a C1-C substituted phenyl, 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, dimethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, and / or triacontyl. 20 It is a phenyl group substituted with an alkyl group or the like.

[0014] The terms "halogen" or "halo" refer to a Group 17 atom or a radical of a Group 17 atom, such as fluoro, chloro, bromo, and iodo. The term "ashless" in reference to the additive means that the composition is metal-free. The term "ash-containing" in reference to the additive means that the composition contains metals. The term "effective amount" with respect to an additive means the amount of the additive in a lubricating oil composition such that the additive provides its desired technical effect. The term "effective minor amount" in reference to an additive means an amount of the additive that is less than 50 mass % of the lubricating oil composition such that the additive provides its desired technical effect. The term "effective major amount" in reference to an additive means an amount of the additive that is 50% by mass or more of the lubricating oil composition such that the additive provides its desired technical effect. The term "ppm" means parts per million by mass based on the total mass of the lubricating oil composition, unless otherwise specified. The term "metal content" of a lubricating oil composition or an additive component, such as the magnesium content, molybdenum content, or total metal content (ie, the sum of all individual metal contents), is measured by ASTM D5185.

[0015] The term "aliphatic hydrocarbyl fatty acid" refers to an aliphatic C7-C 29 , preferably C9 to C 27 , most preferably C 11 ~C 23 This means a monocarboxylic acid having a hydrocarbyl chain. Such compounds are referred to herein as aliphatic (C7-C 29 ), more preferably (C9 to C 27 ), most preferably (C 11 ~C 23 ) may be referred to as hydrocarbyl monocarboxylic acid(s) or hydrocarbyl fatty acid(s) (herein C x ~C yspecifies the total number of carbon atoms in the aliphatic hydrocarbyl chain of the fatty acid, and due to the presence of a carboxyl carbon atom, the fatty acid itself is C x+1 ~C y+1 (having a total number of carbon atoms of 100 to 150 carbon atoms). Preferably, including the carboxyl carbon atom, the aliphatic hydrocarbyl fatty acid has an even number of carbon atoms. The aliphatic hydrocarbyl chain of the fatty acid may be saturated or unsaturated (i.e., containing at least one carbon-carbon double bond); preferably, the aliphatic hydrocarbyl chain is unsaturated and contains at least one carbon-carbon double bond. Such fatty acids may be obtained from natural sources (e.g., from animal or vegetable oils) and / or by reduction of the corresponding saturated fatty acid. It will be understood that a portion of the aliphatic hydrocarbyl chain(s) of the corresponding aliphatic hydrocarbyl fatty acid ester(s) is unsaturated (i.e., containing at least one carbon-carbon double bond) so as to be capable of reacting with other agents, such as sulfur, to form the corresponding functionalized, e.g., sulfurized, aliphatic hydrocarbyl fatty acid ester(s).

[0016] The term "aliphatic hydrocarbyl fatty acid ester" refers to an ester obtained by converting a monocarboxylic acid functional group of the corresponding aliphatic hydrocarbyl fatty acid into an ester group. Suitably, the monocarboxylic acid functional group of the aliphatic hydrocarbyl fatty acid is converted into a hydrocarbyl ester, preferably a C1-C 30 The aliphatic hydrocarbyl fatty acid is converted to an aliphatic hydrocarbyl ester, such as an alkyl ester, preferably a C1-C6 alkyl ester, especially a methyl ester. Alternatively, or additionally, the monocarboxylic acid functionality of the aliphatic hydrocarbyl fatty acid may be in the form of a natural glycerol ester. Thus, the term "aliphatic hydrocarbyl fatty acid ester" refers to the aliphatic hydrocarbyl fatty acid glycerol ester(s) and the aliphatic hydrocarbyl fatty acid C1-C 30It includes aliphatic hydrocarbyl ester(s) [e.g. aliphatic hydrocarbyl fatty acid alkyl ester(s), more preferably aliphatic hydrocarbyl fatty acid C1-C6 alkyl ester(s), especially aliphatic hydrocarbyl fatty acid methyl ester(s)]. Suitably, the term "aliphatic hydrocarbyl fatty acid ester" refers to aliphatic (C7-C 29 ) hydrocarbyl, more preferably aliphatic (C9-C 27 ) hydrocarbyl, most preferably aliphatic (C 11 ~C 23 ) Hydrocarbyl fatty acid glycerol ester(s) and aliphatic (C7-C 29 ) hydrocarbyl, more preferably aliphatic (C9-C 27 ) hydrocarbyl, most preferably aliphatic (C 11 ~C 23 ) Hydrocarbyl fatty acids C1-C 30 Preferably, a portion of the aliphatic hydrocarbyl chain(s) of the fatty acid ester(s) is unsaturated and contains at least one carbon-carbon double bond to allow for functionalization, such as sulfurization, of the aliphatic hydrocarbyl fatty acid ester(s).

[0017] The term "sulfurized aliphatic hydrocarbyl fatty acid ester" means a compound obtained by sulfurizing an aliphatic hydrocarbyl fatty acid ester as defined herein. The terms "absent" or "substantially free" with respect to components contained in the lubricating oil compositions described herein and in the claims thereto mean that the particular component is present at 0 wt.% based on the weight of the lubricating oil composition, or that if present in the lubricating oil composition, the component is present at a level that does not affect the properties of the lubricating oil composition, e.g., less than 10 ppm, or less than 1 ppm, or less than 0.001 ppm. When the term "absent" is used with respect to a monomeric reactant and / or a repeat unit in a (co)polymer described herein, the term means that the component is present at 0 wt.% based on the weight of all (co)monomers in the (co)polymer, or, if present, at a level so low that it does not substantially affect the physical properties of the (co)polymer, e.g., 0.2 wt.% or less, or 0.1 wt.% or less. As used herein, Mn is the number average molecular weight, Mw is the weight average molecular weight, and Mz is the z-average molecular weight. Molecular weight distribution (MWD), also referred to as polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise specified, all molecular weight units (e.g., Mw, Mn, Mz) are reported in g / mole.

[0018] Total Base Number, also referred to as "TBN," with respect to an additive component or a lubricating oil composition (i.e., a virgin lubricating oil composition) means Total Base Number, as determined by ASTM D2896, reported in mg KOH / g. Total Acid Number ("TAN") is measured by ASTM D664. The phosphorus, boron, calcium, zinc, molybdenum, sodium, silicon, and magnesium contents are determined by ASTM D5185. Sulfur content in oil formulations is measured according to ASTM D5185. Sulfated ash ("SASH") content is measured by ASTM D874. Kinematic viscosity (KV100, KV40) was measured according to ASTM D445-19a and is reported in cSt unless otherwise specified. Viscosity index is measured according to ASTM D2270. Saponification number was determined by ASTM D94 and is reported in mg KOH / g. HTCBT, High Temperature Corrosion Bench Test, measured according to ASTM D6594.

[0019] The term "functionalized polymer" refers to a polymer of the functionalized hydrogenated polyisoprene family for use in lubricating oil compositions, which is disclosed in commonly assigned U.S. Provisional Application No. 63 / 379,006, filed October 11, 2022, and incorporated herein by reference in its entirety. For polymers of the functionalized polymer family, the average functionality (also referred to as the average functionality value (Fv)) and functionality distribution (Fd) values ​​are measured by gel permeation chromatography using polystyrene standards as described in the Experimental Section of U.S. Patent Application No. 63 / 379,006. The term "neo acid" refers to a carboxylic acid exhibiting a highly branched structure in which the carboxylic acid functionality is attached to a quaternary carbon atom and the other moiety attached to the quaternary carbon is a saturated linear, branched, or cyclic alkyl group. "Neodecanoic acid" has the common structural formula C 10 H 20 C with O2 10 It is a mixture of neo-acids whose components share the common characteristic of three alkyl groups at carbon two: 2,2,3,5-tetramethylhexanoic acid, 2,4-dimethyl-2-isopropylpentanoic acid, 2,5-dimethyl-2-ethylhexanoic acid, 2,2-dimethyloctanoic acid, and 2,2-diethylhexanoic acid, but are not limited to these.

[0020] Unless otherwise specified, all percentages reported are mass % or weight % on an active ingredient basis, ie, without consideration of carrier or diluent oil. It will also be understood that the various components used, which are not only essential but also optimal and conventional, may react under conditions of preparation, storage, or use, and the present disclosure also provides products obtainable or obtained as a result of any such reactions. Further, it is understood that any upper and lower quantity, range, and ratio limits set forth herein may be independently combined. It will also be understood that the preferred features of each aspect of the disclosure are deemed to be preferred features of every other aspect of the disclosure, and thus the preferred and more preferred features of one aspect of the disclosure may be independently combined with other preferred and / or more preferred features of the same or different aspects of the disclosure.

[0021] Detailed Description of the Invention Where appropriate, features of the disclosure relevant to each and every aspect of the disclosure are described in more detail below. The lubricating oil compositions of this disclosure include components that may or may not be chemically identical before and after mixing with an oil-based carrier (e.g., base oil) and / or other additives. This disclosure encompasses compositions that include the components before mixing, the components after mixing, or both the components before and after mixing.

[0022] The lubricating oil compositions of the present disclosure are particularly suitable for lubricating journal bearings found in internal combustion engines. Referring to FIG. 1, there is shown a cutaway perspective view of an exemplary internal combustion engine 10 illustrating the location of various bearings within the engine that require lubrication. The engine 10 has a connecting rod small end bearing / bushing 20 having a piston pin type journal. The engine 10 also has a main bearing 30 for the crankshaft journal, and a connecting rod big end bearing 40 for the crankshaft journal. The engine 10 further has a camshaft bearing 50 and a rocker arm bushing 60. The inventive lubricating oil compositions of the present disclosure are particularly suitable for lubricating and minimizing wear in each of these bearing / journal types shown in FIG. 1. Referring to FIG. 2, cross-sectional schematic structures and cross-sections of journal bearing shell materials for solid bearings, bimetallic bearings, and tri-material / metal bearings are shown. The solid bearings may include bronze or lead-free bronze. The bimetallic bearings may include AlSn20Cu or AlSn25. The tri-material / metal bearings may include a polymeric or SuCu overlay on lead-free bronze. The inventive lubricating oil composition according to the present disclosure is particularly suitable for lubricating and minimizing wear in each of these bearing structures / materials shown in FIG. 2. In particular, the inventive lubricating oil composition according to the present disclosure has been surprisingly found to reduce bimetallic and tri-material / metal wear when used in internal combustion engines. More particularly, the inventive lubricating oil composition according to the present disclosure has been surprisingly found to reduce SnCu tri-metal and polymeric tri-material wear.

[0023] lubricating oil composition The present disclosure relates to a lubricating oil composition (also referred to as "LOC", "lubricant composition", "lubricating composition", or "lubricant oil composition") comprising: an oil of lubricating viscosity comprising a Group I base oil, a Group II base oil, a Group III base oil, a Group IV base oil, or a combination thereof, in an amount greater than 50 mass % of the composition; an overbased calcium-based detergent having a total base number (KOH / g) of 9 to 500, inclusive, at a treat level capable of delivering 500 to 1,300 ppm calcium by mass to the composition; and a total base number (KOH / g) of 9 to 500, inclusive, at a treat level capable of delivering 500 to 1,300 ppm calcium by mass to the composition. and comprising or incorporating a treat level of an overbased magnesium detergent to deliver 500 to 1300 ppm by weight of magnesium to the composition; wherein the combined weight of calcium and magnesium in the composition is in the range of 1000 ppm to 1800 ppm. The lubricating oil composition may have a total sulfated ash content of 1.0 wt.% or less, a high temperature high shear viscosity (HTHS) at 150°C of 1.8 mPa·s or more and 2.9 mPa·s or less, as measured in accordance with ASTM D4683-20, and a total phosphorus level of 0.080 wt.% or less. The lubricating oil composition provides a 5% to 60% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 Start / Stop Test Method, compared to a lubricating oil composition having a comparable HTHS but not including a mixture of an overbased calcium-based detergent and an overbased magnesium-based detergent in said composition at a combined loading of calcium and magnesium in the range of 1000 ppm to 1800 ppm.

[0024] The lubricating oil compositions disclosed herein have a high temperature high shear viscosity (HTHS or HTHS) at 150° C. as measured in accordance with ASTM D4683-20. 150) may be 1.8 or more to 2.9 mPa·s, or 1.9 to 2.8 mPa·s, or 2.0 to 2.7 mPa·s, or 2.1 to 2.6 mPa·s, or 2.2 to 2.5 mPa·s, or 2.3 to 2.4 mPa·s. The total sulfated ash of the lubricating oil compositions disclosed herein may be 0.9 mass% or less, or 0.8 mass% or less, or 0.7 mass% or less, or 0.6 mass% or less, or 0.5 mass% or less. The phosphorus level in the lubricating oil compositions disclosed herein may be 0.075 wt.% or less, or 0.070 wt.% or less, or 0.065 wt.% or less, or 0.060 wt.% or less, or 0.055 wt.% or less, or 0.050 wt.% or less. The lubricating oil compositions of the present disclosure may have a kinematic viscosity at 100° C. of from 5 to 20 cSt, or from 8 to 18 cSt, or from 10 to 16 cSt. The lubricating oil compositions of the present disclosure may have a total sulfur level of 0.35 wt.% or less, or 0.30 wt.% or less, or 0.25 wt.% or less, or 0.20 wt.% or less. In another aspect of the disclosure, the oil of lubricating viscosity is from 60 to 95 mass %, or from 70 to 90 mass %, or from 75 to 85 mass % of the composition and comprises a Group III base oil, a Group IV base oil, or a combination thereof.

[0025] The overbased magnesium detergent of the lubricating oil composition may be a sulfonate, a salicylate, a phenate, or a combination thereof. Similarly, the overbased calcium detergent of the lubricating oil composition may be a sulfonate, a salicylate, a phenate, or a combination thereof. The overbased magnesium detergent may deliver 500 to 1300 ppm by mass, or 600 to 1200 ppm by mass, or 700 to 1100 ppm by mass, or 800 to 1000 ppm by mass of magnesium to the composition. Similarly, the overbased calcium detergent may deliver 500 to 1300 ppm by mass, or 600 to 1200 ppm by mass, or 700 to 1100 ppm by mass, or 800 to 1000 ppm by mass of calcium to the composition. The combination of overbased magnesium and overbased calcium detergents may deliver a total weight of the combined calcium and magnesium to the composition in the range of 1000 to 1800 ppm, or 1100 to 1700 ppm, or 1200 to 1600 ppm, or 1300 to 1500 ppm. In another embodiment of the lubricating oil composition of the present invention, the ratio of calcium loading to magnesium loading in the composition, based on weight percent in the lubricating oil composition, may be 30:70 to 70:30, or 35:65 to 65:35, or 40:60 to 60:40, or 45:55 to 55:45.

[0026] The lubricating oil composition of the present disclosure is particularly suitable as a heavy-duty diesel oil, a light-duty diesel oil, a hydrogen engine oil, a spark ignition combustion engine oil, or a natural gas engine oil. The lubricating oil composition of the present disclosure is particularly suitable as an SAE grade selected from the group consisting of 0W-8, 0W-12, 0W-16, 0W-20, 0W-30, 5W-20, 5W-30, 10W-30, 15W-40, 5W-40, and 10W-40. More specifically, the lubricating oil composition of the present disclosure is suitable as an SAE grade selected from the group consisting of 0W-8, 0W-12, 0W-16, and 0W-20 (low viscosity engine oil). The lubricating oil compositions of the present disclosure are particularly suitable as passenger car lubricants (PVL) or commercial vehicle lubricants (CVL) and provide a 5 to 60%, or 10 to 55%, or 15 to 50%, or 20 to 45%, or 25 to 40%, or 30 to 35% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 Start / Stop Test Method, compared to a lubricating oil composition having a comparable HTHS but not including a mixture of an overbased calcium-based detergent and an overbased magnesium-based detergent.

[0027] The lubricating oil compositions disclosed herein are particularly suitable for lubricating and reducing the wear tendency of journal bearings for internal combustion engines, where the journal bearings are main bearings for the crankshaft, connecting rod big end bearings for the crankshaft, or connecting rod small end bearings / bushings for piston pins. The journal bearing shell material may be a material selected from the group consisting of bimetal, tri-material / metal, and solid material. For tri-material / metal journal bearings, the tri-material / metal may be a polymer coating or SnCu overlay on lead-free bronze. For bimetal journal bearings, the bimetal may be AlSn20Cu or AlSn25. For solid material journal bearings, the solid material may be bronze or lead-free bronze. In one particular aspect, when the lubricating oil compositions disclosed herein are used to lubricate a polymer-coated tri-material journal bearing shell material, the compositions of the present invention provide a 5 to 40%, or 10 to 35%, or 15 to 30%, or 20 to 25% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 Start / Stop Test Method compared to a lubricating oil composition having a comparable HTHS but not containing a mixture of an overbased calcium-based detergent and an overbased magnesium-based detergent.

[0028] In another specific aspect, when the lubricating oil compositions disclosed herein are used to lubricate SnCu overlay trimetal journal bearing shell material, the compositions of the present invention provide a 10-60%, or 15-55%, or 20-50%, or 25-45%, or 30-40% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 Start / Stop Test Method compared to a lubricating oil composition having a comparable HTHS but not including a mixture of an overbased calcium-based detergent and an overbased magnesium-based detergent. The lubricating oil compositions of the present disclosure may further comprise one or more of the following components: one or more functionalized polymers; one or more friction modifiers; one or more antioxidants; one or more pour point depressants; one or more antifoam agents; one or more viscosity modifiers; one or more dispersants; one or more inhibitors, one or more rust inhibitors; one or more seal swell agents; and / or one or more antiwear agents.

[0029] In an advantageous embodiment, the lubricating oil composition of the present disclosure further comprises one or more dispersants, a high molecular weight, optionally borated, polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn ≧1600 g / mole), one or more low molecular weight, optionally borated, polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn <1600 g / mole), or a combination thereof, wherein the treat level of the combination of high molecular weight PIBSA-PAM and low molecular weight PIBSA-PAM is from 1.0 to 6.0 wt.%, or from 2.0 to 5.0 wt.%, or from 3.0 to 4.0 wt.% of the composition. In another advantageous form, the lubricating oil composition of the present disclosure comprises a high molecular weight PIBSA-PAM dispersant, a low molecular weight PIBSA-PAM dispersant, or a combination thereof, present at a treat level to deliver from 20 to 700 ppm by weight, or from 50 to 600 ppm by weight, or from 100 to 500 ppm by weight, or from 200 to 400 ppm by weight of boron to the lubricating oil composition. In an advantageous embodiment, the lubricating oil composition of this disclosure further comprises one or more antiwear agents comprising one or more zinc dialkyldithiophosphates (ZDDPs) at a treat level capable of delivering up to 840 ppm by weight phosphorus, or up to 800 ppm by weight, or up to 700 ppm by weight, or up to 600 ppm by weight phosphorus to the composition.

[0030] In another advantageous embodiment, the lubricating oil composition of the present disclosure further comprises one or more antioxidants selected from one or more phenolic antioxidants, one or more sulfur based antioxidants, one or more aminic antioxidants, or combinations thereof, wherein the one or more antioxidants have a content of from 1.0 to 6.0 mass %, or from 1.5 to 5.5 mass %, or from 2.0 to 5.0 mass %, or from 2.5 to 4.5 mass %, or from 3.0 to 4.0 mass % of the total lubricating oil composition. In another advantageous embodiment, the lubricating oil composition of the present disclosure further comprises one or more friction modifiers selected from dimeric molybdenum dialkyldithiocarbamate (moly dimer), trimer molybdenum dialkyldithiocarbamate (moly trimer), or combinations thereof, at a treat level to deliver from 12 to 1000 ppm, or from 20 to 500 ppm, or from 20 to 200 ppm, by weight, of molybdenum to the composition. In yet another advantageous form, the lubricating oil compositions of the present disclosure are substantially free of molybdenum.

[0031] In another advantageous embodiment, the lubricating oil composition of the present disclosure further optionally comprises: i) Mw / Mn less than 2, or less than 1.8, or less than 1.6; ii) a functionality distribution (Fd) value less than or equal to 3.5, or less than or equal to 3.2, or less than or equal to 3.0, or less than or equal to 2.5; and iii) the Mn of the polymer before functionalization being 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); However, if the polymer before functionalization is a copolymer of isoprene and butadiene, 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); C 4‐5 One or more functionalized polymers, including amide, imide, and / or ester functionalized partially saturated or fully saturated polymers, including olefins, may be present in an amount of 0.2-2.0%, or 0.4-1.8%, or 0.6-1.6%, or 0.8-1.4%, or 1.0-1.2% by weight of the composition.

[0032] The functionalized polymer of the lubricating oil composition of the present disclosure may have at least 50%, or at least 60%, or at least 70% monomer 1,4 insertions. Additionally, the functionalized polymer of the lubricating oil composition of the present disclosure may comprise a partially saturated or fully saturated homopolyisoprene containing one or more pendant amine groups and having, prior to functionalization, a Mn of 25,000-100,000 g / mol, or 35,000-90,000 g / mol, or 45,000-80,000 g / mol, or 55,000-75,000 g / mol (GPC-PS) and having at least 50%, or at least 60%, or at least 70% 1,4 insertions. The functionalized polymer of the lubricating oil composition of the present disclosure may not contain any styrene repeat units, or may not contain any butadiene repeat units, or is not a homopolyisobutylene, or is not a copolymer of isoprene and butadiene. The lubricating oil composition of the present disclosure is particularly suitable as a heavy duty diesel oil, a light duty diesel oil, or a natural gas engine oil. The lubricating oil composition of the present disclosure is particularly suitable as an SAE grade selected from the group consisting of 0W-8, 0W-12, 0W-20, 0W-30, 5W-20, 5W-30, 10W-30, 15W-40, 5W-40, and 10W-40.

[0033] Also provided herein is a method of lubricating an internal combustion engine, comprising the step of supplying a lubricating oil composition according to the present disclosure to the engine. Also provided herein is a method of supplying motor gasoline (mogas) to the engine and combusting the motor gasoline in the engine, where the motor gasoline is non-renewable motor gasoline, renewable motor gasoline, or a combination thereof, and the engine is a spark ignition combustion engine. Also provided herein is a method of supplying diesel fuel to the engine and combusting the diesel fuel in the engine, where the diesel fuel is non-renewable diesel fuel, renewable diesel fuel, or a combination thereof, and the engine is a diesel engine. Also provided herein is a method of supplying natural gas or hydrogen to the engine and combusting the natural gas or hydrogen in the engine, where the engine is a natural gas engine or a hydrogen engine. The lubricating oil composition of the present disclosure is particularly suitable for improving journal bearing wear performance in internal combustion engines and reducing engine emissions. Accordingly, there is also provided a method for reducing journal bearing wear in an internal combustion engine, comprising the step of supplying to the engine a lubricating oil composition according to the present disclosure. Also provided herein is a method for producing the lubricating oil composition, comprising the step of combining or blending the components of the lubricating oil composition of the present disclosure.

[0034] Suitably, the lubricating oil compositions of the present disclosure may have a Total Base Number (TBN), as measured by ASTM D2896, of from 4 to 16 mg KOH / g, preferably from 5 to 14 mg KOH / g, such as from 7 to 12 mg KOH / g, for example from 8 to 12 mg KOH / g. Alternatively, the lubricating compositions of this disclosure may have a ratio of magnesium atoms to calcium atoms, based on the total weight of the lubricating oil composition, of at least 0.5, preferably at least 0.6, and more preferably at least 0.65, as measured by ASTM D5185. Typically, the lubricating oil composition may contain low levels of sulfur. Preferably, the lubricating oil composition has a maximum of 0.35 mass % sulfur, preferably a maximum of 0.3 mass %, for example 0.1 to 0.35 mass %, based on the total mass of the lubricating oil composition, as measured by ASTM D5185.

[0035] Typically, the lubricating composition may have a low level of sulfated ash, for example, 1.0 mass % or less, or preferably 0.9 mass % or less, or from 0.0001 to 0.9 mass % or less, based on the total mass of the lubricating composition, as measured by ASTM D874-13a(2018). Preferably, the lubricating oil composition of the present disclosure may be a multigrade oil identified by the viscometric descriptors SAE 15W-X, SAE 10W-X, SAE 5W-X, or SAE 0W-X, where X represents any one of 8, 12, 16, 20, 30, 40, and 50; the characteristics of the various viscosity grades can be found in the SAE J300 classification. Alternatively, the lubricating composition may be in the form of a viscosity grade SAE 15W-X, SAE 10W-X, SAE 5W-X, or SAE 0W-X, such as SAE 15W-X or SAE 10W-X, where X represents any one of 8, 12, 16, 20, 30, 40, and 50. Preferably, X is 20, 30, or 40. Alternatively, the lubricating compositions of the present disclosure may be multigrade oils identified by the viscosity descriptors SAE 5W-20, 10W-30, 15W-40, 5W-30, 5W-40, 10W-40 (see standard SAE J300, published in January 2015 by SAE International, formerly the Society of Automotive Engineers).

[0036] In an embodiment, the lubricating oil composition may contain less than 75 ppm boron, alternatively less than 60 ppm, alternatively 1-70 ppm, or the LOC may be free or substantially free of boron. In an embodiment, the lubricating oil composition may comprise 6 wt.% or less (e.g., less than 5 wt.%, such as less than 4 wt.%, such as less than 3 wt.%, such as less than 2 wt.%, such as less than 1 wt.%) of a functionalized (e.g., aminated) polybutene (e.g., polyisobutylene), such as PIBSA-PAM. In an embodiment, the lubricating oil composition may comprise, be substantially free of, or be free of a functionalized (e.g., aminated) polybutene (e.g., polyisobutylene), such as high molecular weight PIBSA-PAM. In an embodiment, the lubricating oil composition may optionally comprise an acylated polymer, such as polyisobutylene succinic acid (PIBSA), having a Mn of 500 to 50,000 g / mol, e.g., 600 to 5,000 g / mol, e.g., 700 to 3000 g / mol. In an embodiment, the lubricating oil composition may comprise an acylated polymer, such as polyisobutylene succinic acid, having a Mn of 500 to 1600 g / mol, e.g., 700 to 1200 g / mol. In an embodiment, the lubricating oil composition comprises greater than 0.1 wt % (e.g., 0.1 to 6 wt %, e.g., 0.5 to 4 wt %) of a functionalized (e.g., aminated) polybutene (e.g., polyisobutylene), e.g., PIBSA-PAM.

[0037] In an embodiment, the lubricating oil composition may comprise up to 20 wt.% (e.g., 15 wt.%, such as 10 wt.%, such as 5 wt.%, such as 3 wt.%, such as 1 wt.%) of a block copolymer, such as a block, star, random, and / or tapered block copolymer. In an embodiment, the lubricating oil composition may be substantially free or free of block copolymers, such as block, star, random, and / or tapered block copolymers. In an embodiment, the lubricating oil composition may comprise up to 20 wt. % (e.g., 15 wt. %, such as 10 wt. %, such as 5 wt. %, such as 3 wt. %, such as 1 wt. %) of a styrene copolymer, such as a block, star, random, and / or tapered styrene block copolymer. In an embodiment, the lubricating oil composition may be substantially free or free of styrenic copolymers, such as block, star, random, and / or tapered styrenic block copolymers. In an embodiment, the lubricating oil composition may comprise less than 20 wt.% (e.g., less than 15 wt.%, such as less than 10 wt.%, such as less than 5 wt.%, such as less than 3 wt.%, for example less than 1 wt.%) of a functionalized diluent, e.g., a functionalized oil. In an embodiment, the lubricating oil composition may contain, be substantially free of, or be free of a functionalized diluent, such as a functionalized oil. In an embodiment, the lubricating oil composition may comprise less than 20 wt.% (e.g. less than 15 wt.%, such as less than 10 wt.%, for example less than 5 wt.%, such as less than 3 wt.%, for example less than 1 wt.%) of a solvent, such as an aromatic solvent.

[0038] In an embodiment, the lubricating oil composition may be substantially free or free of solvents, such as functionalized solvents. In an embodiment, the lubricating oil composition may comprise less than 0.5 mass % (e.g., less than 0.4 mass %, such as less than 0.3 mass %, such as less than 0.2 mass %, such as less than 0.1 mass %, substantially free, or 0 mass %) of secondary and tertiary hydrocarbyl amine compounds based on the mass of the LOC. In an embodiment, the lubricating oil composition may be substantially free or free of secondary hydrocarbyl amine compounds and tertiary hydrocarbyl amine compounds. In embodiments, the lubricating compositions of the present disclosure may be heavy duty diesel oils, light duty diesel oils, or passenger car engine oils for spark ignition combustion engines. In an embodiment, the lubricating compositions of the present disclosure may be natural gas engine oils or hydrogen engine oils. The lubricating compositions disclosed herein have a viscosity of 5 to 20 (e.g., 6 to 18, or 8 to 16, or 10 to 14) cSt (mm 2 / s) at 100°C, and may have a kinematic viscosity of 15 to 30 (e.g., 15 to 25) cSt) (mm 2 The composition may have a kinematic viscosity of 300 nm / s at 40° C.

[0039] Methods of using lubricating oil compositions The disclosure also relates to a method of using the lubricating oil composition, particularly for reducing journal bearing wear in an internal combustion engine, comprising the steps of supplying to an internal combustion engine a lubricating oil composition comprising or incorporating the following: an oil of lubricating viscosity comprising a Group I base oil, a Group II base oil, a Group III base oil, a Group IV base oil, or a combination thereof, in an amount greater than 50% by weight of the composition; an overbased calcium detergent having a total base number (KOH / g) of 9 to 500, inclusive, and a treat level capable of delivering 500 to 1300 ppm by weight of calcium to the composition; and an overbased magnesium detergent having a total base number (KOH / g) of 9 to 500, inclusive, and a treat level capable of delivering 500 to 1300 ppm by weight of magnesium to the composition; wherein the combined weight of calcium and magnesium in the composition is in the range of 1000 ppm to 1800 ppm. The lubricating oil composition may have a total sulfated ash content of 1.0 wt.% or less, a high temperature high shear viscosity (HTHS) at 150°C measured in accordance with ASTM D4683-20 ​​of 1.8 mPa·s or more and 2.9 mPa·s or less, and a total phosphorus level of 0.080 wt.% or less. The disclosed method of reducing journal bearing wear results in a 5% to 60% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 start / stop test method, compared to a lubricating oil composition having a comparable HTHS but not including a mixture of overbased calcium and overbased magnesium detergents at a combined calcium and magnesium loading in the range of 1000 ppm to 1800 ppm in said composition.

[0040] The lubricating oil compositions disclosed herein have surprisingly and unexpectedly been found to reduce journal bearing wear, as measured by maximum average wear in microns using the TE-92 Start / Stop Test Method, compared to lubricating oil compositions having a comparable HTHS but which do not contain a mixture of overbased calcium and overbased magnesium detergents at a combined loading of calcium and magnesium in said composition in the range of 1000 ppm to 1800 ppm. In the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, which is another aspect of the present disclosure, the lubricating oil composition may have a high temperature high shear viscosity (HTHS) at 150°C of at least 1.8 mPa·s to 2.9 mPa·s, or from 1.9 to 2.8 mPa·s, or from 2.0 to 2.7 mPa·s, or from 2.1 to 2.6 mPa·s, or from 2.2 to 2.5 mPa·s, or from 2.3 to 2.4 mPa·s, as measured in accordance with ASTM D4683-20. In another aspect of the present disclosure, in the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition may have a total sulfated ash content of 0.9 wt.% or less, or 0.8 wt.% or less, or 0.7 wt.% or less, or 0.6 wt.% or less, or 0.5 wt.% or less; and a phosphorus level of 0.075 wt.% or less, or 0.070 wt.% or less, or 0.065 wt.% or less, or 0.060 wt.% or less, or 0.055 wt.% or less, or 0.050 wt.% or less.

[0041] In another aspect of the present disclosure, in the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition may have a kinematic viscosity at 100° C. of from 5 to 20 cSt, or from 8 to 18 cSt, or from 10 to 16 cSt; and may have a total sulfur level of 0.35 wt.% or less, or 0.30 wt.% or less, or 0.25 wt.% or less, or 0.20 wt.% or less. In another aspect of the present disclosure, in the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the oil of lubricating viscosity is 60 to 95, or 70 to 90, or 75 to 85, mass % of the composition and comprises a Group III base oil, a Group IV base oil, or a combination thereof.

[0042] In another embodiment of the present disclosure, in the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the overbased magnesium detergent of the lubricating oil composition may be a sulfonate, a salicylate, a phenate, or a combination thereof. Similarly, the overbased calcium detergent of the lubricating oil composition may be a sulfonate, a salicylate, a phenate, or a combination thereof. The overbased magnesium detergent may deliver 500 to 1300 ppm by weight, or 600 to 1200 ppm by weight, or 700 to 1100 ppm by weight, or 800 to 1000 ppm by weight of magnesium to the composition. Similarly, the overbased calcium detergent may deliver 500 to 1300 ppm by weight, or 600 to 1200 ppm by weight, or 700 to 1100 ppm by weight, or 800 to 1000 ppm by weight of calcium to the composition. In another aspect of the present disclosure, in the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition may deliver a combination of overbased magnesium detergent and overbased calcium detergent in the range of 1000 to 1800 ppm, or 1100 to 1700 ppm, or 1200 to 1600 ppm, or 1300 to 1500 ppm of the total weight of the combination of calcium and magnesium to the composition. In another aspect of the present invention method of reducing journal bearing wear, the ratio of calcium loading to magnesium loading in the composition, based on weight percent in the lubricating oil composition, may be 30:70 to 70:30, or 35:65 to 65:35, or 40:60 to 60:40, or 45:55 to 55:45.

[0043] In another aspect of the present disclosure, the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition is particularly suitable as a heavy duty diesel oil, a light duty diesel oil, a hydrogen engine oil, a spark ignition combustion engine oil, or a natural gas engine oil. The lubricating oil composition of the present disclosure is particularly suitable as an SAE grade selected from the group consisting of 0W-8, 0W-12, 0W-16, 0W-20, 0W-30, 5W-20, 5W-30, 10W-30, 15W-40, 5W-40, and 10W-40. In another aspect of the present disclosure, in the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition is particularly suitable as a passenger car lubricant (PVL) or a commercial vehicle lubricant (CVL) and provides a 5 to 60%, or 10 to 55%, or 15 to 50%, or 20 to 45%, or 25 to 40%, or 30 to 35% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 Start / Stop Test Method, compared to a lubricating oil composition having a comparable HTHS but not including a mixture of an overbased calcium-based detergent and an overbased magnesium-based detergent.

[0044] In another aspect of the disclosure, the method of reducing journal bearing wear in an internal combustion engine of the disclosure is particularly suitable for lubricating and reducing the wear tendency of journal bearings for internal combustion engines, the journal bearings being main bearings for a crankshaft, connecting rod big end bearings for a crankshaft, or connecting rod small end bearings / bushings for piston pins. The journal bearing shell material may be a material selected from the group consisting of bimetal, tri-material / metal, and solid material. For tri-material / metal journal bearings, the tri-material / metal may be a polymer coating or SnCu overlay on lead-free bronze. For bimetal journal bearings, the bimetal may be AlSn20Cu or AlSn25. For solid material journal bearings, the solid material may be bronze or lead-free bronze. In one particular aspect, the disclosed method of reducing journal bearing wear in an internal combustion engine is particularly suited when the lubricating oil composition is used to lubricate a polymer-coated tri-material journal bearing shell material. The composition of the present invention provides a 5-40%, or 10-35%, or 15-30%, or 20-25% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 Start / Stop test method, compared to a lubricating oil composition having a comparable HTHS but not including a mixture of an overbased calcium-based detergent and an overbased magnesium-based detergent.

[0045] In another particular aspect, the disclosed method of reducing journal bearing wear in an internal combustion engine is particularly suited when the lubricating oil composition is used to lubricate a SnCu overlay trimetal journal bearing shell material. The composition of the present invention provides a 10-60%, or 15-55%, or 20-50%, or 25-45%, or 30-40% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 start / stop test method, compared to a lubricating oil composition having a comparable HTHS but not including a mixture of an overbased calcium-based detergent and an overbased magnesium-based detergent. In another aspect of the present disclosure, in the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition may further comprise one or more of the following components: one or more functionalized polymers, one or more friction modifiers; one or more antioxidants; one or more pour point depressants; one or more antifoam agents; one or more viscosity modifiers; one or more dispersants; one or more inhibitors, one or more rust inhibitors; one or more seal swell agents; and / or one or more antiwear agents.

[0046] In an advantageous embodiment of the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition further comprises one or more dispersants, optionally borated high molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersants (Mn: 1600 g / mole or greater), one or more optionally borated low molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersants (Mn: less than 1600 g / mole), or combinations thereof, wherein the treat level of the combination of high molecular weight PIBSA-PAM and low molecular weight PIBSA-PAM is from 1.0 to 6.0 mass %, or from 2.0 to 5.0 mass %, or from 3.0 to 4.0 mass % of the composition. In another advantageous form of the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition may comprise a high molecular weight PIBSA-PAM dispersant, a low molecular weight PIBSA-PAM dispersant, or a combination thereof, present at a treat level to deliver from 20 to 700 ppm, or from 50 to 600 ppm, or from 100 to 500 ppm, or from 200 to 400 ppm by weight of boron to the lubricating oil composition. In an advantageous embodiment of the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition may further comprise one or more antiwear agents comprising a treat level of one or more zinc dialkyldithiophosphates (ZDDP) delivering up to 840 ppm by weight phosphorus, or up to 800 ppm by weight, or up to 700 ppm by weight, or up to 600 ppm by weight phosphorus to the composition.

[0047] In another advantageous aspect of the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition may further comprise one or more antioxidants selected from one or more phenolic antioxidants, one or more sulfur based antioxidants, one or more aminic antioxidants, or combinations thereof, wherein the one or more antioxidants have a content of 1.0 to 6.0 mass %, or 1.5 to 5.5 mass %, or 2.0 to 5.0 mass %, or 2.5 to 4.5 mass %, or 3.0 to 4.0 mass %, of the total lubricating oil composition. In another advantageous embodiment of the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition may further comprise one or more friction modifiers selected from dimeric molybdenum dialkyldithiocarbamate (moly dimer), trimer molybdenum dialkyldithiocarbamate (moly trimer), or combinations thereof, at a treat level to deliver from 12 to 1000 ppm, or from 20 to 500 ppm, or from 20 to 200 ppm, by weight, of molybdenum to the composition. In yet another advantageous aspect of the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition is substantially free of molybdenum.

[0048] In another advantageous embodiment of the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition optionally further comprises: i) Mw / Mn less than 2, or less than 1.8, or less than 1.6; ii) a functionality distribution (Fd) value less than or equal to 3.5, or less than or equal to 3.2, or less than or equal to 3.0, or less than or equal to 2.5; and iii) the Mn of the polymer before functionalization being 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); However, if the polymer before functionalization is a copolymer of isoprene and butadiene, 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). C 4‐5 One or more functionalized polymers, including amide, imide, and / or ester functionalized partially saturated or fully saturated polymers, including olefins, may be included in an amount of 0.2 to 2.0%, or 0.4 to 1.8%, or 0.6 to 1.6%, or 0.8 to 1.4%, or 1.0 to 1.2% by weight of the composition.

[0049] Method for producing lubricating oil composition The present disclosure also relates to methods for making lubricating oil compositions, particularly methods for making lubricating oil compositions comprising combining or blending: (i) an oil of lubricating viscosity comprising a Group I base oil, a Group II base oil, a Group III base oil, a Group IV base oil, or a combination thereof, in an amount greater than 50% by weight of the composition; (ii) an overbased calcium detergent having a total base number (KOH / g) of 9 to 500, inclusive, and a treat level capable of delivering 500 to 1300 ppm by weight of calcium to the composition; and (iii) an overbased magnesium detergent having a total base number (KOH / g) of 9 to 500, inclusive, and a treat level capable of delivering 500 to 1300 ppm by weight of magnesium to the composition, wherein the combined weight of calcium and magnesium in the composition is in the range of 1000 ppm to 1800 ppm. The lubricating oil composition may have a total sulfated ash content of 1.0 wt.% or less, a high temperature high shear viscosity (HTHS) at 150°C, measured in accordance with ASTM D4683-20, of 1.8 mPa·s or more and 2.9 mPa·s or less, and a total phosphorus level of 0.080 wt.% or less. The method of making the lubricating oil compositions of the present disclosure provides a 5% to 60% reduction in journal bearing wear, as measured by maximum average wear in microns using the TE-92 Start / Stop Test Method, compared to a lubricating oil composition having a comparable HTHS but not including a mixture of an overbased calcium-based detergent and an overbased magnesium-based detergent at a combined loading of calcium and magnesium in said composition in the range of 1000 ppm to 1800 ppm. In the method for producing the lubricating oil composition of the present disclosure, the lubricating oil composition is particularly suitable as a heavy duty diesel oil, a light duty diesel oil, a hydrogen engine oil, a spark ignition combustion engine oil, or a natural gas engine oil, and is particularly suitable as an SAE grade selected from the group consisting of 0W-8, 0W-12, 0W-16, 0W-20, 0W-30, 5W-20, 5W-30, 10W-30, 15W-40, 5W-40, and 10W-40.

[0050] concentrate A concentrate, also referred to as an additive package, adpak, or addpack, is a composition having less than 50 wt.% (e.g., less than 40 wt.%, such as less than 30 wt.%, such as less than 25 wt.%, such as less than 20 wt.%) of a base oil and lubricant composition additives (e.g., those described herein), which is typically then further blended with additional base oil to form a finished lubricant oil. The present disclosure relates to a concentrate composition comprising or obtained by mixing the following: 1 to 50 mass% or less of one or more base oils; 2 to 25 mass% of an overbased magnesium-based detergent having a total base number (KOH / g) of 9 to 500, both inclusive, based on the mass of the concentrate; and 2 to 25 mass% of an overbased calcium-based detergent having a total base number (KOH / g) of 9 to 500, both inclusive.

[0051] The concentrate may be included in the lubricating oil composition of the present disclosure in an amount from 0.5 to 35 mass %, such as from 5 to 30 mass %, for example from 7.5 to 25 mass %, such as from 10 to 22.5 mass %, for example from 15 to 20 mass %, based on the mass of the lubricating oil composition. Optionally, the concentrate may be free of functionalized oils. In an embodiment, the concentrate composition may optionally be free of solvents (eg, aliphatic or aromatic solvents) and / or functionalized base oils. Optionally, the concentrate may be free of phenolic antioxidants.

[0052] In embodiments, the concentrate may contain less than 75 ppm boron, alternatively less than 60 ppm, alternatively between 1 and 70 ppm boron. Alternatively, the concentrate may be free of boron. In an embodiment, the concentrate may comprise less than 20% by weight (e.g., 15% by weight, such as 10% by weight, such as 5% by weight, such as 3% by weight, such as 1% by weight) of a functionalized (e.g., aminated) polybutene (e.g., polyisobutylene), such as PIBSA-PAM. In an embodiment, the concentrate may comprise, be substantially free of, or be free of a functionalized (e.g., aminated) polybutene (e.g., polyisobutylene), such as PIBSA-PAM. In an embodiment, the concentrate may further comprise one or more of the following components: one or more functionalized polymers, one or more friction modifiers; one or more antioxidants; one or more pour point depressants; one or more antifoam agents; one or more viscosity modifiers; one or more dispersants; one or more inhibitors, one or more rust inhibitors; one or more seal swell agents; and / or one or more antiwear agents. In an embodiment, the concentrate may optionally include an acylated polymer, such as polyisobutylene succinic acid, having a Mn of 500 to 50,000 g / mol, e.g., 600 to 5,000 g / mol, e.g., 700 to 3000 g / mol. In an embodiment, the concentrate may optionally include an acylated polymer, such as polyisobutylene succinic acid, having a Mn of 500 to 1600 g / mol, e.g., 700 to 1200 g / mol.

[0053] In an embodiment, the concentrate may comprise up to 20% by weight (e.g., 15% by weight, such as 10% by weight, such as 5% by weight, such as 3% by weight, such as 1% by weight) of block copolymers, such as block, star, random, and / or tapered block copolymers. In embodiments, the concentrate may be substantially free or free of block copolymers, such as block, star, random, and / or tapered block copolymers. In an embodiment, the concentrate may comprise 20% by weight or less (e.g., 15% by weight or less, such as 10% by weight or less, such as 5% by weight or less, such as 3% by weight or less, such as 1% by weight or less) of a styrene copolymer, such as a block, star, random, and / or tapered styrene block copolymer. In embodiments, the concentrate may be substantially free or free of styrenic copolymers, such as block, star, random, and / or tapered styrenic block copolymers. In an embodiment, the concentrate may comprise less than 20% by weight (e.g., less than 15% by weight, such as less than 10% by weight, such as less than 5% by weight, such as less than 3% by weight, such as 1% by weight) of a functionalized diluent, e.g., a functionalized oil. In embodiments, the concentrate may be substantially free or free of functionalized diluents, such as functionalized oils. In an embodiment, the concentrate may comprise less than 0.5 wt. % (e.g., less than 0.4 wt. %, such as less than 0.3 wt. %, such as less than 0.2 wt. %, such as 0.1 wt. %, or substantially free or free) of secondary hydrocarbyl amine compounds and tertiary hydrocarbyl amine compounds based on the weight of the concentrate. In an embodiment, the concentrate may be substantially free or free of secondary hydrocarbyl amine compounds and tertiary hydrocarbyl amine compounds. In an embodiment, the concentrate may have a kinematic viscosity at 100° C. of less than 1000 cSt, such as less than 500 cSt, for example less than 200 cSt.

[0054] The present disclosure also relates to a method for making a concentrate composition comprising combining: 1 to 50% by weight of one or more base oils; 2 to 25% by weight, based on the weight of the concentrate, of an overbased magnesium detergent having a total base number (KOH / g) of ≥ 9, inclusive, and ≥ 500, inclusive; and 2 to 25% by weight, based on the weight of the concentrate, of an overbased calcium detergent having a total base number (KOH / g) of ≥ 9, inclusive, and ≥ 500, inclusive.

[0055] Lubricating Oil Composition Components and Concentrate Components A. Base oil components Base oils (also referred to as "base stocks," "lubricating oil base stocks," or "oil of lubricating viscosity") useful herein may be a single oil or a blend of oils, and are typically the majority liquid component of a lubricating composition, also referred to as a lubricant, into which additives and any additional oils are blended to produce a lubricating composition, such as a finished lubricant composition, a concentrate, or other lubricating composition. The base oil may be selected from vegetable, animal, mineral, and synthetic lubricating oils, and mixtures thereof. The base oil may range in viscosity from light distillate mineral oils to heavy lubricating oils, such as gas engine oils, mineral lubricating oils, automotive oils, and heavy duty diesel oils. Typically, the kinematic viscosity at 100°C ("KV100") of the base oil measured according to ASTM D445-19a ranges from 1 to 30 cSt, such as 2 to 25 cSt, for example 5 to 20 cSt, in particular 1.0 to 10 cSt, 1.5 to 3.3 cSt, 2.7 to 8.1 cSt, 3.0 to 7.2 cSt, or 2.5 to 6.5 cSt. Typically, the high temperature high shear (HTHS) viscosity at 150°C of the base oil measured according to ASTM D4683-20 ​​ranges from 0.5 to 20 cP, for example 1 to 10 cP, for example 2 to 5 cP.

[0056] Typically, when lubricating oil base stock(s) are used to make the concentrate, it is advantageous that the base stock may be included in a concentrate-forming amount to result in a concentrate containing from 5 to 80 mass %, from 10 to 70 mass %, or from 5 to 50 mass % of the active ingredient, based on the mass of the concentrate. Common oils useful as base oils include animal and vegetable oils (e.g., castor oil and lard oil), liquid petroleum oils, and hydrorefined and / or solvent treated mineral lubricating oils of the paraffinic, naphthenic, and mixed paraffinic and naphthenic types. Oils derived from coal and shale are also useful base oils. Base stocks may be produced using a variety of different processes, including, but not limited to, distillation, solvent refining, hydrotreating, oligomerization, esterification, and rerefining. Synthetic lubricating oils useful herein as base oils include hydrocarbon oils such as homo- and co-olefins, referred to as polyalphaolefins or PAOs or Group IV base oils [as defined in API EOLCS 1509 (American Petroleum Institute Publication 1509, Section E.1.3, 19th Edition, January 2021, www.API.org)]. Examples of PAOs useful as base oils include: poly(ethylene), copolymers of ethylene and propylene, polybutylene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutylene, poly(1-hexene), poly(1-octene), poly(1-decene), C8-C9, C10-C12, C12-C16, C16-C18, C18-C22, C18-C24, C18-C26, C18-C28, C18-C28, C18-C28, C18-C24, C18-C28 ... 20 Alkene homopolymers or copolymers, C8 and / or C 10 , and / or C. 12 Alkene homopolymer or copolymer, C8 / C 10 Copolymer, C8 / C 10 / C 12 Copolymers, and C 10 / C 12 Copolymers, as well as derivatives, analogues, and homologues thereof.

[0057] In another embodiment, the base oil may comprise a polyalphaolefin comprising oligomers of linear olefins having from 6 to 14 carbon atoms, more preferably from 8 to 12 carbon atoms, even more preferably 10 carbon atoms, having a kinematic viscosity at 100° C. (measured by ASTM D445) of 10 or greater; preferably having a viscosity index ("VI") of 100 or greater, preferably 110 or greater, more preferably 120 or greater, more preferably 130 or greater, more preferably 140 or greater, as measured by ASTM D2270; and / or a pour point (measured by ASTM D97) of −5° C. or less, more preferably −10° C. or less, more preferably −20° C. or less. In another embodiment, the polyalphaolefin oligomers useful in the present disclosure are 20 ~C 1500 Paraffin, preferably C 40 ~C 1000 Paraffin, preferably C 50~C 750 Paraffin, preferably C 50 ~C 500 In one embodiment, the PAO oligomer may comprise a C5-C 14 In another embodiment, the alpha-olefin is C6-C 12 In another embodiment, the alpha-olefin is C8-C 12 The olefins are dimers, trimers, tetramers, pentamers, etc. of alpha-olefins. 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 may be essentially 1-decene, and the PAO is a mixture of dimers, trimers, tetramers, and pentamers (and higher) thereof. Useful PAOs are more specifically described, for example, in U.S. Pat. Nos. 5,171,908 and 5,783,531, and in Synthetic Lubricants and High-Performance Functional Fluids 1-52, edited by Leslie R. Rudnick and Ronald L. Shubkin, Marcel Dekker, Inc., 1999.

[0058] The number average molecular weight of the PAOs useful in the present disclosure typically ranges from 100 to 21,000 g / mole in one embodiment, from 200 to 10,000 g / mole in another embodiment, from 200 to 7,000 g / mole in yet another embodiment, from 200 to 2,000 g / mole in yet another embodiment, and from 200 to 500 g / mole in yet another embodiment. Suitable PAOs are commercially available under the trade names SpectraSyn™ Hi-Vis, SpectraSyn™ Low-Vis, SpectraSyn™ plus, SpectraSyn™ Elite PAO's (ExxonMobil Chemical Co., Houston, Tex.), and Durasyn PAO's from Ineos Oligomers USA. Synthetic lubricating oils useful as base oils also include homopolymerized and copolymerized hydrocarbon oils such as: alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2-ethylhexyl)benzene); polyphenols (e.g., biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers, and alkylated diphenyl sulfides; and derivatives, analogs, and congeners thereof. Another suitable class of synthetic lubricating oils useful as base oils includes esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, and alkenyl malonic acids) reacted with various 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.

[0059] The esters useful as synthetic oils herein include those having C5 to C 12 Also included are esters made from monocarboxylic acids and polyols, and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol. Preferred ester base oils are available under the trade name Esterex™ Esters (ExxonMobil Chemical Co., Houston, Tex.). Silicon-based oils, such as the polyalkyl, polyaryl, polyalkoxy, or polyaryloxy silicone 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)siloxane, and poly(methylphenyl)siloxane.

[0060] Other synthetic lubricating oils useful herein include liquid esters of phosphorus-containing acids (eg, tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans. Unrefined, refined, and re-refined oils can be used in the lubricating compositions of the present disclosure. Unrefined oils are oils obtained directly from natural or synthetic sources without further purification treatment. For example, shale oil obtained directly from retorting, petroleum oil obtained directly from distillation, or ester oil obtained directly from esterification and used without further treatment are considered unrefined oils. Refined oils are similar to unrefined oils except that 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 skilled in the art. Re-refined oils are oils obtained by methods similar to those used to obtain refined oils, where the refining methods are applied to previously refined oils that have been used in service in the past. Such re-refined oils are also referred to as reclaimed or reprocessed oils, and are often additionally processed to remove spent additives and oil breakdown products. Re-refined base oils are preferably substantially free of materials introduced through manufacturing, contamination, or past use.

[0061] Other examples of useful base oils include gas-to-liquids ("GTL") base oils, i.e., base oils derived from hydrocarbons produced from synthesis gas ("syn-gas") containing H2 and CO using a Fischer-Tropsch catalyst. These hydrocarbons usually require further processing to be useful as base oils. For example, they may be subjected to hydroisomerization; hydrocracking and hydroisomerization; degreasing; or hydroisomerization and degreasing by methods known in the art. For further information regarding useful GTL base oils and blends thereof, see U.S. Pat. No. 10,913,916 (paragraph 4, line 62 to paragraph 5, line 60) and U.S. Pat. No. 10,781,397 (paragraph 14, line 54 to paragraph 15, line 5, and paragraph 16, line 44 to paragraph 17, line 55). In particular, oils derived from renewable sources, ie, oils based in part on carbon and energy captured from the environment, such as biological sources, are useful herein.

[0062] Various base oils are often classified as Group I, II, III, IV, or V according to the definitions in API EOLCS 1509 (American Petroleum Institute Publication 1509, Section E.1.3, 19th Edition, January 2021, www.API.org). Generally, Group I base stocks have a viscosity index of about 80-120, contain more than about 0.03% sulfur, and / or contain less than about 90% saturates. Group II base stocks have a viscosity index of about 80-120, contain less than about 0.03% sulfur, and contain more than about 90% saturates. Group III base stocks have a viscosity index greater than about 120, contain less than about 0.03% sulfur, and contain more than about 90% saturates. Group IV base stocks contain polyalphaolefins (PAOs). Group V base stocks include base stocks not included in Groups I-IV (viscosity index as measured by ASTM D2270, saturates as measured by ASTM D2007, sulfur as measured by ASTM D5185, D2622, ASTM D4294, ASTM D4927, and ASTM D3120). The base oil for use in the formulated lubricating compositions useful in the present disclosure can be any one, two, three or more of the various oils described herein. In a preferred embodiment, the base oil for use in the formulated lubricating compositions useful in the present disclosure is a base oil 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. Due to their excellent volatility, stability, viscosity and cleanliness properties, the base oil can be Group III, Group III+, IV and Group V base oils. Small amounts of Group I base stocks, such as for diluting additives for blending into prepared lubricant products, can be tolerated, but are typically kept to a minimum, such as amounts associated with use as a diluent / carrier oil for additives used "as received". What is often more useful with Group II stocks is that the Group II base stocks are in the higher quality range associated with that stock, i.e., the viscosity index of the Group II stocks is in the range of 100-120.

[0063] The base oils useful herein may be selected from either synthetic, natural, or rerefined oils (e.g., those commonly used as crankcase lubricants in spark-ignition and compression-ignition engines). Mixtures of synthetic and / or natural base oils and / or rerefined base oils may be used if desired. Multimodal mixtures (e.g., bimodal or trimodal mixtures) of Group I, II, III, IV, and / or V base oils may be used if desired. As used herein, the kinematic viscosity of a base oil or base oil blend at 100°C (measured in accordance with ASTM D445-19a, in centistokes (cSt) or its equivalent in mm 2The kinematic viscosity at 100° C. of the base oil or base oil blend (KV100, reported in kinematic viscosity units / s) is conveniently from about 2 to about 40 cSt, alternatively from 3 to 30 cSt, alternatively from 4 to 20 cSt, alternatively from 5 to 10 cSt. Alternatively, the kinematic viscosity at 100° C. of the base oil or base oil blend may be from 2 to 20 cSt, from 2.5 to 2 cSt, preferably from about 2.5 to about 9 cSt. The saturates content of the base oil or base oil blend, measured according to ASTM D2007, is preferably at least 65 mass%, more preferably at least 75 mass%, such as at least 85 mass%, for example at least 90 mass%.

[0064] Preferably, the sulfur content of the base oil or base oil blend, as measured by ASTM D5185, is less than 1 mass %, preferably less than 0.6 mass %, most preferably less than 0.4 mass %, for example less than 0.3 mass %, based on the total mass of the lubricating composition. In an embodiment, the volatility of the base oil or base oil blend, measured by the Noack test (ASTM D5800, Procedure B), is 30% by mass or less, such as 25% by mass or less, such as 20% by mass or less, such as 16% by mass or less, such as 12% by mass or less, for example 10% by mass or less, based on the total mass of the lubricating composition. In an embodiment, the base oil has a viscosity index (VI) of at least 95, preferably at least 110, more preferably at least 120, even more preferably at least 125, and most preferably from about 130 to 240, especially from about 105 to 140 (as measured by ASTM D2270). The base oil may be provided in major amounts in combination with minor amounts of one or more of the additive components described below to form the lubricant. This may be accomplished by adding the additives directly to the oil, or by adding one or more additives in the form of a concentrate thereof to disperse or dissolve the additive(s). The additives may be added to the oil by any method known to those skilled in the art, before, simultaneously with, or after the addition of other additives.

[0065] The base oil may be provided in minor amounts in combination with minor amounts of one or more of the additive components described below to form an additive concentrate. This may be accomplished by adding the additives directly to the oil, or by adding one or more additives in the form of a solution, slurry, or suspension to disperse or dissolve the additive(s) in the oil. The additives may be added to the oil by any method known to those skilled in the art, either before, simultaneously with, or after the addition of other additives. The base oil typically constitutes the major component of the engine oil lubricant compositions of the present disclosure and is typically present in an amount ranging from about 50 to about 99 weight percent, preferably from about 60 to about 95 weight percent, more preferably from about 70 to about 95 weight percent, and more preferably from about 80 to about 95 weight percent, based on the total weight of the composition. Typically, the one or more base oils are present in the lubricating composition in an amount of at least 32 mass %, alternatively at least 55 mass %, alternatively at least 60 mass %, alternatively at least 65 mass %, based on the total mass of the lubricating composition. Typically, the one or more base oils are present in the lubricating composition in an amount of at most 98 mass %, more preferably at most 95 mass %, even more preferably at most 90 mass %. Alternatively, the one or more base oils are present in the lubricating composition in an amount from 1 to 99 mass %, alternatively from 50 to 97 mass %, alternatively from 60 to 95 mass %, alternatively from 70 to 95 mass %, based on the mass of the lubricating composition.

[0066] The base oils and base oil blends described above are also useful for making concentrates and for making lubricants from the concentrates. Concentrates constitute a convenient means of processing additives prior to use and facilitating dissolution or dispersion of the additive in the lubricant. When preparing lubricants containing multiple additives (sometimes referred to as "additive components"), each additive may be formulated separately in the form of its own concentrate. However, it is often more convenient to provide a so-called additive "package" (also referred to as an "addpack") containing one or more additives / co-additives in a single concentrate as described below. Typically, the one or more base oils are present in the concentrated composition in an amount of 50% by weight or less, alternatively 40% by weight or less, alternatively 30% by weight or less, alternatively 20% by weight or less, based on the total weight of the concentrated composition. Typically, the one or more base oils are present in the concentrated composition in an amount of 0.1 to 49% by weight, alternatively 1 to 40% by weight, alternatively 5 to 40% by weight, alternatively 10 to 30% by weight, alternatively 15 to 25% by weight, based on the total weight of the concentrated composition. In one aspect of the lubricating oil composition disclosed herein, the composition may comprise a Group II base oil, a Group III base oil, a Group IV base oil, or a combination thereof. In another aspect of the lubricating oil composition disclosed herein, the composition may comprise a Group II base oil and is substantially free of Group III base oil and Group IV base oil.

[0067] B. Functionalized polymer component The optional functionalized polymer component of the lubricating oil compositions and concentrate compositions disclosed herein includes polymers having a Mn of about 10,000 g / mol or more, such as 20,000 g / mol or more, such as 25,000 g / mol or more, such as 30,000 g / mol or more, such as 35,000 g / mol or more (GPC-PS) prior to functionalization. Alternatively, the functionalized polymer includes polymers having a Mn of 10,000 to 300,000 g / mol, such as 20,000 to about 150,000 g / mol, such as 30,000 to about 125,000 g / mol, such as 35,000 to about 100,000 g / mol, such as 40,000 to 80,000 g / mol (GPC-PS) prior to functionalization. The Mw / Mn of the polymer before functionalization may be less than 2 (e.g., less than 1.6, e.g., less than 1.5, e.g., 1.4 or less, e.g., 1-1.3, e.g., 1.0-1.25, e.g., 1.0-1.2, e.g., 1.0-1.15, e.g., 1.0-1.1, as measured by GPC-PS). The polymer before functionalization may contain repeat units of one or more olefins having 4-5 carbon atoms (preferably conjugated dienes having 4-5 carbon atoms). Before functionalization, the C 4‐5 The polymer is preferably fully or partially saturated (e.g., fully or partially hydrogenated). 4‐5The functionalized polymer may also be obtained by reacting the polymer with an acylation agent to form an acylated polymer, and then reacting the acylated polymer with an amine or alcohol to form an amide, imide, ester, or combination thereof. 4‐5 Polymers (e.g., commercially available maleated fully or partially hydrogenated C 4‐5 The polymer may be obtained by reacting a tertiary amine such as phenylene oxide with an amine to form an amide, an imide, or a combination thereof.

[0068] The present disclosure further relates to a method for producing a compound according to the present invention, 4‐5 The present invention relates to a lubricating oil composition comprising a functionalized polymer, such as an amide, imide, and / or ester functionalized saturated (e.g., hydrogenated) polymer of a conjugated diene. The functionalized polymer is a C 1000 sintered polymer having a Mw / Mn of less than 2. 4‐5 They are obtained by reacting a fully or partially saturated (e.g., fully or partially hydrogenated) polymer of a conjugated diene with an acylating agent, such as maleic acid or maleic anhydride, and then reacting the acylated polymer with an amine (e.g., a polyamine) to form an imide, amide, or combination thereof. The present disclosure relates to lubricating oil compositions comprising a functionalized polymer having one or more pendant amine groups and at least partially (preferably fully) hydrogenated C 4‐5 They include or are obtained by incorporating an olefin polymer and an acylating agent such as maleic acid or maleic anhydride and then reacting the acylated polymer with a polyamine to form an imide, amide or combination thereof.

[0069] In embodiments, the functionalized polymer is not prepared in an aromatic solvent (e.g., benzene or toluene), or aromatic solvent is present at 2 wt % or less (e.g., 1 wt % or less, e.g., 0.5 wt % or less) based on the weight of the solvent, diluent, and polymer. In embodiments, the functionalized polymer is not prepared in an alkylated naphthylene solvent, or the alkylated naphthylene solvent is present at 5% by weight or less (e.g., 3% by weight or less, e.g., 1% by weight or less) based on the weight of the solvent, diluent, and polymer. The polymers useful in preparing the functionalized polymers herein may be homopolymers of butadiene, isoprene, and the like. In embodiments, the polymers useful in preparing the functionalized polymers herein may be isoprene homopolymers or copolymers of isoprene with less than 5 mol % (e.g., less than 3 mol %, such as less than 1 mol %, e.g., less than 0.1 mol %) of a comonomer. Polymers useful in the preparation of functionalized polymers herein include those consisting of isoprene and styrene, methyl-styrene, 2,3-dimethyl-butadiene, 2-methyl-1,3-pentadiene, myrcene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, 2-phenyl-1,3-pentadiene, 3-phenyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2-hexyl-1,3-butadiene, 3-methyl-1,3-hexadiene, 2-benzyl-1,3-butadiene, 2-p-tolyl-1,3 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2,4-heptadiene, 1,3-octadiene, 2,4-octadiene, 3,5-octadiene, 1,3-nonadiene, 2,4-nonadiene, 3,5-nonadiene, 1,3-decadiene, 2,4-decadiene and 3,5-decadiene (optionally comprising less than 20 mol %, less than 5 mol %, such as less than 3 mol %, for example less than 1 mol %, for example less than 0.1 mol %) of comonomer(s).

[0070] Generally, the polymerized conjugated diene polymers useful for preparing functionalized polymers herein contain a mixture of 1,4 and 1,2 insertions (also known as 2,1 insertions; for butadiene, 1,2 insertions are the same as 3,4 insertions). As measured by 1H NMR, the polymerized conjugated diene polymers useful for preparing functionalized polymers herein have a 1,4 insertion of at least about 50%, such as at least about 75%, such as at least about 80%, such as at least about 90%, such as at least about 95%, such as at least 98%, based on the sum of the 2,1 insertions, 1,4 insertions, and 3,4 insertions of isoprene. For purposes of this disclosure: 1) the expression "1,4 insertion" includes 1,4 insertions and 4,1 insertions, 2) the expression "2,1 insertion" includes 2,1 insertions and 1,2 insertions, and 3) the expression "3,4 insertion" includes 3,4 insertions and 4,3 insertions. Optionally, styrene repeat units may be absent in the polymers useful herein for preparing the functionalized polymers. Optionally, styrene repeat units may be absent in the functionalized hydrogenated / saturated polymers. Optionally, butadiene repeat units may not be present in the polymers useful herein for preparing the functionalized polymers. Optionally, butadiene repeat units may not be present in the functionalized hydrogenated / saturated polymers. Optionally, the polymers useful in preparing the functionalized polymers herein may not be homopolybutylene. Optionally, the functionalized hydrogenated / saturated polymer may not be homopolybutylene. Optionally, the polymers useful in preparing the functionalized polymers herein may not be homopolyisobutylene. Optionally, the functionalized hydrogenated / saturated polymer may not be homopolyisobutylene. In some cases, the polymers useful in preparing the functionalized polymers herein may not be copolymers of isoprene and butadiene. In some cases, the functionalized hydrogenated / saturated polymers may not be copolymers of isoprene and butadiene.

[0071] The polymers useful for preparing the functionalized polymers and / or functionalized polymers herein may be homopolymers or copolymers. The copolymers may be random copolymers, tapered block copolymers, star copolymers, or block copolymers. Block copolymers are formed from a monomer mixture containing one or more first monomers (e.g., isobutylene), for example forming discrete blocks of polymer in which the first monomer is bonded to a second discrete block of polymer formed from a second monomer (e.g., butadiene). Block copolymers have substantially discrete blocks formed from monomers, whereas tapered block copolymers may have one end composed of a relatively pure first monomer and the other end composed of a relatively pure second monomer. In the middle of the tapered block copolymer, the gradient composition of the two monomers may be increased. The Mn of polymers useful herein for preparing functionalized polymers can typically be from 20,000 to 150,000 g / mol, alternatively from 20,000 to about 150,000 g / mol, alternatively from 30,000 to about 125,000 g / mol, alternatively from 35,000 to about 100,000 g / mol, alternatively from 40,000 to 80,000 g / mol (GPC-PS). The Mw / Mn (measured by GPC-PS) of polymers useful herein for preparing functionalized polymers may typically be 1 to 2, alternatively from greater than 1 to less than 2, alternatively from 1.1 to 1.8, alternatively from 1.2 to 1.5. Alternatively, the Mw / Mn of polymers useful herein for preparing functionalized polymers may typically be 1 or from greater than 1 to less than 2 (such as less than 1.8, such as less than 1.7, such as less than 1.6, such as less than 1.5, such as less than 1.4, such as less than 1.3, such as less than 1.2, such as less than 1.15, such as less than 1.12, such as less than 1.10).

[0072] The Mz (measured by GPC-PS) of the polymer used to prepare the functionalized polymer may be from 20,000 to 150,000 g / mol, alternatively from 20,000 to about 150,000 g / mol, alternatively from 30,000 to about 125,000 g / mol, alternatively from 35,000 to about 100,000 g / mol, alternatively from 40,000 to 80,000 g / mol, alternatively from 40,000 to 60,000 g / mol (GPC-PS). Polymers useful herein for preparing functionalized polymers may have a glass transition temperature (Tg) of -25°C or lower, such as -40°C or lower, for example -50°C or lower, as measured by differential scanning calorimetry (DSC) using a Perkin Elmer or TA Instrument thermal analysis system (sample heated from ambient to 210°C at 10°C / min, held at 210°C for 5 minutes, then cooled to -40°C at 10°C / min and held for 5 minutes). Polymers useful herein for preparing functionalized polymers typically have residual unsaturation less than 3%, such as less than 2%, such as less than 1%, such as less than 0.5%, such as less than 0.25%, based on the number of double bonds in the unhydrogenated polymer. The residual metal (eg Li, Co, Al) content of polymers useful herein for preparing functionalized polymers is typically less than 100 ppm, such as less than 50 ppm, such as less than 25 ppm, such as less than 10 ppm, such as less than 5 ppm.

[0073] Hydrogenation C useful in the preparation of functionalized polymers herein 4‐5 The polymers can be partially or fully hydrogenated by any hydrogenating agent known to those skilled in the art. For example, a saturated or partially saturated polymer can be a C 12 polymer having (a) C 12 carboxylic acid or C 16 carboxylic acid moiety that contains unsaturation (e.g., double or triple bonds). 4‐5and (b) hydrogenating at least some or all of the unsaturated moieties (e.g., double or triple bonds) in the polymer in the presence of a hydrogenation agent. In some embodiments, the polymer is fully hydrogenated. In some embodiments, the polymer is partially hydrogenated. In some embodiments, the polymer is 50% or more, such as 60% or more, such as 70% or more, such as 80% or more, such as 90% or more, such as 95% or more, such as 98% or more, such as 99% or more, such as 50-100% saturated (hydrogenated) as measured by the ozone adsorption method described in Martino N. Smits and Dirkman Hoefma, "Quantitative Determination of Olefinic Unsaturation by Measurement of Ozone Absorption Analytical Chemistry", Vol. 44, No. 9, p. 1688, p. 1972, Martino N. Smits. In embodiments, the hydrogenation reagent can be hydrogen in the presence of a hydrogenation catalyst. In some embodiments, the hydrogenation catalyst is Pd, Pd / C, Pt, PtO2, Ru(PPh3)2Cl2, Raney Nickel, or a combination thereof. In embodiments, the catalyst is a Pd catalyst. In another embodiment, the catalyst is 5% Pd / C. In further embodiments, the catalyst can include or be 10% Pd / C in a high pressure reactor, and the hydrogenation reaction is allowed to proceed to completion. Generally, after completion, the reaction mixture can be washed, concentrated, and dried to obtain the corresponding hydrogenated product. Alternatively, any reducing agent capable of reducing C=C bonds to C-C bonds can be used. For example, olefin polymers can be hydrogenated by treatment with hydrazine in the presence of a catalyst such as 5-ethyl-3-methyllumiflavinium perchlorate under an oxygen atmosphere to obtain the corresponding hydrogenated product. The reduction reaction with hydrazine is disclosed in Imada et al., Journal of the American Chemical Society, 2005, No. 127, pp. 14544-14545, which is incorporated herein by reference.

[0074] Acylation A fully saturated or partially saturated (hydrogenated) polymer may be chemically modified (functionalized) to provide the polymer with at least one polar functional group, such as, but not limited to, halogen, epoxy, hydroxy, amino, nitrilo, mercapto, imide, carboxy, and sulfonic acid groups, or combinations thereof. The functionalized polymer can be further modified to obtain a more desired type of functionality. In a preferred example, a fully or partially hydrogenated polymer is functionalized by reacting the fully or partially hydrogenated polymer with an unsaturated carboxylic acid (or its derivative, such as maleic anhydride) to obtain an acylated polymer, which may then be further functionalized as described below. In some embodiments, carboxylic acid functional groups or their reactive equivalents are grafted onto the polymer to form an acylated polymer. Ethylenically unsaturated carboxylic acid materials are typically grafted onto the polymer backbone. These materials attached to the polymer typically contain at least one ethylenic bond (before reaction) and at least one, for example two, carboxylic acid (or its anhydride) groups or polar groups that can be converted to said carboxyl groups by oxidation or hydrolysis. Maleic anhydride or its derivatives are preferred. It is grafted onto the polymer to provide two carboxylic acid functional groups. Examples of additional unsaturated carboxylic acid materials include itaconic anhydride or the corresponding dicarboxylic acids, such as maleic acid, fumaric acid, and their esters, and cinnamic acid, and their esters.

[0075] The ethylenically unsaturated carboxylic acid material may be grafted onto the polymer in a number of ways. The ethylenically unsaturated carboxylic acid material may be grafted onto the polymer in solution or in substantially pure (molten) form, with or without the use of a radical initiator. Free radical induced grafting of the ethylenically unsaturated carboxylic acid material may be carried out in a solvent such as hexane or mineral oil. The grafting may be carried out at elevated temperatures ranging from 100° C. to 250° C., for example from 120° C. to 190° C., or from 150° C. to 180° C., for example above 160° C. Free radical initiators that may be used include peroxides, hydroperoxides, and azo compounds, which typically have boiling points above about 100°C and thermally decompose within the grafting temperature range to form free radicals. Representative examples of these free radical initiators include azobisisobutyronitrile and 2,5-dimethyl-hex-3-yn-2,5-bis-tert-butylperoxide. The initiator may be used in an amount of 0.005 to 1% by weight based on the weight of the reaction mixture solution. The grafting may be carried out in an inert atmosphere, for example under a nitrogen blanket. The resulting acylated polymer intermediate is characterized by having a carboxylic acid acylation functionality as part of its structure. In embodiments, the acylated polymer may have 2 or more anhydride groups per polymer molecule and may contain less than 10% gel. Alternatively, the acylated polymer may have less than 2 anhydride groups per polymer molecule and may contain less than 10% gel. (See also U.S. Pat. No. 5,429,758, col. 17, line 14 to col. 18, line 11.)

[0076] Alternatively, in some embodiments, the gel content of the acylated polymer may be less than about 5%, less than 3%, less than 2%, less than 1%, less than 0.5%, less than 0.1%, or 0% by weight. The gel content is measured by determining the amount of material extractable from the polymer using boiling xylene (or cyclohexane) as the extractant. The percentage of soluble and insoluble (gel) material in the polymer composition is determined by immersing a nominally 0.5 mm thick thin film specimen of the polymer in cyclohexane at 23° C. for 48 hours or refluxing the thin film specimen in boiling xylene for 30 minutes, removing the solvent, weighing the dry residue, and calculating the amount of soluble and insoluble (gel) material. This method is generally described in U.S. Pat. No. 4,311,628, which is incorporated herein by reference. For purposes of this disclosure, gel content is measured using boiling xylene, unless the sample is not soluble in xylene, followed by the cyclohexane method. In an embodiment, the saponification number (SAP) of the acylated polymer, measured by ASTM D94, may be 5 g / KOH or more, such as 10 g / KOH or more, for example 20 g / KOH or more, for example 30 g / KOH or more, for example 50 g / KOH or more, for example from 10 to 60 g / KOH, for example from 20 to 40 g / KOH. In embodiments, the acylated polymer composition may contain less than 5% by weight of unreacted acylating agent (e.g., maleic anhydride), such as less than 4% by weight, such as less than 3% by weight, such as less than 1% by weight, such as less than 0.5% by weight, such as less than 0.25% by weight, such as less than 0.1% by weight, based on the weight of the acylated polymer composition (i.e., polymer, acylating agent, and diluent).

[0077] In embodiments, the acylation reaction described herein may be carried out in a base oil diluent. It is possible to produce a functionalized base oil as a by-product. The oil may itself be acylated. For example, maleated base oil may be present after the acylation reaction described herein. It is contemplated that the functionalized base oil may include acylated oils and / or reaction products of acylated oils with amines to form amides, imides, or combinations thereof. Preferably, the acylated oil and / or reaction products of the acylated oil with an amine or alcohol to form an amide, imide, ester, or combinations thereof may be present in the concentrate in an amount of 40% or less by weight, alternatively 20% or less by weight, alternatively 10% or less by weight, alternatively 5% or less by weight, alternatively 3% or less by weight, preferably 2% or less by weight, preferably 1% or less by weight, preferably 0.1% or less by weight, preferably 0% by weight (for example 0 to 40% by weight, alternatively 0.01 to 40% by weight, alternatively 0.1 to 20% by weight, alternatively 1 to 10% by weight, alternatively 1.5 to 5% by weight).

[0078] Preferably, the one or more functionalized base oils, such as acylated oils, and / or reaction products of acylated oils with amines or alcohols to form amides, imides, esters, or combinations thereof, may be present in the lubricating oil composition in an amount of from 0.01 to 40 mass %, alternatively from 0.1 to 20 mass %, alternatively from 1 to 10 mass %, alternatively from 1.5 to 5 mass % (e.g., 3 mass % or less, preferably 2 mass % or less, preferably 1 mass % or less, preferably 0.1 mass % or less, preferably 0 mass % or less, based on the weight of the lubricating oil composition. In an embodiment, the acylation reaction described herein is carried out in a solvent-containing medium. An acylated / functionalized solvent may be produced as a by-product. In an embodiment, the acylated and / or functionalized solvent may be present in the concentrate composition at 3% or less, preferably 2% or less, preferably 1% or less, preferably 0.1% or less, preferably 0% by weight based on the weight of the concentrate composition. In an embodiment, the functionalized solvent may be present in the lubricating oil composition at 3% or less, preferably 2% or less, preferably 1% or less, preferably 0.1% or less, preferably 0% by weight based on the weight of the lubricating oil composition.

[0079] In embodiments, the acylating agent may be added in a manner that minimizes side reactions (eg, reactions with base oil or other diluents present in the reactor). In an embodiment, the acylation reaction may be carried out with the acylating agent (e.g., maleic acid or maleic anhydride) added in a continuous or semi-continuous (e.g., intermittent) stream (e.g., in a controlled, relatively equal proportion over the reaction time, or greater and / or lesser proportions at different times during the reaction) to minimize functionalized base oil and other side reactions. As an example, the acylating agent may be added in a continuous manner, with the polymer and acylating agent being added in controlled stoichiometric amounts. As another example, the polymer may be added to the reactor in a batch manner, and the acylating agent may be added slowly or in a semi-continuous manner (e.g., the acylating agent is added in 2 or more, such as 5 or more, such as 10 or more, such as 20 or more, such as 30 or more, such as 40 or more, such as 50 or more, such as 60 or more discrete amounts or proportions). Alternatively, the polymer can be added to the reactor in X portions and the acylating agent can be added in 1.5X or more portions (e.g., 2X or more, such as 5X or more, such as 10X or more, such as 20X or more, such as 30X or more, such as 40X or more, such as 50X or more, such as 60X or more) This same effect can also be achieved by diluting or concentrating the polymer solution and / or the acylating agent solution to the same or different extents. Preferably, the acylating agent is added in such a manner as to minimize side reactions, for example in a continuous or semi-continuous manner.

[0080] The reaction may also be carried out in a batch, semi-continuous, or continuous reactor operation using high concentrations of polymer in the diluent, for example 45% by weight or more, or 50% by weight or more, or 55% by weight or more, or 60% by weight or more. For example, the polymer (e.g., hydrogenated isoprene polymer, e.g., hydrogenated homopolyisoprene) may be introduced into a batch, semi-continuous, or continuous reactor operation as a solution or suspension (e.g., a slurry) in a diluent (e.g., an oil (e.g., a base oil, e.g., Group I, II, III, IV, and / or V base oil, e.g., Group II and / or Group III base oil), or an alkane solvent or diluent, or a combination thereof). Here, the polymer may be included in the solution or suspension at 45% by weight or more (or 50% by weight or more, or 55% by weight or more, or 60% by weight or more) based on the weight of the polymer and diluent. In embodiments, side reactions may be minimized by: 1) adding the acylating agent in a continuous or semi-continuous manner; and / or 2) introducing the polymer into a batch, semi-continuous, or continuous reactor operation as a solution or suspension in the diluent, with the polymer comprising 45% or more by weight based on the weight of the polymer and diluent. In embodiments, side reactions may be optionally minimized by adding the acylating agent in a continuous or semi-continuous manner and / or by introducing the fully or partially hydrogenated polymer (e.g., isoprene polymer) into a batch, semi-continuous, or continuous reactor operation as a diluent solution or suspension comprising 45% or more (or 50% or more, or 55% or more, or 60% or more) by weight of the fully or partially hydrogenated polymer based on the weight of the fully or partially hydrogenated polymer and diluent. In embodiments, side reactions are minimized by adding the acylating agent in a continuous or semi-continuous manner and introducing the fully or partially hydrogenated polymer (e.g., isoprene polymer) into a batch, semi-continuous, or continuous reactor operation as a solution or suspension in a diluent, the solution or suspension comprising 45% or more (or 50% or more, or 55% or more, or 60% or more) by weight of the fully or partially hydrogenated polymer based on the weight of the fully or partially hydrogenated polymer and diluent.

[0081] sensualization In embodiments, the acylated polymer may be reacted with an alcohol or amine to form an amide, imide, ester, or combination thereof. The reaction may consist of a condensation to form an imide, amide, half amide, amide ester, diester, or amine salt. Typically, primary amino groups condense to form an amide, or, in the case of maleic anhydride, an imide. It is noted that the amine may have a single primary amino group or multiple primary amino groups. Suitable amines include one or more aromatic amines, such as amines in which a carbon atom of an aromatic ring structure is directly bonded to an amino nitrogen. The amine may be aliphatic. In embodiments, aliphatic amines can be used alone or in combination with each other or in combination with aromatic amines. The amount of aromatic amines may be greater or less than the amount of non-aromatic amines in some embodiments, or in some examples, the composition may be substantially free of aromatic amines. Alternatively, the composition may be substantially free of aliphatic amines.

[0082] Examples of aromatic amines that may be used herein include one or more N-arylphenylenediamine(s) represented by the formula: [ka] wherein R7 is H, -NHaryl, -NHalkaryl, or a branched or linear hydrocarbyl radical having from about 4 to about 24 carbon atoms selected from alkyl, alkenyl, alkoxyl, aralkyl, or alkaryl; R9 is -NH, -(NH(CH) n ) m R is an alkyl, alkenyl, alkoxyl, aralkyl, or alkaryl group having from about 4 to about 24 carbon atoms. Suitable N-arylphenylenediamines include N-phenylphenylenediamines (NPPDA), such as N-phenyl-4,4-phenylenediamine, N-phenyl-1,3-phenylenediamine, and N-phenyl-1,2-phenylenediamine, and N-naphthyl-1,4-phenylenediamine. Other derivatives of NPPDA, such as N-propyl-N'-phenylphenylenediamine, may also be included.

[0083] In embodiments, the amine reacted with the acylated polymer is an amine having at least three or four aromatic groups and may be represented by the formula: [ka] where R is an independent variable 1 may be hydrogen or a C1-C5 alkyl group (typically hydrogen); R 2 may be hydrogen or a C1-C5 alkyl group (typically hydrogen); U may be an aliphatic, alicyclic, or aromatic group, provided that when U is aliphatic, the aliphatic group may be a straight-chain or branched alkylene group having 1 to 5, or 1 to 2 carbon atoms; w may be 1 to 10, or 1 to 4, or 1 to 2 (typically 1). Other examples of aromatic amines include aniline, N-alkylanilines such as N-methylaniline and N-butylaniline, di-(para-methylphenyl)amine, naphthylamine, 4-aminodiphenylamine, N,N-dimethylphenylenediamine, 4-(4-nitro-phenylazo)aniline (Disperse Orange 3), sulfamethazine, 4-phenoxyaniline, 3-nitroaniline, 4-aminoacetanilide, 4-amino-2-hydroxy-benzoic acid phenyl ester (phenyl aminosalicylate), N-(4-amino-5-methoxy-2-methyl-phenyl)-benzamide (Fast Violet B), N-(4-amino-2,5-dimethoxy-phenyl)-benzamide (Fast Blue RR), N-(4-amino-2,5-diethoxy-phenyl)-benzamide (Fast Blue BB), N-(4-amino-phenyl)-benzamide, and 4-phenylazoaniline. Suitable amines are mentioned in US Pat. No. 7,790,661, which is incorporated herein by reference.

[0084] In embodiments, the compound that condenses with the acylated polymer can be represented by the formula: [ka] In the formula, X is an alkylene group having from about 1 to about 4 carbon atoms; R 2 , R 3 , and R 4 is a hydrocarbyl group. [ka] In the formula, X is an alkylene group having from about 1 to about 4 carbon atoms; R 3 and R 4 is a hydrocarbyl group. Alternatively, the amine may be an amine having at least four aromatic groups and an aldehyde (e.g., formaldehyde). The aromatic amine may be represented by the formula: [ka] In the formula, R 1 is hydrogen or C 1‐5 is an alkyl group (typically hydrogen); R 2 is hydrogen or C 1‐5 is an alkyl group (typically hydrogen); U is an aliphatic group, an alicyclic group, or an aromatic group, provided that, optionally, when U is aliphatic, the aliphatic group may be a linear or branched alkylene group having 1, 2, 3, 4, or 5 carbon atoms, or 1 to 2 carbon atoms; w is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9, e.g., 0, 1, 2, or 3, or 0 or 1 (typically 0). For further information on such amines, see, for example, US 2017 / 0073606, p. 5, paragraphs

[0064] to

[0070] and EP 2 401 348.

[0085] Examples of compounds that can be condensed with an acylating agent and further have a tertiary amino group include, but are not limited to: dimethylaminopropylamine, N,N-dimethyl-aminopropylamine, N,N-diethyl-aminopropylamine, N,N-dimethyl-aminoethylamine, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, the isomeric butylenediamines, pentanediamine, hexanediamine, heptanediamine, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, triethylenetetraamine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenetetramine, and bis(hexamethylene)triamine, diaminobenzene, diaminopyridine, and mixtures thereof. Further examples of compounds that can be condensed with an acylating agent and further have a tertiary amino group include aminoalkyl-substituted heterocyclic compounds such as 1-(3-aminopropyl)imidazole and 4-(3-aminopropyl)morpholine, 1-(2-aminoethyl)piperidine, 3,3-di-amino-N-methyldipropylamine, and 3',3-aminobis(N,N-dimethylpropylamine). Further examples of compounds that can be condensed with an acylating agent and further have a tertiary amino group include alkanolamines, including but not limited to triethanolamine, trimethanolamine, N,N-dimethylaminopropanol, N,N-di-ethylaminopropanol, N,N-diethylaminobutanol, N,N,N-tris(hydroxyethyl)amine, and N,N,N-tris(hydroxymethyl)amine. In an embodiment, the polymer may be reacted with a polyether aromatic compound. Typically, a polyether aromatic compound has at least two functional groups, each of which can react with a monocarboxylic acid or its ester, or a dicarboxylic acid, its anhydride or ester, or a mixture thereof. In an embodiment, the polyether aromatic compound is derived from an aromatic compound containing at least one amine group, where the polyether can react with a monocarboxylic acid or its ester, or a dicarboxylic acid, its anhydride or ester.

[0086] Examples of suitable polyether aromatic amines include compounds having the following structure: [ka] wherein A represents an aromatic amine moiety in which a plurality of ether groups are linked together through at least one amine group on the aromatic moiety; R1 and R6 are independently hydrogen, alkyl, alkaryl, aralkyl, aryl, or mixtures thereof; R2, R3, R4, and R5 are independently hydrogen, or alkyl having from about 1 to about 6 carbon atoms, or mixtures thereof; and a and x are independently integers from about 1 to about 50. The acylated polymer may be reacted with a polyetheramine or polyetherpolyamine. A typical polyetheramine compound is a chain containing at least one ether unit and terminated with at least one amine moiety. The polyetherpolyamine may be based on polymers derived from C2-C6 epoxides such as ethylene oxide, propylene oxide, and butylene oxide. Examples of polyetherpolyamines are commercially available from Huntsman (Hunstman) under the Jeffamine™ brand. Amines useful in combination with the acylated polymers herein include one or more of the following: N-phenyldiamines (e.g., N-phenyl-1,4-phenylenediamine, N-phenyl-p-phenylenediamine (also known as 4-amino-diphenylamine, ADPA), N-phenyl-1,3-phenylenediamine, N-phenyl-1,2-phenylenediamine), nitroanilines (e.g., 3-nitroaniline), N-phenylethanediamines (e.g., N1-phenylethane-1,2-diamine), N-aminophenylacetamides (e.g., N-(4-aminophenyl)acetamide), morpholinopropanamines (e.g., 3-morpholinopropan-1-amine), and aminoethylpiperazines (e.g., 1-(2-aminoethyl)piperazine).

[0087] In embodiments, the functionalization (e.g., amination) reactions described herein may be carried out in a diluent (e.g., a base oil or an alkane solvent). As a by-product, a functionalized diluent (e.g., a functionalized base oil) may be produced. It is contemplated that the functionalized diluent (e.g., a functionalized base oil) may include the reaction product of an acylated diluent (e.g., an acylated base oil) with an amine to form an amide, an imide, or a combination thereof. Preferably, reaction products of an acylated diluent (e.g., an acylated oil) with an amine or alcohol to form an amide, imide, ester, or combinations thereof may be present in the concentrate in an amount of 40% or less, alternatively 20% or less, alternatively 10% or less, alternatively 5% or less, alternatively 3% or less, preferably 2% or less, preferably 1% or less, preferably 0.1% or less, preferably 0% (e.g., 0 to 40%, alternatively 0.01 to 40%, alternatively 0.1 to 20%, alternatively 1 to 10%, alternatively 1.5 to 5% by weight based on the weight of the concentrated composition. Preferably, the one or more functionalized base oils, such as reaction products of an acylated diluent (e.g., an acylated base oil) with an amine or an alcohol to form an amide, imide, ester, or combinations thereof, may be present in the lubricating oil composition in an amount from 0.01 to 40 mass %, alternatively from 0.1 to 20 mass %, alternatively from 1 to 10 mass %, alternatively from 1.5 to 5 mass % (e.g., 3 mass % or less, preferably 2 mass % or less, preferably 1 mass % or less, preferably 0.1 mass % or less, preferably 0 mass % or less, based on the weight of the lubricating oil composition.

[0088] In embodiments, the functionalization (e.g., amination) reactions described herein may be carried out in a solvent-containing medium. As a by-product, a functionalized solvent may be produced. In embodiments, the functionalized solvent may be present in the concentrate composition at 3 wt. % or less, preferably 2 wt. % or less, preferably 1 wt. % or less, preferably 0.1 wt. % or less, preferably 0 wt. % based on the weight of the concentrate composition. In embodiments, the functionalized solvent may be present in the lubricating oil composition at 3 wt. % or less, preferably 2 wt. % or less, preferably 1 wt. % or less, preferably 0.1 wt. % or less, preferably 0 wt. % based on the weight of the lubricating oil composition. In embodiments, the acylation base oil / solvent may be removed prior to functionalization. The functionalized polymer may be a homopolymer of a C4 or C5 olefin, such as butadiene and isoprene. In an embodiment, the functionalized polymer may be a homopolymer of isoprene or a copolymer of isoprene and less than 5 mol % (e.g., less than 3 mol %, e.g., less than 1 mol %, e.g., less than 0.1 mol %) of a comonomer. The functionalized polymers are isoprene and; styrene, methyl-styrene, 2,3-dimethyl-butadiene, 2-methyl-1,3-pentadiene, myrcene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, 2-phenyl-1,3-pentadiene, 3-phenyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2-hexyl-1,3-butadiene, 3-methyl-1,3-hexadiene, 2-benzyl-1,3-butadiene, 2-p-tolyl-1,3-butadiene, 1,3-butadiene, The copolymer may comprise or be a copolymer of one or more of 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2,4-heptadiene, 1,3-octadiene, 2,4-octadiene, 3,5-octadiene, 1,3-nonadiene, 2,4-nonadiene, 3,5-nonadiene, 1,3-decadiene, 2,4-decadiene, and 3,5-decadiene (optionally comprising less than 20 mol %, less than 5 mol %, such as less than 3 mol %, for example less than 1 mol %, for example less than 0.1 mol %) of comonomer(s).

[0089] In an embodiment, the functionalized polymer comprises 10% by weight (e.g., 9% by weight, such as 8% by weight, for example 7% by weight, such as 6% by weight, for example 5% by weight, such as 4% by weight, for example 3% by weight, such as 2% by weight, for example 1% by weight) or less of styrene monomer based on the weight of the functionalized polymer. In embodiments, styrene repeat units may not be present in the functionalized polymer. In embodiments, the functionalized polymer may be a block or tapered block copolymer that does not include a styrene block. In embodiments, the functionalized polymer may be a block copolymer or a tapered block copolymer comprising (or consisting of, or consisting essentially of) isoprene. In embodiments, the functionalized polymer may be a block copolymer or a tapered block copolymer comprising 50% or more by weight of isoprene, based on the weight of the copolymer. In an embodiment, the functionalized polymer is 4‐5 Conjugated diene (or C 4‐5 Consists of conjugated dienes or C 4‐5 Consisting essentially of conjugated dienes), preferably 50% by weight (e.g. 60% by weight, such as 70% by weight, such as 80% by weight, such as 90% by weight, such as 95% by weight, such as 98% by weight) or more of C based on the weight of the copolymer. 4‐5 It may be a block copolymer or a tapered block copolymer containing a conjugated diene. In an embodiment, the functionalized polymer may be a copolymer that includes 50% by weight or more (e.g., 60% by weight, such as 70% by weight, such as 80% by weight, such as 90% by weight, such as 95% by weight, such as 98% by weight) isoprene based on the weight of the copolymer. In an embodiment, the functionalized polymer may be a copolymer that includes 50% by weight or more (e.g., 60% by weight, such as 70% by weight, such as 80% by weight, such as 90% by weight, such as 95% by weight, such as 98% by weight) butadiene based on the weight of the copolymer. In an embodiment, the functionalized polymer may be a copolymer that includes 50% by weight (e.g., 60% by weight, such as 70% by weight, such as 80% by weight, such as 90% by weight, such as 95% by weight, such as 98% by weight) or more butadiene and isoprene based on the weight of the copolymer. In embodiments, the functionalized polymer may be a diblock copolymer comprising at least one block of isoprene homopolymer or copolymer. Optionally, butadiene repeat units may be absent from the functionalized polymer. Optionally, the functionalized polymer need not be a homopolyisobutylene. Optionally, the functionalized polymer need not be a copolymer of isoprene and butadiene.

[0090] Generally, the polymerized conjugated diene in the functionalized polymer comprises monomer units inserted into the growing polymer chain by conjugated and non-conjugated addition. In embodiments, 13 The functionalized polymer contains at least about 50%, such as at least about 75%, such as about 80%, for example about 85% to about 100%, of conjugated addition insertions based on the total number of conjugated addition insertions and non-conjugated addition insertions, as determined by C NMR. The insertion of isoprene occurs most frequently by 2,1 insertion, 1,4 insertion (trans and cis), and 3,4 insertion of isoprene (insertion configurations are 1 1 H NMR). 1 As measured by H NMR, the functionalized isoprene polymer contains at least about 50%, such as at least about 75%, such as at least about 80%, such as at least about 90%, such as at least about 95%, such as at least 98% 1,4 insertions, based on the total of 2,1, 1,4, and 3,4 insertions of isoprene. For purposes of this disclosure: 1) the expression "1,4 insertion" includes 1,4 insertions and 4,1 insertions, 2) the expression "2,1 insertion" includes 2,1 insertions and 1,2 insertions, and 3) the expression "3,4 insertion" includes 3,4 insertions and 4,3 insertions.

[0091] The functionalized polymer may be a homopolymer or a copolymer. Optionally, the functionalized polymer may include a homopolymer or copolymer of isoprene. The copolymer may be a random copolymer, a tapered block copolymer, a star copolymer, or a block copolymer. The Mn of the functionalized polymer may typically be from 20,000 to 150,000 g / mol, alternatively from 20,000 to about 150,000 g / mol, alternatively from 30,000 to about 125,000 g / mol, alternatively from 35,000 to about 100,000 g / mol, alternatively from 40,000 to 80,000 g / mol (GPC-PS). The Mn / Mw(GPC-PS) of the polymer before functionalization may typically be 1.0-2, such as 1.1-1.5, such as 1.1-1.3, such as 1.1-1.2. When functionalization occurs, the Mw / Mn range may be broadened. The Mw / Mn (GPC-PS) of the functionalized polymer may typically be 1 to 3, alternatively 1 to 2, alternatively from greater than 1 to less than 2, alternatively from 1.05 to 1.9, alternatively from 1.10 to 1.8, alternatively from 1.10 to 1.7, alternatively from 1.12 to 1.6, alternatively from 1.13 to 1.5, alternatively from 1.15 to 1.4, alternatively from 1.15 to 1.3. Alternatively, the Mw / Mn of the functionalized polymer may typically be 1, or from greater than 1 to less than 2 (such as less than 1.8, such as less than 1.7, such as less than 1.6, such as less than 1.4, such as less than 1.2, such as less than 1.15, such as less than 1.12, for example less than 1.10). In embodiments, the saponification number (SAP) of the functionalized polymer, as measured by ASTM D94, may be greater than or equal to 25 (eg, 28, such as 30, such as 32, such as 34) mg KOH / g. In embodiments, the functionalized polymer may contribute 17% or more (eg, 20% or more, such as 17-40%, such as 20-30%) to the saponification number of the lubricating oil composition. In an embodiment, the average functionality of the functionalized polymer as measured by GPC-PS may be from 1.4 to 20 FG grafts / polymer chain, such as from 1.4 to 15 FG grafts / polymer chain, such as from 3 to 12.5 FG grafts / polymer chain, such as from 4 to 10 FG grafts / polymer chain. The average functionality of the functionalized polymer as measured by GPC-PS may be 15 (eg, 14, 13, 12, 11, 10, 9, 8, 7, or 6) or less FG grafts / polymer chain. The average functionality of the functionalized polymer as measured by GPC-PS may be 1 (e.g., 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, or 4.0) or more of FG grafts / polymer chain. The average functionality of the functionalized polymer as measured by GPC-PS may be 1 (e.g., 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, or 4.0) to 15 (e.g., 14, 13, 12, 11, 10, 9, 8, 7, or 6) FG grafts / polymer chain. In an embodiment, the aromatic content of the functionalized polymer may be 5% or less, such as 3% or less, such as 1% or less, such as 0%, based on the weight of the polymer. In an embodiment, the functionalized polymer is a branched C 2 -C 1 -C 2 -H 2 O 4 polymer having a Mn of 20,000 to 500,000 g / mol and a Mw / Mn of 2 or less, e.g., 1 to 2.0, as measured by GPC-PS. 4‐5 It may also include acylated polymers of the monomers. In embodiments, the number average molecular weight (Mn) of the functionalized polymer as measured by GPC-PS may be 20,000 (eg, 25,000, such as 30,000, such as 35,000, such as 40,000) g / mol or greater.

[0092] In an embodiment, the weight average molecular weight (Mw) of the functionalized polymer as measured by GPC-PS may be up to 50,000 (e.g., 40,000, e.g., 35,000) g / mol. In an embodiment, the weight average molecular weight (Mw) of the functionalized polymer as measured by GPC-PS may be from 1,000 to 50,000 g / mol, e.g., from 5,000 to 40,000 g / mol. In an embodiment, the z-average molecular weight (Mz) of the functionalized polymer may be from 5,000 to 150,000 g / mol, such as from 10,000 to 150,000 g / mol, for example from 15,000 to 70,000 g / mol, for example from 20,000 to 150,000 g / mol, alternatively from 20,000 to about 150,000 g / mol, alternatively from 30,000 to about 125,000 g / mol, alternatively from 35,000 to about 100,000 g / mol, alternatively from 40,000 to 80,000 g / mol, alternatively from 40,000 to 60,000 g / mol (GPC-PS). In embodiments, the functionalized polymer may have a gel content of less than about 5%, less than 3%, less than 2%, less than 1%, less than 0.5%, less than 0.1%, or 0% by weight, where the gel content is measured by determining the amount of material that is extractable from the polymer using boiling xylene (or cyclohexane) as an extractant. The percentage of soluble and insoluble (gel) material in the polymer composition is determined as described herein. In an embodiment, the functionalized polymer may have a functionality distribution (Fd) value of 3.5 or less (e.g., 3.4 or less, e.g., 1-3.3, e.g., 1.1-3.2, e.g., 1.2-3.0, e.g., 1.4-2.9, measured by GPC-PS). The functionality distribution (Fd) value is measured as described in the Examples section below, and the average functionality measured by GPC-PS is 1.4-20 FG grafts / polymer chain, e.g., 1.4-15 FG grafts / polymer chain, e.g., 3-12.5 FG grafts / polymer chain, e.g., 4-10 FG grafts / polymer chain.

[0093] The present disclosure provides a C 2 O 4 copolymer having an Mw / Mn of less than 2 and a functionality distribution (Fd) value of 3.5 or less (e.g., 3.4 or less, e.g., 1 to 3.3, e.g., 1.1 to 3.2, e.g., 1.2 to 3.0, e.g., 1.4 to 2.9, as measured by GPC-PS). 4‐5 Contains olefins (C 4‐5 Consists essentially of olefins, or 4‐5 This invention relates to amide, imide, and / or ester functionalized hydrogenated / saturated polymers of olefins, in which if the polymer before functionalization is a C4 olefin polymer such as polyisobutylene, polybutadiene, or copolymers thereof (preferably polyisobutylene or copolymers of isobutylene and butadiene), the Mn of the C4 olefin polymer is 10,000 g / mol or more (GPC-PS), and if the polymer before functionalization is a C4 / C5 copolymer of isoprene and butadiene, the Mn of the copolymer is greater than 25,000 Mn (GPC-PS). The present disclosure also relates to amide, imide, and / or ester functionalized hydrogenated / saturated polymers having 90 mole % or more of isoprene repeat units, a Mw / Mn less than 2, and a functionality distribution (Fd) value of 3.5 or less (e.g., 3.4 or less, e.g., 1-3.3, e.g., 1.1-3.2, e.g., 1.2-3.0, e.g., 1.4-2.9, as measured by GPC-PS), where the Mn of the polymer before functionalization is 30,000 g / mol or more (GPC-PS).

[0094] The present disclosure also relates to amide, imide, and / or ester functionalized hydrogenated / saturated homopolymers of isoprene having a Mw / Mn less than 2 and a functionality distribution (Fd) value of 3.5 or less (e.g., 3.4 or less, e.g., 1-3.3, e.g., 1.1-3.2, e.g., 1.2-3.0, e.g., 1.4-2.9, as measured by GPC-PS), where the Mn of the polymer before functionalization is 30,000 g / mol or more (as measured by GPC-PS). Lubricating compositions according to the present disclosure may further include one or more additives such as detergents, friction modifiers, antioxidants, pour point depressants, antifoam agents, viscosity modifiers, dispersants, corrosion inhibitors, antiwear agents, extreme pressure additives, demulsifiers, seal compatibility agents, seal swell agents, additive diluent base oils, etc. Specific examples of such additives are described in the Kirk-Othmer Encyclopedia of Chemical Technology, Third Edition, Vol. 14, pp. 477-526, some of which are described in further detail below.

[0095] C. Detergent In addition to the above combinations or mixtures of overbased calcium and overbased magnesium detergents, the lubricating oil compositions and concentrate compositions may also include one or more additive metal detergents (e.g., blends of metal detergents), also referred to as "detergent additives." 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 include a polar head and a long hydrophobic tail, the polar head including a metal salt of an acidic organic compound. The salt may contain substantially stoichiometric amounts of metal, in which case the salt is typically a normal or neutral salt, and its total base number ("TBN", as measured by ASTM D2896) is typically up to 150 mg KOH / g, e.g., 0 to 80 (or 5 to 30) mg KOH / g. Large amounts of metal base may be incorporated by reacting an excess of a metal compound (e.g., oxide or hydroxide) with an acid gas (e.g., carbon dioxide). Such detergents, sometimes referred to as overbased detergents, may have a TBN of 100 mgKOH / g or more (e.g. 200 mgKOH / g or more), typically 250 mgKOH / g or more, for example 300 mgKOH / g or more, for example 200 to 800 mgKOH / g, 225 to 700 mgKOH / g, 250 to 650 mgKOH / g, or 300 to 600 mgKOH / g, for example 150 to 650 mgKOH / g.

[0096] Suitable detergents include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, naphthenates, and other oil-soluble carboxylates of metals, especially 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), especially sodium, potassium, lithium, calcium, and magnesium, e.g., Ca and / or Mg. Additionally, detergents may include hybrid detergents that include 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 Group 1 and / or Group 2 metals. Preferably, the detergent additive(s) useful in the present disclosure comprises calcium and / or magnesium metal salt. The detergent may be a calcium and / or magnesium carboxylate (e.g., salicylate), sulfonate, or phenate detergent. More preferably, the detergent additive is selected from magnesium salicylate, calcium salicylate, magnesium sulfonate, calcium sulfonate, magnesium phenate, calcium phenate, and hybrid detergents comprising two, three, four, or more of these detergents, and / or combinations thereof. Metal-containing detergents also include "hybrid" detergents formed with mixed surfactant systems containing phenate and / or sulfonate components, such as phenate / salicylate, sulfonate / phenate, sulfonate / salicylate, sulfonate / phenate / salicylate.These are described, for example, in U.S. Patent Nos. 6,429,178; 6,429,179; 6,153,565; and 6,281,179.For example, when a hybrid sulfonate / phenate detergent is employed, the hybrid detergent is considered to be equivalent in amount to the separate phenate and sulfonate detergents that incorporate the same amount of phenate and sulfonate soap, respectively.

[0097] The overbased metal-containing detergent may be a sodium, calcium, magnesium salt of a phenate, a sulfur-containing phenate, a sulfonate, a salixarate, and a salicylate, or a mixture thereof. The total base number TBN of the overbased phenates and salicylates is usually 180 to 650 mg KOH / g, for example 200 to 450 mg KOH / g. The total base number of the overbased sulfonates is usually 250 to 600 mg KOH / g, or 300 to 500 mg KOH / g. In an embodiment, the sulfonate detergent may be based on a linear alkylbenzene sulfonate detergent having a metal ratio of at least 8, as described in U.S. Patent Application Publication No. 2005 / 065045 (and issued as U.S. Patent No. 7,407,919), paragraphs

[0026] to

[0037] . The overbased detergent may be present at 0 to 15 mass %, or 0.1 to 10 mass %, or 0.2 to 8 mass %, or 0.2 to 3 mass %, based on the lubricating composition. For example, in a heavy duty diesel engine, the detergent may be present at 2 to 3 mass % of the lubricating composition. In a passenger car engine, the detergent may be present at 0.2 to 1 mass % of the lubricating composition. The detergent additive(s) may comprise one or more magnesium sulfonate detergents. The magnesium detergents may be neutral salts or overbased salts. Suitably, the magnesium detergents are overbased magnesium sulfonates having a TBN of 5 to 700 mg KOH / g (ASTM D2896), or 7 to 600 mg KOH / g, or 9 to 500 mg KOH / g, or 80 to 650 mg KOH / g, such as 200 to 500 mg KOH / g, for example 240 to 450 mg KOH / g.

[0098] Alternatively, the detergent additive(s) is magnesium salicylate. Suitably the magnesium detergent is a magnesium salicylate having a TBN of 5 to 700 mg KOH / g (ASTM D2896), alternatively 7 to 600 mg KOH / g, alternatively 9 to 500 mg KOH / g, alternatively 30 to 650 mg KOH / g, such as 50 to 500 mg KOH / g, for example 200 to 500 mg KOH / g, for example 240 to 450 mg KOH / g, alternatively 150 mg KOH / g or less, such as 100 mg KOH / g or less. Alternatively, the detergent additive(s) is a combination of magnesium salicylate and magnesium sulfonate. The magnesium detergent provides the lubricating composition with an atomic magnesium amount of from 200 to 4000 ppm, preferably from 200 to 2000 ppm, 300 to 1500 ppm, or 450 to 1200 ppm (ASTM D5185). The detergent composition may comprise (or consist of) a combination of one or more magnesium sulfonate detergents and one or more calcium salicylates detergents.

[0099] The combination of the one or more magnesium sulfonate detergents with the one or more calcium salicylate detergents results in a lubricating composition comprising: 1) 200 to 4000 ppm of magnesium atoms, suitably 200 to 2000 ppm, 300 to 1500 ppm, or 450 to 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, for example 500 to 4000 ppm, preferably 750 to 3000 ppm, more preferably 900 to 2000 ppm of atomic calcium (ASTM D5185). The detergent may include one or more calcium detergents, such as a calcium carboxylate (eg salicylate), sulfonate, or phenate detergent. Suitably, the TBN of the calcium detergent is from 30 to 1400 mg KOH / g (ASTM D2896), such as from 80 to 1200 mg KOH / g, for example from 100 to 1000 mg KOH / g, such as from 150 to 800 mg KOH / g, for example from 200 to 600 mg KOH / g, such as from 240 to 550 mg KOH / g, or not more than 150 mg KOH / g, such as not more than 100 mg KOH / g, or not less than 200 mg KOH / g, or not less than 300 mg KOH / g, or not less than 350 mg KOH / g. The TBN of the calcium detergent is preferably greater than or equal to 500 mg KOH / g, or 600 mg KOH / g, or 700 mg KOH / g, or 800 mg KOH / g, or 1000 mg KOH / g, or 1200 mg KOH / g, or 1300 mg KOH / g, or 1400 mg KOH / g.

[0100] Suitably the calcium detergent is a calcium salicylate, sulfonate or phenate having a TBN of 30 to 1400 mg KOH / g, 30 to 1200 mg KOH / g (ASTM D2896), such as 50 to 1000 mg KOH / g, for example 200 to 800 mg KOH / g, for example 240 to 600 mg KOH / g, alternatively 150 mg KOH / g or less, for example 100 mg KOH / g or less, or 200 mg KOH / g or more, or 300 mg KOH / g or more, or 350 mg KOH / g or more, or 500 mg KOH / g or more, or 700 mg KOH / g or more, or 900 mg KOH / g or more, or 1100 mg KOH / g or more, or 1300 mg KOH / g or more. Calcium detergents are typically present in an amount sufficient to provide at least 500 ppm, preferably at least 750 ppm, more preferably at least 900 ppm of atomic calcium in the lubricating oil composition (ASTM D5185). If present, the optional calcium detergent is suitably present in an amount sufficient to provide not more than 4000 ppm, preferably not more than 3000 ppm, more preferably not more than 2000 ppm of atomic calcium in the lubricating oil composition (ASTM D5185). If present, the optional calcium detergent is suitably present in an amount sufficient to provide from 500 to 4000 ppm, preferably from 750 to 3000 ppm, more preferably from 900 to 2000 ppm of atomic calcium in the lubricating oil composition (ASTM D5185). Suitably, the total atomic amount of metals from detergents contained in the lubricating oil composition according to all embodiments of the present disclosure is 5000 ppm or less, preferably 4000 ppm or less, more preferably 2000 ppm or less (ASTM D5185). The total atomic amount of metals from detergents contained in the lubricating oil composition according to all embodiments of the present disclosure is suitably at least 500 ppm, preferably at least 800 ppm, more preferably at least 1000 ppm (ASTM D5185). The total atomic amount of metals from detergents contained in the lubricating oil composition according to all embodiments of the present disclosure is suitably 500 to 5000 ppm, preferably 500 to 3000 ppm, more preferably 500 to 2000 ppm (ASTM D5185).

[0101] Sulfonate detergents may be prepared from sulfonic acids which are typically obtained by sulfonation of alkyl-substituted aromatic hydrocarbons, for example by fractionation of petroleum or alkylation of aromatic hydrocarbons. Examples of sulfonate detergents include detergents 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 using an alkylating agent having from about 3 to less 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 metal oxides, hydroxides, alkoxides, carbonates, carboxylates, sulfides, hydrosulfides, nitrates, borates, and ethers. The amount of metal compound is selected taking into consideration the desired TBN of the final product, but is usually in the range of about 100 to 220% by mass (preferably at least 125% by mass), which is the stoichiometrically required amount.

[0102] Metal salts of phenols and sulfurized phenols may be prepared by reaction with appropriate metal compounds such as oxides or hydroxides to give neutral or overbased products by methods well known in the art. Sulfurized phenols may be prepared by reacting phenol with sulfur or a sulfur-containing compound such as hydrogen sulfide, sulfur monohalides, or sulfur dihalides to form a product that is generally a mixture of compounds in which two or more phenols are bridged by a sulfur-containing bridge. Carboxylate detergents, such as salicylates, are derived from aromatic carboxylic acids (e.g., C 5‐100 , C 9‐30 , C 14‐24The aromatic carboxylic acids can be prepared by reacting an alkyl substituted hydroxybenzoic acid (alkyl substituted hydroxybenzoic acid) with a suitable metal compound such as an oxide or hydroxide to give a neutral or overbased product 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, fused or linked via alkylene bridges.

[0103] The preferred substituents in oil-soluble salicylic acids are alkyl substituents. In alkyl-substituted salicylic acids, the number of carbon atoms in the alkyl group is advantageously 5 to 100, preferably 9 to 30, and particularly 14 to 20. When there are multiple alkyl groups, the average number of carbon atoms in all the alkyl groups is preferably at least 9 to ensure adequate oil solubility. In an embodiment, the ratio of detergent atomic metal to atomic molybdenum in the lubricating oil composition may be less than 3:1, such as less than 2:1. Additionally, metal organic and inorganic base salts used as detergents can contribute to the sulfated ash content of the lubricating oil composition, and therefore, in embodiments of the present disclosure, the amount of such additives is minimized. To maintain low sulfur levels, salicylate detergents can be used, and the lubricating compositions herein may include one or more salicylate detergents, preferably used in an amount ranging from 0.05 to 20.0 mass %, more preferably 1.0 to 10.0 mass %, and most preferably 2.0 to 5.0 mass %, based on the total mass of the lubricating composition.

[0104] The total sulfated ash content of the lubricating compositions herein, as measured by ASTM D874, typically is at a level of 2.0 mass% or less, alternatively 1.0 mass% or less, alternatively 0.8 mass% or less, based on the total mass of the lubricating composition. Furthermore, the TBN (total base number) value of each detergent measured according to ISO 3771 is independently in the range of 10 to 700 mgKOH / g, in the range of 10 to 500 mgKOH / g, alternatively in the range of 100 to 650 mgKOH / g, alternatively in the range of 10 to 500 mgKOH / g, alternatively in the range of 30 to 350 mgKOH / g, or alternatively in the range of 50 to 300 mgKOH / g. The sulfonate detergent (eg, Ca and / or Mg sulfonate detergent) may be present in an amount to provide 0.1 to 1.5 mass %, or 0.15 to 1.2 mass %, or 0.2 to 0.9 mass % of the sulfonate soap in the lubricant composition. The salicylate detergent (eg, Ca and / or Mg salicylate detergent) is present in an amount to provide 0.3 to 1.4 mass %, or 0.35 to 1.2 mass %, or 0.4 to 1.0 mass % salicylate soap in the lubricant composition. The sulfonate soap may be present in an amount from 0.2 to 0.8% by weight of the lubricant composition, and the salicylate soap may be present in an amount from 0.3 to 1.0% by weight of the lubricant composition.

[0105] The total of all alkaline earth metal detergent soaps may be present in an amount from 0.6 to 2.1 percent by weight, or from 0.7 to 1.4 percent by weight of the lubricant composition. Typically, lubricating compositions formulated for use in heavy duty diesel engines contain from about 0.1 to about 10%, alternatively from about 0.5 to about 7.5%, alternatively from about 1 to about 6.5%, by weight of the lubricating composition, of a detergent. Typically, lubricating compositions formulated for use in passenger vehicle engines contain from about 0.1 to about 10%, alternatively from about 0.5 to about 7.5%, alternatively from about 1 to about 6.5%, by weight of the lubricating composition, of detergent. Typically, lubricating compositions formulated for use in a drivetrain (e.g., a transmission) contain from about 0.1 to about 10 percent, alternatively from about 0.5 to about 7.5 percent, alternatively from about 2 to about 6.5 percent, by weight of the lubricating composition, of a detergent.

[0106] D. Friction modifiers A friction modifier is any material or materials capable of changing the coefficient of friction of a surface lubricated by any lubricant or fluid containing such material or materials. Friction modifiers, also known as friction reducers, lubricity agents, or oiliness agents, and other such agents that modify the ability of a base oil, formulated lubricant composition, concentrated composition, or functional fluid to change the lubricated surface friction coefficient, may be effectively used in combination with the base oil or lubricant composition of the present disclosure, if necessary. Friction modifiers that reduce the coefficient of friction are particularly advantageous in combination with the base oil and lubricant composition of the present disclosure. Examples of friction modifiers include organometallic compounds or materials, or mixtures thereof.Exemplary organometallic friction modifiers useful in the lubricating oil formulations of the present disclosure include, for example, tungsten and / or molybdenum compounds, such as molybdenum amines, molybdenum diamines, organotungstates, molybdenum dithiocarbamates, molybdenum dithiophosphates, molybdenum amine complexes, molybdenum carboxylates, and the like, and mixtures thereof.Convenient examples of useful molybdenum-containing compounds include molybdenum dithiocarbamates, such as trinuclear molybdenum compounds described in WO 98 / 26030, molybdenum sulfides, and molybdenum dithiophosphates.

[0107] Other known friction modifiers include oil-soluble organo-molybdenum compounds. Such organo-molybdenum friction modifiers can provide reliable antioxidant and antiwear properties to lubricating oil compositions. Examples of such oil-soluble organo-molybdenum compounds include dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, sulfides, and the like, and mixtures thereof. Molybdenum dithiocarbamates, dialkyldithiophosphates, alkylxanthates, and alkylthioxanthates are particularly preferred. The molybdenum compound may also be an acidic molybdenum compound. These compounds react with basic nitrogen compounds, usually hexavalent, as determined by the ASTM test D664 or D2896 titration procedures. Molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates, as well as other molybdenum salts, such as sodium hydrogen molybdate, MoOC 14 , MoO2Br2, Mo2O3C 16 , molybdenum trioxide, or similar acidic molybdenum compounds. Molybdenum compounds useful in the compositions of the present disclosure include organo-molybdenum compounds of the formula Mo(R"OCS2)4 and Mo(R"SCS2)4, where R" is an organo group selected from the group consisting of alkyl, aryl, aralkyl, and alkoxyalkyl, generally having from 1 to 30 carbon atoms, preferably from 2 to 12 carbon atoms, most preferably alkyl having from 2 to 12 carbon atoms. Dithiocarbamates of molybdenum are particularly preferred.

[0108] Another group of organo-molybdenum compounds useful in the lubricating compositions of the present disclosure includes trinuclear molybdenum compounds, particularly those of the formula MoS k L n Q z and mixtures thereof, where L is an independently selected ligand having an organo group with a sufficient number of carbon atoms to solubilize or disperse the compound in oil, n is 1-4, k is 4-7, Q is selected from the group of neutral electron donor compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0-5, including non-stoichiometric values. At least 21, e.g., at least 25, at least 30, or at least 35 carbon atoms may be present between all ligands / organo groups. Lubricating oil compositions useful in all aspects of the present disclosure preferably contain at least 10 ppm, at least 12 ppm, or at least 20 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, no more than 500 ppm, no more than 350 ppm, or more preferably no more than 200 ppm molybdenum. Lubricating oil compositions useful in all aspects of the present disclosure preferably contain from 12 to 350 ppm, e.g., from 12 to 500 ppm, or from 20 to 200 ppm molybdenum (measured as molybdenum atoms).

[0109] For more detailed information on useful friction modifiers containing Mo, please refer to the specification of U.S. Patent No. 10,829,712 (paragraph 8, line 58 to paragraph 11, line 31). Particularly preferred friction modifiers containing Mo of the present disclosure are dimeric molybdenum dialkyldithiocarbamate (moly dimer), trimer molybdenum dialkyldithiocarbamate (moly trimer), or combinations thereof. Ashless friction modifiers may be included in the lubricating oil composition of the present disclosure and are generally known and include esters formed by reacting carboxylic acids and anhydrides with alkanols, and amine-based friction modifiers. Other useful friction modifiers generally contain a polar end 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 in M. Belzer, Journal of Tribology, Vol. 114, pp. 675-682, 1992, and M. Belzer and S. Jahanmir, Lubrication Science, Vol. 1, pp. 3-26, 1988. Typically, the total amount of organic ashless friction modifiers in a lubricant according to the present disclosure is 5 mass % or less, preferably 2 mass % or less, more preferably 0.5 mass % or less, based on the total mass of the lubricating oil composition.

[0110] Examples of friction modifiers useful in the lubricating compositions described herein include alkoxylated fatty acid esters, alkanolamides, polyol fatty acid esters, borated glycerol fatty acid esters, fatty alcohol ethers, and mixtures thereof. Examples of alkoxylated fatty acid esters include polyoxyethylene stearate, fatty acid polyglycol esters, etc. Examples of these include polyoxypropylene stearate, polyoxybutylene stearate, polyoxyethylene isostearate, polyoxypropylene isostearate, polyoxyethylene palmitate, etc. Examples of alkanolamides include lauric acid diethylalkanolamide, palmitic acid diethylalkanolamide, etc. Examples of these include oleic acid diethyalkanolamide, stearic acid diethylalkanolamide, oleic acid diethylalkanolamide, polyethoxylated hydrocarbyl amides, polypropoxylated hydrocarbyl amides, etc. Examples of polyol fatty acid esters include glycerol monooleate, saturated mono-, di-, and tri-glyceride esters, glycerol monostearate, etc. Examples of these include polyol esters, hydroxyl-containing polyol esters, and the like.

[0111] Examples of borated glycerol fatty acid esters include borated glycerol monooleate, borated saturated mono-, di-, and tri-glyceride esters, borated glycerol monostearate, etc. Besides glycerol polyols, examples include trimethylolpropane, pentaerythritol, sorbitan, etc. These esters can be polyol monocarboxylates, polyol dicarboxylates, and optionally polyol tricarboxylates. Glycerol monooleate, glycerol dioleate, glycerol trioleate, glycerol monooleate, glycerol ditearate, glycerol tristearate, and their corresponding glycerol monopalmitate, glycerol dipalmitate, glycerol tripalmitate, and their respective isostearate, linoleate, etc. are preferred. In particular, fatty acid esters which utilize glycerol as the base polyol and which have been ethoxylated, propoxylated, and / or butoxylated polyols are useful herein. Examples of fatty alcohol ethers include stearyl ether, myristyl ether, etc. Number of carbon atoms: C3 to C 50 Alcohols such as the alcohols of the formula (I) can be ethoxylated, propoxylated, or butoxylated to form the corresponding fatty alkyl ethers. The base alcohol portion is preferably selected from the group consisting of stearyl, myristyl, C 11 -C 13 It can be a hydrocarbon, oleyl, isosteryl, and the like.

[0112] Useful concentrations of friction modifiers may range from 0.01 to 5% by weight, or from about 0.01 to about 2.5% by weight, or from about 0.05 to about 1.5% by weight, or from about 0.051 to about 1% by weight. Concentrations of molybdenum-containing materials are often described in terms of Mo metal concentration. Concentrations of Mo are advantageously in the range of 12 to 350 ppm or more, and often in the range of 20 to 200 ppm is preferred. All types of friction modifiers may be used alone or in mixtures with the materials of the present disclosure. In many cases, mixtures of two or more friction modifiers, or mixtures of friction modifier(s) with alternative surface active material(s) are also desirable. For example, combinations of Mo-containing compounds with polyol fatty acid esters, such as glycerol monooleate, are useful herein.

[0113] E. Antioxidants Antioxidants retard the oxidative degradation of base oils during service. Such degradation can result in deposits on metal surfaces, sludge formation, viscosity increase of the lubricant, etc. A wide variety of antioxidants are useful in lubricating oil compositions. See, for example, Klamann, "Lubricants and Related Products", Wiley VCH, 1984; U.S. Pat. Nos. 4,798,684 and 5,084,197. Useful antioxidants include hindered phenols. These phenolic antioxidants may be ashless (metal-free) phenolic compounds or neutral or basic metal salts of certain phenolic compounds. Typical phenolic antioxidant compounds are hindered phenols containing sterically hindered hydroxyl groups, which include derivatives of dihydroxyaryl compounds in which the hydroxyl groups are in the ortho- or para-position to each other. Typical phenolic antioxidants include C 6+Included are alkyl-substituted hindered phenols and alkylene-linked derivatives of these hindered phenols. Examples of this type of phenolic material include 2-t-butyl-4-heptylphenol; 2-t-butyl-4-octylphenol; 2-t-butyl-4-dodecylphenol; 2,6-di-t-butyl-4-heptylphenol; 2,6-di-t-butyl-4-dodecylphenol; 2-methyl-6-t-butyl-4-heptylphenol; and 2-methyl-6-t-butyl-4-dodecylphenol. Other useful hindered monophenolic antioxidants include, for example, hindered 2,6-di-alkyl-phenolic propionate derivatives. Bisphenolic antioxidants may also be advantageously used herein. Examples of ortho-linked 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-linked bisphenols include, for example, 4,4'-bis(2,6-di-t-butyl-phenol) and 4,4'-methylene-bis(2,6-di-t-butyl-phenol).

[0114] An effective amount of one or more catalytic antioxidants may also be used. The catalytic antioxidant comprises an effective amount of a) one or more oil-soluble polymetallic organic compounds; and an effective amount of b) one or more substituted N,N'-diaryl-o-phenylenediamine compounds, or c) one or more hindered phenol compounds; or a combination of b) and c). Catalytic antioxidants useful herein are more fully described in U.S. Pat. No. 8,048,833. Non-phenolic antioxidants that may be used include aromatic amine antioxidants, which may be used on their own or in combination with phenols. Typical examples of non-phenolic antioxidants include: alkylated and non-alkylated aromatic amines, such as those of the formula R8R9R 10 N aromatic monoamines, in which R8 is an aliphatic, aromatic, or substituted aromatic group, R9 is an aromatic or substituted aromatic group, and R10 is H, alkyl, aryl, or R 11 S(O) X R 12 where R 11 is an alkylene, alkenylene, or aralkylene group; R 12 is an alkyl, alkenyl, aryl, or alkaryl group, and x is 0, 1, or 2. The aliphatic group R8 may have from 1 to about 20 carbon atoms, preferably from about 6 to 12 carbon atoms. The aliphatic group is usually 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. The aromatic groups R8 and R9 may be bonded together with other groups, such as S. Typical aromatic amine antioxidants have alkyl substituents with at least about 6 carbon atoms. Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl, and decyl. Generally, the aliphatic groups have no more than about 14 carbon atoms. General types of amine antioxidants useful in the present compositions include diphenylamines, phenylnaphthylamines, phenothiazines, imidodibenzyls, and diphenylphenylenediamines. Mixtures of two or more aromatic amines are also useful. Polymeric amine antioxidants can also be used. Specific examples of aromatic amine antioxidants useful in the present disclosure include: p,p'-dioctyldiphenylamine; t-octylphenyl-alpha-naphthylamine; phenyl-alpha-naphthylamine; and p-octylphenyl-alpha-naphthylamine.

[0115] 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 the antioxidant additive. For example, sulfurized alkylphenols and their alkali metal or alkaline earth metal salts are also useful antioxidants herein. Suitably, the lubricating oil composition(s) of the present disclosure may comprise one or more sulfur-containing antioxidant(s) in an amount to provide the lubricating oil composition with 0.02 to 0.2 mass %, preferably 0.02 to 0.15 mass %, more preferably 0.02 to 0.1 mass %, and 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) can be a sulfurized C4-C 25 Olefin(s), sulfurized aliphatic (C7-C 29 ) hydrocarbyl fatty acid ester(s), ashless sulfurized phenolic antioxidant(s), sulfur-containing organo-molybdenum compound(s), and combinations thereof. For further information regarding sulfurized materials useful as antioxidants herein, see U.S. Pat. No. 10,731,101 (column 15, line 55 to column 22, line 12). Antioxidants useful herein include hindered phenols and / or arylamines. These antioxidants may be used individually, by type, or in combination with each other. Exemplary antioxidants include: Irganox™ L67, Irganox™ L135, Ethanox™ 4702, Lanxess Additin™ RC 7110, Ethanox™ 4782J, Irganox™ 1135, Irganox™ 5057, sulfurized lard oil, and palm oil fatty acid methyl esters. The antioxidant additives may be used in an amount of about 0.01 to 10 (alternatively 0.01 to 5 mass %, alternatively 0.01 to 3 mass %, alternatively 1 to 6 mass %, alternatively 2 to 5 mass %, alternatively 3 to 4 mass %, alternatively about 0.03 to 5 mass %, alternatively 0.05 to less than 3 mass %) based on the mass of the lubricating composition. Compositions according to the present disclosure may contain additives that have a different set of functions and also have a secondary effect as antioxidants (e.g., phosphorus-containing antiwear agents (e.g., ZDDP) may also have an antioxidant effect). These additives are not included as antioxidants for purposes of determining the amount of antioxidant in a lubricating oil composition or concentrate herein.

[0116] F. Pour Point Depressants If necessary, conventional pour point depressants (also known as lubricant flow improvers) may be added to the compositions of the present disclosure. These pour point depressants may be added to the 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 dialkyl fumarates, vinyl esters of fatty acids, and allyl vinyl ethers. Useful pour point depressants and / or their preparations are described in U.S. Patents 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. Such additives may be used in amounts of about 0.01 to 5 mass %, preferably about 0.01 to 1.5 mass %, based on the mass of the lubricating composition.

[0117] G. Foam inhibitor Advantageously, antifoam agents may be added to the lubricant compositions described herein. Antifoam agents prevent or delay the formation of a stable foam. Silicones and / or organic polymers are typical antifoam agents. For example, silicone oils or polysiloxanes such as polydimethylsiloxane provide antifoam properties. The foam inhibitor is a commercially available product and may be used in a small amount, for example, 5% by mass or less, 3% by mass or less, 1% by mass or less, 0.1% by mass or less, for example, 5% by mass to 0.1 ppm, for example, 3% by mass to 0.5 ppm, for example, 1% by mass to 10 ppm. For example, the lubricating oil composition may include an antifoam agent comprising a polyalkylsiloxane, such as a polydialkylsiloxane, e.g., where alkyl is C1-C 10 The alkyl group is, for example, polydimethylsiloxane (PDMS), also known as silicone oil. Alternatively, the siloxane is poly(R 3 ) siloxane, wherein R 3 are one or more of the same or different linear, branched, or cyclic hydrocarbyl, such as alkyl or aryl, typically having from 1 to 20 carbon atoms. For example, the lubricating oil composition may include a polymeric siloxane compound according to formula 1 below, where R 1 and R 2 is independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl, phenyl, naphthyl, alkyl substituted phenyl, or an isomer thereof (e.g., methyl, phenyl), and n is 2 to 1000, such as 50 to 450, or such as 40 to 100.

[0118] Additionally or alternatively, the lubricating oil composition may contain organo-modified siloxanes (OMS), such as polyethers (e.g., ethylene-propylene oxide copolymers), long chain hydrocarbyls (e.g., C 11 -C 100 alkyl), or aryl (e.g. C6-C 14 For example, the lubricating oil composition may include an organo-modified siloxane compound according to formula 1, where n is 2 to 2000, such as 50 to 450 (or for example 40 to 100), and R 1 and R 2 are the same or different, and optionally, R 1 and R 2are each independently an organo group, such as a polyether (e.g., ethylene-propylene oxide copolymer), a long chain hydrocarbyl (e.g., C 11 -C 100 alkyl), or aryl (e.g. C6-C 14 aryl). Preferably, R 1 and R 2 One of them is CH3. [ka] formula 1

[0119] Siloxanes according to Formula 1 are incorporated to provide from about 0.1 to less than about 30 ppm, or from about 0.1 to about 25 ppm, or from about 0.1 to about 20 ppm, or from about 0.1 to about 15 ppm, or from about 0.1 to about 10 ppm of Si based on the total weight of the lubricant composition. More preferably, the amount of Si is in the range of from about 3 to about 10 ppm. In embodiments, silicone antifoam agents useful herein are available from Dow Corning and Union Carbide, including, for example, FS-1265 (1000 centistokes) from Dow Corning, DC-200 from Dow Corning, and UC-L45 from Union Carbide. Silicone antifoam agents useful herein include polydimethylsiloxanes, phenyl-methylpolysiloxanes, linear, cyclic, or branched siloxanes, silicone polymers and copolymers, and / or organo-silicone copolymers. They may also be substituted or included with siloxane polyether copolymer antifoam agents available from OSI Specialties, Inc., Farmington Hills, Michigan. One such material is sold under the trade name SILWET-L-7220. Acrylate polymeric antifoam agents may also be used herein. Exemplary acrylate defoamers include a polyacrylate defoamer available from Monsanto Polymer Products known as PC-1244. A preferred acrylate polymeric antifoam agent useful herein is PX™ 3841 (i.e., an alkyl acrylate polymer) available from Dorf Ketl, also known as Mobilad™ C402. In an embodiment, a silicone defoamer and an acrylate defoamer can be used in combination, for example, a mass ratio of the silicone defoamer to the acrylate defoamer can be about 5: 1 to about 1: 5. See, for example, U.S. Patent Application Publication No. 2021 / 0189283.

[0120] H. Viscosity modifier Viscosity modifiers (also referred to as viscosity index improvers or viscosity improvers) can be included in the lubricating compositions and concentrate compositions described herein. Viscosity modifiers provide high and low temperature operability to the lubricant. These additives provide shear stability at high temperatures and acceptable viscosity at low temperatures. Suitable viscosity modifiers include high molecular weight hydrocarbons, polyesters, and viscosity modifier dispersants that function as both viscosity modifiers and dispersants. Typical molecular weights of these polymers are about 10,000 to 1,500,000 g / mol, more typically about 20,000 to 1,200,000 g / mol, and even more typically about 50,000 to 1,000,000 g / mol. Examples of suitable viscosity modifiers include linear or star polymers and copolymers of methacrylates, butadienes, olefins, or alkylated styrenes. Polyisobutylene is a commonly used viscosity modifier. Another suitable viscosity modifier is polymethacrylate (e.g., copolymers of alkyl methacrylates of various chain lengths), some formulations of which also act as pour point depressants. Other suitable viscosity modifiers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (e.g., copolymers of acrylates of various chain lengths). Specific examples include styrene-isoprene or styrene-butadiene based polymers with molecular weights of 50,000 to 200,000 g / mol. Copolymers useful as viscosity modifiers include those available from Chevron Oronite under the tradename "PARATONE™" (e.g., "PARATONE™ 8921", "PARATONE™ 68231", "PARATONE™ 8941"); those available from Afton Chemical under the tradename "HiTEC™" (e.g., HiTEC™ 5850B, and HiTEC™ 5777); and those available from Lubrizol under the tradename "Lubrizol™ 7067C". Hydrogenated polyisoprene star polymers useful as viscosity modifiers herein include those available from Infineum International under the tradenames, e.g., "SV200™" and "SV600™". Hydrogenated diene-styrene block copolymers useful as viscosity modifiers herein are available from Infineum International under the tradename, e.g., "SV50™". Polymers useful herein as viscosity modifiers include polymethacrylate or polyacrylate polymers, such as linear polymethacrylate or polyacrylate polymers available from Evnoik Industries under the trade name "Viscoplex™" (e.g., Viscoplex™ 6-954), or star polymers available from Lubrizol under the trade name Asteric™ (e.g., Lubrizol™ 87708 and Lubrizol™ 87725).

[0121] The vinyl aromatic-containing polymers useful herein as viscosity modifiers may be derived from vinyl aromatic hydrocarbon monomers, such as styrenic monomers, such as styrene. Exemplary vinyl aromatic-containing copolymers useful herein may be represented by the following general formula: A-B, where A is a polymeric block derived primarily from vinyl aromatic hydrocarbon monomers (e.g., styrene) and B is a polymeric block derived primarily from conjugated diene monomers (e.g., isoprene). 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, for example 12 cSt or less, but may also be diluted (e.g., in Group I, II, and / or III base stocks) to higher kinematic viscosities at 100°C of 40 cSt or more, for example 100 cSt or more, for example 1000 cSt or more, such as 1000-2000 cSt. Typically, the viscosity modifier may be used in an amount of from about 0.01 to about 10 mass %, such as from about 0.1 to about 7 mass %, for example from about 0.1 to about 4 mass %, for example from about 0.2 to about 2 mass %, for example from about 0.2 to about 1 mass %, and for example from about 0.2 to about 0.5 mass %, based on the total mass of the formulated lubricant composition. Viscosity modifiers are typically added as concentrates in large amounts of diluent oil. The "as delivered" viscosity modifier typically contains from 20 to 75 weight percent active polymer for polymethacrylate or polyacrylate polymers, or from 8 to 20 weight percent active polymer for olefin copolymers, hydrogenated polyisoprene star polymers, or hydrogenated diene-styrene block copolymers, in the "as delivered" polymer concentrate.

[0122] I. Dispersants During engine operation, oil-insoluble oxidation by-products are produced. Dispersants help to keep these by-products in solution and reduce their deposition on metal surfaces. The dispersants used in formulating the lubricating compositions herein may be ashless or have ash-forming properties. Preferably, the dispersants are ashless. So-called ashless dispersants are organic materials that do not substantially form ash upon combustion. For example, non-metal-containing dispersants or borated metal-free dispersants are considered ashless. In contrast, metal-containing detergents tend to form ash upon combustion. Dispersants useful herein typically comprise 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. The hydrocarbon chain typically has from 40 to 500 carbon atoms, for example from 50 to 400 carbon atoms.

[0123] Dispersants of (poly)alkenyl succinic acid derivatives A particularly useful class of dispersants includes (poly)alkenyl succinic acid derivatives, which are usually produced by the reaction of a long chain hydrocarbyl-substituted succinic acid compound, usually a hydrocarbyl-substituted succinic anhydride, with a polyhydroxy or polyamino compound. The long chain hydrocarbyl group which constitutes the lipophilic part of the molecule that confers solubility in oil is often a polyisobutylene group (typically the Mn of the long chain hydrocarbyl group, such as a polyisobutylene group, is 400-3000 g / mol, e.g. 450-2500 g / mol). Many examples of this type of dispersant are known commercially and in the literature. Examples of U.S. patents describing such dispersants include U.S. Pat. Nos. 3,172,892; 3,2145,707; 3,219,666; 3,316,177; 3,341,542; 3,444,170; 3,454,607; 3,541,012; 3,630,904; 3,632,511; 3,787,374, and 4,234,435. Other types of dispersants are described in U.S. Patent Nos. 3,036,003; 3,200,107; 3,254,025; 3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,413,347; 3,697,574; 3,725,277; 3,730,278; 3,800,281; 3,820,282; 3,830,283; 3,840,284; 3,850,285; 3,860,286; 3,870,287; 3,880,289; 3,900,289; 3,920,289; 3,940,289; 3,960,289; 3,980,289; 3,990,289; 3,100,289; 3,100,289; 3,100,289; 3,110,289; 3,120,289; 3,130,289; 3,140,289; 3,150,289; 3,160,289; 3,170,289; 3,180,289; 3,190,289; 3,200,289; 3,210,289; 3,220,289; 3,230,289; 3,240,289; 3,250,289; 3,300,289; 3,300,289 Dispersants useful herein are described in, for example, European Patent Applications Nos. 0 471 071 and 0 451 380, to which reference is made for the present purposes.

[0124] Hydrocarbyl-substituted succinic acid and hydrocarbyl-substituted succinic anhydride derivatives are useful dispersants. In particular, succinimides, succinic esters, or succinic ester amides prepared by reacting a hydrocarbon-substituted succinic acid or anhydride compound (usually having at least 25 carbon atoms in the hydrocarbon substituent, e.g., 28 to 400 carbon atoms) with at least one equivalent of a polyhydroxy or polyamino compound (e.g., an alkylene amine) are particularly useful herein. The number average molecular weight of the hydrocarbyl-substituted succinic acid and hydrocarbyl-substituted succinic anhydride derivatives may be at least 400 g / mol, such as at least 900 g / mol, such as at least 1500 g / mol, such as 400 to 4000 g / mol, such as 800 to 3000 g / mol, such as 2000 to 2800 g / mol, such as about 2100 to 2500 g / mol, such as about 2200 to about 2400 g / mol. Particularly useful succinimides herein are formed by the condensation reaction of: 1) a hydrocarbyl-substituted succinic anhydride, such as polyisobutylene succinic anhydride (PIBSA); and 2) a 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, tetraethylene pentamine (TEPA), pentaethylene hexamine (PEHA), N-phenyl-p-phenylenediamine (ADPA), and other polyamines having an average of 5, 6, 7, 8, or 9 nitrogen atoms per molecule. Mixtures having an average number of nitrogen atoms greater than 7 per polyamine molecule are commonly referred to as heavy polyamines or H-PAMs and may be commercially available under trade names such as HPA™ and HPA-X™ from Dow Chemical and E-100™ from Huntsman Chemical. Examples of hydroxy-substituted polyamines include N-hydroxyalkyl-alkylene polyamines such as N-(2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)piperazine, and / or N-hydroxyalkylated alkylenediamines, for example of the type described in U.S. Pat. No. 4,873,009. Examples of polyoxyalkylene polyamines include polyoxyethylene and / or polyoxypropylene diamines and triamines (and co-oligomers thereof) having an average Mn of about 200 to about 5000 g / mol. Products of this type are commercially available under the trade name Jeffamine™. Representative examples of useful succinimides are described 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 Canadian Patent No. 1,094,044.

[0125] The dispersant may comprise one or more optionally borated high molecular weight (Mn: 1600 g / mol or more, e.g., 1800-3000 g / mol) succinimides, and one or more optionally borated low molecular weight (Mn: less than 1600 g / mol) succinimides. Here, the high molecular weight may be 1600-3000 g / mol, e.g., 1700-2800 g / mol, e.g., 1800-2500 g / mol, e.g., 1850-2300 g / mol; the low molecular weight may be 600-1600 g / mol or less, e.g., 650-1500 g / mol, e.g., 700-1400 g / mol, e.g., 800-1300 g / mol, e.g., 850-1200 g / mol, e.g., 900-1150 g / mol, e.g., 900-1000 g / mol. The high molecular weight succinimide dispersant may be present in the lubricating composition in an amount of 0.5-10%, or 0.8-6%, or 1.0-5%, or 1.5-5%, or 1.5-4.0% by weight; the low molecular weight succinimide dispersant may be present in the lubricating composition in an amount of 1-5%, or 1.5-4.8%, or 1.8-4.6%, or 1.9-4.6%, or 2% or more by weight, for example 2-5% by weight. The difference in molecular weight between the low molecular weight succinimide and the high molecular weight succinimide may be 500 g / mol or more, for example 750 g / mol or more, for example 1000 g / mol or more, for example 1200 g / mol or more, for example 500-3000 g / mol, for example 750-2000 g / mol, for example 1000-1500 g / mol.

[0126] Succinic acid esters useful as dispersants include those formed by the condensation reaction of a hydrocarbyl-substituted succinic anhydride with an alcohol or polyol. For example, the condensation product of a hydrocarbyl-substituted succinic anhydride with pentaerythritol is a useful dispersant. The succinic acid ester amides useful herein are formed by the condensation reaction of hydrocarbyl-substituted succinic anhydrides with alkanolamines.Suitable alkanolamines include ethoxylated polyalkyl polyamines, propoxylated polyalkyl polyamines, and polyalkenyl polyamines, such as polyethylene polyamines, and / or propoxylated hexamethylene diamines.Representative examples are shown in U.S. Pat. No. 4,426,305. Hydrocarbyl-substituted succinic anhydride (e.g., PIBSA) esters of hydrocarbyl-bridged aryloxy alcohols are also useful as dispersants herein. For information regarding such dispersants, see U.S. Pat. No. 7,485,603, particularly column 2, line 65 to column 6, line 22 and column 23, line 40 to column 26, line 46. In particular, PIBSA esters of methylene-bridged naphthyloxyethanols (i.e., 2-hydroxyethyl-1-naphthol ether (or hydroxy-terminated ethylene oxide oligomeric ethers of naphthol)) are useful herein.

[0127] The molecular weight of the hydrocarbyl-substituted succinic anhydrides used in the previous paragraph is usually in the range of 350-4000 g / mol, such as 400-3000 g / mol, such as 450-2800 g / mol, such as 800-2500 g / mol. The (poly)alkenyl succinic acid derivatives described above can be post-reacted with various reagents, such as sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid. The dispersant may be included in the lubricant in an amount from 0.1 to 20% by mass of the composition, for example from 0.2 to 15% by mass, such as from 0.25 to 10% by mass, for example from 0.3 to 5% by mass, such as from 1.0 to 3.0% by mass of the lubricating oil composition. The (poly)alkenyl succinic acid derivatives described above can also be post-reacted with a boron compound, such as boric acid, a borate ester, or a highly borated dispersant, to form a borated dispersant which generally contains from about 0.1 to about 5 moles of boron per mole of dispersant reaction product. Dispersants useful herein include borated succinimides, such as mono-succinimides, bis-succinimides, and / or derivatives derived from mixtures of mono-succinimides and bis-succinimides, where the hydrocarbyl succinimides are derived from hydrocarbylene groups, 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 from about 1000 to about 2000 g / mol, or mixtures of such hydrocarbylene groups, often with high terminal vinylic groups.

[0128] The boron containing dispersant may comprise 0.01 to 20 mass %, or 0.1 to 15 mass %, or 0.1 to 10 mass %, or 0.5 to 8 mass %, or 1.0 to 6.5 mass %, or 0.5 to 2.2 mass % of the lubricating composition. The boron-containing dispersant may be present in an amount to provide from 15 to 2000 ppm, or from 25 to 1000 ppm, or from 40 to 600 ppm, or from 80 to 350 ppm of boron to the composition. Borated dispersants may be used in combination with non-borated dispersants, which may be the same compound as the non-borated dispersant, or may be different compounds. In one embodiment, the lubricating composition may include one or more boron-containing dispersants and one or more non-borated dispersants, where the total amount of dispersants is 0.01 to 20 mass %, or 0.1 to 15 mass %, or 0.1 to 10 mass %, or 0.5 to 8 mass %, or 1.0 to 6.5 mass %, or 0.5 to 2.2 mass %, of the lubricating composition, and the ratio of borated dispersant to non-borated dispersant is 1:10 to 10:1 (mass:mass), or 1:5 to 3:1, or 1:3 to 2:1. The dispersant may comprise one or more borated or non-borated poly(alkenyl) succinimides, where the polyalkyenyl is derived from polyisobutylene and the imide is derived from a polyamine ("PIBSA-PAM").

[0129] The dispersant may comprise one or more PIBSA-PAMs, where the PIB is derived from polyisobutylene with Mn of 600-5000, e.g. 700-4000, e.g. 800-3000, e.g. 900-2500 g / mol, and the polyamine is derived from hydrocarbyl-substituted polyamines such as tetraethylenepentamine, pentaethylenehexamine, tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), N-phenyl-p-phenylenediamine (ADPA) and other polyamines with an average of 5, 6, 7, 8 or 9 nitrogen atoms per molecule. The boration level of the dispersant may be up to 4% by weight, e.g. 1-3% by weight. The dispersant may comprise one or more borated PIBSA-PAMs and one or more non-borated PIBSA-PAMs. The dispersant may comprise one or more borated PIBSA-PAMs derived from PIB having an Mn of 700-1800 g / mol (e.g. 800-1500 g / mol) and one or more non-borated PIBSA-PAMs derived from PIB having an Mn of greater than 1800 to 5000 g / mol (e.g. 2000-3000 g / mol). The dispersant may comprise one or more non-borated PIBSA-PAMs derived from PIB having an Mn of 700-1800 g / mol (e.g. 800-1500 g / mol) and one or more borated PIBSA-PAMs derived from PIB having an Mn of greater than 1800 to 5000 g / mol (e.g. 2000-3000 g / mol). The dispersant may comprise a PIBSA derived from PIB having a Mn of 700-5000 g / mol (e.g., 800-3000 g / mol) and one or more borated or non-borated PIBSA-PAMs derived from PIB having a Mn of 700-5000 g / mol. The dispersant may comprise PIBSA derived from PIB having an Mn of 700-5000 g / mol (e.g. 800-3000 g / mol), and one or more borated PIBSA-PAM derived from PIB having an Mn of 700-1800 g / mol (e.g. 800-1500 g / mol), and one or more non-borated PIBSA-PAM derived from PIB having an Mn of greater than 1800 to 5000 g / mol (e.g. 2000-3000 g / mol). The dispersant may comprise PIBSA derived from PIB with Mn between 700 and 5000 g / mol (e.g. between 800 and 3000 g / mol), one or more non-borated PIBSA-PAM derived from PIB with Mn between 700 and 1800 g / mol (e.g. between 800 and 1500 g / mol), and one or more borated PIBSA-PAM derived from PIB with Mn greater than 1800 to 5000 g / mol (e.g. between 2000 and 3000 g / mol).

[0130] The dispersant may comprise one or more borated or non-borated PIBSA-PAMs, and one or more PIBSA-esters of hydrocarbyl bridged aryloxy alcohols. The dispersant may include one or more borated PIBSA-PAM and one or more non-borated PIBSA-PAM. The dispersant may comprise one or more high molecular weight (Mn: 1600 g / mol or more, e.g. 1800-3000 g / mol) PIBSA-PAMs, optionally borated, and one or more low molecular weight (Mn: less than 1600 g / mol) PIBSA-PAMs, optionally borated, where high molecular weight may be 1600-3000 g / mol, e.g. 1700-2800 g / mol, e.g. 1800-2500 g / mol, e.g. 1850-2300 g / mol; low molecular weight may be 600-1600 g / mol or less, e.g. 650-1500 g / mol, e.g. 700-1400 g / mol, e.g. 800-1300 g / mol, e.g. 850-1200 g / mol, e.g. 900-11500 g / mol, e.g. 900-100 g / mol. The high molecular weight PIBSA-PAM dispersant may be included in the lubricating composition in an amount of 0.5 to 10 mass %, or 0.8 to 6 mass %, or 1.0 to 5 mass %, or 1.5 to 5 mass %, or 1.5 to 4.0 mass %; the low molecular weight PIBSA-PAM dispersant may be included in the lubricating composition in an amount of 1 to 5 mass %, or 1.5 to 4.8 mass %, or 1.8 to 4.6 mass %, or 1.9 to 4.6 mass %, or 2 mass % or more, for example 2 to 5 mass %. In a preferred embodiment, the dispersant may comprise one or more high molecular weight (Mn ≥ 1600 g / mol) PIBSA-PAM, optionally borated, and one or more low molecular weight (Mn < 1600 g / mol) PIBSA-PAM, optionally borated, wherein the high molecular weight PIBSA-PAM is present in the lubricating oil composition at 2.5 wt % or less, or 1.5 wt % or less, or 0.5 wt % or less, or 0.0 wt %. In a preferred embodiment in which the dispersant comprises one or more high molecular weight (Mn ≥ 1600 g / mol) PIBSA-PAM, which may be optionally borated, and one or more low molecular weight (Mn < 1600 g / mol) PIBSA-PAM, which may be optionally borated, the treat level of the combination of high molecular weight PIBSA-PAM and low molecular weight PIBSA-PAM may be in the range of 1.0-6.0 wt%, or 1.5-5.5 wt%, or 2.0-5.0 wt%, or 2.5-4.5 wt%, or 3.0-4.0 wt%.

[0131] Mannich base dispersants Mannich base dispersants useful herein are typically prepared from the reaction of an amine component, a hydroxyaromatic compound (substituted or unsubstituted, e.g., alkyl substituted), such as an alkylphenol, with an aldehyde, such as formaldehyde. See U.S. Patents 4,767,551 and 10,899,986. Processing 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, as well as WO 01 / 42399.

[0132] Dispersing agent of polymethacrylate or polyacrylate derivative Polymethacrylate or polyacrylate derivatives are another class of dispersants useful herein. These dispersants are typically prepared by reacting a nitrogen-containing monomer with a methacrylic or acrylic acid ester having from 5 to 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 low molecular weight. The lubricating compositions of the present disclosure typically comprise a dispersant at 0.1 to 20% by mass of the composition, such as 0.2 to 15% by mass, such as 0.25 to 10% by mass, such as 0.3 to 5% by mass, for example 2.0 to 4.0% by mass of the lubricating oil composition. Alternatively, the dispersant may be present at 0.1 to 5% by mass, or 0.01 to 4% by mass of the lubricating composition. For further information regarding dispersants useful herein, see U.S. Pat. No. 10,829,712, column 13, line 36 to column 16, line 67, and U.S. Pat. No. 7,485,603, column 2, line 65 to column 6, line 22, column 8, line 25 to column 14, line 53, and column 23, line 40 to column 26, line 46. Compositions according to the present disclosure may include additives having a variety of functionalities that also have a secondary effect as dispersants (e.g., the Component B functionalized polymers described above may also have a dispersant effect). These additives are not included as dispersants for purposes of determining the amount of dispersant in a lubricating oil composition or concentrate herein.

[0133] J. Corrosion inhibitors / rust inhibitors Corrosion inhibitors may be used to reduce corrosion of metals and are often alternatively referred to as metal deactivators or metal passivators. Some corrosion inhibitors may alternatively be characterized as antioxidants. Suitable corrosion inhibitors include 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 of these. A particular corrosion inhibitor is benzotriazole, represented by the following structure: [ka] In the formula, R 8 is C1-C, which may be absent (hydrogen) or linear or branched, saturated or unsaturated 20It is a hydrocarbyl or substituted hydrocarbyl group. It may be alkyl or aromatic in nature and / or contain a ring structure with heteroatoms such as N, O, or S. Examples of suitable compounds include benzotriazole, alkyl-substituted benzotriazoles (e.g., tolyltriazole, ethylbenzotriazole, hexylbenzotriazole, octylbenzotriazole, etc.), aryl-substituted benzotriazoles, alkylaryl- or arylalkyl-substituted benzotriazoles, etc., and combinations thereof. For example, the triazole may include or be benzotriazole, and / or alkylbenzotriazoles, where the alkyl group has from 1 to about 20 carbon atoms, or from 1 to about 8 carbon atoms. Non-limiting examples of such corrosion inhibitors may include or be benzotriazole, tolyltriazole, and / or optionally substituted benzotriazoles, such as Irgamet™ 39, available from BASF, Ludwigshafen, Germany. Preferred corrosion inhibitors may include or be benzotriazole and / or tolyltriazole. Additionally, or alternatively, the corrosion inhibitors can include one or more substituted thiadiazoles represented by the following structure: [ka] In the formula, R 15 and R 16are independently hydrogen or a hydrocarbon group, which may be aliphatic or aromatic, including cyclic, alicyclic, aralkyl, aryl, and alkaryl, and each w is independently 1, 2, 3, 4, 5, or 6 (preferably 2, 3, or 4, e.g., 2). These substituted thiadiazoles are derived from the 2,5-dimercapto-1,3,4-thiadiazole (DMTD) molecule. Many derivatives of DMTD have been reported in the art, and any such compound may be included in the fluids 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.

[0134] Further, additionally or alternatively, the corrosion inhibitor may include one or more other derivatives of DMTD, such as carboxylic acid esters, in which R 15 and R 16 may be attached to the sulfur atom of the sulfide through a carbonyl group. The 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 containing at least 10 carbon atoms are described, for example, in U.S. Pat. No. 2,836,564. This method involves the synthesis of R 15 and R 16 HOOC‐CH(R 19 )-(R 19 is a hydrocarbyl group). DMTD derivatives further prepared by amidation or esterification of these terminal carboxylic acid groups may also be useful. The preparation of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazoles is described, for example, in US Pat. No. 3,663,561. A class of DMTD derivatives may include mixtures of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazoles and 2,5-bis-hydrocarbyldithio-1,3,4-thiadiazoles, such as those sold under the tradename HiTEC™ 4313 and available from Afton Chemical Company.

[0135] The preparation of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazoles is described, for example, in US Pat. No. 3,663,561. A class of DMTD derivatives may include mixtures of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazoles and 2,5-bis-hydrocarbyldithio-1,3,4-thiadiazoles, such as those sold under the tradename HiTEC™ 4313 and available from Afton Chemical Company. Additionally or alternatively, the corrosion inhibitor may be B(OR 46 )3, wherein each R 46 may be the same or different. It is usually desirable that the borate salt be compatible with the non-aqueous medium of the composition, so that each R 46 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 base stock, for example, compatibility can usually be improved when the hydrocarbyl moieties are each at least C4. Thus, non-limiting examples of such corrosion inhibitors include, but are not limited to, triethyl borate, tripropyl borates such as triisopropyl borate, tributyl borates such as tri-tert-butyl borate, tripentyl borate, trihexyl borate, trioctyl borates such as tri-(2-ethylhexyl) borate, monohexyl dibutyl borate (monohexyl dibutyl borate), and the like, and combinations thereof.

[0136] If used, the corrosion inhibitor may include a substituted thiadiazole, a substituted benzotriazole, a substituted triazole, a trisubstituted borate, or a combination thereof. If required, corrosion inhibitors may be used in any effective amount, but when used, typically may be used in an amount of about 0.001 to 5.0 mass %, such as 0.005 to 3.0 mass %, or 0.01 to 1.0 mass %, based on the mass of the composition. Alternatively, such additives may be used in an amount of about 0.01 to 5 mass %, preferably about 0.01 to 1.5 mass %, based on the mass of the lubricating composition. In some embodiments, the 3,4-oxypyridinone-containing composition can be substantially free (e.g., 0%, or less than 0.001%, 0.0005% or less by weight, not intentionally added, and / or not at all) of 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. Compositions according to the present disclosure may include additives having a variety of functionalities that also have a secondary effect as corrosion inhibitors (e.g., the Component B functionalized polymers described above may also have a corrosion inhibitor effect). These additives are not included as corrosion inhibitors for purposes of determining the amount of corrosion inhibitor in a lubricating oil composition or concentrate herein.

[0137] K. Anti-wear agents The lubricating oil compositions and concentrate compositions of the present disclosure may contain one or more antiwear agents that can reduce friction and excessive wear. Any antiwear agent known to one of ordinary skill in the art may be used in the lubricating oil composition. Non-limiting examples of suitable antiwear agents include zinc dithiophosphates, metal (e.g., Pb, Sb, Mo, etc.) salts of dithiophosphoric acids, metal (e.g., Zn, Pb, Sb, Mo, etc.) salts of dithiocarbamic acids, metal (e.g., Zn, Pb, Sb, etc.) salts of fatty acids, boron compounds, phosphate esters, phosphites, amine salts of phosphate esters or thiophosphate esters, reaction products of dicyclopentadiene and thiophosphoric acid, and combinations thereof. The amount of antiwear agent may vary from about 0.01 to about 5 mass %, about 0.05 to about 3 mass %, or about 0.1 to about 1 mass %, based on the total mass of the lubricating oil composition. In embodiments, the antiwear agent is or includes a dihydrocarbyl dithiophosphate metal salt, such as a zinc dialkyldithiophosphate compound. 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, from about 3 to about 18, from about 3 to about 12, or from about 3 to about 8 carbon atoms. In further embodiments, the alkyl group is linear or branched.

[0138] Useful antiwear agents also include substituted or unsubstituted thiophosphoric acids, the salts of which include zinc-containing compounds, such as zinc dithiophosphate compounds selected from zinc dialkyldithiophosphates, zinc diaryldithiophosphates, and / or zinc alkylaryldithiophosphates. Metal alkylthiophosphates, more specifically metal dialkyldithiophosphates where the metal component is zinc, or zinc dialkyldithiophosphates (ZDDPs), can be useful components of the lubricating compositions of the present disclosure. ZDDPs can be derived from primary alcohols, secondary alcohols, or mixtures thereof. ZDDP compounds are generally compounds of the formula Zn[SP(S)(OR1)(OR2)]2, where R1 and R2 are C1-C18 Alkyl groups, preferably C2-C 12 The alkyl groups are alkyl groups. These alkyl groups may be linear or branched. The alcohols used in the ZDDP can be 2-propanol, butanol, secondary butanol, pentanol, hexanol, such as 4-methyl-2-pentanol, n-hexanol, n-octanol, 2-ethylhexanol, alkylated phenols, and the like. Mixtures of secondary alcohols or mixtures of primary and secondary alcohols can be used. Alkylaryl groups may also be used. Useful zinc dithiophosphates include secondary zinc dithiophosphates, such as those sold by Lubrizol under the trade names "LZ677A", "LZ1095", and "LZ1371", by Chevron Oronite under the trade name "OLOA262", and by Afton Chemical under the trade name "HiTEC™ 7169".

[0139] In embodiments, the zinc compound can be a zinc dithiocarbamate complex, such as a zinc dithiocarbamate having the formula: [ka] In the formula, R I are each 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, ligand L is selected from the group consisting of water, hydroxide, ammonia, amino, amide, alkylthiolate, halide, and combinations thereof.

[0140] Antiwear additives, such as ZDDP and / or zinc carbamate, are typically used in amounts of about 0.4 to about 1.2 wt.%, preferably about 0.5 to about 1.0 wt.%, more preferably about 0.6 to about 0.8 wt.%, based on the total weight of the lubricating composition, although in many cases greater or less than these amounts can be advantageously used. Preferably, the antiwear additive is a ZDDP, preferably a secondary ZDDP, present in an amount of about 0.6 to about 1.0 wt.%, based on the total weight of the lubricating composition. The lubricating oil compositions of the present disclosure preferably contain a treat level of one or more ZDDPs that delivers 1200 ppm or less, or 1000 ppm or less, or 800 ppm or less, or 600 ppm or less, or 400 ppm or less, or 200 ppm or less, or 0 ppm by weight of phosphorus to the composition. 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. Compositions according to the present disclosure may contain additives having a variety of functions that also have a secondary effect as antiwear agents (e.g., the Component B functionalized polymers described above may also have an antiwear effect). These additives are not included as antiwear agents for purposes of determining the amount of antiwear agent in a lubricating oil composition or concentrate herein.

[0141] L. Demulsifier Demulsifiers useful herein include those described in U.S. Pat. No. 10,829,712 (column 20, lines 34-40). Typically, demulsifiers herein may be used in small amounts. A preferred demulsifier is described in EP 330 522. It is obtained by reacting an alkylene oxide with an adduct obtained by reacting a bis-epoxide with a polyhydric alcohol. Such additives may be used in an amount of about 0.001-5% by weight, preferably about 0.01-2% by weight.

[0142] M. Seal compatibility and seal swelling agents Other optional additives include seal compatibility agents such as organic phosphates, aromatic esters, aromatic hydrocarbons, esters (e.g., butyl benzyl phthalate), and polybutenyl succinic anhydride. Such additives may be used in amounts of about 0.001-5% by weight, preferably about 0.01-2% by weight. In embodiments, the seal compatibility agents are sea swell agents such as PIBSA (polyisobutenyl succinic anhydride).

[0143] N. Extreme pressure agents The lubricating oil composition and concentrate composition of the present disclosure may contain one or more extreme pressure agents that can prevent sliding metal surfaces from sticking together under extreme pressure conditions. Any extreme pressure agent known to those skilled in the art may be used in the lubricating oil composition. In general, extreme pressure agents are compounds that can chemically bond with metals to form a surface film that prevents rough welding of opposing metal surfaces together under high loads. Non-limiting examples of suitable extreme pressure agents include sulfurized animal and vegetable fats and oils, sulfurized animal and 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 acids, fatty acid esters, and alpha-olefins, functionally substituted dihydrocarbyl polysulfides, thia-aldehydes, thia-ketones, epithio compounds, sulfur-containing acetal derivatives, co-sulfurized blends of terpenes and acyclic olefins, polysulfurized olefin products, amine salts of phosphates or thiophosphates, and combinations thereof. The amount of extreme pressure agent may vary from about 0.01 to about 5 mass %, from about 0.05 to about 3 mass %, or from about 0.1 to about 1 mass %, based on the total mass of the lubricating oil composition.

[0144] O. Non-Base Stock Unsaturated Hydrocarbons The lubricating oil compositions and concentrate compositions of the present disclosure may contain one or more unsaturated hydrocarbons. These unsaturated hydrocarbons are distinct from any base oil (Group I, II, III, IV, and / or V lubricating oil base stocks) and / or viscosity modifiers that may be present in the composition, which always have at least one unsaturation per molecule (typically only one in the case of linear alpha-olefins, or LAOs). Without being bound by theory, the unsaturation(s) may provide antioxidant and / or sulfur trapping functionality that may complement and / or replace one or more antioxidant additives and / or one or more corrosion inhibitor additives, but the unsaturated hydrocarbons (LAOs) do not usually provide the only antioxidant or corrosion inhibitor functionality in the lubricating oil composition. Non-limiting examples of unsaturated hydrocarbons include one or more unsaturated C 12 -C 60 Hydrocarbons (e.g. C 12 -C 48 Hydrocarbons, C 12 -C 36 Hydrocarbons, C 12 -C 30 Hydrocarbon, or C 12 -C 24 When there is only one unsaturation, the unsaturated hydrocarbon may be referred to as a linear alpha-olefin (LAO). Other non-limiting examples of unsaturated hydrocarbons include oligomers / polymers of polyisobutylene that retain (or are post-polymerization modified to have) terminal (near) unsaturation, and / or blends thereof. When present, the unsaturated hydrocarbon (LAO) may comprise 0.01 to 5 wt %, particularly 0.1 to 3 wt %, or alternatively 0.1 to 1.5 wt %, based on the total weight of the lubricating oil composition.

[0145] When the lubricating oil composition contains one or more of the additives described above, the additive(s) are typically present in the composition in an amount sufficient to perform its intended function. Typical amounts of such additives useful in the present disclosure, particularly for use in crankcase lubricants, are set forth in the table below. It should be noted that many of the additives are shipped from the additive manufacturer as concentrates that contain one or more additives with a specific amount of base oil or other diluent. Thus, the mass amounts in the table below and other amounts stated herein are intended to be the amount of active ingredient (i.e., the non-diluent portion of the ingredient). The mass percentages (wt%) given below are based on the total mass of the lubricating oil composition. [Table 1]

[0146] The aforementioned additives are typically commercially available materials. These additives may be added individually, but are usually pre-added in packages available from lubricant additive suppliers. Additive packages are available with a variety of ingredients, ratios, and properties, and the appropriate package is selected having regard to the intended use of the final composition.

[0147] fuel The present disclosure also relates to a method of lubricating an internal combustion engine for a passenger vehicle or commercial vehicle during engine operation, the method comprising the steps of: (i) supplying to a crankcase of an internal combustion engine of an automobile, an automobile crankcase, a lubricating oil composition as described herein; (ii) supplying a hydrocarbon fuel to an internal combustion engine of a motor vehicle; and (iii) combusting the fuel in an automotive internal combustion engine, such as a spark ignition or compression ignition two-stroke or four-stroke reciprocating engine, such as a diesel engine or a passenger car engine (e.g. a spark ignition combustion engine).

[0148] The present disclosure also relates to a fuel composition comprising the lubricating oil composition described herein and a hydrocarbon fuel, where the fuel may be derived from petroleum and / or biological sources ("biofuels" or "renewable fuels"). Suitable hydrocarbon-based fuels include diesel fuel, motor gasoline, natural gas fuel, and hydrogen fuel. In an embodiment, the fuel comprises 0.1 to 100 mass % of the renewable fuel, alternatively 1 to 75 mass %, alternatively 5 to 50 mass %, based on 1 to 50 mass % of the total renewable fuel and petroleum-derived fuel. Renewable fuel components are typically produced from vegetable oils (e.g., palm oil, rapeseed oil, soybean oil, jatropha oil), microbial oils (e.g., algae oil), animal fats (e.g., edible oils, animal fats, and / or fish oils), and / or biogas. Renewable fuels refer to biofuels produced from biological resources formed through modern biological methods. In one embodiment, the renewable fuel components are produced by hydroprocessing. Hydroprocessing includes various reactions in which molecular hydrogen reacts with other components or components are molecularly transformed in the presence of molecular hydrogen and a solid catalyst. The reactions include, but are not limited to, hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrocracking, and isomerization. Renewable fuel components may have various distillation ranges that impart desired properties to the components depending on the intended use.

[0149] Purpose The lubricating composition of the present disclosure may be used to lubricate machine engine parts by adding lubricants, especially in internal combustion engines, such as spark-ignited or compression-ignited two-stroke or four-stroke reciprocating engines. Typically, the lubricating composition is a crankcase lubricant, such as a passenger car motor oil or a heavy-duty or light-duty diesel engine lubricant. The lubricating composition of the present disclosure may also be used to lubricate machine engine parts in hydrogen and natural gas engines. In particular, the lubricating compositions of the present disclosure are suitable for use in lubricating the crankcase of spark ignition internal combustion engines, such as passenger vehicle engines. In particular, the lubricating compositions of the present disclosure are suitable for use in lubricating the crankcase of spark ignition, turbocharged internal combustion engines. In particular, the lubricating compositions of the present disclosure are suitable for use in lubricating the crankcase of natural gas or hydrogen engines. In an embodiment, the lubricating oils of the present disclosure are used in spark assisted high compression internal combustion engines, and when used in high compression spark ignition internal combustion engines, the lubricating oil compositions of the present disclosure are useful for lubricating high compression spark ignition engines. In an embodiment, the lubricating compositions of the present disclosure are suitable for use in lubricating the crankcase of engines for heavy duty diesel vehicles (i.e., heavy duty diesel vehicles having a gross vehicle weight rating of 10,000 pounds or greater).

[0150] In an embodiment, the lubricating compositions of the present disclosure are suitable for use in lubricating the crankcase of a passenger vehicle diesel or gasoline engine. 1. A lubricating oil composition comprising: an oil of lubricating viscosity in an amount greater than 50 mass % of the composition comprising a Group I base oil, a Group II base oil, a Group III base oil, a Group IV base oil, or a combination thereof; an overbased calcium detergent having a total base number (KOH / g) of 9 to 500 and capable of delivering 500 to 1,300 ppm by mass of calcium to the composition at a treatment level; and An overbased magnesium detergent having a total base number (KOH / g) of 9 or more and 500 or less and capable of delivering 500 to 1300 mass ppm of magnesium to the composition at a treatment level: or a mixture thereof, The total mass of the combination of calcium and magnesium in the composition is in the range of 1000 ppm to 1800 ppm; the lubricating oil composition has a total sulfated ash content of 1.0 wt.% or less, a high temperature high shear viscosity (HTHS) at 150°C, measured in accordance with ASTM D4683-20, of 1.8 mPa·s or more and 2.9 mPa·s or less, and a total phosphorus level of 0.080 wt.% or less; the lubricating oil composition provides a 5% to 60% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 Start / Stop Test Method, compared to a lubricating oil composition having an equivalent HTHS but not including a mixture of an overbased calcium detergent and an overbased magnesium detergent at a combined loading of calcium and magnesium in the composition in the range of 1000 ppm to 1800 ppm; Lubricating oil composition. 2. The lubricating oil composition according to item 1, wherein the composition has a kinematic viscosity at 100° C. of 5 to 20 cSt and a total sulfur level of 0.35 mass% or less. 3. The lubricating oil composition according to item 1 or 2, wherein the oil of lubricating viscosity is 60 to 95 mass % of the composition and comprises a Group III base oil, a Group IV base oil, or a combination thereof. 4. The lubricating oil composition according to any one of items 1 to 3, wherein the overbased calcium detergent is a sulfonate, a salicylate, a phenate, or a combination thereof. 5. The lubricating oil composition according to any one of items 1 to 4, wherein the overbased magnesium detergent is a sulfonate, a salicylate, a phenate, or a combination thereof. 6. The lubricating oil composition according to items 1 to 5, wherein the overbased calcium detergent is a salicylate, the overbased magnesium detergent is a salicylate, and the total mass of the combination of calcium and magnesium in the composition is in the range of 1600 to 1800 ppm. 7. The lubricating oil composition according to any one of items 1 to 6, wherein the ratio of calcium loading to magnesium loading in the composition is 30:70 to 70:30, based on mass % in the lubricating oil composition. 8. The lubricating oil composition according to claims 1 to 7, which is a heavy duty diesel oil, a light duty diesel oil, a hydrogen engine oil, a spark ignition combustion engine oil, or a natural gas engine oil. 9. The lubricating oil composition according to claims 1 to 8, which is an SAE grade selected from the group consisting of 0W-8, 0W-12, 0W-16, 0W-20, 0W-30, 5W-20, 5W-30, 10W-30, 15W-40, 5W-40, and 10W-40. 10. The lubricating oil composition according to any one of items 1 to 9, which is used as a passenger vehicle lubricant (PVL) or a commercial vehicle lubricant (CVL). 11. The lubricating oil composition according to any one of items 1 to 10, wherein the journal bearing is a main bearing for a crankshaft, a connecting rod big end bearing for a crankshaft, or a connecting rod small end bearing / bushing for a piston pin. 12. The lubricating oil composition according to any one of items 1 to 11, wherein the journal bearing shell material is a material selected from the group consisting of bimetal, trimaterial / metal, and solid materials. 13. The lubricating oil composition according to paragraph 12, wherein the tri-material / metal is a polymer coating or a SnCu overlay on lead-free bronze. 14. The lubricating oil composition according to item 12, wherein the bimetal is AlSn20Cu or AlSn25. 15. The lubricating oil composition according to item 12, wherein the solid material is bronze or lead-free bronze. 16. The lubricating oil composition of claim 13, wherein the polymer-coated tri-material journal bearing shell material provides a 5 to 40% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 Start / Stop Test Method, compared to a lubricating oil composition having a comparable HTHS but not including a mixture of an overbased calcium-based detergent and an overbased magnesium-based detergent. 17. The lubricating oil composition of claim 13, wherein the SnCu overlay trimetal journal bearing shell material provides a 10 to 60% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 Start / Stop test method, compared to a lubricating oil composition having a comparable HTHS but not including a mixture of an overbased calcium-based detergent and an overbased magnesium-based detergent. 18. The lubricating oil composition according to any one of items 1 to 17, further comprising one or more of the following components: one or more functionalized polymers; one or more friction modifiers; one or more antioxidants; one or more pour point depressants; one or more antifoam agents; one or more viscosity modifiers; one or more dispersants; one or more inhibitors, one or more rust inhibitors; one or more seal swell agents; and / or one or more antiwear agents. 19. The lubricating oil composition according to paragraph 18, wherein the one or more dispersants are one or more high molecular weight, optionally borated, polyisobutylene succinimide (PIBSA-PAM) dispersants (Mn: 1600 g / mole or greater), one or more low molecular weight, optionally borated, polyisobutylene succinimide (PIBSA-PAM) dispersants (Mn: less than 1600 g / mole), or a combination thereof, and the treat level of the combination of the high molecular weight PIBSA-PAM and the low molecular weight PIBSA-PAM is from 1.0 to 6.0 wt. % of the composition. 20. The lubricating oil composition of claim 19, wherein the high molecular weight PIBSA-PAM dispersant, the low molecular weight PIBSA-PAM dispersant, or a combination thereof is present at a treat level to deliver 20 to 700 ppm by weight of boron to the lubricating oil composition. 21. The lubricating oil composition according to paragraph 18, wherein the one or more antiwear agents comprise one or more zinc dialkyldithiophosphates (ZDDPs) at a treat level capable of delivering 840 ppm by weight or less of phosphorus to the composition. 22. The lubricating oil composition according to item 18, wherein the one or more antioxidants comprise one or more phenolic antioxidants, one or more sulfur-based antioxidants, one or more aminic antioxidants, or a combination thereof, and the one or more antioxidants comprise 1.0 to 6.0 wt. % of the composition. 23. The lubricating oil composition according to paragraph 18, wherein the one or more friction modifiers comprise a dimeric molybdenum dialkyldithiocarbamate (moly dimer), a trimer molybdenum dialkyldithiocarbamate (moly trimer), or a combination thereof, at a treat level to deliver 12 to 1000 ppm by weight of molybdenum to the composition. 24. The functionalized polymer is in an amount of 0.2 to 2.0% by weight of the composition, and comprises one or more of the following: i) Mw / Mn is less than 2; ii) a functionality distribution (Fd) value of 3.5 or less; and iii) Mn of the polymer before functionalization is 10,000 g / mol or more (GPC-PS); However, if the polymer before functionalization is a copolymer of isoprene and butadiene, the Mn of the copolymer exceeds 25,000 g / mol (GPC-PS). C 4‐5 olefin-containing, amide, imide, and / or ester functionalized partially saturated or fully saturated polymers; Item 19. The lubricating oil composition according to item 18. 25. A method for lubricating an internal combustion engine, comprising the step of supplying the lubricating oil composition according to any one of items 1 to 24 to the engine. 26. A method for reducing journal bearing wear in an internal combustion engine, comprising: A step of supplying the lubricating oil composition according to any one of items 1 to 24 to the internal combustion engine. The method includes: 27. A method for producing a lubricating oil composition comprising the steps of: (i) an oil of lubricating viscosity in an amount greater than 50 mass % of the composition comprising a Group I base oil, a Group II base oil, a Group III base oil, a Group IV base oil, or a combination thereof; (ii) an overbased calcium detergent having a total base number (KOH / g) of 9 to 500 and capable of delivering 500 to 1,300 ppm by mass of calcium to the composition at a treatment level; and (iii) an overbased magnesium-based detergent having a total base number (KOH / g) of 9 to 500 and capable of delivering 500 to 1,300 ppm by mass of magnesium to the composition at a treatment level; Combining or blending wherein the total mass of the combination of calcium and magnesium in the composition is in the range of 1000 ppm to 1800 ppm; the lubricating oil composition has a total sulfated ash content of 1.0 wt.% or less, a high temperature high shear viscosity (HTHS) at 150°C, as measured in accordance with ASTM D4683-20, of 1.8 mPa·s or more and 2.9 mPa·s or less, and a total phosphorus level of 0.080 wt.% or less; the lubricating oil composition provides a 5% to 60% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 Start / Stop Test Method, compared to a lubricating oil composition having an equivalent HTHS but not including a mixture of an overbased calcium detergent and an overbased magnesium detergent in the composition at a combined loading of calcium and magnesium in the range of 1000 ppm to 1800 ppm; method.

[0151] The following non-limiting examples are provided to illustrate the present disclosure.

[0152] experiment All molecular weights are number average molecular weights (Mn) reported in g / mole and are determined by gel permeation chromatography using polystyrene standards unless otherwise noted. "AI", "ai", and "ai" are weight percent active ingredient unless otherwise specified.

[0153] Test procedure KV100 is the kinematic viscosity measured at 100°C according to ASTM D445-19a. KV40 is the kinematic viscosity measured at 40°C according to ASTM D445-19a. The sulfur content in the oil is determined according to ASTM D5185. Sulfated ash (SASH) content is determined by ASTM D874. Phosphorus, boron, calcium, zinc, molybdenum, and magnesium contents are determined by ASTM D5185. The MTM-R test method uses a Mini-Traction Machine (MTM) manufactured by PCS Instruments, London, UK. The MTM-R method uses a reciprocating Mini-Traction Machine (MTM-R) in which a 19mm diameter ball is used as the upper piece, which is reciprocated by applying a load to a disk-shaped lower piece. The ball is made of AISI 52100 grade steel and is unpainted. The disk is made of steel, which is either painted with Al bimetal or polymer tri-material, or is unpainted (steel), with a coating depth of approximately 2μm. Thus, μm 3 The ball and disk were contacted between a ferrous (steel) surface and a painted or unpainted surface to measure the wear scar volume in units. The test conditions are shown in the table below for each disk material tested with the lubricating oil composition. The test disks were 46 mm AISI 52100 steel disks with a surface finish of <0.02 μm Ra and a hardness of 720-780 Hv, and the test balls were 19.05 mm AISI 52100 steel balls with a surface finish of <0.02 μm Ra and a hardness of 800-920 Hv. [Table 2]

[0154] The TE-92 Start / Stop test method includes a test ring and test procedure for measuring journal bearing wear, measured in maximum average wear in microns. This test procedure is included in the following journal article on the TE-92 Start / Stop test method: Summer, F., Grun, F., and Ravenhill, E. R., "Friction and Wear Performance of Various Polymer Coatings for Journal Bearings under Stop Start Sliding," Lubricants, 2020, 8.2020(1), (https: / / doi.org / 10.3390 / lubricants8010001), which is incorporated herein by reference in its entirety. The journal article states that the test strategy began with an initial period of low sliding speed and room temperature for easy and quiet operation. The oil was then heated to an oil bath temperature of 120°C while still standing, after which stop-start sliding was performed up to a maximum speed of 1.2 m / s. The speed ramp was performed as quickly as possible to mimic the stop-start of an engine. The total ramp time from 0 to 1.2 m / s or vice versa is 8 seconds. The test time varied according to the number of stop-start ramps. For the TE-92 Start / Stop test method with SnCu Trimetal, the test is run for 10k cycles. For the TE-92 Start / Stop test method with Polymer Trimetal, the test is run for 40k cycles. The Polymer Trimetal material is less prone to stop / start wear and therefore is run for a higher number of cycles than the SnCu Trimetal material. Pressure Differential Scanning Calorimetry (PDSC) is an oxidation stability test that measures the oxidation induction time in minutes of a lubricant according to test procedure CEC L-85_T-99. High Temperature High Shear Viscosity ("HTHS" or "HTHS150") measures the high temperature high shear viscosity of a lubricating oil, determined in accordance with ASTM D4683 at 150° C. and reported in cPs.

[0155] material [Table 3] TIFF2025069074000015.tif39169 EXAMPLES

[0156] Example 1: Oil Candidates of the Invention Table 1 below shows the formulations of 0W-16 and 0W-12 lubricating oils (Inventive Examples 1 and 2) containing combinations of overbased magnesium and overbased calcium detergents. 150 The values ​​were 2.30 and 2.13, respectively. Table 1 below also shows Comparative Examples 1-3, which contained only calcium-based detergents and no magnesium-based detergents. Comparative Examples 1-3 were either 0W-16 grade or 0W-20 SAE grade engine oils. The additives used in the formulations are shown in Table 1 in mass %. Table 1 also shows the viscosity characteristics of the oil of the present invention and one of the comparative oils. [Table 4]

[0157] One or two of the invention examples and two or three of the comparative examples were evaluated for start / stop connecting rod bearing wear for SnCu trimetal (Figure 3) and polymer trimetal (Figure 4) using the TE-92 start / stop test method described above. The use of calcium and magnesium overbased detergents in a 50:50 to 65:35 (Ca:Mg) mix in the low viscosity engine oil formulations of the present invention improves start / stop connecting rod bearing wear in both SnCu trimetal (Figure 3) and polymer bearings (Figure 4) representative of typical modern bearing systems. The engine oils of the present invention in Examples 1 and 2 also show improved performance at significantly lower viscosity 0W-12 compared to higher viscosities (polymer in Figure 4). Figure 3 also shows the effect of magnesium in combination with calcium (Oil 1, Example 1) on SnCu trimetal wear compared to a comparative engine oil containing all calcium (Oil 2, Comparative Example 1) and comparative oil formulations containing only calcium (Comparative Examples 3 and 4). Inventive Oil 1 of Figure 3, a 0W-16 grade oil containing 940 ppm calcium and 800 ppm magnesium, caused significantly less (about 40% less) start / stop connecting rod bearing wear on SnCu trimetal compared to a comparative engine oil formulation of equal or higher viscosity that contained only calcium and no magnesium. This improvement in start / stop connecting rod bearing wear on SnCu trimetal with the inventive engine oil in combination with calcium and magnesium is surprising and unexpected, since one skilled in the art would not have expected that the combination of two metals (Ca and Mg) would reduce journal bearing wear. Similarly, Figure 4 shows the effect of magnesium in combination with calcium (Oil 3, Inventive Example 2) on polymer tri-material wear compared to two comparative engine oils containing all calcium. Inventive Oil 3 in Figure 4, a 0W-12 grade oil containing 940 ppm calcium and 800 ppm magnesium, caused significantly less (about 10% less) polymer tri-material start / stop connecting rod bearing wear compared to two comparative engine oil formulations of higher viscosity (0W-16 and 0W-20) containing only calcium but no magnesium. This improvement in start / stop connecting rod bearing wear on polymer tri-material with the inventive engine oil in combination with calcium and magnesium is also surprising and unexpected, since one skilled in the art would not have expected that the combination of two metals (Ca and Mg) would reduce journal bearing wear.

[0158] Applicants have unexpectedly discovered that journal bearing wear performance with non-ferrous wear materials in low viscosity engine oils for use with internal combustion engines can be significantly improved by utilizing in the formulation a combination of: an overbased calcium detergent having a total base number (KOH / g) of 9 to 500, inclusive, and a treat level capable of delivering 500 to 1300 ppm by weight of calcium to the composition; and an overbased magnesium detergent having a total base number (KOH / g) of 9 to 500, inclusive, and a treat level capable of delivering 500 to 1300 ppm by weight of magnesium to the composition; wherein the combined total weight of calcium and magnesium in the composition ranges from 1000 ppm to 1800 ppm. The improvement in journal bearing wear was measured and verified using the TE-92 Start / Stop test method, but it is expected that similar improvements will be observed using other wear test methods, such as the MTM-R wear test method.

[0159] All documents described herein are incorporated herein by reference and include any priority documents and / or test procedures to the extent not inconsistent therewith. As is apparent from the general description and specific embodiments above, while aspects of the invention have been shown and described, various modifications can be made without departing from the spirit and scope of the invention. Accordingly, no limitation of the invention is intended. The term "comprising" is considered synonymous with the term "including". Similarly, whenever the transition phrase "comprising" appears before a composition, element, or group of elements, it is understood that the same composition or group of elements is also contemplated with the transition phrase "consisting essentially of," "consisting of," "selected from the group consisting of," or "is," and vice versa, when the recitation of the composition, element, or group of elements is preceded by the transition phrase.

Claims

1. 1. A lubricating oil composition comprising: an oil of lubricating viscosity in an amount greater than 50 mass % of said composition comprising a Group I base oil, a Group II base oil, a Group III base oil, a Group IV base oil, or a combination thereof; an overbased calcium detergent having a total base number (KOH / g) of 9 to 500 inclusive, at a treat level capable of delivering 500 to 1300 ppm by weight of calcium to the composition; and an overbased magnesium detergent having a total base number (KOH / g) of 9 to 500, the detergent having a treatment level capable of delivering 500 to 1,300 ppm by weight of magnesium to the composition; or a mixture thereof, the total mass of calcium and magnesium combined in said composition is in the range of 1000 ppm to 1800 ppm; the lubricating oil composition has a total sulfated ash content of 1.0 wt.% or less, a high temperature high shear viscosity (HTHS) at 150°C, measured in accordance with ASTM D4683-20, of 1.8 mPa·s or more and 2.9 mPa·s or less, and a total phosphorus level of 0.080 wt.% or less; the lubricating oil composition provides a 5% to 60% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 Start / Stop Test Method, compared to a lubricating oil composition having a comparable HTHS but not including a mixture of an overbased calcium-based detergent and an overbased magnesium-based detergent in the composition at a combined loading of calcium and magnesium in the range of 1000 ppm to 1800 ppm; Lubricating oil composition.

2. 2. The lubricating oil composition of claim 1, wherein the composition has a kinematic viscosity at 100° C. of 5 to 20 cSt and a total sulfur level of 0.35 wt. % or less.

3. 2. The lubricating oil composition of claim 1, wherein the oil of lubricating viscosity is 60 to 95 mass % of the composition and comprises a Group III base oil, a Group IV base oil, or a combination thereof.

4. 2. The lubricating oil composition of claim 1, wherein the overbased calcium detergent is a sulfonate, a salicylate, a phenate, or a combination thereof.

5. 2. The lubricating oil composition of claim 1, wherein the overbased magnesium detergent is a sulfonate, a salicylate, a phenate, or a combination thereof.

6. 2. The lubricating oil composition of claim 1, wherein the calcium overbased detergent is a salicylate and the magnesium overbased detergent is a salicylate, and the combined weight percent of calcium and magnesium in the composition is in the range of 1600 to 1800 ppm.

7. 2. The lubricating oil composition of claim 1, wherein the ratio of calcium loading to magnesium loading in said composition is from 30:70 to 70:30, based on weight percent of said lubricating oil composition.

8. 10. The lubricating oil composition of claim 1, which is a heavy duty diesel oil, a light duty diesel oil, a hydrogen engine oil, a spark ignition combustion engine oil, or a natural gas engine oil.

9. 2. The lubricating oil composition of claim 1, which is an SAE grade selected from the group consisting of 0W-8, 0W-12, 0W-16, 0W-20, 0W-30, 5W-20, 5W-30, 10W-30, 15W-40, 5W-40, and 10W-40.

10. 10. The lubricating oil composition of claim 1 for use as a passenger vehicle lubricant (PVL) or a commercial vehicle lubricant (CVL).

11. 2. The lubricating oil composition of claim 1, wherein the journal bearing is a main bearing for a crankshaft, a connecting rod big end bearing for a crankshaft, or a connecting rod small end bearing / bushing for a piston pin.

12. 10. The lubricating oil composition of claim 1, wherein the journal bearing shell material is a material selected from the group consisting of bimetallic, tri-material / metallic, and solid materials.

13. 13. The lubricating oil composition of claim 12, wherein the tri-material / metal is a polymer coating or a SnCu overlay on lead-free bronze.

14. 13. The lubricating oil composition of claim 12, wherein the bimetal is AlSn20Cu or AlSn25.

15. 13. The lubricating oil composition of claim 12, wherein the solid material is bronze or lead-free bronze.

16. 14. The lubricating oil composition of claim 13, wherein the polymer coated tri-material journal bearing shell material provides a 5 to 40% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 Start / Stop test method compared to a lubricating oil composition having a comparable HTHS but not including the mixture of overbased calcium and magnesium detergents.

17. 14. The lubricating oil composition of claim 13, wherein the SnCu overlay trimetal journal bearing shell material provides a 10 to 60% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 Start / Stop test method compared to a lubricating oil composition having a comparable HTHS but not including the mixture of overbased calcium and magnesium detergents.

18. The following ingredients: one or more functionalized polymers; one or more friction modifiers; one or more antioxidants; one or more pour point depressants; one or more antifoam agents; one or more viscosity modifiers; one or more dispersants; one or more inhibitors, one or more rust inhibitors; one or more seal swell agents; and / or one or more antiwear agents, The lubricating oil composition of claim 1, further comprising one or more of:

19. 19. The lubricating oil composition of claim 18, wherein the one or more dispersants are one or more high molecular weight, optionally borated, polyisobutylene succinimide (PIBSA-PAM) dispersants (Mn ≧1600 g / mole), one or more low molecular weight, optionally borated, polyisobutylene succinimide (PIBSA-PAM) dispersants (Mn <1600 g / mole), or a combination thereof, and wherein the treat level of the combination of the high molecular weight PIBSA-PAM and the low molecular weight PIBSA-PAM is from 1.0 to 6.0 wt. % of the composition.

20. 20. The lubricating oil composition of claim 19, wherein the high molecular weight PIBSA-PAM dispersant, the low molecular weight PIBSA-PAM dispersant, or a combination thereof is included at a treat level to deliver 20 to 700 ppm by weight of boron to the lubricating oil composition.

21. 20. The lubricating oil composition of claim 18, wherein the one or more antiwear agents comprise one or more zinc dialkyldithiophosphates (ZDDP) at a treat level capable of delivering up to 840 ppm by weight of phosphorus to the composition.

22. 19. The lubricating oil composition of claim 18, wherein the one or more antioxidants comprise one or more phenolic antioxidants, one or more sulfur-based antioxidants, one or more aminic antioxidants, or combinations thereof, and the one or more antioxidants comprise 1.0 to 6.0 wt. % of the composition.

23. 19. The lubricating oil composition of claim 18, wherein the one or more friction modifiers comprise a dimeric molybdenum dialkyldithiocarbamate (moly dimer), a trimer molybdenum dialkyldithiocarbamate (moly trimer), or a combination thereof, at a treat level delivering from 12 to 1000 ppm by weight of molybdenum to the composition.

24. The functionalized polymer is in an amount of 0.2 to 2.0% by weight of the composition and is selected from the group consisting of: iv) Mw / Mn is less than 2; v) a functionality distribution (Fd) value of 3.5 or less; and vi) Mn of the polymer before functionalization is 10,000 g / mol or more (GPC-PS); provided that if the polymer before functionalization is a copolymer of isoprene and butadiene, the Mn of said copolymer is greater than 25,000 g / mol (GPC-PS); C 4‐5 olefin-containing amide, imide, and / or ester functionalized partially saturated or fully saturated polymers; The lubricating oil composition of claim 18.

25. A method of lubricating an internal combustion engine comprising the step of supplying to the engine a lubricating oil composition according to any one of claims 1 to 24.

26. 1. A method for reducing journal bearing wear in an internal combustion engine, comprising: A method comprising the step of supplying to said internal combustion engine a lubricating oil composition according to any one of claims 1 to 24.

27. 1. A method for producing a lubricating oil composition, comprising: (i) an oil of lubricating viscosity in an amount greater than 50 mass % of the composition comprising a Group I base oil, a Group II base oil, a Group III base oil, a Group IV base oil, or a combination thereof; (ii) an overbased calcium detergent having a total base number (KOH / g) of 9 to 500, and a treat level capable of delivering 500 to 1,300 ppm by weight of calcium to the composition; and (iii) an overbased magnesium detergent having a total base number (KOH / g) of 9 to 500, the total base number being at a treat level capable of delivering 500 to 1,300 ppm by weight of magnesium to the composition; Combining or blending wherein the combined total mass of calcium and magnesium in the composition ranges from 1000 ppm to 1800 ppm; the lubricating oil composition has a total sulfated ash content of 1.0 wt.% or less, a high temperature high shear viscosity (HTHS) at 150°C, as measured in accordance with ASTM D4683-20, of 1.8 mPa·s or more and 2.9 mPa·s or less, and a total phosphorus level of 0.080 wt.% or less; the lubricating oil composition provides a 5% to 60% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 Start / Stop Test Method, compared to a lubricating oil composition having a comparable HTHS but not including a mixture of an overbased calcium-based detergent and an overbased magnesium-based detergent in the composition at a combined loading of calcium and magnesium in the range of 1000 ppm to 1800 ppm; method.

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