Lubricating oil composition and use thereof for improving durability of journal bearings in internal combustion engines

Abstract

To provide a lubricating oil composition that improves wear resistance and durability of journal bearings in internal combustion engines.SOLUTION: The present invention relates to a lubricating oil composition obtained by containing or mixing: (i) a base oil, (ii) one or more overbased metallic detergents, and (iii) 0.2 to 1.0 mass% of a friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof. The composition has a total sulfate ash content of 1.0 mass% 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 determined according to ASTM D4683-20, and a total phosphorus level of 0.080 mass% or less. Also provided are a method for reducing wear of journal bearings in internal combustion engines and a method for producing the lubricating oil composition.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] Priority This application claims priority to and the benefit of U.S. Provisional Application No. 63 / 588,242, filed October 5, 2023.

[0002] The present disclosure relates to lubricating oil compositions and, more particularly, to lubricating oil compositions for use in internal combustion engines that provide improved journal bearing wear and durability. [Background technology]

[0003] There is a continuing trend towards lower viscosity SAE (Society of Automotive Engineers) grades in both factory 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 local emission regulations. In conjunction with this, the established use of start / stop technology in both ICE (internal combustion engine) and hybrid applications is becoming more widespread in the industry. However, internal combustion engine main journal bearing and connecting rod (big end) journal bearing durability is often considered the fundamental issue for the introduction of such low viscosity fluids (<0W-20) because the journal bearings of this system are non-ferrous materials (e.g., aluminum bimetal, SnCu and polymer coated), which are less resistant to wear compared to ferrous and steel materials, and respond differently to traditional lubricant additive ingredients. Historically, bearing systems, due to their contact nature, are considered to be especially susceptible to wear due to the use of lower viscosity fluids and the introduction of start / stop techniques. Traditionally, journal bearings, which are hydrodynamic lubricated systems, rely on lubricant viscosity to minimize contact between surfaces and keep wear under control. In an engine oil viscosity reducing environment, the system is more exposed to boundary lubrication with increased start / stop events, causing increased stress on the contacts, resulting in increased wear levels of internal combustion engine journal bearings.

[0004] Thus, there is a need for new engine oils, particularly for gasoline, diesel, natural gas, and hydrogen engines, that exhibit low viscosity grades that meet these requirements in terms of improved engine wear protection while maintaining the desired fuel economy benefits and reduced engine emissions. This need is particularly evident with respect to passenger vehicle engines and the associated oils for lubricating them. More specifically, there is a need for lower viscosity PVL engine oils that not only provide improved fuel economy, but also provide improved journal bearing wear resistance in internal combustion engines. The present invention relates to lubricating oil compositions that exhibit improved engine wear characteristics. More particularly, the present invention relates to crankcase lubricating oil compositions, referred to as crankcase lubricants, for use in compression ignition or spark ignition internal combustion engines, as well as hydrogen and natural gas engines, and the use of certain additives in such lubricating oil compositions, and particularly in low viscosity engine oils, to reduce wear and improve durability of journal bearings in internal combustion engines. The inventors have now surprisingly found that certain combinations of base oils and a friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof, at 0.2 to 1.0 percent by weight of the composition, when used in a lubricant composition for an internal combustion engine, can provide improved engine wear protection for journal bearings using the TE-92 Start-Stop test method, as compared to a lubricant composition having a comparable viscosity but not comprising a friction modifier comprising 0.2 to 1.0 percent by weight of the composition, of glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof.

[0005] The inventors have also surprisingly found that use in a lubricant composition for an internal combustion engine of a particular combination of a base oil and a friction modifier comprising 0.2 to 1.0 mass % of the composition of glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof can provide a reduction in journal bearing wear, as measured by wear scar volume in μm3 using the MTM-R method, compared to a lubricant composition having a comparable HTHS but not comprising a friction modifier comprising 0.2 to 1.0 mass % of the composition of glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof. Summary of the Invention

[0006] The present invention relates to a lubricating oil composition comprising or resulting from mixing greater than 50%, by weight, of the composition, 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; one or more overbased metal-based detergents having a total base number (KOH / g) of greater than or equal to 9 and less than or equal to 500, at a treat level delivering 1000 to 2000 ppm by weight of metal to the composition; and 0.2 to 1.0%, by weight, of the composition, of a friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or a combination thereof, wherein the lubricating oil composition contains 1.0% by weight or less of total sulfated ash, ASTM A12242- ... and a total phosphorus level of 0.080 wt.% or less, as measured in accordance with D4683-20, and wherein the lubricating oil composition has a high temperature high shear viscosity (HTHS) at 150°C of greater than or equal to 1.8 mPa.s and less than or equal to 2.9 mPa.s, as measured in accordance with D4683-20, and a total phosphorus level of 0.080 wt.% or less, and wherein the lubricating oil composition has a lower friction modifier density (μm) using the MTM-R test method than a lubricating oil composition having a comparable HTHS but not including a friction modifier comprising 0.2 to 1.0 wt.% of the composition, including glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof. 3 The present invention relates to a lubricating oil composition that provides a 10% to 80% reduction in journal bearing wear as measured by unit wear scar volume.

[0007] According to another aspect of the present invention, there is provided a method for reducing journal bearing wear in an internal combustion engine comprising: incorporating into the internal combustion engine a lubricating oil composition comprising or admixed with: greater than 50, by weight of the composition, 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; one or more overbased metal-based detergents having a total base number (KOH / g) of greater than or equal to 9 and less than or equal to 500, at a treat level delivering from 1000 to 2000 ppm by weight of metals to the composition; and from 0.2 to 1.0, by weight of the composition, a friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or a combination thereof; wherein the lubricating oil composition contains less than or equal to 1.0, by weight of total sulfated ash, ASTM A12242-1, 100,000 or more; and a high temperature high shear viscosity (HTHS) at 150°C of greater than or equal to 1.8 mPa.s and less than or equal to 2.9 mPa.s, as measured in accordance with D4683-20, and a total phosphorus level of less than or equal to 0.080 wt.%, wherein the lubricating oil composition has a lower friction modifier content than a lubricating oil composition having a comparable HTHS but not including a friction modifier comprising 0.2 to 1.0 wt.% of the composition, said friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof, using the MTM-R test method. 3 A method is provided that includes providing a lubricating oil composition that provides a 10% to 80% reduction in journal bearing wear as measured by unit wear scar volume.

[0008] According to yet a further aspect of the present invention, there is provided a lubricating oil composition resulting from comprising or mixing (i) greater than 50%, by weight of the composition, of 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; (ii) one or more overbased metal based detergents having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500, at a treat level delivering from 1000 to 2000 ppm by weight of metal to the composition; and (iii) from 0.2 to 1.0%, by weight of the composition, of a friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or a combination thereof, wherein the lubricating oil composition has not more than 1.0%, by weight of total sulfated ash, ASTM and a high temperature high shear viscosity (HTHS) at 150°C, determined 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, and a total phosphorus level of less than or equal to 0.080 wt.%, wherein the lubricating oil composition has a friction modifier comprising 0.2 to 1.0 wt.% of glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof, and ... 3 A method is provided for making a lubricating oil composition that provides a 10% to 80% reduction in journal bearing wear as measured by unit wear scar volume. [Brief description of the drawings]

[0009] [Figure 1] 1 is a cross-sectional perspective view of a typical internal combustion engine showing the locations of the various bearings in the engine that require lubrication; [Diagram 2] 1 is a cross-sectional schematic diagram of a journal bearing shell material for a solid bearing, a bimetallic bearing, and a tri-material / tri-metallic bearing. [Diagram 3] 1 is a bar graph of journal bearing wear as measured by wear scar volume using the MTM-R test method based on the addition of 0.3 wt. % GMO organic friction modifier to a lubricating oil composition for steel and aluminum bimetallic wear surfaces. [Figure 4]1 is a bar graph of journal bearing wear as measured by wear scar volume using the MTM-R test method based on the addition of 0.3 wt. % N-ODSA organic friction modifier to a lubricating oil composition for steel and aluminum bimetallic wear surfaces. [Diagram 5] 1 is a bar graph of journal bearing wear as measured by wear scar volume in the MTM-R test method based on the addition of 0.3 wt. % of an oleamide organic friction modifier to a lubricating oil composition for steel and aluminum bimetallic wear surfaces. [Figure 6] 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 the lubricating oil compositions of Inventive Example 2 (0.3 wt. % GMO) and Comparative Example 5 (0 wt. % GMO). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] definition For purposes of this specification and any claims thereto, the following words and expressions, if and when used, have the meanings set forth below. For purposes of this specification, the new numbering scheme of the Periodic Table of the Elements as set forth in CHEMICAL AND ENGINEERING NEWS, Vol. 63(No. 5), p. 27 (1985) will be 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.). The term "comprising" or any cognate term specifies the presence of the stated features, steps, or integers, or components, but does not exclude the presence or addition of one or more other features, steps, integers, components, or groups thereof. The phrases "consists of" or "consists essentially of" or cognate terms may be subsumed within "comprises" or cognate terms. "Consisting essentially of" permits the inclusion of substances that do not materially affect the characteristics of the composition to which it is applied.

[0011] The term "LOC" means 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 80-99.009% by weight of the composition, for example 80-99.9, 80-99.009% by weight of the composition. The term "small 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 to 0.001% by weight, for example 20 to 0.1% by weight. The term "% by weight", unless otherwise indicated, means the weight percent of a component based on the weight of the composition measured in grams, and is alternatively referred to as weight percent ("weight%", "wt%", or "w / w%"). The term "active ingredient" (also referred to as "ai" or "AI") refers to an additive substance that is not a diluent or solvent. Unless otherwise indicated, amounts herein are listed as active ingredient.

[0012] The terms "oil-soluble" and "oil-dispersible" or related terms used herein do not necessarily indicate that a compound or additive is soluble, dissolvable, miscible, or suspendable in oil in any proportion. However, such terms mean that the compound or additive is, for example, soluble or stably dispersible in oil to a sufficient degree to exert its intended effect in the environment in which the oil is used. Furthermore, the incorporation of other additives may also allow for the incorporation of higher levels of a particular additive, if necessary. The terms "group" and "radical" are used interchangeably herein. The term "hydrocarbon" refers to a compound of hydrogen and carbon atoms. A "heteroatom" is an atom other than carbon or hydrogen. When "hydrocarbons", particularly "refined hydrocarbons", are referred to, the hydrocarbon may also contain minor amounts (e.g., amounts in which the heteroatoms do not substantially alter the hydrocarbon character of the hydrocarbon compound) of one or more heteroatoms or heteroatom-containing groups (e.g., halo, especially chloro and fluoro, amino, alkoxyl, mercapto, alkylmercapto, nitro, nitroso, sulfoxy, etc.).

[0013] The term "hydrocarbyl" refers to a radical that contains hydrogen and carbon atoms. Preferably, the group consists essentially, and more preferably exclusively, 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 nature 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.). The term "alkyl" refers to a radical of carbon and hydrogen (e.g., C1-C 30 Groups, e.g. C1-C 12The alkyl group in the compound is typically directly attached 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.

[0014] 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 12 Radicals). An alkenyl group in a compound is typically directly attached to the compound via a carbon atom. Unless otherwise specified, an alkenyl group can be straight-chained (i.e., unbranched) or branched, cyclic, acyclic, or partly cyclic / acyclic. The term "alkylene" refers to any C1-C alkyl 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," alternatively referred to 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 its appended claims, when a polymer or copolymer is said to comprise 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% to 95% by weight, the monomeric units of the copolymer are derived from isoprene in a polymerization reaction, and such derived units are present at 55% to 95% by weight based on the weight of the copolymer. A "polymer" has two or more of the same or different monomeric units. A "homopolymer" is a polymer having the same monomeric units. A "copolymer" is a polymer having two or more monomeric units that are different from each other. "Different," as used to refer to monomeric units, indicates that the monomeric units differ from each other by at least one atom, or are isomerically different. An "isoprene polymer" or "isoprene copolymer" is a polymer or copolymer that contains at least 50 mole percent units derived from isoprene, a "butadiene polymer" or "butadiene copolymer" is a polymer or copolymer that contains at least 50 mole percent units derived from butadiene, etc. Similarly, when a polymer is "C 4~5 When a polymer or copolymer is referred to as a "partially or fully saturated polymer containing olefins," the C 4~5 Olefins are the polymerized form of olefins, the polymers being partially or fully saturated (eg, by hydrogenation) after polymerization of the monomers.

[0015] 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, and the like. Aryl groups are typically C5-C aryl groups that may be 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 substituted derivatives thereof, particularly phenyl and alkyl substituted derivatives of phenyl. The term "substituted" means that a hydrogen atom has been replaced with a hydrocarbon group, a heteroatom, or a heteroatom-containing group. An alkyl-substituted derivative means that a hydrogen atom has been replaced with an alkyl group. An "alkyl-substituted phenyl" means that a hydrogen atom has been replaced with an alkyl group, such as a C1-C 20 Phenyl groups substituted with alkyl groups, 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. The term "halogen" or "halo" means a Group 17 atom or a radical of a Group 17 atom, for example, fluoro, chloro, bromo, and iodo.

[0016] The term "ashless" with respect to the additive means that the composition is metal-free. The term "ash-containing" with respect to the additive means that the composition contains metals. The term "effective amount" with respect to an additive means the amount of such additive in a lubricating oil composition such that the additive provides its desired technical effect. The term "effective minor amount" with respect to an additive means an amount of such additive that is less than 50 mass % of the lubricating oil composition such that the additive provides the desired technical effect. The term "effective major amount" with respect to an additive means an amount of such additive of 50% by weight or more of a lubricating oil composition such that the additive provides a desired technical effect. The term "ppm," unless otherwise indicated, means mass percentage based on the total mass of the lubricating oil composition. The term "metal content" of a lubricating oil composition or of an additive component, such as the magnesium content, molybdenum content, or total metal content (i.e. the sum of all individual metal contents), is measured according to ASTM D5185.

[0017] The term "aliphatic hydrocarbyl fatty acid" refers to an aliphatic C7-C 29 , preferably C9 to C 27 , most preferably C 11 ~C 23 It 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) hydrocarbyl monocarboxylic acid or hydrocarbyl fatty acid (where Cx-Cy refer to 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 contains a total of Cx+1-Cy+1 carbon atoms). Preferably, the aliphatic hydrocarbyl fatty acid has an even number of carbon atoms, including the carboxyl carbon atom. The aliphatic hydrocarbyl chain of the fatty acid may be saturated or unsaturated (i.e., contains at least one carbon-carbon double bond). Preferably, the aliphatic hydrocarbyl chain is unsaturated and contains at least one carbon-carbon double bond, and such fatty acids can be obtained from natural sources (e.g., derived from animal or vegetable oils) and / or by reduction of the corresponding saturated fatty acid. It will be understood that a portion of the aliphatic hydrocarbyl chain of the corresponding aliphatic hydrocarbyl fatty acid ester is unsaturated (i.e., contains at least one carbon-carbon double bond) and can be reacted with other agents, such as sulfur, to form the corresponding functionalized, e.g., sulfurized, aliphatic hydrocarbyl fatty acid ester.

[0018] The term "aliphatic hydrocarbyl fatty acid ester" refers to an ester obtainable by converting a monocarboxylic acid functional group of a 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 fatty acid functional group of the aliphatic hydrocarbyl fatty acid may be converted to an aliphatic hydrocarbyl ester, such as an alkyl ester, preferably a C1-C6 alkyl ester, in particular a methyl ester. Alternatively or additionally, the monocarboxylic acid functional group of the aliphatic hydrocarbyl fatty acid may be in the form of a natural glycerol ester. Thus, the term "aliphatic hydrocarbyl fatty acid ester" includes aliphatic hydrocarbyl fatty acid glycerol esters and aliphatic hydrocarbyl fatty acid C1-C 30It includes aliphatic hydrocarbyl esters [e.g., aliphatic hydrocarbyl fatty acid alkyl esters, more preferably aliphatic hydrocarbyl fatty acid C1-C6 alkyl esters, especially aliphatic hydrocarbyl fatty acid methyl esters]. Suitably, the term "aliphatic hydrocarbyl fatty acid ester" includes aliphatic (C7-C 29 ) hydrocarbyl, more preferably aliphatic (C9-C 27 ) hydrocarbyl, most preferably aliphatic (C 11 ~C 23 ) Hydrocarbyl fatty acid glycerol esters 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 of the fatty acid ester is unsaturated and contains at least one carbon-carbon double bond to allow for functionalization, e.g., sulfurization, of the aliphatic hydrocarbyl fatty acid ester.

[0019] 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 within the lubricating oil compositions and claims thereto described herein mean that a particular component is present at 0 wt. % based on the weight of the lubricating oil composition, or if present in the lubricating oil composition, the component is present at a level that does not affect the lubricating oil composition properties, e.g., less than 10 ppm, or less than 1 ppm, or less than 0.001 ppm. The term "absent", when used in reference to monomeric reactants and / or repeat units in a (co)polymer described herein, means that the component is present at 0 wt. % or at a level so low that, if present, 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, based on the weight of all (co)monomers in the (co)polymer.

[0020] 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 called polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise stated, all molecular weight units (e.g., Mw, Mn, Mz) are reported in g / mole. "Total Base Number," also referred to as "TBN," with respect to an additive component or of a lubricating oil composition (i.e., a virgin lubricating oil composition) means the Total Base Number as determined by ASTM D2896 and is reported in mg KOH / g.

[0021] Total Acid Number ("TAN") is determined 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 by ASTM D5185. Sulfated ash ("SASH") content is measured by ASTM D874. Kinematic viscosity (KV100, KV40) was determined according to ASTM D445-19a and is reported in cSt unless otherwise specified. Viscosity index is determined in accordance with ASTM D2270.

[0022] Saponification number was determined by ASTM D94 and is reported in mg KOH / g. HTCBT, High Temperature Corrosion Bench Test, is determined in accordance with ASTM D6594. The term "functionalized polymer" refers to polymers of the functionalized hydrogenated polyisoprene family for use in lubricating oil compositions, which are disclosed in commonly owned U.S. Patent Application No. 63 / 379,006, filed October 11, 2022, which is incorporated herein by reference in its entirety. For the functionalized polymer family of polymers, the average functionality (also referred to as the average functionality value (Fv)) and functionality distribution (Fd) values ​​are determined by gel permeation chromatography using polystyrene standards, as described in the experimental section of U.S. Patent Application No. 18 / 480,571, filed October 4, 2023, which claims priority to 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 moieties attached to the quaternary carbon are saturated linear, branched, or cyclic alkyl groups.

[0023] "Neodecanoic acid" has the general structural formula C 10 H 20 C with O2 10 It is a mixture of neo-acids, the components of which are acids that share the common property of having three alkyl groups at the 2-carbon position, including, but not limited to, 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. Unless otherwise indicated, all percentages reported are weight percent or weight percent (wt%) on an active ingredient basis, that is, without regard to carrier or diluent oil, unless otherwise indicated. It will also be understood that the various ingredients used, essential as well as optional and conventional ingredients, may react under conditions of formulation, storage, or use, and that the present disclosure also provides products that may result or are obtained as a result of any such reactions. Further, it is understood that all upper and lower amount, 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.

[0024] Detailed Description of the Invention The features of the present disclosure with respect to each and every aspect of the present disclosure will now be described in further detail, where appropriate, as follows: The lubricating oil compositions of this disclosure contain components that may or may not remain chemically the same before and after mixing with an oil-based carrier (e.g., base oil) and / or other additives. This disclosure encompasses compositions that contain the components before mixing, after mixing, or both before and after mixing. The lubricating oil compositions of the present disclosure are particularly suitable for lubricating journal bearings found in internal combustion engines. Referring to FIG. 1, a cutaway perspective view of an exemplary internal combustion engine 10 is shown showing the location of various bearings in the engine requiring lubrication. The engine 10 includes a connecting rod small end bearing / bushing 20 having a piston pin type journal. The engine 10 also includes a crankshaft journal main bearing 30 and a connecting rod big end bearing 40 for the crankshaft journal. The engine 10 further includes 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 of each of these bearing / journal types shown in FIG. 1.

[0025] Referring to FIG. 2, the structures and cross-sections of solid bearings, bimetallic bearings, and tri-material / tri-metallic bearings, and cross-sectional schematics of journal bearing shell materials of solid bearings, bimetallic bearings, and tri-material / tri-metallic bearings are shown. The solid bearings may include bronze or lead-free bronze. The bimetallic bearings may include AlSn20Cu or AlSn25. The tri-material / tri-metallic bearings may include a polymeric overlay or a SuCu overlay on lead-free bronze. The inventive lubricating oil composition of the present disclosure is particularly suitable for lubricating and minimizing wear of each of these bearing structures / materials shown in FIG. 2. In particular, the inventive lubricating oil composition of the present disclosure has been surprisingly found to reduce bimetallic and tri-material / tri-metallic wear when used in internal combustion engines. More particularly, the inventive lubricating oil composition of the present disclosure has been surprisingly found to reduce wear of SnCu tri-metallic and polymeric tri-material.

[0026] 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 or resulting from mixing greater than 50%, by weight of the composition, 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, one or more overbased metal-based detergents having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500, at a treat level delivering 1000 to 2000 ppm metal by weight to the composition, and 0.2 to 1.0%, by weight of the composition, of a friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or a combination thereof. The lubricating oil composition may have a total sulfated ash content of 1.0 mass % 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 determined in accordance with ASTM D4683-20, and a total phosphorus level of 0.080 mass % or less. The lubricating oil composition has a lower friction modifier content in μm using the MTM-R test method compared to a lubricating oil composition having a comparable HTHS but not including a friction modifier comprising 0.2 to 1.0 mass % of the composition of glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof. 3 Provides a 10% to 80% reduction in journal bearing wear as measured by unit wear scar volume.

[0027] The lubricating oil composition may also provide a 10% to 70% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 Start-Stop Test Method, as compared to a lubricating oil composition having a comparable HTHS but not including a friction modifier comprising 0.2 to 1.0 weight percent of the composition of glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof. In one embodiment, the lubricating oil composition comprises a friction modifier comprising glycerol monooleate. In another embodiment, the friction modifier comprises 0.2 to 1.0 mass % of the composition of glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof, or 0.3 to 0.9 mass %, or 0.4 to 0.8 mass %, or 0.5 to 0.7 mass %. In yet another embodiment, the lubricating oil composition comprises 0.3 to 0.5 mass % of the composition of a friction modifier comprising glycerol monooleate. The lubricating oil compositions disclosed herein have a High Temperature High Shear Viscosity (HTHS or HTHS) at 150° C., as determined according to ASTM D4683-20, of 1.8 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. 150 The lubricating oil compositions disclosed herein may have a total sulfated ash content of 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.

[0028] The lubricating oil compositions disclosed herein may have phosphorus levels 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. The lubricating oil compositions of this 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 this 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 constitutes from 60% to 95%, or from 70 to 90%, or from 75 to 85% by weight of the composition and comprises a Group III base oil, a Group IV base oil, or a combination thereof.

[0029] In the case of the one or more overbased metallic detergents of the lubricating oil composition, it may be a sulfonate, a salicylate, a phenate, or a combination thereof. The one or more overbased metallic detergents may deliver 1000 to 2000 ppm, or 1200 to 1800 ppm, or 1400 to 1600 ppm of metal by weight to the composition. The metal of the one or more overbased metallic detergents may be selected from the group consisting of sodium, potassium, lithium, calcium, and magnesium, and combinations thereof. 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. Even more particularly, 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 vehicle lubricants (PVL) or commercial vehicle lubricants (CVL) and provide a 10% to 70%, or 15 to 60%, or 20 to 50%, 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 friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof.

[0030] The lubricating oil compositions also have a lower friction modifier density than lubricating oil compositions having a comparable HTHS but containing glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof, compared to lubricating oil compositions having a lower friction modifier density using the MTM-R test method. 3It may provide a 10% to 80%, or 15% to 70%, or 20% to 60%, or 25% to 50%, or 30% to 40% reduction in journal bearing wear as measured by unit wear scar volume. The lubricating oil compositions disclosed herein are particularly suitable for lubricating and reducing the wear tendency of journal bearings in internal combustion engines, the journal bearings being crankshaft main bearings, crankshaft connecting rod big end bearings, or piston pin connecting rod small end bearings / bushings. The journal bearing shell material may be a material selected from the group consisting of bimetal, tri-material / trimetal, and solid material. In the case of tri-material / trimetal journal bearings, the tri-material / trimetal may be a polymeric coating or a SnCu overlay on lead-free bronze. In the case of bimetal journal bearings, the bimetal may be AlSn20Cu or AlSn25. In the case of solid material journal bearings, the solid material may be bronze or lead-free bronze.

[0031] In one particular aspect, the inventive lubricating oil compositions disclosed herein, when used to lubricate aluminum bimetal journal bearing shell material, provide a 50% to 70%, or 52% to 68%, or 55% to 65%, or 58% to 63% reduction in journal bearing wear as measured by wear scar volume in μm3 using the MTM-R test method, compared to a lubricating oil composition having a comparable HTHS but not containing a friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof. In another specific aspect, the inventive lubricating oil compositions disclosed herein, when used to lubricate a SnCu overlay trimetal journal bearing shell material, provide a 30% to 50%, or 32 to 48%, or 35% to 45%, or 38% to 43% 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 friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof.

[0032] 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 other 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 advantageous embodiment, the lubricating oil composition of the present disclosure further comprises one or more dispersants, a higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g / mole or greater), which may be borated, one or more lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g / mole), which may be borated, or a combination thereof, wherein the treat level of the combination of the higher molecular weight PIBSA-PAM and the lower 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, the lubricating oil composition of the present disclosure comprises a higher molecular weight PIBSA-PAM dispersant, a lower molecular weight PIBSA-PAM dispersant, or a combination thereof, present at a treat level to deliver from 20 ppm to 700 ppm, or from 50 to 600 ppm, or from 100 to 500 ppm, or from 200 to 400 ppm of boron by weight to the lubricating oil composition.

[0033] In an advantageous form, the lubricating oil composition of this disclosure further comprises one or more antiwear agents comprising a treat level of one or more zinc dialkyldithiophosphates (ZDDPs) to deliver 840 ppm or less, or 800 ppm or less, or 700 ppm or less, or 600 ppm or less of phosphorus by weight to the composition. 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 constitute 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 form, the lubricating oil composition of the present disclosure further comprises one or more other friction modifiers selected from molybdenum dimeric dialkyldithiocarbamate (moly dimer), molybdenum trimer dialkyldithiocarbamate (moly trimer), or combinations thereof, at a treat level to deliver from 12 ppm to 1000 ppm, or from 20 ppm to 500 ppm, or from 20 ppm to 200 ppm of molybdenum by weight to the composition.

[0034] In yet another advantageous form, the lubricating oil compositions of the present disclosure are substantially free of molybdenum. In another advantageous form, the lubricating oil composition of the present disclosure comprises: i) Mw / Mn less than 2, or less than 1.8, or less than 1.6; ii) a functionality distribution (Fd) value of 3.5 or less, or 3.2 or less, or 3.0 or less, or 2.5 or less, and iii) Mn of the polymer before functionalization of 10,000 g / mol or more, or 15,000 g / mol or more, or 20,000 g / mol or more, or 25,000 g / mol or more (GPC-PS); 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 4~5Optionally, the composition further comprises 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 one or more functionalized polymers including amide, imide, and / or ester functionalized partially or fully saturated polymers with olefins.

[0035] The functionalized polymer of the lubricating oil composition of the present disclosure may comprise at least 50%, or at least 60%, or at least 70% of the monomers with 1,4-insertion. Additionally, the functionalized polymer of the lubricating oil composition of the present disclosure may comprise a partially or fully saturated homopolyisoprene containing one or more pendant amine groups and having, prior to functionalization, a Mn of 25,000-100,000 g / mole, or 35,000-90,000 g / mole, or 45,000-80,000 g / mole, or 55,000-75,000 g / mole (GPC-PS), and at least 50%, or at least 60%, or at least 70% 1,4-insertion.

[0036] The functionalized polymer of the lubricating oil composition of the present disclosure may be free of styrene repeat units, or may be free of 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. Also provided herein is a method for lubricating an internal combustion engine, the method 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 an engine and combusting the motor gasoline in the engine, the motor gasoline being non-renewable motor gasoline, renewable motor gasoline, or a combination thereof, and the engine being a spark ignition combustion engine. Also provided herein is a method of supplying diesel fuel to an engine and combusting the diesel fuel in the engine, the diesel fuel being non-renewable diesel fuel, renewable diesel fuel, or a combination thereof, and the engine being a diesel engine. Also provided herein is a method of supplying natural gas or hydrogen to an engine and combusting the natural gas or hydrogen in the engine, the engine being a natural gas engine or a hydrogen engine.

[0037] The lubricating oil compositions of the present disclosure are particularly suitable for improving journal bearing wear performance in internal combustion engines and for 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 making a lubricating oil composition, comprising the step of combining or mixing the components of the lubricating oil composition of the present disclosure. 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. Typically, the lubricating oil composition may contain low levels of sulfur. Preferably, the lubricating oil composition contains up to 0.35, more preferably up to 0.3, for example 0.1 to 0.35, mass % sulfur, based on the total mass of the lubricating oil composition, as measured by ASTM D5185.

[0038] Typically, the lubricating oil composition may contain low levels of sulfated ash, for example 1.0 mass % or less, or preferably 0.9 mass % or less, alternatively 0.0001 to 0.9 mass % or less, of sulfated ash, 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 viscosity descriptors SAE 15W-X, SAE 10W-X, SAE 5W-X, or SAE 0W-X, where X is 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 viscosity grades SAE 15W-X, SAE 10W-X, SAE 5W-X, or SAE 0W-X, such as SAE 15W-X or SAE 10W-X, where X is 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 known as the Society of Automotive Engineers).

[0039] In an embodiment, the lubricating oil composition may contain less than 75 ppm boron, alternatively less than 60 ppm boron, alternatively 1-70 ppm boron. Alternatively, the LOC may be free of boron 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 a high molecular weight PIBSA-PAM. In an embodiment, the lubricating oil composition may comprise an acylated polymer, e.g., polyisobutylene succinic acid (PIBSA), optionally 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, e.g., polyisobutylene succinic acid, optionally 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.

[0040] In an embodiment, the lubricating oil composition may comprise up to 20 (e.g., 15, e.g., 10, e.g., 5, e.g., 3, e.g., 1) wt % of a block copolymer, such as a block, star, random, and / or tapered block copolymer. In embodiments, the lubricating oil composition may be substantially free of or may be 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 (e.g., 15, e.g., 10, e.g., 5, e.g., 3, e.g., 1) wt. % of a styrenic copolymer, such as a block, star, random, and / or tapered styrenic copolymer. In an embodiment, the lubricating oil composition may be substantially free of, or may be free of, styrenic copolymers, such as block, star, random, and / or tapered styrenic copolymers. In an embodiment, the lubricating oil composition may comprise less than 20 (eg, 15, such as 10, such as 5, such as 3, such as 1) mass % of a functionalized diluent, such as a functionalized oil.

[0041] In an embodiment, the lubricating oil composition may include, be substantially free of, or be free of a functionalized diluent, e.g., a functionalized oil. In an embodiment, the lubricating oil composition may comprise less than 20 (eg 15, such as 10, such as 5, such as 3, such as 1) mass % of a solvent, such as an aromatic solvent. In embodiments, the lubricating oil composition may be substantially free of solvent, such as functionalized solvents, or may be free of solvent, 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 absent or zero mass %) of secondary hydrocarbyl amine compounds and tertiary hydrocarbyl amine compounds, based on the mass of the LOC.

[0042] In an embodiment, the lubricating oil composition may be substantially free of or free of secondary hydrocarbyl amine compounds and tertiary hydrocarbyl amine compounds. In embodiments, the lubricating compositions of this disclosure may be heavy duty diesel oils, light duty diesel oils, or passenger vehicle 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) and 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.

[0043] Methods for using lubricating oil compositions The present disclosure also relates to methods for using the lubricating oil composition, particularly for reducing journal bearing wear in an internal combustion engine, comprising the step of supplying to an internal combustion engine a lubricating oil composition comprising or resulting from mixing: greater than 50 wt. % of the composition of 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; one or more overbased metal-based detergents having a total base number (KOH / g) of greater than or equal to 9 and less than or equal to 500, at a treat level delivering from 1000 to 2000 ppm by weight of metal to the composition; and 0.2 to 1.0 wt. % of the composition of a friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or a combination thereof. 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 greater than or equal to 1.8 mPa.s and less than or equal to 2.9 mPa.s, as determined in accordance with ASTM D4683-20, and a total phosphorus level of 0.080 wt.% or less. The lubricating oil composition provides a 10% to 80% reduction in journal bearing wear as measured by wear scar volume in μm3 using the MTM-R test method compared to a lubricating oil composition having a comparable HTHS but not including a friction modifier comprising 0.2 to 1.0 wt.% of the composition, glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof.

[0044] Also, a method for using the lubricating oil composition, particularly a method for reducing journal bearing wear in an internal combustion engine, can provide a 10% to 70% 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 friction modifier comprising 0.2% to 1.0% by weight of the composition of glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof. The lubricating oil compositions disclosed herein surprisingly and unexpectedly exhibit improved wear in microns using the TE-92 Start-Stop Test Method and improved wear in μm using the MTM-R Test Method compared to lubricating oil compositions having a comparable HTHS but not containing a friction modifier comprising 0.2 to 1.0 weight percent of the composition, including glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof. 3 It has been found to reduce journal bearing wear as measured by unit wear scar volume.

[0045] In another aspect of the present disclosure, in the method for reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition may have a High Temperature High Shear Viscosity (HTHS) at 150° C. determined according to ASTM D4683-20 ​​of greater than or equal to 1.8 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. In another aspect of the present disclosure, in the method for 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. In another aspect of the disclosure, in the method for reducing journal bearing wear in an internal combustion engine of the disclosure, the lubricating oil composition may have a kinematic viscosity at 100° C. from 5 to 20 cSt, or from 8 to 18 cSt, or from 10 to 16 cSt; and 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.

[0046] In another aspect of the disclosure, in the method for reducing journal bearing wear in an internal combustion engine of the disclosure, the oil of lubricating viscosity constitutes 60% to 95%, or 70 to 90%, or 75 to 85%, by weight of the composition and comprises a Group III base oil, a Group IV base oil, or a combination thereof. In another aspect of the present disclosure, the method for reducing journal bearing wear in an internal combustion engine of the present disclosure, in the case of an overbased magnesium detergent of the lubricating oil composition, it 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, or 600 to 1200 ppm, or 700 to 1100 ppm, or 800 to 1000 ppm of magnesium by mass to the composition. Similarly, the overbased calcium detergent may deliver 500 to 1300 ppm, or 600 to 1200 ppm, or 700 to 1100 ppm, or 800 to 1000 ppm of calcium by mass to the composition.

[0047] In another aspect of the present disclosure, the method for reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition may include one or more overbased metallic detergents which may be sulfonates, salicylates, phenates, or combinations thereof. The one or more overbased metallic detergents may deliver 1000 to 2000 ppm, or 1200 to 1800 ppm, or 1400 to 1600 ppm of metal by weight to the composition. The metal of the one or more overbased metallic detergents may be selected from the group consisting of sodium, potassium, lithium, calcium, and magnesium, and combinations thereof. In another aspect of the present disclosure, the method for 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.

[0048] In another aspect of the present disclosure, the method for reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition is particularly suitable as a passenger vehicle lubricant (PVL) or commercial vehicle lubricant (CVL) and provides a 10% to 70%, or 15 to 60%, or 20 to 50%, 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 friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof. In yet another aspect of the present disclosure, the disclosed method for reducing journal bearing wear in an internal combustion engine, the lubricating oil composition is characterized in that the lubricating oil composition has a comparable HTHS but does not contain a friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or a combination thereof, and the lubricating oil composition has a friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or a combination thereof, and the lubricating oil composition has a friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or a combination thereof, the friction modifier having a ... 3 It may provide a 10% to 80%, or 15% to 70%, or 20% to 60%, or 25% to 50%, or 30% to 40% reduction in journal bearing wear as measured by unit wear scar volume.

[0049] In another aspect of the present disclosure, the method for reducing journal bearing wear in an internal combustion engine of the present disclosure is particularly suitable for lubricating and reducing the wear tendency of journal bearings in an internal combustion engine, the journal bearing being a crankshaft main bearing, a crankshaft connecting rod big end bearing, or a piston pin connecting rod small end bearing / bushing. The journal bearing shell material may be a material selected from the group consisting of bimetal, tri-material / tri-metal, and solid material. In the case of tri-material / tri-metal journal bearings, the tri-material / tri-metal may be a polymeric coating or a SnCu overlay on lead-free bronze. In the case of bimetal journal bearings, the bimetal may be AlSn20Cu or AlSn25. In the case of solid material journal bearings, the solid material may be bronze or lead-free bronze. In one particular aspect, the disclosed method for reducing journal bearing wear in an internal combustion engine is particularly suitable when the inventive lubricating oil composition disclosed herein is used to lubricate an aluminum bimetal journal bearing shell, where the lubricating oil composition has a lower friction coefficient than a lubricating oil composition having a comparable HTHS but not including a friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or a combination thereof, using the MTM-R test method. 3 Provides a 50% to 70%, or 52% to 68%, or 55% to 65%, or 58% to 63% reduction in journal bearing wear as measured by unit wear scar volume.

[0050] Also, in another particular aspect, the disclosed method for reducing journal bearing wear in an internal combustion engine is particularly suitable when the inventive lubricating oil compositions disclosed herein are used to lubricate a SnCu overlay trimetal journal bearing shell material, where the lubricating oil composition provides a 30% to 50%, or 32 to 48%, or 35% to 45%, or 38% to 43% 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 friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof. In another aspect of the present disclosure, in the method for 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 other 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.

[0051] In an advantageous embodiment, in the method for reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition further comprises one or more dispersants, a higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g / mole or greater), which may be borated, one or more lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g / mole), which may be borated, or a combination thereof, wherein the treat level of the combination of the higher molecular weight PIBSA-PAM and the lower 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 embodiment, in the method for reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition may contain a higher molecular weight PIBSA-PAM dispersant, a lower molecular weight PIBSA-PAM dispersant, or a combination thereof, present at a treat level providing the lubricating oil composition with from 20 ppm to 700 ppm, or from 50 to 600 ppm, or from 100 to 500 ppm, or from 200 to 400 ppm of boron by weight. In an advantageous embodiment, in the method for reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition may further comprise one or more anti-wear agents comprising a treat level of one or more zinc dialkyldithiophosphates (ZDDP) to deliver 840 ppm or less, or 800 ppm or less, or 700 ppm or less, or 600 ppm or less of phosphorus by weight to the composition.

[0052] In another advantageous form, in the method for 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 constitute from 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, the method for reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition may further comprise one or more other friction modifiers selected from molybdenum dimeric dialkyldithiocarbamate (moly dimer), molybdenum trimer dialkyldithiocarbamate (moly trimer), or combinations thereof, at a treat level to deliver from 12 ppm to 1000 ppm, or from 20 ppm to 500 ppm, or from 20 ppm to 200 ppm of molybdenum by weight to the composition.

[0053] In yet another advantageous embodiment, in the method for reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition is substantially free of molybdenum. In another advantageous embodiment, in the method for reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition comprises: i) Mw / Mn less than 2, or less than 1.8, or less than 1.6; ii) a functionality distribution (Fd) value of 3.5 or less, or 3.2 or less, or 3.0 or less, or 2.5 or less, and iii) Mn of the polymer before functionalization of 10,000 g / mol or more, or 15,000 g / mol or more, or 20,000 g / mol or more, or 25,000 g / mol or more (GPC-PS); 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 Optionally, the composition may further comprise 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 one or more functionalized polymers including amide, imide, and / or ester functionalized partially or fully saturated polymers with olefins.

[0054] Method for making a lubricating oil composition The present disclosure also relates to methods for making lubricating oil compositions, and in particular to methods for making lubricating oil compositions comprising the steps of combining or mixing: (i) greater than 50%, by weight of the composition, of 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; (ii) one or more overbased metal-based detergents having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500, at a treat level delivering from 1000 to 2000 ppm by weight of metal to the composition; and (iii) from 0.2 to 1.0%, by weight of the composition, of a friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or a combination thereof. 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 of 1.8 mPa.s or more and 2.9 mPa.s or less as determined in accordance with ASTM D4683-20, and a total phosphorus level of 0.080 wt.% or less. The method for making the lubricating oil composition comprises measuring the friction modifier level in μm using the MTM-R test method compared to a lubricating oil composition having a comparable HTHS but not including a friction modifier comprising 0.2 to 1.0 wt.% of the composition, glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof. 3 A composition is provided that exhibits a 10% to 80% reduction in journal bearing wear as measured by unit wear scar volume.

[0055] The method for making a lubricating oil composition may also provide a composition that provides a 10% to 70% 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 friction modifier comprising 0.2 to 1.0 wt. % of the composition, including glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof. The method for making the lubricating oil composition of the present disclosure is particularly suitable for use 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 for use 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.

[0056] concentrate A concentrate, also called an additive package, adpak, or addpack, is a composition having less than 50 mass % (e.g., less than 40 mass %, such as less than 30 mass %, such as less than 25 mass %, such as less than 20 mass %) of a base oil and a lubricant composition additive (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 resulting from mixing 1 to 50 wt. % of one or more base oils having a total base number (KOH / g) of 9 to 500, 2 to 25 wt. % of one or more overbased metallic detergents, based on the weight of the concentrate, and 2 to 25 wt. % of a friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or a combination thereof. The concentrate may be present in the lubricating oil composition of the present disclosure in an amount from 0.5% to 35% by weight, such as from 5% to 30% by weight, such as from 7.5% to 25% by weight, such as from 10 to 22.5% by weight, for example from 15 to 20% by weight, based on the weight of the lubricating oil composition.

[0057] Optionally, the concentrate may be free of functionalized oils. In an embodiment, the concentrate composition may optionally be free of solvent (eg, aliphatic or aromatic solvents) and / or free of functionalized base oil. Optionally, the concentrate may be free of phenolic antioxidants. In an embodiment, the concentrate may contain less than 75 ppm boron, alternatively less than 60 ppm boron, alternatively between 1 and 70 ppm boron. Alternatively, the concentrate may be free of boron. In an embodiment, the concentrate may comprise up to 20 (e.g. 15, e.g. 10, e.g. 5, e.g. 3, e.g. 1) wt. % of a functionalized (e.g. aminated) polybutene (e.g. polyisobutylene), e.g. PIBSA-PAM. In an embodiment, the concentrate is substantially free of or free of a functionalized (e.g. aminated) polybutene (e.g. polyisobutylene), e.g. PIBSA-PAM.

[0058] In an embodiment, the concentrate may further comprise one or more of the following components: one or more functionalized polymers, one or more other 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 comprise an acylated polymer, e.g., polyisobutylene succinic acid, optionally 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 comprise an acylated polymer, e.g., polyisobutylene succinic acid, optionally having a Mn of 500 to 1600 g / mol, e.g., 700 to 1200 g / mol. In an embodiment, the concentrate may comprise up to 20 (eg 15, eg 10, eg 5, eg 3, eg 1) wt % of block copolymers, such as block, star, random, and / or tapered block copolymers. In embodiments, the concentrate may be substantially free of block copolymers, e.g., block, star, random, and / or tapered block copolymers, or may be free of block copolymers, e.g., block, star, random, and / or tapered block copolymers.

[0059] In an embodiment, the concentrate may contain 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 styrenic copolymer, such as a block, star, random, and / or tapered styrenic block copolymer. In embodiments, the concentrate may be substantially free of or may be free of styrenic copolymers, such as block, star, random, and / or tapered styrenic block copolymers. In an embodiment, the concentrate may contain 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 of functionalized diluents, such as functionalized oils, or may be free of functionalized diluents, such as functionalized oils.

[0060] In an embodiment, the concentrate may contain less than 0.5% (e.g., 0.4%, such as less than 0.3%, such as less than 0.2%, such as 0.1%, substantially absent, or zero) by weight 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 of secondary hydrocarbyl amine compounds and tertiary hydrocarbyl amine compounds, or may be 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. The present disclosure also relates to a method for making a concentrate composition comprising combining 1 to 50 wt. % of one or more base oils, 2 to 25 wt. % of an overbased magnesium-based detergent having a total base number (KOH / g) of 9 or more and 500 or less, and 2 to 25 wt. % of an overbased calcium-based detergent having a total base number (KOH / g) of 9 or more and 500 or less, based on the weight of the concentrate.

[0061] Lubricating Oil Composition Components and Concentrate Components A. Base Oil Components Base oils (also called "base stocks," "lubricating oil base stocks," or "oils of lubricating viscosity") useful herein can be a single oil or a blend of oils and are typically the large liquid component of a lubricating composition, also called a lubricant, into which, for example, additives and optionally additional oils are blended to produce a lubricating composition, e.g., a finished lubricant composition, a concentrate, or other lubricating composition. The base oil can be selected from vegetable oils, animal oils, mineral oils, and synthetic lubricating oils, and mixtures thereof. The base oil can range in viscosity from light distillate mineral oils to heavy lubricating oils, such as those for gas engine oils, mineral lubricating oils, power vehicle oils, and heavy duty diesel oils. In general, the kinematic viscosity at 100°C ("KV100") of the base oil, determined according to ASTM D445-19a, ranges from 1 to 30, such as 2 to 25 cSt, such as 5 to 20 cSt, in particular 1.0 cSt to 10 cSt, 1.5 cSt to 3.3 cSt, 2.7 cSt to 8.1 cSt, 3.0 cSt to 7.2 cSt, or 2.5 cSt to 6.5 cSt. Generally, the high temperature high shear viscosity (HTHS) of the base oil at 150° C., as determined according to ASTM D4683-20, is in the range of 0.5 to 20 cP, such as 1 to 10 cP, for example 2 to 5 cP.

[0062] Typically, when a lubricating oil base stock is used to make a concentrate, the lubricating oil base stock may advantageously be present in a concentrate-forming amount that results in a concentrate containing from 5% to 80%, from 10% to 70%, or from 5% to 50% by weight of the active ingredient, based on the weight 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-naphthenic types. Oils derived from coal or shale are also useful base oils. Base stocks can 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 homopolymerized and copolymerized olefins, referred to as polyalphaolefins or PAOs or Group IV base oils [as defined by API EOLCS 1509 (see 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 to C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C20, C22, C23, C24, C25, C26, C27, C28, C29, C30, C31, C32, C33, C34, C35, C35, C46, ​​C47, C48, C49, C51, C52, C53, C54, C55, C56, C57, C58, C59, C60, C61, C62, C63, C64, C65, C65, C66, C67, C68, C69, C70, C71, C72, C73, C74, C75, C75, C75, C76, C77, C78, ​​C79, C71, C72, C73, C74 ... 20 Homopolymers or copolymers of alkenes, C8 and / or C 10 and / or C. 12 Homopolymer or copolymer of alkenes, C8 / C 10 Copolymer, C8 / C 10 / C 12 Copolymers, and C 10 / C 12 Copolymers, as well as derivatives, analogs, and congeners thereof.

[0063] 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, more preferably 10 carbon atoms, having a kinematic viscosity at 100° C. (as 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 determined by ASTM D2270, and / or a pour point (as measured by ASTM D97) of −5° C. or less, more preferably −10° C. or less, more preferably −20° C. or less.

[0064] In another embodiment, the polyalphaolefin oligomer useful in the present disclosure is 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 is a C5-C 14 Alpha-olefins, and in another embodiment C-C 12 Alpha-olefins, and in another embodiment C-C 12The 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 alternatively may be essentially 1-decene, and the PAO is a mixture of these dimers, trimers, tetramers, and pentamers (and higher). Useful PAOs are described in more detail, for example, in U.S. Pat. Nos. 5,171,908 and 5,783,531, and in Synthetic Lubricants and High-Performance Functional Fluids, pages 1-52 (Leslie R. Rudnick & Ronald L. Shubkin, eds., Marcel Dekker, Inc., 1999).

[0065] The PAOs useful in this disclosure typically have a number average molecular weight of 100 to 21,000 g / mole in one embodiment, 200 to 10,000 g / mole in another embodiment, 200 to 7,000 g / mole in yet another embodiment, 200 to 2,000 g / mole in yet another embodiment, and 200 to 500 g / mole in yet another embodiment. Suitable PAOs are commercially available as SpectraSyn™ Hi-Vis, SpectraSyn™ Low-Vis, SpectraSyn™ plus, SpectraSyn™ Elite PAOs (ExxonMobil Chemical Company, Houston, Texas) and Durasyn PAOs from Ineos Oligomers USA LLC. Synthetic lubricating oils useful as base oils also include hydrocarbon oils such as homopolymeric and copolymeric 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.

[0066] Another suitable class of synthetic lubricating oils useful as base oils comprises the 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 such 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.

[0067] Esters useful as synthetic oils herein include those having C5-C 12 Also included are those made from monocarboxylic acids and polyols, as well as polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol. Preferred ester base oils are available commercially as Esterex™ esters (ExxonMobil Chemical Company, Houston, Tex.). Silicon-based oils, such as polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy silicone oils and silicate oils, constitute 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. 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.

[0068] 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 retort operation, petroleum oil obtained directly from distillation, or ester oil obtained directly from esterification process 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 refining 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 method is applied to a previously refined oil that was previously used in service. Such re-refined oils are also called reclaimed or reprocessed oils, and are often additionally processed to remove waste additives and oil breakdown products. Re-refined base oils are preferably substantially free of materials introduced by manufacturing, contaminants, or previous use.

[0069] Another example of a useful base oil is a gas-to-liquid (GTL) base oil, i.e., a base oil derived from hydrocarbons made from synthesis gas ("syn-gas") containing H2 and CO using a Fischer-Tropsch catalyst. Such hydrocarbons typically require further processing to be useful as base oils. For example, such hydrocarbons may be hydroisomerized, hydrocracked and hydroisomerized, dewaxed, or hydroisomerized and dewaxed by methods known in the art. For more information on useful GTL base oils and blends thereof, see U.S. Pat. No. 10,913,916 (column 4, line 62 to column 5, line 60) and U.S. Pat. No. 10,781,397 (column 14, line 54 to column 15, line 5, and column 16, line 44 to column 17, line 55).

[0070] In particular, renewable resources, ie, carbon and energy captured from the environment, such as oil that is based in part on biological sources, are useful herein. Various base oils are often classified as Group I, II, III, IV, or V according to the API EOLCS 1509 definition (see American Petroleum Institute Publication 1509, Section E.1.3, 19th Edition, January 2021, www.API.org). Generally speaking, Group I base stocks have a viscosity index of about 80-120 and contain more than about 0.03% sulfur and / or less than about 90% saturates. Group II base stocks have a viscosity index of about 80-120 and contain less than about 0.03% sulfur and more than about 90% saturates. Group III base stocks have a viscosity index greater than about 120 and contain less than about 0.03% sulfur and more than about 90% saturates. Group IV base stocks include polyalphaolefins (PAOs). Group V base stocks include base stocks not included in Groups I-IV. (Viscosity index is measured by ASTM D2270, saturates are measured by ASTM D2007, sulfur is measured by ASTM D5185, D2622, ASTM D4294, ASTM D4927, and ASTM D3120).

[0071] The base oil for use in the formulated lubricant composition useful in the present disclosure is any one, two, three or more of the various oils described herein. In a preferred embodiment, the base oil for use in the formulated lubricant composition useful in the present disclosure is described as API Group I (including Group I+), Group II (including Group II+), Group III (including Group III+), Group IV, and Group V oils, and mixtures thereof, preferably API Group II, Group III, Group IV, and Group V oils, and mixtures thereof. The base oil may be Group III, Group III+, IV, and Group V base oils, due to their excellent volatility, stability, viscosity, and clarity characteristics. Small amounts of Group I base stocks, for example, those used to dilute additives for blending into a formulated lubricant product, can be tolerated, but are typically kept to a minimum, for example, those amounts related only to their use as diluents / carrier oils for additives used on an "as received" basis. With regard to Group II stocks, it is often more useful for a Group II base stock to be in the higher quality range associated with that stock, i.e. a Group II stock having a viscosity index in the range of 100-120.

[0072] The base oils useful herein can be selected from either synthetic, natural, or rerefined oils (e.g., those typically used as crankcase lubricants in spark-ignition and compression-ignition engines). Mixtures of synthetic and / or natural and / or rerefined base oils can be used if desired. Multimodal mixtures (e.g., bimodal or trimodal mixtures) of Group I, II, III, IV, and / or V base stocks can be used if desired. The base oil or base oil blend used herein conveniently has a kinematic viscosity at 100°C (KV100, measured in accordance with ASTM D445-19a and reported in centistokes (cSt) or equivalent mm2 / s) of from about 2 to about 40 cSt, alternatively from 3 to 30 cSt, alternatively from 4 to 20 cSt at 100°C, alternatively from 5 to 10 cSt, alternatively the base oil or base oil blend may have a kinematic viscosity at 100°C of from 2 to 20 cSt, from 2.5 to 2 cSt, preferably from about 2.5 cSt to about 9 cSt.

[0073] The base oil or base oil blend preferably has a saturate content of at least 65% by mass, more preferably at least 75% by mass, such as at least 85% by mass, for example at least 90% by mass, as determined by ASTM D2007. Preferably, the base oil or base oil blend will have a sulfur content of less than 1 mass %, preferably less than 0.6 mass %, most preferably less than 0.4 mass %, for example less than 0.3 mass %, based on the total mass of the lubricating composition, as measured by ASTM D5185. In an embodiment, the volatility of the base oil or base oil blend is not more than 30% by weight, such as not more than 25% by weight, such as not more than 20% by weight, such as not more than 16% by weight, such as not more than 12% by weight, such as not more than 10% by weight, based on the total weight of the lubricating composition, as measured by the Noack test (ASTM D5800, Procedure B). 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 determined by ASTM D2270). A major amount of base oil may be provided in combination with a minor amount of one or more additive components, as described below, that make up the lubricant. This preparation can be accomplished by adding the additives directly to the oil, or by adding one or more additives in the form of a concentrate thereof and dispersing or dissolving the additive. The additives can 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.

[0074] The base oil may be provided in small amounts in combination with small amounts of one or more additive components as described below to form an additive concentrate. This preparation can 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 thereof, so that the additives are dispersed or dissolved in the oil. The additives can 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 majority 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, 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 32 mass% or more, alternatively 55 mass% or more, alternatively 60 mass% or more, alternatively 65 mass% or more, 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 98 mass% or less, more preferably 95 mass% or less, even more preferably 90 mass% or less. Alternatively, the one or more base oils are present in the lubricating composition in an amount of 1 to 99 mass%, alternatively 50 to 97 mass%, alternatively 60 to 95 mass%, alternatively 70 to 95 mass%, based on the mass of the lubricating composition. The above described base oils and blends thereof are also useful for making concentrates and for making lubricants therefrom.

[0075] Concentrates are a convenient means of facilitating additive handling prior to use, as well as dissolving or dispersing the additive in the lubricant. When preparing a lubricant containing more than one type of additive (sometimes referred to as "additive components"), each additive can be incorporated separately, each in the form of a concentrate. However, it is often convenient to provide a so-called additive "package" (also called an "add pack") that contains one or more additives / co-additives, as described below, in a single concentrate. Typically, the one or more base oils are present in the concentrate 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 concentrate composition. Typically, the one or more base oils are present in the concentrate 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 weight of the concentrate 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.

[0076] B. Functionalized Polymer Components The optional functionalized polymer component of the lubricating oil and concentrate compositions disclosed herein comprises a polymer having, prior to functionalization, 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). Alternatively, the functionalized polymer comprises a polymer having, prior to functionalization, 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). The polymer before functionalization may have a Mw / Mn of 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 determined by GPC-PS). The polymer before functionalization may comprise repeat units of one or more olefins having 4-5 carbon atoms (preferably conjugated dienes having 4-5 carbon atoms). Prior to functionalization, the C 4~5The polymer is preferably fully or partially saturated (e.g., fully or partially hydrogenated). The functionalized polymer is 4~5 The functionalized polymer can 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 also be obtained by reacting a tertiary amine with an amine to form an amide, an imide, or a combination thereof.

[0077] The present disclosure relates to a C 4~5 The C20 polymers described herein can be 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. 4~5 The invention further relates to lubricating oil compositions comprising functionalized polymers, including amide, imide, and / or ester functionalized saturated (eg, hydrogenated) polymers of conjugated dienes. The present disclosure provides a C amine ester compound that contains one or more pendant amine groups and is at least partially (preferably fully) hydrogenated. 4~5 The present invention relates to lubricating oil compositions comprising functionalized polymers that include or are derived from mixing an olefin polymer with 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.

[0078] In embodiments, the functionalized polymer is not prepared in an aromatic solvent (e.g., benzene or toluene), or aromatic solvent is present at 2% by weight or less (e.g., 1% by weight or less, e.g., 0.5% by weight 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 herein for preparing the functionalized polymers may be homopolymers such as butadiene or isoprene. In embodiments, the polymers useful herein for preparing functionalized polymers may be homopolymers of isoprene or copolymers 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.

[0079] Polymers useful herein for preparing functionalized polymers include those made from 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 may be a copolymer with one or more of 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 the comonomer is present at less than 20 mol%, such as less than 5 mol%, for example less than 3 mol%, such as less than 1 mol%, for example less than 0.1 mol%).

[0080] Generally, the polymerized conjugated diene polymers useful herein for preparing functionalized polymers 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). The polymerized conjugated diene polymers useful herein for preparing functionalized polymers contain at least about 50% 1,4-insertions, such as at least about 75% 1,4 insertions, such as at least about 80% 1,4 insertions, such as at least about 90% 1,4 insertions, such as at least about 95% 1,4 insertions, such as at least 98% 1,4 insertions, based on the sum of the 2,1 insertions, 1,4 insertions, and 3,4 insertions of isoprene, as determined by 1H NMR. For purposes of this disclosure, 1) the phrase "1,4 insertion" includes 1,4 and 4,1 insertions, 2) the phrase "2,1 insertion" includes 2,1 and 1,2 insertions, and 3) the phrase "3,4 insertion" includes 3,4 insertions and 4,3 insertions. Optionally, the polymers useful herein for preparing functionalized polymers may be free of styrene repeat units. Optionally, the functionalized hydrogenated / saturated polymers may be free of styrene repeat units.

[0081] Optionally, the polymers useful herein for preparing functionalized polymers may be free of butadiene repeat units. Optionally, the functionalized hydrogenated / saturated polymers may be free of butadiene repeat units. Optionally, the polymers useful herein for preparing the functionalized polymers may not be homopolybutylene. Optionally, the functionalized hydrogenated / saturated polymers may not be homopolybutylene. Optionally, the polymers useful herein for preparing the functionalized polymers may not be homopolyisobutylene. Optionally, the functionalized hydrogenated / saturated polymers may not be homopolyisobutylene. Optionally, the polymers useful herein for preparing the functionalized polymers may not be copolymers of isoprene and butadiene. Optionally, the functionalized hydrogenated / saturated polymers may not be copolymers of isoprene and butadiene.

[0082] The polymers and / or functionalized polymers useful herein for preparing functionalized polymers 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 that includes one or more first monomers (e.g., isobutylene), for example, the first monomer forms a separate block of polymer that is bound to a second separate block of polymer formed from a second monomer (e.g., butadiene). Block copolymers have substantially separate blocks formed from monomers, whereas tapered block copolymers may be composed of a relatively pure first monomer at one end and a relatively pure second monomer at the other end. The middle section of the tapered block copolymer may have a gradient composition of more of the two monomers. Polymers useful herein for preparing the functionalized polymers may typically have a Mn 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).

[0083] Polymers useful herein for preparing functionalized polymers may typically have a Mw / Mn (determined by GPC-PS) of 1 to 2, alternatively greater than 1 and less than 2, alternatively from 1.1 to 1.8, alternatively from 1.2 to 1.5. Alternatively, polymers useful herein for preparing functionalized polymers may typically have a Mw / Mn of 1 or greater than 1 and less than 2 (e.g. less than 1.8, such as less than 1.7, for example less than 1.6, such as less than 1.5, for example less than 1.4, such as less than 1.3, for example less than 1.2, for example less than 1.15, for example less than 1.12, for example less than 1.10). Polymers useful herein for preparing the functionalized polymer may have a Mz (determined by GPC-PS) of 20,000 to 150,000 g / mol, alternatively 20,000 to about 150,000 g / mol, alternatively 30,000 to about 125,000 g / mol, alternatively 35,000 to about 100,000 g / mol, alternatively 40,000 to 80,000 g / mol, alternatively 40,000 to 60,000 g / mol (GPC-PS).

[0084] Polymers useful herein for preparing functionalized polymers may have a glass transition temperature (Tg) of -25°C or less, such as -40°C or less, such as -50°C or less, as determined by differential scanning calorimetry (DSC) using a Perkin Elmer or TA Instrument Thermal Analysis System (sample heated from ambient temperature to 210°C at 10°C / min, held at 210°C for 5 minutes, then cooled at 10°C / min to -40°C and held for 5 minutes). Polymers useful herein for preparing functionalized polymers typically have less than 3% residual unsaturation, based on the number of double bonds in the unhydrogenated polymer, such as less than 2%, such as less than 1%, such as less than 0.5%, such as less than 0.25%. The polymers useful herein for preparing functionalized polymers typically have a residual metal (e.g., Li, Co, and Al) content of 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.

[0085] Hydrogenation C useful herein for preparing functionalized polymers 4~5 The polymers can be partially or fully hydrogenated with any hydrogenating agent known to those skilled in the art. For example, saturated or partially saturated polymers can be prepared by: (a) hydrogenating a C 1 -C 2 -C ... 4~5The method can be prepared by (b) providing a polymer, and (b) hydrogenating at least some or all of the unsaturation (e.g., double or triple bonds) of the polymer in the presence of a hydrogenation reagent. 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 saturated (hydrogenated), 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 determined by the ozone adsorption method described in Martino N. Smits and Dirkman Hoefman, Quantitative Determination of Olefinic Unsaturation by Measurement of Ozone Absorption Analytical Chemistry, Vol. 44, No. 9, p. 1688, 1972, Martino N. Smits.

[0086] In an embodiment, the hydrogenation reagent may 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 an embodiment, the catalyst is a Pd catalyst. In another embodiment, the catalyst is 5% Pd / C. In a further embodiment, the catalyst may 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 hydrogenation product. Alternatively, any reducing agent capable of reducing C=C bonds to CC 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 hydrogenation product. The reduction reaction with hydrazine is disclosed in Imada et al., J Am. Chem. Soc., vol. 127, pp. 14544-14545 (2005), which is incorporated herein by reference.

[0087] Acylation A fully or partially saturated (hydrogenated) polymer can be chemically modified (functionalized) to provide a polymer having at least one polar functional group, such as, but not limited to, a halogen group, an epoxy group, a hydroxy group, an amino group, a nitrilo group, a mercapto group, an imide group, a carboxy group, and a sulfonic acid group, or a combination thereof. The functionalized polymer can be further modified to provide a more desired type of functionality. In a preferred case, the fully or partially hydrogenated polymer is functionalized by a method that includes reacting the fully or partially hydrogenated polymer with an unsaturated carboxylic acid (or a derivative thereof, such as maleic anhydride) to provide an acylated polymer, which can then be further functionalized as described below. In some embodiments, carboxylic acid functionality or its reactive equivalent is grafted onto the polymer to form an acylated polymer. Typically, an ethylenically unsaturated carboxylic acid material is grafted onto the polymer backbone. Such materials attached to the polymer typically contain at least one ethylenic bond (before reaction) and at least one, for example, two carboxylic acid (or anhydride) groups, or polar groups that can be converted to said carboxyl groups by oxidation or hydrolysis. Maleic anhydride or its derivatives are suitable. Such materials are grafted onto the polymer to provide two carboxylic acid functionalities. 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 its esters.

[0088] Ethylenically unsaturated carboxylic acid materials can be grafted onto the polymer in a number of ways. They can be grafted onto the polymer in solution or in essentially pure (molten) form, with or without the use of a radical initiator. Free radical induced grafting of the ethylenically unsaturated carboxylic acid material can also be carried out in a solvent, such as hexane or mineral oil. Free radical induced grafting of the ethylenically unsaturated carboxylic acid material may be carried out at elevated temperatures in the range of 100°C to 250°C, such as 120°C to 190°C or 150°C to 180°C, for example above 160°C. Free radical initiators that can be used include peroxides, hydroperoxides, and azo compounds, typically those having boiling points greater than about 100° C. that thermally decompose within the grafting temperature range to provide free radicals. Representative examples of such free radical initiators include azobisisobutyronitrile and 2,5-dimethyl-hex-3-yn-2,5-bis-tertiary-butylperoxide. The initiator can 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.

[0089] In embodiments, the acylated polymer may have two or more anhydride groups per polymer molecule, and less than 10% may exhibit gelation. Alternatively, the acylated polymer may have less than two anhydride groups per polymer molecule, and less than 10% may exhibit gelation. (See also U.S. Pat. No. 5,429,758, column 17, line 14 to column 18, line 11.) Alternatively, in some embodiments, the acylated 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 extractable from the polymer using boiling xylene (or cyclohexane) as the extractant. The percentage of soluble and insoluble (gel) material in a polymer composition is determined by immersing a polymer film specimen of nominal thickness 0.5 mm in cyclohexane for 48 hours at 23° C. or refluxing the 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, and if the sample is not soluble in xylene, the cyclohexane method is used.

[0090] In an embodiment, the acylated polymer may have a saponification number (SAP), as determined by ASTM D94, of 5 g / KOH or more, such as 10 g / KOH or more, for example 20 g / KOH or more, such as 30 g / KOH, for example 50 g / KOH or more, such as from 10 to 60 g / KOH, for example from 20 to 40 g / KOH. In embodiments, the acylated polymer composition may have less than 5% by weight, 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, of unreacted acylating agent (e.g., maleic anhydride) based on the weight of the acylated polymer composition (i.e., polymer, acylating agent, and diluent). In embodiments, the acylation reaction described herein may occur in the base oil diluent. As a by-product, a functionalized base oil may be produced. The oil itself may be acylated. For example, maleated base oil may be present after the acylation reaction described herein.

[0091] 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 amines or alcohols to form amides, imides, esters, or combinations thereof, may be present in the concentrate in an amount of 40% by weight or less, alternatively 20% by weight or less, alternatively 10% by weight or less, alternatively 5% by weight or less, alternatively 3% by weight or less, preferably 2% by weight or less, preferably 1% by weight or less, preferably 0.1% by weight or less, preferably 0% by weight (e.g., 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), based on the weight of the concentrate composition. Preferably, the one or more functionalized base oils, for example 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 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 %) based on the weight of the lubricating oil composition.

[0092] In an embodiment, the acylation reaction described herein occurs in a solvent-containing medium. As a by-product, an acylated / functionalized solvent may be produced. In an embodiment, the acylated and / or 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 an embodiment, 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 acylating agent may be added to minimize side reactions (eg, reactions with base oil or other diluents present in the reaction vessel).

[0093] In an embodiment, the acylation reaction can occur by adding the acylating agent (e.g., maleic acid or maleic anhydride) in a continuous or semi-continuous (e.g., intermittent) flow (e.g., in relatively equal amounts over the reaction time, or in controlled amounts of greater and / or lesser amounts at various times during the reaction) to minimize functionalized base oil and other side reactions. As an example, the acylating agent can be added in a continuous mode in which the amount of polymer and acylating agent are added in controlled stoichiometric amounts. As another example, the polymer can be added to the reaction vessel in a batch mode, and the acylating agent can be added slowly or in a semi-continuous mode (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 separate amounts or portions). Alternatively, the polymer may be added to the reaction vessel in X portions and the acylating agent may 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) The 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.

[0094] Preferably, the acylating agent is added in a manner that minimizes side reactions, for example in a continuous or semi-continuous manner. The reaction can also be carried out to minimize side reactions by 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, in a batch, semi-continuous, or continuous reactor operation. For example, the polymer (e.g., a hydrogenated isoprene polymer, such as a hydrogenated homo-polyisoprene) can 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, such as Group I, II, III, IV, and / or V base oil, such as Group II and / or Group III base oil), or an alkane solvent or diluent, or a combination thereof), and the polymer can be present 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 can 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 where the polymer is present at 45% by weight or more based on the weight of the polymer and diluent.

[0095] In embodiments, side reactions are 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 solution or suspension in the diluent 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 and the diluent. In embodiments, side reactions are optionally minimized by adding the acylating agent in a continuous or semi-continuous manner and by 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 the diluent 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 and the diluent.

[0096] sensualization In embodiments, the acylated polymers can be reacted with alcohols or amines to form amides, imides, esters, or combinations thereof. The reaction may consist of condensation to form imides, amides, half amides, amide-esters, diesters, or amine salts. Typically, primary amino groups will condense to form amides, or in the case of maleic anhydride, imides. It is noted that the amines may have a single primary amino group or multiple primary amino groups. Suitable amines may include one or more aromatic amines, such as amines in which a carbon atom of an aromatic ring structure is directly bonded to the amino nitrogen. The amine may also be aliphatic. In embodiments, aliphatic amines may 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 cases, the composition may be substantially free of aromatic amines. Alternatively, the composition may be substantially free of aliphatic amines.

[0097] Examples of aromatic amines that can be used herein include those of the formula: [ka]

[0033] The compound may comprise one or more N-arylphenylenediamines represented by 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, alkoxy, aralkyl, or alkaryl; R9 is -NH, -(NH(CH) n ) m NH2, -NHalkyl, -NHaralkyl, -CH2-aryl-NH2, where n and m each have a value of from about 1 to about 10, and R8 is hydrogen, or an alkyl, alkenyl, alkoxy, aralkyl, or alkaryl having from about 4 to about 24 carbon atoms.

[0098] Suitable N-arylphenylenediamines include N-phenylphenylenediamines (NPDA), 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.

[0099] In embodiments, the amine reacted with the acylated polymer is an amine having at least three or four aromatic groups and has the following formula: [ka] It can be expressed as: where, independently, each variable R 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 or branched alkylene group containing 1 to 5 or 1 to 2 carbon atoms, and w may be 1 to 10, or 1 to 4, or 1 to 2 (typically 1).

[0100] 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 (phenylaminosalicylate), 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 referenced in US Pat. No. 7,790,661, which is incorporated herein by reference.

[0101] In embodiments, the compound that is condensed with the acylated polymer can be represented by the formula: [ka] where X is an alkylene group containing from about 1 to about 4 carbon atoms; R 2 , R 3 , and R 4 is a hydrocarbyl group. [ka] where X is an alkylene group containing from about 1 to about 4 carbon atoms; R 3 and R 4 is a hydrocarbyl group.

[0102] Alternatively, the amine may be an amine having at least four aromatic groups and an aldehyde (e.g., formaldehyde). Aromatic amines have the formula: [ka] It can be expressed as: In the formula, R 1 is hydrogen or C 1~5 is an alkyl group (typically hydrogen), and R 2 is hydrogen or C 1~5 where U is an alkyl group (typically hydrogen), U is an aliphatic, alicyclic, or aromatic group, and optionally, when U is aliphatic, the aliphatic group may be a linear or branched alkylene group containing 1, 2, 3, 4, or 5, or 1 to 2 carbon atoms, and 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 Patent Application Publication No. 2017 / 0073606, page 5, paragraphs

[0064] to

[0070] and EP 2 401 348.

[0103] 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, or mixtures thereof. Compounds that can be condensed with the acylating agent and further have a tertiary amino group can further 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, 3',3-aminobis(N,N-dimethylpropylamine). Other examples of compounds that can be condensed with the 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.

[0104] In an embodiment, the polymer may be reacted with a polyether aromatic compound. Typically, the polyether aromatic compound will have 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 that contains at least one amine group, and the polyether can react with a monocarboxylic acid or its ester, or a dicarboxylic acid, its anhydride or ester.

[0105] Examples of suitable polyether aromatic amines include those having the following structures: [ka] and a compound having the formula: wherein A represents an aromatic amine moiety to which an ether group is linked via at least one amine group on the aromatic moiety; R1 and R6 are independently hydrogen, alkyl, alkaryl, aralkyl, or aryl, or mixtures thereof; R2, R3, R4, and R5 are independently hydrogen, or alkyl containing from about 1 to about 6 carbon atoms, or mixtures thereof; and a and x are independently integers from about 1 to about 50.

[0106] The acylated polymer may be reacted with a polyetheramine or polyetherpolyamine. A typical polyetheramine compound contains at least one ether unit and is chain 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 sold under the Jeffamine™ brand and are commercially available from Hunstman Corporation.

[0107] Amines useful herein for combination with the acylated polymers 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-phenylethane-diamines (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).

[0108] In embodiments, the functionalization (e.g., amination) reaction described herein may occur 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 the acylated diluent (e.g., acylated oil) with amines or alcohols to form amides, imides, esters, or combinations thereof may be present in the concentrate in an amount of 40% by weight or less, alternatively 20% by weight or less, alternatively 10% by weight or less, alternatively 5% by weight or less, alternatively 3% by weight or less, preferably 2% by weight or less, preferably 1% by weight or less, preferably 0.1% by weight or less, preferably 0% by weight (e.g., 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), based on the weight of the concentrate composition.

[0109] Preferably, one or more functionalized base oils, for example, reaction products of an acylated diluent (e.g., an acylated 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 %) based on the weight of the lubricating oil composition. In embodiments, the functionalization (e.g., amination) reactions described herein may occur 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.

[0110] In embodiments, the acylated 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 embodiments, 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 %, such as 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. It may comprise or be a copolymer with one or more of 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 the comonomer is present at 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%).

[0111] In an embodiment, the functionalized polymer comprises up to 10 (eg 9, such as 8, for example 7, for example 6, for example 5, for example 4, for example 3, for example 2, for example 1) weight percent styrene monomer based on the weight of the functionalized polymer. In embodiments, the functionalized polymer may be free of styrene repeat units. 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 or tapered block copolymer comprising (or consisting of, or consisting essentially of) isoprene. In embodiments, the functionalized polymer may be a block or 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 4~5Containing (or consisting of or consisting essentially of) a conjugated diene, preferably having 50 (e.g. 60, e.g. 70, e.g. 80, e.g. 90, e.g. 95, e.g. 98) wt. % or more C based on the weight of the copolymer. 4~5 It may also be a block or tapered block copolymer containing a conjugated diene.

[0112] In an embodiment, the functionalized polymer may be a copolymer that includes 50 (eg, 60, such as 70, such as 80, such as 90, such as 95, such as 98) weight percent or greater isoprene, based on the weight of the copolymer. In an embodiment, the functionalized polymer may be a copolymer that includes 50 (eg 60, such as 70, such as 80, such as 90, such as 95, such as 98) weight percent or more of butadiene, based on the weight of the copolymer. In an embodiment, the functionalized polymer may be a copolymer comprising 50 (eg, 60, such as 70, such as 80, such as 90, such as 95, such as 98) weight percent or more of butadiene and isoprene, based on the weight of the copolymer. In embodiments, the functionalized polymer may be a diblock copolymer that includes at least one block of an isoprene homopolymer or copolymer. Optionally, the functionalized polymer may be free of butadiene repeat units. Optionally, the functionalized polymer may not be a homopolyisobutylene. Optionally, the functionalized polymer may not be a copolymer of isoprene and butadiene.

[0113] Generally, the polymerized conjugated diene in the functionalized polymer comprises monomer units inserted into the growing polymer chain by conjugated addition and non-conjugated addition. In an embodiment, the functionalized polymer comprises: 13 Based on the total number of conjugate addition and non-conjugate addition insertions as measured by C NMR, it includes at least about 50% conjugate addition insertions, such as at least about 75% conjugate addition insertions, such as about 80% conjugate addition insertions, for example about 85% to about 100% conjugate addition insertions. The insertion of isoprene occurs most frequently through 2,1 insertion, 1,4 insertion (trans and cis), and 3,4 insertion of isoprene. (Measurements of insertion geometry are 1 The functionalized isoprene polymer is 1 Based on the sum of 2,1, 1,4, and 3,4 insertions of isoprene, the isoprene includes at least about 50% 1,4-insertions, such as at least about 75% 1,4 insertions, such as at least about 80% 1,4 insertions, such as at least about 90% 1,4 insertions, such as at least about 95% 1,4 insertions, such as at least 98% 1,4 insertions, as determined by H NMR. For purposes of this disclosure, 1) the phrase "1,4 insertion" includes 1,4 and 4,1 insertions, 2) the phrase "2,1 insertion" includes 2,1 and 1,2 insertions, and 3) the phrase "3,4 insertion" includes 3,4 insertions and 4,3 insertions.

[0114] The functionalized polymer may be a homopolymer or a copolymer. Optionally, the functionalized polymer comprises a homopolymer or a copolymer of isoprene. The copolymer may be a random copolymer, a tapered block copolymer, a star copolymer, or a block copolymer. The functionalized polymer may typically have a Mn from 20,000 to 150,000 g / mol, alternatively 20,000 to about 150,000 g / mol, alternatively 30,000 to about 125,000 g / mol, alternatively 35,000 to about 100,000 g / mol, alternatively 40,000 to 80,000 g / mol (GPC-PS). The polymer before functionalization may typically have a Mn / Mw(GPC-PS) of 1.0 to 2, such as 1.1 to 1.5, such as 1.1 to 1.3, such as 1.1 to 1.2. As functionalization occurs, Mw / Mn broadening may occur.

[0115] The functionalized polymer may typically have a Mw / Mn (GPC-PS) of 1 to 3, alternatively 1 to 2, alternatively greater than 1 and less than 2, alternatively 1.05 to 1.9, alternatively 1.10 to 1.8, alternatively 1.10 to 1.7, alternatively 1.12 to 1.6, alternatively 1.13 to 1.5, alternatively 1.15 to 1.4, alternatively 1.15 to 1.3. Alternatively, the functionalized polymer may typically have a Mw / Mn of 1 or greater than 1 and less than 2 (such as less than 1.8, such as less than 1.7, for example less than 1.6, such as less than 1.4, for example less than 1.2, such as less than 1.15, for example less than 1.12, for example less than 1.10). In embodiments, the functionalized polymer may have a saponification number (SAP) of 25 (eg, 28, eg, 30, eg, 32, eg, 34) mg KOH / g or greater, as determined by ASTM D94. In an embodiment, 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 embodiments, the functionalized polymer may have an average functionality, as determined by GPC-PS, of 1.4 to 20 FG grafts / polymer chain, such as 1.4 to 15 FG grafts / polymer chain, such as 3 to 12.5 FG grafts / polymer chain, such as 4 to 10 FG grafts / polymer chain.

[0116] The functionalized polymer may have an average functionality of up to 15 (eg, 14, 13, 12, 11, 10, 9, 8, 7, or 6) FG grafts / polymer chain, as determined by GPC-PS. The functionalized polymer may have an average functionality of 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) FG grafts / polymer chain or greater, as determined by GPC-PS. The functionalized polymer may have an average functionality of 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 (14, 13, 12, 11, 10, 9, 8, 7, or 6) FG grafts / polymer chains as determined by GPC-PS.

[0117] In an embodiment, the functionalized polymer may have an aromatic content of 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 olefin 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 determined by GPC-PC. 4~5 It may also comprise an acylated polymer of the monomer. In embodiments, the functionalized polymer may have a number average molecular weight (Mn) of 20,000 (eg, 25,000, eg, 30,000, eg, 35,000, eg, 40,000) or greater, as determined by GPC-PS. In embodiments, the functionalized polymer may have a weight average molecular weight (Mw) of up to 50,000 (e.g., 40,000, e.g., 35,000) g / mol, as determined by GPC-PS. In embodiments, the functionalized polymer may have a weight average molecular weight (Mw) of from 1000 to 50,000 g / mol, e.g., from 5000 to 40,000 g / mol, as determined by GPC-PS.

[0118] In an embodiment, the functionalized polymer may have a z-average molecular weight (Mz) of from 5000 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 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 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, as determined by GPC-PS), the functionality distribution (Fd) value being determined as shown in the Examples section below, and the average functionality being 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, as determined by GPC-PS.

[0119] The present disclosure provides a C olefin copolymer having a Mw / Mn of less than 2, 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). 4~5The present invention relates to amide, imide, and / or ester functionalized hydrogenated / saturated polymers comprising (consisting essentially of or consisting of) olefins, where if the polymer before functionalization is a C4 olefin polymer, e.g., polyisobutylene, polybutadiene, or copolymers thereof (preferably polyisobutylene or a copolymer of isobutylene and butadiene), the C4 olefin polymer has a Mn of 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).

[0120] The present disclosure also relates to amide, imide, and / or ester functionalized hydrogenated / saturated polymers comprising 90 mole % or more isoprene repeat units, having a Mw / Mn of less than 2, a functionality distribution (Fd) value of 3.5 or less (e.g., 3.4 or less, such as 1-3.3, such as 1.1-3.2, such as 1.2-3.0, such as 1.4-2.9 as measured by GPC-PS), where the polymer prior to functionalization has a Mn of 30,000 g / mol or more (GPC-PS).

[0121] The present disclosure also relates to amide, imide, and / or ester functionalized hydrogenated / saturated homopolymers of isoprene having a Mw / Mn of less than 2, 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 determined by GPC-PS), where the polymer prior to functionalization has a Mn of 30,000 g / mol or more (as determined by GPC-PS).

[0122] 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, for example, in the Kirk-Othmer Encyclopedia of Chemical Technology, Third Edition, Vol. 14, pages 477-526, some of which are discussed in more detail below.

[0123] C. Detergents In addition to the combination or mixture of overbased calcium-based and overbased magnesium-based detergents described above, the lubricating oil and concentrate compositions may also include one or more additional metal detergents (e.g., blends of metal detergents), also referred to as "detergent additives." Metal detergents typically function as both detergents and acid neutralizers or rust inhibitors to reduce or remove deposits, thereby reducing wear and corrosion and extending engine life. Detergents generally include a polar head with a long-chain hydrophobic tail, which includes a metal salt of an acidic organic compound. Such salts may include substantially stoichiometric amounts of metal, in which case they are usually described as normal or neutral salts, and will typically have a total base number ("TBN" as measured by ASTM D2896) of up to 150 mg KOH / g, e.g., 0 to 80 (or 5 to 30) mg KOH / g. Large amounts of metal base can 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, may have a TBN of 100 mg KOH / g or more (e.g., 200 mg KOH / g or more), and will typically have a TBN of 250 mg KOH / g or more, such as 300 mg KOH / g or more, for example, 200-800 mg KOH / g, 225-700 mg KOH / g, 250-650 mg KOH / g, or 300-600 mg KOH / g, for example, 150-650 mg KOH / g.

[0124] 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 comprising any combination of sodium, potassium, lithium, calcium, or magnesium salts of sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and naphthenates, or other oil-soluble carboxylates of Group 1 and / or Group 2 metals. Preferably, the detergent additive useful in the present disclosure comprises a calcium and / or magnesium metal salt. The detergent may be a calcium and / or magnesium carboxylate (e.g., salicylate), a calcium and / or magnesium sulfonate, or a calcium and / or magnesium 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 such detergents and / or combinations thereof.

[0125] Metal-containing detergents may 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, as 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 used, the hybrid detergent would be considered to be the same amount as the separate phenate and sulfonate detergents that incorporate similar amounts of phenate soap and sulfonate soap, respectively. The overbased metal-containing detergent may be a sodium, calcium, magnesium salt of phenates, sulfur-containing phenates, sulfonates, salixarates, and salicylates, or mixtures thereof. The overbased phenates and salicylates typically have a total base number of 180 to 650 mg KOH / g, for example 200 to 450 TBN mg KOH / g. The overbased sulfonates typically have a total base number of 250 to 600 mg KOH / g, or 300 to 500 mg KOH / g. In an embodiment, the sulfonate detergent may be a linear alkylbenzene sulfonate detergent having a metal ratio of at least 8, as described in U.S. Patent Application Publication No. 2005 / 065045 (issued as U.S. Patent No. 7,407,919), paragraphs

[0026] to

[0037] . The overbased detergent may be present at 0% to 15%, or 0.1% to 10%, or 0.2% to 8%, or 0.2% to 3%, by weight of the lubricating composition. For example, in a heavy duty diesel engine, the detergent may be present at 2% to 3% by weight of the lubricating composition. For passenger car engines, the detergent may be present at 0.2% to 1% by weight of the lubricating composition.

[0126] The detergent additive may comprise one or more magnesium sulphonate detergents. The magnesium detergents may be neutral salts or overbased salts. Suitably, the magnesium detergents are overbased magnesium sulphonates 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, for example 200 to 500 mg KOH / g, for example 240 to 450 mg KOH / g. Alternatively, the detergent additive is magnesium salicylate.Suitably the magnesium detergent is a magnesium salicylate having a TBN of 5-700 mg KOH / g (ASTM D2896), or 7-600 mg KOH / g, or 9-500 mg KOH / g, 30-650 mg KOH / g, such as 50-500 mg KOH / g, for example 200-500 mg KOH / g, such as 240-450 mg KOH / g, or alternatively 150 mg KOH / g or less, such as 100 mg KOH / g or less. Alternatively, the detergent additive is a combination of magnesium salicylate and magnesium sulfonate.

[0127] The magnesium detergent provides the lubricating composition with 200 to 4000 ppm of magnesium atoms, preferably 200 to 2000 ppm, 300 to 1500 ppm, or 450 to 1200 ppm of magnesium atoms (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. The combination of one or more magnesium sulfonate detergents and one or more calcium salicylates detergents provides the lubricating composition with 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), calcium sulfonate, or calcium phenate detergent.

[0128] Suitably, the calcium detergent has a TBN of 30-1400 mg KOH / g (ASTM D2896), such as 80-1200 mg KOH / g, for example 100-1000 mg KOH / g, such as 150-800 mg KOH / g, for example 200-600 mg KOH / g, for example 240-550 mg KOH / g, or alternatively 150 mg KOH / g or less, such as 100 mg KOH / g or less, or 200 mg KOH / g or more, or 300 mg KOH / g or more, or 350 mg KOH / g or more. The calcium detergent preferably has a TBN of 500, or 600, or 700, or 800, or 1000, or 1200, or 1300, or 1400 mg KOH / g or more. Suitably the calcium detergent is a calcium salicylate, calcium sulfonate, or calcium 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, or alternatively 150 mg KOH / g or less, such as 100 mg KOH / g or less, or 200 mg KOH / g or more, or 300 mg KOH / g or more, or 350 mg KOH / g or more, 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.

[0129] Calcium detergents are typically present in an amount sufficient to provide the lubricating oil composition with at least 500 ppm, preferably at least 750, more preferably at least 900 ppm of atomic calcium (ASTM D5185). If present, any calcium detergent is suitably present in an amount sufficient to provide the lubricating oil composition with no more than 4000 ppm, preferably no more than 3000 ppm, more preferably no more than 2000 ppm of atomic calcium (ASTM D5185). If present, any calcium detergent is suitably present in an amount sufficient to provide the lubricating oil composition with from 500 to 4000 ppm, preferably from 750 to 3000 ppm, more preferably from 900 to 2000 ppm of atomic calcium (ASTM D5185).

[0130] Suitably, the total amount of metal atoms derived from detergents in the lubricating oil composition according to all aspects of the present disclosure is 5000 ppm or less, preferably 4000 ppm or less, more preferably 2000 ppm or less (ASTM D5185). The total amount of metal atoms derived from detergents in the lubricating oil composition according to all aspects 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 amount of metal atoms derived from detergents in the lubricating oil composition according to all aspects of the present disclosure is suitably 500 to 5000 ppm, preferably 500 to 3000 ppm, more preferably 500 to 2000 ppm (ASTM D5185).

[0131] Sulfonate detergents can typically be prepared from sulfonic acids obtained by sulfonation of alkyl-substituted aromatic hydrocarbons, such as those obtained from petroleum fractionation or by alkylation of aromatic hydrocarbons. Examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl, or their halogen derivatives, such as chlorobenzene, chlorotoluene, and chloronaphthalene. The alkylation can be carried out in the presence of a catalyst with an alkylating agent having from about 3 to more than 70 carbon atoms. 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 can be neutralized with oxides, hydroxides, alkoxides, carbonates, carboxylates, sulfides, hydrosulfides, nitrates, borates, and ethers of the metal. The amount of metal compound is selected having regard to the desired TBN of the final product, but is typically in the range of about 100-220% by weight (preferably at least 125% by weight) of the amount stoichiometrically required.

[0132] Metal salts of phenols and sulfurized phenols are prepared by reaction with the appropriate metal compounds, such as oxides or hydroxides, and neutral or overbased products can be obtained by methods well known in the art. Sulfurized phenols can be prepared by reacting phenols with sulfur or sulfur-containing compounds, such as hydrogen sulfide, sulfur monohalides, 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 prepared by reacting aromatic carboxylic acids (e.g., C 5~100 , C 9~30 , C 14~24 The 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, and neutral and / or overbased products can be obtained by methods well known in the art. The aromatic moiety of the aromatic carboxylic acid may contain heteroatoms, such as nitrogen and oxygen. Preferably, the moiety contains only carbon atoms, more preferably, the moiety contains 6 or more carbon atoms. For example, a preferred moiety is benzene. The aromatic carboxylic acid may contain one or more aromatic moieties, such as one or more benzene rings, either fused or connected via alkylene bridges.

[0133] Preferred substituents in oil-soluble salicylic acids are alkyl substituents. In alkyl-substituted salicylic acids, the alkyl group advantageously contains from 5 to 100, preferably from 9 to 30, especially from 14 to 20 carbon atoms. When more than one alkyl group is present, the average number of carbon atoms of all of the alkyl groups is preferably at least 9 to ensure adequate oil solubility. In an embodiment, the ratio of atomic detergent metal to atomic molybdenum in the lubricating oil composition may be less than 3:1, such as less than 2:1. 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 in the range of 0.05 to 20.0 mass %, more preferably in the range of 1.0 to 10.0 mass %, and most preferably in the range of 2.0 to 5.0 mass %, based on the total mass of the lubricating composition. The total sulfated ash content of the lubricating compositions herein, as determined by ASTM D874, is typically 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.

[0134] Further, each of the detergents usefully independently has a TBN (total base number) value as measured by ISO 3771 in the range of 10 to 700 mg KOH / g, 10 to 500 mg KOH / g, alternatively in the range of 100 to 650, alternatively in the range of 10 to 500 mg KOH / g, alternatively in the range of 30 to 350 mg KOH / g, alternatively in the range of 50 to 300 mg KOH / g. The sulfonate detergent (e.g., Ca and / or Mg sulfonate detergent) may be present in an amount to deliver 0.1% to 1.5%, or 0.15 to 1.2%, or 0.2% to 0.9% by weight of sulfonate soap to the lubricant composition. The salicylate detergent (e.g., Ca and / or Mg salicylate detergent) is present in an amount to deliver 0.3% to 1.4%, or 0.35% to 1.2%, or 0.4% to 1.0% by weight of salicylate soap to 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.

[0135] The total of all alkaline earth metal detergent soaps may be present in an amount from 0.6% to 2.1%, or from 0.7% to 1.4% 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 mass %, alternatively from about 0.5 to about 7.5 mass %, alternatively from about 1 to about 6.5 mass %, of a detergent, based on the lubricating composition. Typically, lubricating compositions formulated for use in passenger vehicle engines contain from about 0.1 to about 10 mass %, alternatively from about 0.5 to about 7.5 mass %, alternatively from about 1 to about 6.5 mass %, of the detergent, based on the lubricating composition. Typically, lubricating compositions formulated for use in a drivetrain (e.g., a transmission) contain from about 0.1 to about 10 mass %, alternatively from about 0.5 to about 7.5 mass %, alternatively from about 2 to about 6.5 mass %, of a detergent, based on the lubricating composition.

[0136] D. Friction Modifiers Friction modifiers are any one or more substances that can change the coefficient of friction of a surface lubricated by any lubricant or fluid containing such substances.Friction modifiers, also known as friction reducers or lubricity agents or oily agents, and other such agents that change the ability of base oils, formulated lubricant compositions, concentrate compositions, or functional fluids to adjust the coefficient of friction of lubricated surfaces, can be effectively used in combination with the base oils or lubricant compositions of the present disclosure, as needed.Friction modifiers that reduce the coefficient of friction are particularly advantageous when combined with the base oils and lubricant compositions of the present disclosure. Exemplary friction modifiers may include, for example, organometallic compounds or materials or mixtures thereof. Exemplary organometallic friction modifiers useful in the lubricating oil formulations of the present disclosure may include, for example, tungsten and / or molybdenum compounds, such as molybdenum amines, molybdenum diamines, organotungstenates, molybdenum dithiocarbamates, molybdenum dithiophosphates, molybdenum amine complexes, and molybdenum carboxylates, and mixtures thereof. Examples of useful molybdenum-containing compounds may conveniently include molybdenum dithiocarbamates, such as the trinuclear molybdenum compounds described in WO 98 / 26030, sulfides of molybdenum, and molybdenum dithiophosphates.

[0137] Other known friction modifiers include oil-soluble organomolybdenum compounds. Such organomolybdenum friction modifiers can also provide antioxidant and antiwear benefits to lubricating oil compositions. Examples of such oil-soluble organomolybdenum compounds include dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, sulfides, and the like, and mixtures thereof. Particularly preferred are molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum alkylxanthates, and molybdenum alkylthioxanthates. Additionally, the molybdenum compound may be an acidic molybdenum compound. Such compounds react with basic nitrogen compounds and are typically hexavalent as measured by ASTM test D664 or D2896 titration procedures. Molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, such as sodium hydrogen molybdate, MoOC l4 , MoO2Br2, Mo2O3C l6 , molybdenum trioxide, or similar acidic molybdenum compounds.

[0138] Molybdenum compounds useful in the compositions of the present disclosure include organomolybdenum compounds of the formula Mo(R"OCS2)4 and Mo(R"SCS2)4, where R" is an organic radical selected from the group consisting of alkyl, aryl, aralkyl, and alkoxyalkyl, generally from 1 to 30 carbon atoms, preferably from 2 to 12 carbon atoms, and most preferably alkyl from 2 to 12 carbon atoms. Particularly preferred are the dialkyldithiocarbamates of molybdenum. Another group of organo-molybdenum compounds useful in the lubricating compositions of the present disclosure are trinuclear molybdenum compounds, particularly those of the formula Mo3SkLnQz, and mixtures thereof, where L is an independently selected ligand having an organic group having a sufficient number of carbon atoms to render the compound soluble or dispersible in oil, n is 1 to 4, k is in the range of 4 to 7, Q is selected from the group of neutral electron donor compounds, e.g., water, amines, alcohols, phosphines, and ethers, and z is in the range of 0 to 5, including non-stoichiometric values. There should be at least 21 carbon atoms in all ligands / organic groups, e.g., at least 25, at least 30, or at least 35 carbon atoms.

[0139] Lubricating oil compositions useful in all aspects of the present disclosure preferably contain at least 10 ppm, or 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). For further information regarding useful friction modifiers containing Mo, see U.S. Patent No. 10,829,712 (column 8, line 58 to column 11, line 31). Particularly preferred friction modifiers containing Mo of the present disclosure are molybdenum dimeric dialkyldithiocarbamates (moly dimers), molybdenum trimer dialkyldithiocarbamates (moly trimers), or combinations thereof.

[0140] Ashless friction modifiers may be present in the lubricating oil composition of the present disclosure, which 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 include polar end groups (e.g., carboxyl or hydroxyl) covalently attached 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 (1992), Vol. 114, pp. 675-682, and M. Belzer and S. Jahanmir, Lubrication Science (1988), Vol. 1, pp. 3-26. Typically, the total amount of organic ashless friction modifiers in the lubricant according to the present disclosure does not exceed 5 mass %, preferably does not exceed 2 mass %, and more preferably does not exceed 0.5 mass %, based on the total mass of the lubricating oil composition. Exemplary friction modifiers useful in the lubricating compositions described herein include, for example, alkoxylated fatty acid esters, alkanolamides, polyol fatty acid esters, borated glycerol fatty acid esters, fatty alcohol ethers, and mixtures thereof.

[0141] Exemplary alkoxylated fatty acid esters include, for example, polyoxyethylene stearates and fatty acid polyglycol esters, such as polyoxypropylene stearate, polyoxybutylene stearate, polyoxyethylene isostearate, polyoxypropylene isostearate, and polyoxyethylene palmitate. Exemplary alkanolamides include, for example, lauric acid diethylalkanolamide and palmic acid diethylalkanolamide, etc. These may include oleic acid diethylalkanolamide, stearic acid diethylalkanolamide, oleic acid diethylalkanolamide, polyethoxylated hydrocarbyl amides, and polypropoxylated hydrocarbyl amides, etc. Exemplary polyol fatty acid esters include, for example, glycerol monooleate, saturated mono-, di-, and triglyceride esters, glycerol monostearate, etc. These can include polyol esters and hydroxyl-containing polyol esters, etc.

[0142] Exemplary borated glycerol fatty acid esters include, for example, borated glycerol monooleate, borated saturated mono-, di-, and triglyceride esters, and borated glycerol monostearate. In addition to glycerol polyols, these can include trimethylolpropane, pentaerythritol, and sorbitan. These esters can be polyol monocarboxylic acid esters, polyol dicarboxylic acid esters, and in some cases polyol tricarboxylic acid esters. Preferred can be glycerol monooleate, glycerol dioleate, glycerol trioleate, glycerol monooleate, glycerol distearate, and glycerol tristearate, as well as the corresponding glycerol monopalmitate, glycerol dipalmitate, and glycerol tripalmitate, as well as the respective isostearate and linoleate. Useful herein are, in particular, ethoxylated, propoxylated, and / or butoxylated fatty acid esters of polyols, where glycerol is used as the base polyol.

[0143] Exemplary fatty alcohol ethers include, for example, stearyl ether and myristyl ether.50 Alcohols, including those having carbon numbers of 1 to 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 5 11 ~C 13 Hydrocarbons, oleyl, isosteryl, and the like. Useful concentrations of friction modifiers may range from 0.01% to 5% by weight, or from about 001% 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. Advantageous concentrations of Mo may range from 12 ppm to 350 ppm or higher, with the preferred range often being 20 to 200 ppm. Friction modifiers of any type may be used alone or in admixture with the materials of the present disclosure. In many cases, mixtures of two or more friction modifiers, or mixtures of friction modifiers with alternative surface active materials, are also desirable. For example, combinations of Mo-containing compounds with polyol fatty acid esters, such as glycerol monooleate, are useful herein.

[0144] E. Antioxidants Antioxidants retard the oxidative deterioration of base oils during service. Such deterioration can result in deposits on metal surfaces, the presence of sludge, and increased viscosity of the lubricant. A wide variety of oxidation inhibitors are useful in lubricating oil compositions. See, for example, Lubricants and Related Products, Klamann, Wiley VCH, 1984; U.S. Patent Nos. 4,798,684 and 5,084,197. Useful antioxidants include hindered phenols. Such 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 phenolic materials that contain sterically hindered hydroxyl groups, including derivatives of dihydroxyaryl compounds in which the hydroxyl groups are in the o- or p-position relative to each other. Typical phenolic antioxidants include C 6+ These include alkyl-substituted hindered phenols and alkylene-coupled 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 can include, for example, hindered 2,6-di-alkyl-phenolic propionate derivatives. Bis-phenolic antioxidants can also be used advantageously herein. Examples of ortho-coupled phenols include 2,2'-bis(4-heptyl-6-t-butyl-phenol), 2,2'-bis(4-octyl-6-t-butyl-phenol), and 2,2'-bis(4-dodecyl-6-t-butyl-phenol). Examples of para-coupled bisphenols include 4,4'-bis(2,6-di-t-butyl-phenol) and 4,4'-methylene-bis(2,6-di-t-butyl-phenol).

[0145] Also, an effective amount of one or more catalytic antioxidants can be used. The catalytic antioxidant comprises an effective amount of a) one or more oil-soluble polymetal 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 both b) and c). Catalytic antioxidants useful herein are described in more detail in U.S. Pat. No. 8,048,833. Non-phenolic oxidation inhibitors that can be used include aromatic amine antioxidants, which can be used either on their own or in combination with phenolic materials. 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 group, an aromatic group, or a substituted aromatic group; R9 is an aromatic group or a substituted aromatic group; and R 10 is H, alkyl, aryl, or R 11 S(O)XR 12 where R 11 is an alkylene group, an alkenylene group, or an aralkylene group; R 12 is an alkyl group, or an alkenyl group, an aryl group, or an alkaryl group, and x is 0, 1, or 2. The aliphatic group R8 may contain from 1 to about 20 carbon atoms, and preferably contains from about 6 to 12 carbon atoms. The aliphatic group is typically a saturated aliphatic group. Preferably, R8 and R9 are both 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 combined with other groups, such as S.

[0146] Typical aromatic amine antioxidants have an alkyl substituent of at least about 6 carbon atoms. Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl, and decyl. In general, the aliphatic groups will not contain more than about 14 carbon atoms. Common 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.

[0147] Sulfur-containing antioxidants are also useful herein. In particular, one or more oil-soluble or oil-dispersible sulfur-containing antioxidants can be used as antioxidant additives. For example, sulfurized alkylphenols and their alkali metal or alkaline earth metal salts are also useful antioxidants herein. Suitably, the lubricating oil composition of the present disclosure may contain one or more sulfur-containing antioxidants in an amount to provide the lubricating oil composition with 0.02 to 0.2, preferably 0.02 to 0.15, even more preferably 0.02 to 0.1, 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 is a sulfurized C4-C 25 Olefins, sulfurized aliphatic (C7-C 29 ) hydrocarbyl fatty acid esters, ashless sulfurized phenolic antioxidants, sulfur-containing organomolybdenum compounds, 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).

[0148] Antioxidants useful herein include hindered phenols and / or arylamines. These antioxidants can be used individually by type or in combination with each other. Typical antioxidants include Irganox™ L67, Irganox™ L135, Ethanox™ 4702, Lanxess Additin™ RC7110; Ethanox™ 4782J; Irganox™ 1135, Irganox™ 5057, sulfurized lard oil, and palm oil fatty acid methyl esters. The antioxidant additive can be used in an amount of about 0.01 to 10 mass % (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 less than 0.05 to 3 mass %) based on the weight of the lubricating composition. Compositions according to the present disclosure may contain additives having various stated functions that also have a secondary effect as antioxidants (e.g., phosphorus-containing antiwear agents (e.g., ZDDP) can also exhibit antioxidant effects), and such additives are not included as antioxidants herein for purposes of determining the amount of antioxidant in a lubricating oil composition or concentrate.

[0149] F. Pour Point Depressants Conventional pour point depressants (also known as lubricant flow improvers) can be added to the compositions of the present disclosure, if necessary. Such pour point depressants can be added to the lubricant 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.

[0150] G. Defoamers Advantageously, antifoaming agents can be added to the lubricant compositions described herein. Such agents prevent or delay the formation of stable foam. Silicones and / or organic polymers are typical antifoaming agents. For example, polysiloxanes, such as silicon oils or polydimethylsiloxanes, provide antifoaming properties. Antifoaming agents are commercially available and can be used in small amounts, 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.

[0151] For example, the lubricating oil composition may include an antifoam agent comprising a polyalkylsiloxane, such as a polydialkylsiloxane, where the alkyl is, for example, C1 to C 10 Antifoaming agents that are alkyl groups may also be included, such as polydimethylsiloxane (PDMS), also known as silicone oil. Alternatively, the siloxane may be poly(R3 ) siloxane, R 3 is one or more of the same or different linear, branched, or cyclic hydrocarbyls, such as alkyl or aryl, typically having 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, for example, 50 to 450, alternatively, for example, 40 to 100.

[0152] Additionally or alternatively, the lubricating oil composition may comprise an organically modified siloxane (OMS), e.g., a siloxane having an organic 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 For example, the lubricating oil composition may include an organically modified siloxane compound according to formula 1, where n is 2 to 2000, for example 50 to 450 (alternatively 40 to 100), and R 1 and R 2 are the same or different, and optionally, R 1 and R 2 Each of the groups may independently be an organic 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

[0153] Based on the total weight of the lubricant composition, the siloxanes according to Formula 1 are incorporated to provide from about 0.1 to less than about 30 ppm Si, or from about 0.1 to about 25 ppm Si, or from about 0.1 to about 20 ppm Si, or from about 0.1 to about 15 ppm Si, or from about 0.1 to about 10 ppm Si, more preferably in the range of from about 3 to 10 ppm Si. In embodiments, silicone antifoam agents useful herein are available from Dow Corning Corporation and Union Carbide Corporation, such as Dow Corning FS-1265 (1000 centistokes), Dow Corning DC-200, and Union Carbide UC-L45. Silicone antifoam agents useful herein include polydimethylsiloxanes, phenyl-methylpolysiloxanes, linear, cyclic, or branched siloxanes, silicone polymers and copolymers, and / or organosilicone 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 as SILWET-L-7220.

[0154] Acrylate polymeric defoamers may also be used herein. Exemplary acrylate defoamers include the polyacrylate defoamer known as PC-1244 available from Monsanto Polymer Products Co. A preferred acrylate polymeric defoamer useful herein is PX™ 3841 (i.e., an alkyl acrylate polymer) available from Dorf Ketl, also known as Mobilad™ C402. In embodiments, a combination of silicone antifoam and acrylate antifoam can be used, for example, in a weight ratio of silicone antifoam to acrylate antifoam of about 5:1 to about 1:5. See, e.g., U.S. Patent Application Publication No. 2021 / 0189283.

[0155] H. Viscosity modifier Viscosity modifiers (also called viscosity index improvers or viscosity improvers) can be included in the lubricant and concentrate compositions described herein. Viscosity modifiers provide high and low temperature operability to the lubricant. Such additives impart shear stability at high temperatures and acceptable viscosity at low temperatures. Suitable viscosity modifiers include high molecular weight hydrocarbons, polyesters, and viscosity modifying dispersants that can function as both viscosity modifiers and dispersants. Typical molecular weights of such 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 are 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.

[0156] Copolymers useful as viscosity modifiers include those available from Chevron Oronite Company LLC under the tradename "PARATONE™" (e.g., PARATONE™ 8921, PARATONE™ 68231, and PARATONE™ 8941); those available from Afton Chemical Corporation under the tradename "HiTEC™" (e.g., HiTEC™ 5850B and HiTEC™ 5777); and those available from The Lubrizol Corporation under the tradename "Lubrizol™ 7067C". Hydrogenated polyisoprene star polymers useful herein as viscosity modifiers include those available from Infineum International Limited under the tradenames, for example, SV200™ and SV600™. Hydrogenated diene-styrene block copolymers useful as viscosity modifiers herein are commercially available from Infineum International Limited, for example under the trade designation "SV50™". Polymers useful herein as viscosity modifiers include polymethacrylate or polyacrylate polymers, such as linear polymethacrylate or polyacrylate polymers, such as those available from Evnoik Industries under the trade name "Viscoplex™" (e.g., Viscoplex™ 6-954), or star polymers available from Lubrizol Corporation under the trade name Asteric™ (e.g., Lubrizol™ 87708 and Lubrizol™ 87725).

[0157] The vinyl aromatic-containing polymers useful herein as viscosity modifiers can be derived from vinyl aromatic hydrocarbon monomers, such as styrenic monomers, such as styrene. Exemplary vinyl aromatic-containing copolymers useful herein can be represented by the following general formula: AB, where A is the polymeric block that is derived primarily from vinyl aromatic hydrocarbon monomers (e.g., styrene), and B is the polymeric block that is 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, such as 12 cSt or less, but may be diluted (e.g., with Group I, II, and / or III base stocks) to higher kinematic viscosities at 100° C., such as 40 cSt or more, such as 100 cSt or more, such as 1000 cSt or more, e.g., 1000-2000 cSt. Typically, the viscosity modifier can be used in an amount of about 0.01 to about 10 mass %, such as about 0.1 to about 7 mass %, for example, 0.1 to about 4 mass %, for example, about 0.2 to about 2 mass %, for example, about 0.2 to about 1 mass %, for example, 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 to large amounts of diluent oil. An "as delivered" viscosity modifier typically contains 20% to 75% by weight active polymer in the case of polymethacrylate or polyacrylate polymers, or 8% to 20% by weight active polymer in the case of olefin copolymers, hydrogenated polyisoprene star polymers, or hydrogenated diene-styrene block copolymers, in the "as delivered" polymer concentrate.

[0158] I. Dispersants During engine operation, oil-insoluble oxidation by-products are produced. Dispersants help keep these by-products in solution, thus reducing by-product deposition on metal surfaces. The dispersants used in formulating the lubricating compositions herein may be ashless or ash-forming in nature. 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 comprises at least one element of nitrogen, oxygen, or phosphorus. A typical hydrocarbon chain comprises from 40 to 500, for example from 50 to 400, carbon atoms.

[0159] Dispersants of (poly)alkenyl succinic acid derivatives A particularly useful class of dispersants includes (poly)alkenyl succinic acid derivatives, typically 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 portion of the molecule that confers solubility in oil, is often a polyisobutylene group (typically, the long-chain hydrocarbyl group, e.g., the polyisobutylene group, has an Mn of 400-3000 g / mol, e.g., 450-2500 g / mol). Many examples of this type of dispersant are known commercially and in the literature. Exemplary U.S. patents in which such dispersants are described 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 disclosed in U.S. Pat. Nos. 3,036,003, 3,200,107, 3,254,025, 3,275,554, 3,438,757, 3,454,555, 3,565,804, 3,413,347, 3,697,574, 3,725,277, 3, Dispersants useful herein are described in, for example, European Patent Applications Nos. 0 471 071 and 0 451 380, and are hereby incorporated by reference.

[0160] 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 (typically 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 hydrocarbyl-substituted succinic acid and hydrocarbyl-substituted succinic anhydride derivatives may have a number average molecular weight of at least 400 g / mol, such as at least 900 g / mol, such as at least 1500 g / mol, such as 400 to 4000 g / mol, such as 800 to 3000, such as 2000 to 2800 g / mol, such as about 2100 to 2500 g / mol, such as about 2200 to about 2400 g / mol.

[0161] Succinimides that are particularly useful herein are formed by the condensation reaction of 1) a hydrocarbyl-substituted succinic anhydride, such as polyisobutylene succinic anhydride (PIBSA), with 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 seven 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 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 shown in U.S. Pat. Nos. 3,087,936, 3,172,892, 3,219,666, 3,272,746, 3,322,670, 3,652,616, 3,948,800, and 6,821,307, and Canadian Patent No. 1,094,044.

[0162] The dispersant may comprise one or more optionally borated higher molecular weight (Mn 1600 g / mol or more, e.g. 1800-3000 g / mol) succinimides, and one or more optionally borated lower molecular weight (Mn less than 1600 g / mol) succinimides, the higher molecular weight being 1600-3000 g / mol, for example 1700-2800 g / mol, for example 1800-2500 g / mol, for example 1850-2300 g / mol, and the lower molecular weight being 600-1600 g / mol or less, for example 650-1500 g / mol, for example 700-1400 g / mol, for example 800-1300 g / mol, for example 850-1200 g / mol, for example 900-1150 g / mol, for example 900-1000 g / mol. The higher molecular weight succinimide dispersant may be present in the lubricating composition at 0.5-10%, or 0.8-6%, or 1.0-5%, or 1.5-5%, or 1.5-4.0% by weight, and the lower molecular weight succinimide dispersant may be present in the lubricating composition at 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 lower molecular weight succinimide may differ from the higher molecular weight succinimide by 500 g / mol or more, for example 750 g / mol or more, for example 1000 g / mol or more, for example 1200 g / mol, for example 500-3000 g / mol, for example 750-2000 g / mol, for example 1000-1500 g / mol.

[0163] Succinic acid esters useful as dispersants include those formed by the condensation reaction of hydrocarbyl-substituted succinic anhydrides with alcohols or polyols. 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 polyalkylpolyamines, propoxylated polyalkylpolyamines, and polyalkenylpolyamines, such as polyethylenepolyamines, and / or propoxylated hexamethylenediamines. 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.

[0164] The molecular weight of the hydrocarbyl-substituted succinic anhydrides used in the preceding paragraph will typically be 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 may be post-reacted with various reagents, such as sulfur, oxygen, formaldehyde, carboxylic acids, such as oleic acid. The dispersant may be present in the lubricant in an amount from 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, for example 0.3 to 5% by mass, such as 1.0% to 3.0% by mass of the lubricating oil composition.

[0165] The above (poly)alkenyl succinic acid derivatives may 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, generally having from about 0.1 to about 5 moles of boron per mole of dispersant reaction product. Dispersants useful herein include borated succinimides including derivatives derived from monosuccinimides, bissuccinimides, and / or mixtures of monosuccinimides and bissuccinimides, where the hydrocarbyl succinimides are derived from hydrocarbylene groups, e.g., polyisobutylene having an Mn of from about 300 to about 5000 g / mole, or from about 500 to about 3000 g / mole, or from about 1000 to about 2000 g / mole, or mixtures of such hydrocarbylene groups often with higher terminal vinyl groups.

[0166] The boron-containing dispersant may be present at 0.01% to 20%, or 0.1% to 15%, or 0.1% to 10%, or 0.5% to 8%, or 1.0% to 6.5%, or 0.5% to 2.2% by weight of the lubricating composition. The boron-containing dispersant may be present in an amount to deliver from 15 ppm to 2000 ppm, or from 25 ppm to 1000 ppm, or from 40 ppm to 600 ppm, or from 80 ppm to 350 ppm of boron to the composition. Borated dispersants may be used in combination with non-borated dispersants and may be the same compound as the non-borated dispersants 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, the total amount of dispersants may be from 0.01% to 20%, or from 0.1% to 15%, or from 0.1% to 10%, or from 0.5% to 8%, or from 1.0% to 6.5%, or from 0.5% to 2.2%, by weight of the lubricating composition, and the ratio of borated dispersant to non-borated dispersant may be from 1:10 to 10:1 (weight:weight), or from 1:5 to 3:1, or from 1:3 to 2:1. The dispersant may comprise one or more borated or non-borated poly(alkenyl)succinimides ("PIBSA-PAM"), where the polyalkenyl is derived from polyisobutylene and the imide is derived from a polyamine.

[0167] The dispersant may comprise one or more PIBSA-PAMs, where the PIB is derived from polyisobutylene having an 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, e.g. tetraethylenepentamine, pentaethylenehexamine, tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), N-phenyl-p-phenylenediamine (ADPA), and other polyamines having an average of 5, 6, 7, 8, or 9 nitrogen atoms per molecule. The dispersant may be borated, typically at a level of 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 a Mn of 700-1800 g / mol (e.g., 800-1500 g / mol) and one or more non-borated PIBSA-PAMs derived from PIB having a 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 a Mn of greater than 1800 to 5000 g / mol (e.g., 2000-3000 g / mol). The dispersant may comprise one or more borated PIBSA-PAMs derived from PIB having a Mn of greater than 1800 to 5000 g / mol (e.g., 2000-3000 g / mol).

[0168] The dispersant may comprise a PIBSA derived from a 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 a PIB having a Mn of 700-5000 g / mol. The dispersant may comprise a PIBSA derived from a PIB having a Mn of 700-5000 g / mol (e.g. 800-3000 g / mol), one or more borated PIBSA-PAMs derived from a PIB having a Mn of 700-1800 g / mol (e.g. 800-1500 g / mol), and one or more non-borated PIBSA-PAMs derived from a PIB having a Mn of greater than 1800 to 5000 g / mol (e.g. 2000-3000 g / mol). The dispersant may comprise a PIBSA derived from a PIB having a Mn of 700-5000 g / mol (e.g., 800-3000 g / mol), one or more non-borated PIBSA-PAMs derived from a PIB having a Mn of 700-1800 g / mol (e.g., 800-1500 g / mol), and one or more borated PIBSA-PAMs derived from a PIB having a Mn of greater than 1800 to 5000 g / mol (e.g., 2000-3000 g / mol).

[0169] 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 comprise one or more borated PIBSA-PAMs and one or more non-borated PIBSA-PAMs. The dispersant may comprise one or more optionally borated higher molecular weight (Mn 1600 g / mol or more, e.g. 1800-3000 g / mol) PIBSA-PAMs, and one or more optionally borated lower molecular weight (Mn less than 1600 g / mol) PIBSA-PAMs, the higher molecular weight being 1600-3000 g / mol, for example 1700-2800 g / mol, for example 1800-2500 g / mol, for example 1850-2300 g / mol, and the lower molecular weight being less than 600-1600 g / mol, for example 650-1500 g / mol, for example 700-1400 g / mol, for example 800-1300 g / mol, for example 850-1200 g / mol, for example 900-11500 g / mol, for example 900-100 g / mol. The higher molecular weight PIBSA-PAM dispersant may be present in the lubricating composition at 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 % and the lower molecular weight PIBSA-PAM dispersant may be present in the lubricating composition at 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 %.

[0170] In one preferred form, the dispersant may comprise one or more higher molecular weight (Mn ≥ 1600 g / mol) PIBSA-PAMs which may be borated, and one or more lower molecular weight (Mn < 1600 g / mol) PIBSA-PAMs which may be borated, wherein the higher molecular weight PIBSA-PAMs are present in the lubricating oil composition at 2.5 mass % or less, or 1.5 mass % or less, or 0.5 mass % or less, or 0.0 mass %. In a preferred form, the dispersant comprises one or more higher molecular weight (Mn ≥ 1600 g / mol) PIBSA-PAMs, which may be borated, and one or more lower molecular weight (Mn < 1600 g / mol) PIBSA-PAMs, which may be borated, and the treat level of the combination of the higher molecular weight PIBSA-PAM and the lower 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%.

[0171] Mannich base dispersants Mannich base dispersants useful herein are typically made from the reaction of an amine component, a hydroxyaromatic compound (substituted or unsubstituted, e.g., alkyl substituted), such as an alkylphenol, with an aldehyde, e.g., formaldehyde. See U.S. Patents 4,767,551 and 10,899,986. Processing aids and catalysts, e.g., oleic acid and sulfonic acids, may also be part of the reaction mixture. Representative examples are shown in U.S. Pat. Nos. 3,697,574, 3,703,536, 3,704,308, 3,751,365, 3,756,953, 3,798,165, 3,803,039, 4,231,759, 9,938,479, 7,491,248, and 10,899,986, and WO 01 / 42399.

[0172] Dispersing agent of polymethacrylate or polyacrylate derivative Polymethacrylate or polyacrylate derivatives are another type of dispersant useful herein. Such dispersants are typically prepared by reacting a nitrogen-containing monomer with a methacrylic or acrylic acid ester containing 5 to 25 carbon atoms in the ester group. Representative examples are shown in U.S. Patents 2,100,993 and 6,323,164. Polymethacrylate and polyacrylate dispersants are typically of lower molecular weight.

[0173] The lubricating compositions of the present disclosure typically comprise from 0.1% to 20% by weight of the composition, such as from 0.2 to 15%, such as from 0.25 to 10%, such as from 0.3 to 5%, for example from 2.0% to 4.0% by weight of the lubricating oil composition of a dispersant. Alternatively, the dispersant may be present at from 0.1% to 5%, or from 0.01% to 4% by weight 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.

[0174] Compositions according to the present disclosure may contain additives having various stated functions that also have a secondary effect as dispersants (e.g., the Component B functionalized polymers described above can also exhibit dispersant effects), but such additives are not included as dispersants for purposes of determining the amount of dispersant in a lubricating oil composition or concentrate herein.

[0175] J. Corrosion Inhibitors / Rust Prevention Agents Corrosion inhibitors can be used to reduce the corrosion of metals and are often alternatively referred to as metal deactivators or metal passivators. Some corrosion inhibitors may alternatively be characterized as antioxidants.

[0176] Suitable corrosion inhibitors may include nitrogen and / or sulfur containing heterocyclic compounds such as triazoles (e.g., benzotriazoles), substituted thiadiazoles, imidazoles, thiazoles, tetrazoles, hydroxyquinolines, oxazolines, imidazolines, thiophenes, indoles, indazoles, quinolines, benzoxazines, dithiols, oxazoles, oxatriazoles, pyridines, piperazines, triazines, and derivatives of any one or more of these. Particular corrosion inhibitors have the following structure: [ka] is a benzotriazole represented by the formula: In the formula, R 8 is C1-C which may be absent (hydrogen) or linear or branched, saturated or unsaturated 20 The corrosion inhibitor is a hydrocarbyl or substituted hydrocarbyl group. It may be alkyl or aromatic in nature and / or contain a ring structure containing heteroatoms such as N, O, or S. Examples of suitable compounds may include benzotriazole, alkyl-substituted benzotriazoles (e.g., tolyltriazole, ethylbenzotriazole, hexylbenzotriazole, octylbenzotriazole, etc.), aryl-substituted benzotriazoles, and alkylaryl- or arylalkyl-substituted benzotriazoles, and the like, and combinations thereof. For example, the triazole may include or be benzotriazole, and / or alkylbenzotriazoles, where the alkyl group contains from 1 to about 20 carbon atoms or from 1 to about 8 carbon atoms. Non-limiting examples of such corrosion inhibitors include or may be benzotriazole, tolyltriazole, and / or optionally substituted benzotriazoles, such as Irgamet™ 39, available from BASF, Ludwigshafen, Germany. Preferred corrosion inhibitors include or may be benzotriazole and / or tolyltriazole.

[0177] Additionally or alternatively, the corrosion inhibitor may have the structure: [ka]

[0033] The substituted thiadiazoles may include one or more substituted thiadiazoles represented by In the formula, R 15 and R 16 are independently hydrogen or a hydrocarbon group, the hydrocarbon group 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). Such substituted thiadiazoles are derived from the 2,5-dimercapto-1,3,4-thiadiazole (DMTD) molecule. Many derivatives of DMTD have been described in the art, and any such compound may be included in the fluids used in the present disclosure. For example, U.S. Patents 2,719,125, 2,719,126, and 3,087,937 describe the preparation of various 2,5-bis-(hydrocarbon dithio)-1,3,4-thiadiazoles.

[0178] Further, in addition or alternatively, the corrosion inhibitor may be one or more other derivatives of DMTD, such as R 15 and R 16 The thioester-containing DMTD derivatives may include carboxylic acid esters in which R may be bonded to the sulfur atom of the sulfide through a carbonyl group. The preparation of such thioester-containing DMTD derivatives is described, for example, in U.S. Pat. No. 2,760,933. DMTD derivatives produced by condensation of DMTD with alpha-halogenated aliphatic carboxylic acids having at least 10 carbon atoms are described, for example, in U.S. Pat. No. 2,836,564. This process provides the compounds R 15 and R 16 HOOC-CH(R 19 )-(R 19 is a hydrocarbyl group. DMTD derivatives further prepared by amidation or esterification of such terminal carboxylic acid groups may also be useful.

[0179] 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 can include mixtures of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazole and 2,5-bis-hydrocarbyldithio-1,3,4-thiadiazole, such as those sold under the trade name HiTEC™ 4313 and available from Afton Chemical Company. 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 can include mixtures of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazole and 2,5-bis-hydrocarbyldithio-1,3,4-thiadiazole, such as those sold under the trade name HiTEC™ 4313 and available from Afton Chemical Company.

[0180] In addition, or alternatively, the corrosion inhibitor may be of the structure B(OR 46 )3, wherein each R 46 may be the same or different. Since it may be desirable for the borates to be compatible with the non-aqueous medium of the composition, each R 46may in particular comprise or be a hydrocarbyl C1-C8 moiety. For example, in compositions in which the non-aqueous medium comprises or is a lubricating oil base stock, typically better compatibility can be achieved 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 borate, such as triisopropyl borate, tributyl borate, such as tri-tert-butyl borate, tripentyl borate, trihexyl borate, trioctyl borate, such as tri-(2-ethylhexyl) borate, and monohexyl dibutyl borate, and the like, and combinations thereof.

[0181] If used, the corrosion inhibitor may include a substituted thiadiazole, a substituted benzotriazole, a substituted triazole, a trisubstituted borate, or a combination thereof. Optionally, corrosion inhibitors can be used in any effective amount, but when used, typically 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 can 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, intentionally not added, and / or not present 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 any corrosion inhibitors.

[0182] Compositions according to the present disclosure may contain additives having various stated functions that also have a secondary effect as corrosion inhibitors (e.g., the Component B functionalized polymers described above can also exhibit corrosion inhibitor effects), and such additives are not included as corrosion inhibitors for purposes of determining the amount of corrosion inhibitor in a lubricating oil composition or concentrate herein.

[0183] K. Antiwear agent The lubricating oil compositions and concentrate compounds of the present disclosure may include one or more antiwear agents that can reduce friction and excessive wear. Any antiwear agent known to those skilled 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, and Mo, etc.) salts of dithiophosphates, metal (e.g., Zn, Pb, Sb, and Mo, etc.) salts of dithiocarbamates, metal (e.g., Zn, Pb, and 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 range from about 0.01 wt. % to about 5 wt. %, from about 0.05 wt. % to about 3 wt. %, or from about 0.1 wt. % to about 1 wt. %, based on the total weight of the lubricating oil composition. In embodiments, the 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 metal or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel, or copper. In some embodiments, the metal is zinc. In other embodiments, the alkyl group of the dihydrocarbyl dithiophosphate metal salt has from about 3 to about 22 carbon atoms, from about 3 to about 18 carbon atoms, from about 3 to about 12 carbon atoms, or from about 3 to about 8 carbon atoms. In further embodiments, the alkyl group is linear or branched.

[0184] 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 and more specifically metal dialkyldithiophosphates or zinc dialkyldithiophosphates (ZDDPs) where the metal component is zinc 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 of the formula Zn[SP(S)(OR1)(OR2)]2, where R1 and R2 are C1-C 18 Alkyl groups, preferably C2-C 12 The alkyl group is an alkyl group. Such alkyl groups may be linear or branched. The alcohols used in the ZDDP may be 2-propanol, butanol, secondary butanol, pentanol, hexanol, such as 4-methyl-2-pentanol, n-hexanol, n-octanol, 2-ethylhexanol, and alkylated phenols. Mixtures of secondary alcohols or mixtures of primary and secondary alcohols may be used. Alkylaryl groups may also be used. Useful zinc dithiophosphates include secondary zinc dithiophosphates, such as those available from The Lubrizol Corporation under the trade names "LZ 677A", "LZ 1095", and "LZ 1371", those available from Chevron Oronite under the trade name "OLOA 262", and those available from Afton Chemical under the trade name "HiTEC™ 7169".

[0185] In embodiments, the zinc compound is a zinc dithiocarbamate complex, for example, a zinc dithiocarbamate complex having the formula: [ka]

[0033] Alternatively, the zinc dithiocarbamate may be represented by the following formula: In the formula, each RI is independently a linear, cyclic, or branched, saturated or unsaturated aliphatic hydrocarbon moiety having from 1 to about 10 carbon atoms, n is 0, 1, or 2, L is a ligand that saturates the coordination sphere of zinc, and x is 0, 1, 2, 3, or 4. In certain embodiments, the ligand L is selected from the group consisting of water, hydroxide, ammonia, amino, amide, alkylthiolate, halide, and combinations thereof.

[0186] The anti-wear additive, e.g., ZDDP and / or zinc carbamate, is typically used in an amount of about 0.4 wt.% to about 1.2 wt.%, preferably about 0.5 wt.% to about 1.0 wt.%, more preferably about 0.6 wt.% to about 0.8 wt.%, based on the total weight of the lubricating composition, although in many cases greater or lesser amounts can be advantageously used. Preferably, the anti-wear additive is a ZDDP, preferably a secondary ZDDP, present in an amount of about 0.6 to 1.0 wt.% of the total weight of the lubricating composition. The lubricating oil composition of the present disclosure preferably contains a treat level of one or more ZDDPs to deliver 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 or less of phosphorus to the composition by weight.

[0187] Anti-wear additives useful herein also include boron-containing compounds, such as boric acid esters, borated aliphatic amines, borated epoxides, alkali metal (or mixed alkali metal or alkaline earth metal) borates, and borated overbased metal salts.

[0188] Compositions according to the present disclosure may contain additives having various stated functions that also have a secondary effect as antiwear agents (e.g., the Component B functionalized polymers described above can also exhibit antiwear effects), and such additives are not included as antiwear agents for purposes of determining the amount of antiwear agent in a lubricating oil composition or concentrate herein.

[0189] L. Demulsifiers Demulsifiers useful herein include those described in U.S. Pat. No. 10,829,712 (column 20, lines 34-40). Typically, small amounts of demulsifying components can be used herein. A preferred demulsifying component is described in EP 330 522. It is obtained by reacting an alkylene oxide with an adduct obtained by reaction of a bisepoxide with a polyhydric alcohol. Such additives can be used in an amount of about 0.001-5% by weight, preferably about 0.01-2% by weight.

[0190] M. Seal compatibility and seal expansion 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 can be used in amounts of about 0.001-5 wt%, preferably about 0.01-2 wt%. In an embodiment, the seal compatibility agent is a sea swell agent, such as PIBSA (polyisobutenyl succinic anhydride).

[0191] 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 the seizure of sliding metal surfaces under extreme pressure conditions. Any extreme pressure agent known to those skilled in the art can be used in the lubricating oil composition. In general, extreme pressure agents are compounds that can chemically combine with metals to form a surface film that prevents the welding of asperities on opposing metal surfaces under high loads. Non-limiting examples of suitable extreme pressure agents include sulfurized animal or vegetable fats or oils, sulfurized animal or vegetable fatty acid esters, fully or partially esterified esters of trivalent or pentavalent acids of phosphorus, sulfurized olefins, dihydrocarbyl polysulfides, sulfurized Diels-Alder adducts, sulfurized dicyclopentadiene, sulfurized or co-sulfurized mixtures of fatty acid esters and monounsaturated olefins, co-sulfurized blends of fatty 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, and polysulfide olefin products, amine salts of phosphate esters or thiophosphate esters, and combinations thereof. The amount of extreme pressure agent may range from about 0.01 wt. % to about 5 wt. %, from about 0.05 wt. % to about 3 wt. %, or from about 0.1 wt. % to about 1 wt. %, based on the total weight of the lubricating oil composition.

[0192] O. Non-Base Stock Unsaturated Hydrocarbons The lubricating oil and concentrate compositions of the present disclosure may contain one or more unsaturated hydrocarbons. Such unsaturated hydrocarbons are different from any base oils (lubricating oil base stocks of Groups I, II, III, IV, and / or V) that may be present in the composition and / or viscosity modifiers, 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 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) will typically not provide the only antioxidant or the only 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 only one unsaturation is present, 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 modified after polymerization to exhibit) terminal (near) unsaturation, and / or blends thereof. When present, the unsaturated hydrocarbon (LAO) may be present at 0.01 to 5 mass % (particularly 0.1 to 3 mass %, alternatively 0.1 to 1.5 mass %) based on the total mass of the lubricating oil composition.

[0193] When the lubricating oil composition includes one or more of the additives discussed above, the additive is typically blended into 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.

[0194] It should be noted that many of the additives are shipped from the additive manufacturer as concentrates that contain one or more additives together with a certain amount of base oil or other diluent. Thus, the amounts by weight in the table below, as well as other amounts referred to herein, refer to the amount of active ingredient (i.e., the undiluted portion of the ingredient). The mass percents (wt%) listed below are based on the total mass of the lubricating oil composition. [Table 1]

[0195] The additives mentioned above are typically commercially available materials. Although such additives may be added separately, they are usually premixed into packages that can be obtained from lubricant additive suppliers. Additive packages are available with a variety of ingredients, ratios, and characteristics, and the appropriate package will be selected taking into account the use of the final composition.

[0196] fuel The present disclosure provides a method for lubricating a passenger vehicle or commercial vehicle internal combustion engine during engine operation, comprising: (i) delivering a lubricating oil composition as described herein to a crankcase of a vehicle internal combustion engine; (ii) supplying a hydrocarbon fuel to a vehicle internal combustion engine; and (iii) combusting the fuel in a vehicle internal combustion engine, for example 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). The present invention also relates to a method comprising the steps of: The present disclosure also relates to a fuel composition comprising a lubricating oil composition as described herein and a hydrocarbon fuel, where the fuel may be derived from petroleum and / or biological sources ("biofuel" or "renewable fuel"). 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 % renewable fuel, alternatively 1 to 75 mass % renewable fuel, alternatively 5 to 50 mass % renewable fuel, based on the total mass of 1 to 50 mass % renewable fuel and petroleum-derived fuel.

[0197] Renewable fuel components are typically produced from vegetable oils (e.g., palm oil, rapeseed oil, soybean oil, jatropha oil), microbial oils (e.g., algal oil), animal fats (e.g., cooking oils, animal fats, and / or fish fats), and / or biogas. Renewable fuels refer to biofuels produced from biological resources formed from modern biological processes. In one embodiment, the renewable fuel components are produced by a hydrotreating process. Hydrotreating includes various reactions in which molecular hydrogen reacts with other components or components undergo molecular transformation in the presence of molecular hydrogen and a solid catalyst. Reactions include, but are not limited to, hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrification, hydrodemetallization, hydrocracking, and isomerization. Renewable fuel components may have different distillation ranges that provide the components with desired properties depending on the intended use.

[0198] use The lubricating compositions of the present disclosure can be used to lubricate mechanical engine parts, particularly in internal combustion engines, such as spark-ignition or compression-ignition two-stroke or four-stroke reciprocating engines, by adding lubricants thereto.Typically, the lubricating compositions of the present disclosure are crankcase lubricants, such as passenger car motor oils or heavy-duty diesel or light-duty diesel engine lubricants.The lubricating compositions of the present disclosure can also be used to lubricate mechanical engine parts in hydrogen engines and natural gas engines. In particular, the lubricating compositions of the present disclosure are suitably used to lubricate the crankcase of a spark ignition internal combustion engine, such as a passenger vehicle engine. In particular, the lubricating compositions of the present disclosure are preferably used to lubricate the crankcase of a spark ignition, turbocharged internal combustion engine. In particular, the lubricating compositions of the present disclosure are preferably used to lubricate the crankcase of a natural gas or hydrogen engine. In an embodiment, the lubricating oils of this 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 this disclosure are useful for lubricating high compression spark ignition internal combustion engines.

[0199] In an embodiment, the lubricating compositions of the present disclosure are suitably used to lubricate the crankcase of an engine in a heavy duty diesel vehicle (i.e., a heavy duty diesel vehicle having a gross vehicle weight rating of 10,000 pounds or greater). In an embodiment, the lubricating compositions of the present disclosure are suitably used to lubricate the crankcase of a passenger car diesel or gasoline engine.

[0200] The invention further relates to the following: 1. A lubricating oil composition comprising: greater than 50 mass % of the composition of 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; one or more overbased metal detergents having a total base number (KOH / g) of 9 or more and 500 or less, at a treat level delivering 1000 to 2000 ppm by weight of metal to the composition; and 0.2 to 1.0% by weight of the composition of a friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or a combination thereof; The lubricating oil composition has a total sulfated ash content of 1.0 mass % 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 mass % or less; The lubricating oil compositions were compared to lubricating oil compositions having a comparable HTHS but not containing a friction modifier comprising 0.2 to 1.0 mass % of glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof, using the MTM-R test method. 3 A lubricating oil composition that provides a 10% to 80% reduction in journal bearing wear as measured by unit wear scar volume. 2. The lubricating oil composition of paragraph 1, which provides a 10% to 70% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 Start-Stop Test Method, as compared to a lubricating oil composition having a comparable HTHS but not including a friction modifier comprising 0.2 to 1.0 mass % of the composition of glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof. 3. The lubricating oil composition of paragraphs 1-2, wherein the friction modifier comprises glycerol monooleate. 4. The lubricating oil composition of paragraphs 1-3, wherein the friction modifier comprises 0.3 to 0.5 weight percent of the composition. 5. The lubricating oil composition of paragraphs 1-4, 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. 6. The lubricating oil composition of paragraphs 1-5, wherein the oil of lubricating viscosity is 60% to 95% by weight of the composition and comprises a Group III base oil, a Group IV base oil, or a combination thereof. 7. The lubricating oil composition of paragraphs 1-6, wherein the one or more overbased metallic detergents are a sulfonate, a salicylate, a phenate, or a combination thereof. 8. The lubricating oil composition of paragraph 7, wherein the metal of the one or more overbased metal detergents is selected from the group consisting of sodium, potassium, lithium, calcium, and magnesium, and combinations thereof. 9. The lubricating oil composition according to paragraphs 1 to 8, 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. 10. The lubricating oil composition of paragraphs 1-9, 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. 11. The lubricating oil composition according to paragraphs 1 to 10 for use as a passenger vehicle lubricant (PVL) or a commercial vehicle lubricant (CVL). 12. The lubricating oil composition according to paragraphs 1-11, wherein the journal bearing is a crankshaft main bearing, a crankshaft connecting rod big end bearing, or a piston pin connecting rod small end bearing / bushing. 13. The lubricating oil composition of paragraphs 1-12, wherein the journal bearing shell material is a material selected from the group consisting of bimetallic, tri-material / trimetallic, and solid materials. 14. The lubricating oil composition according to paragraph 13, wherein the tri-material / tri-metal is a polymeric coating or a SnCu overlay on lead-free bronze. 15. The lubricating oil composition according to paragraph 13, wherein the bimetal is AlSn20Cu or AlSn25. 16. The lubricating oil composition according to paragraph 13, wherein the solid material is bronze or lead-free bronze. 17. The lubricating oil composition of paragraph 15, wherein for an aluminum bimetal journal bearing shell material, the lubricating oil composition provides a 50% to 70% reduction in journal bearing wear, as measured by wear scar volume in μm3 using the MTM-R test method, compared to a lubricating oil composition having a comparable HTHS but not including a friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof. 18. The lubricating oil composition of paragraph 14, wherein for a SnCu overlay trimetal journal bearing shell material, the lubricating oil composition provides a 30% to 50% 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 friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof. 19. The lubricating oil composition of paragraphs 1-18, further comprising one or more of the following components: one or more functional polymers, one or more other 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. 20. The lubricating oil composition of paragraph 19, wherein the one or more dispersants are one or more higher molecular weight optionally borated polyisobutylene succinimide (PIBSA-PAM) dispersants (Mn ≥ 1600 g / mole), one or more lower molecular weight optionally borated polyisobutylene succinimide (PIBSA-PAM) dispersants (Mn < 1600 g / mole), or a combination thereof, and the treat level of the combination of the higher molecular weight PIBSA-PAM and the lower molecular weight PIBSA-PAM is from 1.0 to 6.0 wt. % of the composition. 21. The lubricating oil composition of paragraph 20, wherein the higher molecular weight PIBSA-PAM dispersant, the lower molecular weight PIBSA-PAM dispersant, or a combination thereof is included at a treat level to deliver from 20 ppm to 700 ppm by weight of boron to the lubricating oil composition. 22. The lubricating oil composition of paragraph 19, wherein the one or more antiwear agents comprise one or more zinc dialkyldithiophosphates (ZDDPs) at a treat level delivering less than or equal to 840 ppm by weight of phosphorus to the composition. 23. The lubricating oil composition of paragraph 19, 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 constitute 1.0 to 6.0 mass % of the composition. 24. The lubricating oil composition of paragraph 19, wherein the one or more other 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 from 12 ppm to 1000 ppm by weight of molybdenum to the composition. 25. The functionalized polymer is 0.2 to 2.0% by weight of the composition and comprises one or more of the following: i) Mw / Mn less than 2; ii) a functionality distribution (Fd) value of 3.5 or less; and iii) Mn of the polymer before functionalization ≧10,000 g / mol (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; C 4~5 20. The lubricating oil composition of paragraph 19, comprising an amide, imide, and / or ester functionalized partially or fully saturated polymer with olefins. 26. A method for lubricating an internal combustion engine, comprising the step of supplying to the engine a lubricating oil composition according to any one of paragraphs 1 to 25. 27. A method for reducing journal bearing wear in an internal combustion engine, comprising: For internal combustion engines, greater than 50 mass % of the composition of 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; one or more overbased metal detergents having a total base number (KOH / g) of 9 or more and 500 or less, at a treat level delivering 1000 to 2000 ppm by weight of metal to the composition; and A friction modifier comprising 0.2 to 1.0% by weight of the composition of glycerol monooleate, glycerol dioleate, glycerol trioleate, or a combination thereof. A lubricating oil composition obtained by comprising or mixing The lubricating oil composition has a total sulfated ash content of 1.0 mass % 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 mass % or less; The lubricating oil compositions were compared to lubricating oil compositions having a comparable HTHS but not containing a friction modifier comprising 0.2 to 1.0 mass % of glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof, using the MTM-R test method. 3 A lubricating oil composition that provides a 10% to 80% reduction in journal bearing wear as measured by unit wear scar volume. providing a 28. The method of paragraph 27, wherein the lubricating oil composition provides a 10% to 70% 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 friction modifier comprising 0.2 to 1.0 mass % of the composition of glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof. 29. The method of paragraphs 27-28, wherein the friction modifier comprises glycerol monooleate. 30. The method of paragraphs 27-29, wherein the friction modifier comprises 0.3 to 0.5 weight percent of the composition. 31. The method of paragraphs 27-30, 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. 32. The method of paragraphs 27-31, wherein the oil of lubricating viscosity is 60% to 95% by weight of the composition and comprises a Group III base oil, a Group IV base oil, or a combination thereof. 33. The method of paragraphs 27-32, wherein the one or more overbased metal detergents is a sulfonate, a salicylate, a phenate, or a combination thereof. 34. The method of paragraph 33, wherein the metal of the one or more overbased metal detergents is selected from the group consisting of sodium, potassium, lithium, calcium, and magnesium, and combinations thereof. 35. The method of paragraphs 27-34, wherein the lubricating oil composition 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. 36. The method of paragraphs 27-35, wherein the lubricating oil composition 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. 37. The method of paragraphs 27-36, wherein the lubricating oil composition is used as a passenger vehicle lubricant (PVL) or a commercial vehicle lubricant (CVL). 38. The method of paragraphs 27-37, wherein the journal bearing is a crankshaft main bearing, a crankshaft connecting rod big end bearing, or a piston pin connecting rod small end bearing / bushing. 39. The method of paragraphs 27-38, wherein the journal bearing shell material is a material selected from the group consisting of bimetallic, tri-material / trimetallic, and solid materials. 40. The method of paragraph 39, wherein the tri-material / tri-metal is a polymeric coating or a SnCu overlay on lead-free bronze. 41. The method of paragraph 39, wherein the bimetal is AlSn20Cu or AlSn25. 42. The method of paragraph 39, wherein the solid material is bronze or lead-free bronze. 43. The method of paragraph 41, wherein, for an aluminum bimetal journal bearing shell material, the lubricating oil composition provides a 50% to 70% reduction in journal bearing wear, as measured by wear scar volume in μm3 using the MTM-R test method, compared to a lubricating oil composition having a comparable HTHS but not including a friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof. 44. The method of paragraph 40, wherein for a SnCu overlay trimetal journal bearing shell material, the lubricating oil composition provides a 30% to 50% 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 friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof. 45. The method of paragraphs 27-44, further comprising one or more of the following components: one or more functional polymers, one or more other 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. 46. ​​The method of paragraph 45, wherein the one or more dispersants are one or more higher molecular weight optionally borated polyisobutylene succinimide (PIBSA-PAM) dispersants (Mn 1600 g / mole or greater), one or more lower 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 higher molecular weight PIBSA-PAM and the lower molecular weight PIBSA-PAM is 1.0 to 6.0 wt. % of the composition. 47. The method of paragraph 46, wherein the higher molecular weight PIBSA-PAM dispersant, the lower molecular weight PIBSA-PAM dispersant, or a combination thereof is included at a treat level to deliver from 20 ppm to 700 ppm by weight of boron to the lubricating oil composition. 48. The method of paragraph 45, wherein the one or more antiwear agents comprise one or more zinc dialkyldithiophosphates (ZDDPs) at a treat level to deliver 840 ppm by weight or less to the phosphorus composition. 49. The method of paragraph 45, 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 constitute 1.0 to 6.0% by weight of the composition. 50. The method of paragraph 45, wherein the one or more other 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 from 12 ppm to 1000 ppm by weight of molybdenum to the composition. 51. The functionalized polymer is 0.2 to 2.0% by weight of the composition and is one of the following: i) Mw / Mn less than 2; ii) a functionality distribution (Fd) value of 3.5 or less; and iii) Mn of the polymer before functionalization ≧10,000 g / mol (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; C 4~5 46. ​​The method of paragraph 45, comprising an amide, imide, and / or ester functionalized partially or fully saturated polymer comprising an olefin. 52. A method for making a lubricating oil composition, comprising: (i) greater than 50 mass % of the composition of 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; (ii) one or more overbased metal detergents having a total base number (KOH / g) of 9 or more and 500 or less, at a treat level delivering 1000 to 2000 ppm by weight of metal to the composition; and (iii) 0.2 to 1.0% by weight of the composition of a friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or a combination thereof. Combining or mixing The lubricating oil composition has a total sulfated ash content of 1.0 mass % or less, a high temperature high shear viscosity (HTHS) at 150°C, determined 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 mass % or less; The lubricating oil compositions were compared to lubricating oil compositions having a comparable HTHS but not containing a friction modifier comprising 0.2 to 1.0 mass % of glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof, using the MTM-R test method. 3 The method provides a 10% to 80% reduction in journal bearing wear as measured by unit wear scar volume. 53. The method of paragraph 52, wherein the lubricating oil composition provides a 10% to 70% 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 friction modifier comprising 0.2 to 1.0 mass % of the composition of glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof.

[0201] The following non-limiting examples are provided to illustrate the present disclosure.

[0202] experiment All molecular weights are number average molecular weights (Mn) determined by gel permeation chromatography using polystyrene standards and reported in g / mole unless otherwise noted. "AI", "ai", and "ai" are weight percent active ingredient unless otherwise indicated.

[0203] 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 of the oil is measured by ASTM D5185. Sulfated ash ("SASH") content is measured by ASTM D874. The phosphorus, boron, calcium, zinc, molybdenum, and magnesium contents are determined by ASTM D5185.

[0204] 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 specimen, which reciprocates under load against a disk-shaped lower specimen. The ball was made of AISI 52100 grade steel and was uncoated. The disks were made of steel that had been coated with either an aluminum bimetallic, a polymeric tri-material, or were uncoated (steel). The coating depth was approximately 2μm. Thus, contact between the ball and disk was measured to determine the wear scar volume in μm. 3 The test conditions for each of the disc materials tested with the lubricating oil compositions are shown in the table below. The test discs were made of 46mm AISI 52100 steel with a surface finish of <0.02μm Ra and a hardness of 720-780Hv, and the test balls were made of 19.05mm AISI 52100 steel with a surface finish of <0.02μm Ra and a hardness of 800-920Hv. [Table 2]

[0205] The TE-92 Start / Stop Test Method includes a test rig and test procedure for measuring journal bearing wear as measured by maximum average wear in microns. This test procedure is contained in the following journal article: Summer, F., Grun, F., and Ravenhill, E. R. (2020). Friction and Wear Performance of Various Polymer Coatings for Journal Bearings under Stop Start Sliding. Lubricants, 8. 2020(1), [1] https: / / doi.org / 10.3390 / lubricants8010001, which is incorporated herein by reference in its entirety with respect to the TE-92 Start / Stop Test Method. The paper states, "The test strategy began with an initial period at slower rocking speeds at room temperature to facilitate gentle break-in. The oil was then heated to an oil bath temperature of 120°C during settling, before a stop-start rocking was performed to a maximum speed of 1.2 m / s. The speed ramp was performed as quickly as possible to mimic an engine stop-start. The total ramp duration from 0 to 1.2 m / s and back lasted 8 seconds. The test duration varied depending on the number of stop-start ramps." When using the TE-92 start-stop test method with SnCu trimetal, the test is performed for 10k cycles. When using the TE-92 start-stop test method with polymeric trimetal, the test is performed for 40k cycles. The polymeric trimetal material is tested for more cycles than the SnCu trimetal material due to the reduced propensity for stop-start wear.

[0206] 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 and was determined according to ASTM D4683 at 150°C and reported in cP. material Ingredient Chart [Table 3] TIFF2025072303000015.tif39169 EXAMPLES

[0207] Example 1 Oil candidates of the present invention Tables 1 and 2 below show the formulations of various 0W-16 and 0W-20 lubricants (Inventive Examples 1-2 and Comparative Examples 1 and 3-5) with and without three different organic friction modifiers (OFMs). Some of the lubricants (Table 1) were tested for wear performance using the MTM-R test method and others were tested for wear performance using the TE-92 start-stop test method (Table 2). The additives used in the formulations are listed in Tables 1 and 2 in weight percent. Tables 1 and 2 also provide the viscosity characteristics of the lubricants tested.

[0208] The organic friction modifiers tested were glycerol monooleate (GMO), N-ODSA (n-octadecyl succinic anhydride), and oleamide, and the loading of OFM in the lubricant was kept constant at 0.3 wt.% of the total lubricant composition. Using the MTM-R test method and steel and aluminum bimetal as wear surfaces, the wear performance results of the three different OFMs are shown in Figures 3, 4, and 5 for GMO, N-ODSA, and oleamide, respectively. As can be seen from Figure 3, for the aluminum bimetal wear surface (non-ferrous journal bearing analog), the lubricant containing 0.3 wt.% GMO provided nearly a 60% reduction in wear scar volume compared to the baseline results (same formulation but without GMO). As can also be seen from Figure 3, for the steel wear surface (ferrous journal bearing analog), the lubricant containing 0.3 wt.% GMO provided a very slight reduction in wear scar volume compared to the baseline results (same formulation but without GMO). As can be seen from Figures 4 and 5, for an aluminum bimetal wear surface (non-ferrous journal bearing analog), the lubricant containing 0.3 wt. % N-ODSA and oleamide OFM provided a significant reduction in wear scar volume compared to the baseline results (same formulation but without N-ODSA or oleamide). As can also be seen from Figures 4 and 5, for a steel wear surface (ferrous journal bearing analog), the lubricant containing 0.3 wt. % N-ODSA and oleamide OFM provided a very slight reduction in wear scar volume compared to the baseline results (same formulation but without N-ODSA or oleamide). Based on these results, it can be concluded that glycerol monooleate friction modifier surprisingly and unexpectedly improves journal bearing wear performance of non-ferrous materials, as other OFMs (N-ODSA and oleamide) provided a negative impact on wear performance as opposed to the significant benefit demonstrated with the GMO OFM. In contrast, for the steel wear surface in the MTM-R test method, all three OFMs exhibited similar, negligible reductions in wear scar volume compared to baseline results. [Table 4]

[0209] With reference to Table 2 and Figure 6, two 0W-16 lubricant compositions were tested for wear performance in the TE-92 Start / Stop test with SnCu trimetal wear material. Inventive Example 2 contained 0.5 wt.% glycerol monooleate, while Comparative Example 5 contained no GMO. As can be seen from Figure 6, the 0W-16 lubricant composition of the present invention containing 0.5 wt.% GMO provided nearly a 40% reduction in maximum average wear in microns compared to Comparative Example 5 (0% GMO). These results confirm that significant wear performance benefits can be obtained from GMO organic friction modifiers, even using different wear test methods.

[0210] In conclusion, it has been surprisingly and unexpectedly discovered that glycerol monooleate organic friction modifier improves journal bearing wear performance of non-ferrous materials.Other OFMs, such as N-ODSA and oleamide, have a significant negative impact on wear performance, while GMOs have a significant benefit on wear performance.This is unexpected and surprising.It is also expected that glycerol dioleate, glycerol trioleate, and the combination of glycerol monooleate, glycerol dioleate, and glycerol trioleate will perform very similarly to glycerol monooleate in terms of unexpectedly improving the wear performance of lubricating oil compositions for non-ferrous wear materials. [Table 5]

[0211] Applicants have unexpectedly discovered that the journal bearing wear performance of low viscosity engine oils for use in internal combustion engines with non-ferrous wear materials can be significantly improved by using in the formulation a friction modifier comprising 0.2 to 1.0 weight percent of the composition of glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof. The improvements in journal bearing wear were measured and verified using the MTM-R test method and the TE-92 start-stop test method, but it is expected that similar improvements will be seen in other wear test methods.

[0212] All documents described herein, including any priority documents and / or testing procedures, are incorporated herein by reference to the extent that they are not inconsistent with the text. As is apparent from the basic description and specific embodiments above, forms of the invention have been shown and described, but various modifications can be made without departing from the spirit and scope of the invention. Thus, the invention is not intended to be limited thereby. The term "comprising" is considered synonymous with the term "including". Similarly, when a composition, element, or group of elements is preceded by the transition phrase "comprising", it is understood that the same composition or group of elements with the transition phrase "consisting essentially of", "consisting of", "selected from the group consisting of", or "is" preceding the description of the composition, element, or elements is also contemplated, and vice versa.

Claims

1. 1. A lubricating oil composition comprising: greater than 50 mass % of the composition of 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; one or more overbased metal detergents having a total base number (KOH / g) of ≧9 and ≦500, at a treat level delivering 1000-2000 ppm by weight of metal to the composition; and 0.2 to 1.0% by weight of the composition of a friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof. A lubricating oil composition obtained by comprising or mixing The lubricating oil composition has a total sulfated ash content of 1.0 mass % 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 determined in accordance with ASTM D4683-20, and a total phosphorus level of 0.080 mass % or less; The lubricating oil compositions have a comparable HTHS but do not contain a friction modifier comprising 0.2 to 1.0 mass % of glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof, using the MTM-R test method. 3 A lubricating oil composition that provides a 10% to 80% reduction in journal bearing wear as measured by unit wear scar volume.

2. 10. The lubricating oil composition of claim 1, which provides a 10% to 70% 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 friction modifier comprising 0.2 to 1.0 mass % of the composition of glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof.

3. 3. The lubricating oil composition of claim 1 or 2, wherein the friction modifier comprises glycerol monooleate.

4. The lubricating oil composition of any one of claims 1 to 3, wherein the friction modifier comprises 0.3 to 0.5 weight percent of the composition.

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

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

7. 2. The lubricating oil composition of claim 1, wherein the one or more overbased metallic detergents are a sulfonate, a salicylate, a phenate, or a combination thereof.

8. 8. The lubricating oil composition of claim 7, wherein the metal of the one or more overbased metallic detergents is selected from the group consisting of sodium, potassium, lithium, calcium, and magnesium, and combinations thereof.

9. 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.

10. 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.

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

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

13. 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 / tri-metallic, and solid materials.

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

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

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

17. 16. The lubricating oil composition of claim 15, which for an aluminum bimetal journal bearing shell material provides a 50% to 70% reduction in journal bearing wear as measured by wear scar volume in μm using the MTM-R test method compared to a lubricating oil composition having a comparable HTHS but not including a friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof.

18. 15. The lubricating oil composition of claim 14, wherein for the SnCu overlay trimetal journal bearing shell material, the lubricating oil composition provides a 30% to 50% 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 friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof.

19. 10. The lubricating oil composition of claim 1, further comprising one or more of the following components: one or more functional polymers, one or more other 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.

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

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

22. 20. The lubricating oil composition of claim 19, wherein the one or more antiwear agents comprise one or more zinc dialkyldithiophosphates (ZDDP) at a treat level delivering up to 840 ppm by weight of phosphorus to the composition.

23. 20. The lubricating oil composition of claim 19, 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.

24. 20. The lubricating oil composition of claim 19, wherein the one or more other 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 from 12 ppm to 1000 ppm by weight of molybdenum to the composition.

25. The functionalized polymer is 0.2 to 2.0% by weight of the composition and is selected from the group consisting of: iv) Mw / Mn less than 2; v) a functionality distribution (Fd) value of 3.5 or less; and vi) the Mn of said polymer before functionalization is 10,000 g / mol or more (GPC-PS) provided that, when the polymer, prior to functionalization, is a copolymer of isoprene and butadiene, the Mn of the copolymer is greater than 25,000 g / mol; C 4~5 20. The lubricating oil composition of claim 19, comprising an amide, imide, and / or ester functionalized partially or fully saturated polymer with olefins.

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

27. A method for reducing journal bearing wear in an internal combustion engine, comprising the step of supplying to said engine a lubricating oil composition according to any one of claims 1 to 25.

28. 1. A method for making a lubricating oil composition, comprising: (i) greater than 50 mass % of the composition of 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; (ii) one or more overbased metal detergents having a total base number (KOH / g) of 9 or more and 500 or less, at a treat level delivering 1000 to 2000 ppm by weight of metal to the composition; and (iii) 0.2 to 1.0% by weight of the composition of a friction modifier comprising glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof. Combining or mixing The lubricating oil composition has a total sulfated ash content of 1.0 mass % 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 determined in accordance with ASTM D4683-20, and a total phosphorus level of 0.080 mass % or less; The lubricating oil compositions have a comparable HTHS but do not contain a friction modifier comprising 0.2 to 1.0 mass % of glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof, using the MTM-R test method. 3 The method provides a 10% to 80% reduction in journal bearing wear as measured by unit wear scar volume.

29. 30. The method of claim 28, wherein the lubricating oil composition provides a 10% to 70% 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 friction modifier comprising 0.2 to 1.0 mass % of the composition of glycerol monooleate, glycerol dioleate, glycerol trioleate, or combinations thereof.

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