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

Abstract

The present invention relates to a lubricating oil composition comprising or being obtained by mixing (i) a base oil, (ii) an overbased calcium-based detergent at a treatment rate that provides the composition with calcium of from 500 to 1300 ppm by weight; (iii) an overbased magnesium-based detergent at a process rate that provides 500 to 1300 ppm by weight of magnesium to the composition; the total weight of the total calcium and magnesium is 1000 to 1800 ppm. The composition has a total sulfate ash content of less than or equal to 1.0 wt%, an elevated temperature high shear viscosity at 150 DEG C of 1.8-2.9 mPa.s, and a total phosphorus content of less than or equal to 0.080 wt%. The composition of the present invention provides a reduction in journal bearing wear from 5% to 60% as measured by maximum average wear in microns using a TE-92 start / stop test method as compared to a lubricating oil composition comparable to HTHS but not comprising a mixture of overbased calcium-based detergent and overbased magnesium-based detergent. A method of reducing journal bearing wear in an internal combustion engine and a method of making a lubricating oil composition are also provided.

Description

priority This application claims priority to and the benefit of U.S. patent application No. USSN 63 / 588,238, filed on October 5, 2023. Inventor Greg Stidder and Emma Ravenhill. Technical Field

[0001] The present disclosure relates to lubricating oil compositions. More particularly, it relates to lubricating oil compositions for internal combustion engines having improved journal bearing wear. Background Art

[0002] There is a growing trend towards lower and lower viscosity SAE (Society of Automotive Engineers) grades for both passenger vehicle applications (PVL) and commercial vehicle applications (CVL) for both factory and service fill oils. This is due to the desire for improved fuel economy (FE) as a result of regional emission requirements. Related to this is the established use of start / stop technology prevalent in the industry in ICE (internal combustion engine) and hybrid applications.

[0003] However, durability of main journal bearings and connecting rod (big end) journal bearings in internal combustion engines is often considered a potential problem with the use of these low viscosity fluids (<0W-20) because the journal bearings in this system are non-ferrous materials (e.g., aluminum bimetal, SnCu, and polymer coatings) that have lower wear resistance than iron and steel materials and react differently to traditional lubricant additive components. In the past, bearing systems were considered particularly susceptible to wear due to the use of lower viscosity fluids and the use of start / stop technology due to the nature of the contact. Traditionally, in hydrodynamic lubrication systems, journal bearings rely on lubricant viscosity to keep contact between surfaces to a minimum and keep wear under control. In an environment where engine oil viscosity is reduced, as start / stop events increase, the system experiences more boundary lubrication, resulting in increased contact stresses, leading to higher levels of wear on journal bearings in internal combustion engines.

[0004] Therefore, there is a need for new engine oils with 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, especially for engine oils for gasoline engines, diesel engines, natural gas engines and hydrogen engines. These needs are particularly prominent for passenger car engines and related oils used for lubrication thereof. More particularly, 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 for internal combustion engines.

[0005] The present invention relates to lubricating oil compositions exhibiting improved engine wear characteristics. More particularly, the present invention relates to crankcase lubricating oil compositions for compression-ignited or spark-ignited internal combustion engines and hydrogen and natural gas engines, such compositions being referred to as crankcase lubricants; and to the use of specific additives in such lubricating oil compositions for reducing wear of journal bearings in internal combustion engines.

[0006] The present inventors have now surprisingly found that specific combinations of a base oil and a mixture of an overbased calcium-based detergent and an overbased magnesium-based detergent can be used in lubricant compositions for internal combustion engines to provide improved engine wear protection in journal bearings when using the TE-92 start / stop test method compared to lubricant compositions of comparable viscosity but which do not contain a mixture of an overbased calcium-based detergent and an overbased magnesium-based detergent. Summary of the invention

[0007] The present invention relates to a lubricating oil composition, comprising or obtained by mixing the following components: greater than 50% by weight of an oil of lubricating viscosity of the composition, which includes a Group I base oil, a Group II base oil, a Group III base oil, a Group IV base oil, or a combination thereof; an overbased calcium-based detergent having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500 and at a treat rate providing 500 to 1300 wt ppm of calcium to the composition; and an overbased magnesium-based detergent having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500 and at a treat rate providing 500 to 1300 wt ppm of magnesium to the composition; wherein the total weight of the combined calcium and magnesium in the composition is 1000 ppm to 1800 ppm; the lubricating oil composition has a total sulfated ash less than or equal to 1.0 wt %, a ASTM D 1000 of ... % as measured by D4683-20 ​​at 150°C and a total phosphorus content of less than or equal to 0.080 weight percent, and wherein the lubricating oil composition provides a 5% to 60% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 start / stop test method compared to a lubricating oil composition having a comparable HTHS but not comprising a mixture of overbased calcium-based detergent and overbased magnesium-based detergent in an amount of from 1000 ppm to 1800 ppm combined calcium and magnesium loadings in the composition.

[0008] According to another aspect of the present invention, there is provided a method for reducing journal bearing wear in an internal combustion engine, comprising: providing a lubricating oil composition to the internal combustion engine, the lubricating oil composition comprising the following components or being obtained by mixing the following components: greater than 50% by weight of an oil of lubricating viscosity of the composition, which comprises a Group I base oil, a Group II base oil, a Group III base oil, a Group IV base oil or a combination thereof; a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500 and in the range of 500 to 1300 when providing the composition an overbased calcium-based detergent at a treat rate of 0.1 wt ppm calcium; and an overbased magnesium-based detergent having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500 and at a treat rate providing 500 to 1300 wt ppm magnesium to the composition; wherein the total weight of the combined calcium and magnesium in the composition is from 1000 ppm to 1800 ppm; the lubricating oil composition has a total sulfated ash less than or equal to 1.0 wt %, a % sulphated ash greater than or equal to 1.8 mPa.s and less than or equal to 2.9 mPa.s according to ASTM % as measured by D4683-20 ​​at 150°C and a total phosphorus content of less than or equal to 0.080 weight percent, and wherein the lubricating oil composition provides a 5% to 60% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 start / stop test method compared to a lubricating oil composition having a comparable HTHS but not comprising a mixture of overbased calcium-based detergent and overbased magnesium-based detergent in an amount of from 1000 ppm to 1800 ppm combined calcium and magnesium loadings in the composition.

[0009] According to yet another aspect of the present invention, there is provided a method of making a lubricating oil composition comprising combining or blending: (i) greater than 50% by weight of an oil of lubricating viscosity of the composition comprising a Group I base oil, a Group II base oil, a Group III base oil, a Group IV base oil, or a combination thereof; (ii) an overbased calcium-based detergent having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500 and at a treat rate providing 500 to 1300 ppm by weight of calcium to the composition; and (iii) an overbased magnesium-based detergent having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500 and at a treat rate providing 500 to 1300 ppm by weight of magnesium to the composition; wherein the total weight of combined calcium and magnesium in the composition is from 1000 ppm to 1800 ppm; the lubricating oil composition having a total sulfated ash less than or equal to 1.0 wt%, a ASTM D 1765 of greater than or equal to 1.8 mPa.s and a ASTM D 1765 of greater than or equal to 2.9 mPa.s. % as measured by D4683-20 ​​at 150°C and a total phosphorus content of less than or equal to 0.080 weight percent, and wherein the lubricating oil composition provides a 5% to 60% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 start / stop test method compared to a lubricating oil composition having a comparable HTHS but not comprising a mixture of overbased calcium-based detergent and overbased magnesium-based detergent in an amount of from 1000 ppm to 1800 ppm combined calcium and magnesium loadings in the composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1 is a cross-sectional perspective view of a representative internal combustion engine showing the locations of the various bearings in the engine that require lubrication.

[0011] Figure 2 Schematic diagram of cross-sections of journal bearing shell materials for solid bearings, bimetallic bearings, and tri-material / metallic bearings.

[0012] Figure 3 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 lubricating oil compositions of the present invention and comparative lubricating oil compositions.

[0013] Figure 4 is another bar graph of journal bearing wear as measured by maximum average wear in microns using the TE-92 Start / Stop Test Method for lubricating oil compositions of the present invention and comparative lubricating oil compositions. definition

[0014] For purposes of this specification and all claims herein, if the following words and expressions are used, they shall have the meanings given below.

[0015] For purposes herein, the new numbering scheme of the periodic table is used as described in CHEMICAL AND ENGINEERING NEWS, 63(5), 27 (1985), i.e., alkali metals are Group 1 metals (e.g., Li, Na, K, etc.) and alkaline earth metals are Group 2 metals (e.g., Mg, Ca, Ba, etc.).

[0016] The term "comprising" or any cognates specifies the presence of stated elements, steps or integers or components, but does not exclude the presence or addition of one or more other elements, steps, integers, components or combinations thereof. The expression "consisting of" or "consisting essentially of" or cognates may be encompassed within "comprising" or cognates, wherein "consisting essentially of" allows the inclusion of substances that do not substantially affect the characteristics of the composition to which it is applied.

[0017] The term "LOC" refers to a lubricating oil composition.

[0018] The term "major amount" means more than 50 mass % of the composition, such as more than 60 mass % of the composition, such as more than 70 mass % of the composition, such as 80 to 99.009 mass % of the composition, such as 80 to 99.9 mass %, such as 80 to 99.009 mass % of the composition, based on the mass of the composition.

[0019] The term "minor amount" means 50 mass % or less of the composition; such as 40 mass % or less of the composition; such as 30 mass % or less of the composition, such as 20 to 0.001 mass %, such as 20 to 0.1 mass %, based on the mass of the composition.

[0020] Unless otherwise indicated, the term "mass %" refers to the mass percentage of a component based on the mass of the composition measured in grams, and is alternatively referred to as weight percent ("weight %", "wt %" or "% w / w").

[0021] The term "active ingredient" (also referred to as "ai" or "AI") refers to an additive material that is neither a diluent nor a solvent. Unless otherwise indicated, amounts herein are described as active ingredients.

[0022] As used herein, the terms "oil-soluble" and "oil-dispersible" or cognate terms do not necessarily mean that the compound or additive is soluble, dissolvable, miscible or capable of being suspended in the oil in all proportions. However, these mean that they are soluble or stably dispersible in the oil, for example, to an extent sufficient to exert their intended effect in the environment in which the oil is used. In addition, the additional incorporation of other additives may also allow the incorporation of higher amounts of a particular additive, if desired.

[0023] The terms "group" and "radical" are used interchangeably herein.

[0024] The term "hydrocarbon" refers to a compound of hydrogen and carbon atoms. A "heteroatom" is an atom other than carbon or hydrogen. When referred to as a "hydrocarbon", especially as a "refined hydrocarbon", the hydrocarbon may also contain a minor amount (e.g., wherein the heteroatom does not substantially change the hydrocarbon nature of the hydrocarbon compound) of one or more heteroatoms or heteroatom-containing groups (e.g., halogens, especially chlorine and fluorine, amino, alkoxy, mercapto, alkylmercapto, nitro, nitroso, sulfinyl (sulfoxy), etc.).

[0025] The term "hydrocarbyl" refers to a group containing hydrogen and carbon atoms. Preferably, unless otherwise specified, the group consists essentially of hydrogen and carbon atoms, more preferably consists only of hydrogen and carbon atoms. Preferably, the hydrocarbyl comprises an aliphatic hydrocarbyl. The term "hydrocarbyl" includes "alkyl", "alkenyl", "alkynyl" and "aryl" as defined herein. The hydrocarbyl may contain one or more atoms / groups other than carbon and hydrogen, as long as they do not affect the basic hydrocarbyl nature of the hydrocarbyl. Such atoms / groups (e.g., halogens, especially chlorine and fluorine, amino, alkoxy, mercapto, alkylthiol, nitro, nitroso, sulfinyl (sulfoxy), etc.) are known to those skilled in the art.

[0026] The term "alkyl" refers to a carbon and hydrogen radical (e.g., C1 to C 30 , such as C1 to C 12 The alkyl group in a compound is usually directly bonded to the compound via a carbon atom. Unless otherwise specified, the alkyl group may be straight chain (i.e., unbranched) or branched, cyclic, acyclic or partially cyclic / acyclic. Preferably, the alkyl group comprises a straight chain or branched acyclic alkyl group. Representative examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, dimethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, and triacontyl.

[0027] The term "alkenyl" refers to a carbon and hydrogen group (e.g., C2 to C 30 Groups such as C2 to C 12 The alkenyl group in a compound is usually directly bonded to the compound via a carbon atom. Unless otherwise specified, the alkenyl group may be straight chain (ie, unbranched) or branched, cyclic, acyclic or partially cyclic / acyclic.

[0028] The term "alkylene" refers to a C1 to C 20 , preferably C1 to C 10A divalent saturated aliphatic group which may be straight chain or branched. Representative examples of alkylene groups 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.

[0029] "Olefins," also referred to as "alkenes," are straight chain, branched, or cyclic hydrocarbons having at least one double bond. For purposes of this specification and the claims thereto, when a polymer or copolymer is referred to as comprising an olefin, the olefin present in such a 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, it is understood that the monomer units in the copolymer are derived from isoprene in the polymerization reaction, the derived units being present at 55% to 95% by weight based on the weight of the copolymer. A "polymer" has two or more monomer units that are the same or different. A "homopolymer" is a polymer having the same monomer units. A "copolymer" is a polymer having two or more monomer units that are different from each other. "Different" as used to refer to monomer units means that the monomer 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 comprises at least 50 mole percent isoprene-derived units, a "butadiene polymer" or "butadiene copolymer" is a polymer or copolymer that comprises at least 50 mole percent butadiene-derived units, and so forth. Likewise, when a polymer is referred to as "partially or fully saturated" comprising C 4-5 When a polymer or copolymer is used as a "polymer of olefins", the C 4-5 The olefin is the polymerized form of the olefin, and the polymer has been partially or fully saturated (eg, by hydrogenation) after polymerization of the monomers.

[0030] The term "alkynyl" refers to a C2 to C16 radical containing at least one carbon-carbon triple bond. 30 (such as C2 to C 12 ) group.

[0031] The term "aryl" refers to a group containing at least one aromatic ring, such as cyclopentadiene, phenyl, naphthyl, anthracenyl, etc. Aryl is usually C5 to C 40 (such as C5 to C 18 , such as C6 to C 14 ) aryl, optionally substituted by one or more hydrocarbon groups, heteroatoms or heteroatom-containing groups (such as halogen, hydroxyl, alkoxy and amino). Preferred aryl groups include phenyl and naphthyl and substituted derivatives thereof, especially phenyl and alkyl substituted derivatives of phenyl.

[0032] The term "substituted" means that the hydrogen atom has been replaced by a hydrocarbon group, a heteroatom or a heteroatom-containing group. Alkyl substituted derivatives mean that the hydrogen atom has been replaced by an alkyl group. "Alkyl substituted phenyl" is a phenyl group in which the hydrogen atom has been replaced by an alkyl group, such as a C1 to C 20 Alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, dimethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and / or triacontyl substituted phenyl.

[0033] The term "halogen" or "halo" refers to a Group 17 atom or a group of a Group 17 atom, such as fluorine, chlorine, bromine and iodine.

[0034] The term "ashless" with respect to an additive means that the composition contains no metals.

[0035] The term "ash-containing" with respect to an additive means that the composition contains metals.

[0036] The term "effective amount" with respect to an additive refers to the amount of such additive in the lubricating oil composition such that the additive provides the desired technical effect.

[0037] The term "effective minor amount" with respect to an additive refers to 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.

[0038] The term "effective major amount" with respect to an additive refers to an amount of such additive constituting 50 mass % or more of the lubricating oil composition such that the additive provides the desired technical effect.

[0039] Unless otherwise indicated, the term "ppm" means parts per million by mass based on the total mass of the lubricating oil composition.

[0040] The term "metal content" of a lubricating oil composition or additive component, such as magnesium content, molybdenum content or total metal content (ie, the sum of all individual metal contents) is measured by ASTM D5185.

[0041] The term "aliphatic hydrocarbon fatty acid" refers to an aliphatic C7 to C 29 , preferably C9 to C 27 , the most preferred 11 To C 23 Such compounds may be referred to herein as aliphatic (C7 to C 29 ), more preferably (C9 to C 27 ), most preferably (C 11 To C 23) hydrocarbyl monocarboxylic acids or hydrocarbyl fatty acids (wherein Cx to Cy represent the total number of carbon atoms in the aliphatic hydrocarbyl chain of the fatty acid, the fatty acid itself comprising a total of Cx+1 to Cy+1 carbon atoms due to the presence of the carboxyl carbon atom). Preferably, the aliphatic hydrocarbyl fatty acid, including the carboxyl carbon atom, has an even number of carbon atoms. The aliphatic hydrocarbyl chain of the fatty acid may be saturated or unsaturated (i.e. comprising at least one carbon-carbon double bond); preferably, the aliphatic hydrocarbyl chain is unsaturated and comprises at least one carbon-carbon double bond - such fatty acids may be obtained from natural sources (e.g. derived from animal or vegetable oils) and / or by reduction of the corresponding saturated fatty acids. It will be appreciated that a certain proportion of the aliphatic hydrocarbyl chains of the corresponding aliphatic hydrocarbyl fatty acid esters are unsaturated (i.e. comprising at least one carbon-carbon double bond) to allow reaction with other reagents, such as sulfur, to form the corresponding functionalized (e.g. sulfurized) aliphatic hydrocarbyl fatty acid esters.

[0042] The term "aliphatic hydrocarbon fatty acid ester" refers to an ester obtainable by converting the monocarboxylic acid functional group of the corresponding aliphatic hydrocarbon fatty acid into an ester group. Suitably, the monocarboxylic acid functional group of the aliphatic hydrocarbon fatty acid is converted into a hydrocarbon ester, preferably a C1 to C 30 Aliphatic hydrocarbon esters, such as alkyl esters, preferably C1 to C6 alkyl esters, especially methyl esters. Alternatively or additionally, the monocarboxylic acid functional group of the aliphatic hydrocarbon fatty acid may be in the form of a natural glyceride. Accordingly, the term "aliphatic hydrocarbon fatty acid ester" includes aliphatic hydrocarbon fatty acid glycerides and aliphatic hydrocarbon fatty acid C1 to C6 30 Aliphatic hydrocarbon esters, [e.g., aliphatic hydrocarbon fatty acid alkyl esters, more preferably aliphatic hydrocarbon fatty acid C1 to C6 alkyl esters, especially aliphatic hydrocarbon fatty acid methyl esters]. Suitably, the term "aliphatic hydrocarbon fatty acid esters" includes aliphatic (C7 to C 29 ) hydrocarbon group, more preferably aliphatic (C9 to C 27 ) hydrocarbon group, most preferably aliphatic (C 11 To C 23 ) Hydrocarbyl fatty acid glycerides and aliphatic (C7 to C 29 ) hydrocarbon group, more preferably aliphatic (C9 to C 27 ) hydrocarbon group, most preferably aliphatic (C 11 To C 23 ) Hydrocarbyl fatty acid C1 to C 30 Aliphatic hydrocarbyl esters. Suitably, in order to allow functionalisation, such as sulphurisation, of the aliphatic hydrocarbyl fatty acid esters, a proportion of the aliphatic hydrocarbyl chains of the fatty acid esters are unsaturated and comprise at least one carbon-carbon double bond.

[0043] The term "sulfurized aliphatic hydrocarbyl fatty acid ester" refers to a compound obtained by sulfiding an aliphatic hydrocarbyl fatty acid ester as defined herein.

[0044] The term "absent" or "substantially free" when referring to a component included in the lubricating oil composition described herein and in the claims thereto means that the 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 an amount that does not affect the properties of the lubricating oil composition, such as less than 10 ppm or less than 1 ppm or less than 0.001 ppm. When the term "absent" is used with respect to monomer reactants and / or with respect to repeating units in the (co)polymers described herein, it means that the components are present at 0 wt% based on the weight of all (co)monomers in the (co)polymer, or if present, the amounts are so low that they do not substantially affect the physical properties of the (co)polymer, such as 0.2 wt% or less or 0.1 wt% or less.

[0045] 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 known as polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise indicated, all molecular weight units (e.g., Mw, Mn, Mz) are reported in g / mol.

[0046] With respect to an additive component or a lubricating oil composition (ie, an unused lubricating oil composition), Total Base Number, also referred to as "TBN," refers to the Total Base Number as measured by ASTM D2896 and reported in units of mgKOH / g.

[0047] Total Acid Number ("TAN") is determined by ASTM D664.

[0048] Phosphorus, boron, calcium, zinc, molybdenum, sodium, silicon and magnesium contents were measured by ASTM D5185.

[0049] The sulfur content in the oil formulations was measured by ASTM D5185.

[0050] Sulfated ash ("SASH") content is measured by ASTM D874.

[0051] Kinematic viscosity (KV100, KV40) was determined according to ASTM D445-19a and is reported in cSt unless otherwise specified.

[0052] The viscosity index is measured according to ASTM D2270.

[0053] Saponification value is determined by ASTM D94 and is reported in mgKOH / g.

[0054] HTCBT, high temperature corrosion bench test (high temperature corrosion bench test) is measured according to ASTMD6594.

[0055] The term "functionalized polymer" refers to a polymer of the functionalized hydrogenated polyisoprene series for use in lubricating oil compositions, which is disclosed in co-owned U.S. Provisional Application No. 63 / 379,006, filed on October 11, 2022, which is incorporated herein by reference in its entirety. For the polymers of this functionalized polymer series, the average functionality [also referred to as the average functionality value (Fv)] and the functionality distribution (Fd) values ​​are determined by gel permeation chromatography using polystyrene standards as described in the experimental section of USSN 63 / 379,006.

[0056] The term "neo acids" refers to carboxylic acids exhibiting a highly branched structure, wherein the carboxylic acid functional group is attached to a quaternary carbon atom, and wherein the other moiety bonded to the quaternary carbon is a saturated straight chain, branched or cyclic alkyl group.

[0057] "Neodecanoic acid" is a compound with the general structural formula C 10 H 20 O2 C 10 A mixture of neoacids. The components of the mixture are acids having the common property of having three alkyl groups at carbon 2, 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.

[0058] Unless otherwise indicated, all percentages reported are mass % or weight % on an active ingredient basis, ie, without taking into account carrier or diluent oil, unless otherwise indicated.

[0059] It is also understood that the various components used (essential as well as optimal and conventional) may react under conditions of formulation, storage or use, and the present disclosure also provides products obtainable or obtained as a result of any such reaction.

[0060] Furthermore, it is to be understood that any upper and lower limits of amounts, ranges, and ratios recited herein are independently combinable.

[0061] It is also to be understood that the preferred features of each aspect of the present disclosure are considered as the preferred features of each other aspect of the present disclosure. Accordingly, the preferred and more preferred features of one aspect of the present disclosure can be independently combined with other preferred and / or more preferred features of the same or different aspects of the present disclosure. DETAILED DESCRIPTION

[0062] The features of the present disclosure are now described in more detail as follows, which pertain to each and all aspects of the present disclosure where appropriate.

[0063] The lubricating oil compositions of the present disclosure include components that may or may not remain chemically identical before and after mixing with an oily carrier (such as a base oil) and / or other additives. The present disclosure encompasses compositions comprising components before mixing, or components after mixing, or components before and after mixing.

[0064] The lubricating oil composition of the present disclosure is particularly suitable for lubricating journal bearings present in internal combustion engines. Figure 1 , depicts a cross-sectional perspective view of an exemplary internal combustion engine 10 showing the locations of various bearings in the engine that require lubrication. The engine 10 includes a connecting rod small end bearing / bushing 20 having a piston pin journal. The engine 10 also includes a main bearing 30 for a crankshaft journal and a connecting rod big end bearing 40 for a crankshaft journal. The engine 10 further includes a camshaft bearing 50 and a rocker arm bushing 60. The inventive lubricating oil composition of the present disclosure is particularly suitable for lubricating Figure 1 Each of these bearing / journal types depicted in and minimizes wear.

[0065] refer to Figure 2 , depicting the structures and cross-sections of solid bearings, bimetallic bearings, and tri-material / metallic bearings, and schematic cross-sectional views of journal bearing shell materials for solid bearings, bimetallic bearings, and tri-material / metallic bearings. Solid bearings may include bronze or lead-free bronze. Bimetallic bearings may include AlSn20Cu or AlSn25. Tri-material / metallic bearings may include a polymer or SuCu coating on lead-free bronze. The inventive lubricating oil compositions disclosed herein are particularly suitable for lubricating Figure 2 In particular, it has been surprisingly found that the inventive lubricating oil compositions of the present disclosure reduce bimetallic and tri-material / metallic wear when used in internal combustion engines. More particularly, it has been surprisingly found that the inventive lubricating oil compositions of the present disclosure reduce SnCu trimetallic and polymer tri-material wear. Lubricating oil composition

[0066] The present disclosure is directed to a lubricating oil composition (also referred to as a "LOC," "lubricant composition," "lubricating composition," or "lubricant oil composition") comprising or admixed from: greater than 50 weight percent 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; an overbased calcium-based detergent having a total base number (KOH / g) greater than, or equal to, 9 and less than, or equal to, 500 and at a treat rate providing 500 to 1300 weight ppm of calcium to the composition; and an overbased magnesium-based detergent having a total base number (KOH / g) greater than, or equal to, 9 and less than, or equal to, 500 and at a treat rate providing 500 to 1300 weight ppm of magnesium to the composition; wherein the total weight of combined calcium and magnesium in the composition is from 1000 ppm to 1800 ppm. The lubricating oil composition may have a total sulfated ash less than or equal to 1.0 wt%, a high temperature high shear viscosity (HTHS) at 150°C measured according to ASTM D4683-20 ​​greater than or equal to 1.8 mPa.s and less than or equal to 2.9 mPa.s, and a total phosphorus content less than or equal to 0.080 wt%. The lubricating oil composition provides a 5% to 60% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 start / stop test method compared to a lubricating oil composition having a comparable HTHS but not including a mixture of overbased calcium-based detergent and overbased magnesium-based detergent in the composition at a combined calcium and magnesium loading of 1000 ppm to 1800 ppm.

[0067] The lubricating oil composition disclosed herein may have a high temperature high shear viscosity (HTHS or HTHS 150° C.) measured according to ASTM D4683-20 ​​of greater than or equal to 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 of less than or equal to 0.9 wt%, or less than or equal to 0.8 wt%, or less than or equal to 0.7 wt%, or less than or equal to 0.6 wt%, or less than or equal to 0.5 wt%.

[0068] The lubricating oil compositions disclosed herein may have a phosphorus content of less than or equal to 0.075 wt. %, or less than or equal to 0.070 wt. %, or less than or equal to 0.065 wt. %, or less than or equal to 0.060 wt. %, or less than or equal to 0.055 wt. %, or less than or equal to 0.050 wt. %.

[0069] The lubricating oil composition of the present disclosure may have a kinematic viscosity at 100° C. of 5 to 20 cSt, or 8 to 18 cSt, or 10 to 16 cSt. The lubricating oil composition of the present disclosure may have a total sulfur content of less than or equal to 0.35 wt.%, or less than or equal to 0.30 wt.%, or less than or equal to 0.25 wt.%, or less than or equal to 0.20 wt.%.

[0070] In another form of the disclosure, the oil of lubricating viscosity constitutes 60 to 95 wt %, or 70 to 90 wt %, or 75 to 85 wt % of the composition and comprises a Group III base oil, a Group IV base oil, or a combination thereof.

[0071] Regarding the overbased magnesium-based detergent of the lubricating oil composition, it can be a sulfonate, salicylate, phenate or a combination thereof. Similarly, the overbased calcium-based detergent of the lubricating oil composition can be a sulfonate, salicylate, phenate or a combination thereof. The overbased magnesium-based detergent can provide 500 to 1300ppm, or 600 to 1200ppm, or 700 to 1100ppm, or 800 to 1000ppm of magnesium by weight to the composition. Similarly, the overbased calcium-based detergent can provide 500 to 1300ppm, or 600 to 1200ppm, or 700 to 1100ppm, or 800 to 1000ppm of calcium by weight to the composition.

[0072] The combined overbased magnesium-based detergent and overbased calcium-based detergent may provide 1000 to 1800 ppm, or 1100 to 1700 ppm, or 1200 to 1600 ppm, or 1300 to 1500 ppm of total weight of combined calcium and magnesium to the composition. In another form of the lubricating oil composition of the present invention, the ratio of calcium loading to magnesium loading in the composition may be 30:70 to 70:30, or 35:65 to 65:35, or 40:60 to 60:40, or 45:55 to 55:45, based on weight % in the lubricating oil composition.

[0073] The lubricating oil composition of the present disclosure is particularly suitable as a heavy-duty diesel engine oil, a light-duty diesel engine oil, a hydrogen engine oil, a spark-ignition internal 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 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 (low viscosity engine oil) selected from 0W-8, 0W-12, 0W-16, 0W-20.

[0074] The lubricating oil compositions of the present disclosure are particularly suitable as passenger vehicle lubricants (PVL) or commercial vehicle lubricants (CVL) and provide a reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 Start / Stop test method of 5% to 60%, or 10 to 55%, or 15 to 50%, or 20 to 45%, or 25 to 40%, or 30 to 35% compared to a lubricating oil composition comparable to the HTHS but not containing a mixture of an overbased calcium-based detergent and an overbased magnesium-based detergent.

[0075] The lubricating oil composition disclosed herein is particularly suitable for lubricating and reducing the wear tendency of journal bearings of internal combustion engines, wherein the journal bearing is a main bearing for a crankshaft, a connecting rod big end bearing for a crankshaft, or a connecting rod small end bearing / bushing for a piston pin. The journal bearing shell material can be a material selected from bimetal, tri-material / metal and solid material. For tri-material / metal journal bearings, the tri-material / metal can be a polymer coating or SuCu coating on lead-free bronze. For bimetal journal bearings, the bimetal can be AlSn20Cu or AlSn25. For solid material journal bearings, the solid material can be bronze or lead-free bronze.

[0076] In one specific form, when the lubricating oil compositions disclosed herein are used to lubricate a polymer coated three-material journal bearing shell material, the compositions of the invention provide a 5% to 40%, or 10 to 35%, or 15 to 30%, or 20 to 25% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 start / stop test method compared to a lubricating oil composition comparable to the HTHS but not containing a mixture of an overbased calcium-based detergent and an overbased magnesium-based detergent.

[0077] In another specific form, when the lubricating oil compositions disclosed herein are used to lubricate SnCu faced tri-metal journal bearing shell materials, the compositions of the invention provide a reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 start / stop test method of 10% to 60%, or 15 to 55%, or 20 to 50%, or 25 to 45%, or 30 to 40%, compared to a lubricating oil composition comparable to the HTHS but not containing a mixture of an overbased calcium-based detergent and an overbased magnesium-based detergent.

[0078] The lubricating oil compositions of the present disclosure may further comprise one or more of the following components: one or more functionalized polymers, one or more friction modifiers; one or more antioxidants; one or more pour point depressants; one or more defoamers; one or more viscosity improvers; 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.

[0079] In one advantageous form, the lubricating oil composition of the present disclosure further comprises one or more optionally boronated higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersants (Mn of 1600 g / mol or more), one or more optionally boronated lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersants (Mn less than 1600 g / mol), or a combination thereof, and wherein the treat rate of the combination of the higher molecular weight PIBSA-PAM and the lower molecular weight PIBSA-PAM is 1.0 to 6.0 wt %, or 2.0 to 5.0 wt %, or 3.0 to 4.0 wt % 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, and is comprised at a treat rate that provides 20 ppm to 700 ppm, or 50 to 600 ppm, or 100 to 500 ppm, or 200 to 400 ppm of boron by weight to the lubricating oil composition.

[0080] In one advantageous form, the lubricating oil composition of the present disclosure further comprises one or more antiwear agents comprising one or more zinc dialkyl dithiophosphates (ZDDPs) providing a treat rate to the composition of less than or equal to 840 ppm, or less than or equal to 800 ppm, or less than or equal to 700 ppm, or less than or equal to 600 ppm by weight of phosphorus.

[0081] In another advantageous form, 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, and wherein the one or more antioxidants constitute 1.0 to 6.0 wt. %, or 1.5 to 5.5 wt. %, or 2.0 to 5.0 wt. %, or 2.5 to 4.5 wt. %, or 3.0 to 4.0 wt. % of the total lubricating oil composition.

[0082] In another advantageous form, the lubricating oil composition of the present disclosure further comprises one or more friction modifiers selected from moly dimer, moly trimer, or combinations thereof at a treat rate to provide 12 ppm to 1000 ppm, or 20 ppm to 500 ppm, or 20 ppm to 200 ppm by weight of molybdenum to the composition.

[0083] In yet another advantageous form, the lubricating oil composition of the present disclosure is substantially free of molybdenum.

[0084] In another advantageous form, the lubricating oil composition of the present disclosure further optionally comprises 0.2 to 2.0 wt. %, or 0.4 to 1.8 wt. %, or 0.6 to 1.6 wt. %, or 0.8 to 1.4 wt. %, or 1.0 to 1.2 wt. % of the composition of one or more functionalized polymers, which include amide, imide and / or ester functionalized partially or fully saturated C 4-5 A polymer of an olefin having: i) a Mw / Mn of less than 2, or less than 1.8, or less than 1.6, ii) a functionality distribution (Fd) value of 3.5 or less, or 3.2 or less, or 3.0 or less, or 2.5 or less, and iii) an Mn (GPC-PS) 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, Provided that if the polymer prior to functionalization is a copolymer of isoprene and butadiene, the copolymer has an Mn 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).

[0085] 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% 1,4-insertions of the monomer. Additionally, the functionalized polymer of the lubricating oil composition of the present disclosure may include a partially or fully saturated homopolyisoprene containing one or more pendant amine groups prior to functionalization and having an Mn (GPC-PS) of 25,000 to 100,000 g / mol, or 35,000 to 90,000 g / mol, or 45,000 to 80,000 g / mol, or 55,000 to 75,000 g / mol and at least 50%, or at least 60%, or at least 70% 1,4-insertions.

[0086] The functionalized polymer of the lubricating oil composition of the present disclosure may be free of styrene repeating units, or free of butadiene repeating units, or not be homopolyisobutylene, or not be a copolymer of isoprene and butadiene.

[0087] The lubricating oil composition of the present disclosure is particularly suitable as a heavy-duty diesel engine oil, a light-duty diesel 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 0W-8, 0W-12, 0W-20, 0W-30, 5W-20, 5W-30, 10W-30, 15W-40, 5W-40 and 10W-40.

[0088] Also provided herein is a method for lubricating an internal combustion engine, comprising supplying a lubricating oil composition according to the present disclosure to the engine. Also provided herein is a method for providing mogas to an engine and burning the mogas in the engine, wherein the mogas is non-renewable mogas, renewable mogas, or a combination thereof, and wherein the engine is a spark-ignited internal combustion engine. Also provided herein is a method for providing diesel fuel to an engine and burning the diesel fuel in the engine, wherein the diesel fuel is non-renewable diesel fuel, renewable diesel fuel, or a combination thereof, and wherein the engine is a diesel engine. Also provided herein is a method for providing natural gas or hydrogen to an engine and burning natural gas or hydrogen in an engine, wherein the engine is a natural gas engine or a hydrogen engine.

[0089] The lubricating oil composition of the present disclosure is particularly suitable for improving the wear performance of journal bearings in internal combustion engines and reducing emissions of the engine. Therefore, a method of reducing journal bearing wear in an internal combustion engine is also provided, which comprises supplying the lubricating oil composition according to the present disclosure to the engine. A method of making a lubricating oil composition is also provided herein, which comprises combining or mixing the components of the lubricating oil composition of the present disclosure.

[0090] Suitably, the lubricating oil composition of the present disclosure may have a total base number (TBN) of 4 to 16 mgKOH / g, preferably 5 to 14 mgKOH / g, such as 7 to 12 mgKOH / g, such as 8 to 12 mgKOH / g, as measured by ASTM D2896.

[0091] Alternatively, the lubricating oil composition of the present disclosure may contain a ratio of magnesium atoms to calcium atoms of at least 0.5, preferably at least 0.6, more preferably at least 0.65, based on the total mass of the lubricating composition, as measured by ASTM D5185.

[0092] Typically, the lubricating oil composition may contain a low sulphur content. Preferably, the lubricating composition contains at most 0.35, more preferably at most 0.3, such as 0.1 to 0.35 mass % sulphur based on the total mass of the lubricating oil composition as measured by ASTM D5185.

[0093] Typically, the lubricating oil composition may contain a low sulfated ash content, such as 1.0 mass % or less, or preferably 0.9 mass % or less, or 0.0001 to 0.9 mass % or less sulfated ash, based on the total mass of the lubricating composition as measured by ASTM D874-13a (2018).

[0094] Preferably, the lubricating oil composition of the present disclosure may be a multigrade oil designated by the viscosity descriptor SAE 15W-X, SAE 10W-X, SAE 5W-X or SAE 0W-X, wherein X represents any one of 8, 12, 16, 20, 30, 40 and 50; the characteristics of the different viscosity grades can be found in the SAE J300 classification. Alternatively, the lubricating composition may be in the form of a viscosity grade SAE 15W-X, SAE 10W-X, SAE 5W-X or SAE 0W-X, such as SAE 15W-X or SAE 10W-X, wherein X represents any one of 8, 12, 16, 20, 30, 40 and 50. Preferably, X is 20, 30 or 40. Alternatively, the lubricating composition of the present disclosure may be a multigrade oil designated 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 Society of Automotive Engineers).

[0095] In embodiments, the lubricating oil composition may contain less than 75 ppm boron, or less than 60 ppm boron, or from 1 to 70 ppm boron. Alternatively, the LOC may be absent or substantially free of boron.

[0096] In an embodiment, the lubricating oil composition may include less than or equal to 6 (e.g., less than 5, such as less than 4, such as less than 3, such as less than 2, such as less than 1) mass % of a functionalized (e.g., aminated) polybutene (e.g., polyisobutylene), such as PIBSA-PAM. In an embodiment, the lubricating oil composition may include, may be substantially free of, or may be absent of a functionalized (e.g., aminated) polybutene (e.g., polyisobutylene), such as a high molecular weight PIBSA-PAM.

[0097] In an embodiment, the lubricating oil composition may include an acylated polymer, such as polyisobutylene succinic acid (PIBSA), which optionally has an Mn of 500 to 50,000 g / mol, such as 600 to 5,000 g / mol, such as 700 to 3000 g / mol. In an embodiment, the lubricating oil composition may include an acylated polymer, such as polyisobutylene succinic acid, having an Mn of 500 to 1600 g / mol, such as 700 to 1200 g / mol. In an embodiment, the lubricating oil composition includes greater than 0.1 (such as 0.1 to 6, such as 0.5 to 4) mass % of a functionalized (such as aminated) polybutene (such as polyisobutylene), such as PIBSA-PAM.

[0098] In embodiments, the lubricating oil composition may include 20 (eg, 15, eg, 10, eg, 5, eg, 3, eg, 1) mass % or less of a block copolymer, such as a block, star, random and / or tapered block copolymer.

[0099] In embodiments, the lubricating oil composition may be substantially free of or may be absent block copolymers, such as block, radial, random and / or tapered block copolymers.

[0100] In embodiments, the lubricating oil composition may include 20 (eg, 15, eg, 10, eg, 5, eg, 3, eg, 1) mass % or less of a styrenic copolymer, such as a block, star, random and / or tapered styrenic block copolymer.

[0101] In embodiments, the lubricating oil composition may be substantially free of or absent styrenic copolymers, such as block, radial, random and / or tapered styrenic block copolymers.

[0102] In embodiments, the lubricating oil composition may comprise less than 20 (eg, less than 15, such as less than 10, such as less than 5, such as less than 3, such as less than 1) mass % of a functionalized diluent, such as a functionalized oil.

[0103] In embodiments, the lubricating oil composition may include, may be substantially free of, or may be absent a functionalized diluent, such as a functionalized oil.

[0104] In embodiments, the lubricating oil composition may comprise less than 20 (eg, less than 15, such as less than 10, such as less than 5, such as less than 3, such as less than 1) mass % of a solvent, such as an aromatic solvent.

[0105] In embodiments, the lubricating oil composition may be substantially free of or absent solvents, such as functionalized solvents.

[0106] In embodiments, the lubricating oil composition may comprise less than 0.5 (eg, 0.4, such as less than 0.3, such as less than 0.2, such as less than 0.1, substantially absent or 0) weight % of secondary and tertiary hydrocarbyl amine compounds based on the weight of the LOC.

[0107] In embodiments, the lubricating oil composition may be substantially absent or may be free of secondary and tertiary hydrocarbyl amine compounds.

[0108] In embodiments, the lubricating composition of the present disclosure may be a heavy duty diesel engine oil, a light duty diesel engine oil, or a passenger car engine oil for a spark ignition internal combustion engine.

[0109] In embodiments, the lubricating composition of the present disclosure may be a natural gas engine oil or a hydrogen engine oil.

[0110] The lubricating compositions disclosed herein may have a viscosity of 5 to 20 (e.g., 6 to 18, or 8 to 16, or 10 to 14) cSt (mm 2 / s) of kinematic viscosity at 100°C as measured by ASTM D-445 and 15 to 30 (e.g., 15 to 25) cSt (mm 2 / s) at 40°C. Method of using the lubricating oil composition

[0111] The present disclosure also relates to methods of using lubricating oil compositions, particularly methods of reducing journal bearing wear in an internal combustion engine, comprising: providing a lubricating oil composition to an internal combustion engine, the lubricating oil composition comprising or admixed from: 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; an overbased calcium-based detergent having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500 and at a treat rate providing 500 to 1300 ppm by weight of calcium to the composition; and an overbased magnesium-based detergent having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500 and at a treat rate providing 500 to 1300 ppm by weight of magnesium to the composition; wherein the total weight of combined calcium and magnesium in the composition is from 1000 ppm to 1800 ppm. The lubricating oil composition may have a total sulfated ash less than or equal to 1.0 wt%, a high temperature high shear viscosity (HTHS) at 150°C as measured according to ASTM 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 content less than or equal to 0.080 wt%. The disclosed method of reducing journal bearing wear provides a 5% to 60% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 start / stop test method compared to a lubricating oil composition having a comparable HTHS but not including a mixture of overbased calcium-based detergent and overbased magnesium-based detergent in the composition at a combined calcium and magnesium loading of 1000 ppm to 1800 ppm.

[0112] It has been surprisingly and unexpectedly discovered that the lubricating oil compositions disclosed herein reduce journal bearing wear as measured by maximum average wear in microns using the TE-92 Start / Stop test method compared to lubricating oil compositions having HTHS comparable values ​​but which do not contain a mixture of overbased calcium-based detergents and overbased magnesium-based detergents in the composition at a combined calcium and magnesium loading of from 1000 ppm to 1800 ppm.

[0113] In another form of the present disclosure, the method of 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. measured according to ASTM D4683-20 ​​of greater than or equal to 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.

[0114] In another form of the present disclosure, the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition may have a total sulfated ash content of less than or equal to 0.9 wt%, or less than or equal to 0.8 wt%, or less than or equal to 0.7 wt%, or less than or equal to 0.6 wt%, or less than or equal to 0.5 wt%; and a phosphorus content of less than or equal to 0.075 wt%, or less than or equal to 0.070 wt%, or less than or equal to 0.065 wt%, or less than or equal to 0.060 wt%, or less than or equal to 0.055 wt%, or less than or equal to 0.050 wt%.

[0115] In another form of the present disclosure, the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition may have a kinematic viscosity at 100° C. of 5 to 20 cSt, or 8 to 18 cSt, or 10 to 16 cSt; and a total sulfur content of less than or equal to 0.35 wt. %, or less than or equal to 0.30 wt. %, or less than or equal to 0.25 wt. %, or less than or equal to 0.20 wt. %.

[0116] In another form of the present disclosure, the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the oil of lubricating viscosity constitutes 60 wt % to 95 wt %, or 70 to 90 wt %, or 75 to 85 wt % of the composition and comprises a Group III base oil, a Group IV base oil, or a combination thereof.

[0117] In another form of the present disclosure, the method for reducing journal bearing wear in an internal combustion engine of the present disclosure, with respect to the overbased magnesium-based detergent of the lubricating oil composition, it can be a sulfonate, salicylate, phenate or a combination thereof. Similarly, the overbased calcium-based detergent of the lubricating oil composition can be a sulfonate, salicylate, phenate or a combination thereof. The overbased magnesium-based detergent can provide 500 to 1300ppm, or 600 to 1200ppm, or 700 to 1100ppm, or 800 to 1000ppm of magnesium by weight to the composition. Similarly, the overbased calcium-based detergent can provide 500 to 1300ppm, or 600 to 1200ppm, or 700 to 1100ppm, or 800 to 1000ppm of calcium by weight to the composition.

[0118] In another form of the present disclosure, the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the total weight of the overbased magnesium-based detergent and the overbased calcium-based detergent of the lubricating oil composition can provide 1000 to 1800 ppm, or 1100 to 1700 ppm, or 1200 to 1600 ppm, or 1300 to 1500 ppm of the total weight of the total calcium and magnesium in the composition. In another form of the method of reducing journal bearing wear of the present invention, the ratio of calcium loading to magnesium loading in the composition can be 30:70 to 70:30, or 35:65 to 65:35, or 40:60 to 60:40, or 45:55 to 55:45, based on the weight % in the lubricating oil composition.

[0119] In another form of the present disclosure, the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition is particularly suitable as a heavy-duty diesel engine oil, a light-duty diesel engine oil, a hydrogen engine oil, a spark-ignition internal 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 0W-8, 0W-12, 0W-16, 0W-20, 0W-30, 5W-20, 5W-30, 10W-30, 15W-40, 5W-40 and 10W-40.

[0120] In another form of the present disclosure, the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition is particularly suitable as a passenger car lubricant (PVL) or a commercial vehicle lubricant (CVL) and provides a reduction in journal bearing wear measured by maximum average wear in microns using the TE-92 start / stop test method of 5% to 60%, or 10 to 55%, or 15 to 50%, or 20 to 45%, or 25 to 40%, or 30 to 35% compared to a lubricating oil composition comparable to HTHS but not containing a mixture of an overbased calcium-based detergent and an overbased magnesium-based detergent.

[0121] In another form of the present disclosure, the method of 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 of an internal combustion engine, wherein the journal bearing is a main bearing for a crankshaft, a connecting rod big end bearing for a crankshaft, or a connecting rod small end bearing / bushing for a piston pin. The journal bearing shell material can be a material selected from bimetal, tri-material / metal and monolithic material. For tri-material / metal journal bearings, the tri-material / metal can be a polymer coating or SuCu coating on lead-free bronze. For bimetal journal bearings, the bimetal can be AlSn20Cu or AlSn25. For monolithic journal bearings, the monolithic material can be bronze or lead-free bronze.

[0122] In one specific form, the disclosed method of reducing journal bearing wear in an internal combustion engine is particularly suitable when the lubricating oil composition is used to lubricate a polymer coated three-material journal bearing shell material, and the composition of the invention provides a reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 start / stop test method of 5% to 40%, or 10 to 35%, or 15 to 30%, or 20 to 25%, compared to a lubricating oil composition comparable to HTHS but not containing a mixture of an overbased calcium-based detergent and an overbased magnesium-based detergent.

[0123] In another specific form, the disclosed method of reducing journal bearing wear in an internal combustion engine is particularly suitable when the lubricating oil composition is used to lubricate a SnCu clad tri-metal journal bearing shell material, and the composition of the invention provides a reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 start / stop test method of 10% to 60%, or 15 to 55%, or 20 to 50%, or 25 to 45%, or 30 to 40%, compared to a lubricating oil composition comparable to HTHS but not containing a mixture of an overbased calcium-based detergent and an overbased magnesium-based detergent.

[0124] In another form of the present disclosure, the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition may further comprise one or more of the following components: one or more functionalized polymers, one or more friction modifiers; one or more antioxidants; one or more pour point depressants; one or more defoamers; one or more viscosity improvers; 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.

[0125] In one advantageous form, the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition further comprises one or more optionally boronated higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersants (Mn of 1600 g / mol or more), one or more optionally boronated lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersants (Mn less than 1600 g / mol), or a combination thereof, and wherein the treat rate of the combination of the higher molecular weight PIBSA-PAM and the lower molecular weight PIBSA-PAM is 1.0 to 6.0 weight %, or 2.0 to 5.0 weight %, or 3.0 to 4.0 weight % of the composition. In another advantageous form, the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition may include a higher molecular weight PIBSA-PAM dispersant, a lower molecular weight PIBSA-PAM dispersant, or a combination thereof, and is contained at a treat rate providing 20 ppm to 700 ppm, or 50 to 600 ppm, or 100 to 500 ppm, or 200 to 400 ppm by weight of boron to the lubricating oil composition.

[0126] In one advantageous form, the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition may further comprise one or more antiwear agents comprising one or more zinc dialkyl dithiophosphates (ZDDPs) providing a treat rate to the composition of less than or equal to 840 ppm, or less than or equal to 800 ppm, or less than or equal to 700 ppm, or less than or equal to 600 ppm by weight of phosphorus.

[0127] In another advantageous form, the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition may further comprise one or more antioxidants selected from one or more phenolic antioxidants, one or more sulfur-based antioxidants, one or more amine antioxidants, or combinations thereof, and wherein the one or more antioxidants constitute 1.0 to 6.0 wt. %, or 1.5 to 5.5 wt. %, or 2.0 to 5.0 wt. %, or 2.5 to 4.5 wt. %, or 3.0 to 4.0 wt. % of the total lubricating oil composition.

[0128] In another advantageous form, the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition may further include one or more friction modifiers selected from dimer dialkyl dithiocarbamate molybdenum (moly dimer), trimer dialkyl dithiocarbamate molybdenum (moly trimer) or a combination thereof providing a treat rate of 12 ppm to 1000 ppm, or 20 ppm to 500 ppm, or 20 ppm to 200 ppm by weight of molybdenum to the composition.

[0129] In yet another advantageous form, the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition is substantially free of molybdenum.

[0130] In another advantageous form, the method of reducing journal bearing wear in an internal combustion engine of the present disclosure, the lubricating oil composition may further optionally comprise 0.2 to 2.0 wt. %, or 0.4 to 1.8 wt. %, or 0.6 to 1.6 wt. %, or 0.8 to 1.4 wt. %, or 1.0 to 1.2 wt. % of the composition of one or more functionalized polymers comprising amide, imide and / or ester functionalized partially or fully saturated C 4-5 A polymer of an olefin having: i) a Mw / Mn of less than 2, or less than 1.8, or less than 1.6, ii) a functionality distribution (Fd) value of 3.5 or less, or 3.2 or less, or 3.0 or less, or 2.5 or less, and iii) an Mn (GPC-PS) 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, Provided that if the polymer prior to functionalization is a copolymer of isoprene and butadiene, the copolymer has an Mn 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). Method for producing lubricating oil composition

[0131] The present disclosure also relates to methods of making lubricating oil compositions, and in particular to a method of making a lubricating oil composition comprising combining or mixing: (i) greater than 50 weight percent 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) an overbased calcium-based detergent having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500 and at a treat rate providing 500 to 1300 weight ppm of calcium to the composition; and (iii) an overbased magnesium-based detergent having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500 and at a treat rate providing 500 to 1300 weight ppm of magnesium to the composition; wherein the total weight of combined calcium and magnesium in the composition is from 1000 ppm to 1800 ppm.

[0132] The lubricating oil composition may have a total sulfated ash less than or equal to 1.0 wt %, a high temperature high shear viscosity (HTHS) at 150° C. measured according to ASTM 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 content less than or equal to 0.080 wt %.

[0133] The method of making a lubricating oil composition of the present disclosure provides a 5% to 60% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 start / stop test method compared to a lubricating oil composition having a HTHS equivalent but not comprising a mixture of overbased calcium-based detergent and overbased magnesium-based detergent in the composition at a combined calcium and magnesium loading of 1000 ppm to 1800 ppm.

[0134] In the method for producing the lubricating oil composition disclosed herein, the lubricating oil composition is particularly suitable as a heavy-duty diesel engine oil, a light-duty diesel engine oil, a hydrogen engine oil, a spark-ignition internal combustion engine oil or a natural gas engine oil. The lubricating oil composition disclosed herein is particularly suitable as an SAE grade selected from 0W-8, 0W-12, 0W-16, 0W-20, 0W-30, 5W-20, 5W-30, 10W-30, 15W-40, 5W-40 and 10W-40. Concentrates

[0135] A concentrate, also referred to as an additive package, adpak or addpack, is a composition having less than 50 mass % (such as less than 40 mass %, such as less than 30 mass %, such as less than 25 mass %, such as less than 20 mass %) of base oil and lubricant composition additives (as described herein), which is typically subsequently further blended with additional base oil to form a lubricant product.

[0136] The present disclosure relates to a concentrate composition comprising or derived from a mixture of: 1 to less than or equal to 50 weight percent of one or more base oils; 2 to 25 weight percent, based on the weight of the concentrate, of an overbased magnesium-based detergent having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500; and 2 to 20 weight percent of an overbased calcium-based detergent having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500.

[0137] The concentrate may be present in the lubricating oil composition of the present disclosure at 0.5 to 35 mass %, such as 5 to 30 mass %, such as 7.5 to 25 mass %, such as 10 to 22.5 mass %, such as 15 to 20 mass %, based on the mass of the lubricating oil composition.

[0138] Optionally, the concentrate may be free of functionalized oil.

[0139] In embodiments, the concentrate composition may optionally be absent of solvents (eg, aliphatic or aromatic solvents) and / or absent of functionalized base oils.

[0140] Optionally, the concentrate may be free of phenolic antioxidants.

[0141] In embodiments, the concentrate may contain less than 75 ppm boron, or less than 60 ppm boron, or from 1 to 70 ppm boron. Alternatively, the concentrate may be free of boron.

[0142] In embodiments, the concentrate may contain less than or equal to 20 (e.g., 15, such as 10, such as 5, such as 3, such as 1) mass % of a functionalized (e.g., aminated) polybutene (e.g., polyisobutylene), such as PIBSA-PAM. In embodiments, the concentrate contains, is substantially free of, or is absent of a functionalized (e.g., aminated) polybutene (e.g., polyisobutylene), such as PIBSA-PAM.

[0143] In embodiments, the concentrate may further comprise one or more of the following components: one or more functionalized polymers, one or more friction modifiers; one or more antioxidants; one or more pour point depressants; one or more defoamers; 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.

[0144] In embodiments, the concentrate may include an acylated polymer, such as polyisobutylene succinic acid, optionally having an Mn of 500 to 50,000 g / mol, such as 600 to 5,000 g / mol, such as 700 to 3000 g / mol. In embodiments, the concentrate may include an acylated polymer, such as polyisobutylene succinic acid, having an Mn of 500 to 1600 g / mol, such as 700 to 1200 g / mol.

[0145] In embodiments, the concentrate may comprise 20 (eg, 15, eg, 10, eg, 5, eg, 3, eg, 1) mass % or less of a block copolymer, such as a block, star, random and / or tapered block copolymer.

[0146] In embodiments, the concentrate may be substantially free of or absent block copolymers, such as block, radial, random and / or tapered block copolymers.

[0147] In embodiments, the concentrate may comprise 20 mass % or less (e.g., 15 mass % or less, such as 10 mass % or less, such as 5 mass % or less, such as 3 mass % or less, such as 1 mass % or less) of a styrenic copolymer, such as a block, star, random and / or tapered styrenic block copolymer.

[0148] In embodiments, the concentrate may be substantially free of or absent styrenic copolymers, such as block, radial, random and / or tapered styrenic block copolymers.

[0149] In embodiments, the concentrate may comprise less than 20 (eg, less than 15, such as 10, such as less than 5, such as less than 3, such as 1) mass % of a functionalized diluent, such as a functionalized oil.

[0150] In embodiments, the concentrate may be substantially free of or absent functionalized diluents, such as functionalized oils.

[0151] In embodiments, the concentrate may contain less than 0.5 (eg, less than 0.4, such as less than 0.3, such as less than 0.2, such as 0.1, substantially absent, 0) weight percent of secondary and tertiary hydrocarbyl amine compounds based on the weight of the concentrate.

[0152] In embodiments, the concentrate may be substantially absent or may be free of secondary and tertiary hydrocarbyl amine compounds.

[0153] In embodiments, the concentrate may have a kinematic viscosity at 100°C of less than 1000 cSt, such as less than 500 cSt, such as less than 200 cSt.

[0154] The present disclosure is also directed to a method of making a concentrate composition comprising combining: 1 to less than or equal to 50 weight percent of one or more base oils; 2 to 25 weight percent, based on the weight of the concentrate, of an overbased magnesium-based detergent having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500; and 2 to 25 weight percent of an overbased calcium-based detergent having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500. Lubricating oil composition components and concentrate components A. Base oil components

[0155] The base oils useful herein (also referred to as "base stocks", "lubricating base stocks" or "oils of lubricating viscosity") may be single oils or blends of oils, and are generally the major liquid component of lubricating compositions (also referred to as lubricants) into which additives and optional additional oils are mixed, for example, to make lubricating compositions, such as finished lubricant compositions, concentrates or other lubricating compositions.

[0156] Base oil can be selected from vegetable oil, animal oil, mineral oil and synthetic lubricating oil and mixture thereof.Its viscosity range is from light fraction mineral oil to heavy lubricating oil, such as those used for gas engine oil, mineral lubricating oil, motor vehicle oil and heavy diesel engine oil.Usually, the kinematic viscosity (" KV100 ") of base oil at 100 ℃ is 1 to 30, such as 2 to 25 cSt, such as 5 to 20 cSt (measured according to ASTM D445-19a), particularly 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.Usually, the high temperature high shear (HTHS) viscosity of base oil at 150 ℃ is 0.5 to 20 cP, such as 1 to 10 cP, such as 2 to 5 cP (measured according to ASTM D4683-20).

[0157] In general, when the lubricating oil base stock is used to make a concentrate it may advantageously be present in a concentrate-forming amount to provide a concentrate containing from 5 to 80 weight percent, from 10 to 70 weight percent or from 5 to 50 weight percent of the active ingredient, based on the weight of the concentrate.

[0158] Common oils that can be used as base oils include animal oils and vegetable oils (e.g., castor oil and lard), liquid petroleum oils, and hydrorefined and / or solvent treated paraffinic, naphthenic, and mixed paraffinic-naphthenic mineral lubricating oils. Oils derived from coal or shale are also available base oils. Base oil stocks can be manufactured using a variety of methods, including but not limited to distillation, solvent refining, hydroprocessing, oligomerization, esterification, and re-refining.

[0159] Synthetic lubricating oils useful as base oils herein include hydrocarbon oils such as homo- and co-olefins, known as polyalphaolefins or PAOs or Group IV base oils [as defined in API EOLCS 1509 (American Petroleum Institute Publication 1509, see Section E.1.3, 19th Edition, January 2021, www.API.org)]. Examples of PAOs useful as base oils include: poly(ethylene), ethylene-propylene copolymers, polybutene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutene, poly(1-hexene), poly(1-octene), poly(1-decene), C8 to C 20 Homopolymers or copolymers of olefins, C8 and / or C 10 and / or C 12 Homopolymer or copolymer of olefins, C8 / C 10 Copolymer, C8 / C 10 / C 12 Copolymer and C 10 / C 12Copolymers, and their derivatives, analogs and homologs.

[0160] In another embodiment, the base oil may comprise a polyalphaolefin, including 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 more; preferably having a viscosity index ("VI") as measured by ASTM D2270 of 100 or more, preferably 110 or more, more preferably 120 or more, more preferably 130 or more, more preferably 140 or more; and / or having a pour point of -5°C or less (as measured by ASTM D97), more preferably -10°C or less, more preferably -20°C or less.

[0161] In another embodiment, the polyalphaolefin oligomers useful in the present disclosure may comprise C 20 To C 1500 Alkanes, preferably C 40 To C 1000 Alkanes, preferably C 50 To C 750 Alkanes, preferably C 50 To C 500 In one embodiment, the PAO oligomer is C5 to C 14 α-olefins, and in another embodiment C6 to C 12 α-olefins, and in another embodiment C8 to C 12 The dimer, trimer, tetramer, pentamer etc. of alpha-olefin. Suitable olefins include 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene and 1-dodecene. In one embodiment, olefin is a combination of 1-octene, 1-decene and 1-dodecene, or can be substantially 1-decene, and PAO is a mixture of its dimer, trimer, tetramer and pentamer (and higher). Available PAO is more particularly described in, for example, U.S. Patent Nos. 5,171,908 and 5,783,531 and Synthetic Lubricants and High-Performance Functional Fluids 1-52 (Leslie R.Rudnick & Ronald L.Shubkin, ed.Marcel Dekker, Inc.1999).

[0162] PAOs useful in the present disclosure typically have a number average molecular weight of 100 to 21,000 g / mol in one embodiment, and 200 to 10,000 g / mol in another embodiment, and 200 to 7,000 g / mol in yet another embodiment, and 200 to 2,000 g / mol in yet another embodiment, and 200 to 500 g / mol in yet another embodiment. TM Hi-Vis, SpectraSyn TM Low-Vis, SpectraSyn TM plus、SpectraSyn TM Elite PAO's (ExxonMobil Chemical Company, Houston Texas) and Durasyn PAO's from Ineos Oligomers USA LLC were purchased.

[0163] Synthetic lubricating oils useful as base oils also include hydrocarbon oils such as homopolymers and copolymers of: alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2-ethylhexyl)benzene); polyphenols (benzenes) (e.g., biphenyl, terphenyl, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides; and their derivatives, analogs and homologs.

[0164] Another class of suitable synthetic lubricating oils that can be used as base oils include 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, alkylmalonic acid, alkenylmalonic acid) reacted with various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, didecyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, and a complex ester formed by reacting 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid.

[0165] Esters useful as synthetic oils herein also include C5 to C 12 Those made from monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.

[0166] Esterex is an ideal ester base oil. TMAvailable from Esters (ExxonMobil Chemical Company, Houston, Texas).

[0167] Silicone-based oils, such as polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxy-silicone oils and silicate oils constitute another class of useful synthetic lubricants for use herein; such oils include tetraethyl silicate, tetraisopropyl silicate, tetrakis-(2-ethylhexyl) silicate, tetrakis-(4-methyl-2-ethylhexyl) silicate, tetrakis-(p-tert-butylphenyl) silicate, hexa-(4-methyl-2-ethylhexyl) disiloxane, poly(methyl)siloxanes and poly(methylphenyl)-siloxanes.

[0168] Other synthetic lubricating oils useful herein include liquid esters of phosphorus-containing acids (eg, tricresyl phosphate, trioctyl phosphate, diethyl decylphosphonate) and polymeric tetrahydrofuran.

[0169] Unrefined oils, refined oils and re-refined oils can be used in lubricating compositions of the present disclosure. Unrefined oils are those obtained directly from natural or synthetic sources without further purification treatment. For example, shale oils obtained directly from retorting operations, petroleum oils obtained directly from distillation, or ester oils obtained directly from esterification processes and used without further treatment are considered to be unrefined oils. Refined oils are similar to unrefined oils, except that they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques are used by those skilled in the art, such as distillation, solvent extraction, acid or base extraction, filtration and percolation. Re-refined oils are oils obtained by processes similar to those used to obtain refined oils, wherein the refining process is applied to refined oils that have previously been put to use. Such re-refined oils are also referred to as regenerated oils or reprocessed oils, and are usually processed in addition to remove waste additives and oil cracking products. Re-refined base oils are preferably substantially free of materials introduced by manufacturing, contamination or previous use.

[0170] Other examples of useful base oils are gas-to-liquid ("GTL") base oils, i.e., oils derived from hydrocarbons made from synthesis gas ("syn gas") containing H2 and CO using a Fischer-Tropsch catalyst. These hydrocarbons generally require further processing before they can be used as base oils. For example, they can be hydroisomerized; hydrocracked and hydroisomerized; dewaxed; or hydroisomerized and dewaxed by methods known in the art. For further 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).

[0171] In particular, oils from renewable sources, ie based in part on carbon and energy captured from the environment, such as biogenic sources, are useful herein.

[0172] Various base oils are generally classified as Class I, Class II, Class III, Class IV, or Class V according to the API EOLCS1509 definition (American Petroleum Institute Publication 1509, see Section E.1.3, 19th Edition, January 2021, www.API.org). In general, Class I base stocks have a viscosity index between about 80 and 120 and contain more than about 0.03% sulfur and / or less than about 90% saturates. Class II base stocks have a viscosity index between about 80 and 120 and contain less than or equal to about 0.03% sulfur and greater than or equal to about 90% saturates. Class III base stocks have a viscosity index greater than about 120 and contain less than or equal to about 0.03% sulfur and greater than about 90% saturates. Class IV base stocks include polyalphaolefins (PAOs). Class V base stocks include base stocks not included in Class I-IV. (Viscosity index is measured by ASTM D 2270, saturates are measured by ASTM D2007, and sulfur is measured by ASTM D5185, D2622, ASTM D4294, ASTM D4927, and ASTM D3120).

[0173] The base oil used in the formulated lubricating composition that can be used in the present disclosure is any one, two, three or more of the various oils described herein. In an ideal embodiment, the base oil used in the formulated lubricating composition that can be used in the present disclosure is described as API Class I (including Class I+), Class II (including Class II+), Class III (including Class III+), Class IV and Class V oils and mixtures thereof, preferably those of API Class II, Class III, Class IV and Class V oils and mixtures thereof. Due to their outstanding volatility, stability, viscosity and cleanliness characteristics, the base oil can be Class III, Class III+, Class IV and Class V base oils. A small amount of Class I base oil stock can be allowed, such as the amount used to dilute additives for incorporation into the formulated lubricating oil product, but is generally kept to a minimum, such as only the amount associated with their use as a diluent / carrier oil for additives used on an "as-received" basis. With respect to Group II oils, it is generally more useful to have Group II base stocks in the higher quality range associated with such oils, ie, Group II oils having a viscosity index of 100 to 120.

[0174] The base oils useful herein may be selected from any synthetic oil, natural oil or re-refined oil (such as those commonly used as crankcase lubricating oils for spark ignition and compression ignition engines). If desired, mixtures of synthetic and / or natural oils and / or re-refined base oils may be used. If desired, multi-modal mixtures (such as bi-modal or tri-modal mixtures) of Group I, II, III, IV and / or V base stocks may be used.

[0175] 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 its equivalent unit, mm2 / s) of from about 2 to about 40 cSt, or from 3 to 30 cSt, or from 4 to 20 cSt, or from 5 to 10 cSt at 100°C, or 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.

[0176] The base oil or base oil blend preferably has a saturates content of at least 65 mass %, more preferably at least 75 mass %, such as at least 85 mass %, such as at least 90 mass % as determined by ASTM D2007.

[0177] Preferably, the base oil or base oil blend has a sulfur content of less than 1 mass %, preferably less than 0.6 mass %, most preferably less than 0.4 mass %, such as less than 0.3 mass % based on the total mass of the lubricating composition as measured by ASTM D5185.

[0178] In an embodiment, the volatility of the base oil or base oil blend as measured by the Noack test (ASTM D5800, Procedure B) is less than, or equal to, 30 mass %, such as less than, or equal to, 25 mass %, such as less than, or equal to, 20 mass %, such as less than, or equal to, 16 mass %, such as less than, or equal to, 12 mass %, such as less than, or equal to, 10 mass %, based on the total mass of the lubricating composition.

[0179] In embodiments, 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, most preferably about 130 to 240, especially about 105 to 140 (as determined by ASTM D2270).

[0180] The base oil can be provided in a major amount, which is combined with one or more additive components as described below in a minor amount to form a lubricant. This preparation can be achieved by adding the additive directly to the oil or by adding the one or more additives in the form of its concentrate to disperse or dissolve the additive. The additive can be added to the oil before, simultaneously or after adding other additives by any method known to those skilled in the art.

[0181] Base oil can be provided with minor amount, and it is combined with one or more additive components as described below of minor amount, to constitute additive concentrate.Can realize this preparation by adding additive directly in oil or by adding described one or more additives with additive dispersion or dissolution in oil in the form of its solution, slurry or suspension.Additive can be added in oil before, simultaneously or afterwards adding other additives by any method well known to those skilled in the art.

[0182] The base oil generally constitutes the major component of the engine oil lubricant composition of the present disclosure and is generally present in an amount of about 50 to about 99 weight percent, preferably about 60 to about 95 weight percent, preferably about 70 to about 95 weight percent, more preferably about 80 to about 95 weight percent, based on the total weight of the composition.

[0183] Typically, the one or more base oils are present in the lubricating composition in an amount of 32 wt % or more, or 55 wt % or more, or 60 wt % or more, or 65 wt % or more, based on the total weight of the lubricating composition. Typically, the one or more base oils are present in the lubricating composition in an amount of 98 wt % or less, more preferably 95 wt % or less, and even more preferably 90 wt % or less. Alternatively, the one or more base oils are present in the lubricating composition in an amount of 1 to 99 mass %, or 50 to 97 mass %, or 60 to 95 mass %, or 70 to 95 mass %, based on the weight of the lubricating composition.

[0184] The above base oils and blends thereof may also be used in making concentrates, and in making lubricants therefrom.

[0185] Concentrates constitute a convenient means of manipulating additives prior to their use and of facilitating their dissolution or dispersion in the lubricant. When preparing a lubricant containing more than one type of additive (sometimes referred to as an "additive component"), each additive may be incorporated separately in the form of a concentrate. However, in many cases it is convenient to provide a so-called additive "package" (also called an "addpack") containing one or more additives / co-additives as described below in a single concentrate.

[0186] Typically, the one or more base oils are present in the concentrate composition in an amount of 50 wt % or less, or 40 wt % or less, or 30 wt % or less, or 20 wt % 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 mass %, or 1 to 40 mass %, or 5 to 40 mass %, or 10 to 30 mass %, or 15 to 25 mass %, based on the weight of the concentrate composition.

[0187] In one form of the lubricating oil composition disclosed herein, the composition may include a Group II base oil, a Group III base oil, a Group IV base oil, or a combination thereof. In another form of the lubricating oil composition disclosed herein, the composition may include a Group II base oil and be substantially free of Group III base oil and Group IV base oil. B. Functionalized polymer components

[0188] The optional functionalized polymer component of the lubricating oil composition and concentrate composition disclosed herein comprises a polymer having an Mn(GPC-PS) 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 prior to functionalization. Alternatively, the functionalized polymer comprises a polymer having an Mn(GPC-PS) 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 prior to functionalization. The polymer before functionalization may have an Mw / Mn of less than 2 (e.g., less than 1.6, such as less than 1.5, such as 1.4 or lower, such as 1 to 1.3, such as 1.0 to 1.25, such as 1.0 to 1.2, such as 1.0 to 1.15, such as 1.0 to 1.1, as determined by GPC-PS). The polymer before functionalization may contain repeating units of one or more olefins having 4 to 5 carbon atoms (preferably conjugated dienes having 4 to 5 carbon atoms). Before functionalization, C 4-5 The polymer is preferably fully or partially saturated (e.g. fully or partially hydrogenated). The functionalized polymer can be obtained by making C 4-5 The functionalized polymer can also be obtained by reacting the acylated polymer with an acylating agent to form an acylated polymer and then reacting the acylated polymer with an amine or an alcohol to form an amide, an imide, an ester, or a combination thereof. 4-5 Polymers (such as commercially available maleated fully or partially hydrogenated C 4-5The polymer) is reacted with an amine to form an amide, an imide or a combination thereof.

[0189] The present disclosure further relates to lubricating oil compositions comprising a functionalized polymer comprising a C 4-5 Saturated (eg hydrogenated) polymers of amides, imides and / or esters of conjugated dienes functionalized by making C 4-5 Obtained by reacting a fully or partially saturated (eg fully or partially hydrogenated) polymer of a conjugated diene with an acylating agent, such as maleic acid or maleic anhydride and thereafter reacting the acylated polymer with an amine (eg polyamine) to form an imide, amide or a combination thereof.

[0190] The present disclosure relates to lubricating oil compositions comprising a functionalized polymer having one or more pendant amine groups and comprising or being a mixture of at least partially (preferably fully) hydrogenated C 4-5 The olefin polymer is reacted with an acylating agent, such as maleic acid or maleic anhydride, and thereafter the acylated polymer is reacted with a polyamine to form an imide, amide, or a combination thereof.

[0191] In embodiments, the functionalized polymer is not prepared in an aromatic solvent such as benzene or toluene, or the aromatic solvent is present at 2 wt % or less (such as 1 wt % or less, such as 0.5 wt % or less) based on the weight of solvent, diluent and polymer.

[0192] In embodiments, the functionalized polymer is not prepared in an alkylated naphthylenic solvent, or the alkylated naphthylenic solvent is present at 5 wt % or less (eg, 3 wt % or less, such as 1 wt % or less), based on the weight of solvent, diluent and polymer.

[0193] The polymers useful herein for preparing the functionalized polymers may be homopolymers of butadiene, isoprene, and the like.

[0194] In embodiments, the polymers useful herein for preparing the functionalized polymers can be homopolymers of isoprene, or copolymers of isoprene and less than 5 mol % (such as less than 3 mol %, such as less than 1 mol %, such as less than 0.1 mol %) of comonomer.

[0195] The polymers useful for preparing the functionalized polymers herein can be copolymers of isoprene and one or more of the following: 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-pent ... 1,3-butadiene, 2-p-tolyl-1,3-butadiene, 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%, such as less than 1 mol%, such as less than 0.1 mol%].

[0196] Typically, the polymerized conjugated diene polymers useful herein for preparing the functionalized polymers include 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). 1 The polymerized conjugated diene polymers useful for preparing the functionalized polymers herein 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 total amount of 2,1 insertions, 1,4 insertions, and 3,4 insertions of isoprene, as measured by H NMR. For purposes of the present 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 and 4,3 insertions.

[0197] Optionally, styrene repeating units may be absent in the polymers useful herein for preparing the functionalized polymers. Optionally, styrene repeating units may be absent in the functionalized hydrogenated / saturated polymers.

[0198] Optionally, butadiene repeating units may be absent in the polymers useful herein for preparing the functionalized polymers. Optionally, butadiene repeating units may be absent in the functionalized hydrogenated / saturated polymers.

[0199] Optionally, the polymer useful herein for preparing the functionalized polymer may not be homopolybutene. Optionally, the functionalized hydrogenated / saturated polymer may not be homopolybutene.

[0200] Optionally, the polymer useful herein for preparing the functionalized polymer may not be homopolyisobutylene. Optionally, the functionalized hydrogenated / saturated polymer may not be homopolyisobutylene.

[0201] Optionally, the polymers useful herein for preparing the functionalized polymers may not be copolymers of isoprene and butadiene. Optionally, the functionalized hydrogenated / saturated polymer may not be copolymers of isoprene and butadiene.

[0202] The polymer and / or functionalized polymer that can be used to prepare functionalized polymers herein can be a homopolymer or a copolymer.The copolymer can be a random copolymer, a tapered block copolymer, a star copolymer or a block copolymer.Block copolymers are formed by a monomer mixture comprising one or more first monomers (such as isobutylene), wherein, for example, the first monomer forms a discrete block of the polymer, which is connected to the second discrete block of the polymer formed by the second monomer (such as butadiene).Although block copolymers have basic discrete blocks formed by monomers, tapered block copolymers can be composed of a relatively pure first monomer at one end and a relatively pure second monomer at the other end.The middle of the tapered block copolymer can be more of a gradient combination of these two monomers.

[0203] Polymers useful herein for preparing functionalized polymers may generally have an Mn(GPC-PS) of 20,000 to 150,000 g / mol, or 20,000 to about 150,000 g / mol, or 30,000 to about 125,000 g / mol, or 35,000 to about 100,000 g / mol, or 40,000 to 80,000 g / mol.

[0204] The polymers that can be used to prepare the functionalized polymers herein may generally have a Mw / Mn (measured by GPC-PS) of 1 to 2, or greater than 1 to less than 2, or 1.1 to 1.8, or 1.2 to 1.5. Alternatively, the polymers that can be used to prepare the functionalized polymers herein may generally have a Mw / Mn of 1 or greater than 1 to less than 2 (such as less than 1.8, such as less than 1.7, such as less than 1.6, such as less than 1.5, such as less than 1.4, such as less than 1.3, such as less than 1.2, such as less than 1.15, such as less than 1.12, such as less than 1.10).

[0205] The polymer used to prepare the functionalized polymer can have an Mz (as determined by GPC-PS) of 20,000 to 150,000 g / mol, or 20,000 to about 150,000 g / mol, or 30,000 to about 125,000 g / mol, or 35,000 to about 100,000 g / mol, or 40,000 to 80,000 g / mol, or 40,000 to 60,000 g / mol (GPC-PS).

[0206] The polymers useful for preparing the functionalized polymers herein may have a glass transition temperature (Tg) of -25°C or lower, such as -40°C or lower, such as -50°C or lower, as measured by differential scanning calorimetry (DSC) using a Perkin Elmer or TA Instrument Thermal Analysis System (the sample is heated from ambient temperature to 210°C at 10°C / min and held at 210°C for 5 minutes, then cooled to -40°C at 10°C / min and held for 5 minutes).

[0207] The polymers useful herein for preparing the functionalized polymers typically have less than 3%, such as less than 2%, such as less than 1%, such as less than 0.5%, such as less than 0.25% residual unsaturation based on the number of double bonds in the non-hydrogenated polymer.

[0208] The polymers useful herein for preparing the functionalized polymers typically have a residual metal (eg, 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. hydrogenation

[0209] This paper can be used to prepare functionalized polymers 4-5 The polymer may be partially or fully hydrogenated by any hydrogenating agent known to those skilled in the art. For example, a saturated or partially saturated polymer may be prepared by: (a) providing a C 4-5Polymer; and (b) hydrogenating at least a portion or all of the unsaturation (such as double bonds or triple bonds) in the polymer in the presence of a hydrogenating agent. In some embodiments, the polymer is completely hydrogenated. In some embodiments, the polymer is partially hydrogenated. In some embodiments, the polymer is 50% or more, such as 60% or more, such as 70% or more, such as 80% or more, such as 90% or more, such as 95% or more, such as 98% or more, such as 99% or more saturated (hydrogenated), such as 50 to 100% saturated (hydrogenated), by Martino N. Smits and Dirkman Hoefman, Quantative Determination of Olefinic Unsaturation by Measurement of Ozone Absorption Analytical Chemistry Vol 44, No. 9, page 1688, 1972, Martino N. Smits described in ozone adsorption determination.

[0210] In embodiments, the hydrogenation agent can be hydrogen in the presence of a hydrogenation catalyst. In some embodiments, the hydrogenation catalyst is Pd, Pd / C, Pt, PtO2, Ru(PPh3)2Cl2, Raney nickel or a combination thereof. In embodiments, the catalyst is a Pd catalyst. In another embodiment, the catalyst is 5% Pd / C. In further embodiments, the catalyst may comprise or be 10% Pd / C in a high pressure reaction vessel, and the hydrogenation reaction is allowed to proceed until completion. Typically, after completion, the reaction mixture can be washed, concentrated and dried to obtain the corresponding hydrogenated product. Alternatively, any reducing agent that can reduce the C=C bond to a C-C bond can also be used. For example, an olefin polymer can be hydrogenated by treating with hydrazine in the presence of a catalyst such as 5-ethyl-3-methyllumiflavinium perchlorate under an oxygen atmosphere to obtain the corresponding hydrogenated product. Reduction reactions with hydrazine are disclosed in Imada et al., JAm. Chem. Soc., 127, pp. 14544-14545, (2005), which is incorporated herein by reference. Acylation

[0211] The 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 halogen, epoxy, hydroxyl, amino, nitrilo, sulfhydryl, imido, carboxyl and sulfonic acid groups or a combination thereof. The functionalized polymer can be further modified to provide a more desired functional type. In a preferred case, the fully or partially hydrogenated polymer is functionalized by a method comprising 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).

[0212] In some embodiments, the carboxylic acid function or its reactive equivalent is grafted onto the polymer to form an acylated polymer. Typically, an olefinically unsaturated carboxylic acid material is grafted onto the polymer backbone. These materials attached to the polymer typically contain at least one olefinic bond (before the reaction) and at least one, such as two carboxylic acid (or its anhydride) groups or polar groups that can be converted into the carboxyl group by oxidation or hydrolysis. Maleic anhydride or its derivatives are suitable. It is grafted onto the polymer to provide two carboxylic acid functions. Examples of other unsaturated carboxylic acid materials include itaconic anhydride or corresponding dicarboxylic acids, such as maleic acid, fumaric acid and esters thereof, and cinnamic acid and esters thereof.

[0213] The ethylenically unsaturated carboxylic acid material can be grafted onto the polymer in a variety of ways. It can be grafted onto the polymer in solution or in substantially pure (molten) form, with or without the use of a free radical initiator. The free radical initiated grafting of the ethylenically unsaturated carboxylic acid material can also be carried out in a solvent, such as hexane or mineral oil. It can be carried out at an elevated temperature of 100°C to 250°C, such as 120°C to 190°C, or 150°C to 180°C, such as above 160°C.

[0214] Free radical initiators that can be used include peroxides, hydroperoxides, and azo compounds, typically those that have a boiling point greater than about 100°C and thermally decompose within the grafting temperature range to provide free radicals. Representatives of these free radical initiators include azobisisobutyronitrile and 2,5-dimethyl-hex-3-yn-2,5-di-tert-butyl peroxide. The initiator can be used in an amount of 0.005 wt % to 1 wt % based on the weight of the reaction mixture solution. The grafting can be carried out in an inert atmosphere, such as under a nitrogen blanket. The resulting acylated polymer intermediate is characterized in having a carboxylic acid acylation function as part of its structure.

[0215] In embodiments, the acylated polymer may have 2 or more anhydride groups per polymer molecule and may exhibit less than 10% gel. Alternatively, the acylated polymer may have less than 2 anhydride groups per polymer molecule and may exhibit less than 10% gel. (See also U.S. Pat. No. 5,429,758, col. 17, line 14 - col. 18, line 11).

[0216] Alternatively, in some embodiments, the acylated polymer may have a gel content of less than about 5 wt%, less than 3 wt%, less than 2 wt%, less than 1 wt%, less than 0.5 wt%, less than 0.1 wt%, or 0 wt%, wherein the gel content is measured by determining the amount of material extractable from the polymer using boiling xylene (or cyclohexane) as an extractant. The percentage of soluble and insoluble (gel) material in a polymer composition is determined by soaking a nominal 0.5 mm thick polymer film specimen in cyclohexane for 48 hours at 23°C or refluxing the film specimen in boiling xylene for half an hour, 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 the present disclosure, gel content is measured using boiling xylene unless the sample is insoluble in xylene, in which case the cyclohexane method is used.

[0217] In an embodiment, the acylated polymer may have a saponification value (SAP) of 5 g / KOH or more, such as 10 g / KOH or more, such as 20 g / KOH or more, such as 30 g / KOH or more, such as 50 g / KOH or more, such as from 10 to 60 g / KOH, such as from 20 to 40 g / KOH as determined by ASTM D94.

[0218] In an embodiment, the acylated polymer composition may have less than 5 wt % unreacted acylating agent (e.g., maleic anhydride), such as less than 4 wt %, such as less than 3 wt %, such as less than 1 wt %, such as less than 0.5 wt %, such as less than 0.25 wt %, such as less than 0.1 wt %, based on the weight of the acylated polymer composition (i.e., polymer, acylating agent, and diluent).

[0219] In embodiments, the acylation reaction described herein can be carried out in a base oil diluent. As a byproduct, a functionalized base oil can be produced. The oil itself may be acylated. For example, a maleated base oil may be present after the acylation reaction described herein.

[0220] It is contemplated that the functionalized base oil may comprise an acylated oil and / or the reaction product of an acylated oil with an amine to form an amide, an imide, or a combination thereof.

[0221] Preferably, the acylated oil and / or the reaction product of the acylated oil with an amine or alcohol (to form an amide, imide, ester or a combination thereof) may be present in the concentrate in an amount of 40% by weight or less, or 20% by weight or less, or 10% by weight or less, or 5% by weight or less, or 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., from 0 to 40% by weight, or from 0.01 to 40% by weight, or from 0.1 to 20% by weight, or from 1 to 10% by weight, or from 1.5 to 5% by weight), based on the weight of the concentrate composition.

[0222] Preferably, one or more functionalized base oils, such as acylated oils and / or reaction products of acylated oils with amines or alcohols (to form amides, imides, esters or combinations thereof) may be present in the lubricating oil composition in an amount of from 0.01 to 40 mass %, or from 0.1 to 20 mass %, or from 1 to 10 mass %, or 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.

[0223] In an embodiment, the acylation reaction described herein is carried out in a solvent-containing medium. As a by-product, an acylation / functionalized solvent may be produced. In an embodiment, the acylation and / or functionalized solvent may be present in the concentrate composition at 3% by mass or less, preferably 2% by mass or less, preferably 1% by mass or less, preferably 0.1% by mass or less, preferably 0% by mass, based on the weight of the concentrate composition. In an embodiment, the functionalized solvent may be present in the lubricating oil composition at 3% by mass or less, preferably 2% by mass or less, preferably 1% by mass or less, preferably 0.1% by mass or less, preferably 0% by mass, based on the weight of the lubricating oil composition.

[0224] In embodiments, the acylating agent may be added in a manner that minimizes side reactions, such as reactions with the base oil or other diluents present in the reaction vessel.

[0225] In embodiments, the acylation reaction may occur wherein the acylating agent (e.g., maleic acid or maleic anhydride) is added in a continuous or semi-continuous (e.g., intermittent) stream (e.g., in controlled, relatively equal portions over the reaction time, or in larger and / or smaller portions at different points in the reaction) to minimize functionalized base oil and other side reactions. As an example, the acylating agent may be added in a continuous manner wherein the amounts of polymer and acylating agent are added in controlled stoichiometric amounts. As another example, the polymer may be added to the reaction vessel in batches while the acylating agent is added slowly or in a semi-continuous manner (e.g., the acylating agent is added in discrete amounts or portions of 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). Alternatively, the polymer may be added to the reaction vessel in X portions, while the acylating agent is added in 1.5X or more (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) portions. This same effect may also be achieved by diluting or concentrating the polymer solution and / or the acylating agent solution to the same or different extents.

[0226] Preferably, the acylating agent may be added in a manner that minimizes side reactions, such as in a continuous or semi-continuous manner.

[0227] Side reactions can also be minimized by running the reaction in a batch, semi-continuous or continuous reactor operation using a high concentration of polymer (such as 45 wt % or more, or 50 wt % or more, or 55 wt % or more, or 60 wt % or more) in the diluent. For example, the polymer (such as a hydrogenated isoprene polymer such as hydrogenated homopolyisoprene) can be introduced into a batch, semi-continuous or continuous reactor operation as a solution or suspension (such as a slurry) in a diluent such as an oil (e.g., a base oil such as a Group I, II, III, IV, and / or V base oil such as a Group II and / or Group III base oil) or an alkane solvent or diluent or a combination thereof, wherein the polymer can be present in the solution or suspension at 45 wt % or more (such as 50 wt % or more, or 55 wt % or more, or 60 wt % or more) based on the weight of the polymer and the diluent.

[0228] In embodiments, side reactions may be minimized by 1) adding the acylating agent in a continuous or semi-continuous manner, and / or 2) introducing the polymer as a solution or suspension in a diluent into a batch, semi-continuous or continuous reactor operation, wherein the polymer is present at 45 wt % or more based on the weight of the polymer and the diluent.

[0229] In embodiments, side reactions are minimized, optionally by adding the acylating agent in a continuous or semi-continuous manner, and / or by introducing the fully or partially hydrogenated polymer (such as an isoprene polymer) into a batch, semi-continuous, or continuous reactor operation as a solution or suspension in a diluent comprising 45 wt % or more (such as 50 wt % or more, or 55 wt % or more, or 60 wt % or more) of the fully or partially hydrogenated polymer based on the weight of the fully or partially hydrogenated polymer and the diluent.

[0230] In embodiments, side reactions are minimized, optionally by adding the acylating agent in a continuous or semi-continuous manner, and by introducing the fully or partially hydrogenated polymer (such as an isoprene polymer) into a batch, semi-continuous or continuous reactor operation as a solution or suspension in a diluent comprising 45 wt % or more (such as 50 wt % or more, or 55 wt % or more, or 60 wt % or more) of the fully or partially hydrogenated polymer based on the weight of the fully or partially hydrogenated polymer and the diluent. Functionalization

[0231] In embodiments, the acylated polymer may react with an alcohol or an amine to form an amide, an imide, an ester, or a combination thereof. The reaction may consist of a condensation to form an imide, an amide, a half-amide, an amide-ester, a diester, or an amine salt. The primary amino groups will typically condense to form an amide, or in the case of maleic anhydride to form an imide. It is noted that the amine may have a single primary amino group or multiple primary amino groups.

[0232] Suitable amines may include one or more aromatic amines, such as amines in which the carbon atoms of the aromatic ring structure are directly attached to the amino nitrogen. The amines may also be aliphatic. In embodiments, aliphatic amines may be used alone, or in combination with each other or in combination with aromatic amines. In some embodiments, the amount of aromatic amines may be a major or minor amount compared to the amount of non-aromatic amines, or in some cases, the composition may be substantially free of aromatic amines. Alternatively, the composition may be substantially free of aliphatic amines.

[0233] Examples of aromatic amines useful herein include one or more N-arylphenylenediamines represented by the following formula: wherein R7 is H, —NHaryl, —NHalkaryl, or a branched or straight chain hydrocarbon group having from about 4 to about 24 carbon atoms selected from alkyl, alkenyl, alkoxy, aralkyl, or alkaryl; and R9 is —NH2, —(NH(CH2) n ) mNH2, -NHalkyl, -NHaralkyl, -CH2-aryl-NH2, wherein n and m each have a value of about 1 to about 10; and R8 is hydrogen, or an alkyl, alkenyl, alkoxy, aralkyl or alkaryl group having about 4 to about 24 carbon atoms.

[0234] Suitable N-arylphenylenediamines include N-phenylphenylenediamine (NPPDA), such as N-phenyl-4,4-phenylenediamine, N-phenyl-1,3-phenylenediamine, 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.

[0235] In embodiments, the amine that reacts with the acylated polymer is an amine having at least 3 or 4 aromatic groups and can be represented by the formula: Independent of each variable, R 1 Can be hydrogen or C l to C5 alkyl (usually hydrogen); R 2 Can be hydrogen or C l to C5 alkyl (usually hydrogen); U can be an aliphatic, alicyclic or aromatic group, provided that when U is aliphatic, the aliphatic group can be a straight chain or branched alkylene group containing 1 to 5, or 1 to 2 carbon atoms; and w can be 1 to 10, or 1 to 4, or 1 to 2 (usually 1).

[0236] Other examples of aromatic amines include aniline, N-alkylanilines such as N-methylaniline and N-butylaniline, di-(p-methylphenyl)amine, naphthylamine, 4-aminodiphenylamine, N,N-dimethylphenylenediamine, 4-(4-nitro-phenylazo)aniline (Disperse Orange 3), sulfadimethazine, 4-phenoxyaniline, 3-nitroaniline, 4-aminoacetanilide, 4-amino-2-hydroxy-benzoic acid phenyl ester (phenylamino salicylate), N-(4-amino-5-methoxy-2-methyl-phenyl)-benzamide (Fast Violet B), N-(4-amino-2,5-dimethoxy-phenyl)-benzamide (Fast Blue RR), N-(4-amino-2,5-diethoxy-phenyl)-benzamide (Fast Blue BB), N-(4-amino-phenyl)-benzamide and 4-phenylazoaniline. Suitable amines are mentioned in US Pat. No. 7,790,661 and are incorporated herein by reference.

[0237] In embodiments, the compound that is condensed with the acylated polymer may be represented by the formula: wherein X is an alkylene group containing from about 1 to about 4 carbon atoms; R 2 , R 3 and R 4 It is a hydrocarbon group. wherein X is an alkylene group containing from about 1 to about 4 carbon atoms; R 3 and R 4 It is a hydrocarbon group.

[0238] Alternatively, the amine can be an amine having at least 4 aromatic groups and an aldehyde (such as formaldehyde). The aromatic amine can be represented by the following formula: Among them, R 1 is hydrogen or C 1-5 Alkyl (usually hydrogen); R 2 is hydrogen or C 1-5 alkyl (usually hydrogen); U is an aliphatic, alicyclic or aromatic group, optionally with the proviso that when U is aliphatic, the aliphatic group may be a straight chain 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, such as 0, 1, 2 or 3, or 0 or 1 (usually 0). For further information on such amines, see, for example, US2017 / 0073606, page 5, paragraphs

[0064] -

[0070] and European Patent No. 2401 348.

[0239] Examples of the compound capable of condensing with the acylating agent and further having a tertiary amino group may 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, isomeric butanediamines, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenetetramine and bis(hexamethylene)triamine, diaminobenzene, diaminopyridine or a mixture thereof. The compound capable of condensing with the acylating agent and further having a tertiary amino group may further include aminoalkyl-substituted heterocyclic compounds, such as 1-(3-aminopropyl)imidazole and 4-(3-aminopropyl)morpholine, 1-(2-aminoethyl)piperidine, 3,3-diamino-N-methyldipropylamine, 3',3-aminobis(N,N-dimethylpropylamine). Another example of the compound capable of condensing with the acylating agent and having a tertiary amino group includes alkanolamines, including but not limited to triethanolamine, trimethanolamine, N,N-dimethylaminopropanol, N,N-diethylaminopropanol, N,N-diethylaminobutanol, N,N,N-tris(hydroxyethyl)amine, N,N,N-tris(hydroxymethyl)amine.

[0240] In embodiments, the polymer may be reacted with a polyether aromatic compound. Typically, the polyether aromatic compound has at least two functional groups, each capable of reacting with a monocarboxylic acid or ester thereof, or a dicarboxylic acid, anhydride or ester thereof, or a mixture thereof. In embodiments, the polyether aromatic compound is derived from an aromatic compound containing at least one amine group, and wherein the polyether is capable of reacting with a monocarboxylic acid or ester thereof, or a dicarboxylic acid, anhydride or ester thereof.

[0241] Examples of suitable polyether arylamines include compounds having the following structure: wherein A represents an aromatic amine moiety wherein the ether group is attached 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 an alkyl group containing from about 1 to about 6 carbon atoms, or mixtures thereof; a and x are independently integers from about 1 to about 50.

[0242] The acylated polymer may be reacted with a polyetheramine or polyetherpolyamine. Typical polyetheramine compounds contain at least one ether unit and are 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 Jeffamine TM The brand is sold and available from Hunstman Corporation.

[0243] Amines that can be used in combination with the acylated polymer herein include one or more of the following: N-phenyldiamine (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), nitroaniline (e.g., 3-nitroaniline), N-phenylethylenediamine (e.g., N1-phenylethylene-1,2-diamine), N-aminophenylacetamide (e.g., N-(4-aminophenyl)acetamide), morpholinopropylamine (e.g., 3-morpholinopropan-1-amine), and aminoethylpiperazine (e.g., 1-(2-aminoethyl)piperazine).

[0244] In embodiments, the functionalization (e.g., amination) reaction described herein may be carried out in a diluent (e.g., a base oil or an alkane solvent). As a byproduct, 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) and an amine to form an amide, an imide, or a combination thereof.

[0245] Preferably, the reaction product of the acylated diluent (such as an acylated oil) and an amine or alcohol (to form an amide, imide, ester or a combination thereof) may be present in the concentrate in an amount of 40% by weight or less, or 20% by weight or less, or 10% by weight or less, or 5% by weight or less, or 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 (such as 0 to 40% by weight, or 0.01 to 40% by weight, or 0.1 to 20% by weight, or 1 to 10% by weight, or 1.5 to 5% by weight), based on the weight of the concentrate composition.

[0246] Preferably, one or more functionalized base oils, such as the reaction product of an acylated diluent (e.g., an acylated base oil) and an amine or alcohol (to form an amide, an imide, an ester or a combination thereof) may be present in the lubricating oil composition in an amount of from 0.01 to 40 mass %, or from 0.1 to 20 mass %, or from 1 to 10 mass %, or 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.

[0247] In an embodiment, the functionalization (e.g., amination) reaction described herein may be carried out in a solvent-containing medium. As a byproduct, a functionalized solvent may be produced. In an embodiment, the functionalized solvent may be present in the concentrate composition at 3% by mass or less, preferably 2% by mass or less, preferably 1% by mass or less, preferably 0.1% by mass or less, preferably 0% by mass, based on the weight of the concentrate composition. In an embodiment, the functionalized solvent may be present in the lubricating oil composition at 3% by mass or less, preferably 2% by mass or less, preferably 1% by mass or less, preferably 0.1% by mass or less, preferably 0% by mass, based on the weight of the lubricating oil composition.

[0248] In embodiments, the acylated base oil / solvent may be removed prior to functionalization.

[0249] The functionalized polymer may be a homopolymer of a C4 or C5 olefin, such as butadiene and isoprene.

[0250] In embodiments, the functionalized polymer can be a homopolymer of isoprene, or a copolymer of isoprene and less than 5 mole percent (such as less than 3 mole percent, such as less than 1 mole percent, such as less than 0.1 mole percent) of a comonomer.

[0251] The functionalized polymer may comprise or be a copolymer of isoprene and one or more of styrene, methyl-styrene, 2,3-dimethyl-butadiene, 2-methyl-1,3-pentadiene, myrcene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, 2-phenyl-1,3-pentadiene, 3-phenyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2-hexyl-1,3-butadiene, 3-methyl-1,3-hexadiene, 2-benzyl-1,3- butadiene, 2-p-tolyl-1,3-butadiene, 1,3-butadiene, 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%, such as less than 1 mol%, such as less than 0.1 mol%).

[0252] In embodiments, the functionalized polymer comprises 10 (eg, 9, eg, 8, eg, 7, eg, 6, eg, 5, eg, 4, eg, 3, eg, 2, eg, 1) wt % or less styrene monomer based on the weight of the functionalized polymer.

[0253] In embodiments, styrene repeating units may be absent in the functionalized polymer.

[0254] In embodiments, the functionalized polymer may be a block copolymer or a tapered block copolymer that does not include styrene blocks.

[0255] In embodiments, the functionalized polymer may be a block copolymer comprising, consisting of, or consisting essentially of isoprene or a tapered block copolymer.

[0256] In embodiments, the functionalized polymer may be a block copolymer or a tapered block copolymer comprising 50 weight percent or more isoprene based on the weight of the copolymer.

[0257] In an embodiment, the functionalized polymer may be a 4-5 Conjugated diene (or C 4-5 The conjugated diene consists essentially of C 4-5 The conjugated diene composition preferably contains 50 (such as 60, such as 70, such as 80, such as 90, such as 95, such as 98) weight % or more of C 4-5 Block copolymers or tapered block copolymers of conjugated dienes.

[0258] In embodiments, the functionalized polymer can be a copolymer comprising 50 (such as 60, such as 70, such as 80, such as 90, such as 95, such as 98) weight percent or more isoprene based on the weight of the copolymer.

[0259] In embodiments, 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 butadiene based on the weight of the copolymer.

[0260] In embodiments, the functionalized polymer may be a copolymer comprising 50 (such as 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.

[0261] In embodiments, the functionalized polymer may be a diblock copolymer comprising at least one isoprene homopolymer or copolymer block.

[0262] Optionally, butadiene repeating units may be absent in the functionalized polymer.

[0263] Optionally, the functionalized polymer may not be homopolyisobutylene.

[0264] Optionally, the functionalized polymer may not be a copolymer of isoprene and butadiene.

[0265] Typically, the polymerized conjugated diene in the functionalized polymer includes monomer units that have been inserted into the growing polymer chain by conjugated and non-conjugated additions. 13 The functionalized polymer contains at least about 50% insertions by conjugated addition, such as at least about 75% insertions by conjugated addition, such as about 80% insertions by conjugated addition, such as from about 85% to about 100% insertions by conjugated addition, based on the total number of conjugated addition and non-conjugated insertions as measured by C NMR.

[0266] Insertion of isoprene most commonly occurs via 2,1 insertion, 1,4 insertion (trans and cis), and 3,4 insertion of isoprene. 1 H NMR determination of the insertion geometry). 1The functionalized isoprene polymer contains 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 total amount of 2,1 insertions, 1,4 insertions, and 3,4 insertions of isoprene as measured by H NMR. For purposes of this disclosure: 1) the phrase "1,4 insertion" includes both 1,4 and 4,1 insertions, 2) the phrase "2,1 insertion" includes both 2,1 and 1,2 insertions, and 3) the phrase "3,4 insertion" includes both 3,4 and 4,3 insertions.

[0267] 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.

[0268] The functionalized polymer may typically have an Mn(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.

[0269] 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 proceeds, Mw / Mn broadening may occur.

[0270] The functionalized polymer may typically have an Mw / Mn (GPC-PS) of 1 to 3, or 1 to 2, or greater than 1 to less than 2, or 1.05 to 1.9, or 1.10 to 1.8, or 1.10 to 1.7, or 1.12 to 1.6, or 1.13 to 1.5, or 1.15 to 1.4, or 1.15 to 1.3. Alternatively, the functionalized polymer may typically have an Mw / Mn of 1 or greater than 1 to less than 2 (such as less than 1.8, such as less than 1.7, such as less than 1.6, such as less than 1.4, such as less than 1.2, such as less than 1.15, such as less than 1.12, such as less than 1.10).

[0271] In embodiments, the functionalized polymer may have a saponification value (SAP) of 25 (eg, 28, such as 30, such as 32, such as 34) mgKOH / g or more as determined by ASTM D94.

[0272] In embodiments, the functionalized polymer may contribute 17% or more (eg, 20% or more, such as from 17 to 40%, such as from 20 to 30%) to the saponification value of the lubricating oil composition.

[0273] In embodiments, the functionalized polymer may have an average functionality 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 as determined by GPC-PS.

[0274] The functionalized polymer may have an average functionality of 15 (eg, 14, 13, 12, 11, 10, 9, 8, 7, or 6) or fewer FG grafts per polymer chain as determined by GPC-PS.

[0275] 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) or more FG grafts per polymer chain as determined by GPC-PS.

[0276] 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 (e.g., 14, 13, 12, 11, 10, 9, 8, 7, or 6) FG grafts per polymer chain as determined by GPC-PS.

[0277] In embodiments, 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.

[0278] In embodiments, the functionalized polymer may include a branched C polymer having a Mn of 20,000 to 500,000 g / mol having a Mw / Mn of 2 or less, such as 1 to 2.0, as determined by GPC-PS. 4-5 Acylated polymers of monomers.

[0279] In embodiments, the functionalized polymer may have a number average molecular weight (Mn) of 20,000 (eg, 25,000, such as 30,000, such as 35,000, such as 40,000) g / mol or more as determined by GPC-PS.

[0280] In an embodiment, the functionalized polymer may have a weight average molecular weight (Mw) of 50,000 (e.g., 40,000, e.g., 35,000) g / mol or less as measured by GPC-PS. In an embodiment, the functionalized polymer may have a weight average molecular weight (Mw) of 1000 to 50,000 g / mol, e.g., 5000 to 40,000 g / mol as measured by GPC-PS.

[0281] In embodiments, the functionalized polymer may have a z-average molecular weight (Mz) (GPC-PS) of 5000 to 150,000 g / mol, such as 10,000 to 150,000 g / mol, such as 15,000 to 70,000 g / mol, such as 20,000 to 150,000 g / mol, or 20,000 to about 150,000 g / mol, or 30,000 to about 125,000 g / mol, or 35,000 to about 100,000 g / mol, or 40,000 to 80,000 g / mol, or 40,000 to 60,000 g / mol.

[0282] In embodiments, the functionalized polymer may have a gel content of less than about 5 wt%, less than 3 wt%, less than 2 wt%, less than 1 wt%, less than 0.5 wt%, less than 0.1 wt%, or 0 wt%, wherein the gel content is measured by determining the amount of material extractable from the polymer using boiling xylene (or cyclohexane) as an extractant. The percentage of soluble and insoluble (gel) material in a polymer composition is determined as described herein.

[0283] In an embodiment, the functionalized polymer may have a functionality distribution (Fd) value of 3.5 or less (e.g., 3.4 or less, such as 1 to 3.3, such as 1.1 to 3.2, such as 1.2 to 3.0, such as 1.4 to 2.9, as determined by GPC-PS). The functionality distribution (Fd) value is determined as described in the Examples section below, and is an average functionality 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 as determined by GPC-PS.

[0284] The present disclosure relates to amide, imide and / or ester functionalized C 4-5 Olefins (basically composed of C 4-5 Olefins are composed of or consist of C 4-5The invention relates to a hydrogenated / saturated polymer having an olefin composition (e.g., a C4 olefin composition) having an 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 to 3.3, such as 1.1 to 3.2, such as 1.2 to 3.0, such as 1.4 to 2.9, as determined by GPC-PS), and wherein if the polymer before functionalization is a C4 olefin polymer, such as polyisobutylene, polybutadiene or a copolymer thereof (preferably polyisobutylene or a copolymer of isobutylene and butadiene), the C4 olefin polymer has an Mn (GPC-PS) of 10,000 g / mol or more, and if the polymer before functionalization is a copolymer of C4 / C5 isoprene and butadiene, the Mn of the copolymer is greater than 25,000 Mn (GPC-PS).

[0285] The present disclosure is also directed to amide, imide and / or ester functionalized hydrogenated / saturated polymers comprising 90 mol% or more of isoprene repeating units having a Mw / Mn of less than 2, a functionality distribution (Fd) value of 3.5 or less (such as 3.4 or less, such as from 1 to 3.3, such as from 1.1 to 3.2, such as from 1.2 to 3.0, such as from 1.4 to 2.9 as determined by GPC-PS), and wherein the polymer prior to functionalization has a Mn (GPC-PS) of 30,000 g / mol or more.

[0286] The present disclosure is also directed to amide, imide and / or ester functionalized hydrogenated / saturated isoprene homopolymers having a Mw / Mn of less than 2, a functionality distribution (Fd) value of 3.5 or less (such as 3.4 or less, such as from 1 to 3.3, such as from 1.1 to 3.2, such as from 1.2 to 3.0, such as from 1.4 to 2.9, as determined by GPC-PS), and wherein the polymer prior to functionalization has a Mn of 30,000 g / mol or more (as determined by GPC-PS).

[0287] The lubricating compositions according to the present disclosure may further comprise one or more additives, such as detergents, friction modifiers, antioxidants, pour point depressants, defoamers, viscosity modifiers, dispersants, corrosion inhibitors, antiwear agents, extreme pressure additives, demulsifiers, seal compatibilizers, seal swell agents, additive diluent base oils, etc. Specific examples of such additives are described, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, 3rd Edition, Vol. 14, pp. 477-526, several of which are discussed in more detail below. C. Detergent

[0288] The lubricating oil composition and the concentrate composition may contain one or more additional metal detergents (such as a blend of metal detergents), also referred to as "detergent additives", in addition to the combination or mixture of the overbased calcium-based detergents and the overbased magnesium-based detergents described above. Metal detergents generally act both as detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life. Detergents generally comprise a polar head and a long hydrophobic tail, the polar head comprising a metal salt of an acidic organic compound. The salts may contain substantially stoichiometric amounts of metal, in which case they are generally described as normal or neutral salts, and generally have a total base number ("TBN", measured by ASTM D2896) of up to 150 mg KOH / g, such as 0 to 80 (or 5-30) mg KOH / g. Large amounts of metal bases may be introduced by reacting an excess of a metal compound (e.g., an oxide or hydroxide) with an acidic gas (e.g., carbon dioxide). Such detergents, sometimes referred to as overbased, may have a TBN of 100 mg KOH / g or more, such as 200 mg KOH / g or more, and typically have a TBN of 250 mg KOH / g or more, such as 300 mg KOH / g or more, such as 200 to 800 mg KOH / g, 225 to 700 mg KOH / g, 250 to 650 mg KOH / g, or 300 to 600 mg KOH / g, such as 150 to 650 mg KOH / g.

[0289] Suitable detergents include metals, particularly alkali metals (Group 1 metals, such as Li, Na, K, Rb) or alkaline earth metals (Group 2 metals, such as Be, Mg, Ca, Sr, Ba), particularly sodium, potassium, lithium, calcium and magnesium, such as oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, naphthenates and other oil-soluble carboxylates of Ca and / or Mg. In addition, the detergent may include hybrid detergents containing any combination of sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates and naphthenates or other oil-soluble carboxylates of Group 1 and / or 2 metals of sodium, potassium, lithium, calcium or magnesium.

[0290] 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), sulfonate, or phenate detergent. More preferably, the detergent additive is selected from magnesium salicylate, calcium salicylate, magnesium sulfonate, calcium sulfonate, magnesium phenate, calcium phenate, and hybrid detergents comprising two, three, four, or more of these detergents and / or combinations thereof.

[0291] 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. Pat. Nos. 6,429,178; 6,429,179; 6,153,565; and 6,281,179. When, for example, a hybrid sulfonate / phenate detergent is used, the hybrid detergent is considered equivalent to the amounts of separate phenate and sulfonate detergents incorporating similar amounts of phenate and sulfonate soaps, respectively.

[0292] Overbased metal-containing detergents can be sodium salts, calcium salts, magnesium salts or mixtures thereof of phenates, sulfur-containing phenates, sulfonates, salixarates and salicylates. Overbased phenates and salicylates typically have a total base number of 180 to 650 mg KOH / g, such as 200 to 450 TBN mg KOH / g. 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 can be primarily a linear alkylbenzene sulfonate detergent having a metal ratio of at least 8 as described in paragraphs

[0026] to

[0037] of U.S. Patent Application Publication No. 2005 / 065045 (granted as U.S. Patent No. 7,407,919). The overbased detergent may be present at 0 to 15 wt %, or 0.1 to 10 wt %, or 0.2 to 8 wt %, or 0.2 to 3 wt % based on the lubricating composition. For example, in a heavy-duty diesel engine, the detergent may be present at 2 to 3 wt % of the lubricating composition. For a passenger car engine, the detergent may be present at 0.2 to 1 wt % of the lubricating composition.

[0293] The detergent additive may comprise one or more magnesium sulfonate detergents. The magnesium detergent may be a neutral salt or an overbased salt. Suitably, the magnesium detergent is an overbased magnesium sulfonate having a TBN of 5 to 700 mgKOH / g (ASTM D2896), or 7 to 600 mgKOH / g, or 9 to 500 mgKOH / g, or 80 to 650 mgKOH / g, such as 200 to 500 mgKOH / g, such as 240 to 450 mgKOH / g.

[0294] Alternatively, the detergent additive is magnesium salicylate. Suitably, the magnesium detergent is magnesium salicylate having a TBN of 5 to 700 mgKOH / g (ASTM D2896), or 7 to 600 mgKOH / g, or 9 to 500 mgKOH / g, 30 to 650 mgKOH / g, such as 50 to 500 mgKOH / g, such as 200 to 500 mgKOH / g, such as 240 to 450 mgKOH / g, or 150 mg KOH / g or less, such as 100 mg KOH / g or less.

[0295] Alternatively, the detergent additive is a combination of magnesium salicylate and magnesium sulfonate.

[0296] The magnesium detergent provides 200-4000 ppm of magnesium atoms, suitably 200-2000 ppm, 300 to 1500 ppm or 450-1200 ppm of magnesium atoms to the lubricating composition thereof (ASTM D5185).

[0297] The detergent composition may comprise (or consist of) a combination of one or more magnesium sulfonate detergents and one or more calcium salicylate detergents.

[0298] The combination of one or more magnesium sulfonate detergents and one or more calcium salicylate detergents provides to the lubricating composition thereof: 1) 200-4000 ppm of atomic magnesium, suitably 200-2000 ppm, 300 to 1500 ppm or 450-1200 ppm of atomic magnesium (ASTM D5185), and 2) at least 500 ppm, preferably at least 750 ppm, more preferably at least 900 ppm of atomic calcium, such as 500-4000 ppm, preferably 750-3000 ppm, more preferably 900-2000 ppm of atomic calcium (ASTM D5185).

[0299] The detergent may comprise one or more calcium detergents, such as calcium carboxylate (eg salicylate), sulfonate or phenate detergents.

[0300] Suitably, the calcium detergent has a TBN of 30 to 1400 mgKOH / g (ASTM D2896), such as 80 to 1200 mgKOH / g, such as 100 to 1000 mgKOH / g, such as 150 to 800 mgKOH / g, such as 200 to 600 mgKOH / g, such as 240 to 550 mgKOH / g, or 150 mgKOH / g or less, such as 100 mgKOH / g or less, or 200 mgKOH / g or more, or 300 mgKOH / g or more, or 350 mgKOH / g or more. The calcium detergent preferably has a TBN greater than or equal to 500, or 600, or 700, or 800, or 1000, or 1200, or 1300 or 1400 mgKOH / g.

[0301] Suitably, the calcium detergent is a calcium salicylate, calcium sulfonate or calcium phenate having a TBN of 30 to 1400 mgKOH / g, 30 to 1200 mgKOH / g (ASTM D2896), such as 50 to 1000 mgKOH / g, such as 200 to 800 mgKOH / g, such as 240 to 600 mgKOH / g, or 150 mgKOH / g or less, such as 100 mgKOH / g or less, or 200 mgKOH / g or more, or 300 mgKOH / g or more, or 350 mgKOH / g or more, or 500 mgKOH / g or more, or 700 mgKOH / g or more, or 900 mgKOH / g or more, or 1100 mgKOH / g or more, or 1300 mgKOH / g or more.

[0302] The calcium detergent is typically present in an amount sufficient to provide at least 500 ppm, preferably at least 750, more preferably at least 900 ppm of atomic calcium to the lubricating oil composition (ASTM D5185). If present, any calcium detergent is suitably present in an amount sufficient to provide no more than 4000 ppm, preferably no more than 3000 ppm, more preferably no more than 2000 ppm of atomic calcium to the lubricating oil composition (ASTM D5185). If present, any calcium detergent is suitably present in an amount sufficient to provide 500-4000 ppm, preferably 750-3000 ppm, more preferably 900-2000 ppm of atomic calcium to the lubricating oil composition (ASTM D5185).

[0303] Suitably, the total atomic weight of metals from detergents in lubricating compositions according to all aspects of the present disclosure is no more than 5000 ppm, preferably no more than 4000 ppm, more preferably no more than 2000 ppm (ASTM D5185). The total atomic weight of metals from detergents in lubricating oil compositions 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 atomic weight of metals from detergents in lubricating oil compositions according to all aspects of the present disclosure is suitably from 500 to 5000 ppm, preferably from 500 to 3000 ppm, more preferably from 500 to 2000 ppm (ASTM D5185).

[0304] Sulfonate detergents can be prepared from sulfonic acids, which are generally obtained by sulfonation of alkyl-substituted aromatic hydrocarbons (such as those obtained by fractionation of petroleum or by alkylation of aromatic hydrocarbons). Examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, biphenyl or their halogen derivatives, such as chlorobenzene, chlorotoluene and chloronaphthalene. Alkylation can be carried out with an alkylating agent having from about 3 to more than 70 carbon atoms in the presence of a catalyst. Alkaryl sulfonates generally contain from about 9 to about 80 or more carbon atoms per alkyl-substituted aromatic moiety, preferably from about 16 to about 60 carbon atoms. The oil-soluble sulfonates or alkaryl sulfonic acids can be neutralized with metal oxides, hydroxides, alkoxides, carbonates, carboxylates, sulfides, hydrosulfides, nitrates, borates and ethers. The amount of the metal compound is selected in consideration of the desired TBN of the final product, but is generally about 100 to 220 mass % (preferably at least 125 mass %) of the stoichiometrically required amount.

[0305] Metal salts of phenols and sulfurized phenols are prepared by reaction with 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 or sulfur dihalides) to form a product that is generally a mixture of compounds in which two or more phenols are bridged by sulfur-containing bridges.

[0306] Carboxylate detergents (e.g. salicylates) can be prepared by reacting aromatic carboxylic acids (e.g. C 5-100 , C 9-30 , C 14-24 The aromatic carboxylic acid may be prepared by reacting an alkyl-substituted hydroxybenzoic acid) with an appropriate metal compound, such as an oxide or hydroxide, and a neutral or overbased product may be obtained by methods known in the art. The aromatic moiety of the aromatic carboxylic acid may contain heteroatoms, such as nitrogen and oxygen. The moiety preferably contains only carbon atoms; the moiety more preferably contains six or more carbon atoms; for example, benzene is a preferred moiety. The aromatic carboxylic acid may contain one or more aromatic moieties, such as one or more benzene rings, fused or connected via an alkylene bridge.

[0307] Preferred substituents in oil-soluble salicylic acids are alkyl substituents. In alkyl-substituted salicylic acids, the alkyl group advantageously contains 5 to 100, preferably 9 to 30, especially 14 to 20 carbon atoms. If more than one alkyl group is present, the average number of carbon atoms in all alkyl groups is preferably at least 9 to ensure sufficient oil solubility.

[0308] In an embodiment, the ratio of detergent atomic metal to atomic molybdenum in the lubricating oil composition may be less than 3:1, such as less than 2:1.

[0309] In addition, since metal organic and inorganic base salts used as detergents can contribute to the sulfated ash content of the lubricating oil composition, in embodiments of the present disclosure, the amount of such additives is minimized. In order to maintain a low sulfur content, salicylate detergents may be used and the lubricating compositions herein may include one or more salicylate detergents (the detergents are preferably used in an amount of 0.05 to 20.0 wt. %, more preferably 1.0 to 10.0 wt. %, and most preferably 2.0 to 5.0 wt. %, based on the total weight of the lubricating composition).

[0310] The lubricating compositions herein generally have a total sulfated ash content of no greater than 2.0 wt%, or at a level of no greater than 1.0 wt%, or at a level of no greater than 0.8 wt%, based on the total weight of the lubricating composition as determined by ASTM D874.

[0311] Furthermore, it is useful that each detergent independently has a TBN value (Total Base Number) as measured by ISO 3771 in the range of 10 to 700 mg KOH / g, 10 to 500 mg KOH / g, or in the range of 100 to 650 mg KOH / g, or in the range of 10 to 500 mg KOH / g, or in the range of 30 to 350 mg KOH / g, or in the range of 50 to 300 mg KOH / g.

[0312] Sulfonate detergents (such as Ca and / or Mg sulfonate detergents) may be present in amounts to provide the lubricant composition with 0.1 wt % to 1.5 wt %, or 0.15 to 1.2 wt %, or 0.2 wt % to 0.9 wt % sulfonate soap.

[0313] The salicylate detergent (such as a Ca and / or Mg salicylate detergent) is present in an amount to provide the lubricant composition with 0.3 wt % to 1.4 wt %, or 0.35 wt % to 1.2 wt %, or 0.4 wt % to 1.0 wt % salicylate soap.

[0314] 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.

[0315] All alkaline earth metal detergent soaps combined may be present in an amount from 0.6 wt % to 2.1 wt %, or from 0.7 wt % to 1.4 wt % of the lubricant composition.

[0316] Typically, lubricating compositions formulated for 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 % detergent based on the lubricating composition.

[0317] 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 % detergent based on the lubricating composition.

[0318] Typically, lubricating compositions formulated for use in transmission systems (eg, gearboxes) contain about 0.1 to about 10 mass %, or about 0.5 to about 7.5 mass %, or about 2 to about 6.5 mass % detergent based on the lubricating composition. D. Friction modifier

[0319] Friction modifiers are any materials that can change the coefficient of friction of a surface lubricated with any lubricant or fluid containing such a material. If desired, friction modifiers, also known as friction reducers or lubricity agents or oiliness agents, and other such agents that change the ability of a base oil, formulated lubricating composition, concentrate composition, or functional fluid to adjust the coefficient of friction of a lubricated surface can be effectively used in combination with the base oil or lubricating composition of the present disclosure. Friction modifiers that reduce the coefficient of friction are particularly advantageously combined with the base oil and lubricating composition of the present disclosure.

[0320] Exemplary friction modifiers may include, for example, organometallic compounds or materials or mixtures thereof. Exemplary organometallic friction modifiers that may be used in lubricating oil formulations of the present disclosure include, for example, tungsten and / or molybdenum compounds, such as molybdenum amines, molybdenum diamines, organic tungstates, molybdenum dithiocarbamates, molybdenum dithiophosphates, molybdenum amine complexes, molybdenum carboxylates, and the like, and mixtures thereof. Examples of available molybdenum-containing compounds may conveniently include molybdenum dithiocarbamates, trinuclear molybdenum compounds, molybdenum sulfides, and molybdenum dithiophosphates, such as described in PCT Publication No. WO 98 / 26030.

[0321] Other known friction modifiers include oil-soluble organic molybdenum compounds. Such organic molybdenum friction modifiers can also provide antioxidant and antiwear benefits to the lubricating oil composition. Examples of such oil-soluble organic molybdenum compounds include dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, sulfides, and the like, and mixtures thereof. Particularly preferred are molybdenum dithiocarbamates, molybdenum dialkyl dithiophosphates, molybdenum alkyl xanthates, and molybdenum alkyl thioxanthates.

[0322] In addition, the molybdenum compound can be an acidic molybdenum compound. These compounds react with basic nitrogen compounds as measured by ASTM test D664 or D2896 titration procedures and are generally hexavalent. They include molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate and other alkali metal molybdates and other molybdenum salts, such as sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide or similar acidic molybdenum compounds.

[0323] Molybdenum compounds useful in the compositions of the present disclosure include organic molybdenum compounds of the formula Mo(R"OCS2)4 and Mo(R"SCS2)4, wherein R" is an organic group selected from alkyl, aryl, aralkyl and alkoxyalkyl groups generally having 1 to 30 carbon atoms, preferably 2 to 12 carbon atoms, and most preferably an alkyl group having 2 to 12 carbon atoms. Particularly preferred are dialkyl dithiocarbamates of molybdenum.

[0324] Another class of organic molybdenum compounds useful in the lubricating compositions of the present disclosure are trinuclear molybdenum compounds, particularly those of the formula Mo3S k L n Q z Those and mixtures thereof, wherein 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 4 to 7, Q is selected from neutral electron donating compounds such as water, amines, alcohols, phosphines and ethers, and z is 0 to 5 and includes non-stoichiometric values. At least 21 carbon atoms should be present in all ligands / organic groups, such as at least 25, at least 30 or at least 35 carbon atoms.

[0325] 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 of 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 of molybdenum. Lubricating oil compositions useful in all aspects of the present disclosure preferably contain 12 to 350 ppm, such as 12 to 500 ppm, or 20 to 200 ppm of molybdenum (measured as molybdenum atoms).

[0326] For more information on useful Mo-containing friction modifiers, see US Pat. No. 10,829,712 (column 8, line 58 to column 11, line 31). Particularly preferred Mo-containing friction modifiers of the present disclosure are moly dimers, moly trimers, or combinations thereof.

[0327] Ashless friction modifiers may be present in the lubricating oil composition of the present disclosure and are well known, and include esters formed by reacting carboxylic acids and anhydrides with alkanols and amine-based friction modifiers. Other available friction modifiers typically include polar end groups (e.g., carboxyl or hydroxyl groups) covalently bonded to lipophilic hydrocarbon chains. Esters of carboxylic acids and anhydrides with alkanols are described in U.S. Patent No. 4,702,850. M. Belzer in "Journal of Tribology" (1992), Vol. 114, pp. 675-682 and M. Belzer and S. Jahanmir in "Lubrication Science" (1988), Vol. 1, pp. 3-26 describe examples of other conventional organic friction modifiers. Typically, the total amount of organic ashless friction modifiers in the lubricant according to the present disclosure is no more than 5% by mass, preferably no more than 2% by mass, and more preferably no more than 0.5% by mass based on the total mass of the lubricating oil composition.

[0328] Exemplary friction modifiers useful in the lubricating compositions described herein include, for example, alkoxylated fatty acid esters, alkanolamides, polyol fatty acid esters, boronated glycerol fatty acid esters, fatty alcohol ethers, and mixtures thereof.

[0329] Exemplary alkoxylated fatty acid esters include, for example, polyoxyethylene stearates, fatty acid polyglycol esters, etc. These may include polyoxypropylene stearate, polyoxybutylene stearate, polyoxyethylene isostearate, polyoxypropylene isostearate, polyoxyethylene palmitate, and the like.

[0330] Exemplary alkanolamides include, for example, lauric acid diethyl alkanolamide, palmitic acid diethyl alkanolamide, etc. These may include oleic acid diethyl alkanolamide, stearic acid diethyl alkanolamide, oleic acid diethyl alkanolamide, polyethoxylated hydrocarbyl amides, polypropoxylated hydrocarbyl amides, and the like.

[0331] Exemplary polyol fatty acid esters include, for example, glycerol monooleate, saturated mono-, di- and triglycerides, glycerol monostearate, etc. These may include polyol esters, hydroxyl-containing polyol esters, and the like.

[0332] Exemplary boronized glycerol fatty acid esters include, for example, boronized glycerol monooleate, boronized saturated mono-, di- and triglycerides, boronized glycerol monostearate, etc. In addition to glycerol polyols, these may also include trimethylolpropane, pentaerythritol, sorbitan, etc. These esters may be polyol monocarboxylates, polyol dicarboxylates and sometimes, polyol tricarboxylates. Preferred may be glycerol monooleate, glycerol dioleate, glycerol trioleate, glycerol monostearate, glycerol distearate and glycerol tristearate and corresponding glycerol monopalmitate, glycerol dipalmitate and glycerol tripalmitate, and respective isostearates, linoleate, etc. Ethoxylated, propoxylated and / or butoxylated fatty acid esters of polyols (especially using glycerol as the base polyol) may be used for this.

[0333] Exemplary fatty alcohol ethers include, for example, stearyl ether, myristic ether, and the like. 50 The alcohols of the carbon number of the base are ethoxylated, propoxylated or butoxylated to form the corresponding fatty alkyl ethers. The base alcohol portion may preferably be stearyl, myristyl, C 11 -C 13 Hydrocarbon, oleyl, isostearyl, etc.

[0334] Useful concentrations of friction modifiers may be 0.01 wt % to 5 wt %, or about 0.01 wt % to about 2.5 wt %, or about 0.05 wt % to about 1.5 wt %, or about 0.051 wt % to about 1 wt %. The concentration of molybdenum-containing materials is typically described as Mo metal concentration. Advantageous concentrations of Mo may be 12 ppm to 350 ppm or more, typically preferably in the range of 20 to 200 ppm. All types of friction modifiers may be used alone or in combination with materials disclosed herein. A mixture of two or more friction modifiers or a mixture of a friction modifier with an alternative surface active material is also typically desirable. For example, a combination of a Mo-containing compound and a polyol fatty acid ester (such as glycerol monooleate) may be used herein. E. Antioxidants

[0335] Antioxidants delay oxidative degradation of base oils during use. Such degradation may result in deposits on metal surfaces, the presence of sludge, increased viscosity in lubricants, etc. A wide variety of oxidation inhibitors can be used in lubricating oil compositions. See, for example, Lubricants and Related Products, Klamann, Wiley VCH, 1984; U.S. Pat. Nos. 4,798,684 and 5,084,197.

[0336] Useful antioxidants include hindered phenols. These phenolic antioxidants can be ashless (metal-free) phenolic compounds or neutral or alkaline metal salts of certain phenolic compounds. Typical phenolic antioxidant compounds are hindered phenols containing sterically hindered hydroxyl groups. These include derivatives of dihydroxy aromatic compounds in which the hydroxyl groups are in the ortho or para position to each other. Typical phenolic antioxidants include C 6+ Alkyl-substituted hindered phenols and alkylene coupled derivatives of these hindered phenols. Examples of this type of phenolic material include 2-tert-butyl-4-heptylphenol; 2-tert-butyl-4-octylphenol; 2-tert-butyl-4-dodecylphenol; 2,6-di-tert-butyl-4-heptylphenol; 2,6-di-tert-butyl-4-dodecylphenol; 2-methyl-6-tert-butyl-4-heptylphenol; and 2-methyl-6-tert-butyl-4-dodecylphenol. Other useful hindered mono-phenolic antioxidants may include, for example, hindered 2,6-di-alkyl-phenol propionate derivatives. Bis-phenolic antioxidants may also be advantageously used herein. Examples of ortho-coupled phenols include: 2,2'-bis(4-heptyl-6-tert-butyl-phenol); 2,2'-bis(4-octyl-6-tert-butyl-phenol); and 2,2'-bis(4-dodecyl-6-tert-butyl-phenol). Para-coupled bisphenols include, for example, 4,4'-bis(2,6-di-tert-butyl-phenol) and 4,4'-methylene-bis(2,6-di-tert-butyl-phenol).

[0337] An effective amount of one or more catalytic antioxidants may also be used. The catalytic antioxidant comprises an effective amount of a) one or more oil-soluble multimetallic organic compounds; and an effective amount of b) one or more substituted N,N'-diaryl-o-phenylenediamine compounds, or c) one or more hindered phenol compounds; or a combination of b) and c). Catalytic antioxidants useful herein are more fully described in U.S. Pat. No. 8,048,833.

[0338] Non-phenolic oxidation inhibitors which may be used include aromatic amine antioxidants, which may be used as such or in combination with phenolic types. Typical examples of non-phenolic antioxidants include: alkylated and non-alkylated aromatic amines, such as those of formula R 8 R 9 R 10 N-aromatic monoamine, wherein R 8 is an aliphatic, aromatic or substituted aromatic group, R 9 is an aromatic or 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 or alkenyl, aryl or alkaryl group, and x is 0, 1 or 2. The aliphatic group R 8It may contain 1 to about 20 carbon atoms, preferably about 6 to 12 carbon atoms. The aliphatic group is typically a saturated aliphatic group. Preferably, R 8 and R 9 are all aromatic or substituted aromatic groups, and the aromatic group may be a condensed ring aromatic group, such as naphthyl. 8 and R 9 It can be linked to other groups such as S.

[0339] Typical aromatic amine antioxidants have an alkyl substituent containing at least about 6 carbon atoms. Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl and decyl. Typically, aliphatic groups do not contain more than about 14 carbon atoms. General types of amine antioxidants that can be used in the present composition include diphenylamine, phenylnaphthylamine, phenothiazine, iminodibenzyls and diphenylphenylenediamine. Mixtures of two or more aromatic amines are also available. Polymeric amine antioxidants can also be used. Specific examples of aromatic amine antioxidants that can be used in the present disclosure include: p, p'-dioctyldiphenylamine; tert-octylphenyl-α-naphthylamine; phenyl-α-naphthylamine; and p-octylphenyl-α-naphthylamine.

[0340] Sulfur-containing antioxidants may also be used herein. In particular, one or more oil-soluble or oil-dispersible sulfur-containing antioxidants may be used as antioxidant additives. For example, sulfurized alkylphenols and alkali metal or alkaline earth metal salts thereof are also antioxidants useful herein. Suitably, the lubricating oil composition of the present disclosure may contain one or more sulfur-containing antioxidants in an amount providing the lubricating oil composition with 0.02 to 0.2, preferably 0.02 to 0.15, even more preferably 0.02 to 0.1, even more preferably 0.04 to 0.1 mass % sulfur based on the total mass of the lubricating oil composition. Optionally, the oil-soluble or oil-dispersible sulfur-containing antioxidant is selected from sulfurized C4 to C 25 Olefins, sulfurized aliphatic (C7 to C 29 ) hydrocarbon fatty acid esters, ashless sulfurized phenolic antioxidants, sulfur-containing organic molybdenum compounds and combinations thereof. For further information on sulfurized materials that can be used as antioxidants herein, see U.S. Pat. No. 10,731,101 (column 15, line 55 to column 22, line 12).

[0341] The antioxidants useful herein include hindered phenols and / or arylamines. These antioxidants can be used independently or in combination with each other according to their type.

[0342] Typical antioxidants include: Irganox TM L67, Irganox TM L135, Ethanox TM 4702、LanxessAdditin TMRC 7110; Ethanox TM 4782J; Irganox TM 1135. Irganox TM 5057, Sulphurized lard and palm oil fatty acid methyl esters.

[0343] The antioxidant additive may be used in an amount of about 0.01 to 10 (or 0.01 to 5, or 0.01 to 3) wt %, or 1 to 6 wt %, or 2 to 5 wt %, or 3 to 4 wt %, or about 0.03 to 5 wt %, or 0.05 to less than 3 wt %, based on the weight of the lubricating composition.

[0344] The compositions according to the present disclosure may contain additives having different listed functions and also having a secondary effect as antioxidants (e.g., phosphorus-containing antiwear agents such as ZDDP may also have an antioxidant effect). These additives are not counted as antioxidants for determining the amount of antioxidant in the lubricating oil compositions or concentrates herein. F. Pour point depressant

[0345] If desired, conventional pour point depressants (also known as lubricant flow improvers) may be added to the compositions of the present disclosure. These pour point depressants may be added to the lubricating compositions of the present disclosure to reduce the minimum temperature required for the fluid to flow or pour. Examples of suitable pour point depressants include polymethacrylates, polyacrylates, polyacrylamides, condensation products of halogenated paraffins and aromatic compounds, carboxylic acid vinyl ester polymers, and terpolymers of dialkyl fumarates, fatty acid vinyl esters, and allyl vinyl ethers. U.S. Patent Nos. 1,815,022; 2,015,748; 2,191,498; 2,387,501; 2,655,479; 2,666,746; 2,721,877; 2,721,878; and 3,250,715 describe useful pour point depressants and / or their preparation. Such additives may be used in amounts of about 0.01 to 5 wt %, preferably about 0.01 to 1.5 wt %, based on the weight of the lubricating composition. G. Defoaming agent

[0346] Defoamers can be advantageously added to the lubricant compositions described herein. These agents prevent or delay the formation of stable foam. Silicones and / or organic polymers are typical defoamers. For example, polysiloxanes, such as silicone oils or polydimethylsiloxanes provide defoaming properties.

[0347] Defoamers are commercially available and can be used in minor amounts, such as 5 wt% or less, 3 wt% or less, 1 wt% or less, 0.1 wt% or less, such as 5 wt% to 0.1 ppm, such as 3 wt% to 0.5 ppm, such as 1 wt% to 10 ppm.

[0348] For example, it is possible that the lubricating oil composition comprises a defoamer comprising a polyalkylsiloxane, such as a polydialkylsiloxane, wherein the alkyl group is C1-C 10 Alkyl, such as polydimethylsiloxane (PDMS), also known as silicone oil. Alternatively, siloxane is poly(R 3 ) siloxane, wherein R 3 is one or more identical or different linear, branched or cyclic hydrocarbon groups, such as alkyl or aryl groups, which generally have 1 to 20 carbon atoms. It is possible, for example, that the lubricating oil composition comprises a polymeric siloxane compound according to the following formula 1, wherein R 1 and R 2 are independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl, phenyl, naphthyl, alkyl-substituted phenyl or isomers thereof (such as methyl, phenyl), and n is 2 to 1000, such as 50 to 450, or such as 40 to 100.

[0349] Additionally or alternatively, it is possible that the lubricating oil composition comprises an organo-modified siloxane (OMS), such as a polyether (e.g. ethylene oxide-propylene oxide copolymer), a long-chain hydrocarbon group (e.g. C 11 -C 100 Alkyl) or aryl (e.g. C6-C 14 It is possible, for example, that the lubricating oil composition comprises an organic modified siloxane compound according to Formula 1, wherein n is 2 to 2000, such as 50 to 450 (or such as 40 to 100), and wherein R 1 and R 2 Same or different, any one of R 1 and R 2 Each independently is an organic group, such as selected from polyethers (such as ethylene oxide-propylene oxide copolymers), long-chain hydrocarbon groups (such as C 11 -C 100 Alkyl) or aryl (e.g. C6-C 14 Preferably, R 1 and R 2 One of them is CH3.

[0350] The siloxane according to Formula 1 is incorporated to provide about 0.1 to less than about 30 ppm Si, or about 0.1 to about 25 ppm Si, or about 0.1 to about 20 ppm Si, or about 0.1 to about 15 ppm Si, or about 0.1 to about 10 ppm Si, based on the total weight of the lubricant composition. More preferably, it is in the range of about 3-10 ppm Si.

[0351] In embodiments, silicone defoamers 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 defoamers useful herein include polydimethylsiloxanes, phenyl-methylpolysiloxanes, linear, cyclic or branched siloxanes, silicone polymers and copolymers, and / or organo-silicone copolymers. Silicone polyether copolymer defoamers available from OSI Specialties, Inc. of Farmington Hills, Michigan may also be substituted or included. One such material is sold as SILWET-L-7220.

[0352] Acrylate polymer defoamers may also be used herein. Typical acrylate defoamers include the polyacrylate defoamer known as PC-1244 available from Monsanto Polymer Products Co. A preferred acrylate polymer defoamer useful herein is PX TM 3841 (i.e. alkyl acrylate polymer), also known as Mobilad TM C402.

[0353] In an embodiment, a combination of a silicone defoamer and an acrylate defoamer may be used, such as in a weight ratio of silicone defoamer / acrylate defoamer of about 5:1 to about 1:5, see, for example, U.S. Patent Application Publication No. 2021 / 0189283. H. Viscosity Improver

[0354] Viscosity modifiers (also referred to as viscosity index improvers or viscosity modifiers) may be included in the lubricating compositions and concentrate compositions described herein. Viscosity modifiers provide high and low temperature operability to lubricants. These additives provide shear stability at elevated temperatures and acceptable viscosity at low temperatures. Suitable viscosity modifiers include high molecular weight hydrocarbons, polyesters, and viscosity modifier dispersants that can act as both viscosity modifiers and dispersants. The typical molecular weight of these polymers is between about 10,000 and 1,500,000 g / mol, more typically about 20,000 to 1,200,000 g / mol, and more typically about 50,000 to 1,000,000 g / mol.

[0355] Examples of suitable viscosity modifiers are linear or star polymers and copolymers of methacrylates, butadiene, 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 of which also serve as pour point depressants. Other suitable viscosity modifiers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (e.g., copolymers of acrylates of various chain lengths). Specific examples include styrene-isoprene or styrene-butadiene type polymers of 50,000 to 200,000 g / mol molecular weight.

[0356] Copolymers useful as viscosity modifiers include those available under the trade name "PARATONE TM "(such as "PARATONE TM 8921"、"PARATONE TM 68231" and "PARATONE TM 8941") from Chevron Oronite Company LLC; under the trade name "HiTEC TM "(such as HiTEC TM 5850B and HiTEC TM 5777) from Afton Chemical Corporation; and under the trade name "Lubrizol TM 7067C" available from The Lubrizol Corporation. Hydrogenated polyisoprene star polymers useful as viscosity modifiers herein include those available from Infineum International Limited, such as those sold under the trade designation "SV200 TM "and" SV600 TM ". Hydrogenated diene-styrene block copolymers useful as viscosity modifiers herein are available from Infineum International Limited, for example under the trade name "SV 50 TM ".

[0357] Polymers useful as viscosity modifiers herein include polymethacrylate or polyacrylate polymers, such as linear polymethacrylate or polyacrylate polymers, such as those available under the trade name "Viscoplex TM "(e.g. Viscoplex TM 6-954) available from Evonik Industries, or under the trade name Asteric TM (e.g. Lubrizol TM87708 and Lubrizol TM 87725) is a star polymer available from Lubrizol Corporation.

[0358] The vinyl aromatic polymers useful as viscosity modifiers herein may be derived from vinyl aromatic monomers, such as styrenic monomers, such as styrene. Exemplary vinyl aromatic copolymers useful herein may be represented by the following general formula: AB, wherein A is a polymeric block primarily derived from a vinyl aromatic monomer (such as styrene), and B is a polymeric block primarily derived from a conjugated diene monomer (such as isoprene).

[0359] Vinyl aromatic-containing polymers useful as viscosity improvers may have a kinematic viscosity at 100°C of 20 cSt or less, such as 15 cSt or less, such as 12 cSt or less, but may be diluted (such as in Group I, II and / or III base stocks) to a higher kinematic viscosity at 100°C, such as to 40 cSt or more, such as 100 cSt or more, such as 1000 cSt or more, such as 1000 to 2000 cSt.

[0360] Typically, the viscosity modifier can be used in an amount of about 0.01 to about 10 weight percent, such as about 0.1 to about 7 weight percent, such as 0.1 to about 4 weight percent, such as about 0.2 to about 2 weight percent, such as about 0.2 to about 1 weight percent, and such as about 0.2 to about 0.5 weight percent, based on the total weight of the formulated lubricant composition.

[0361] Viscosity improvers are usually added as concentrates in a large amount of diluent oil. "As delivered" viscosity improvers usually contain from 20 to 75 weight percent active polymer in the "as delivered" polymer concentrate (for polymethacrylate or polyacrylate polymers), or from 8 to 20 weight percent active polymer for olefin copolymers, hydrogenated polyisoprene star polymers or hydrogenated diene-styrene block copolymers). I. Dispersant

[0362] During the operation of the engine, oil-insoluble oxidation byproducts are produced. Dispersants help keep these byproducts in solution, thereby reducing their deposition on metal surfaces. The dispersants used in the formulation of the lubricating composition herein can be ashless or ash-forming in nature. The dispersant is preferably ashless. So-called ashless dispersants are organic materials that do not substantially form ash when burned. For example, metal-free dispersants or boronized metal-free dispersants are considered ashless. In contrast, metal-containing detergents tend to form ash when burned.

[0363] Dispersants useful herein typically contain a polar group attached to a relatively high molecular weight hydrocarbon chain. The polar group typically contains at least one element of nitrogen, oxygen or phosphorus. Typical hydrocarbon chains contain 40 to 500, such as 50 to 400 carbon atoms. (Poly)alkenyl succinic acid derivative dispersant

[0364] One particularly useful class of dispersants includes (poly) alkenyl succinic acid derivatives, typically prepared by the reaction of a long chain hydrocarbyl-substituted succinic acid compound (typically a hydrocarbyl-substituted succinic anhydride) with a polyhydroxy or polyamino compound. The long chain hydrocarbyl group that constitutes the lipophilic portion of the molecule (which provides oil solubility) is typically a polyisobutylene group (the long chain hydrocarbyl group, such as a polyisobutylene group, typically has an Mn of 400 to 3000 g / mol, such as 450 to 2500 g / mol). Many examples of this type of dispersant are well known commercially and in the literature. Exemplary U.S. patents describing such dispersants include U.S. Patent Nos. 3,172,892; 3,2145,707; 3,219,666; 3,316,177; 3,341,542; 3,444,170; 3,454,607; 3,541,012; 3,630,904; 3,632,511; 3,787,374 and 4,234,435. Other types of dispersants are described in U.S. Patent Nos. 3,036,003; 3,200,107; 3,254,025; 3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,413,347; 3,697,574; 3,725,277; 3,725,480; 3,726,882; 4,454,059; 3,329,658; 3,449,250; 3,519,565; 3,666,730; 3,687,849; 3,702,300; 4,100,082; 5,705,458. Further descriptions of dispersants useful herein can be found, for example, in European Patent Application Nos. 0 471 071 and 0 451 380, to which reference is made for this purpose.

[0365] Hydrocarbyl-substituted succinic acid and hydrocarbyl-substituted succinic anhydride derivatives are useful dispersants. In particular, succinimide, succinate or succinate amide prepared by the reaction of a hydrocarbyl-substituted succinic acid or anhydride compound (typically having at least 25 carbon atoms, such as 28 to 400 carbon atoms in the hydrocarbyl substituent) with at least 1 equivalent of a polyhydroxy or polyamino compound (such as an alkyleneamine) are particularly useful for this. Hydrocarbyl-substituted succinic acid and hydrocarbyl-substituted succinic anhydride derivatives can 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, and such as about 2200 to about 2400 g / mol.

[0366] Succinimides particularly useful herein are formed by the condensation reaction between 1) a hydrocarbyl-substituted succinic anhydride, such as polyisobutylene succinic anhydride (PIBSA); and 2) a polyamine (PAM). Examples of suitable polyamines include: polyhydrocarbyl polyamines, polyalkylene polyamines, hydroxy-substituted polyamines, polyoxyalkylene polyamines, and combinations thereof. Examples of polyamines include 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. Mixtures in which the average number of nitrogen atoms per polyamine molecule is greater than 7 are generally referred to as heavy polyamines or H-PAMs and may be referred to by trade names such as HPA. TM and HPA-X TM Purchased from Dow Chemical as E-100 TM Available from Huntsman Chemical, etc. Examples of hydroxy substituted polyamines include N-hydroxyalkyl-alkylene polyamines such as N-(2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)piperazine and / or N-hydroxyalkylated alkylene diamines of the type described, for example, in U.S. Pat. No. 4,873,009. Examples of polyoxyalkylene polyamines include polyoxyethylene and / or polyoxypropylene diamines and triamines (and co-oligomers thereof) having an average Mn of from about 200 to about 5000 g / mol. Products of this type are available under the trade name Jeffamine TM Representative examples of useful succinimides are shown in U.S. Patent Nos. 3,087,936; 3,172,892; 3,219,666; 3,272,746; 3,322,670; 3,652,616; 3,948,800; and 6,821,307; and in Canadian Patent No. 1,094,044.

[0367] The dispersant may comprise one or more optionally boronated higher molecular weight (Mn 1600 g / mol or higher, such as 1800 to 3000 g / mol) succinimides and one or more optionally boronated lower molecular weight (Mn less than 1600 g / mol) succinimides, wherein the higher molecular weight may be 1600 to 3000 g / mol, such as 1700 to 2800 g / mol, such as 1800 to 2500 g / mol, such as 1850 to 2300 g / mol; the lower molecular weight may be 600 to less than 1600 g / mol, such as 650 to 1500 g / mol, such as 700 to 1400 g / mol, such as 800 to 1300 g / mol, such as 850 to 1200 g / mol, such as 900 to 1150 g / mol, such as 900 to 1000 g / mol. The higher molecular weight succinimide dispersant may be present in the lubricating composition in an amount of 0.5 to 10 wt %, or 0.8 to 6 wt %, or 1.0 to 5 wt %, or 1.5 to 5 wt %, or 1.5 to 4.0 wt %; the lower molecular weight succinimide dispersant may be present in the lubricating composition in an amount of 1 to 5 wt %, or 1.5 to 4.8 wt %, or 1.8 to 4.6 wt %, or 1.9 to 4.6 wt %, or 2 wt % or more, such as 2 to 5 wt %. The lower molecular weight succinimide may differ from the higher molecular weight succinimide by 500 g / mol or more, such as by 750 g / mol or more, such as by 1000 g / mol or more, such as by 1200 g / mol or more, such as by 500 to 3000 g / mol, such as by 750 to 2000 g / mol, such as by 1000 to 1500 g / mol.

[0368] Succinic acid esters useful as dispersants include those formed by the condensation reaction between a hydrocarbyl-substituted succinic anhydride and an alcohol or polyol. For example, the condensation product of a hydrocarbyl-substituted succinic anhydride and pentaerythritol is a useful dispersant.

[0369] The succinic acid ester amides available herein are formed by the condensation reaction between a hydrocarbyl-substituted succinic anhydride and an alkanolamine. Suitable alkanolamines include ethoxylated polyalkyl polyamines, propoxylated polyalkyl polyamines and polyalkenyl polyamines, such as polyethylene polyamines and / or propoxylated hexamethylene diamine. Representative examples are shown in U.S. Patent No. 4,426,305.

[0370] Hydrocarbyl-substituted succinic anhydride (e.g., PIBSA) esters of hydrocarbyl-bridged aryloxy alcohols can also be used as dispersants herein. For information on such dispersants, see U.S. Patent No. 7,485,603, particularly at column 2, line 65 to column 6, line 22 and column 23, line 40 to column 26, line 46. In particular, the PIBSA esters of methylene-bridged naphthoxyethanols (i.e., 2-hydroxyethyl-1-naphthol ethers (or hydroxy-terminated naphthol ethylene oxide oligomer ethers)) can be used herein.

[0371] The molecular weight of the hydrocarbyl-substituted succinic anhydride used in the preceding paragraphs is typically 350 to 4000 g / mol, such as 400 to 3000 g / mol, such as 450 to 2800 g / mol, such as 800 to 2500 g / mol. The above (poly) alkenyl succinic acid derivatives can be post-reacted with various reagents, such as sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid.

[0372] The dispersant may be present in the lubricant in an amount of 0.1 to 20 mass % of the composition, such as 0.2 to 15 mass %, such as 0.25 to 10 mass %, such as 0.3 to 5 mass %, such as 1.0 to 3.0 mass % of the lubricating oil composition.

[0373] The (poly)alkenyl succinic acid derivatives described above may also be post-reacted with a boron compound such as boric acid, boric acid esters or perborated dispersants to form a borated dispersant typically having from about 0.1 to about 5 moles of boron per mole of dispersant reaction product.

[0374] Dispersants useful herein include boronated succinimides, including those derivatives from monosuccinimides, bis-succinimides and / or mixtures of mono- and bis-succinimides, wherein the hydrocarbyl succinimide is derived from a hydrocarbylene group, such as polyisobutylene, having an Mn of from about 300 to about 5000 g / mol, or from about 500 to about 3000 g / mol, or from about 1000 to about 2000 g / mol, or a mixture of such hydrocarbylene groups, typically having a high terminal vinyl group.

[0375] The boron-containing dispersant may be present at 0.01 wt % to 20 wt %, or 0.1 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 0.5 wt % to 8 wt %, or 1.0 wt % to 6.5 wt %, or 0.5 wt % to 2.2 wt % of the lubricating composition.

[0376] The boron-containing dispersant may be present in an amount to provide 15 ppm to 2000 ppm, or 25 ppm to 1000 ppm, or 40 ppm to 600 ppm, or 80 ppm to 350 ppm boron to the composition.

[0377] Borated dispersants may be used in combination with non-borated dispersants and may be the same or different compounds as the non-borated dispersants. In one embodiment, the lubricating composition may include one or more boronated dispersants and one or more non-borated dispersants, wherein the total amount of dispersants may be from 0.01 wt % to 20 wt %, or from 0.1 wt % to 15 wt %, or from 0.1 wt % to 10 wt %, or from 0.5 wt % to 8 wt %, or from 1.0 wt % to 6.5 wt %, or from 0.5 wt % to 2.2 wt % of the lubricating composition, and wherein the ratio of the borated dispersant to the 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.

[0378] The dispersant may comprise one or more boronated or unborated poly(alkenyl)succinimides, wherein the polyalkenyl group is derived from polyisobutylene and the imide is derived from a polyamine ("PIBSA-PAM").

[0379] The dispersant may comprise one or more PIBSA-PAMs, wherein the PIB is derived from polyisobutylene having an Mn of 600 to 5000, such as 700 to 4000, such as 800 to 3000, such as 900 to 2500 g / mol, and the polyamine is derived from a hydrocarbyl-substituted polyamine such as 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 boronated, typically at a level of up to 4 mass %, such as 1 to 3 mass %. The dispersant may comprise one or more boronated PIBSA-PAMs and one or more non-boronated PIBSA-PAMs. The dispersant may comprise one or more boronated PIBSA-PAMs derived from a PIB having an Mn of 700 to 1800 g / mol (e.g., 800 to 1500 g / mol) and one or more non-boronated PIBSA-PAMs derived from a PIB having an Mn of greater than 1800 to 5000 g / mol (e.g., 2000 to 3000 g / mol). The dispersant may comprise one or more non-boronated PIBSA-PAMs derived from a PIB having an Mn of 700 to 1800 g / mol (e.g., 800 to 1500 g / mol) and one or more boronated PIBSA-PAMs derived from a PIB having an Mn of greater than 1800 to 5000 g / mol (e.g., 2000 to 3000 g / mol).

[0380] The dispersant may comprise a PIBSA derived from a PIB having a Mn of 700 to 5000 g / mol, such as 800 to 3000 g / mol, and one or more boronated or non-boronated PIBSA-PAMs derived from a PIB having a Mn of 700 to 5000 g / mol.

[0381] The dispersant may comprise a PIBSA derived from a PIB having an Mn of 700 to 5000 g / mol, such as 800 to 3000 g / mol, and one or more boronated PIBSA-PAMs derived from a PIB having an Mn of 700 to 1800 g / mol, such as 800 to 1500 g / mol, and one or more non-boronated PIBSA-PAMs derived from a PIB having an Mn of greater than 1800 to 5000 g / mol, such as 2000 to 3000 g / mol. The dispersant may comprise a PIBSA derived from a PIB having an Mn of 700 to 5000 g / mol, such as 800 to 3000 g / mol, one or more non-borated PIBSA-PAMs derived from a PIB having an Mn of 700 to 1800 g / mol, such as 800 to 1500 g / mol, and one or more borated PIBSA-PAMs derived from a PIB having an Mn of greater than 1800 to 5000 g / mol, such as 2000 to 3000 g / mol.

[0382] The dispersant may comprise one or more boronated or non-boronated PIBSA-PAMs and one or more PIBSA esters of hydrocarbyl-bridged aryloxy alcohols.

[0383] The dispersant may comprise one or more boronated PIBSA-PAMs and one or more non-boronated PIBSA-PAMs.

[0384] The dispersant may comprise one or more optionally boronated higher molecular weight (Mn 1600 g / mol or higher, such as 1800 to 3000 g / mol) PIBSA-PAMs and one or more optionally boronated lower molecular weight (Mn less than 1600 g / mol) PIBSA-PAMs, wherein the higher molecular weight may be 1600 to 3000 g / mol, such as 1700 to 2800 g / mol, such as 1800 to 2500 g / mol, such as 1850 to 2300 g / mol; the lower molecular weight may be 600 to less than 1600 g / mol, such as 650 to 1500 g / mol, such as 700 to 1400 g / mol, such as 800 to 1300 g / mol, such as 850 to 1200 g / mol, such as 900 to 1150 g / mol, such as 900 to 1000 g / mol. The higher molecular weight PIBSA-PAM dispersant can be present in the lubricating composition in an amount of 0.5 to 10 wt %, or 0.8 to 6 wt %, or 1.0 to 5 wt %, or 1.5 to 5 wt %, or 1.5 to 4.0 wt %; the lower molecular weight PIBSA-PAM dispersant can be present in the lubricating composition in an amount of 1 to 5 wt %, or 1.5 to 4.8 wt %, or 1.8 to 4.6 wt %, or 1.9 to 4.6 wt %, or 2 wt % or more, such as 2 to 5 wt %.

[0385] In a preferred form, the dispersant may comprise one or more optionally boronated higher molecular weight (Mn of 1600 g / mol or more) PIBSA-PAMs and one or more optionally boronated lower molecular weight (Mn less than 1600 g / mol) PIBSA-PAMs, wherein the higher molecular weight PIBSA-PAM is included in the lubricating oil composition at less than or equal to 2.5 wt. %, or less than or equal to 1.5 wt. %, or less than or equal to 0.5 wt. %, or 0.0 wt. %. In the preferred form wherein the dispersant comprises one or more optionally boronated higher molecular weight (Mn of 1600 g / mol or more) PIBSA-PAMs and one or more optionally boronated lower molecular weight (Mn less than 1600 g / mol) PIBSA-PAMs, the treat rate of the combination of higher molecular weight PIBSA-PAM and lower molecular weight PIBSA-PAM can be from 1.0 to 6.0 wt%, or from 1.5 to 5.5 wt%, or from 2.0 to 5.0 wt%, or from 2.5 to 4.5 wt%, or from 3.0 to 4.0 wt%. Mannich base dispersants

[0386] Mannich base dispersants useful herein are generally made by the reaction of an amine component, a hydroxy aromatic compound (substituted or unsubstituted, such as alkyl substituted), such as an alkyl phenol, and an aldehyde, such as formaldehyde. See U.S. Pat. Nos. 4,767,551 and 10,899,986. Processing aids and catalysts, such as oleic acid and sulfonic acid, 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 PCT Publication No. WO 01 / 42399. Polymethacrylate or polyacrylate derivative dispersants

[0387] Polymethacrylate or polyacrylate derivatives are another class of dispersants useful herein. These dispersants are typically prepared by reacting nitrogen-containing monomers with methacrylate or acrylate containing 5-25 carbon atoms in the ester group. Representative examples are shown in U.S. Pat. Nos. 2,100,993 and 6,323,164. Polymethacrylate and polyacrylate dispersants are typically of relatively low molecular weight.

[0388] The lubricating composition of the present disclosure typically comprises 0.1 to 20 mass % of the composition, such as 0.2 to 15 mass %, such as 0.25 to 10 mass %, such as 0.3 to 5 mass %, such as 2.0 to 4.0 mass % of the lubricating oil composition of the dispersant. Alternatively, the dispersant may be present at 0.1 to 5 wt %, or 0.01 to 4 wt % of the lubricating composition.

[0389] For further information on dispersants useful herein, see U.S. Pat. No. 10,829,712 at column 13, line 36 to column 16, line 67, and U.S. Pat. No. 7,485,603 at 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.

[0390] The compositions according to the present disclosure may contain additives having different listed functions and also having a second effect as a dispersant (e.g., the above-mentioned component B functionalized polymers may also have a dispersant effect). For determining the amount of dispersant in the lubricating oil composition or concentrate herein, these additives are not counted as dispersants. J. Corrosion Inhibitors / Rust Inhibitors

[0391] Corrosion inhibitors can be used to reduce the corrosion of metals and are also commonly referred to as metal deactivators or metal passivators. Some corrosion inhibitors can also be characterized as antioxidants.

[0392] Suitable corrosion inhibitors may include nitrogen and / or sulfur containing heterocyclic compounds such as triazoles (e.g., benzotriazole), substituted thiadiazoles, imidazoles, thiazoles, tetrazoles, hydroxyquinolines, oxazolines, imidazolines, thiophenes, indoles, indazoles, quinolines, benzoxazines, dithiols, oxazoles, oxatriazoles, pyridines, piperazines, triazines, and derivatives of any one or more thereof. A specific corrosion inhibitor is benzotriazole as shown in the following structure: Where R 8 There is no (hydrogen) or it may be a linear or branched, saturated or unsaturated C1 to C 20 Hydrocarbyl or substituted hydrocarbyl. It may contain a ring structure that is alkyl or aryl in nature and / or contain heteroatoms, such as N, O or S. Examples of suitable compounds may include benzotriazole, alkyl substituted benzotriazoles (e.g., tolyltriazole, ethylbenzotriazole, hexylbenzotriazole, octylbenzotriazole, etc.), aryl substituted benzotriazoles, alkylaryl- or arylalkyl-substituted benzotriazoles, and the like, and combinations thereof. For example, the triazole may comprise or be benzotriazole and / or an alkylbenzotriazole, wherein the alkyl group contains 1 to about 20 carbon atoms, or 1 to about 8 carbon atoms. Non-limiting examples of such corrosion inhibitors may comprise or be benzotriazole, tolyltriazole and / or optionally, substituted benzotriazoles, such as Irgamet available from BASF of Ludwigshafen, Germany. TM 39. Preferred corrosion inhibitors may comprise or be benzotriazole and / or tolyltriazole.

[0393] Additionally or alternatively, the corrosion inhibitor may include one or more substituted thiadiazoles of the following structures: Where R 15 and R 16 is independently hydrogen or a hydrocarbon group, which group can be aliphatic or aromatic, including cyclic, alicyclic, aralkyl, aryl and alkaryl, and wherein each w is independently 1, 2, 3, 4, 5 or 6 (preferably 2, 3 or 4, such as 2). These substituted thiadiazoles are derived from 2,5-dimercapto-1,3,4-thiadiazole (DMTD) molecules. Many derivatives of DMTD have been described in the art, and any such compound may be included in the fluid used in the present disclosure. For example, U.S. Patent Nos. 2,719,125; 2,719,126; and 3,087,937 describe the preparation of various 2,5-bis-(hydrocarbon dithio)-1,3,4-thiadiazoles.

[0394] Additionally or alternatively, the corrosion inhibitor may include one or more other DMTD derivatives, such as carboxylic acid esters, wherein R 15 and R16 The carbonyl group may be attached to the sulfide sulfur atom. The preparation of these thioester-containing DMTD derivatives is described, for example, in U.S. Pat. No. 2,760,933. DMTD derivatives prepared by condensation of DMTD with an α-halogenated aliphatic carboxylic acid having at least 10 carbon atoms are described, for example, in U.S. Pat. No. 2,836,564. This method produces DMTD derivatives in which R 15 and R 16 It is HOOC-CH(R 19 )(R 19 DMTD derivatives further prepared by amidation or esterification of these terminal carboxylic acid groups are also useful.

[0395] The preparation of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazoles is described, for example, in US Pat. No. 3,663,561.

[0396] One class of DMTD derivatives may include a mixture of 2-alkyldithio-5-mercapto-1,3,4-thiadiazole and 2,5-bis-alkyldithio-1,3,4-thiadiazole. Such a mixture may be marketed under the trade name HiTEC TM 4313 is sold and available from Afton Chemical Company.

[0397] The preparation of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazoles is described, for example, in US Pat. No. 3,663,561.

[0398] One class of DMTD derivatives may include a mixture of 2-alkyldithio-5-mercapto-1,3,4-thiadiazole and 2,5-bis-alkyldithio-1,3,4-thiadiazole. Such a mixture may be marketed under the trade name HiTEC TM 4313 is sold and available from Afton Chemical Company.

[0399] Additionally or alternatively, the corrosion inhibitor may include a compound having the structure B(OR 46 )3 trifunctional borate ester, wherein each R 46 Since the borate ester is generally ideally compatible with the non-aqueous medium of the composition, each R 46In particular, it may comprise or be a hydrocarbyl C1-C8 moiety. For compositions wherein the non-aqueous medium comprises or is a lubricating oil base stock, for example, when the hydrocarbyl moieties are each at least C4, better compatibility can generally be achieved. Non-limiting examples of such corrosion inhibitors therefore 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, monohexyl dibutyl borate, etc., and combinations thereof.

[0400] When used, the corrosion inhibitor may comprise a substituted thiadiazole, a substituted benzotriazole, a substituted triazole, a trisubstituted borate, or a combination thereof.

[0401] When desired, corrosion inhibitors may be used in any effective amount, but when used, may generally be used in an amount of about 0.001 wt % to 5.0 wt %, such as 0.005 wt % to 3.0 wt % or 0.01 wt % to 1.0 wt %, based on the weight of the composition. Alternatively, such additives may be used in an amount of about 0.01 to 5 wt %, preferably about 0.01 to 1.5 wt %, based on the weight of the lubricating composition.

[0402] In some embodiments, the 3,4-oxypyridone-containing composition can be substantially free (e.g., 0, or less than 0.001 wt %, 0.0005 wt % or less, no intentional addition, and / or absolutely free) of triazole, benzotriazole, substituted thiadiazole, imidazole, thiazole, tetrazole, hydroxyquinoline, oxazoline, imidazoline, thiophene, indole, indazole, quinoline, benzoxazine, dithiol, oxazole, oxatriazole, pyridine, piperazine, triazine, derivatives thereof, combinations thereof, or all corrosion inhibitors.

[0403] The compositions according to the present disclosure may contain additives having different listed functions and also having a second effect as corrosion inhibitors (e.g., the above-mentioned component B functionalized polymers may also have a corrosion inhibitor effect). For determining the amount of corrosion inhibitor in the lubricating oil composition or concentrate herein, these additives are not counted as corrosion inhibitors. K. Anti-wear agent

[0404] The lubricating oil composition and concentrate composition of the present disclosure may contain one or more anti-wear agents that can reduce friction and excessive wear. Any anti-wear agent known to those of ordinary skill in the art can be used in the lubricating oil composition. Non-limiting examples of suitable anti-wear agents include zinc dithiophosphates, metal (e.g., Pb, Sb, Mo, etc.) salts of dithiophosphoric acid, metal (e.g., Zn, Pb, Sb, Mo, etc.) salts of dithiocarbamic acid, metal (e.g., Zn, Pb, Sb, etc.) salts of fatty acids, boron compounds, phosphates, phosphites, amine salts of phosphates or thiophosphoric acid esters, reaction products of dicyclopentadiene and thiophosphoric acid, and combinations thereof. Based on the gross weight of the lubricating oil composition, the amount of the anti-wear agent may be 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 %.

[0405] In embodiments, the antiwear agent is or comprises a dihydrocarbyl dithiophosphate metal salt, such as a dialkyl dithiophosphate zinc compound. The metal of the dihydrocarbyl dithiophosphate metal salt can be an alkali metal or an 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 about 3 to about 22 carbon atoms, about 3 to about 18 carbon atoms, about 3 to about 12 carbon atoms, or about 3 to about 8 carbon atoms. In further embodiments, the alkyl group is straight chain or branched.

[0406] Useful antiwear agents also include substituted or unsubstituted thiophosphoric acids, salts thereof including zinc-containing compounds such as zinc dithiophosphate compounds selected from the group consisting of dialkyl-, diaryl- and / or alkylaryl-zinc dithiophosphates.

[0407] Metal alkylthiophosphates, more particularly metal dialkyl dithiophosphates wherein the metal component is zinc, or zinc dialkyl dithiophosphate (ZDDP) can be useful components of the lubricating compositions of the present disclosure. ZDDP can be derived from a primary alcohol, a secondary alcohol, or a mixture thereof. ZDDP compounds generally have the formula Zn[SP(S)(OR 1 )(OR 2 )]2, where R 1 and R 2 It is C1-C 18 Alkyl, preferably C2-C 12Alkyl. These alkyl groups can be straight chain or branched. The alcohol used in ZDDP can be 2-propanol, butanol, sec-butanol, amyl alcohol, hexanol, such as 4-methyl-2-pentanol, n-hexanol, n-octanol, 2-ethylhexanol, alkylated phenols, etc. A secondary alcohol mixture or a mixture of a primary alcohol and a secondary alcohol can be used. Alkyl aryl groups can also be used. Available 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", from Chevron Oronite under the trade name "OLOA 262" and from HiTEC TM 7169" from Afton Chemical.

[0408] In an embodiment, the zinc compound may be a zinc dithiocarbamate complex, such as a zinc dithiocarbamate of the formula: Among them, each R I is independently a linear, cyclic or branched, saturated or unsaturated aliphatic hydrocarbon moiety having 1 to about 10 carbon atoms, n is 0, 1 or 2, L is a ligand that saturates the zinc coordination sphere, and x is 0, 1, 2, 3 or 4. In certain embodiments, the ligand L is selected from water, hydroxide, ammonia, amino, amido, alkylthiolate, halide, and combinations thereof.

[0409] Antiwear additives, such as ZDDP and / or zinc carbamate are 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 more or less may often be used to advantage. Preferably, the antiwear additive is a ZDDP, preferably a secondary ZDDP, and is present in an amount of about 0.6 to 1.0 wt % of the total weight of the lubricating composition. The lubricating oil compositions of the present disclosure preferably contain one or more ZDDPs at a treat rate that provides the composition with less than or equal to 1200 ppm, or 1000 ppm, or 800 ppm, or 600 ppm, or 400 ppm, or 200 ppm, or 0 ppm by weight of phosphorus.

[0410] Antiwear additives useful herein also include boron-containing compounds such as borate esters, borated fatty amines, borated epoxides, alkali metal (or mixed alkali metal or alkaline earth metal) borates and borated overbased metal salts.

[0411] The compositions according to the present disclosure may contain additives having different listed functions and also having a second effect as antiwear agents (e.g., the above-mentioned component B functionalized polymers may also have an antiwear effect). For determining the amount of antiwear agent in the lubricating oil composition or concentrate herein, these additives are not counted as antiwear agents. L. Demulsifier

[0412] Demulsifiers useful herein include those described in U.S. Patent No. 10,829,712 (column 20, lines 34 to 40). Generally, a small amount of demulsifying components may be used herein. Preferred demulsifying components are described in European Patent No. 330 522. They are obtained by reacting an alkylene oxide with an adduct obtained by reacting a diepoxide with a polyol. Such additives may be used in an amount of about 0.001 to 5% by weight, preferably about 0.01 to 2% by weight. M. Seal compatibilizer and seal swelling agent

[0413] Other optional additives include seal compatibilizers such as organic phosphates, aromatic esters, aromatic hydrocarbons, esters (e.g., butyl benzyl phthalate), and polybutenyl succinic anhydride. Such additives may be used in an amount of about 0.001 to 5 wt %, preferably about 0.01 to 2 wt %. In an embodiment, the seal compatibilizer is a seal swelling agent such as PIBSA (polyisobutylenyl succinic anhydride). N. Extreme pressure agent

[0414] The lubricating oil composition and concentrate composition of the present disclosure may contain one or more extreme pressure agents that can prevent the sliding metal surfaces from seizing under extreme pressure conditions. Any extreme pressure agent known to those of ordinary skill in the art can be used in the lubricating oil composition. Generally, extreme pressure agents are compounds that can chemically bond with metals to form a surface film that prevents the welding of asperities in opposing metal surfaces under high loads. Non-limiting examples of suitable extreme pressure agents include sulfurized animal or vegetable fats or oils, sulfurized animal or vegetable fatty acid esters, fully or partially esterified esters of trivalent or pentavalent phosphorus-containing acids, 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 α-olefins, functionally substituted dihydrocarbyl polysulfides, thioaldehydes, thioketones, epithio compounds, sulfur-containing acetal derivatives, co-sulfurized blends of terpenes and acyclic olefins, polysulfide olefin products, amine salts of phosphates or thiophosphates, and combinations thereof. Based on the total weight of the lubricating oil composition, the amount of the extreme pressure agent may vary from about 0.01 wt % to about 5 wt %, from about 0.05 wt % to about 3 wt %, or from about 0.1 wt % to about 1 wt %. O. Non-base oil unsaturated hydrocarbons

[0415] The lubricating oil compositions and concentrate compositions of the present disclosure may contain one or more unsaturated hydrocarbons. These unsaturated hydrocarbons are different from any base oil (Group I, II, III, IV and / or V lubricating oil base stocks) and / or viscosity improvers that may be present in the composition, and always have at least one (usually only one in the case of linear alpha olefins or LAOs) unsaturation per molecule. Without being bound by theory, the unsaturation may provide antioxidant function and / or sulfur capture function, which may supplement and / or replace one or more antioxidant additives and / or one or more corrosion inhibitor additives, but unsaturated hydrocarbons (LAOs) generally do not provide the only antioxidant function and the only corrosion inhibition function in the lubricating oil composition. Non-limiting examples of unsaturated hydrocarbons may include one or more unsaturated C 12 -C 60 Hydrocarbons (such as C 12 -C 48 Hydrocarbon, C 12 -C 36 Hydrocarbon, C 12 -C 30 Hydrocarbon or C 12 -C 24 The unsaturated hydrocarbon (LAO) may be present in an amount of 0.01 to 5% by weight (particularly 0.1 to 3% by weight, or 0.1 to 1.5% by weight), based on the total weight of the lubricating oil composition.

[0416] When the lubricating oil composition contains one or more of the additives discussed above, the additives are generally blended into the composition in an amount sufficient to enable them to perform their intended function. Typical amounts of such additives useful in the present disclosure, especially for crankcase lubricants, are shown in the following table.

[0417] It is noted that many additives are shipped from additive manufacturers as concentrates containing one or more additives together with a certain amount of base oil or other diluent. Therefore, the weights in the following table and other amounts mentioned herein relate to the amount of active ingredient (i.e., the diluent-free portion of the ingredient). The weight % (mass %) shown below is based on the total weight of the lubricating oil composition. Typical amounts of lubricant components

[0418] The above-mentioned additives are generally commercially available materials. These additives can be added separately, but are usually pre-combined in additive packages available from lubricant additive suppliers. Additive packages with various ingredients, proportions and properties are available and the selection of a suitable additive package will take into account the use of the final composition. fuel

[0419] The present disclosure also relates to a method for lubricating an internal combustion engine of a passenger car or commercial vehicle during operation of the engine, comprising: (i) providing a crankcase of a vehicle internal combustion engine with a vehicle crankcase lubricating oil composition as described herein; (ii) providing a hydrocarbon fuel in a vehicle internal combustion engine; and (iii) combusting the fuel in a vehicular internal combustion engine, such as a spark ignition or compression ignition two-stroke or four-stroke reciprocating engine, such as a diesel engine or a passenger car engine (such as a spark ignition internal combustion engine).

[0420] The present disclosure also relates to a fuel composition comprising a lubricating oil composition as described herein and a hydrocarbon fuel, wherein the fuel may be derived from petroleum and / or biological sources ("biofuel" or "renewable fuel"). Suitable hydrocarbon-based fuels include diesel fuel, mogas, natural gas fuel, and hydrogen fuel. In embodiments, the fuel comprises 0.1 to 100 mass % renewable fuel, or 1 to 75 mass % renewable fuel, or 5 to 50 mass % renewable fuel, based on the total mass of renewable fuel and petroleum-derived fuel.

[0421] Renewable fuel components are typically made from vegetable oils (such as palm oil, rapeseed oil, soybean oil, jatropha oil), microbial oils (such as algae oil), animal fats (such as edible oils, animal fats and / or fish fats) and / or biogas. Renewable fuel refers to biofuels made from biological resources formed by contemporary biological processes. In one embodiment, the renewable fuel component is made with the aid of a hydrotreating process. Hydrotreating involves various reactions in which molecular hydrogen reacts with other components, or components undergo molecular transformations in the presence of molecular hydrogen and a solid catalyst. The reaction includes, but is not limited to, hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrocracking and isomerization. Renewable fuel components can have different distillation ranges to provide the component with desired properties according to the intended use. use

[0422] The lubricating compositions of the present disclosure can be used to lubricate mechanical engine components by adding lubricants thereto, particularly in internal combustion engines, such as spark ignition or compression ignition two-stroke or four-stroke reciprocating engines. Typically, they are crankcase lubricants, such as passenger car motor oils or heavy or light diesel engine lubricants. The lubricating compositions of the present disclosure can also be used to lubricate mechanical engine components of hydrogen and natural gas engines.

[0423] In particular, the lubricating composition of the present disclosure is suitably used for lubrication of the crankcase of a spark-ignition internal combustion engine, such as a passenger car engine.

[0424] In particular, the lubricating composition of the present disclosure is suitably used for lubrication of the crankcase of a spark-ignition turbocharged internal combustion engine.

[0425] In particular, the lubricating composition of the present disclosure is suitably used for lubrication of a crankcase of a natural gas engine or a hydrogen engine.

[0426] In embodiments, the lubricating oils of the present disclosure are used in spark-assisted high compression internal combustion engines, and when used in high compression spark-ignition internal combustion engines, the lubricating oil compositions of the present disclosure can be used to lubricate high compression spark-ignition engines.

[0427] In embodiments, the lubricating compositions of the present disclosure are suitably used for lubrication of the crankcase of an engine of a heavy-duty diesel vehicle (ie, a heavy-duty diesel vehicle having a gross vehicle weight of 10,000 pounds or more).

[0428] In an embodiment, the lubricating composition of the present disclosure is suitably used for lubrication of the crankcase of a passenger car diesel or gasoline engine. 1. A lubricating oil composition comprising the following components or a mixture of the following components: 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; an overbased calcium-based detergent having a total base number (KOH / g) greater than, or equal to, 9 and less than, or equal to, 500 and at a treat rate providing 500 to 1300 ppm by weight of calcium to the composition; and an overbased magnesium-based detergent having a total base number (KOH / g) greater than, or equal to, 9 and less than, or equal to, 500 and at a treat rate providing 500 to 1300 ppm by weight of magnesium to the composition; wherein the total weight of calcium and magnesium combined in the composition is from 1000 ppm to 1800 ppm; The lubricating oil composition has a total sulfated ash less than or equal to 1.0 wt %, a high temperature high shear viscosity (HTHS) at 150° C. measured according to ASTM 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 content of less than or equal to 0.080 wt %, and The lubricating oil composition provides a 5% to 60% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 Start / Stop test method compared to a lubricating oil composition having a HTHS equivalent but not comprising a mixture of an overbased calcium-based detergent and an overbased magnesium-based detergent in the composition at a combined calcium and magnesium loading of 1000 ppm to 1800 ppm. 2. The lubricating oil composition of paragraph 1, wherein the composition has a kinematic viscosity at 100° C. of 5 to 20 cSt and a total sulfur content of less than or equal to 0.35 wt %. 3. The lubricating oil composition of paragraphs 1-2, wherein the oil of lubricating viscosity is 60 wt % to 95 wt % of the composition and comprises a Group III base oil, a Group IV base oil, or a combination thereof. 4. The lubricating oil composition of paragraphs 1-3, wherein the overbased calcium-based detergent is a sulfonate, a salicylate, a phenate, or a combination thereof. 5. The lubricating oil composition of paragraphs 1-4, wherein the overbased magnesium-based detergent is a sulfonate, a salicylate, a phenate, or a combination thereof. 6. The lubricating oil composition of paragraphs 1-5, wherein the overbased calcium-based detergent is a salicylate, the overbased magnesium-based detergent is a salicylate, and the total weight of combined calcium and magnesium in the composition is from 1600 ppm to 1800 ppm. 7. The lubricating oil composition of paragraphs 1-6, wherein the ratio of calcium loading to magnesium loading in the composition is from 30:70 to 70:30 based on weight % in the lubricating oil composition. 8. The lubricating oil composition of paragraphs 1-7, wherein the lubricating oil composition is a heavy duty diesel engine oil, a light duty diesel engine oil, a hydrogen engine oil, a spark ignition internal combustion engine oil, or a natural gas engine oil. 9. The lubricating oil composition of paragraphs 1-8, wherein the lubricating oil composition is an SAE grade selected from 0W-8, 0W-12, 0W-16, 0W-20, 0W-30, 5W-20, 5W-30, 10W-30, 15W-40, 5W-40 and 10W-40. 10. The lubricating oil composition of paragraphs 1 to 9, wherein the lubricating oil composition is used as a passenger vehicle lubricant (PVL) or a commercial vehicle lubricant (CVL). 11. The lubricating oil composition of paragraphs 1-10, wherein the journal bearing is a main bearing for a crankshaft, a connecting rod big end bearing for a crankshaft, or a connecting rod small end bearing / bushing for a piston pin. 12. The lubricating oil composition of paragraphs 1-11, wherein the journal bearing shell material is a material selected from the group consisting of bimetallic, tri-material / metallic, and monolithic materials. 13. The lubricating oil composition of paragraph 12, wherein the three materials / metals are a polymer coating or a SuCu overlay on lead-free bronze. 14. The lubricating oil composition of paragraph 12, wherein the bimetal is AlSn20Cu or AlSn25. 15. The lubricating oil composition of paragraph 12, wherein the bulk material is bronze or lead-free bronze. 16. The lubricating oil composition of paragraph 13, wherein the polymer coated three-material journal bearing shell material provides a 5% to 40% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 start / stop test method compared to a HTHS comparable lubricating oil composition but not comprising a mixture of an overbased calcium-based detergent and an overbased magnesium-based detergent. 17. The lubricating oil composition of paragraph 13, wherein the SnCu faced tri-metal journal bearing shell material provides a 10% to 60% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 start / stop test method compared to a HTHS comparable lubricating oil composition but not comprising a mixture of an overbased calcium-based detergent and an overbased magnesium-based detergent. 18. The lubricating oil composition of paragraphs 1-17, further comprising one or more of the following components: one or more functionalized polymers, one or more friction modifiers; one or more antioxidants; one or more pour point depressants; one or more defoamers; one or more viscosity improvers; one or more dispersants; one or more inhibitors, one or more rust inhibitors; one or more seal swell agents; and / or one or more antiwear agents. 19. The lubricating oil composition of paragraph 18, wherein the one or more dispersants are one or more optionally boronated higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersants (Mn of 1600 g / mol or greater), one or more optionally boronated lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersants (Mn less than 1600 g / mol), or a combination thereof, and wherein the treat rate of the combination of higher molecular weight PIBSA-PAM and lower molecular weight PIBSA-PAM is from 1.0 to 6.0 weight percent of the composition. 20. The lubricating oil composition of paragraph 19, wherein the higher molecular weight PIBSA-PAM dispersant, the lower molecular weight PIBSA-PAM dispersant, or a combination thereof is included at a treat rate that provides 20 wt ppm to 700 wt ppm of boron to the lubricating oil composition. 21. The lubricating oil composition of paragraph 18, wherein the one or more antiwear agents include one or more zinc dialkyl dithiophosphates (ZDDPs) that provide a treat rate of less than or equal to 840 ppm by weight of phosphorus to the composition. 22. The lubricating oil composition of paragraph 18, wherein the one or more antioxidants include one or more phenolic antioxidants, one or more sulfur-based antioxidants, one or more amine antioxidants, or combinations thereof, and wherein the one or more antioxidants constitute 1.0 to 6.0 weight percent of the composition. 23. The lubricating oil composition of paragraph 18, wherein the one or more friction modifiers include a molydimer, a moly trimer, or a combination thereof that provides a treat rate of 12 wt ppm to 1000 wt ppm of molybdenum to the composition. 24. The lubricating oil composition of paragraph 18, wherein the functionalized polymer is 0.2 to 2.0 wt. % of the composition, and comprises amide, imide and / or ester functionalized partially or fully saturated C 4-5 A polymer of an olefin, the polymer having: i) Mw / Mn less than 2, ii) a functionality distribution (Fd) value of 3.5 or less, and iii) an Mn (GPC-PS) of the polymer before functionalization of 10,000 g / mol or more, Provided that if the polymer prior to functionalization is a copolymer of isoprene and butadiene, the Mn of said copolymer is greater than 25,000 g / mol (GPC-PS). 25. A method of lubricating an internal combustion engine comprising supplying to the engine a lubricating oil composition according to any one of paragraphs 1 to 24. 26. A method of reducing journal bearing wear in an internal combustion engine, comprising: A lubricating oil composition according to any one of paragraphs 1 to 24 is provided to an internal combustion engine. 27. A method of making a lubricating oil composition comprising combining or mixing the following components: (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) an overbased calcium-based detergent having a total base number (KOH / g) greater than, or equal to, 9 and less than, or equal to, 500 and at a treat rate providing from 500 to 1300 ppm by weight of calcium to the composition; and (iii) an overbased magnesium-based detergent having a total base number (KOH / g) greater than, or equal to, 9 and less than, or equal to, 500 and at a treat rate providing from 500 to 1300 ppm by weight of magnesium to the composition; wherein the total weight of calcium and magnesium combined in the composition is from 1000 ppm to 1800 ppm; The lubricating oil composition has a total sulfated ash less than or equal to 1.0 wt %, a high temperature high shear viscosity (HTHS) at 150° C. measured according to ASTM 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 content of less than or equal to 0.080 wt %, and The lubricating oil composition provides a 5% to 60% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 Start / Stop test method compared to a lubricating oil composition having a HTHS equivalent but not comprising a mixture of an overbased calcium-based detergent and an overbased magnesium-based detergent in the composition at a combined calcium and magnesium loading of 1000 ppm to 1800 ppm.

[0429] The following non-limiting examples are provided to illustrate the present disclosure. experiment

[0430] Unless otherwise noted, all molecular weights are number average molecular weight (Mn) reported in g / mol as determined by gel permeation chromatography using polystyrene standards. Unless otherwise noted, "AI", "ai" and "ai" are weight % active ingredient. Testing Procedure

[0431] KV100 is the kinematic viscosity measured at 100°C according to ASTM D445-19a.

[0432] KV40 is the kinematic viscosity measured at 40°C according to ASTM D445-19a.

[0433] Sulfur content in oil is measured by ASTM D5185.

[0434] Sulfated ash ("SASH") content is measured by ASTM D874.

[0435] Phosphorus, boron, calcium, zinc, molybdenum and magnesium contents were measured by ASTM D5185. The MTM-R test method uses a Mini-Traction Machine (MTM) manufactured by PCS Instruments of London, United Kingdom. The MTM-R method uses a Mini-Traction Machine (MTM-R) with a reciprocating function, and the machine uses a 19 mm diameter ball as an upper specimen, which reciprocates against a lower specimen in the form of a disc under an applied load. The ball is made of AISI52100 grade steel and is uncoated. The disc is made of steel that has been coated or uncoated (steel) with an Al bimetallic, polymer tri-material, with a coating depth of approximately 2 μm. The contact between the ball and the disc is therefore made between the ferrous (steel) surface and the coated or uncoated surface to measure the friction loss in μm. 3 The wear scar volume was measured. The test conditions are given in the table below for each disc material tested with the lubricating oil composition. The test discs were 46 mm AISI 52100 steel with a surface finish of <0.02 μm Ra and a hardness of 720-780 Hv, and the test balls were 19.05 mm AISI 52100 steel with a surface finish of <0.02 μm Ra and a hardness of 800-920 Hv. condition Al bimetallic polymer steel Temperature / ℃ 100 100 100 Load / N 5 5 5 Stroke length / mm 4 4 4 Disc roughness 0.34 0.82 0.3 Average lambda ratio 0.019 0.019 0.019 Frequency / Hz 5 20 4 Ball speed / mm / s 143 464 133 Travel distance / m 54 54 54

[0436] The TE-92 start / stop test method includes a test rig and test procedures for measuring journal bearing wear measured by maximum average wear in microns. The test procedures are included in the following journal article, the entire contents of which are incorporated herein by reference regarding the TE-92 start / stop test method: Summer, F., Grün, F., & Ravenhill, ER (2020). Friction and Wear Performance of Various Polymer Coatings for Journal Bearings under Stop Start Sliding. Lubricants, 8.2020(1), (https: / / doi.org / 10.3390 / lubricants8010001). In the journal article it is stated that "the test strategy starts with an initial period at room temperature at slow sliding speeds to promote gentle running-in. Thereafter, the oil is heated to an oil bath temperature of 120°C during still-stand and then stop start sliding is performed up to a maximum speed of 1.2 m / s. Speed ​​ramps are performed as fast as possible to simulate engine stop starts. The total ramp duration from 0 to 1.2 m / s and back lasts for 8 seconds. The test duration varies depending on the number of stop start ramps." Using the TE-92 start / stop test method for SnCu trimetal, the test is run for 10k cycles. Using the TE-92 start / stop test method for polymeric trimetal, the test is run for 40k cycles. The test is run for more cycles for polymeric trimetal materials than for SnCu trimetal materials due to the reduced propensity for stop / start wear.

[0437] Pressure Differential Scanning Calorimetry (PDSC) is an oxidation stability test that measures the oxidation induction time in minutes of a lubricating oil according to test procedure CEC L-85_T-99.

[0438] High Temperature High Shear Viscosity ("HTHS" or "HTHS150") measures the high temperature high shear viscosity of a lubricating oil and is determined at 150°C according to ASTM D4683 and is reported in cPs. Material Component table Example Example 1: Oil candidate of the present invention

[0439] Table 1 below shows the formulations of 0W-16 and 0W-12 lubricating oils (Examples 1 and 2 of the present invention) which include a combination of an overbased magnesium-based detergent and an overbased calcium-based detergent. Examples 1 and 2 have HTHS of 2.30 and 2.13, respectively. 150 Values. Comparative Examples 1-3 are also provided in Table 1 below, which include only calcium-based detergents and no magnesium-based detergents. Comparative Examples 1-3 are 0W-16 or 0W-20 SAE grade engine oils. The additives used in the formulations are shown in Table 1 in weight %. Viscosity properties of the oil of the present invention and one of the comparative oils are also provided in Table 1. Table 1

[0440] The TE-92 start / stop test method described above was used to evaluate the performance of one or two of the embodiments of the present invention and two or three of the comparative examples in the SnCu trimetallic ( Figure 3 ) and polymer three materials ( Figure 4 )The start / stop linkage bearing on the

[0441] The use of a mixture of calcium and magnesium overbased detergents in the range of 50:50 to 65:35 (Ca:Mg) in the low viscosity engine oil formulations of the present invention is useful in the SnCu trimetallic ( Figure 3 ) and polymer bearings ( Figure 4 ) (which represent typical modern bearing systems). For the inventive engine oils of Examples 1 and 2, performance gains can be seen even at the significantly lower viscosity of 0W-12 compared to higher viscosities (in Figure 4 In addition, Figure 3 In the present invention, the effect of magnesium combined with calcium (Oil 1, Example 1) on SnCu trimetallic wear was compared to a comparative engine oil including calcium alone (Oil 2, Comparative Example 1) and competitive oil formulations including calcium alone (Comparative Examples 3 and 4). Compared to the same or higher viscosity comparative engine oil formulations including calcium alone without magnesium, Figure 3 Inventive Oil 1 (0W-16 grade oil containing 940 ppm calcium and 800 ppm magnesium) provided significantly lower (approximately 40% lower) start / stop rod bearing wear on the SnCu tri-metal. This improvement in start / stop rod bearing wear on the SnCu tri-metal for the inventive engine oils including a combination of calcium and magnesium was surprising and unexpected because one skilled in the art would not have expected that the combination of these two metals (Ca and Mg) would reduce journal bearing wear.

[0442] Similarly, in Figure 4The effect of a calcium-magnesium combination (Oil 3, Example 2 of the invention) on polymer tri-material wear is shown in Figure 1 compared to two comparative engine oils including calcium only. Compared to two higher viscosity (0W-16 and 0W-20) comparative engine oil formulations including calcium only without magnesium, Figure 4 Inventive Oil 3 (0W-12 grade oil containing 940 ppm calcium and 800 ppm magnesium) provided significantly lower (approximately 10% lower) start / stop rod bearing wear on the polymer tri-material. This improvement in start / stop rod bearing wear on the polymer tri-material for the inventive engine oils including a combination of calcium and magnesium was also surprising and unexpected because one skilled in the art would not have expected that the combination of these two metals (Ca and Mg) would reduce journal bearing wear.

[0443] Applicants have unexpectedly discovered that the journal bearing wear performance of low viscosity engine oils for internal combustion engines against non-ferrous wear materials can be significantly improved by utilizing in a formulation a combination of an overbased calcium-based detergent having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500 and at a treat rate providing 500 to 1300 ppm by weight of calcium and an overbased magnesium-based detergent having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500 and at a treat rate providing 500 to 1300 ppm by weight of magnesium to the composition, and wherein the total weight of combined calcium and magnesium in the composition is from 1000 ppm to 1800 ppm. Although the journal bearing wear improvement was measured and verified using the TE-92 start / stop test method, it is expected that similar improvements will be seen using other wear test methods, such as the MTM-R wear test method.

[0444] All documents described herein are incorporated herein by reference to the extent that they do not contradict this article, including any priority documents and / or test procedures. It is apparent from the above general description and specific embodiments that, although the form of the present invention has been illustrated and described, various modifications can be made without departing from the spirit and scope of the present invention. Accordingly, it is not intended to limit the present invention thus. The term "comprising" is considered to be synonymous with the term "including". Similarly, as long as the conjunction "comprising" is present before the composition, element or element group, it is to be understood that we also consider the same composition or element group with conjunction "substantially consisting of", "consisting of", "selected from" or "being" before the enumeration of the composition, element or multiple elements, and vice versa.

Claims

1. A lubricating oil composition comprising the following components or a mixture of the following components: 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; an overbased calcium-based detergent having a total base number (KOH / g) greater than, or equal to, 9 and less than, or equal to, 500 and at a treat rate providing 500 to 1300 ppm by weight of calcium to the composition; and an overbased magnesium-based detergent having a total base number (KOH / g) greater than, or equal to, 9 and less than, or equal to, 500 and at a treat rate providing 500 to 1300 ppm by weight of magnesium to the composition; wherein the total weight of calcium and magnesium combined in the composition is from 1000 ppm to 1800 ppm; The lubricating oil composition has a total sulfated ash less than or equal to 1.0 wt %, a high temperature high shear viscosity (HTHS) at 150° C. measured according to ASTM 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 content of less than or equal to 0.080 wt %, and The lubricating oil composition provides a 5% to 60% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 Start / Stop test method compared to a lubricating oil composition having a HTHS equivalent but not comprising a mixture of an overbased calcium-based detergent and an overbased magnesium-based detergent in the composition at a combined calcium and magnesium loading of 1000 ppm to 1800 ppm.

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

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

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

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

6. The lubricating oil composition of claim 1 wherein the overbased calcium-based detergent is a salicylate, the overbased magnesium-based detergent is a salicylate, and the total weight of combined calcium and magnesium in the composition is from 1600 ppm to 1800 ppm.

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

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

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

10. The lubricating oil composition according to claim 1, wherein the lubricating oil composition is used as a passenger vehicle lubricant (PVL) or a commercial vehicle lubricant (CVL).

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

12. The lubricating oil composition of claim 1, wherein the journal bearing shell material is a material selected from the group consisting of bimetal, tri-material / metal, and monolithic material.

13. The lubricating oil composition of claim 12, wherein the three materials / metals are a polymer coating or a SuCu overlay on lead-free bronze.

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

15. The lubricating oil composition according to claim 12, wherein the bulk material is bronze or lead-free bronze.

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

17. The lubricating oil composition of claim 13, wherein the SnCu clad tri-metallic journal bearing shell material provides a 10% to 60% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 start / stop test method compared to a HTHS comparable lubricating oil composition but not comprising a mixture of an overbased calcium-based detergent and an overbased magnesium-based detergent.

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

19. The lubricating oil composition of claim 18, wherein the one or more dispersants are one or more optionally boronated higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersants (Mn of 1600 g / mol or more), one or more optionally boronated lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersants (Mn less than 1600 g / mol), or a combination thereof, and wherein the treat rate of the combination of higher molecular weight PIBSA-PAM and lower molecular weight PIBSA-PAM is from 1.0 to 6.0 weight percent of the composition.

20. The lubricating oil composition of claim 19, wherein the higher molecular weight PIBSA-PAM dispersant, the lower molecular weight PIBSA-PAM dispersant, or a combination thereof is included at a treat rate to provide 20 to 700 ppm by weight of boron to the lubricating oil composition.

21. The lubricating oil composition of claim 18, wherein the one or more antiwear agents include one or more zinc dialkyl dithiophosphates (ZDDPs) that provide a treat rate of less than or equal to 840 ppm by weight of phosphorus to the composition.

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

23. The lubricating oil composition of claim 18, wherein the one or more friction modifiers include a moly dimer, a moly trimer, or a combination thereof providing a treat rate of 12 wt ppm to 1000 wt ppm of molybdenum to the composition.

24. The lubricating oil composition of claim 18, wherein the functionalized polymer is 0.2 to 2.0 wt. % of the composition and comprises an amide, imide and / or ester functionalized partially or fully saturated C 4-5 A polymer of an olefin, the polymer having: i) Mw / Mn less than 2, ii) a functionality distribution (Fd) value of 3.5 or less, and iii) an Mn (GPC-PS) of the polymer before functionalization of 10,000 g / mol or more, Provided that if the polymer prior to functionalization is a copolymer of isoprene and butadiene, the Mn of said copolymer is greater than 25,000 g / mol (GPC-PS).

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

26. A method of reducing journal bearing wear in an internal combustion engine, comprising: A lubricating oil composition according to any one of claims 1 to 24 is provided to an internal combustion engine.

27. A method of making a lubricating oil composition comprising combining or mixing the following components: (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) an overbased calcium-based detergent having a total base number (KOH / g) greater than, or equal to, 9 and less than, or equal to, 500 and at a treat rate providing from 500 to 1300 ppm by weight of calcium to the composition; and (iii) an overbased magnesium-based detergent having a total base number (KOH / g) greater than, or equal to, 9 and less than, or equal to, 500 and at a treat rate providing from 500 to 1300 ppm by weight of magnesium to the composition; wherein the total weight of calcium and magnesium combined in the composition is from 1000 ppm to 1800 ppm; The lubricating oil composition has a total sulfated ash less than or equal to 1.0 wt %, a high temperature high shear viscosity (HTHS) at 150° C. measured according to ASTM 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 content of less than or equal to 0.080 wt %, and The lubricating oil composition provides a 5% to 60% reduction in journal bearing wear as measured by maximum average wear in microns using the TE-92 Start / Stop test method compared to a lubricating oil composition having a HTHS equivalent but not comprising a mixture of an overbased calcium-based detergent and an overbased magnesium-based detergent in the composition at a combined calcium and magnesium loading of 1000 ppm to 1800 ppm.

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