Lubricant composition providing robust (Robust) valve mechanism wear protection in Ford 6.7 L engine tests

Abstract

A lubricant composition that provides robust valve mechanism wear protection in Ford 6.7 L engine tests. The present invention relates to a lubricating oil composition containing less than 1000 ppm phosphorus, comprising or being obtained by mixing A) one or more base oils, B) one or more dispersants wherein the one or more dispersants comprise at least 2.0 mass% of one or more non-boronized poly (alkenyl) succinimides, based on the total mass of the lubricating oil composition, and C) one or more non-boronized poly (alkenyl) succinimides, based on the total mass of the lubricating oil composition, wherein the polyalkenyl is derived from a polyisobutylene and the imide is derived from a polyamine ("PIBSA-PAM"); and C) one or more detergents, wherein the one or more detergents together provide the lubricating oil composition with soap in an amount of 0.1 to 0.9 mass% based on the total mass of the lubricating oil composition; wherein the ratio of the one or more non-boronized PIBSA-PAM of the lubricating oil composition to the mass% of soap based on the total mass of the lubricating oil composition is 6.65 or more.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to the use of a specific ratio of unborated PIBSA - PAM and soap in a lubricant composition having good anti - wear properties, particularly for heavy - duty diesel engine applications. BACKGROUND OF THE INVENTION

[0002] The present invention relates to lubricating oil compositions that exhibit improved anti - wear characteristics even at phosphorus contents below 1000 ppm, such as heavy - duty diesel engine oils. More specifically, the present invention relates to automotive crankcase lubricating oil compositions for natural gas engines, hydrogen engines (H2ICE), gasoline (spark - ignition) and diesel (compression - ignition) internal combustion engines, such compositions being referred to as crankcase lubricants; and to the use of a specific ratio of PIBSA - PAM and soap in such lubricating oil compositions for reducing friction and / or wear between the moving parts of such engines and / or improving the fuel economy performance of engines lubricated with said lubricating oil compositions.

[0003] In the selection of lubricants, engine durability is an important consideration, especially for heavy - duty diesel (HDD) engine applications. Original equipment manufacturers are constantly increasing their oil change intervals, and the average vehicle life has been steadily increasing over the past few decades. Similarly, there is a trend towards using ashless anti - wear agents, which have a lower impact on after - treatment systems such as diesel particulate filters in heavy - duty diesel vehicles.

[0004] Environmental and regulatory requirements drive the need to improve the efficiency of internal combustion engines. Lower - viscosity lubricants require less energy to be pumped around the engine and can thus improve its fuel economy. However, lower - viscosity lubricants result in thinner oil films between the engine contact parts (e.g., in the valve train, piston area, and bearings), which can lead to higher wear rates, reduced friction modification, etc. Conventionally, zinc dialkyldithiophosphate (ZDDP) is often used as a lubricant additive to prevent engine wear and / or reduce friction under boundary lubrication mechanisms.

[0005] In addition to driving the improvement of fuel economy, it is also desirable to reduce emissions from vehicles. The control of exhaust emissions is typically achieved through after - treatment devices such as catalytic converters, which typically use noble - metal catalysts to convert combustion products into less - objectionable species. However, these catalysts are particularly poisoned by phosphorus and sulfur, which affects their catalytic activity. Another after - treatment device is the particulate filter, which can be clogged by sulfate ash or sludge generated by the combustion of heavy - duty diesel engine oils. Therefore, it is desirable to reduce the content of sulfate ash, phosphorus, and sulfur (SAPS) derived from heavy - duty diesel engine oils. ZDDP additives contribute a significant amount of SAPS to lubricating oils, so it is also desirable to reduce the use of ZDDP.

[0006] In December 2016, the American Petroleum Institute (API) released the latest heavy-duty diesel engine oil performance categories: CK-4 and FA-4. Additionally, 800 ppm phosphorus oils have been gaining an increasing market share. Shortly after implementation, Ford Motor Company began to be reluctant to use CK-4 and FA-4 oils with a phosphorus content below 800 ppm, for fear that the phosphorus content was too low to protect its diesel engines from valve train wear. Against this backdrop, Ford developed the Ford 6.7L Power Stroke diesel engine test for soot-induced wear and viscosity control, which evaluates the anti-wear performance of heavy-duty diesel engine oils based on visual inspection of valve train components. The pass criteria for the Ford 6.7L test are: Single test: < 100 mg average rocker arm mass loss Multiple tests: < 115 mg average rocker arm mass loss. Oils that do not meet these targets shall not be approved.

[0007] During engine operation, oil-insoluble oxidation by-products such as soot are generated. Dispersants help keep these by-products suspended or dissolved, thereby reducing their deposition on metal surfaces. Common dispersants include (poly)alkenyl succinic derivatives such as hydrocarbon-substituted succinic anhydrides such as polyisobutylene succinic anhydride (PIBSA), and hydrocarbon-substituted succinimides such as polyisobutylene succinimide (PIBSA-PAM), such as those derived from the reaction of maleated polyisobutylene with N-phenyl-p-phenylenediamine.

[0008] U.S. Patent Application USSN 18 / 480,571, filed on October 4, 2023 (which claims priority to USSN 63 / 379,006, filed on October 11, 2022), discloses the use of amide-, imide- and / or ester-functionalized polymers containing specific C 4-5 olefins as additives in lubricating oil compositions to reduce wear. U.S. Patent Application USSN 63 / 584,675, filed on September 22, 2023, further discloses lubricating oil compositions containing functionalized polymers containing a specific olefin homopolymer or copolymer backbone, while conventional polyalkenyl succinimide dispersants (wherein the polyalkenyl is derived from polyisobutylene and the imide is derived from polyamine (PIBSA-PAM)) are reduced or completely absent.

[0009] There is still a need to provide additional or improved engine / transmission oil compositions that provide excellent anti-wear properties and fuel economy while also maintaining the phosphorus content of the lubricating oil composition below 1000 ppm. In particular, there is still a need to provide engine / transmission oil compositions that pass stringent wear tests, such as the Ford 6.7L Power Stroke diesel engine test for soot-induced wear and viscosity control, while meeting the latest standards of performance categories.

[0010] The inventors of the present invention have surprisingly found that using a specific ratio of unborated PIBSA-PAM dispersant to soap in lubricant compositions, such as heavy-duty diesel engine oils, significantly improves anti-wear properties, thereby providing improved durability. In addition, it has been surprisingly found that using the specific ratio of unborated PIBSA-PAM dispersant to soap in lubricant compositions is beneficial for passing the Ford 6.7L Power Stroke diesel engine test for soot-induced wear and viscosity control, even at a phosphorus content of less than 1000 ppm, such as 800 ppm. Summary of the Invention

[0011] The present invention relates to a lubricating oil composition containing less than 1000 ppm phosphorus (determined by ASTM D5185), which comprises: A) at least 50% by mass, based on the total mass of the lubricating oil composition, of one or more base oils; B) one or more dispersants, wherein the one or more dispersants comprise 2.0 to 6.00% by mass, based on the total mass of the lubricating oil composition, of one or more poly(alkenyl) succinimides, wherein the polyalkenyl is derived from polyisobutene and the imide is derived from polyamine (“PIBSA-PAM”); wherein the one or more PIBSA-PAMs comprise at least 2.0% by mass, based on the total mass of the lubricating oil composition, of one or more unborated PIBSA-PAMs; and C) one or more detergents, wherein the one or more detergents together provide an amount of soap of 0.1 to 0.9% by mass, based on the total mass of the lubricating oil composition, to the lubricating oil composition; wherein: i) the ratio of the one or more unborated PIBSA-PAMs to soap in the lubricating oil composition, by mass%, based on the total mass of the lubricating oil composition, is above 6.65, and ii) the lubricating oil composition has an SAE viscosity grade of 20W-X, 15W-X, 10W-X or 5W-X, where X represents any one of 8, 12, 16, 20, 30 and 40, such as 30 or 40, such as 30.

[0012] The present invention further relates to a lubricating oil composition containing less than 1000 ppm phosphorus (determined by ASTM D5185), which comprises: A) at least 50% by mass, based on the total mass of the lubricating oil composition, of one or more base oils; B) one or more dispersants, wherein the one or more dispersants comprise 2 to 10% by mass, based on the total mass of the lubricating oil composition, of one or more poly(alkenyl)succinimides, wherein the alkenyl is derived from polyisobutene and the imide is derived from a polyamine ("PIBSA-PAM"); wherein the one or more PIBSA-PAMs comprise at least 2.0% by mass, based on the total mass of the lubricating oil composition, of one or more unborated PIBSA-PAMs; and C) one or more detergents, wherein the one or more detergents together provide an amount of soap of 0.1 to 0.9% by mass, based on the total mass of the lubricating oil composition; wherein the one or more detergents comprise less than 50% by mass of calcium salicylate, based on the total mass of the detergents present in the lubricating oil composition; wherein: i) the ratio of the one or more unborated PIBSA-PAMs of the lubricating oil composition to the soap, in % by mass based on the total mass of the lubricating oil composition, is 6.65 or more, and ii) the lubricating oil composition has an SAE viscosity grade of 20W-X, 15W-X, 10W-X or 5W-X, where X represents any one of 8, 12, 16, 20, 30 and 40, such as 30 or 40, such as 30.

[0013] Preferably, the ratio of the one or more unborated PIBSA-PAMs of the lubricating oil composition to the soap, in % by mass based on the total mass of the lubricating oil composition, is 7.0 to 15.0, such as 7.2 to 13.0, such as 7.4 to 11.0, such as 7.6 to 10.0, such as 7.8 to 9.0, such as 8.0 to 8.5.

[0014] The present invention further relates to a lubricating oil composition containing less than 1000 ppm phosphorus (determined by ASTM D5185), which comprises: A) at least 50% by mass, based on the total mass of the lubricating oil composition, of one or more base oils; B) one or more dispersants, wherein the one or more dispersants comprise 2 to 10% by mass, based on the total mass of the lubricating oil composition, of one or more poly(alkenyl)succinimides, wherein the alkenyl is derived from polyisobutene and the imide is derived from a polyamine ("PIBSA-PAM"); wherein the one or more PIBSA-PAMs comprise one or more unborated PIBSA-PAMs in an amount of at least 2.0% by mass based on the total mass of the lubricating oil composition; and C) one or more detergents, wherein the one or more detergents together provide an amount of soap in the lubricating oil composition in the range of 0.1 to 0.9% by mass based on the total mass of the lubricating oil composition; and P) amide-, imide- and / or ester-functionalized polymers comprising a polymer backbone of a partially or fully saturated polymer comprising C 4-5 olefins, the polymer having the following characteristics: i) Mw / Mn is less than 2, ii) the functionality distribution (Fd) value is 3.5 or less, and iii) the Mn of the polymer before functionalization is 10,000 g / mol or more (GPC-PS); wherein: i) the ratio of the mass % of the one or more unborated PIBSA-PAMs to the soap in the lubricating oil composition based on the total mass of the lubricating oil composition is 6.65 or more, and ii) the lubricating oil composition has an SAE viscosity grade of 20W-X, 15W-X, 10W-X or 5W-X, where X represents any one of 8, 12, 16, 20, 30 and 40, such as 30 or 40, such as 30.

[0015] According to another aspect, the present invention provides a concentrate comprising the following components or obtained by mixing the following components: A) one or more base oils in an amount of 1 to less than 50% by mass based on the total mass of the concentrate; B) one or more dispersants, wherein the one or more dispersants comprise one or more unborated poly(alkenyl)succinimides, wherein the polyalkenyl is derived from polyisobutene and the imide is derived from a polyamine ("PIBSA-PAM"); and C) one or more detergents, wherein the one or more detergents provide soap for the concentrate; wherein the one or more detergents comprise less than 50% by mass of calcium salicylate based on the total mass of the detergents present in the concentrate; wherein: i) the ratio of the mass % of the one or more unborated PIBSA-PAMs to the soap in the concentrate based on the total mass of the concentrate is 6.65 or more.

[0016] Preferably, the ratio of the one or more unborated PIBSA-PAMs of the concentrate to the mass % based on the total mass of the concentrate of the soap is from 7.0 to 15.0, such as from 7.2 to 13.0, such as from 7.4 to 11.0, such as from 7.6 to 10.0, such as from 7.8 to 9.0, such as from 8.0 to 8.5.

[0017] According to a further aspect, the present invention provides a lubricating oil composition comprising or consisting of a concentrate as disclosed herein mixed with one or more base oils.

[0018] According to a further aspect, the present invention provides a method of lubricating an internal combustion engine during engine operation, the method comprising: (i) providing to the crankcase of the internal combustion engine a lubricating composition as described herein; (ii) providing fuel in the internal combustion engine; and (iii) combusting the fuel in the internal combustion engine.

[0019] According to a further aspect, the present invention provides a method of improving the antiwear ability of a lubricating oil composition containing (as determined by ASTM D5185) less than 1000 ppm of phosphorus, the method comprising including in the lubricating oil composition: i) at least 50% by mass, based on the total mass of the lubricating oil composition, of one or more base oils; ii) one or more dispersants, wherein the one or more dispersants comprise from 2.0 to 6.00% by mass, based on the total mass of the lubricating oil composition, of one or more poly(alkenyl) succinimides, wherein the polyalkenyl is derived from polyisobutene and the imide is derived from a polyamine ("PIBSA-PAM"); wherein the one or more PIBSA-PAMs comprise at least 2.0% by mass, based on the total mass of the lubricating oil composition, of one or more unborated PIBSA-PAMs; and iii) one or more detergents, wherein the one or more detergents together provide to the lubricating oil composition an amount of soap of from 0.1 to 0.9% by mass based on the total mass of the lubricating oil composition; wherein: i) the ratio of the one or more unborated PIBSA-PAMs of the lubricating oil composition to the mass % based on the total mass of the lubricating oil composition of the soap is above 6.65, and ii) the lubricating oil composition has an SAE viscosity grade of 20W-X, 15W-X, 10W-X or 5W-X, where X represents any one of 8, 12, 16, 20, 30 and 40, such as 30 or 40, such as 30.

[0020] According to a further aspect, the present invention provides a method for improving the anti-wear ability of a lubricating oil composition containing less than 1000 ppm phosphorus (as determined by ASTM D5185), the method comprising including in the lubricating oil composition: i) at least 50% by mass, based on the total mass of the lubricating oil composition, of one or more base oils; ii) one or more dispersants, wherein the one or more dispersants comprise 2 to 10% by mass, based on the total mass of the lubricating oil composition, of one or more poly(alkenyl) succinimides, wherein the alkenyl is derived from polyisobutene and the imide is derived from a polyamine ("PIBSA-PAM"); wherein the one or more PIBSA-PAMs comprise at least 2.0% by mass, based on the total mass of the lubricating oil composition, of one or more unborated PIBSA-PAMs; and iii) one or more detergents, wherein the one or more detergents together provide the lubricating oil composition with an amount of soap of 0.1 to 0.9% by mass, based on the total mass of the lubricating oil composition; wherein the one or more detergents comprise less than 50% by mass of calcium salicylate, based on the total mass of the detergents present in the lubricating oil composition; wherein: i) the ratio of the one or more unborated PIBSA-PAMs of the lubricating oil composition to the soap, in % by mass based on the total mass of the lubricating oil composition, is 6.65 or more, and ii) the lubricating oil composition has an SAE viscosity grade of 20W-X, 15W-X, 10W-X or 5W-X, where X represents any one of 8, 12, 16, 20, 30 and 40, such as 30 or 40, such as 30.

[0021] Preferably, the anti-wear ability is improved such that the valve train rocker arm wear as determined by the Ford 6.7L Valve Train Wear (VTW) test is less than 120 mg, such as less than 110 mg, such as less than 100 mg, such as less than 90 mg, such as less than 80 mg, such as less than 70 mg, such as less than 60 mg, such as less than 50 mg, such as less than 40 mg.

[0022] According to a further aspect, the present invention provides a method for manufacturing a lubricating oil composition containing less than 1000 ppm phosphorus (as determined by ASTM D5185), the method comprising combining: i) at least 50% by mass, based on the total mass of the lubricating oil composition, of one or more base oils; ii) one or more dispersants, wherein said one or more dispersants comprise from 2.0 to 6.00 mass % of one or more poly(alkenyl) succinimides, based on the total mass of the lubricating oil composition, wherein the alkenyl is derived from polyisobutene and the imide is derived from a polyamine ("PIBSA-PAM"); wherein said one or more PIBSA-PAMs comprise at least 2.0 mass % of one or more unborated PIBSA-PAMs, based on the total mass of the lubricating oil composition; and iii) one or more detergents, wherein said one or more detergents together provide an amount of soap of from 0.1 to 0.9 mass %, based on the total mass of the lubricating oil composition; wherein: i) the ratio of the mass % of said one or more unborated PIBSA-PAMs to soap, based on the total mass of the lubricating oil composition, is above 6.65, and ii) the lubricating oil composition has an SAE viscosity grade of 20W-X, 15W-X, 10W-X or 5W-X, where X represents any one of 8, 12, 16, 20, 30 and 40, such as 30 or 40, such as 30.

[0023] According to a further aspect, the present invention provides a method for manufacturing a lubricating oil composition containing less than 1000 ppm phosphorus (as determined by ASTM D5185), the method comprising combining: i) at least 50 mass % of one or more base oils, based on the total mass of the lubricating oil composition; ii) one or more dispersants, wherein said one or more dispersants comprise from 2 to 10 mass % of one or more poly(alkenyl) succinimides, based on the total mass of the lubricating oil composition, wherein the alkenyl is derived from polyisobutene and the imide is derived from a polyamine ("PIBSA-PAM"); wherein said one or more PIBSA-PAMs comprise at least 2.0 mass % of one or more unborated PIBSA-PAMs, based on the total mass of the lubricating oil composition; and iii) one or more detergents, wherein said one or more detergents together provide an amount of soap of from 0.1 to 0.9 mass %, based on the total mass of the lubricating oil composition; wherein said one or more detergents comprise less than 50 mass % of calcium salicylate, based on the total mass of the detergents present in the lubricating oil composition; Wherein: i) the ratio of the mass % of the one or more unborated PIBSA-PAMs and the soap in the lubricating oil composition based on the total mass of the lubricating oil composition is 6.65 or more, and ii) the lubricating oil composition has an SAE viscosity grade of 20W-X, 15W-X, 10W-X or 5W-X, where X represents any one of 8, 12, 16, 20, 30 and 40, such as 30 or 40, such as 30.

[0024] According to a further aspect of the present disclosure, there is provided the use of a lubricating oil composition as described herein, wherein the lubricating oil composition has a valve train rocker arm wear of less than 120 mg, such as less than 110 mg, such as less than 100 mg, such as less than 90 mg, such as less than 80 mg, such as less than 70 mg, such as less than 60 mg, such as less than 50 mg, such as less than 40 mg (determined by the Ford 6.7L Power Stroke diesel engine test for soot-induced wear and viscosity control). Definitions

[0025] For the purposes of this specification and all claims of the present invention, if the following words and expressions are used, they shall have the meanings given hereinafter.

[0026] For the purposes of this document, as described in CHEMICAL AND ENGINEERING NEWS, 63(5), 27(1985), the new numbering scheme for the periodic table of elements is used, i.e., the alkali metals are Group 1 metals (e.g., Li, Na, K, etc.), and the alkaline earth metals are Group 2 metals (e.g., Mg, Ca, Ba, etc.).

[0027] The term "comprising" or any cognate word specifies the presence of the element, step or integer or component, but does not exclude the presence or addition of one or more other elements, steps, integers, components or combinations thereof. The expressions "consisting of" or "consisting essentially of" or cognate words may be subsumed within "comprising" or cognate words, where "consisting essentially of" allows the inclusion of substances that do not materially affect the characteristics of the composition to which it is applied.

[0028] The term "absent" (or "free of") when referring to a component or active ingredient included in the lubricating oil composition described herein and in its claims means that the particular component or active ingredient is present at 0.000 wt% based on the weight of the lubricating oil composition, or if "substantially absent", the component or active ingredient is present in an amount that does not affect the properties of the lubricating oil composition, such as less than 100 ppm, such as less than 10 ppm, less than 1 ppm or less than 0.001 ppm.

[0029] The term "about" means approximate and includes values obtained by rounding. As used herein, the term "about" modifying the amount of a component, ingredient or reactant of the present invention used means a variation in the numerical amount that can occur, for example, by typical measuring and liquid handling procedures used in making the concentrate or lubricating oil composition. In addition, variations may occur due to inadvertent errors in the measuring procedures, differences in the manufacture, source or purity of the ingredients used in making the composition or performing the method, etc. In one aspect, the term "about" means within 10% of the reported numerical value. In another aspect, the term "about" means within 5% of the reported numerical value. In yet another aspect, the term "about" means within 10, 9, 8, 7, 6, 5, 4, 3, 2 or 1% of the reported numerical value.

[0030] The term "LOC" means a lubricating oil composition (this term is used interchangeably herein with the terms "lubricant oil composition" or "lubricating composition" or "lubricant composition").

[0031] The term "major amount" means more than 50% by mass of the composition, such as more than 60% by mass of the composition, such as more than 70% by mass of the composition, such as 80 to 99.009% by mass of the composition, such as 80 to 99.9% by mass of the composition, such as 80 to 99.009% by mass of the composition, based on the mass of the composition.

[0032] The term "minor amount" means 50% by mass or less of the composition; such as 40% by mass or less of the composition; such as 30% by mass or less of the composition, such as 20 to 0.001% by mass, such as 20 to 0.1% by mass, based on the mass of the composition.

[0033] The term "effective amount" with respect to an additive means the amount of such additive in the lubricating oil composition that causes the additive to provide the desired technical effect.

[0034] Unless otherwise specified, the term "mass %" means the mass percentage of a component based on the mass of the composition measured in grams and is interchangeably referred to as weight percentage ("weight %", "wt %" or "% w / w").

[0035] The term "active ingredient" (also referred to as "ai", "a.i.", "AI" or "A.I.") means an additive material that is neither a diluent nor a solvent. For example, a dispersant component in a lubricating oil composition may contain a specific dispersant and a diluent oil (the specific dispersant in the dispersant component is expressed, for example, as a mass % based on the mass of the entire dispersant component including the diluent oil). The active ingredient content in a lubricating oil composition is not the content of the dispersant component including the diluent oil, but the content of the specific dispersant itself. Unless otherwise specified, all amounts, ranges and ratios in this specification and claims refer to the active ingredient. In addition, unless otherwise specified, all active ingredient percentages of additives in an additive component or in a lubricating oil composition or in a concentrate refer to mass %.

[0036] 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 oil at all ratios. However, these mean that they are soluble or stably dispersible in oil, for example, to an extent sufficient to exert their intended effect in the environment of use of the oil. In addition, if desired, the additional incorporation of other additives may also permit the incorporation of higher amounts of a particular additive.

[0037] The term "hydrocarbon" means a compound of hydrogen and carbon atoms. "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 minor amounts (such as where the heteroatoms do not substantially alter the hydrocarbon nature of the hydrocarbon compound) of one or more heteroatoms or heteroatom-containing groups (such as halogens, especially chlorine and fluorine, amino, alkoxy, mercapto, alkylmercapto, nitro, nitroso, sulfoxy, etc.).

[0038] The terms "unborated" and "non-borated" are used interchangeably herein.

[0039] The terms "group" and "radical" are used interchangeably herein.

[0040] The term "hydrocarbyl" means a group containing hydrogen and carbon atoms. Preferably, unless otherwise specified, the group consists essentially of hydrogen and carbon atoms, and more preferably consists only of hydrogen and carbon atoms. Preferably, the hydrocarbyl contains 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, provided that they do not affect the basic hydrocarbyl nature of the hydrocarbyl. Such atoms / groups are known to those skilled in the art (such as halogens, especially chlorine and fluorine, amino, alkoxy, mercapto, alkylmercapto, nitro, nitroso, sulfoxy, etc.).

[0041] The term "alkyl" means a group of carbon and hydrogen (such as C1 to C30 , such as C1 to C 12 group). The alkyl group in the compound is usually directly bonded to the compound via a carbon atom. Unless otherwise specified, the alkyl group can 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 the alkyl group 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.

[0042] The term "alkenyl" refers to a group of carbon and hydrogen having at least one double bond (such as C2 to C 30 group, such as C2 to C 12 group). The alkenyl group in the compound is usually directly bonded to the compound via a carbon atom. Unless otherwise specified, the alkenyl group can be straight-chain (i.e., unbranched) or branched, cyclic, acyclic, or partially cyclic / acyclic.

[0043] The term "alkylene" refers to C1 to C 20 , preferably C1 to C 10 divalent saturated aliphatic group, which can be straight-chain or branched. Representative examples of the alkylene group 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.

[0044] "Olefin", also known as "alkene", is a straight-chain, branched or cyclic hydrocarbon having at least one double bond. "α-olefin" is an olefin having a double bond at the α-position. "Conjugated diene" is an olefin having two double bonds separated by a single bond. For the purposes of this specification and the appended claims, styrene is considered a conjugated diene. For the purposes of this specification and the appended claims, when a polymer or copolymer is said to contain an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an "isoprene" content of 55% to 95% by weight, it is understood that the monomer units in the copolymer are derived from isoprene in the polymerization reaction, and the derived units are present in an amount of 55% to 95% by weight based on the weight of the copolymer. "Polymer" has two or more identical or different monomer units. "Homopolymer" is a polymer having the same monomer units. "Copolymer" is a polymer having two or more monomer units that are different from each other. "Different" used to denote monomer units means that the monomer units differ from each other by at least one atom or are isomerically different. "Isoprene polymer" or "isoprene copolymer" is a polymer or copolymer containing at least 50 mol% isoprene-derived units, "butadiene polymer" or "butadiene copolymer" is a polymer or copolymer containing at least 50 mol% butadiene-derived units, and so on. Similarly, when a polymer is referred to as a "partially or fully saturated polymer containing C 4-5 olefins", the C 4-5 olefins present in such polymer or copolymer are the polymerized form of the olefin, and the polymer has been partially or fully saturated (such as by hydrogenation) after monomer polymerization. The "main chain" of a polymer is the polymer main chain containing monomer units, usually without any (subsequent) functionalization / before any (subsequent) functionalization.

[0045] The term "alkynyl" refers to a C2 to C 30 (such as C2 to C 12 ) group containing at least one carbon-carbon triple bond.

[0046] The term "aryl" refers to a group containing at least one aromatic ring, such as cyclopentadiene, phenyl, naphthyl, anthracenyl, etc. An aryl group is usually a C5 to C 40 (such as C5 to C 18 , such as C6 to C 14 ) aryl group, optionally substituted by one or more hydrocarbon groups, heteroatoms or heteroatom-containing groups (such as halogen, hydroxy, alkoxy and amino). Preferred aryl groups include phenyl and naphthyl and their substituted derivatives, especially phenyl and alkyl-substituted derivatives of phenyl.

[0047] The term "substituted" means that a hydrogen atom has been replaced by a hydrocarbon group, a heteroatom, or a heteroatom-containing group. An alkyl-substituted derivative means that a hydrogen atom has been replaced by an alkyl group. "Alkyl-substituted phenyl" is one in which a hydrogen atom has been replaced by an alkyl group, such as a C1 to C 20 alkyl group, 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.

[0048] The term "halogen" or "halo group" means a Group 17 atom or a group of Group 17 atoms, such as fluorine, chlorine, bromine, and iodine.

[0049] The term "ashless" with respect to an additive means that it does not include a metal.

[0050] The term "ash-containing" with respect to an additive means that it includes a metal.

[0051] Unless otherwise specified, the term "ppm" means parts per million by mass based on the total mass of the lubricating oil composition.

[0052] The "metal content" of a lubricating oil composition or an additive component, such as the magnesium content, the molybdenum content, or the total metal content (i.e., the sum of all individual metal contents), is measured by ASTM D5185.

[0053] The term "aliphatic hydrocarbon-based fatty acid" means a monocarboxylic acid having an aliphatic C7 to C 29 , preferably C9 to C 27 , most preferably C 11 to C 23 hydrocarbon chain. 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 (where Cx to Cy represent the total number of carbon atoms in the aliphatic hydrocarbon radical chain of the fatty acid, and the fatty acid itself includes a total of Cx + 1 to Cy + 1 carbon atoms due to the presence of the carboxyl carbon atom). Preferably, the aliphatic hydrocarbon radical fatty acid, including the carboxyl carbon atom, has an even number of carbon atoms. The aliphatic hydrocarbon radical chain of the fatty acid can be saturated or unsaturated (i.e., includes at least one carbon-carbon double bond); preferably, the aliphatic hydrocarbon radical chain is unsaturated and includes at least one carbon-carbon double bond - such fatty acids can be obtained from natural sources (e.g., derived from animal or vegetable oils) and / or obtained by reduction of the corresponding saturated fatty acids. It is to be recognized that a certain proportion of the aliphatic hydrocarbon radical chains of the corresponding aliphatic hydrocarbon radical fatty acid esters are unsaturated (i.e., include at least one carbon-carbon double bond) to allow reaction with other reagents, such as sulfur, to form the corresponding functionalized (e.g., sulfided) aliphatic hydrocarbon radical fatty acid esters.

[0054] The term "aliphatic hydrocarbon radical fatty acid ester" refers to an ester that can be obtained by converting the monocarboxylic acid functional group of the corresponding aliphatic hydrocarbon radical fatty acid into an ester group. Suitably, the monocarboxylic acid functional group of the aliphatic hydrocarbon radical fatty acid is converted into a hydrocarbyl ester, preferably a C1 to C 30 aliphatic hydrocarbyl ester, such as an alkyl ester, preferably a C1 to C6 alkyl ester, especially a methyl ester. Alternatively or additionally, the monocarboxylic acid functional group of the aliphatic hydrocarbon radical fatty acid can be in the form of a natural glyceride. Accordingly, the term "aliphatic hydrocarbon radical fatty acid ester" includes aliphatic hydrocarbon radical fatty acid glycerides and aliphatic hydrocarbon radical fatty acid C1 to C 30 aliphatic hydrocarbyl esters, [such as aliphatic hydrocarbon radical fatty acid alkyl esters, more preferably aliphatic hydrocarbon radical fatty acid C1 to C6 alkyl esters, especially aliphatic hydrocarbon radical fatty acid methyl esters]. Suitably, the term "aliphatic hydrocarbon radical fatty acid ester" includes aliphatic (C7 to C 29 ) hydrocarbyl, more preferably aliphatic (C9 to C 27 ) hydrocarbyl, most preferably aliphatic (C 11 to C 23 ) hydrocarbyl fatty acid glycerides and aliphatic (C7 to C 29 ) hydrocarbyl, more preferably aliphatic (C9 to C 27 ) hydrocarbyl, most preferably aliphatic (C 11 to C 23 ) hydrocarbyl fatty acid C1 to C 30 aliphatic hydrocarbyl esters. Suitably, in order to allow functionalization of the aliphatic hydrocarbon radical fatty acid ester, such as sulfidation, a certain proportion of the aliphatic hydrocarbon radical chains of the fatty acid ester are unsaturated and include at least one carbon-carbon double bond.

[0055] The term "sulfided aliphatic hydrocarbon radical fatty acid ester" refers to a compound obtained by sulfiding an aliphatic hydrocarbon radical fatty acid ester as defined herein.

[0056] When the term "absent" is used with respect to a monomer reactant and / or with respect to a repeating unit in a (co)polymer described herein, it means present at 0 weight percent based on the weight of all (co)monomers in the (co)polymer, or if present, in such low amounts that they essentially do not affect the physical properties of the (co)polymer, such as less than 0.2 weight percent or less than 0.1 weight percent.

[0057] 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. The molecular weight distribution (MWD), also known as the polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise specified, all molecular weight units (e.g., Mw, Mn, Mz) are reported in g / mol.

[0058] When used in the context of a functionalized polymer (such as a dispersant, a functionalized styrenic polymer, etc.), the molecular weight is typically reported for the base polymer prior to modification. For example, the molecular weight of a PIBSA-PAM dispersant is typically reported for the base polyisobutene polymer prior to functionalization with an acylating agent (maleic acid or anhydride) and a functional group (such as a polyamine).

[0059] With respect to an additive component or a lubricating oil composition (i.e., an unused lubricating oil composition), the total base number, also known as "TBN", is the total base number measured by ASTM D2896 and reported in mgKOH / g.

[0060] The total acid number ("TAN") is determined by ASTM D664.

[0061] As used herein, the term "soap" refers to the amount of the metal salt of the organic acid provided by said one or more detergents, particularly alkali metal or alkaline earth metal salts, excluding any overbased material. The detergent is obtained by neutralizing an organic acid molecule with a metal base. When the detergent is overbased, the organic acid is usually neutralized with a strong metal base in the presence of an acidic gas (usually carbon dioxide). Thus, both the organic acid and the acidic gas are converted into metal salts, and the amount of metal contained in the detergent exceeds the amount required to neutralize the organic acid. The amount of metal salt present in the detergent in addition to the metal salt of the organic acid represents the "alkaline reserve" or "overbasing material" of the detergent. For example, if an overbased detergent is neutralized with a metal base in the presence of carbon dioxide, the overbasing material consists mainly of metal carbonates. In other words, the amount of the detergent (active ingredient) comprises or consists of the amount of the soap of the detergent plus an optional amount of the overbasing material of the detergent. Thus, if a lubricating oil composition or concentrate contains an overbased detergent, based on the total mass of the lubricating oil composition or concentrate, the mass % of the soap is less than the mass % of the detergent. If the lubricating oil composition or concentrate contains only a neutral detergent without any overbasing material, based on the total mass of the lubricating oil composition or concentrate, the mass % of the soap and the mass % of the detergent are similar. The amount of the soap can be determined directly or can be derived from the manufacturing process mass balance. For sulfonates, particularly calcium sulfonate, the amount of the soap can be measured by ASTM D3712. In addition, the amount of the soap can be derived by using titration methods (including two-phase titration methods), such as the total acid number (TAN) determined using ASTM D664, dialysis, and other well-known analytical techniques. The amount of the alkali metal or alkaline earth metal organic salt present in the detergent can be determined by dialyzing the detergent and quantifying the amount of the residue. If the average molecular weight of the organic salt is not known, the residue of the detergent from dialysis can be treated with a strong acid to convert the salt into its acid form, analyzed by chromatography, proton NMR, and mass spectrometry, and correlated with an organic acid of known properties.

[0062] The phosphorus, boron, calcium, zinc, molybdenum, sodium, silicon, and magnesium contents are measured by ASTM D5185.

[0063] The sulfur content in the oil formulation is measured by ASTM D5185.

[0064] The sulfate ash ("SASH") content is measured by ASTM D874.

[0065] Unless otherwise specified, the kinematic viscosities (KV100, KV40) are determined according to ASTM D445-19a and reported in cSt.

[0066] The viscosity index is determined according to ASTM D2270.

[0067] The saponification value is determined by ASTM D94 and reported in mg KOH / g.

[0068] HTCBT, the high temperature corrosion bench test, is determined according to ASTM D6594.

[0069] The average functionality [also referred to as the average functionality value (Fv)] and the functionality distribution (Fd) value are determined by gel permeation chromatography using polystyrene standards as described in the experimental section of U.S. Patent Application USSN 18 / 480,571, filed October 4, 2023, which claims the priority of USSN 63 / 379,006, filed October 11, 2022.

[0070] PIBSA refers to polyisobutylene succinic anhydride.

[0071] PIBSA-PAM refers to polyisobutylene succinimide, e.g., the reaction product of PIBSA and polyamine.

[0072] Unless otherwise specified, all percentages reported are mass % based on the active ingredient, i.e., without considering the carrier or diluent oil, unless otherwise specified. Unless otherwise specified, "mass %" has the same meaning as "weight %" or "wt %" herein.

[0073] It is also understood that the various components (basic as well as optional and conventional) used may react under the formulation, storage, or use conditions, and the present disclosure also provides the products that may be obtained or have been obtained due to any such reaction.

[0074] In addition, it is understood that any upper and lower limits of the amounts, ranges, and ratios listed herein may be combined independently.

[0075] It is also understood that the preferred features of each aspect of the present disclosure are considered to be 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 may be combined independently with the other preferred and / or more preferred features of the same or different aspects of the present disclosure. Detailed Description

[0076] The features of the present disclosure are now described in more detail as follows, which relate to each and all aspects of the present disclosure where appropriate.

[0077] The lubricating oil compositions of the present disclosure contain components that may or may not remain chemically the same before and after mixing with an oily carrier (such as a base oil) and / or other additives. The present disclosure encompasses compositions containing the components before mixing, or the components after mixing, or the components before and after mixing. Lubricating oil composition

[0078] The present disclosure relates to a lubricating oil composition (also referred to as "LOC", "lubricant composition", "lubricating composition" or "lubricant oil composition") containing less than 1000 ppm of phosphorus, which comprises the following components or is obtained by mixing the following components: A) At least 50% by mass of one or more base oils based on the total mass of the lubricating oil composition; B) One or more dispersants, wherein the one or more dispersants comprise 2 to 10% by mass of one or more poly(alkenyl)succinimides based on the total mass of the lubricating oil composition, wherein the alkenyl is derived from polyisobutene and the imide is derived from polyamine ("PIBSA-PAM"); wherein the one or more PIBSA-PAMs comprise at least 2.0% by mass of one or more unborated PIBSA-PAMs based on the total mass of the lubricating oil composition; and C) One or more detergents, wherein the one or more detergents together provide an amount of soap of 0.1 to 0.9% by mass based on the total mass of the lubricating oil composition; wherein: i) the ratio of the mass% of the one or more unborated PIBSA-PAMs to the soap in the lubricating oil composition based on the total mass of the lubricating oil composition is 6.65 or more, wherein the lubricating oil composition preferably exhibits: a) An SAE viscosity grade of 20W-X, 15W-X, 10W-X or 5W-X, where X represents any one of 8, 12, 16, 20, 30 and 40, such as 30 or 40, such as 30; and b) Valve train rocker arm wear of less than 120 mg, such as less than 110 mg, such as less than 100 mg, such as less than 90 mg, such as less than 80 mg, such as less than 70 mg, such as less than 60 mg, such as less than 50 mg, such as less than 40 mg as determined by the Ford 6.7L Power Stroke diesel engine test for soot-induced wear and viscosity control.

[0079] The present disclosure also relates to a lubricating oil composition containing less than 1000 ppm of phosphorus, which comprises the following components or is obtained by mixing the following components: A) At least 50% by mass of one or more base oils based on the total mass of the lubricating oil composition; B) 2 to 15% by mass of one or more dispersants based on the total mass of the lubricating oil composition, wherein the one or more dispersants comprise 2 to 10% by mass of one or more poly(alkenyl)succinimides based on the total mass of the lubricating oil composition, wherein the alkenyl is derived from polyisobutene and the imide is derived from a polyamine ("PIBSA-PAM"); wherein the one or more PIBSA-PAMs comprise at least 2.0% by mass of one or more unborated PIBSA-PAMs based on the total mass of the lubricating oil composition; and C) 0.1 to 5% by mass of one or more detergents based on the total mass of the lubricating oil composition, wherein the one or more detergents together provide an amount of soap of 0.1 to 0.9% by mass based on the total mass of the lubricating oil composition; wherein: i) the ratio of the mass % of the one or more unborated PIBSA-PAMs of the lubricating oil composition to the soap based on the total mass of the lubricating oil composition is above 6.65, wherein the lubricating oil composition preferably exhibits: a) an SAE viscosity grade of 20W-X, 15W-X, 10W-X or 5W-X, where X represents any one of 8, 12, 16, 20, 30 and 40, such as 30 or 40, such as 30; and b) valve train rocker arm wear of less than 120 mg, such as less than 110 mg, such as less than 100 mg, such as less than 90 mg, such as less than 80 mg, such as less than 70 mg, such as less than 60 mg, such as less than 50 mg, such as less than 40 mg as determined by the Ford 6.7L Power Stroke diesel engine test for soot-induced wear and viscosity control.

[0080] The present disclosure also relates to a lubricating oil composition containing less than 1000 ppm of phosphorus, which comprises the following components or is obtained by mixing the following components: A) at least 50% by mass of one or more base oils based on the total mass of the lubricating oil composition; B) 2 to 15% by mass of one or more dispersants based on the total mass of the lubricating oil composition, wherein the one or more dispersants comprise 2 to 10% by mass of one or more poly(alkenyl)succinimides based on the total mass of the lubricating oil composition, wherein the alkenyl is derived from polyisobutene and the imide is derived from a polyamine ("PIBSA-PAM"); wherein the one or more PIBSA-PAMs comprise at least 2.0% by mass of one or more unborated PIBSA-PAMs based on the total mass of the lubricating oil composition; and C) 0.1 to 5% by mass of one or more detergents based on the total mass of the lubricating oil composition, wherein said one or more detergents together provide an amount of soap in the lubricating oil composition in an amount of 0.1 to 0.9% by mass based on the total mass of the lubricating oil composition; D) Optionally, based on the total weight of the lubricating oil composition, 0.01 to 5% by mass (especially 0.01% by weight to about 2.5% by weight, or about 0.02% by weight to about 1.5% by weight, or about 0.03% by weight to about 1.0% by weight, or about 0.04% by weight to about 0.5% by weight, or about 0.05% by weight to about 0.2% by weight) of one or more friction improvers (such as a blend of friction improvers); E) Optionally, based on the total weight of the lubricating oil composition, 0.01 to 10% by weight (especially 0.05 to 5% by weight, or 0.1 to 4.5% by mass, or 0.5 to 4% by weight, or 1 to 3.5% by weight, or 2.5 to 3.5% by weight) of one or more antioxidants (such as a blend of antioxidants); F) Optionally, based on the total weight of the lubricating oil composition, 0.01 to 5% by weight (especially 0.01 to 3% by mass, or 0.1 to 1.5% by mass) of one or more pour point depressants (such as a blend of pour point depressants); G) Optionally, based on the total weight of the lubricating oil composition, 0.001 to 5% by weight (especially 0.002 to 3% by mass, or 0.003 to 1% by mass) of one or more antifoaming agents (such as a blend of antifoaming agents); H) Optionally, based on the total weight of the lubricating oil composition, 0.001 to 10% by weight (especially 0.01 to 6% by weight, or 0.01 to 5% by mass, or 0.1 to 4% by weight, or 0.2 to 2% by weight, or 0.2 to 1% by weight) of one or more viscosity improvers (such as a blend of viscosity improvers); J) Optionally, based on the total weight of the lubricating oil composition, 0.001 to 5% by weight (especially 0.005% by weight to 3.0% by weight, or 0.01 to 1.5% by weight, or 0.03 to 1.0% by weight, or 0.05 to 0.5% by mass) of one or more corrosion inhibitors and / or rust inhibitors (such as a blend of corrosion inhibitors and / or rust inhibitors); K) Optionally, based on the total weight of the lubricating oil composition, 0.001 to 10% by weight (especially 0.01 to 5% by weight, or 0.05 to 3% by mass, or 0.1 to 2% by weight, or 0.4 to 1.2% by weight, or 0.5 to 1.0% by weight, or 0.6 to 0.8% by weight) of one or more antiwear agents (such as a blend of antiwear agents, such as ZDDP); M) Optionally, based on the total weight of the lubricating oil composition, 0.01 to 5% by weight (in particular 0.05 to 2% by mass, or 0.1 to 1% by mass) of one or more seal compatibilizers, such as seal swelling agents, N) Optionally, based on the total weight of the lubricating oil composition, 0.01 to 5% by weight (in particular 0.05 to 3% by mass, or 0.1 to 1% by mass) of one or more extreme pressure agents, O) Optionally, based on the total weight of the lubricating oil composition, 0.01 to 5% by weight (in particular 0.1 to 3% by mass, or 0.1 to 1.5% by mass) of one or more unsaturated C 12 -C 60 hydrocarbons (such as C 12 -C 24 linear alpha-olefins (LAO), oligomers / polymers of polyisobutene, and / or blends thereof), and / or P) Optionally, based on the total weight of the lubricating oil composition, 0.001 to 10% by weight (in particular 0.01 to 6% by mass, or 0.01 to 5% by mass, or 0.05 to 4% by mass, or 0.1 to 3% by mass, or 0.2 to 1.0% by mass, or 0.4 to 0.8% by mass) of one or more functionalized polymers (such as blends of functionalized polymers); wherein: i) the ratio of the mass% of the one or more unborated PIBSA-PAMs to the soap in the lubricating oil composition, based on the total mass of the lubricating oil composition, is 6.65 or more, wherein the lubricating oil composition preferably exhibits: a) an SAE viscosity grade of 20W-X, 15W-X, 10W-X or 5W-X, where X represents any one of 8, 12, 16, 20, 30 and 40, such as 30 or 40, such as 30; and b) valve train rocker arm wear of less than 120 mg, such as less than 110 mg, such as less than 100 mg, such as less than 90 mg, such as less than 80 mg, such as less than 70 mg, such as less than 60 mg, such as less than 50 mg, such as less than 40 mg, as determined by the Ford 6.7L Power Stroke diesel engine test for soot-induced wear and viscosity control.

[0081] In certain embodiments of the lubricating oil composition of the present invention, A) one or more dispersants of the lubricating oil composition of the present invention comprise 2.0 to 6.00% by mass of one or more poly(alkenyl)succinimides based on the total mass of the lubricating oil composition, wherein the polyalkenyl is derived from polyisobutene and the imide is derived from polyamine ("PIBSA-PAM").

[0082] In certain embodiments of the lubricating oil composition of the present invention, A) one or more dispersants of the lubricating oil composition of the present invention comprise 2 to 10% by mass, such as 2.5 to 10% by mass, such as 3 to 8% by mass, such as 3.5 to 6% by mass of one or more poly(alkenyl) succinimides based on the total mass of the lubricating oil composition, wherein the polyalkenyl is derived from polyisobutene and the imide is derived from a polyamine ("PIBSA-PAM"); and B) one or more detergents comprise less than 50% by mass of calcium salicylate based on the total mass of the detergents present in the lubricating oil composition.

[0083] In certain embodiments of the lubricating oil composition of the present invention, A) one or more dispersants of the lubricating oil composition of the present invention comprise 2 to 10% by mass, such as 2.5 to 10% by mass, such as 3 to 8% by mass, such as 3.5 to 6% by mass of one or more poly(alkenyl) succinimides based on the total mass of the lubricating oil composition, wherein the polyalkenyl is derived from polyisobutene and the imide is derived from a polyamine ("PIBSA-PAM"); and The lubricating oil composition further comprises P) an amide-, imide- and / or ester-functionalized polymer comprising a polymer backbone comprising partially or fully saturated C 4-5 olefins, the polymer having the following characteristics: i) Mw / Mn is less than 2, ii) the functionality distribution (Fd) value is 3.5 or less, and iii) the Mn of the polymer before functionalization is 10,000 g / mol or more (GPC-PS).

[0084] For the purposes of the present disclosure, component P) the functionalized polymer is not included in components B, C, D, E, F, G, H, I, J, K, M and / or O above to determine the weight percentages, although they may exhibit similar properties. For example, component P) the functionalized polymer may affect viscosity and may have dispersant activity, but is not included in component B) or H) to determine the weight percentage of the dispersant or viscosity improver.

[0085] In an embodiment, all components D, E, F, G, H, J, K, M, N, O and P are present in addition to the base oil, the one or more detergents and the one or more dispersants described herein.

[0086] In an embodiment, components D, E, F, G, H, K, J and P are present in addition to the base oil, the one or more detergents and the one or more dispersants described herein.

[0087] In an embodiment, in addition to the base oil, the one or more detergents, and the one or more dispersants described herein, components F, G, H, K, and P are present.

[0088] In an embodiment, in addition to the base oil, the one or more detergents, and the one or more dispersants described herein, component K is present.

[0089] In an embodiment, in addition to the base oil, the one or more detergents, and the one or more dispersants described herein, component P is present.

[0090] In the present invention, it has been found that by using the disclosed ratio of unborated PIBSA-PAM dispersant and soap in a lubricating oil composition such as a heavy-duty diesel engine oil, the anti-friction and anti-wear properties of the lubricating oil composition can be significantly improved. Further, it has been found that in the present invention, using the disclosed ratio of unborated PIBSA-PAM dispersant and soap in a lubricant composition such as a heavy-duty diesel engine oil provides favorable anti-wear properties at a phosphorus content of less than 1000 ppm, such as 800 ppm. In particular, it has been found that in the present invention, using the disclosed ratio of unborated PIBSA-PAM dispersant and soap in a lubricant composition such as a heavy-duty diesel engine oil can pass the Ford 6.7L Power Stroke diesel engine test for soot-induced wear and viscosity control at a phosphorus content of less than 1000 ppm, such as 800 ppm.

[0091] In the present invention, it has further been found that when using the disclosed ratio of unborated PIBSA-PAM dispersant and soap in a lubricating oil composition having an SAE viscosity grade of 10W-30 or 5W-30, the above-mentioned improved anti-wear properties can also be obtained.

[0092] In an embodiment, i) the ratio of the one or more unborated PIBSA-PAMs and soap in the lubricating oil composition, based on the total mass of the lubricating oil composition, is from 7.0 to 15.0, such as from 7.2 to 13.0, such as from 7.4 to 11.0, such as from 7.6 to 10.0, such as from 7.8 to 9.0, such as from 8.0 to 8.5.

[0093] Suitably, the lubricant composition may have a total base number (TBN) of from 2 to 15 mg KOH / g, preferably from 5 to 13 mg KOH / g, such as from 6 to 11 mg KOH / g, such as from 7 to 9 mg KOH / g, as measured by ASTM D4739.

[0094] The lubricating composition of the present disclosure may contain a low phosphorus content, i.e., less than 1000, preferably less than 900, more preferably less than 850 parts per million by mass (ppm) of phosphorus, expressed as phosphorus atoms, measured by ASTM D5185, based on the total mass of the lubricating composition.

[0095] Suitably, the lubricant composition may contain 700 ppm to 900 ppm, or 750 ppm to 850 ppm, or about 800 ppm of phosphorus, measured by ASTM D5185.

[0096] Generally, the lubricating composition may contain a low sulfur content. Preferably, the lubricating composition contains at most 0.4, more preferably at most 0.3, most preferably at most 0.2, such as 0.1 to 0.4 mass% of sulfur, measured by ASTM D5185, based on the total mass of the lubricating oil composition.

[0097] Generally, the lubricating composition may contain a low sulfated ash content, such as 1.2% or less, such as 1.0 mass% or less, preferably 0.9 mass% or less, or 0.0001 to 0.9 mass% or less of sulfated ash, measured by ASTM D874-13a(2018), based on the total mass of the lubricating composition.

[0098] Generally, the kinematic viscosity ("KV100") of the lubricating composition at 100 °C may be 2 to 30 cSt (mm 2 / s), such as 2 to 20 cSt (mm 2 / s), such as 5 to 15 cSt (mm 2 / s), such as 7 to 13 cSt (mm 2 / s), such as 9 to 11 cSt (mm 2 / s), such as 9.5 to 10 cSt (mm 2 / s) (determined according to ASTM D 445-19a).

[0099] The lubricating composition disclosed herein, such as a diesel engine lubricating composition, may have a high temperature high shear viscosity (HTHS) of less than 4.5 mPa·s, or less than 4.4 mPa·s, or less than 4.3 mPa·s, or less than 4.2 mPa·s, measured at 150 °C by ASTM D4683. In another embodiment, the HTHS of the lubricating composition is 2.0 to 4.5 mPa·s, or 2.3 to 4.4 mPa·s, or 2.5 to 4.3 mPa·s, or 2.7 to 4.2 mPa·s, such as 2.7 to 3.5 mPa·s or 3.3 to 4.2 mPa·s.

[0100] Preferably, the lubricating composition of the present disclosure can be a multigrade oil specified by the viscosity descriptors SAE 20W-X, SAE 15W-X, SAE 10W-X, SAE 5W-X, or SAE 0W-X, where X represents any one of 8, 12, 16, 20, 30, 40, and 50; the characteristics of different viscosity grades can be found in the SAE J300 classification. Alternatively, the lubricating composition can be in the form of viscosity grades SAE 15W-X, SAE 10W-X, SAE 5W-X, or SAE 0W-X, such as in the form of SAE 10W-X or SAE 5W-X, where X represents any one of 8, 12, 16, 20, 30, 40, and 50. X is preferably 30 or 40. Alternatively, the lubricating composition of the present disclosure can be a multigrade oil specified by the viscosity descriptors SAE 10W-30, 15W-40, 5W-30, 5W-40, 10W-40, 5W-50. (See the standard SAE J300 released by SAE International, formerly known as the Society of Automotive Engineers, in January 2015). In an embodiment, the lubricating oil composition has an SAE viscosity grade of 15W-40, 5W-30, or 10W-30. In a specific embodiment, the lubricating oil composition has an SAE viscosity grade of 10W-30. In another specific embodiment, the lubricating oil composition has an SAE viscosity grade of 5W-30.

[0101] Optionally, the lubricating composition may be absent or substantially absent of phenolic antioxidants.

[0102] Optionally, the lubricating composition may be absent or substantially absent of phenate detergents.

[0103] Optionally, the lubricating composition may be absent of colloidal particles containing ZnO cores.

[0104] In an embodiment, the lubricating oil composition may contain less than 75 ppm boron, or less than 70 ppm boron, or 1 to 70 ppm boron.

[0105] In an embodiment, the lubricating composition of the present disclosure can be a heavy-duty diesel engine oil (e.g., for a heavy-duty diesel vehicle, i.e., an engine of a heavy-duty diesel vehicle with a gross vehicle weight rating of over 10,000 pounds).

[0106] In an embodiment, the lubricating composition of the present disclosure can be a passenger car motor oil.

[0107] In an embodiment, the lubricating composition of the present disclosure can be hydrogen fuel and / or natural gas. Concentrate

[0108] A concentrate, also known as an additive package, adpak or addpack, is a composition having less than 50% by mass (such as less than 40% by mass, such as less than 30% by mass, such as less than 25% by mass, such as less than 20% by mass) of a base oil and lubricant composition additives (as described herein), which is typically subsequently further blended with additional base oil to form a lubricating oil product.

[0109] This disclosure relates to concentrate compositions comprising the following components or made by mixing the following components: A) one or more base oils in an amount of from 1 to less than 50% by mass, based on the total mass of the concentrate; B) one or more dispersants, wherein the one or more dispersants comprise one or more unborated poly(alkenyl) succinimides, wherein the alkenyl is derived from polyisobutene and the imide is derived from a polyamine ("PIBSA-PAM"); and C) one or more detergents, wherein the one or more detergents provide soap for the concentrate; wherein: i) the ratio of the one or more unborated PIBSA-PAM of the concentrate to the mass % of the soap, based on the total mass of the concentrate, is 6.65 or more.

[0110] In an embodiment, this disclosure relates to concentrate compositions comprising the following components or made by mixing the following components: A) one or more base oils in an amount of from 1 to less than 50% by mass, based on the total mass of the concentrate; B) one or more dispersants, wherein the one or more dispersants comprise one or more unborated poly(alkenyl) succinimides, wherein the alkenyl is derived from polyisobutene and the imide is derived from a polyamine ("PIBSA-PAM"); and C) one or more detergents, wherein the one or more detergents provide soap for the concentrate; wherein the one or more detergents comprise less than 50% by mass of calcium salicylate, based on the total mass of the detergents present in the concentrate; wherein: i) the ratio of the one or more unborated PIBSA-PAM of the concentrate to the mass % of the soap, based on the total mass of the concentrate, is 6.65 or more.

[0111] In an embodiment, this disclosure relates to concentrate compositions comprising the following components or made by mixing the following components: A) one or more base oils in an amount of from 1 to less than 50% by mass, based on the total mass of the concentrate; B) one or more dispersants, wherein said one or more dispersants comprise one or more unborated poly(alkenyl) succinimides, wherein the alkenyl is derived from polyisobutene and the imide is derived from a polyamine (“PIBSA-PAM”); and C) one or more detergents, wherein said one or more detergents provide soap for said concentrate; and P) an amide-, imide- and / or ester-functionalized polymer comprising a polymer backbone of a partially or fully saturated C 4-5 -olefin-containing polymer, said polymer having the following characteristics: i) Mw / Mn is less than 2, ii) the functionality distribution (Fd) value is 3.5 or less, and iii) the Mn of the polymer before functionalization is 10,000 g / mol or more (GPC-PS), wherein: i) the ratio of the mass % of said one or more unborated PIBSA-PAM of said concentrate to the soap, based on the total mass of the concentrate, is 6.65 or more.

[0112] Optionally, the concentrate composition of the present invention comprises one or more additional additives selected from friction modifiers, antioxidants, pour point depressants, defoamers, viscosity improvers, corrosion inhibitors, rust inhibitors, antiwear agents, seal compatibilizers, unsaturated C 12 -C 60 -hydrocarbons and functionalized polymers.

[0113] In an embodiment, i) the ratio of the mass % of said one or more unborated PIBSA-PAM of said concentrate to the soap, based on the total mass of the concentrate, is from 7.0 to 15.0, such as from 7.2 to 13.0, such as from 7.4 to 11.0, such as from 7.6 to 10.0, such as from 7.8 to 9.0, such as from 8.0 to 8.5.

[0114] In an embodiment, the concentrate composition may optionally be free of a solvent (such as an aliphatic or aromatic solvent) and / or free of a functionalized base oil.

[0115] Optionally, the concentrate may be free or substantially free of phenolic antioxidants.

[0116] Optionally, the concentrate may be free or substantially free of phenates or detergents.

[0117] Optionally, the concentrate may be free or substantially free of colloidal particles comprising a ZnO core.

[0118] In an embodiment, the concentrate may be absent or substantially absent an unborated PIBSA-PAM in which the polyene group is derived from polyisobutene having a Mn (GPC-PS) of less than 1600 g / mol (“low molecular weight PIBSA-PAM”) and the imide is derived from tetraethylenepentamine.

[0119] In an embodiment, the ratio of the one or more unborated high molecular weight PIBSA-PAMs to the one or more unborated low molecular weight PIBSA-PAMs in the concentrate is less than 3 to 1, such as less than 2.5 to 1, such as less than 2 to 1.

[0120] Further details and preferences regarding the components of the lubricating oil compositions and concentrates of the present invention are described below. A. Base Oil

[0121] The base oil useful herein (also referred to as “base stock”, “lubricating oil base stock” or “oil having lubricating viscosity”) may be a single oil or a blend of oils and is typically the major liquid component of a lubricating composition (also referred to as a lubricant), into which additives and optionally additional oils are incorporated to, for example, manufacture a lubricating composition such as a final lubricant composition, a concentrate or other lubricating composition.

[0122] The base oil may be selected from vegetable oils, animal oils, mineral oils and synthetic lubricating oils and mixtures thereof. Its viscosity ranges from light distillate mineral oils to heavy lubricating oils such as those used in gas engine oils, mineral lubricating oils, motor vehicle oils and heavy duty diesel engine oils. Generally, the kinematic viscosity of the base oil at 100 °C (“KV100”) is 1 to 30 cSt, such as 2 to 25 cSt, such as 5 to 20 cSt (determined 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. Generally, the high temperature high shear (HTHS) viscosity of the base oil at 150 °C is 0.5 to 20 cP, such as 1 to 10 cP, such as 2 to 5 cP (determined according to ASTM D4683-20).

[0123] Generally, when the lubricating oil base stock is used to manufacture a concentrate, it may advantageously be present in an amount to form a concentrate that results in a concentrate containing 5 wt% to 80 wt%, 10 wt% to 70 wt%, or 5 wt% to 50 wt% of active ingredient based on the weight of the concentrate.

[0124] Common oils that can be used as base oils include animal and vegetable oils (such as castor oil and lard), liquid petroleum, and hydrorefined and / or solvent-treated paraffinic, naphthenic, and mixed paraffin-naphthenic mineral lubricating oils. Oils derived from coal or shale are also available as base oils. Base stocks can be manufactured using a variety of different methods, including but not limited to distillation, solvent refining, hydroprocessing, oligomerization, esterification, and re-refining.

[0125] Synthetic lubricating oils that can be used as base oils in this document include hydrocarbon oils such as homopolymers and copolymers of olefins, known as polyalphaolefins or PAO 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 PAO that can be used as base oils include: poly(ethylene), ethylene-propylene copolymer, polybutene, polypropylene, propylene-isobutylene copolymer, chlorinated polybutene, poly(1-hexene), poly(1-octene), poly(1-decene), homopolymers or copolymers of C8 to C 20 olefins, C8 and / or C 10 and / or C 12 olefins, C8 / C 10 copolymers, C8 / C 10 / C 12 copolymers and C 10 / C 12 copolymers, as well as their derivatives, analogs, and homologs.

[0126] In another embodiment, the base oil can comprise polyalphaolefins, including oligomers of linear olefins having 6 to 14 carbon atoms, more preferably 8 to 12 carbon atoms, and even more preferably 10 carbon atoms, which have a kinematic viscosity (measured by ASTM D445) of more than 10 at 100 °C; preferably having a viscosity index ("VI") of more than 100, preferably more than 110, more preferably more than 120, more preferably more than 130, and even more preferably more than 140, as determined by ASTM D2270; and / or having a pour point of less than -5 °C (measured by ASTM D97), more preferably less than -10 °C, and even more preferably less than -20 °C.

[0127] In another embodiment, the polyalphaolefin oligomers that can be used in the present disclosure can 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 500Paraffins. PAO oligomers are in one embodiment C5 to C 14 alpha-olefins, and in another embodiment C6 to C 12 alpha-olefins, and in another embodiment C8 to C 12 dimers, trimers, tetramers, pentamers, etc. of alpha-olefins. Suitable olefins include 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene. In one embodiment, the olefins are a combination of 1-octene, 1-decene, and 1-dodecene, or can be substantially 1-decene, and the PAO is a mixture of its dimers, trimers, tetramers, and pentamers (and higher). Available PAOs are more particularly described, for example, in 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).

[0128] PAOs useful in the present disclosure generally have a number average molecular weight of in one embodiment 100 to 21,000 g / mol, and in another embodiment 200 to 10,000 g / mol, and in yet another embodiment 200 to 7,000 g / mol, and in yet another embodiment 200 to 2,000 g / mol, and in yet another embodiment 200 to 500 g / mol. Desirable PAOs are available as SpectraSyn TM Hi-Vis, SpectraSyn TM Low-Vis, SpectraSyn TM plus, SpectraSyn TM ElitePAO's (ExxonMobil Chemical Company, Houston Texas) and Durasyn PAO's from Ineos Oligomers USA LLC.

[0129] 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); polyphenyls (biphenyls) (e.g., biphenyl, terphenyl, alkylated polyphenyls); and alkylated diphenyl ethers and alkylated diphenyl sulfides; as well as their derivatives, analogs, and homologs.

[0130] Another class of suitable synthetic lubricating oils that can be used as base oils includes esters formed by reacting dicarboxylic acids (such as phthalic acid, succinic acid, alkyl succinic acid and alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid) with various alcohols (such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of these esters include dibutyl adipate, bis(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, didocosyl 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.

[0131] Esters that can be used as synthetic oils herein also include those made from C5 to C 12 monocarboxylic acids and polyols and polyol ethers (such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol).

[0132] Desirable ester base oils are available as Esterex TM Esters (ExxonMobil Chemical Company, Houston, Texas).

[0133] Silicone oils, such as polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxy-silicone oils and silicate oils, constitute another class of useful synthetic lubricants that can be used herein; such oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) silicate, tetra-(p-tert-butylphenyl) silicate, hexakis-(4-methyl-2-ethylhexyl) disiloxane, poly(methyl)siloxane and poly(methylphenyl)-siloxane.

[0134] Other synthetic lubricating oils that can be used herein include liquid esters of phosphorus-containing acids (such as tricresyl phosphate, trioctyl phosphate, diethyl decylphosphonate) and polymeric tetrahydrofuran.

[0135] Unrefined oils, refined oils, and re-refined oils can be used in the lubricating compositions of the present disclosure. Unrefined oils are those that are obtained directly from natural or synthetic sources without further purification treatment. For example, shale oil obtained directly from a dry distillation operation, petroleum obtained directly from distillation, or ester oils obtained directly from an esterification process and used without further treatment are considered unrefined oils. Refined oils are similar to unrefined oils, except that they have been further processed 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 a process similar to the process used to obtain refined oils, where the refining process is applied to a refined oil that has been previously put into use. Such re-refined oils are also known as regenerated oils or reprocessed oils and are typically further processed to remove spent additives and oil cracking products. The re-refined base oil is preferably substantially free of materials introduced by manufacture, contamination, or previous use.

[0136] Some other examples of available base oils are gas-to-liquid (“GTL”) base oils, i.e., the base oil is derived from hydrocarbons made from synthesis gas (“syn gas”) containing H2 and CO using a Fischer-Tropsch catalyst. These hydrocarbons typically need to be further processed to 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 regarding available GTL base oils and their blends, see U.S. Patent No. 10,913,916 (column 4, line 62 to column 5, line 60) and U.S. Patent No. 10,781,397 (column 14, line 54 to column 15, line 5, and column 16, line 44 to column 17, line 55).

[0137] In particular, oils from renewable sources, i.e., those that are partially based on carbon and energy captured from the environment, such as biogenic sources, are available herein.

[0138] Various base oils are typically classified as Group I, Group II, Group III, Group IV, or Group V according to the API EOLCS 1509 definition (American Petroleum Institute Publication 1509, see Section E.1.3, 19th Edition, January 2021, www.API.org). Generally speaking, Group I base stocks have a viscosity index between approximately 80 and 120 and contain more than approximately 0.03% sulfur and / or less than approximately 90% saturates. Group II base stocks have a viscosity index between approximately 80 and 120 and contain less than or equal to approximately 0.03% sulfur and greater than or equal to approximately 90% saturates. Group III base stocks have a viscosity index greater than approximately 120 and contain less than or equal to approximately 0.03% sulfur and greater than approximately 90% saturates. Group IV base stocks include polyalphaolefins (PAO). Group V base stocks include base stocks not included in Groups I - IV. (The 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).

[0139] The base oils useful in the formulated lubricating compositions of the present disclosure are any one, two, three, or more of the various oils described herein. In an ideal embodiment, the base oils useful in the formulated lubricating compositions of the present disclosure are those described as API Group I, Group II, Group III (including Group III+), Group IV, and Group V oils and mixtures thereof, preferably Group II, Group III, Group IV, and Group V oils and mixtures thereof, and more preferably Group III, Group III+, Group IV, and Group V base oils due to their excellent volatility, stability, viscosity, and cleanliness characteristics. Small amounts of Group I base stocks are admissible, such as amounts used to dilute additives for incorporation into formulated lubricating oil products, but are typically kept to a minimum, e.g., only amounts related to their use as diluent / carrier oils for additives used on an "as - received" basis. With respect to Group II stocks, it is generally more useful that the Group II base stocks be in the higher quality range associated with that stock, i.e., Group II stocks having a viscosity index of 100 to 120.

[0140] The base oil available for use in this article may be selected from any synthetic oil, natural oil or re-refined oil (such as those commonly used as crankcase lubricants for spark-ignition and compression-ignition engines). If desired, a mixture of synthetic oil and / or natural oil and / or re-refined base oil may be used. If desired, a multi-modal mixture (such as a bimodal or trimodal mixture) of Group I, II, III, IV and / or V base stocks may be used.

[0141] The base oil or base oil blend used in this article conveniently has a kinematic viscosity at 100 °C (KV100, measured according to ASTM D445-19a and reported in centistokes (cSt) or its equivalent unit mm2 / s) of about 2 to about 40 cSt, or 3 to 30 cSt, or 4 to 20 cSt, or 5 to 10 cSt at 100 °C, or the base oil or base oil blend may have a kinematic viscosity at 100 °C of 2 to 20 cSt, 2.5 to 2 cSt, preferably about 2.5 cSt to about 9 cSt.

[0142] The base oil or base oil blend preferably has a saturate content of at least 65 mass%, more preferably at least 75 mass%, such as at least 85 mass%, such as at least 90 mass% as determined by ASTM D2007.

[0143] 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.

[0144] 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.

[0145] In an embodiment, the viscosity index (VI) of the base oil is at least 95, preferably at least 110, more preferably at least 120, still more preferably at least 125, most preferably about 130 to 240, especially about 105 to 140 (determined by ASTM D2270).

[0146] Base oil can be provided in a major amount and combined with a minor amount of one or more additive components as described below to form a lubricant. This preparation can be achieved by adding the additives directly to the oil or by adding the one or more additives in the form of their concentrates to disperse or dissolve the additives. The additives can be added to the oil by any method known to those skilled in the art before, simultaneously with, or after adding other additives.

[0147] Base oil can be provided in a minor amount and combined with a minor amount of one or more additive components as described below to form an additive concentrate. This preparation can be achieved by adding the additives directly to the oil or by adding the one or more additives in the form of their solutions, slurries, or suspensions to disperse or dissolve the additives in the oil. The additives can be added to the oil by any method known to those skilled in the art before, simultaneously with, or after adding other additives.

[0148] 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 at least 50% by weight, such as from about 50 to about 99% by weight, preferably from about 70 to about 95% by weight, more preferably from about 80 to about 95% by weight, based on the total weight of the composition. In certain embodiments, the lubricating oil composition of the present disclosure comprises from 50 to 95% by mass, such as from 60 to 90% by mass, such as from 70 to 85% by mass, of one or more base oils, based on the total mass of the lubricating oil composition.

[0149] The base oil of the present invention can consist entirely of one or more Group II base oils, one or more Group III base oils, or a mixture of one or more Group II base oils and one or more Group III base oils. In certain embodiments, the base oil comprises at least 50% by mass, such as at least 70% by mass, such as at least 90% by mass, of one or more Group II base oils (based on the total mass of the base oils present in the lubricating oil composition). In certain embodiments, the base oil is a mixture of one or more Group II base oils and one or more Group III base oils, wherein the base oil comprises at least 50% by mass, such as at least 70% by mass, such as at least 90% by mass, of one or more Group II base oils (based on the total mass of the base oils present in the lubricating oil composition). In certain embodiments, the base oil is entirely one or more Group II base oils. In certain embodiments, the lubricating oil composition of the present invention comprises at least 50% by mass, such as at least 60% by mass, such as at least 65% by mass, of Group II base oils, based on the total mass of the lubricating oil composition.

[0150] In certain embodiments, the Group II base oil comprises at least 10%, such as at least 25%, such as at least 50%, such as at least 75%, up to 100% (based on the total mass of the base oil present in the lubricating oil composition) of Group II base oil having a viscosity of 6 to 7 cSt, such as 6.5 cSt and / or Group II base oil having a viscosity of 4 to 5 cSt, such as 4.6 cSt. In certain embodiments, the lubricating oil composition comprises at least 45% by mass of Group II oil having a viscosity of less than 6.5 cSt, such as less than 6.0 cSt, such as less than 5.5 cSt, such as less than 5.0 cSt.

[0151] The above base oils and their blends can also be used to manufacture concentrates and to manufacture lubricants therefrom.

[0152] Concentrates constitute a convenient means for handling additives prior to their use and for facilitating the dissolution or dispersion of additives in lubricants. When preparing lubricants containing more than one type of additive (sometimes referred to as "additive components"), each additive can be incorporated separately in the form of a concentrate. However, in many cases, it is convenient to provide a so-called additive "package" (also referred to as an "addpack") that contains one or more of the additives / co-additives described below in a single concentrate.

[0153] Typically, one or more base oils are present in the concentrate composition in an amount of less than 50% by weight, or less than 40% by weight, or less than 30% by weight, or less than 20% by weight, based on the total weight of the concentrate composition. Typically, one or more base oils are present in the concentrate composition in an amount of 0.1 to 49% by mass, or 5 to 40% by mass, or 10 to 30% by mass, or 15 to 25% by mass, based on the weight of the concentrate composition.

[0154] In the present disclosure, for the sake of clarity, any diluent used to dilute the active ingredients in the components of the lubricating oil composition or the components of the concentrate of the present invention is not considered to be a "base oil" in the sense of a separate component as described herein. B. Dispersants

[0155] During engine operation, oil-insoluble oxidation by-products are generated. Dispersants help keep these by-products in solution, thereby reducing their deposition on metal surfaces. The dispersants used in the formulation of the lubricating compositions herein can be ashless or ash-forming in nature. The dispersants are preferably ashless. So-called ashless dispersants are organic materials that form substantially no ash upon combustion. For example, metal-free dispersants or borated metal-free dispersants are considered ashless. In contrast, metal-containing detergents tend to form ash upon combustion.

[0156] Dispersants useful herein generally contain polar groups attached to relatively high molecular weight hydrocarbon chains. The polar groups generally contain at least one element of nitrogen, oxygen or phosphorus. Typical hydrocarbon chains contain from 40 to 500, such as 50 to 400 carbon atoms. (Poly)alkenyl succinic derivative dispersants

[0157] A particularly useful class of dispersants includes (poly)alkenyl succinic derivatives typically made by the reaction of a succinic compound (usually a hydrocarbyl-substituted succinic anhydride) substituted by a long-chain hydrocarbyl group with a polyhydroxy or polyamino compound. The long-chain hydrocarbyl group that constitutes the lipophilic part of the molecule (which provides oil solubility) is typically a polyisobutylene group (the long-chain hydrocarbyl group, such as a polyisobutylene group typically has a Mn of 400 to 3000 g / mol, such as 450 to 2500 g / mol). Many examples of this type of dispersant are known in the commercial and 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, which are hereby incorporated by reference.

[0158] Hydrocarbyl-substituted succinic acids and hydrocarbyl-substituted succinic anhydride derivatives are useful dispersants. In particular, succinimides, succinate esters, or succinate amides prepared by the reaction of a hydrocarbyl-substituted succinic acid or anhydride compound (which typically has 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 alkylene amine, are particularly useful herein. Hydrocarbyl-substituted succinic acids 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.

[0159] The succinimides particularly useful herein are formed by a 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 are available under trade names such as HPA TM and HPA-X TM from Dow Chemical, and under the name E-100 TM 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. Patent No. 4,873,009. Examples of polyoxyalkylene polyamines include polyoxyethylene and / or polyoxypropylene diamines and triamines (and their co-oligomers) having an average Mn of about 200 to about 5000 g / mol. Products of this type are available under the trade name Jeffamine TM and can be obtained. 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 Canadian Patent No. 1,094,044.

[0160] The dispersant may comprise one or more optionally borated higher molecular weight succinimides (Mn above 1600 g / mol, such as 1800 to 3000 g / mol) and one or more optionally borated lower molecular weight succinimides (Mn less than 1600 g / mol), 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. In certain embodiments, the higher molecular weight succinimide dispersant is 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 1.2 to 4 wt%, or 1.5 to 3.0 wt%. In certain embodiments, the higher molecular weight succinimide dispersant is 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 1.2 to 4 wt%, or 1.5 to 3.0 wt%; the lower 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 1.2 to 4 wt%, or 1.5 to 3.0 wt%. The lower molecular weight succinimide may differ from the higher molecular weight succinimide by more than 500 g / mol, such as by more than 750 g / mol, such as by more than 1000 g / mol, such as by more than 1200 g / mol, such as by 500 to 3000 g / mol, such as by 750 to 2000 g / mol, such as by 1000 to 1500 g / mol.

[0161] Succinic 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.

[0162] The succinic ester amides useful herein are formed by the condensation reaction between a hydrocarbyl-substituted succinic anhydride and an alkanolamine. Suitable alkanolamines include ethoxylated polyalkylpolyamines, propoxylated polyalkylpolyamines, and polyenepolyamines, such as polyethylenepolyamines and / or propoxylated hexamethylenediamine. Representative examples are shown in U.S. Patent No. 4,426,305.

[0163] Hydrocarbyl-substituted succinic anhydride (such as 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 columns 2, line 65 to column 6, line 22 and column 23, line 40 to column 26, line 46. In particular, the PIBSA ester of methylene-bridged naphthoxy ethanol (i.e., 2-hydroxyethyl-1-naphthol ether (or hydroxy-terminated naphthol ethylene oxide oligomer ether)) can be used herein. In certain embodiments of the present invention, the lubricating oil composition or concentrate does not contain or substantially does not contain the PIBSA ester of methylene-bridged naphthoxy ethanol, such as less than 0.6% by mass, such as less than 0.4% by mass, such as less than 0.2% by mass, such as less than 0.1% by mass, based on the total mass of the lubricating oil composition. In certain embodiments, the lubricating oil composition or concentrate is free or substantially free of the PIBSA ester of methylene-bridged naphthoxy ethanol.

[0164] The molecular weight of the hydrocarbyl-substituted succinic anhydride used in the previous paragraphs is generally 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 derivatives can be post-reacted with various reagents such as sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid.

[0165] The above (poly)alkenyl succinic derivatives can also be post-reacted with boron compounds such as boric acid, borate esters or hyperborated dispersants to form borated dispersants that generally have from about 0.1 to about 5 moles of boron / mole of dispersant reaction product.

[0166] Dispersants useful herein include borated succinimides, including those derivatives from mono-succinimides, bis-succinimides and / or mixtures of mono-succinimides and bis-succinimides, wherein the hydrocarbyl succinimides are derived from a hydrocarbylene group having a Mn of about 300 to about 5000 g / mol, or about 500 to about 3000 g / mol, or about 700 to about 2000 g / mol, such as polyisobutene, or mixtures of such hydrocarbylene groups that generally have high terminal vinyl.

[0167] The dispersants together can be present in the lubricant in an amount of 2% to 20% by mass, such as 2 to 15% by mass, such as 2 to 10% by mass, such as 3 to 8% by mass, such as 4 to 6% by mass, such as 4.5 to 5.5% by mass, based on the total mass of the lubricating oil composition.

[0168] The boron-containing dispersant may be present in an amount of 0.01 wt% to 20 wt%, or 0.02 wt% to 15 wt%, or 0.04 wt% to 10 wt%, or 0.06 wt% to 5 wt%, or 0.08 wt% to 1 wt%, or 0.1 wt% to 0.5 wt% based on the total mass of the lubricating composition.

[0169] The boron-containing dispersant may be present in an amount that provides 15 ppm to 2000 ppm, or 25 ppm to 1000 ppm, or 40 ppm to 600 ppm, or 45 ppm to 350 ppm, or 50 ppm to 150 ppm, or 60 ppm to 100 ppm of boron to the composition.

[0170] The borated dispersant may be used in combination with a non-borated dispersant and may be the same or a different compound from the non-borated dispersant. In one embodiment, the lubricating composition may include one or more boron-containing dispersants and one or more non-borated dispersants, wherein the total amount of the dispersants may be 2 wt% to 20 wt%, such as 2 to 15 wt%, such as 2 to 10 wt%, such as 3 to 8 wt%, such as 4 to 6 wt%, such as 4.5 to 5.5 wt% based on the total mass of the lubricating oil composition, and wherein the ratio of the borated dispersant to the non-borated dispersant may be at most 1:40 (weight:weight) or at most 1:30, or at most 1:20, such as 1:10 to 1:30, or 1:15 to 1:20.

[0171] The dispersant of the present invention comprises one or more unborated (and optionally one or more borated) poly(vinyl) succinimides, wherein the polyvinyl is derived from polyisobutene and the imide is derived from a polyamine ("PIBSA-PAM").

[0172] The dispersant may comprise one or more PIBSA-PAMs, wherein the PIB is derived from polyisobutene having a 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 borated, typically at a level of up to 4 mass%, such as 1 to 3 mass%. The dispersant may comprise one or more borated PIBSA-PAMs and one or more non-borated PIBSA-PAMs. The dispersant may comprise one or more borated PIBSA-PAMs derived from PIB having a Mn of 700 to 1800 g / mol (such as 800 to 1500 g / mol) and one or more non-borated PIBSA-PAMs derived from PIB having a Mn of greater than 1800 to 5000 g / mol (such as 2000 to 3000 g / mol). The dispersant may comprise one or more non-borated PIBSA-PAMs derived from PIB having a Mn of 700 to 1800 g / mol (such as 800 to 1500 g / mol) and one or more borated PIBSA-PAMs derived from PIB having a Mn of greater than 1800 to 5000 g / mol (such as 2000 to 3000 g / mol).

[0173] The dispersant may comprise PIBSA derived from PIB having a Mn of 700 to 5000 g / mol (such as 800 to 3000 g / mol) and one or more borated or non-borated PIBSA-PAMs derived from PIB having a Mn of 700 to 5000 g / mol.

[0174] The dispersant may comprise PIBSA derived from PIB having a Mn of 700 to 5000 g / mol (such as 800 to 3000 g / mol) and one or more boronated PIBSA-PAMs derived from PIB having a Mn of 700 to 1800 g / mol (such as 800 to 1500 g / mol) and one or more non-boronated PIBSA-PAMs derived from PIB having a Mn greater than 1800 to 5000 g / mol (such as 2000 to 3000 g / mol). The dispersant may comprise PIBSA derived from PIB having a Mn of 700 to 5000 g / mol (such as 800 to 3000 g / mol), one or more non-boronated PIBSA-PAMs derived from PIB having a Mn of 700 to 1800 g / mol (such as 800 to 1500 g / mol) and one or more boronated PIBSA-PAMs derived from PIB having a Mn greater than 1800 to 5000 g / mol (such as 2000 to 3000 g / mol).

[0175] The dispersant may comprise one or more boronated or non-boronated PIBSA-PAMs and one or more PIBSA esters of a hydrocarbyl-bridged aryloxy alcohol. In certain embodiments, the dispersant does not contain or substantially does not contain PIBSA esters of a hydrocarbyl-bridged naphthyloxy alcohol, such as less than 0.6 mass%, such as less than 0.4 mass%, such as less than 0.2 mass%, such as less than 0.1 mass% based on the total mass of the lubricating oil composition. In certain embodiments, the lubricating oil composition or concentrate does not contain or substantially does not contain an aromatic dispersant, such as less than 0.5 mass%, such as less than 0.2 mass%, such as less than 0.1 mass% of an aromatic dispersant based on the total mass of the lubricating oil composition.

[0176] The dispersant may comprise one or more borated PIBSA-PAMs and one or more non-borated PIBSA-PAMs. Preferably, the unborated and borated PIBSA-PAMs of the lubricating oil composition are present together in an amount of 2.5 to 10% by mass, such as 3 to 8% by mass, such as 3.5 to 6% by mass. In an embodiment, the unborated and borated PIBSA-PAMs of the lubricating oil composition are present together in an amount of 2.0 to 6.00% by mass, such as 2.5 to 5.8% by mass, such as 3.0 to 5.5% by mass, such as 3.5 to 5.2% by mass, such as 4.0 to 5.0% by mass, such as 4.2 to 4.8% by mass, based on the total mass of the lubricating oil composition. Preferably, the one or more unborated PIBSA-PAMs are present in an amount of at least 2.0% by mass, such as 2.5 to 5.5% by mass, such as 3.5 to 5.0% by mass, such as 4.0 to 5.0% by mass, based on the total mass of the lubricating oil composition. Preferably, the one or more borated PIBSA-PAMs are present in an amount of 0.05 - 0.5% by mass, such as 0.1 - 0.4% by mass, such as 0.15 - 0.3% by mass, such as 0.2 - 0.25% by mass, based on the total mass of the lubricating oil composition.

[0177] The dispersant may comprise one or more unborated PIBSA-PAMs (“high molecular weight PIBSA-PAM”) in which the polyvinyl group is derived from polyisobutene having an Mn (GPC-PS) of more than 1600 g / mol, one or more unborated PIBSA-PAMs (“low molecular weight PIBSA-PAM”) in which the polyvinyl group is derived from polyisobutene having an Mn (GPC-PS) of less than 1600 g / mol, and optionally one or more borated low molecular weight and / or high molecular weight PIBSA-PAMs, wherein the higher molecular weight may be from 1600 to 3000 g / mol, such as from 1700 to 2800 g / mol, such as from 1800 to 2500 g / mol, such as from 2000 to 2300 g / mol; the lower molecular weight may be from 600 to less than 1600 g / mol, such as from 650 to 1500 g / mol, such as from 700 to 1400 g / mol, such as from 750 to 1300 g / mol, such as from 800 to 1200 g / mol, such as from 850 to 1150 g / mol, such as from 900 to 1000 g / mol. The higher molecular weight PIBSA-PAM dispersant may be present in the lubricating composition in an amount of 0.5 to 10 wt%, or 0.5 to 4 wt%, such as 1.0 to 3.5 wt%, such as 1.5 to 3.0 wt%, such as 2.0 to 2.5 wt% based on the total mass of the lubricating oil composition; the lower molecular weight PIBSA-PAM dispersant may be present in the lubricating composition in an amount of 0.5 to 4 wt%, such as 1 to 3 wt%, such as 1.8 to 2.5 wt% based on the total mass of the lubricating oil composition. Preferably, the one or more unborated PIBSA-PAMs of the lubricating oil composition comprise one or more unborated high molecular weight PIBSA-PAMs in an amount of 0.5 to 4 wt%, such as 1.0 to 3.5 wt%, such as 1.5 to 3.0 wt%, such as 2.0 to 2.5 wt% based on the total mass of the lubricating oil composition. More preferably, the one or more unborated PIBSA-PAMs of the lubricating oil composition comprise one or more unborated high molecular weight PIBSA-PAMs in an amount of 0.5 to 4 wt%, such as 1.0 to 3.5 wt%, such as 1.5 to 3.0 wt%, such as 2.0 to 2.5 wt% based on the total mass of the lubricating oil composition and one or more unborated low molecular weight PIBSA-PAMs in an amount of 0.5 to 4 wt%, such as 1 to 3 wt%, such as 1.8 to 2.5 wt% based on the total mass of the lubricating oil composition. In certain embodiments, the dispersant used in the lubricating oil compositions and concentrates of the present invention comprises, particularly consists of, a first higher molecular weight PIBSA-PAM and second and third lower molecular weight PIBSA-PAMs (optionally, one of which is borated), wherein preferably the ratio of the higher molecular weight PIBSA PAM to the lower molecular weight PIBSA-PAM is from about 1:1 to about 2:3.Preferably, the dispersants used in the lubricant oil compositions and concentrates of the present invention comprise a first PIBSA-PAM dispersant derived from 1800 to 2500 Mn PIB and second and third PIBSA-PAM dispersants derived from PIB having a Mn of less than 1600, particularly consisting of them, wherein at least one of the second PIBSA-PAM dispersant and the third PIBSA-PAM dispersant is unborated (optionally, at least one of the second PIBSA-PAM dispersant and the third PIBSA-PAM dispersant is borated). More preferably, the dispersants used in the lubricant oil compositions and concentrates of the present invention comprise a first unborated PIBSA-PAM dispersant derived from 2200 Mn PIB, a second unborated PIBSA-PAM dispersant derived from 950 Mn PIB, and a third unborated PIBSA-PAM dispersant derived from 950 Mn PIB, particularly consisting of them.

[0178] In particular, it has been found that a specific ratio of unborated PIBSA-PAM to soap provides a lubricating oil composition, particularly a lubricating oil composition having less than 1000 ppm, such as 700 ppm to 900 ppm phosphorus, with favorable antiwear properties. Accordingly, preferably, the one or more unborated PIBSA-PAMs of the lubricating oil composition of the present invention are present in an amount such that the ratio of the one or more unborated PIBSA-PAMs of the lubricating oil composition to the mass % of soap, based on the total mass of the lubricating oil composition, is 7.0 to 15.0, such as 7.2 to 13.0, such as 7.4 to 11.0, such as 7.6 to 10.0, such as 7.8 to 9.0, such as 8.0 to 8.5.

[0179] In certain embodiments, the ratio of the one or more unborated high molecular weight PIBSA-PAMs to the one or more unborated low molecular weight PIBSA-PAMs, based on the total mass of the lubricating oil composition, is less than 3.65, such as less than 3.5, such as less than 3.0, such as less than 2.5, such as less than 2.0, such as less than 1.5.

[0180] In certain embodiments, the one or more unborated low molecular weight PIBSA-PAMs are not derived from tetraethylenepentamine (TEPA). In certain embodiments, the one or more borated and unborated PIBSA-PAMs are derived from N-phenyl-p-phenylenediamine (ADPA). Mannich base dispersant

[0181] The Mannich base dispersants useful herein are generally made by the reaction of an amine component, a hydroxyaromatic compound (substituted or unsubstituted, such as alkyl-substituted), such as an alkylphenol, and an aldehyde, such as formaldehyde. See U.S. Patent Nos. 4,767,551 and 10,899,986. Processing aids and catalysts, such as oleic acid and sulfonic acid, can also be part of the reaction mixture. Representative examples are shown in U.S. Patent Nos. 3,697,574; 3,703,536; 3,704,308; 3,751,365; 3,756,953; 3,798,165; 3,803,039; 4,231,759; 9,938,479; 7,491,248; and 10,899,986 and PCT Publication No. WO 01 / 42399. Polymethacrylate or polyacrylate derivative dispersants

[0182] Polymethacrylate or polyacrylate derivatives are another class of dispersants useful herein. These dispersants are generally prepared by reacting a nitrogen-containing monomer with a methacrylate or acrylate containing 5-25 carbon atoms in the ester group. Representative examples are shown in U.S. Patent Nos. 2,100,993 and 6,323,164. Polymethacrylate and polyacrylate dispersants are generally of lower molecular weight.

[0183] In certain embodiments, the dispersants used in the lubricating oil compositions and additive concentrates of the present invention are free of Mannich base dispersants and / or poly(meth)acrylate dispersants.

[0184] The lubricating compositions of the present disclosure generally contain from 0.1 mass% to 20 mass%, such as from 0.2 to 15 mass%, such as from 0.25 to 10 mass%, such as from 0.3 to 5 mass%, such as from 2.0 mass% to 4.0 mass% of the lubricating oil composition, of the dispersant. Alternatively, the dispersant can be present at from 0.1 wt% to 5 wt%, or from 0.01 wt% to 4 wt% of the lubricating composition.

[0185] For further information regarding the dispersants useful herein, see U.S. Patent No. 10,829,712, column 13, line 36 to column 16, line 67, and U.S. Patent No. 7,485,603, column 2, line 65 to column 6, line 22, column 8, line 25 to column 14, line 53, and column 23, line 40 to column 26, line 46.

[0186] The compositions according to the present disclosure can contain additives having different recited functions and also having a secondary effect as a dispersant (e.g., functionalized polymer P, particularly as described below as a functionalized polymer comprising a partially or fully saturated C 4-5Polymers of olefins having amide, imide, and / or ester functionalization on the polymer backbone, which may also have a dispersant effect). For determining the amount of dispersant in the lubricating oil compositions or concentrates herein, these additives are not counted as dispersants. C. Detergents

[0187] The lubricating composition may contain one or more metal detergents (such as blends of metal detergents), also known as "detergent additives". 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 typically comprise a polar head and a long hydrophobic tail, the polar head comprising a metal salt of an acidic organic compound. The salt may contain a stoichiometric amount of metal, in which case they are typically 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. A large amount of metal base can be incorporated by reacting an excess metal compound (such as an oxide or hydroxide) with an acidic gas (such as carbon dioxide). Such detergents, sometimes referred to as overbased, may have a TBN of above 100 mg KOH / g (such as above 200 mg KOH / g), and generally have a TBN of above 250 mg KOH / g, such as above 300 mg KOH / g, such as 150 to 800 mg KOH / g, 200 to 700 mg KOH / g, 225 to 600 mg KOH / g, such as 275 to 500 mg KOH / g, such as 300 to 450 mg KOH / g. Preferably, the detergents of the present disclosure are overbased detergents, more preferably detergents having a TBN of above 100 mg KOH / g, such as above 200 mg KOH / g, such as above 250 mg KOH / g, such as above 300 mg KOH / g, such as 150 to 800 mg KOH / g, 200 to 700 mg KOH / g, 225 to 600 mg KOH / g, such as 275 to 500 mg KOH / g, such as 300 to 450 mg KOH / g.

[0188] Suitable detergents include metals, especially 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), especially 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 comprise a hybrid detergent containing any combination of sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, naphthenates, and / or other oil-soluble carboxylates of sodium, potassium, lithium, calcium, or magnesium and Group 1 and / or Group 2 metals.

[0189] Overbased metal detergents can be sodium, calcium, magnesium salts or mixtures thereof of phenates, sulfur-containing phenates, sulfonates, salixarates and salicylates. Overbased phenates and salicylates typically have a total base number TBN of 180 to 650 mg KOH / g, such as 200 to 450 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 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 (issued as U.S. Patent No. 7,407,919).

[0190] The one or more detergents can together be present in an amount of 0 wt% to 15 wt%, or 0.1 wt% to 10 wt%, or 0.2 wt% to 8 wt%, or 0.2 wt% to 3 wt% based on the total mass of the lubricating composition. Preferably, the one or more detergents of the present invention together are present in an amount of 0.1 to 4 mass%, such as 0.2 to 3 mass%, such as 0.4 to 2 mass%, such as 0.5 to 1.5 mass%, such as 0.8 to 1.2 mass% based on the total mass of the lubricating oil composition. For example, in a heavy-duty diesel engine, the detergent can be present at 0.8 wt% to 1.2 wt% of the lubricating composition. For a passenger car engine, the detergent can be present, for example, at 0.2 wt% to 1 wt% of the lubricating composition. Preferably, the one or more detergents useful in the present disclosure comprise calcium and / or magnesium metal salts. The detergent can be a calcium and / or magnesium carboxylate (e.g., salicylate), sulfonate or phenate detergent. More preferably, the detergent 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. More preferably, the detergent is selected from one or more calcium sulfonates, one or more magnesium sulfonates, one or more calcium salicylates, one or more magnesium salicylates and combinations of two or more of them (including but not limited to combinations of calcium salicylate and magnesium sulfonate). Even more preferably, the detergent is selected from one or more calcium sulfonates, one or more magnesium sulfonates and mixtures thereof. Even more preferably, the detergent is selected from calcium sulfonate, magnesium sulfonate and mixtures. Particularly preferably, the detergent is a mixture of calcium sulfonate and magnesium sulfonate.

[0191] The metal detergent may also include "hybrid" detergents formed with mixed surfactant systems including phenate and / or sulfonate components such as phenate / salicylate, sulfonate / phenate, sulfonate / salicylate, sulfonate / phenate / salicylate as described, for example, in U.S. Patent Nos. 6,429,178; 6,429,179; 6,153,565; and 6,281,179. When, for example, a hybrid sulfonate / phenate detergent is used, the hybrid detergent is considered equivalent to the amounts of the individual phenate and sulfonate detergents separately introducing similar amounts of phenate and sulfonate soaps. In certain embodiments, the lubricating oil composition of the present invention does not contain or substantially does not contain phenate detergents, such as less than 0.5% by mass, such as less than 0.2% by mass, such as less than 0.1% by mass of the lubricating oil composition or the concentrate composition. In certain embodiments, there is no or substantially no phenate detergent in the lubricating oil composition or concentrate of the present disclosure.

[0192] The detergent additive may comprise one or more magnesium sulfonate detergents. The magnesium sulfonate may be a neutral salt or an overbased salt. Suitably, the magnesium sulfonate is an overbased magnesium sulfonate having a TBN of 100 to 650 mg KOH / g (ASTM D2896), such as 200 to 500 mg KOH / g, such as 350 to 450 mg KOH / g.

[0193] Alternatively, the detergent additive may comprise calcium sulfonate. The calcium sulfonate may be a neutral salt or an overbased salt. Suitably, the calcium sulfonate is an overbased calcium sulfonate having a TBN of 100 to 650 mg KOH / g (ASTM D2896), such as 150 to 500 mg KOH / g, such as 200 to 400 mg KOH / g, such as 250 to 350 mg KOH / g.

[0194] In certain embodiments, the detergent contains less than 50% by mass, such as less than 50% by mass, such as less than 40% by mass, such as less than 30% by mass, such as less than 20% by mass, such as less than 10% by mass of calcium salicylate based on the total mass of the detergents present in the lubricating oil composition or concentrate.

[0195] Preferably, the detergent additive is a combination of calcium sulfonate and magnesium sulfonate. More preferably, the calcium sulfonate has a TBN of 100 to 650 mg KOH / g (ASTM D2896), such as 150 to 500 mg KOH / g, such as 200 to 400 mg KOH / g, such as 250 to 350 mg KOH / g, and the magnesium sulfonate has a TBN of 100 to 650 mg KOH / g (ASTM D2896), such as 200 to 500 mg KOH / g, such as 350 to 450 mg KOH / g.

[0196] In certain embodiments, the magnesium detergent provides 200 - 4000 ppm of magnesium atoms, suitably 200 - 2000 ppm, 300 to 1500, 450 - 1200 ppm, 500 - 1000 ppm, 600 to 900 ppm or 700 to 800 ppm of magnesium atoms (ASTM D5185) to its lubricating composition.

[0197] The detergent may comprise one or more calcium detergents such as calcium carboxylates (e.g., salicylates), sulfonates or phenates detergents.

[0198] Suitably, the calcium detergent has a TBN of 30 to 700 mgKOH / g (ASTM D2896), such as 50 to 650 mgKOH / g, such as 200 to 500 mgKOH / g, such as 240 to 450 mgKOH / g, or below 150 mgKOH / g, such as below 100 mgKOH / g, or above 200 mgKOH / g, or above 300 mgKOH / g, or above 350 mgKOH / g.

[0199] Suitably, the calcium detergent is calcium salicylate, calcium sulfonate or calcium phenate having a TBN of 30 to 700 mgKOH / g, 30 to 650 mgKOH / g (ASTM D2896), such as 50 to 650 mgKOH / g, such as 200 to 500 mgKOH / g, such as 240 to 450 mgKOH / g, or below 150 mgKOH / g, such as below 100 mgKOH / g, or above 200 mgKOH / g, or above 300 mgKOH / g, or above 350 mgKOH / g.

[0200] The calcium detergent is generally present in an amount sufficient to provide at least 500 ppm, preferably at least 750, more preferably at least 900 ppm, more preferably at least 1000 ppm atomic calcium to the lubricating oil composition (ASTM D5185). If present, the 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, more preferably no more than 1500 ppm atomic calcium to the lubricating oil composition (ASTM D5185). If present, the calcium detergent is suitably present in an amount sufficient to provide 500 - 4000 ppm, preferably 750 - 3000 ppm, more preferably 900 - 2000 ppm, more preferably 1000 to 1500 ppm atomic calcium to the lubricating oil composition (ASTM D5185).

[0201] Suitably, the total atomic weight of the metal of the detergent in the lubricating composition from all aspects according to the present disclosure is not greater than 5000 ppm, preferably not greater than 3000 ppm, more preferably not greater than 2500 ppm (ASTM D5185). The total atomic metal amount of the detergent in the lubricating oil composition from all aspects according to the present disclosure is suitably at least 500 ppm, preferably at least 1000 ppm, more preferably at least 1500 ppm (ASTM D5185). The total atomic metal amount of the detergent in the lubricating oil composition from all aspects according to the present disclosure is suitably 500 to 5000 ppm, preferably 1000 to 3000 ppm, more preferably 1500 to 2500 ppm (ASTM D5185).

[0202] The sulfonate detergent 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. The alkaryl sulfonates generally contain from about 9 to about 80 or more carbon atoms per alkyl-substituted aromatic structural moiety, preferably from about 16 to about 60 carbon atoms. The oil-soluble sulfonate or alkaryl sulfonic acid can be neutralized with metal oxides, hydroxides, alkoxides, carbonates, carboxylates, sulfides, hydrosulfides, nitrates, borates and ethers. The amount of the metal compound is selected considering the required TBN of the final product, but is generally about 100 to 220 mass% (preferably at least 125 mass%) of the stoichiometrically required amount.

[0203] The metal salts of phenols and sulfurized phenols are prepared by reaction with suitable 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 monohalide or sulfur dihalide) to form products that are generally mixtures of compounds in which 2 or more phenols are bridged by sulfur-containing bridges.

[0204] Carboxylate detergents (such as salicylates) can be prepared by reacting aromatic carboxylic acids (such as C 5-100 、C 9-30 、C 14-24It is prepared by reacting an alkyl-substituted hydroxybenzoic acid) with a suitable metal compound, such as an oxide or hydroxide, and neutral or overbased products can be obtained by methods well known in the art. The aromatic structural part of the aromatic carboxylic acid may contain heteroatoms, such as nitrogen and oxygen. Preferably, this structural part contains only carbon atoms; more preferably, this structural part contains six or more carbon atoms; for example, benzene is a preferred structural part. The aromatic carboxylic acid may contain one or more aromatic structural parts fused or linked via an alkylene bridge, such as one or more benzene rings.

[0205] Preferred substituents in the oil-soluble salicylic acid are alkyl substituents. In the alkyl-substituted salicylic acid, the alkyl advantageously contains 5 to 100, preferably 9 to 30, especially 14 to 20 carbon atoms. If there is more than one alkyl, the average number of carbon atoms in all alkyls is preferably at least 9 to ensure sufficient oil solubility.

[0206] In addition, the metal organic and inorganic base salts used as detergents can contribute to the sulfate ash content of the lubricating oil composition. In the embodiments of the present disclosure, the amount of such additives is minimized. To maintain a low sulfur content, salicylate detergents can be used and the lubricating compositions herein may contain one or more salicylate detergents (the detergents are preferably used in an amount of 0.05 to 20.0% by weight, more preferably 1.0 to 10.0% by weight, and most preferably 2.0 to 5.0% by weight based on the total weight of the lubricating composition).

[0207] As determined by ASTM D874, based on the total weight of the lubricating composition, the total sulfate ash (SASH) content of the lubricating compositions herein is generally not greater than 2.0% by weight, or not greater than 1.0% by weight, or not greater than 0.9% by weight, or not greater than 0.85% by weight.

[0208] In addition, it is useful that each detergent independently has a TBN value (total base number) measured by ISO 3771 or ASTM D2896 in the range of 10 to 700 mgKOH / g, or in the range of 100 to 650 mgKOH / g, or in the range of 150 to 600, or in the range of 200 to 500 mgKOH / g, or in the range of 250 to 450 mgKOH / g.

[0209] Preferably, the one or more detergents are present together in an amount of soap less than 0.8% by mass, such as less than 0.7% by mass, such as less than 0.6% by mass, such as less than 0.55% by mass based on the total mass of the lubricating oil composition. More preferably, the one or more detergents are present together in an amount of soap of 0.2 to 0.8% by mass, such as 0.3 to 0.7% by mass, such as 0.4 to 0.6% by mass, such as 0.45 to 0.55% by mass based on the total mass of the lubricating oil composition.

[0210] In certain embodiments, the sulfonate detergent (such as Ca and / or Mg sulfonate detergents) may be present in an amount providing 0.2 to 0.8 mass%, such as 0.3 to 0.7 mass%, such as 0.4 to 0.6 mass%, such as 0.45 to 0.55 mass% of the sulfonate soap based on the total mass of the lubricating oil composition.

[0211] Alternatively, the salicylate detergent (such as Ca and / or Mg salicylate detergents) may be present in an amount providing 0.2 to 0.8 mass%, such as 0.3 to 0.7 mass%, such as 0.4 to 0.6 mass%, such as 0.45 to 0.55 mass% of the soap based on the total mass of the lubricating oil composition.

[0212] Alternatively, the sulfonate soap may be present in an amount of 0.1 wt% to 0.8 wt% of the lubricant composition, and the salicylate soap may be present in an amount of 0.1 wt% to 0.8 wt% of the lubricant composition.

[0213] Generally, a lubricating composition formulated for a heavy-duty diesel engine comprises a detergent in an amount of 0.1 to 4 mass%, such as 0.2 to 3 mass%, such as 0.4 to 2 mass%, such as 0.5 to 1.5 mass%, such as 0.8 to 1.2 mass% based on the total mass of the lubricating oil composition. Preferably, a lubricating composition formulated for a heavy-duty diesel engine comprises a soap providing less than 0.8 mass%, such as less than 0.7 mass%, such as less than 0.6 mass%, such as less than 0.55 mass% based on the total mass of the lubricating oil composition; more preferably a detergent in an amount of 0.2 to 0.8 mass%, such as 0.3 to 0.7 mass%, such as 0.4 to 0.6 mass%, such as 0.45 to 0.55 mass% of the soap based on the total mass of the lubricating oil composition.

[0214] In certain embodiments, the lubricating oil compositions and concentrates of the present invention are free of phenate detergents and / or free of salicylate detergents. Preferably, the lubricating oil compositions and additive concentrates of the present invention do not contain or substantially do not contain phenate detergents, such as less than 1.2 mass%, such as less than 1.0 mass%, such as less than 0.5 mass% based on the total mass of the lubricating oil composition or additive concentrate, and / or do not contain or substantially do not contain salicylate detergents, such as less than 1.2 mass%, such as less than 1.0 mass%, such as less than 0.5 mass% based on the total mass of the lubricating oil composition or additive concentrate. More preferably, the detergents used in the lubricating oil compositions and additive concentrates of the present invention consist particularly of a mixture of calcium sulfonate and magnesium sulfonate.

[0215] The lubricating oil compositions and concentrates according to the present disclosure may further comprise one or more additives, such as friction modifiers, antioxidants, pour point depressants, antifoaming agents, viscosity improvers, corrosion inhibitors, antiwear agents, extreme pressure additives, demulsifiers, seal compatibility agents, additive diluent base oils, functionalized polymers, etc. Specific examples of such additives are described, for example, in Kirk - Othmer Encyclopedia of Chemical Technology, 3rd Edition, Volume 14, pages 477 - 526, and several will be discussed in more detail below. D. Friction Modifiers

[0216] A friction modifier is any material 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 reagents that alter the ability of a base oil, formulated lubricating composition, or functional fluid to condition the coefficient of friction of a lubricated surface can be effectively used in combination with the base oils or lubricating compositions of the present disclosure. Friction modifiers that reduce the coefficient of friction are particularly advantageously combined with the base oils and lubricating compositions of the present disclosure.

[0217] Exemplary friction modifiers can include, for example, organometallic compounds or materials or mixtures thereof. Exemplary organometallic friction modifiers useful in the lubricating oil formulations of the present disclosure include, for example, tungsten and / or molybdenum compounds, such as molybdenum amines, molybdenum diamines, organotungstates, molybdenum dithiocarbamates, molybdenum dithiophosphates, molybdenum amine complexes, molybdenum carboxylates, etc., and mixtures thereof. Examples of available molybdenum - containing compounds can conveniently include molybdenum dithiocarbamates, trinuclear molybdenum compounds such as those described in PCT Publication No. WO 98 / 26030, sulfides of molybdenum, and molybdenum dithiophosphates.

[0218] Other known friction modifiers include oil - soluble organomolybdenum compounds. Such organomolybdenum friction modifiers can also provide antioxidant and antiwear benefits to the lubricating oil composition. Examples of such oil - soluble organomolybdenum compounds include dithiocarbamates, dithiophosphates, dithiophosphites, xanthates, thioxanthates, sulfides, etc., and mixtures thereof. Particularly preferred are molybdenum dithiocarbamates, dialkyldithiophosphates of molybdenum, alkylxanthates of molybdenum, and alkylthioxanthates of molybdenum.

[0219] Alternatively, the molybdenum compound can be an acidic molybdenum compound. These compounds react with basic nitrogen compounds as measured by ASTM test methods 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.

[0220] Molybdenum compounds useful in the compositions of the present disclosure include organomolybdenum compounds of the formulas Mo(R"OCS2)4 and Mo(R"SCS2)4, where R" is an organic group selected from alkyl, aryl, aralkyl, and alkoxyalkyl groups generally having from 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 dialkyldithiocarbamates of molybdenum.

[0221] Another class of organomolybdenum 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 and mixtures thereof, where L is an independently selected ligand having an organic group with a sufficient number of carbon atoms to render the compound soluble or dispersible in oil, n ranges from 1 to 4, k ranges from 4 to 7, Q is selected from neutral electron-donating compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. There should be at least 21 carbon atoms in all ligands / organic groups, such as at least 25, at least 30, or at least 35 carbon atoms.

[0222] In certain embodiments of the present invention, the friction modifier is an inorganic or organometallic molybdenum compound. In certain embodiments, the friction modifier is molybdenum dialkyldithiocarbamate. In certain embodiments, the friction modifier is a trinuclear molybdenum compound.

[0223] In certain embodiments, the lubricating oil compositions of the present disclosure contain at least 10 ppm, at least 30 ppm, at least 40 ppm, more preferably at least 50 ppm or at least 60 ppm of molybdenum (measured as molybdenum atoms). In certain other embodiments, the lubricating oil composition does not contain or substantially does not contain molybdenum (Mo), such as less than 60 ppm, such as less than 50 ppm, such as less than 40 ppm of Mo.

[0224] For more information on available Mo-containing friction modifiers, see U.S. Patent No. 10,829,712 (column 8, line 58 to column 11, line 31).

[0225] Ashless friction modifiers can be present in the lubricating oil compositions of the present disclosure and are well-known and include esters formed by reacting carboxylic acids and acid anhydrides with alkanols and amine-based friction modifiers. Other available friction modifiers generally include polar end groups (such as carboxyl or hydroxyl groups) covalently bonded to lipophilic hydrocarbon chains. Esters of carboxylic acids and acid anhydrides with alkanols are described in U.S. Patent No. 4,702,850. Examples of other conventional organic friction modifiers are described by M. Belzer in "Journal of Tribology" (1992), Volume 114, pages 675-682 and by M. Belzer and S. Jahanmir in "Lubrication Science" (1988), Volume 1, pages 3-26. Generally, the total amount of organic ashless friction modifier in the lubricant according to the present disclosure is not more than 5% by mass, preferably not more than 2% by mass, more preferably not more than 0.5% by mass based on the total mass of the lubricating oil composition.

[0226] Exemplary friction modifiers useful in the lubricating compositions described herein include, for example, alkoxylated fatty acid esters, alkanolamides, polyol fatty acid esters, borated glycerol fatty acid esters, fatty alcohol ethers, and mixtures thereof.

[0227] Exemplary alkoxylated fatty acid esters include, for example, polyethylene glycol stearate, fatty acid polyglycol esters, etc. These can include polypropylene glycol stearate, polybutylene glycol stearate, polyethylene glycol isostearate, polypropylene glycol isostearate, polyethylene glycol palmitate, etc.

[0228] Exemplary alkanolamides include, for example, diethyl alkanolamide laurate, diethyl alkanolamide palmitate, etc. These can include diethyl alkanolamide oleate, diethyl alkanolamide stearate, diethyl alkanolamide oleate, polyethoxylated hydrocarbon amides, polypropoxylated hydrocarbon amides, etc.

[0229] Exemplary polyol fatty acid esters include, for example, glycerol monooleate, saturated mono-, di-, and triglycerides, glycerol monostearate, etc. These can include polyol esters, hydroxy-containing polyol esters, etc. In certain embodiments of the present invention, the friction modifier is an organic ashless friction modifier, particularly glycerol monooleate.

[0230] Exemplary borated glycerol fatty acid esters include, for example, borated glycerol monooleate, borated saturated mono-, di- and triglycerides, borated glycerol monostearate, etc. In addition to glycerol polyols, these may also include trimethylolpropane, pentaerythritol, sorbitan, etc. These esters can be polyol monocarboxylic esters, polyol dicarboxylic esters and sometimes, polyol tricarboxylic esters. Preferred may be glycerol monooleate, glycerol dioleate, glycerol trioleate, glycerol monostearate, glycerol distearate and glycerol tristearate and the corresponding glycerol monopalmitate, glycerol dipalmitate and glycerol tripalmitate, as well as their respective isostearates, linoleates, etc. Ethoxylated, propoxylated and / or butoxylated fatty acid esters of polyols (especially using glycerol as the base polyol) can be used herein.

[0231] Exemplary fatty alcohol ethers include, for example, stearyl ethers, myristyl ethers, etc. Alcohols, including those having C3 to C 50 carbon atoms, can be ethoxylated, propoxylated or butoxylated to form the corresponding fatty alkyl ethers. The base alcohol moiety may preferably be stearyl, myristyl, C 11 -C 13 hydrocarbons, oleyl, isostearyl, etc.

[0232] If present, the useful concentration of the friction modifier can be 0.01 wt% to 5 wt%, or about 0.01 wt% to about 2.5 wt%, or about 0.02 wt% to about 1.5 wt%, or about 0.03 wt% to about 1.0 wt%, or about 0.04 wt% to about 0.5 wt%, or about 0.05 wt% to about 0.2 wt%. The concentration of molybdenum (Mo)-containing materials is usually described in terms of Mo metal concentration. The advantageous concentration of Mo in the lubricating oil composition can be 25 ppm to 700 ppm or more, and the generally preferred range is 50 - 200 ppm. All types of friction modifiers can be used alone or in combination with the materials of the present disclosure. Mixtures of two or more friction modifiers or mixtures of friction modifiers with alternative surface-active materials are generally also desirable. For example, a combination of a Mo-containing compound with a polyol fatty acid ester (such as glycerol monooleate) can be used herein. E. Antioxidants

[0233] Antioxidants delay the oxidative degradation of the base oil during use. Such degradation can lead to deposits on metal surfaces, the presence of sludge, an increase in viscosity in the lubricant, etc. A wide variety of oxidation inhibitors can be used in the lubricating oil composition. See, for example, Lubricants and Related Products, Klamann, Wiley VCH, 1984; U.S. Patent Nos. 4,798,684 and 5,084,197.

[0234] Available antioxidants include hindered phenols. These phenolic antioxidants can be ashless (metal-free) phenolic compounds or neutral or basic metal salts of certain phenolic compounds. Typical phenolic antioxidant compounds are hindered phenols containing sterically hindered hydroxyl groups, which include derivatives of dihydroxyaryl compounds where the hydroxyl groups are in the ortho or para positions to each other. Typical phenolic antioxidants include hindered phenols substituted with C 6+ alkyl groups and alkylene-coupled derivatives of these hindered phenols. Examples of phenolic materials of this type 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 available hindered mono-phenolic antioxidants can include, for example, hindered 2,6-di-alkyl-phenolpropionate derivatives. Bisphenolic antioxidants can 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'-methylenebis(2,6-di-tert-butyl-phenol).

[0235] An effective amount of one or more catalytic antioxidants can also be used. The catalytic antioxidants comprise an effective amount of a) one or more oil-soluble polymetallic organic compounds; and an effective amount of b) one or more substituted N,N'-diaryl-o-phenylenediamine compounds, or c) one or more hindered phenol compounds; or a combination of b) and c). The catalytic antioxidants available herein are more fully described in U.S. Patent No. 8,048,833.

[0236] Non-phenolic oxidation inhibitors that can be used include aromatic amine antioxidants, which can be used as such or in combination with phenols. Typical examples of non-phenolic antioxidants include: alkylated and non-alkylated aromatic amines, such as aromatic monoamines of the formula R 8 R 9 R 10 N, where 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, alkenylene or aralkylene group, R 12 is an alkyl or alkenyl, aryl or alkaryl group, and x is 0, 1 or 2. The aliphatic group R 8may contain from 1 to about 20 carbon atoms, preferably from about 6 to 12 carbon atoms. The aliphatic group is typically a saturated aliphatic group. Preferably, R 8 and R 9 are both aromatic or substituted aromatic groups, and the aromatic group may be a polycyclic aromatic group such as naphthyl. The aromatic groups R 8 and R 9 may be linked together with other groups such as S.

[0237] 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. Generally, the aliphatic group contains no more than about 14 carbon atoms. General types of amine antioxidants useful in the present composition include diphenylamine, phenylnaphthylamine, phenothiazine, imidodibenzyls, and diphenylbenzene diamine. Mixtures of two or more aromatic amines may also be used. Polymer amine antioxidants may also be used. Specific examples of aromatic amine antioxidants useful in the present disclosure include: p,p'-dioctyldiphenylamine; tert-octylphenyl-α-naphthylamine; phenyl-α-naphthylamine; and p-octylphenyl-α-naphthylamine.

[0238] 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 their alkali metal or alkaline earth metal salts are also antioxidants useful herein. Suitably, the lubricating oil composition of the present disclosure may comprise the one or more sulfur-containing antioxidants in an amount providing from 0.02 to 0.2, preferably from 0.02 to 0.15, more preferably from 0.02 to 0.1, and even more preferably from 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-based fatty acid esters, ashless sulfurized phenolic antioxidants, sulfur-containing organomolybdenum compounds, and combinations thereof. For further information on sulfurized materials useful as antioxidants herein, see U.S. Patent No. 10,731,101 (column 15, line 55 to column 22, line 12).

[0239] Other typical antioxidants include: Irganox TM L67, Ethanox TM 4702, Lanxess Additin TM RC 7110; Ethanox TM 4782J; Irganox TM 1135, Irganox TM5057, sulfurized lard, rapeseed oil, and methyl esters of palm oil fatty acids.

[0240] Antioxidants useful herein include sulfurized methyl ester antioxidants such as methyl esters of sulfurized rapeseed oil fatty acids, hindered phenols, and / or aromatic amines. In certain embodiments, the antioxidants useful herein are selected from sulfurized methyl ester antioxidants such as methyl esters of sulfurized rapeseed oil fatty acids, and / or aromatic amines. These antioxidants can be used alone by type or in combination with each other. In a particular embodiment, the antioxidants used in the lubricating oil compositions and concentrates of the present invention comprise and particularly consist of alkylated diphenylamine antioxidants and sulfurized methyl ester antioxidants (such as methyl esters of sulfurized rapeseed oil fatty acids).

[0241] The antioxidant additive can be used in an amount of about 0.01 to 10% by mass, or 0.05 to 5% by weight, or 0.1 to 4.5% by mass, or 0.5 to 4% by weight, or 1 to 3.5% by weight, or 2.5 to 3.5% by weight based on the weight of the lubricating composition.

[0242] The compositions according to the present disclosure may contain additives having different recited functions and also having a secondary effect as antioxidants (for example, phosphorus-containing antiwear agents (such as ZDDP) may also have an antioxidant effect). For determining the amount of antioxidants in the lubricating oil compositions or concentrates herein, these additives are not counted as antioxidants. F. Pour Point Depressant

[0243] If desired, conventional pour point depressants (also known as lubricating oil flow improvers) can be added to the compositions of the present disclosure. These pour point depressants can be added to the lubricating compositions of the present disclosure to lower the minimum temperature at which the fluid can flow or be poured. 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 can be used in an amount of about 0.01 to 5% by weight, preferably about 0.01 to 1.5% by weight based on the weight of the lubricating composition. G. Antifoaming Agent

[0244] Defoamers can be advantageously added to the lubricant compositions described herein. These reagents prevent or delay the formation of stable foams. Silicones and / or organic polymers are typical defoamers. For example, polysiloxanes such as silicone oils or polydimethylsiloxane provide defoaming properties.

[0245] Defoamers are commercially available and can be used in minor amounts, such as below 5 wt%, below 3 wt%, below 1 wt%, below 0.1 wt%, such as from 0.001 wt% to 5 wt%, such as from 0.002 to 3 wt%, such as from 0.003 to 1 wt% based on the total mass of the lubricating composition.

[0246] For example, it is possible that the lubricating oil composition contains a defoamer containing a polyalkylsiloxane, such as a polydialkylsiloxane, wherein the alkyl group is a C1-C 10 alkyl group, such as polydimethylsiloxane (PDMS), also known as silicone oil. Alternatively, the siloxane is a poly(R 3 ) siloxane, wherein R 3 is one or more identical or different straight-chain, branched or cyclic hydrocarbon groups, such as alkyl or aryl groups, which generally have 1 to 20 carbon atoms. It is possible that, for example, the lubricating oil composition contains a polymeric siloxane compound according to formula 1 below, 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 its isomers (such as methyl, phenyl), and n is from 2 to 1000, such as from 50 to 450, or such as from 40 to 100.

[0247] Additionally or alternatively, it is possible that the lubricating oil composition contains an organically modified siloxane (OMS), such as a siloxane modified with an organic group such as a polyether (e.g., ethylene oxide-propylene oxide copolymer), a long-chain hydrocarbon group (e.g., C 11 -C 100 alkyl group) or an aryl group (e.g., C6-C 14 aryl group). It is possible that, for example, the lubricating oil composition contains an organically modified siloxane compound according to formula 1, wherein n is from 2 to 2000, such as from 50 to 450 (or such as from 40 to 100), and wherein R 1 and R 2 are the same or different, optionally wherein R 1 and R 2 are each independently an organic group, such as an organic group selected from polyethers (e.g., ethylene oxide-propylene oxide copolymer), long-chain hydrocarbon groups (e.g., C 11 -C 100 alkyl group) or aryl groups (e.g., C6-C 14 aryl group). Preferably, one of R 1 and R 2 is CH3.

[0248] Based on the total weight of the lubricant composition, a siloxane according to Formula 1 is incorporated to provide from about 0.1 to less than about 30 ppm Si, or from about 0.1 to about 25 ppm Si, or from about 0.1 to about 20 ppm Si, or from about 0.1 to about 15 ppm Si, or from about 0.1 to about 10 ppm Si. More preferably, it is in the range of about 3 - 10 ppm Si.

[0249] In embodiments, the 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. The silicone defoamers useful herein include polydimethylsiloxane, phenyl - methyl polysiloxane, 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 used in place of or in addition to. One such material is sold as SILWET - L - 7220.

[0250] Acrylate polymer defoamers may also be used herein. Typical acrylate defoamers include the polyacrylate defoamer designated PC - 1244 available from Monsanto Polymer Products Co. A preferred acrylate polymer defoamer useful herein is PX TM 3841 (i.e., an alkyl acrylate polymer), also known as Mobilad TM C402.

[0251] In embodiments, a combination of a silicone defoamer and an acrylate defoamer may be used, such as at a weight ratio of silicone defoamer / acrylate defoamer of from about 5:1 to about 1:5, see for example U.S. Patent Application Publication No. 2021 / 0189283. H. Viscosity Improver

[0252] Viscosity modifiers (also known as viscosity index improvers or viscosity improvers) may be included in the lubricating compositions described herein. Viscosity improvers provide high and low temperature operability to lubricants. These additives provide shear stability at elevated temperatures and acceptable viscosities at low temperatures. Suitable viscosity improvers include high molecular weight hydrocarbons, polyesters, and viscosity modifier dispersants that can act both as viscosity improvers and dispersants. The typical molecular weights of these polymers are between about 10,000 and 1,500,000 g / mol, more typically about 20,000 to 1,200,000 g / mol, and even more typically about 50,000 to 1,000,000 g / mol.

[0253] Examples of suitable viscosity improvers are linear or star polymers and copolymers of methacrylates, butadienes, olefins, or alkylated styrenes. Polyisobutene is a commonly used viscosity improver. Another suitable viscosity improver is polymethacrylate (e.g., copolymers of alkyl methacrylates of various chain lengths), some formulations of which also act as pour point depressants. Other suitable viscosity improvers 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 with molecular weights of 50,000 to 200,000 g / mol.

[0254] Copolymers that can be used as viscosity improvers include those available under the trade names "PARATONE" TM "(such as "PARATONE" TM 8921", "PARATONE" T 68231", "PARATONE" TM 24EX" and "PARATONE" TM 8941") purchased from Chevron Oronite Company LLC; those available under the trade name "HiTEC" TM "(such as HiTEC" TM 5850B) purchased from Afton Chemical Corporation; and those available under the trade names "Lubrizol" TM 7067C" and "Lubrizol" TM 7077D" purchased from The Lubrizol Corporation. Hydrogenated polyisoprene star polymers that can be used as viscosity improvers in this article include those available from Infineum International Limited, such as those available under the trade names "SV203" TM ", "SV200" TM " and "SV600" TM". The hydrogenated diene-styrene block copolymer that can be used as a viscosity improver in this article is available from Infineum International Limited, for example, under the trade name "SV 50 TM ".

[0255] Polymers that can be used as viscosity improvers in this article include polymethacrylate or polyacrylate polymers, such as linear polymethacrylate or polyacrylate polymers, such as those that can be obtained under the trade name "Viscoplex TM "(e.g., Viscoplex TM 6-954) from Evonik Industries, or those that can be obtained under the trade name Asteric TM (e.g., Lubrizol TM 87708 and Lubrizol TM 87725) star polymers from Lubrizol Corporation.

[0256] Polymers containing vinyl aromatic hydrocarbons that can be used as viscosity improvers in this article can be derived from vinyl aromatic hydrocarbon monomers, such as styrenic monomers, such as styrene. Exemplary vinyl aromatic hydrocarbon copolymers useful in this article can be represented by the general formula: A-B, where A is a polymeric block mainly derived from vinyl aromatic hydrocarbon monomers (such as styrene), and B is a polymeric block mainly derived from conjugated diene monomers (such as isoprene).

[0257] Polymers containing vinyl aromatic hydrocarbons that can be used as viscosity improvers can have a kinematic viscosity at 100 °C of less than 20 cSt, such as less than 15 cSt, such as less than 12 cSt, but can be diluted (e.g., in Group I, II, and / or III base oils) to a higher kinematic viscosity at 100 °C, such as to more than 40 cSt, such as more than 100 cSt, such as more than 1000 cSt, such as 1000 to 2000 cSt.

[0258] Generally, if present, the viscosity improver can be used in an amount of about 0.01 to about 13 wt%, such as about 0.1 to about 7 wt%, such as 0.1 to about 4 wt%, such as about 0.2 to about 2 wt%, such as about 0.2 to about 1 wt%, and such as about 0.2 to about 0.5 wt% based on the total weight of the formulated lubricant composition.

[0259] Viscosity improvers are typically added as concentrates in a large amount of diluent oil. The "as delivered" viscosity improver typically contains 20 wt% to 75 wt% of active polymer in the "as delivered" polymer concentrate (for polymethacrylate or polyacrylate polymers), or 8 wt% to 20 wt% of active polymer (for olefin copolymers, hydrogenated polyisoprene star polymers or hydrogenated diene-styrene block copolymers).

[0260] The compositions according to the present disclosure may contain additives having different recited functions and also having a secondary effect as a viscosity improver (e.g., component P-functionalized polymers, particularly the following amide, imide, ester, and / or alcohol-functionalized polymers, may also have a viscosity improving effect). For determining the amount of viscosity improver in the lubricating oil compositions or concentrates herein, these additives are not counted as viscosity improvers. J. Corrosion Inhibitors / Rust Inhibitors

[0261] Corrosion inhibitors can be used to mitigate the corrosion of metals and are often also referred to as metal deactivators or metal passivators. Some corrosion inhibitors can also be characterized as antioxidants.

[0262] Suitable corrosion inhibitors can 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 the benzotriazole shown by the following structure: wherein R 8 is absent (hydrogen) or can be a C1 to C 20 hydrocarbyl or substituted hydrocarbyl group that is straight-chain or branched, saturated or unsaturated. It can 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 can include benzotriazole, alkyl-substituted benzotriazoles (e.g., tolyltriazole, ethylbenzotriazole, hexylbenzotriazole, octylbenzotriazole, etc.), aryl-substituted benzotriazoles, alkylaryl- or arylalkyl-substituted benzotriazoles, etc., and combinations thereof. For example, the triazole can comprise or be benzotriazole and / or alkylbenzotriazole, wherein the alkyl contains 1 to about 20 carbon atoms, or 1 to about 8 carbon atoms. Non-limiting examples of such corrosion inhibitors can comprise or be benzotriazole, tolyltriazole, and / or optionally, substituted benzotriazoles such as Irgamet TM 39 available from BASF of Ludwigshafen, Germany. Preferred corrosion inhibitors can comprise or be benzotriazole and / or tolyltriazole.

[0263] Additionally or alternatively, the corrosion inhibitor may include one or more substituted thiadiazoles having the following structures: wherein R 15 and R 16 are independently hydrogen or a hydrocarbon group, which may be aliphatic or aromatic, including cyclic, cycloaliphatic, 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 compounds may be included in the fluids 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-(hydrocarbyldithio)-1,3,4-thiadiazoles.

[0264] Additionally or alternatively, the corrosion inhibitor may include one or more other DMTD derivatives, such as carboxylic acid esters, wherein R 15 and R 16 may be connected to the sulfide sulfur atom via a carbonyl group. The preparation of these sulfur-containing ester DMTD derivatives is described, for example, in U.S. Patent No. 2,760,933. DMTD derivatives made by the condensation of DMTD with α-haloaliphatic carboxylic acids having at least 10 carbon atoms are described, for example, in U.S. Patent No. 2,836,564. This method produces DMTD derivatives wherein R 15 and R 16 are HOOC-CH(R 19 )(R 19 is a hydrocarbon group). DMTD derivatives further made by the amidation or esterification of these terminal carboxylic acid groups are also useful.

[0265] The preparation of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazole is described, for example, in U.S. Patent No. 3,663,561.

[0266] One class of DMTD derivatives may include a mixture of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazole and 2,5-bis-hydrocarbyldithio-1,3,4-thiadiazole. Such a mixture may be sold under the trade name HiTEC TM 4313 and is available from Afton Chemical Company.

[0267] The preparation of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazole is described, for example, in U.S. Patent No. 3,663,561.

[0268] 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.

[0269] 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 46 In 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, and the like, and combinations thereof.

[0270] When used, the corrosion inhibitor may comprise a substituted thiadiazole, a substituted benzotriazole, a substituted triazole, a trisubstituted borate, or a combination thereof.

[0271] 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 0.05 to 1.5 wt %, based on the weight of the lubricating composition.

[0272] In some embodiments, the 3,4-oxypyridone-containing composition can be substantially free (e.g., 0, or less than 0.001 wt %, less than 0.0005 wt %, 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.

[0273] 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 component P functionalized polymer described below 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. Antiwear Agent

[0274] The lubricating oil composition of the present disclosure may contain one or more antiwear agents that can reduce friction and excessive wear. Any antiwear agent known to those of ordinary skill in the art can be used in the lubricating oil composition. Non-limiting examples of suitable antiwear agents include zinc dialkyldithiophosphates, metal (such as Pb, Sb, Mo, etc.) salts of dithiophosphoric acid, metal (such as Zn, Pb, Sb, Mo, etc.) salts of dithiocarbamic acid, metal (such as Zn, Pb, Sb, etc.) salts of fatty acids, boron compounds, phosphoric acid esters, phosphorous acid esters, amine salts of phosphoric acid esters or thiophosphoric acid esters, reaction products of dicyclopentadiene and dithiophosphoric acid, and combinations thereof. Based on the total weight of the lubricating oil composition, the amount of the antiwear agent can be approximately 0.01 wt% to approximately 5 wt%, approximately 0.05 wt% to approximately 3 wt%, approximately 0.1 wt% to approximately 2 wt%, approximately 0.5 wt% to approximately 1 wt%, or approximately 0.6 wt% to approximately 0.8 wt%.

[0275] In an embodiment, the antiwear agent is or comprises a metal salt of a dihydrocarbyl dithiophosphate, such as a zinc dialkyldithiophosphate compound. The metal of the metal salt of a dihydrocarbyl dithiophosphate 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 metal salt of a dihydrocarbyl dithiophosphate has approximately 3 to approximately 22 carbon atoms, approximately 3 to approximately 18 carbon atoms, approximately 3 to approximately 12 carbon atoms, or approximately 3 to approximately 8 carbon atoms. In a further embodiment, the alkyl group is straight-chain or branched.

[0276] Available antiwear agents also include substituted or unsubstituted thiophosphoric acid, and its salts include zinc-containing compounds, such as zinc dithiophosphate compounds selected from dialkyl-, diaryl-, and / or alkylaryl-dithiophosphates.

[0277] Metal alkyl thiophosphates, more particularly metal dialkyl dithiophosphates in which the metal component is zinc, or zinc dialkyldithiophosphates (ZDDP) can be useful components of the lubricating composition of the present disclosure. ZDDP can be derived from primary alcohols, secondary alcohols, or mixtures thereof. ZDDP compounds generally have the formula Zn[SP(S)(OR 1 )(OR 2 )]2, where R 1 and R 2 are C1-C 18 alkyl groups, preferably C2-C 12Alkyl groups. These alkyl groups can be straight-chain or branched. The alcohols used in ZDDP can be 2-propanol, butanol, sec-butanol, pentanol, hexanol, such as 4-methyl-2-pentanol, n-hexanol, n-octanol, 2-ethylhexanol, alkylated phenols, etc. A secondary alcohol mixture or a mixture of primary and secondary alcohols can be used. Alkyl aryls can also be used. Available zinc dialkyldithiophosphates include secondary zinc dialkyldithiophosphates, 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" TM 262" and from Afton Chemical under the trade name "HiTEC" TM 7169".

[0278] In an embodiment, the zinc compound can be a zinc dithiocarbamate complex, a zinc dithiocarbamate as shown by the following formula: where each R I is independently a straight-chain, cyclic or branched, saturated or unsaturated aliphatic hydrocarbon structural moiety having 1 to about 10 carbon atoms, n is 0, 1 or 2, L is a ligand that saturates the zinc coordination layer, and x is 0, 1, 2, 3 or 4. In certain embodiments, the ligand L is selected from water, hydroxide, ammonia, amino group, amido group, alkylthiolate, halide and combinations thereof.

[0279] Antiwear additives, such as ZDDP and / or zinc carbamate, are generally 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. Preferably, the antiwear additive is ZDDP, such as primary ZDDP, secondary ZDDP, or a mixture of primary and secondary ZDDP, and is present in an amount of 0.4 wt% to 1.2 wt%, preferably 0.5 wt% to 1.0 wt%, more preferably 0.6 wt% to 0.8 wt% based on the total weight of the lubricating composition. As described above, the lubricating oil composition of the present invention contains less than 1000 ppm phosphorus. Therefore, the antiwear additive, preferably ZDDP, is present in an amount that provides less than 1000 ppm phosphorus based on the total mass of the lubricating composition, measured by ASTM D5185. Preferably, the antiwear additive, preferably ZDDP, is present in an amount that provides less than 900 ppm phosphorus, such as less than 850 ppm phosphorus, based on the total mass of the lubricating composition, measured by ASTM D5185. More preferably, the antiwear additive, preferably ZDDP, is present in an amount that provides 700 ppm to 900 ppm phosphorus based on the total mass of the lubricating composition, measured by ASTM D5185.

[0280] The antiwear additives useful herein also include boron-containing compounds such as borate esters, boronized fatty amines, boronized epoxides, alkali metal (or mixed alkali metals or alkaline earth metals) borates, and boronized overbased metal salts.

[0281] The compositions according to the present disclosure may contain additives having different recited functions and also having a secondary effect as antiwear agents (e.g., the above-described Component B dispersants and the following Component P functionalized polymers may also have an antiwear effect). For determining the amount of antiwear agent in the lubricating oil compositions or concentrates herein, these additives are not counted as antiwear agents. L. Demulsifiers

[0282] The demulsifiers useful herein include those described in U.S. Patent No. 10,829,712 (column 20, lines 34 to 40). Generally, small amounts of demulsifying components can be used herein. Preferred demulsifying components are described in European Patent No. 330 522. It is obtained by reacting an alkylene oxide with an adduct obtained by reacting a diepoxide with a polyol. Such additives can be used in an amount of about 0.001 to 5 wt%, preferably about 0.01 to 2 wt%. M. Seal compatibilizers

[0283] Other optional additives include seal compatibilizers such as organophosphates, aromatic esters, aromatic hydrocarbons, esters (e.g., butyl benzyl phthalate), and polybutenyl succinic anhydride. Such additives can be used in an amount of about 0.001 to 5 wt%, preferably about 0.01 to 2 wt%, more preferably 0.05 to 1 wt%, and even more preferably 0.1 to 0.5 wt%. In an embodiment, the seal compatibilizer is a seal swelling agent such as PIBSA (polyisobutenyl succinic anhydride). N. Extreme pressure agents

[0284] The lubricating oil composition of the present disclosure may contain one or more extreme pressure agents that can prevent seizure of sliding metal surfaces 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, an extreme pressure agent is a compound that can chemically bond with a metal to form a surface film that prevents 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, dialkyl polysulfides, sulfurized Diels-Alder adducts, sulfurized dicyclopentadiene, sulfurized or co-sulfurized mixtures of fatty acid esters and mono-unsaturated olefins, co-sulfurized blends of fatty acids, fatty acid esters, and α-olefins, functionally substituted dialkyl polysulfides, thioaldehydes, thioketones, episulfide compounds, sulfur-containing acetal derivatives, co-sulfurized blends of terpenes and acyclic olefins, polysulfide olefin products, amine salts of phosphate esters or thiophosphate esters, and combinations thereof. Based on the total weight of the lubricating oil composition, the amount of the extreme pressure agent can range from about 0.01 wt% to about 5 wt%, from about 0.05 wt% to about 3 wt%, or from about 0.1 wt% to about 1 wt%. O. Non-base oil unsaturated hydrocarbons

[0285] The lubricating oil composition 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 improver that may be present in the composition and always have at least one (usually only one in the case of linear α-olefins or LAOs) unsaturation per molecule. Without being bound by theory, this unsaturation can provide antioxidant functionality and / or sulfur capture functionality, which can 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 functionality and the only corrosion inhibition functionality in a 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 hydrocarbons, C 12 -C 36 hydrocarbons, C 12 -C 30 hydrocarbons, or C 12 -C 24Hydrocarbons). When there is only one unsaturation, the unsaturated hydrocarbon can be referred to as a linear alpha-olefin (LAO). Other non-limiting examples of unsaturated hydrocarbons can include polyisobutene oligomers / polymers and / or blends thereof that retain (or are post-polymerization modified to exhibit) (near) terminal unsaturation. When present, the unsaturated hydrocarbon (LAO) can be present in an amount of 0.01 to 5 wt% (especially 0.1 to 3 wt%, or 0.1 to 1.5 wt%) based on the total weight of the lubricating oil composition. P. Functionalized polymers

[0286] In an embodiment, the lubricating oil composition or concentrate of the present invention comprises one or more functionalized polymers. Suitable functionalized polymers include functionalized polyolefins, such as ethylene-propylene copolymers that have been functionalized with an acylating agent, such as maleic anhydride and an amine; polymethacrylates functionalized with an amine or an esterified styrene-maleic anhydride copolymer reacted with an amine. A more detailed description of functionalized polymers is disclosed in WO 2006 / 015130 or U.S. Patent Nos. 4,863,623; 6,107,257; 6,107,258; and 6,117,825. In an embodiment, the functionalized polymers can include those described in U.S. 4,863,623 (see column 2, lines 15 to column 3, line 52) or WO 2006 / 015130 (see page 2, paragraph

[0008] and the preparation examples described in paragraphs

[0065] to

[0073] ). Preferred functionalized polymers include the functionalized polymers described in U.S. Patent Application USSN 18 / 480,571 filed on October 4, 2023 and U.S. Patent Application USSN 63 / 379,006 filed on October 11, 2022, including but not limited to amide, imide, ester, and / or alcohol functionalized partially or fully saturated polymers containing C 4至5 polymers of olefins having an Mw / Mn of less than 2, a functionality parameter of 1.4 to 15 / 10,000 g / mol, and wherein the polymer before functionalization has an Mn (GPC-polystyrene standard) of greater than 30,000 g / mol, such as amine-functionalized partially or fully saturated polyisoprene, wherein the GPC-polystyrene standard, Mw / Mn, and functionality parameter are as described in U.S. Patent Application USSN 18 / 480,571 filed on October 4, 2023 and U.S. Patent Application USSN 63 / 379,006 filed on October 11, 2022, which are hereby incorporated by reference herein.

[0287] In certain embodiments, the lubricating oil composition or concentrate comprises amide, imide, and / or ester functionalized polymers that comprise partially or fully saturated polymers containing C 4-5The polymer main chain of an olefin, the polymer having i) an Mw / Mn of less than 2, such as less than 1.6, such as less than 1.5, such as 1.4 or less, 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, ii) a functionality distribution (Fd) value of 3.5 or less, and iii) an Mn (determined by GPC-PS) of the polymer before functionalization of 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, or 10,000 to 300,000 g / mol, such as 20,000 to 150,000 g / mol, such as 30,000 to 125,000 g / mol, such as 35,000 to 100,000 g / mol, such as 40,000 to 80,000 g / mol.

[0288] The polymers herein useful for preparing amide, imide, and / or ester functionalized polymers and / or the functionalized polymers can be homopolymers or copolymers. Copolymers can be random copolymers, gradient block copolymers, star copolymers, or block copolymers. Block copolymers are formed from a monomer mixture comprising one or more first monomers (such as isobutene), where, for example, the first monomer forms discrete blocks of the polymer that are attached to second discrete blocks of the polymer formed from a second monomer (such as butadiene). Although block copolymers have substantially discrete blocks formed from monomers, gradient block copolymers can consist of a relatively pure first monomer at one end and a relatively pure second monomer at the other end. The middle of the gradient block copolymer can be more of a gradient composition of these two monomers.

[0289] The polymers herein useful for preparing amide, imide, and / or ester functionalized polymers can be copolymers or homopolymers of butadiene, isoprene, etc.

[0290] Polymers useful in the preparation of amide, imide, and / or ester functionalized polymers 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 - 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%).

[0291] In an embodiment, the functionalized polymer comprises 10 (such as 9, such as 8, such as 7, such as 6, such as 5, such as 4, such as 3, such as 2, such as 1) weight percent or less of styrene monomer based on the weight of the functionalized polymer.

[0292] In an embodiment, styrene repeat units may be absent in the functionalized polymer.

[0293] In an embodiment, the functionalized polymer can be a block copolymer or a gradient block copolymer that does not contain a styrene block.

[0294] In an embodiment, the functionalized polymer can be a block copolymer or a gradient block copolymer that comprises isoprene (or consists of or consists essentially of isoprene).

[0295] In an embodiment, the functionalized polymer can be a block copolymer or a gradient block copolymer that comprises 50 weight percent or more of isoprene based on the weight of the copolymer.

[0296] In an embodiment, the functionalized polymer can be a block copolymer or a gradient block copolymer that comprises C 4-5 conjugated diene (or consists of or consists essentially of C 4-5 conjugated diene), preferably 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 C 4-5 conjugated diene based on the weight of the copolymer. 4-5 conjugated diene of the block copolymer or gradient block copolymer.

[0297] In an embodiment, the functionalized polymer can be a copolymer comprising more than 50 (such as 60, such as 70, such as 80, such as 90, such as 95, such as 98) wt% isoprene based on the weight of the copolymer.

[0298] In an embodiment, the functionalized polymer can be a copolymer comprising more than 50 (such as 60, such as 70, such as 80, such as 90, such as 95, such as 98) wt% butadiene based on the weight of the copolymer.

[0299] In an embodiment, the functionalized polymer can be a copolymer comprising more than 50 (such as 60, such as 70, such as 80, such as 90, such as 95, such as 98) wt% butadiene and isoprene based on the weight of the copolymer.

[0300] In an embodiment, the functionalized polymer can be a diblock copolymer comprising at least one isoprene homopolymer or copolymer block.

[0301] In an embodiment, the polymer herein useful for preparing amide, imide, and / or ester functionalized polymers is a homopolymer of isoprene, or a copolymer 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%) comonomer.

[0302] Preferably, the polymer backbone of the functionalized polymer is derived from a homopolymer or copolymer of partially or fully hydrogenated isoprene or butadiene, preferably a homopolymer. More preferably, the polymer backbone of the functionalized polymer comprises at least 90% partially or fully hydrogenated isoprene repeating units. More preferably, the polymer backbone of the functionalized polymer is partially or fully hydrogenated homopolyisoprene. More preferably, the polymer backbone of the functionalized polymer is partially or fully hydrogenated homopolyisoprene having a Mn (GPC-PS) of more than 30,000 g / mol.

[0303] Optionally, the polymer backbone comprises repeating units of one or more polar monomers, such as (but not limited to) those selected from fumarate esters, acrylate esters, and combinations thereof.

[0304] Optionally, styrene repeating units may be absent in the polymer herein useful for preparing the functionalized polymer. Optionally, styrene repeating units may be absent in the functionalized hydrogenated / saturated polymer.

[0305] Optionally, butadiene repeating units may be absent in the polymer herein useful for preparing the functionalized polymer. Optionally, butadiene repeating units may be absent in the functionalized hydrogenated / saturated polymer.

[0306] Optionally, the polymers useful herein for preparing functionalized polymers may not be homopolybutene. Optionally, the functionalized hydrogenated / saturated polymers may not be homopolybutene.

[0307] Optionally, the polymers useful herein for preparing functionalized polymers may not be homopolyisobutene. Optionally, the functionalized hydrogenated / saturated polymers may not be homopolyisobutene.

[0308] Optionally, the polymers useful herein for preparing functionalized polymers may not be copolymers of isoprene and butadiene. Optionally, the functionalized hydrogenated / saturated polymers may not be copolymers of isoprene and butadiene.

[0309] Typically, the polymerized conjugated dienes in the functionalized polymers include monomer units that have been inserted into the growing polymer chain by both conjugate addition and non-conjugate addition. In embodiments, as measured by 13 13C NMR, based on the total of conjugate addition and non-conjugate insertion, the functionalized polymer contains at least about 50% insertion by conjugate addition, such as at least about 75% insertion by conjugate addition, such as about 80% insertion by conjugate addition, such as from about 85% to about 100% insertion by conjugate addition.

[0310] Typically, the polymerized conjugated diene polymers useful herein for preparing amide, imide, and / or ester functionalized polymers include a mixture of 1,4- and 1,2-insertions (also known as 2,1-insertions; for butadiene, 1,2-insertion is the same as 3,4-insertion). As measured by 1 1H NMR, the polymerized conjugated diene polymers useful herein for preparing functionalized polymers contain at least about 50% 1,4-insertion, such as at least about 75% 1,4-insertion, such as at least about 80% 1,4-insertion, such as at least about 90% 1,4-insertion, such as at least about 95% 1,4-insertion, such as at least 98% 1,4-insertion, based on the total of 2,1-insertion, 1,4-insertion, and 3,4-insertion of isoprene. For the purposes of this disclosure: 1) the phrase "1,4-insertion" includes 1,4- and 4,1-insertions, 2) the phrase "2,1-insertion" includes 2,1- and 1,2-insertions, and 3) the phrase "3,4-insertion" includes 3,4- and 4,3-insertions.

[0311] Insertion of isoprene most typically occurs by 2,1-insertion, 1,4-insertion (trans and cis), and 3,4-insertion of isoprene. (Measurement of insertion geometry by 1 1H NMR). By 1For ¹H NMR measurements, the functionalized isoprene polymers contain at least about 50% 1,4 - insertion, based on the total of 2,1 - insertion, 1,4 - insertion, and 3,4 - insertion based on isoprene, such as at least about 75% 1,4 - insertion, such as at least about 80% 1,4 - insertion, such as at least about 90% 1,4 - insertion, such as at least about 95% 1,4 - insertion, such as at least 98% 1,4 - insertion. For the present disclosure: 1) the phrase "1,4 - insertion" includes 1,4 - and 4,1 - insertion, 2) the phrase "2,1 - insertion" includes 2,1 - and 1,2 - insertion, and 3) the phrase "3,4 - insertion" includes 3,4 - and 4,3 - insertion.

[0312] The polymers useful herein for preparing functionalized polymers may generally have a Mn (i.e., before functionalization) of 10,000 to 150,000 g / mol, or about 10,000 to about 100,000 g / mol, or 20,000 to about 150,000 g / mol, or 30,000 to about 125,000 g / mol, such as about 30,000 to about 50,000 g / mol, such as about 30,000 to about 40,000 g / mol, or 35,000 to about 100,000 g / mol, or 40,000 to 80,000 g / mol (GPC - PS). Alternatively, the polymer before functionalization may have a Mn (GPC - PS) of at least 25,000 g / mol, such as at least 30,000 g / mol.

[0313] The polymers useful herein for preparing functionalized polymers may generally have an Mw / Mn (determined 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 useful herein for preparing functionalized polymers may generally 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 1.5, such as less than 1.4, such as less than 1.3, such as below 1.25, such as less than 1.2, such as less than 1.15, such as less than 1.12, such as less than 1.10). As functionalization proceeds, Mw / Mn broadening may occur.

[0314] In an embodiment, the functionalized polymer may have a number - average molecular weight (Mn) of greater than 15,000 (such as 20,000, such as 25,000, such as 30,000, such as 35,000, such as 40,000) g / mol as determined by GPC - PS. In certain embodiments, the functionalized polymer may have a number - average molecular weight (Mn) of 20,000 to 60,000, particularly 30,000 to 40,000 g / mol (GPC - PS).

[0315] In embodiments, the functionalized polymer may have a weight-average molecular weight (Mw) of 50,000 g / mol or less (such as 40,000 g / mol, such as 35,000 g / mol) as determined by GPC-PS. In embodiments, the functionalized polymer may have a weight-average molecular weight (Mw) of 1,000 to 50,000 g / mol, such as 5,000 to 40,000 g / mol as determined by GPC-PS.

[0316] The functionalized polymer may generally 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 generally 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).

[0317] The polymer used to prepare the functionalized polymer may have an Mz (determined by GPC-PS) of 20,000 to 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, such as about 50,000 to about 60,000 g / mol, or 40,000 to 60,000 g / mol (GPC-PS).

[0318] In embodiments, the functionalized polymer may have a z-average molecular weight (Mz) of 5,000 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 (GPC-PS).

[0319] The polymers useful herein for preparing functionalized polymers can have a glass transition temperature (Tg) of -25 °C or lower, such as -40 °C or lower, such as -50 °C or lower, as determined by differential scanning calorimetry (DSC) using a Perkin Elmer or TA Instrument Thermal Analysis System (heating the sample from ambient temperature to 210 °C at 10 °C / min and holding at 210 °C for 5 minutes, then cooling to -40 °C at 10 °C / min and holding for 5 minutes).

[0320] The polymers useful herein for preparing functionalized polymers typically have a residual unsaturation of less than 3%, such as less than 2%, such as less than 1%, such as less than 0.5%, such as less than 0.25%, based on the number of double bonds in the non-hydrogenated polymer.

[0321] The polymers useful herein for preparing functionalized polymers typically have a residual metal (such as 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.

[0322] The amide-, imide-, and / or ester-functionalized fully or partially saturated (such as fully or partially hydrogenated) C 4-5 Polymers of conjugated dienes can be obtained by reacting a fully or partially saturated (such as fully or partially hydrogenated) C 4-5 polymer of conjugated dienes having an Mw / Mn of less than 2 with an acylating agent, such as maleic acid or maleic anhydride, and thereafter reacting the acylated polymer with an amine (such as a polyamine) to form an imide, an amide, or a combination thereof.

[0323] Details regarding the hydrogenation, acylation, and functionalization of polymers to prepare the amide-, imide-, and / or ester-functionalized polymers of the present invention are disclosed in U.S. Patent Application USSN 18 / 480,571, filed October 4, 2023, particularly paragraphs

[0223] to

[0262] , and U.S. Patent Application USSN 63 / 379,006, filed October 11, 2022, particularly paragraphs

[0213] to

[0252] .

[0324] In embodiments, the amide-, imide-, and / or ester-functionalized polymers are 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 the solvent, diluent, and polymer.

[0325] In embodiments, amide, imide, and / or ester functionalized polymers are not prepared in alkylated naphthylenic solvents, or the alkylated solvents are present at 5 wt% or less, such as 3 wt% or less, such as 1 wt% or less, based on the weight of the solvent, diluent, and polymer.

[0326] 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, for example 7, 8, or 9 FG grafts / polymer chain.

[0327] The functionalized polymer may have an average functionality of 15 (such as 14, 13, 12, 11, 10, 9, 8, 7, or 6) or fewer FG grafts / polymer chain as determined by GPC-PS.

[0328] The functionalized polymer may have an average functionality of 1 (such as 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 / polymer chain as determined by GPC-PS.

[0329] The functionalized polymer may have an average functionality of 1 (such as 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 (such as 14, 13, 12, 11, 10, 9, 8, 7, or 6) FG grafts / polymer chain as determined by GPC-PS.

[0330] 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.

[0331] In embodiments, the functionalized polymer may comprise a branched C monomer acylated polymer having an Mw / Mn of 2 or less, such as 1 to 2.0 as determined by GPC-PS and having a Mn of 20,000 to 500,000 g / mol. 4-5 monomer.

[0332] In embodiments, the functionalized polymer can 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%, where the gel content is measured by determining the amount of material extractable from the polymer using boiling xylene (or cyclohexane) as the extractant. The percentage of soluble and insoluble (gel) materials in the polymer composition is measured by determining the amount of material extractable from the polymer using boiling xylene (or cyclohexane) as the extractant. The percentage of soluble and insoluble (gel) materials in the polymer composition is determined by soaking a nominally 0.5 mm thick polymer film specimen in cyclohexane at 23 °C for 48 hours 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) materials. This method is generally described in U.S. Patent No. 4,311,628, which is incorporated herein by reference. For the purposes of this disclosure, the gel content is measured using boiling xylene, unless the sample is insoluble in xylene, in which case the cyclohexane method is used.

[0333] In embodiments, the functionalized polymer can have a functionality distribution (Fd) value of 3.5 or less (such as 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, such as 1.7 to 1.9, as determined by GPC-PS), and 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, such as 7, 8, or 9 FG grafts / polymer chain, as determined by GPC-PS.

[0334] In certain embodiments, the lubricating oil composition or concentrate comprises an amide-, imide-, and / or ester-functionalized polymer comprising C 4-5 olefins (consisting essentially of C 4-5 olefins or consisting of C 4-5 olefins), a hydrogenated / saturated polymer having an Mw / Mn of less than 2 and a functionality distribution (Fd) value of 3.5 or less (such as 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 polyisobutene, polybutadiene, or a copolymer thereof (preferably polyisobutene or a copolymer of isobutene and butadiene), the C4 olefin polymer has a Mn (GPC-PS) of 10,000 g / mol or more, and if the polymer before functionalization is a C4 / C5 copolymer of isoprene and butadiene, the copolymer has a Mn greater than 25,000 Mn (GPC-PS).

[0335] In certain embodiments, the lubricating oil composition or concentrate comprises an amide-, imide- and / or ester-functionalized hydrogenated / saturated polymer comprising greater than 90 mole % isoprene repeat units, having an 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 an Mn (GPC-PS) of greater than 10,000 g / mol, such as greater than 30,000 g / mol.

[0336] In certain embodiments, the lubricating oil composition or concentrate comprises an amide-, imide- and / or ester-functionalized hydrogenated / saturated isoprene homopolymer having an Mw / Mn of less than 2, such as less than 1.8, a functionality distribution (Fd) value of 3.5 or less (such as 3.4 or less, such as 2.5 or less, or 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), an average functionality (Fv) of 4 to 10 functional groups grafted / polymer chain, and wherein the polymer prior to functionalization has an Mn (as determined by GPC-PS) of greater than 20,000 g / mol, such as from 20,000 to 50,000 g / mol.

[0337] In certain embodiments, the functionalized polymers used in the lubricating oil compositions and concentrates of the present invention have an Mw / Mn of 1.0 to 2, such as 1.1 to 1.8, such as 1.2 to 1.5; a functionality distribution (Fd) value of 1.0 to 3.5, such as 1.5 to 2.5, such as 1.9 to 2.1, as determined by GPC-PS disclosed herein; an average functionality (Fv) of 4 to 10, such as 6 to 8 (as determined as disclosed herein); an Mn (GPC-PS) of 20,000 to 50,000 g / mol, such as 30,000 to 40,000 g / mol; and / or an Mz (GPC-PS) of 40,000 to 70,000 g / mol, such as 50,000 to 60,000 g / mol; and / or have a homopolyisoprene backbone that has been functionalized with maleic anhydride and further reacted with a polyamine, such as N-phenyl-p-phenylenediamine (NPPDA), such as 4-amino-diphenylamine (ADPA).

[0338] In certain embodiments, the amide-, imide- and / or ester-functionalized polymers of the present invention are present in the lubricating oil composition in an amount of 0.01 to 5 mass %, such as 0.05 to 4 mass %, such as 0.1 to 3 mass %, such as 0.2 to 2 mass %, such as 0.3 to 1.0 mass %, such as 0.4 to 0.8 mass %, based on the total mass of the lubricating oil composition.

[0339] In certain embodiments, the lubricating oil composition or concentrate does not contain or substantially does not contain an amine-functionalized hydrogenated isoprene polymer having an average functionality (Fv) of 7.0, a functionality distribution (Fd) value of 1.86, an Mw / Mn of 1.250, an Mn (GPC-PS) of 35,140 g / mol, and an Mz (GPC-PS) of 55,726 g / mol, such as less than 0.6 mass %, such as less than 0.5 mass %, such as less than 0.4 mass %, such as less than 0.3 mass %, such as less than 0.2 mass %, such as less than 0.1 mass %, based on the total mass of the lubricating oil composition.

[0340] In the lubricating oil compositions and concentrates according to the present disclosure, component P), in particular amide, imide, and / or ester-functionalized polymers as described herein, are considered dispersants in addition to the dispersants of component B) (in particular the PIBSA-PAM dispersants of component B)). Thus, the dispersants of component B), in particular the PIBSA-PAM of component B), and the functionalized polymers of component P), in particular amide, imide, and / or ester-functionalized polymers as described herein, are used together to determine the amount of dispersant in the lubricating oil compositions or concentrates disclosed herein. However, it is to be understood that the functionalized polymers of component P), in particular amide, imide, and / or ester-functionalized polymers as described herein, are not PIBSA-PAM. In certain embodiments, the one or more dispersants comprise 0.01 to 50 mass %, such as 0.1 to 40 mass %, such as 1 to 30 mass %, such as 5 to 25 mass %, such as 10 to 20 mass %, such as 12 to 16 mass % of amide, imide, and / or ester-functionalized polymers, based on the total mass of the dispersant.

[0341] When the lubricating oil composition contains one or more of the additives discussed above, the additives are typically incorporated 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, particularly for crankcase lubricants, are shown in the table below.

[0342] It should be noted that many additives are shipped by the additive manufacturer as concentrates containing one or more additives together with a quantity of base oil or other diluent. Thus, the weights in the table below and other amounts mentioned herein relate to the amount of active ingredient (i.e., the undiluted portion of the ingredient). The weight % (mass %) shown below is based on the total weight of the lubricating oil composition. Typical amounts of optional lubricating oil components

[0343] The above additives are typically commercially available materials. These additives can be added independently, but are usually pre - combined in additive packages obtainable from lubricant additive suppliers. Additive packages with various compositions, ratios, and properties are available and the choice of appropriate packaging will take into account the use of the final composition.

[0344] The following non - limiting examples are provided to illustrate the present disclosure. Fuel

[0345] The present disclosure also relates to a method of lubricating an internal combustion engine during engine operation, which includes: (i) providing a lubricating composition as described herein to the crankcase of the internal combustion engine; (ii) providing a hydrocarbon fuel in the internal combustion engine; and (iii) combusting the fuel in an 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).

[0346] The present disclosure also relates to a fuel composition comprising a lubricating composition as described herein and a hydrocarbon fuel, wherein the fuel may be derived from petroleum and / or biological sources (“biofuel” or “renewable fuel”). In an embodiment, the fuel comprises 0.1 to 100% by mass of renewable fuel, or 1 to 75% by mass of renewable fuel, or 5 to 50% by mass of renewable fuel, based on the total mass of the renewable fuel and the petroleum - derived fuel.

[0347] Renewable fuel components are typically made from vegetable oils (such as palm oil, rapeseed oil, soybean oil, jatropha oil), microbial oils (such as algal oil), animal fats (such as edible oil, animal fat, and / or fish fat), and / or biogas. Renewable fuel refers to biofuels made from biological resources formed through contemporary biological processes. In one embodiment, the renewable fuel component is made by a hydrotreating process. Hydrotreating involves various reactions in which molecular hydrogen reacts with other components, or components undergo molecular transformation in the presence of molecular hydrogen and a solid catalyst. The reactions include, but are not limited to, hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrocracking, and isomerization. Renewable fuel components can have different distillation ranges to provide the desired properties for the component according to the intended use.

[0348] In certain embodiments, the fuel is one or more of a hydrocarbon fuel, a renewable fuel, a hydrogen fuel, natural gas, or any blend thereof, preferably a hydrocarbon fuel.

[0349] In certain embodiments, the engine is a diesel engine, such as a heavy - duty diesel engine or an automotive diesel engine.

[0350] In certain embodiments, the engine is a motorcycle engine, a stationary gas engine or a diesel-powered engine, a locomotive engine or a four-stroke medium-speed trunk piston engine. Use

[0351] The lubricating compositions of the present disclosure can be used to lubricate mechanical engine components by adding a lubricant thereto, particularly in internal combustion engines, such as spark-ignited or compression-ignited two-stroke or four-stroke reciprocating engines. Generally, they are crankcase lubricants, such as passenger car motor oils or heavy-duty diesel engine lubricants.

[0352] In particular, the lubricating compositions of the present disclosure are suitably used for lubricating the crankcase of a compression-ignition internal combustion engine, such as a heavy-duty diesel engine.

[0353] In particular, the lubricating compositions of the present disclosure are suitably used for lubricating the crankcase of a spark-ignited turbocharged internal combustion engine.

[0354] In an embodiment, the lubricating oil of the present disclosure is used in a spark-assisted high-compression internal combustion engine, and when used in a high-compression spark-ignited internal combustion engine, the lubricating oil composition of the present disclosure can be used to lubricate the high-compression spark-ignited engine.

[0355] In an embodiment, the lubricating compositions of the present disclosure are suitably used for lubricating the crankcase of an engine of a heavy-duty diesel vehicle (i.e., a heavy-duty diesel vehicle with a gross vehicle weight rating of more than 10,000 pounds).

[0356] In an embodiment, the lubricating compositions of the present disclosure are suitably used for lubricating the crankcase of a passenger car diesel engine.

[0357] In particular, the lubricating oil formulations of the present disclosure are particularly useful for compression-ignition internal combustion engines that use low-viscosity oils (such as API FA-4) and future oil categories where wear protection of the valve train becomes challenging, i.e., heavy-duty diesel engines.

[0358] The present disclosure further relates to the following items: 1. A lubricating oil composition containing less than 1000 ppm of phosphorus, which comprises: A) At least 50% by mass of one or more base oils, based on the total mass of the lubricating oil composition; B) One or more dispersants, wherein the one or more dispersants comprise 2.0 to 6.00% by mass of one or more poly(alkenyl) succinimides, based on the total mass of the lubricating oil composition, wherein the polyalkenyl is derived from polyisobutene and the imide is derived from a polyamine (“PIBSA-PAM”); wherein the one or more PIBSA-PAMs comprise one or more unborated PIBSA-PAMs in an amount of at least 2.0% by mass based on the total mass of the lubricating oil composition; and C) one or more detergents, wherein the one or more detergents together provide an amount of soap in the lubricating oil composition of 0.1 to 0.9% by mass based on the total mass of the lubricating oil composition; wherein: i) the ratio of the one or more unborated PIBSA-PAMs of the lubricating oil composition to the % by mass of soap based on the total mass of the lubricating oil composition is 6.65 or more, and ii) the lubricating oil composition has an SAE viscosity grade of 20W-X, 15W-X, 10W-X or 5W-X, where X represents any one of 8, 12, 16, 20, 30 and 40, such as 30 or 40, such as 30. 2. The lubricating oil composition of item 1, wherein: A) the one or more base oils are present together in an amount of at least 50% by mass based on the total mass of the lubricating oil composition; B) the one or more dispersants are present together in an amount of 2 to 15% by mass based on the total mass of the lubricating oil composition; and C) the one or more detergents are present together in an amount of 0.1 to 5% by mass based on the total mass of the lubricating oil composition. 3. The lubricating oil composition of item 1 or item 2, which further comprises one or more additional additives selected from friction modifiers, antioxidants, pour point depressants, defoamers, viscosity improvers, corrosion inhibitors, rust inhibitors, antiwear agents, seal compatibility agents, extreme pressure agents, unsaturated C 12 -C 60 hydrocarbons and functionalized polymers. 4. The lubricating oil composition of any one of the preceding items, which further comprises one or more additional additives selected from: D) one or more friction modifiers in an amount of 0.01 to 5% by mass based on the total mass of the lubricating oil composition; E) one or more antioxidants in an amount of 0.01 to 13 (such as 0.1 to 10% by mass) based on the total mass of the lubricating oil composition; F) one or more pour point depressants in an amount of 0.01 to 5% by mass based on the total mass of the lubricating oil composition; G) one or more defoamers in an amount of 0.001 to 5% by mass based on the total mass of the lubricating oil composition; H) one or more viscosity improvers in an amount of 0.001 to 10% by mass based on the total mass of the lubricating oil composition; J) 0.001 to 5% by mass, based on the total mass of the lubricating oil composition, of one or more corrosion inhibitors and / or rust inhibitors; K) 0.001 to 10% by mass, based on the total mass of the lubricating oil composition, of one or more antiwear agents; M) 0.01 to 5% by weight, based on the total weight of the lubricating oil composition, of one or more seal compatibilizers, such as seal swelling agents; N) Optionally, 0.01 to 5% by mass, based on the total mass of the lubricating oil composition, of one or more extreme pressure agents, O) 0.01 to 5% by mass, based on the total mass of the lubricating oil composition, of one or more unsaturated C 12 -C 60 hydrocarbons, and P) 0.001 to 10% by mass, based on the total weight of the lubricating oil composition, of one or more functionalized polymers. 5. The lubricating oil composition of any one of the preceding items, which contains less than 900 ppm, such as less than 850 ppm, of phosphorus. 6. The lubricating oil composition of any one of the preceding items, which contains 700 ppm to 900 ppm of phosphorus. 7. The lubricating oil composition of any one of the preceding items, which comprises 50 to 95% by mass, such as 60 to 90% by mass, such as 70 to 85% by mass, of one or more base oils, based on the total mass of the lubricating oil composition. 8. The lubricating oil composition of any one of the preceding items, wherein the one or more base oils comprise one or more Group II base oils and optionally one or more Group III base oils. 9. The lubricating oil composition of any one of the preceding items, wherein the one or more base oils comprise at least 50% by mass, such as at least 70% by mass, such as at least 90% by mass, of Group II base oils, based on the total mass of the base oils present in the lubricating oil composition. 10. The lubricating oil composition of any one of the preceding items, which comprises at least 50% by mass, such as at least 60% by mass, such as at least 65% by mass, of Group II base oils, based on the total mass of the lubricating oil composition. 11. The lubricating oil composition of any one of the preceding items, wherein the one or more detergents are selected from oil-soluble neutral or overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, naphthenates, other oil-soluble carboxylates, and mixtures thereof, of alkali metals or alkaline earth metals. 12. The lubricating oil composition of any one of the preceding items, wherein the one or more detergents are selected from oil-soluble neutral or overbased sulfonates, salicylates, and mixtures thereof, of calcium and / or magnesium. 13. The lubricating oil composition of any one of the foregoing items, wherein the one or more detergents comprise calcium salicylate in an amount of 50% by mass or less based on the total mass of the detergents present in the lubricating oil composition. 14. The lubricating oil composition of any one of the foregoing items, wherein the one or more detergents are selected from oil-soluble overbased sulfonates of calcium and / or magnesium. 15. The lubricating oil composition of any one of the foregoing items, which does not contain or substantially does not contain phenolic detergent, such as less than 0.5% by mass, such as less than 0.2% by mass, such as less than 0.1% by mass of phenolic detergent based on the total mass of the lubricating oil composition. 16. The lubricating oil composition of any one of the foregoing items, wherein the lubricating oil composition does not contain or substantially does not contain phenolic detergent. 17. The lubricating oil composition of any one of the foregoing items, wherein the one or more detergents are present together in an amount of 0.1 to 4% by mass, such as 0.2 to 3% by mass, such as 0.4 to 2% by mass, such as 0.5 to 1.5% by mass, such as 0.8 to 1.2% by mass based on the total mass of the lubricating oil composition. 18. The lubricating oil composition of any one of the foregoing items, wherein the one or more detergents together provide less than 0.8% by mass, such as less than 0.7% by mass, such as less than 0.6% by mass, such as less than 0.55% by mass of soap based on the total mass of the lubricating oil composition. 19. The lubricating oil composition of any one of the foregoing items, wherein the one or more detergents together provide 0.2 to 0.8% by mass, such as 0.3 to 0.7% by mass, such as 0.4 to 0.6% by mass, such as 0.45 to 0.55% by mass of soap based on the total mass of the lubricating oil composition. 20. The lubricating oil composition of any one of the foregoing items, wherein the one or more unborated PIBSA-PAMs are present in an amount of 2.5 to 5.5% by mass, such as 3.5 to 5.0% by mass, such as 4.0 to 4.5% by mass based on the total mass of the lubricating oil composition. 21. The lubricating oil composition of any one of the foregoing items, wherein the one or more unborated PIBSA-PAMs comprise one or more unborated PIBSA-PAMs in which the polyalkenyl is derived from polyisobutene having a Mn (GPC-PS) of more than 1600 g / mol ("high molecular weight PIBSA-PAM"), and optionally one or more unborated PIBSA-PAMs in which the polyalkenyl is derived from polyisobutene having a Mn (GPC-PS) of less than 1600 g / mol ("low molecular weight PIBSA-PAM"). 22. A lubricating oil composition according to any one of the preceding items, wherein said one or more unborated PIBSA-PAMs are present in an amount of 0.5 to 4% by mass, such as 1.0 to 3.5% by mass, such as 1.5 to 3.0% by mass, such as 2.0 to 2.5% by mass, based on the total mass of the lubricating oil composition, of one or more unborated high molecular weight PIBSA-PAMs. 23. A lubricating oil composition according to any one of the preceding items, wherein said one or more unborated PIBSA-PAMs are present in an amount of 0.5 to 4% by mass, such as 1.0 to 3.5% by mass, such as 1.5 to 3.0% by mass, such as 2.0 to 2.5% by mass, based on the total mass of the lubricating oil composition, of one or more unborated high molecular weight PIBSA-PAMs, and in an amount of 0.5 to 4% by mass, such as 1 to 3% by mass, such as 1.8 to 2.5% by mass, based on the total mass of the lubricating oil composition, of one or more unborated low molecular weight PIBSA-PAMs. 24. A lubricating oil composition according to any one of the preceding items, wherein the ratio of the mass % based on the total mass of the lubricating oil composition of said one or more unborated high molecular weight PIBSA-PAMs to said one or more unborated low molecular weight PIBSA-PAMs is less than 3.65, such as less than 3.5, such as less than 3.0, such as less than 2.5, such as less than 2.0, such as less than 1.5. 25. A lubricating oil composition according to any one of the preceding items, wherein said one or more unborated low molecular weight PIBSA-PAMs are not derived from tetraethylenepentamine. 26. A lubricating oil composition according to any one of the preceding items, wherein said one or more dispersants further comprise one or more borated PIBSA-PAMs, wherein said one or more borated PIBSA-PAMs are present in an amount of 0.05 - 0.5% by mass, such as 0.1 - 0.4% by mass, such as 0.15 - 0.3% by mass, such as 0.2 - 0.25% by mass, based on the total mass of the lubricating oil composition. 27. A lubricating oil composition according to any one of the preceding items, wherein said unborated PIBSA-PAMs and borated PIBSA-PAMs together are present in an amount of 2.5 to 5.8% by mass, such as 3.0 to 5.5% by mass, such as 3.5 to 5.2% by mass, such as 4.0 to 5.0% by mass, such as 4.2 to 4.8% by mass, based on the total mass of the lubricating oil composition. 28. A lubricating oil composition according to any one of the preceding items, wherein said one or more dispersants together are present in an amount of 2 to 10% by mass, such as 3 to 8% by mass, such as 4 to 6% by mass, such as 4.5 to 5.5% by mass, based on the total mass of the lubricating oil composition. 29. The lubricating oil composition of any one of the foregoing items, which does not contain or substantially does not contain an aromatic dispersant, such as less than 0.5% by mass, such as less than 0.2% by mass, such as less than 0.1% by mass of the aromatic dispersant based on the total mass of the lubricating oil composition. 30. The lubricating oil composition of any one of the foregoing items, which does not contain or substantially does not contain the PIBSA ester of a hydrocarbyl-bridged naphthoxy alcohol, such as less than 0.6% by mass, such as less than 0.4% by mass, such as less than 0.2% by mass, such as less than 0.1% by mass based on the total mass of the lubricating oil composition. 31. The lubricating oil composition of any one of the foregoing items, wherein the lubricating oil composition is absent or substantially absent of the PIBSA ester of a hydrocarbyl-bridged naphthoxy alcohol. 32. The lubricating oil composition of any one of the foregoing items, wherein i) the ratio of the mass % of the one or more unborated PIBSA-PAMs and the soap in the lubricating oil composition based on the total mass of the lubricating oil composition is from 7.0 to 15.0, such as from 7.2 to 13.0, such as from 7.4 to 11.0, such as from 7.6 to 10.0, such as from 7.8 to 9.0, such as from 8.0 to 8.5. 33. The lubricating oil composition of any one of the foregoing items, wherein ii) the lubricating oil composition has an SAE viscosity grade of 15W-40, 5W-30 or 10W-30. 34. The lubricating oil composition of any one of the foregoing items, which further comprises an amide-, imide- and / or ester-functionalized polymer, which comprises a polymer backbone of a partially or fully saturated polymer comprising C 4-5 olefins, and the polymer has the following characteristics: i) Mw / Mn is less than 2, ii) the functionality distribution (Fd) value is 3.5 or less, and iii) the Mn of the polymer before functionalization is 10,000 g / mol or more (GPC-PS). 35. The lubricating oil composition of item 34, wherein the polymer backbone of the functionalized polymer is derived from a homopolymer or copolymer of partially or fully hydrogenated isoprene and butadiene. 36. The lubricating oil composition of item 34, wherein the polymer backbone of the functionalized polymer comprises at least 90% of partially or fully hydrogenated isoprene repeating units. 37. The lubricating oil composition of item 34, wherein the polymer backbone of the functionalized polymer is a partially or fully hydrogenated homopolyisoprene. 38. The lubricating oil composition of item 34, wherein the polymer backbone of the functionalized polymer is a partially or fully hydrogenated homopolyisoprene having a Mn (GPC-PS) of 30,000 g / mol or more. 39. A lubricating oil composition according to any one of items 34 to 38, wherein the functionalized polymer is present in an amount of 0.01 to 5% by mass, such as 0.05 to 4% by mass, such as 0.1 to 3% by mass, such as 0.2 to 2% by mass, such as 0.3 to 1.0% by mass, such as 0.4 to 0.8% by mass, based on the total mass of the lubricating oil composition. 40. A lubricating oil composition according to any one of the preceding items, which does not contain or substantially does not contain, such as less than 0.6% by mass, such as less than 0.5% by mass, such as less than 0.4% by mass, such as less than 0.3% by mass, such as less than 0.2% by mass, such as less than 0.1% by mass, based on the total mass of the lubricating oil composition, an amine-functionalized hydrogenated isoprene polymer having an average functionality (Fv) of 7.0, a functionality distribution (Fd) value of 1.86, an Mw / Mn of 1.250, an Mn (GPC-PS) of 35,140 g / mol, and an Mz (GPC-PS) of 55,726 g / mol. 41. A lubricating oil composition according to any one of the preceding items, wherein the lubricating oil composition is a heavy-duty diesel engine oil. 42. A lubricating oil composition according to any one of the preceding items, wherein the lubricating oil composition provides less than 120 mg, such as less than 110 mg, such as less than 100 mg, such as less than 90 mg, such as less than 80 mg, such as less than 70 mg, such as less than 60 mg, such as less than 50 mg, such as less than 40 mg of wear of the valve train rocker arm, as determined by the Ford 6.7L Power Stroke diesel engine test for soot-induced wear and viscosity control. 43. A lubricating oil composition according to any one of the preceding items, wherein the lubricating oil composition contains one or more molybdenum (Mo)-containing compounds, and wherein the one or more Mo-containing compounds together provide at least 50 ppm, such as at least 60 ppm Mo, to the lubricating oil composition. 44. A lubricating oil composition according to any one of items 1 to 41, which does not contain or substantially does not contain molybdenum (Mo), such as less than 60 ppm, such as less than 50 ppm, such as less than 40 ppm of Mo. 45. A lubricating oil composition containing less than 1000 ppm phosphorus, which comprises: A) at least 50% by mass, based on the total mass of the lubricating oil composition, of one or more base oils; B) one or more dispersants, wherein the one or more dispersants comprise 2 to 10% by mass, based on the total mass of the lubricating oil composition, of one or more poly(alkenyl) succinimides, wherein the polyalkenyl is derived from polyisobutene and the imide is derived from a polyamine ("PIBSA-PAM"); wherein said one or more PIBSA-PAMs comprise at least 2.0% by mass of one or more unborated PIBSA-PAMs based on the total mass of the lubricating oil composition; and C) one or more detergents, wherein said one or more detergents together provide an amount of soap of 0.1 to 0.9% by mass based on the total mass of the lubricating oil composition; and wherein said one or more detergents comprise less than 50% by mass of calcium salicylate based on the total mass of the detergents present in the lubricating oil composition; wherein: i) the ratio of the mass % of said one or more unborated PIBSA-PAMs of the lubricating oil composition to the soap based on the total mass of the lubricating oil composition is 6.65 or more, and ii) the lubricating oil composition has an SAE viscosity grade of 20W-X, 15W-X, 10W-X or 5W-X, where X represents any one of 8, 12, 16, 20, 30 and 40, such as 30 or 40, such as 30. 46. The lubricating oil composition of item 45, wherein said one or more PIBSA-PAMs are present in an amount of 2.5 to 10% by mass, such as 3 to 8% by mass, such as 3.5 to 6% by mass, based on the total mass of the lubricating composition. 47. The lubricating oil composition of item 45 or item 46, wherein the lubricating oil composition is further defined as in any one of items 2 to 44. 48. A lubricating oil composition containing less than 1000 ppm of phosphorus, which comprises: A) at least 50% by mass of one or more base oils based on the total mass of the lubricating oil composition; B) one or more dispersants, wherein said one or more dispersants comprise 2 to 10% by mass of one or more poly(alkenyl) succinimides based on the total mass of the lubricating oil composition, wherein the polyalkenyl is derived from polyisobutene and the imide is derived from a polyamine ("PIBSA-PAM"); wherein said one or more PIBSA-PAMs comprise at least 2.0% by mass of one or more unborated PIBSA-PAMs based on the total mass of the lubricating oil composition; and C) one or more detergents, wherein said one or more detergents together provide an amount of soap of 0.1 to 0.9% by mass based on the total mass of the lubricating oil composition; and P) an amide-, imide- and / or ester-functionalized polymer comprising a polymer backbone comprising partially or fully saturated C 4-5 olefin polymers, the polymer having the following characteristics: i) Mw / Mn is less than 2, ii) the functionality distribution (Fd) value is 3.5 or less, and iii) the Mn of the polymer before functionalization is 10,000 g / mol or more (GPC - PS); wherein: i) the ratio of the mass % of the one or more unborated PIBSA - PAM and soap in the lubricating oil composition based on the total mass of the lubricating oil composition is 6.65 or more, and ii) the lubricating oil composition has an SAE viscosity grade of 20W - X, 15W - X, 10W - X or 5W - X, where X represents any one of 8, 12, 16, 20, 30 and 40, such as 30 or 40, such as 30. 49. The lubricating oil composition of item 48, wherein the lubricating oil composition is further defined as in any one of items 2 to 44. 50. A concentrate comprising the following components or obtained by mixing the following components: A) 1 to less than 50 mass % of one or more base oils based on the total mass of the concentrate; B) one or more dispersants, wherein the one or more dispersants comprise one or more unborated poly(alkenyl) succinimides, wherein the polyalkenyl is derived from polyisobutene and the imide is derived from polyamine ("PIBSA - PAM"); and C) one or more detergents, wherein the one or more detergents provide soap for the concentrate; wherein the one or more detergents comprise 50 mass % or less of calcium salicylate based on the total mass of the detergents present in the concentrate; wherein: i) the ratio of the mass % of the one or more unborated PIBSA - PAM and soap in the concentrate based on the total mass of the concentrate is 6.65 or more. 51. The concentrate of item 50, which further comprises one or more additional additives selected from friction improvers, antioxidants, pour point depressants, defoamers, viscosity improvers, corrosion inhibitors, rust inhibitors, anti - wear agents, seal compatibilizers, extreme pressure agents, unsaturated C 12 - C 60 hydrocarbons and functionalized polymers. 52. The concentrate of item 50 or item 51, wherein the one or more detergents are selected from oil - soluble neutral or over - based sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, naphthenates, other oil - soluble carboxylates of alkali metals or alkaline earth metals and mixtures thereof. 53. The concentrate according to any one of items 50 to 52, wherein the one or more detergents are selected from oil-soluble neutral or overbased sulfonates, salicylates, and mixtures thereof of calcium and / or magnesium. 54. The concentrate according to any one of items 50 to 53, wherein the one or more detergents are selected from oil-soluble neutral or overbased sulfonates of calcium and / or magnesium. 55. The concentrate according to any one of items 50 to 54, wherein the concentrate is free or substantially free of phenolic detergent. 56. The concentrate according to any one of items 50 to 55, wherein the one or more unborated PIBSA-PAMs comprise one or more unborated PIBSA-PAMs in which the polyalkenyl is derived from polyisobutene having a Mn (GPC-PS) of more than 1600 g / mol ("high molecular weight PIBSA-PAM"), and optionally one or more unborated PIBSA-PAMs in which the polyalkenyl is derived from polyisobutene having a Mn (GPC-PS) of less than 1600 g / mol ("low molecular weight PIBSA-PAM"). 57. The concentrate according to any one of items 50 to 56, wherein the ratio of the mass % of the one or more unborated high molecular weight PIBSA-PAMs to the one or more unborated low molecular weight PIBSA-PAMs, based on the total mass of the concentrate, is less than 3.65, such as less than 3.5, such as less than 3.0, such as less than 2.5, such as less than 2.0, such as less than 1.5. 58. The concentrate according to any one of items 50 to 57, wherein the one or more unborated low molecular weight PIBSA-PAMs are not derived from tetraethylenepentamine. 59. The concentrate according to any one of items 50 to 58, wherein the one or more dispersants further comprise one or more borated PIBSA-PAMs. 60. The concentrate according to any one of items 50 to 59, which does not contain or substantially does not contain aromatic dispersants, such as less than 0.5 mass %, such as less than 0.2 mass %, such as less than 0.1 mass % of aromatic dispersants based on the total mass of the concentrate. 61. The concentrate according to any one of items 50 to 60, which contains less than 8.0 mass %, such as less than 7.0 mass %, such as less than 6 mass %, such as less than 5 mass %, such as less than 4 mass %, such as less than 3 mass %, such as less than 2 mass %, such as less than 1 mass % of PIBSA esters of hydrocarbon-bridged naphthoxy alcohols based on the total mass of the concentrate. 62. The concentrate according to any one of items 50 to 61, wherein the concentrate is free or substantially free of PIBSA esters of hydrocarbon-bridged naphthoxy alcohols. 63. A concentrate according to any one of items 50 to 62, wherein i) the ratio of the mass % of the one or more unborated PIBSA-PAMs of the lubricating oil composition to the soap, based on the total mass of the concentrate, is from 7.0 to 15.0, such as from 7.2 to 13.0, such as from 7.4 to 11.0, such as from 7.6 to 10.0, such as from 7.8 to 9.0, such as from 8.0 to 8.5. 64. A concentrate according to any one of items 50 to 63, which further comprises an amide-, imide- and / or ester-functionalized polymer, which comprises a polymer backbone of a partially or fully saturated polymer comprising C 4-5 olefins, the polymer having the following characteristics: i) Mw / Mn is less than 2, ii) the functionality distribution (Fd) value is 3.5 or less, and iii) the Mn of the polymer before functionalization is 10,000 g / mol or more (GPC-PS). 65. The concentrate of item 64, wherein the polymer backbone of the functionalized polymer is derived from a homopolymer or copolymer of partially or fully hydrogenated isoprene and butadiene. 66. The concentrate of item 64, wherein the polymer backbone of the functionalized polymer comprises at least 90% of partially or fully hydrogenated isoprene repeat units. 67. The concentrate of item 64, wherein the polymer backbone of the functionalized polymer is partially or fully hydrogenated homopolyisoprene. 68. The concentrate of item 64, wherein the polymer backbone of the functionalized polymer is partially or fully hydrogenated homopolyisoprene having a Mn (GPC-PS) of 30,000 g / mol or more. 69. A concentrate according to any one of items 50 to 68, which does not contain or substantially does not contain, such as less than 0.6 mass %, such as less than 0.5 mass %, such as less than 0.4 mass %, such as less than 0.3 mass %, such as less than 0.2 mass %, such as less than 0.1 mass % based on the total mass of the concentrate, of an amine-functionalized hydrogenated isoprene polymer having an average functionality (Fv) of 7.0, a functionality distribution (Fd) value of 1.86, a Mw / Mn of 1.250, a Mn (GPC-PS) of 35,140 g / mol and a Mz (GPC-PS) of 55,726 g / mol. 70. A lubricating oil composition comprising or consisting of a concentrate according to any one of items 50 to 69 mixed with one or more base oils. 71. The lubricating oil composition of item 70, wherein the one or more base oils comprise one or more Group II base oils and / or one or more Group III base oils. 72. A lubricating oil composition for item 70, wherein the lubricating oil composition is as defined in any one of items 1 to 49. 73. A method of lubricating an internal combustion engine during engine operation, comprising: (i) providing the lubricating composition of any one of items 1 to 49 or 70 to 72 to the crankcase of the internal combustion engine; (ii) providing fuel in the internal combustion engine; and (iii) combusting the fuel in the internal combustion engine. 74. The method of item 73, wherein the fuel is one or more of a hydrocarbon fuel, a renewable fuel, a hydrogen fuel, or any blend thereof. 75. The method of item 73, wherein the fuel is a hydrocarbon fuel. 76. The method of any one of items 73 to 75, wherein the engine is a diesel engine, such as a heavy-duty diesel engine or an automotive diesel engine. 77. The method of any one of items 73 to 75, wherein the engine is a motorcycle engine, a stationary gas engine or a diesel-powered engine, a locomotive engine or a four-stroke medium-speed trunk piston engine. 78. A method of improving the antiwear ability of a lubricating oil composition containing less than 1000 ppm phosphorus, The method comprising including in the lubricating oil composition: i) at least 50% by mass of one or more base oils, based on the total mass of the lubricating oil composition; ii) one or more dispersants, wherein the one or more dispersants comprise 2.0 to 6.00% by mass of one or more poly(alkenyl) succinimides, based on the total mass of the lubricating oil composition, wherein the polyalkenyl is derived from polyisobutene and the imide is derived from a polyamine ("PIBSA-PAM"); wherein the one or more PIBSA-PAMs comprise at least 2.0% by mass of one or more unborated PIBSA-PAMs, based on the total mass of the lubricating oil composition; and iii) one or more detergents, wherein the one or more detergents together provide an amount of soap of 0.1 to 0.9% by mass, based on the total mass of the lubricating oil composition; wherein: i) the ratio of the one or more unborated PIBSA-PAMs of the lubricating oil composition to the soap, based on the total mass of the lubricating oil composition, is 6.65 or more, and ii) the lubricating oil composition has an SAE viscosity grade of 20W-X, 15W-X, 10W-X or 5W-X, where X represents any one of 8, 12, 16, 20, 30 and 40, such as 30 or 40, such as 30. 79. A method for improving the antiwear ability of a lubricating oil composition containing less than 1000 ppm phosphorus, the method comprising including in the lubricating oil composition: i) at least 50% by mass, based on the total mass of the lubricating oil composition, of one or more base oils; ii) one or more dispersants, wherein the one or more dispersants comprise 2 to 10% by mass, based on the total mass of the lubricating oil composition, of one or more poly(alkenyl) succinimides, where the polyalkenyl is derived from polyisobutene and the imide is derived from a polyamine ("PIBSA-PAM"); wherein the one or more PIBSA-PAMs comprise at least 2.0% by mass, based on the total mass of the lubricating oil composition, of one or more unborated PIBSA-PAMs; and iii) one or more detergents, wherein the one or more detergents together provide the lubricating oil composition with an amount of soap of 0.1 to 0.9% by mass, based on the total mass of the lubricating oil composition; wherein the one or more detergents comprise less than 50% by mass of calcium salicylate, based on the total mass of the detergents present in the lubricating oil composition; wherein: i) the ratio of the one or more unborated PIBSA-PAMs of the lubricating oil composition to the soap, based on the total mass of the lubricating oil composition, is 6.65 or more, and ii) the lubricating oil composition has an SAE viscosity grade of 20W-X, 15W-X, 10W-X or 5W-X, where X represents any one of 8, 12, 16, 20, 30 and 40, such as 30 or 40, such as 30. 80. The method of item 76 or item 77, wherein the antiwear ability is improved such that the wear of the valve train rocker arm is less than 120 mg, such as less than 110 mg, such as less than 100 mg, such as less than 90 mg, such as less than 80 mg, such as less than 70 mg, such as less than 60 mg, such as less than 50 mg, such as less than 40 mg, as determined by the Ford 6.7L Power Stroke diesel engine test for soot-induced wear and viscosity control. 81. A method for manufacturing a lubricating oil composition containing less than 1000 ppm phosphorus, which comprises combining: A) At least 50% by mass of one or more base oils, based on the total mass of the lubricating oil composition; B) One or more dispersants, wherein the one or more dispersants comprise 2.0 to 6.00% by mass of one or more poly(alkenyl)succinimides, based on the total mass of the lubricating oil composition, wherein the alkenyl is derived from polyisobutene and the imide is derived from polyamine ("PIBSA-PAM"); wherein the one or more PIBSA-PAMs comprise at least 2.0% by mass of one or more unborated PIBSA-PAMs, based on the total mass of the lubricating oil composition; and C) One or more detergents, wherein the one or more detergents together provide an amount of soap of 0.1 to 0.9% by mass, based on the total mass of the lubricating oil composition; wherein: i) the ratio of the one or more unborated PIBSA-PAMs of the lubricating oil composition to the soap, in % by mass based on the total mass of the lubricating oil composition, is above 6.65, and ii) the lubricating oil composition has an SAE viscosity grade of 20W-X, 15W-X, 10W-X or 5W-X, where X represents any one of 8, 12, 16, 20, 30 and 40, such as 30 or 40, such as 30. 82. A method for manufacturing a lubricating oil composition containing less than 1000 ppm of phosphorus, which comprises combining: A) At least 50% by mass of one or more base oils, based on the total mass of the lubricating oil composition; B) One or more dispersants, wherein the one or more dispersants comprise 2 to 10% by mass of one or more poly(alkenyl)succinimides, based on the total mass of the lubricating oil composition, wherein the alkenyl is derived from polyisobutene and the imide is derived from polyamine ("PIBSA-PAM"); wherein the one or more PIBSA-PAMs comprise at least 2.0% by mass of one or more unborated PIBSA-PAMs, based on the total mass of the lubricating oil composition; and C) One or more detergents, wherein the one or more detergents together provide an amount of soap of 0.1 to 0.9% by mass, based on the total mass of the lubricating oil composition; and wherein the one or more detergents comprise 50% by mass or less of calcium salicylate, based on the total mass of the detergents present in the lubricating oil composition; wherein: i) the ratio of the one or more unborated PIBSA-PAMs of the lubricating oil composition to the soap, based on the total mass of the lubricating oil composition, is 6.65 or more, and ii) the lubricating oil composition has an SAE viscosity grade of 20W-X, 15W-X, 10W-X, or 5W-X, where X represents any one of 8, 12, 16, 20, 30, and 40, such as 30 or 40, such as 30. 83. A fuel composition comprising the lubricating oil composition of any one of items 1 to 49 or 70 to 72 and one or more of the following: hydrocarbon fuel (including but not limited to natural gas), renewable fuel, hydrogen fuel, or any blend thereof. The present disclosure further relates to the following:

[0359] In certain embodiments, the present disclosure relates to the following items: A1. A lubricating oil composition containing less than 1000 ppm phosphorus, which comprises: A) at least 50% by mass, based on the total mass of the lubricating oil composition, of one or more base oils; B) one or more dispersants, wherein the one or more dispersants comprise 2.0 to 6.00% by mass, based on the total mass of the lubricating oil composition, of one or more poly(alkenyl) succinimides, where the polyalkenyl is derived from polyisobutene and the imide is derived from a polyamine ("PIBSA-PAM"); wherein the one or more PIBSA-PAMs comprise at least 2.0% by mass, based on the total mass of the lubricating oil composition, of one or more unborated PIBSA-PAMs; and C) one or more detergents, wherein the one or more detergents together provide an amount of soap in the lubricating oil composition of 0.1 to 0.9% by mass, based on the total mass of the lubricating oil composition; wherein: i) the ratio of the one or more unborated PIBSA-PAMs of the lubricating oil composition to the soap, based on the total mass of the lubricating oil composition, is 6.65 or more, and ii) the lubricating oil composition has an SAE viscosity grade of 20W-X, 15W-X, 10W-X, or 5W-X, where X represents any one of 8, 12, 16, 20, 30, and 40, such as 30 or 40, such as 30. A2. The lubricating oil composition of item A1, wherein: A) the one or more base oils are present together in an amount of at least 50% by mass, based on the total mass of the lubricating oil composition; B) the one or more dispersants are present together in an amount of 2 to 15% by mass, based on the total mass of the lubricating oil composition; and C) the one or more detergents are present together in an amount of 0.1 to 5% by mass, based on the total mass of the lubricating oil composition; and wherein the lubricating oil composition preferably further comprises one or more additional additives selected from: D) one or more friction modifiers in an amount of 0.01 to 5% by mass, based on the total mass of the lubricating oil composition; E) one or more antioxidants in an amount of 0.01 to 10% by mass, based on the total mass of the lubricating oil composition; F) one or more pour point depressants in an amount of 0.01 to 5% by mass, based on the total mass of the lubricating oil composition; G) one or more antifoaming agents in an amount of 0.001 to 5% by mass, based on the total mass of the lubricating oil composition; H) one or more viscosity improvers in an amount of 0.001 to 10% by mass, based on the total mass of the lubricating oil composition; J) one or more corrosion inhibitors and / or rust inhibitors in an amount of 0.001 to 5% by mass, based on the total mass of the lubricating oil composition; K) one or more antiwear agents in an amount of 0.001 to 10% by mass, based on the total mass of the lubricating oil composition; M) one or more seal compatibilizers, such as seal swelling agents, in an amount of 0.01 to 5% by weight, based on the total weight of the lubricating oil composition; N) optionally, one or more extreme pressure agents in an amount of 0.01 to 5% by mass, based on the total mass of the lubricating oil composition, O) one or more unsaturated C 12 -C 60 hydrocarbons, and P) one or more functionalized polymers in an amount of 0.001 to 10% by mass, based on the total weight of the lubricating oil composition. A3. The lubricating oil composition according to any one of items A1 to A2 above, which contains 700 ppm to 900 ppm of phosphorus. A4. The lubricating oil composition according to any one of items A1 to A3 above, which comprises one or more base oils in an amount of 50 to 95% by mass, such as 60 to 90% by mass, such as 70 to 85% by mass, based on the total mass of the lubricating oil composition; wherein preferably, the one or more base oils comprise one or more Group II base oils and optionally one or more Group III base oils. A lubricating oil composition according to any one of the preceding items A1 to A4, wherein the one or more detergents together provide 0.2 to 0.8% by mass, such as 0.3 to 0.7% by mass, such as 0.4 to 0.6% by mass, such as 0.45 to 0.55% by mass of soap based on the total mass of the lubricating oil composition. A6. The lubricating oil composition according to any one of the preceding items A1 to A5, wherein the one or more unborated PIBSA-PAMs are present in an amount of 2.5 to 5.5% by mass, such as 3.5 to 5.0% by mass, such as 4.0 to 4.5% by mass based on the total mass of the lubricating oil composition. A7. The lubricating oil composition according to any one of the preceding items A1 to A6, wherein the one or more dispersants together are present in an amount of 2 to 10% by mass, such as 3 to 8% by mass, such as 4 to 6% by mass, such as 4.5 to 5.5% by mass based on the total mass of the lubricating oil composition. A8. A concentrate comprising the following components or obtained by mixing the following components: A) One or more base oils in an amount of 1 to less than 50% by mass based on the total mass of the concentrate; B) One or more dispersants, wherein the one or more dispersants comprise one or more unborated poly(alkenyl) succinimides, wherein the polyalkenyl is derived from polyisobutene and the imide is derived from a polyamine ("PIBSA-PAM"); and C) One or more detergents, wherein the one or more detergents provide soap for the concentrate; wherein the one or more detergents comprise less than 50% by mass of calcium salicylate based on the total mass of the detergents present in the concentrate; wherein: i) the ratio of the mass % of the one or more unborated PIBSA-PAMs to the soap in the concentrate based on the total mass of the concentrate is 6.65 or more. A9. The concentrate of item A8, which further comprises one or more additional additives selected from friction modifiers, antioxidants, pour point depressants, defoamers, viscosity improvers, corrosion inhibitors, rust inhibitors, antiwear agents, seal compatibilizers, extreme pressure agents, unsaturated C 12 -C 60 hydrocarbons and functionalized polymers. A10. The lubricating oil composition or concentrate according to any one of the preceding items A1 to A9, wherein the one or more detergents are selected from oil-soluble neutral or overbased sulfonates, salicylates of calcium and / or magnesium, and mixtures thereof; preferably wherein the one or more detergents are selected from oil-soluble overbased sulfonates of calcium and / or magnesium. A lubricating oil composition or concentrate according to any one of the preceding items A1 to A10, wherein said one or more unborated PIBSA-PAMs comprise one or more unborated PIBSA-PAMs in which the polyalkenyl is derived from polyisobutene having a Mn (GPC-PS) of more than 1600 g / mol ("high molecular weight PIBSA-PAM"), and optionally one or more unborated PIBSA-PAMs in which the polyalkenyl is derived from polyisobutene having a Mn (GPC-PS) of less than 1600 g / mol ("low molecular weight PIBSA-PAM"); wherein preferably, the ratio of the mass% of said one or more unborated high molecular weight PIBSA-PAMs to said one or more unborated low molecular weight PIBSA-PAMs based on the total mass of the lubricating oil composition or concentrate is less than 3.65, such as less than 3.5, such as less than 3.0, such as less than 2.5, such as less than 2.0, such as less than 1.5. A lubricating oil composition or concentrate according to any one of the preceding items A1 to A11, wherein said one or more dispersants further comprise one or more borated PIBSA-PAMs. A lubricating oil composition or concentrate according to any one of the preceding items A1 to A12, wherein i) the ratio of the mass% of said one or more unborated PIBSA-PAMs of the lubricating oil composition to the soap based on the total mass of the lubricating oil composition or concentrate is from 7.0 to 15.0, such as from 7.2 to 13.0, such as from 7.4 to 11.0, such as from 7.6 to 10.0, such as from 7.8 to 9.0, such as from 8.0 to 8.5. A lubricating oil composition or concentrate according to any one of the preceding items A1 to A13, which further comprises an amide-, imide- and / or ester-functionalized polymer, which comprises a polymer backbone comprising partially or fully saturated C 4-5 olefin polymers, said polymer having the following characteristics: i) Mw / Mn is less than 2, ii) the functionality distribution (Fd) value is 3.5 or less, and iii) the Mn of the polymer before functionalization is 10,000 g / mol or more (GPC-PS). A lubricating oil composition comprising or obtained by mixing a concentrate according to any one of items A8 to A14 with one or more base oils. A method of lubricating an internal combustion engine during engine operation, comprising: (i) providing a lubricating composition according to any one of items A1 to A12 or A15 to the crankcase of the internal combustion engine; (ii) providing fuel in the internal combustion engine; and (iii) combusting the fuel in the internal combustion engine. A17. A method for improving the antiwear ability of a lubricating oil composition containing less than 1000 ppm phosphorus, The method includes including in the lubricating oil composition: i) at least 50% by mass of one or more base oils based on the total mass of the lubricating oil composition; ii) one or more dispersants, wherein the one or more dispersants contain 2.0 to 6.00% by mass of one or more poly(alkenyl) succinimides based on the total mass of the lubricating oil composition, wherein the alkenyl is derived from polyisobutene and the imide is derived from polyamine ("PIBSA-PAM"); wherein the one or more PIBSA-PAMs contain at least 2.0% by mass of one or more unborated PIBSA-PAMs based on the total mass of the lubricating oil composition; and iii) one or more detergents, wherein the one or more detergents together provide an amount of soap of 0.1 to 0.9% by mass based on the total mass of the lubricating oil composition; wherein: i) the ratio of the mass % of the one or more unborated PIBSA-PAMs to the soap in the lubricating oil composition based on the total mass of the lubricating oil composition is more than 6.65, and ii) the lubricating oil composition has an SAE viscosity grade of 20W-X, 15W-X, 10W-X or 5W-X, where X represents any one of 8, 12, 16, 20, 30 and 40, such as 30 or 40, such as 30; wherein preferably the antiwear ability is improved such that the wear of the valve train rocker arm is less than 120 mg, such as less than 110 mg, such as less than 100 mg, such as less than 90 mg, such as less than 80 mg, such as less than 70 mg, such as less than 60 mg, such as less than 50 mg, such as less than 40 mg, as determined by the Ford 6.7L Power Stroke diesel engine test for soot-induced wear and viscosity control. A18. A fuel composition comprising the lubricating oil composition of any one of items A1 to A12 or A15 and one or more of the following: hydrocarbon fuel, renewable fuel, hydrogen fuel or any blend thereof.

[0360] The following non-limiting examples are provided to illustrate the present disclosure. Experiment

[0361] Unless otherwise specified, all molecular weights are number average molecular weights (Mn) reported in g / mol determined by gel permeation chromatography using polystyrene standards. Unless otherwise indicated, "A.I.", "ai", "a.i." and "ai" are weight % active ingredient. Test program

[0362] The viscosity index is measured according to ASTM D2270.

[0363] The high temperature high shear viscosity ("HTHS" or "HTHS150") is determined at 150 °C according to ASTM D4683 and reported in cPs.

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

[0365] Unless otherwise specified, the Cold Crank Simulator ("CCS") at -25 °C is a measure of the cold start characteristics of the crankcase lubricant and is determined as described in ASTM D5293-92.

[0366] The phosphorus, boron, calcium, zinc, molybdenum and magnesium contents are measured by ASTM D5185.

[0367] The sulfate ash ("SASH") content is measured by ASTM D874.

[0368] The Ford 6.7L Power Stroke diesel engine test for soot-induced wear and viscosity control is conducted in a 6.7L Power Stroke diesel engine. The test is 200 hours at peak power of 2800 rpm / WOT. Samples are taken every 25 hours for soot measurement according to ASTM D5967, TGA. The soot content is typically in the range of 5.5 to 6.5% at the end of the test. After the test is completed, the rocker arms are disassembled and weighed and compared with the weight before the test to determine the weight loss. The KV100 of the oil sample is also measured every 25 hours to determine the viscosity of the oil.

[0369] The moments of molecular weight (Mw, Mn, Mz) are determined by gel permeation chromatography ("GPC-PS") using polystyrene standards (Acquity TM APC polystyrene high MW calibration kit, 266-1,760,000 Da) and software provided by the vendor (Empower TM3, Version 7.41.00.00) is determined as follows. Molecular weights [number average molecular weight (Mn), weight average molecular weight (Mw), and z average molecular weight (Mz)] are determined using an Agilent Acuity P-SM-FTN and P-15m high temperature GPC-SEC (Gel Permeation / Size Exclusion Chromatograph) equipped with an on-line differential refractive index (DRI) detector and PDA UV detectors for wavelengths 215, 254, and 304. The GPC uses 3 Agilent PLgel 10 micron Mixed B LS columns. Column separation is carried out using a flow rate of 0.25 mL / min and a nominal injection volume of 10 microliters. When in the low flow mode (idle), the detector and columns are maintained at 30 °C and heated to 35 °C when preparing to run a sample. The stream leaving the SEC column is directed into an optical flow cell and then into the DRI detector. The solvent used for the SEC experiment is uninhibited THF (tetrahydrofuran). The polymer solution is prepared by placing the dried polymer in a glass container and adding the required amount of THF. Once the sample is added to the machine, a certain amount of time is allowed to elapse before the run begins to reach 35 °C. The GPC runs a pre-run programmed equilibration of approximately 1.5 hours. Depending on solubility, the sample is stirred for 2 to 15 hours. The sample is filtered after stirring and before running. All amounts are measured by gravimetric analysis. The THF density used to express the polymer concentration in mass / volume units is 0.887 g / mL at 68 °C. The injected sample concentration is 3 mg / mL. Before running each sample, the DRI detector and syringe are purged. Then the flow rate in the apparatus is increased from 0.01 to 0.25 mL / min and the DRI is allowed to stabilize for 4 to 5 hours before injecting the first sample. The software used to run the GPC and prepare the report is Empower TM 3, Version 7.41.00.00. Material

[0370] F-H-PI is 7.0-F-H-polyisoprene-A. An amine-functionalized hydrogenated isoprene polymer with an average functionality (Fv) of 7.0 is prepared using SA-H-polyisoprene-A (succinate functionality 7.0) by adding 1 equivalent of amine (4-amino-diphenylamine, ADPA) per succinate unit at 170 °C under nitrogen (determined by SAP, ASTM D94). Let the reaction continue and heat soak for up to 2 hours, after which it is diluted with additional oil (Group III, 4 cSt (Yubase TM 4)) and allowed to cool to ambient temperature. During cooling, the material is mixed with an ethoxylated alcohol such as Berol TM 1214 or Surfonic TML24-4, Huntsman) was incorporated at 10 wt% of the reaction mixture. 7.15-F-H-polyisoprene-A has a functionality distribution (Fd) value of 1.76, a Mw / Mn of 1.239, a Mn of 31629 g / mol, a Mz of 47835 g / mol, and is used as a blend in oil with ai of 0.5 wt% unless otherwise stated.

[0371] PIB is polyisobutene.

[0372] PIBSA is polyisobutene succinic anhydride.

[0373] PIBSA-PAM is polyisobutene succinic anhydride-polyalkyleneamine. Component Table

[0374] In the following table of examples, the amounts indicated for each material refer to the amount of "component" (as shown in the component table above, which contains a certain amount of active ingredient in oil). For example, the component PIBSA-PAM 2200Mn has an active ingredient (a.i.) content of approximately 55 wt%, and the balance of this component is diluent oil (see the component table above). This means that, for example, the active ingredient content of PIBSA-PAM 2200Mn in Oil A (see Table 1 below, which indicates the content of the PIBSA-PAM 2200Mn component as 4.0 mass%) is 2.2 mass% (i.e., 4.0 mass% × 0.55). Similarly, the active ingredient content of unborated PIBSA-PAM in Oil A (which indicates the content of the PIBSA-PAM 2200Mn component as 4.0 mass% and the content of the PIBSA-PAM 950Mn component as 4.0 mass%) is 4.24 mass% (i.e., 4.0 mass% × 0.55 + 4.0 mass% × 0.51). In addition, the soap of Oil A is obtained by adding up the soap mass% provided by each detergent, i.e., 1.0 mass% x 29 mass% + 0.85 mass% x 26 mass% = 0.511 mass%. In this Oil A, the ratio of unborated PIBSA-PAMs to soap is therefore 4.24 mass% / 0.511 mass% = 8.30. The ratios of unborated PIBSA-PAM to soap for other oils can be calculated similarly based on the mass% of each component indicated in the example table below and using the active ingredient content indicated for each component in the component table above. Examples Example 1: Ford 6.7L Power Stroke Diesel Engine Test for Soot-Induced Wear and Viscosity Control

[0375] Oils A and B, and comparative oils C1 and C2 were prepared as shown in Table 1.1 below and tested for soot-induced wear and viscosity control in the above-described Ford 6.7L PowerStroke Diesel engine test. Table 1.1 *Results of 4 tests of Oil A, **These formulations have the same amounts of calcium and magnesium sulfonates from adpak, ZDDP, DPA antioxidant, methyl ester of sulfonated fatty acid, defoamer, corrosion inhibitor, PIB, PIBSA, LOFI, diluent

[0376] Oils A and B are characterized by a higher ratio of unborated PIBSA-PAM to soap in the lubricating oil composition compared to comparative oils C1 and C2. Oils A and B exhibit a substantial improvement in antiwear properties, providing only 37 mg and 39 mg of valve train rocker arm loss, respectively. In addition, Oils A and B clearly pass the Ford 6.7L PowerStroke Diesel engine test with only 800 ppm phosphorus (passing criterion: < 100 mg rocker arm mass loss).

[0377] All documents described herein are hereby incorporated by reference to the extent that they are not inconsistent with the present disclosure, including any priority documents and / or test procedures. From the foregoing general description and specific embodiments, it will be apparent that, although the forms of the invention have been illustrated and described, various modifications may be made without departing from the spirit and scope of the invention. Accordingly, it is not intended to limit the invention hereby. The term "comprising" is considered to be synonymous with the term "including". Similarly, whenever a composition, element or group of elements is preceded by the connecting word "comprising", it is understood that we also contemplate the same composition or group of elements preceded by the connecting words "consisting essentially of", "consisting of", "selected from" or "being", and vice versa.

Claims

1. A lubricating oil composition containing less than 1000 ppm phosphorus, It contains: A) at least 50 mass % of one or more base oils, based on the total mass of the lubricating oil composition; B) one or more dispersants, wherein the one or more dispersants comprises 2.0 to 6.00 mass % of one or more poly(alkenyl) succinimides, based on the total mass of the lubricating oil composition, wherein the polyalkenyl is derived from polyisobutylene and the imide is derived from a polyamine ("PIBSA-PAM"); wherein the one or more PIBSA-PAMs comprise at least 2.0 mass % of one or more unboronated PIBSA-PAMs, based on the total mass of the lubricating oil composition; and C) one or more detergents, wherein the one or more detergents together provide soap to the lubricating oil composition in an amount of 0.1 to 0.9 mass % based on the total mass of the lubricating oil composition; in: i) the lubricating oil composition has a ratio of the mass % of the one or more unboronated PIBSA-PAMs to soap, based on the total mass of the lubricating oil composition, of 6.65 or more, and ii) the lubricating oil composition has an SAE viscosity grade of 20W-X, 15W-X, 10W-X or 5W-X, wherein X represents any one of 8, 12, 16, 20, 30 and 40, such as 30 or 40, such as 30.

2. The lubricating oil composition according to claim 1, wherein: A) the one or more base oils together are present in an amount of at least 50 mass %, based on the total mass of the lubricating oil composition; B) the one or more dispersants are present together in an amount of 2 to 15 mass % based on the total mass of the lubricating oil composition; and C) The one or more detergents are present together in an amount of 0.1 to 5 mass % based on the total mass of the lubricating oil composition.

3. The lubricating oil composition according to claim 1, further comprising one or more additional additives selected from the group consisting of: D) 0.01 to 5 mass % of one or more friction modifiers, based on the total mass of the lubricating oil composition; E) 0.01 to 10 mass % of one or more antioxidants, based on the total mass of the lubricating oil composition; F) 0.01 to 5 mass % of one or more pour point depressants, based on the total mass of the lubricating oil composition; G) 0.001 to 5 mass % of one or more defoaming agents, based on the total mass of the lubricating oil composition; H) 0.001 to 13 mass % of one or more viscosity improvers, based on the total mass of the lubricating oil composition; J) 0.001 to 5 mass % of one or more corrosion inhibitors and / or rust inhibitors, based on the total mass of the lubricating oil composition; K) 0.001 to 10 mass % of one or more antiwear agents, based on the total mass of the lubricating oil composition; M) 0.01 to 5 mass % of one or more seal compatibilizers, such as seal swell agents, based on the total mass of the lubricating oil composition; N) optionally, based on the total mass of the lubricating oil composition, 0.01 to 5 mass % of one or more extreme pressure agents, O) 0.01 to 5 mass % of one or more unsaturated C 12 -C 60 Hydrocarbons, and P) 0.001 to 10 mass % of one or more functionalized polymers, based on the total weight of the lubricating oil composition.

4. The lubricating oil composition according to claim 1, comprising 700 ppm to 900 ppm of phosphorus.

5. The lubricating oil composition of claim 1, wherein the one or more base oils comprise at least 50 mass % of a Group II base oil, based on the total mass of base oils present in the lubricating oil composition.

6. The lubricating oil composition of claim 1, wherein the one or more detergents are selected from the group consisting of oil-soluble neutral or overbased sulfonates of calcium and / or magnesium, salicylates, and mixtures thereof.

7. The lubricating oil composition of claim 1, wherein the one or more detergents comprise 50 mass % or less of calcium salicylate based on the total mass of detergents present in the lubricating oil composition.

8. The lubricating oil composition of claim 1, wherein the one or more detergents are selected from oil-soluble overbased sulfonates of calcium and / or magnesium.

9. The lubricating oil composition of claim 1, wherein the lubricating oil composition is absent or substantially absent of phenate detergent.

10. The lubricating oil composition of claim 1 , wherein the one or more detergents together are present in an amount of 0.1 to 4 mass % based on the total mass of the lubricating oil composition, and optionally wherein the one or more detergents together provide less than 0.8 mass % soap based on the total mass of the lubricating oil composition.

11. The lubricating oil composition of claim 1 , wherein the one or more unboronated PIBSA-PAMs are present in an amount of 2.5 to 5.5 mass % based on the total mass of the lubricating oil composition, and wherein the one or more unboronated PIBSA-PAMs comprise: 1) one or more unboronated PIBSA-PAMs wherein the polyalkenyl groups of the PIBSA-PAMs are derived from polyisobutylene having an Mn(GPC-PS) of 1600 g / mol or more ("high molecular weight PIBSA-PAMs"), and 2) optionally, one or more unboronated PIBSA-PAMs wherein the polyalkenyl groups of the PIBSA-PAMs are derived from polyisobutylene having an Mn(GPC-PS) of less than 1600 g / mol ("low molecular weight PIBSA-PAMs").

12. The lubricating oil composition of claim 11, wherein the one or more unboronated PIBSA-PAMs comprise one or more unboronated high molecular weight PIBSA-PAMs in an amount of 0.5 to 4 mass %, based on the total mass of the lubricating oil composition, and one or more unboronated low molecular weight PIBSA-PAMs in an amount of 0.5 to 4 mass %, based on the total mass of the lubricating oil composition.

13. The lubricating oil composition of claim 12, wherein the ratio of mass % of the one or more unboronated high molecular weight PIBSA-PAMs to the one or more unboronated low molecular weight PIBSA-PAMs, based on the total mass of the lubricating oil composition, is less than 3.

65.

14. The lubricating oil composition of claim 1, wherein the one or more unboronated low molecular weight PIBSA-PAMs are not derived from tetraethylenepentamine.

15. The lubricating oil composition of claim 1, wherein the one or more dispersants further comprise one or more boronated PIBSA-PAMs, wherein the one or more boronated PIBSA-PAMs are present in an amount of 0.05-0.5 mass % based on the total mass of the lubricating oil composition.

16. The lubricating oil composition of claim 1, wherein the one or more dispersants are present together in an amount of 2 to 10 mass % based on the total mass of the lubricating oil composition.

17. The lubricating oil composition according to claim 1, comprising no or substantially no aromatic dispersant based on the total mass of the lubricating oil composition.

18. The lubricating oil composition of claim 1, comprising no or substantially no PIBSA ester of a hydrocarbyl-bridged naphthoxy alcohol, based on the total mass of the lubricating oil composition.

19. The lubricating oil composition of claim 1, wherein i) the ratio of the mass % of the one or more unboronated PIBSA-PAMs to soap of the lubricating oil composition, based on the total mass of the lubricating oil composition, is from 7.0 to 15.

0.

20. The lubricating oil composition according to claim 1, wherein ii) the lubricating oil composition has an SAE viscosity grade of 15W-40, 5W-30 or 10W-30.

21. The lubricating oil composition of claim 1, further comprising an amide, imide and / or ester functionalized polymer comprising a partially or fully saturated C 4-5 A polymer backbone of an olefin, the polymer having the following characteristics: i) Mw / Mn is less than 2, ii) a functionality distribution (Fd) value of 3.5 or less, and iii) the Mn of the polymer before functionalization is above 10,000 g / mol (GPC-PS), The functionalized polymer is optionally present in an amount of 0.01 to 5 mass % based on the total mass of the lubricating oil composition.

22. The lubricating oil composition according to claim 21, wherein: 1) the polymer backbone of the functionalized polymer is derived from a homopolymer or copolymer of partially or fully hydrogenated isoprene and butadiene; or 2) the polymer backbone of the functionalized polymer comprises at least 90% partially or fully hydrogenated isoprene repeating units, the polymer backbone optionally having an Mn (GPC-PS) of 30,000 g / mol or more.

23. The lubricating oil composition of claim 1 comprising no or substantially no amine functionalized hydrogenated isoprene polymer having an average functionality (Fv) of 7.0, a functionality distribution (Fd) value of 1.86, a Mw / Mn of 1.250, a Mn (GPC-PS) of 35,140 g / mol, and a Mz (GPC-PS) of 55,726 g / mol, based on the total mass of the lubricating oil composition.

24. The lubricating oil composition of claim 1, wherein the lubricating oil composition provides less than 120 mg valve train rocker arm wear as measured by the Ford 6.7L Power Stroke Diesel Engine Test for Soot Induced Wear and Viscosity Control.

25. The lubricating oil composition of claim 1, wherein the lubricating oil composition comprises one or more molybdenum (Mo) containing compounds, wherein the one or more Mo containing compounds together provide at least 50 ppm Mo to the lubricating oil composition.

26. The lubricating oil composition of claim 1, comprising no or substantially no molybdenum (Mo).

27. A lubricating oil composition containing less than 1000 ppm phosphorus, It contains: A) at least 50 mass % of one or more base oils, based on the total mass of the lubricating oil composition; B) one or more dispersants, wherein the one or more dispersants comprise 2 to 10 mass % of one or more poly(alkenyl) succinimides, based on the total mass of the lubricating oil composition, wherein the polyalkenyl is derived from polyisobutylene and the imide is derived from a polyamine ("PIBSA-PAM"); wherein the one or more PIBSA-PAMs comprise at least 2.0 mass % of one or more unboronated PIBSA-PAMs, based on the total mass of the lubricating oil composition; and C) one or more detergents, wherein the one or more detergents together provide soap to the lubricating oil composition in an amount of 0.1 to 0.9 mass % based on the total mass of the lubricating oil composition; and wherein the one or more detergents comprise 50 mass % or less of calcium salicylate, based on the total mass of detergents present in the lubricating oil composition; in: i) the lubricating oil composition has a ratio of the mass % of the one or more unboronated PIBSA-PAMs to soap, based on the total mass of the lubricating oil composition, of 6.65 or more, and ii) the lubricating oil composition has an SAE viscosity grade of 20W-X, 15W-X, 10W-X or 5W-X, wherein X represents any one of 8, 12, 16, 20, 30 and 40, such as 30 or 40, such as 30.

28. The lubricating oil composition of claim 27, wherein the one or more PIBSA-PAMs are present in an amount of 2.5 to 10 mass %, such as 3 to 8 mass %, such as 3.5 to 6 mass %, based on the total mass of the lubricating composition.

29. A lubricating oil composition containing less than 1000 ppm phosphorus, It contains: A) at least 50 mass % of one or more base oils, based on the total mass of the lubricating oil composition; B) one or more dispersants, wherein the one or more dispersants comprise 2 to 10 mass % of one or more poly(alkenyl) succinimides, based on the total mass of the lubricating oil composition, wherein the polyalkenyl is derived from polyisobutylene and the imide is derived from a polyamine ("PIBSA-PAM"); wherein the one or more PIBSA-PAMs comprise at least 2.0 mass % of one or more unboronated PIBSA-PAMs, based on the total mass of the lubricating oil composition; and C) one or more detergents, wherein the one or more detergents together provide soap to the lubricating oil composition in an amount of 0.1 to 0.9 mass % based on the total mass of the lubricating oil composition; and P) amide, imide and / or ester functionalized polymers comprising partially or fully saturated C 4-5 A polymer backbone of an olefin, the polymer having the following characteristics: i) Mw / Mn is less than 2, ii) a functionality distribution (Fd) value of 3.5 or less, and iii) the Mn of the polymer before functionalization is 10,000 g / mol or more (GPC-PS); wherein: i) the ratio of the mass % of the one or more unboronated PIBSA-PAMs to the soap of the lubricating oil composition, based on the total mass of the lubricating oil composition, is 6.65 or more, and ii) the lubricating oil composition has an SAE viscosity grade of 20W-X, 15W-X, 10W-X or 5W-X, wherein X represents any one of 8, 12, 16, 20, 30 and 40, such as 30 or 40, such as 30.

30. A concentrate comprising or obtained by mixing the following components: A) 1 to less than 50 mass % of one or more base oils, based on the total mass of the concentrate; B) one or more dispersants, wherein the one or more dispersants comprise one or more unboronated poly(alkenyl)succinimides wherein the polyalkenyl is derived from polyisobutylene and the imide is derived from a polyamine ("PIBSA-PAM"); and C) one or more detergents, wherein the one or more detergents provide soap to the concentrate; wherein the one or more detergents comprise 50 mass % or less of calcium salicylate, based on the total mass of detergents present in the concentrate; in: i) the concentrate has a ratio of the mass % of the one or more unboronated PIBSA-PAMs to soap, based on the total mass of the concentrate, of 6.65 or greater.

31. The concentrate of claim 30, further comprising one or more additional additives selected from the group consisting of friction modifiers, antioxidants, pour point depressants, defoamers, viscosity modifiers, corrosion inhibitors, rust inhibitors, antiwear agents, seal compatibility agents, extreme pressure agents, unsaturated C 12 -C 60 Hydrocarbons and functionalized polymers.

32. The concentrate of claim 30, wherein the one or more detergents are selected from oil-soluble neutral or overbased sulfonates of calcium and / or magnesium and the concentrate is absent or substantially absent of phenate detergents.

33. The concentrate of claim 30, wherein the one or more unboronated PIBSA-PAMs comprise: 1) one or more unboronated PIBSA-PAMs wherein the polyalkenyl groups of the PIBSA-PAM are derived from polyisobutylene having an Mn(GPC-PS) of 1600 g / mol or more ("high molecular weight PIBSA-PAMs"); and 2) optionally, one or more unboronated PIBSA-PAMs wherein the polyalkenyl groups of the PIBSA-PAM are derived from polyisobutylene having an Mn(GPC-PS) of less than 1600 g / mol ("low molecular weight PIBSA-PAMs").

34. The concentrate of claim 30, wherein the ratio of mass % of the one or more non-boronated high molecular weight PIBSA-PAMs to the one or more non-boronated low molecular weight PIBSA-PAMs, based on the total mass of the concentrate, is less than 3.

65.

35. The concentrate of claim 30, wherein the one or more unboronated low molecular weight PIBSA-PAMs are not derived from tetraethylenepentamine.

36. The concentrate of claim 30, wherein the one or more dispersants further comprise one or more boronated PIBSA-PAMs.

37. The concentrate of claim 30, comprising no or substantially no aromatic dispersant, based on the total mass of the concentrate.

38. The concentrate of claim 30, wherein the concentrate is absent or substantially absent of PIBSA esters of hydrocarbyl-bridged naphthoxy alcohols.

39. The concentrate of claim 30, wherein i) the ratio of the mass % of the one or more unboronated PIBSA-PAMs to soap of the lubricating oil composition, based on the total mass of the concentrate, is from 7.0 to 15.

0.

40. The concentrate of claim 30, further comprising an amide, imide and / or ester functionalized polymer comprising a partially or fully saturated C 4-5 A polymer backbone of an olefin, the polymer having the following characteristics: i) Mw / Mn is less than 2, ii) a functionality distribution (Fd) value of 3.5 or less, and iii) The Mn of the polymer before functionalization is 10,000 g / mol or more (GPC-PS).

41. The concentrate of claim 40 comprising no or substantially no amine functionalized hydrogenated isoprene polymer having an average functionality (Fv) of 7.0, a functionality distribution (Fd) value of 1.86, a Mw / Mn of 1.250, a Mn (GPC-PS) of 35,140 g / mol, and a Mz (GPC-PS) of 55,726 g / mol.

42. A method of lubricating an internal combustion engine during operation of the engine, comprising: (i) providing a lubricating composition according to any one of claims 1 to 29 or a concentrate according to any one of claims 30 to 41 to a crankcase of an internal combustion engine; (ii) providing fuel in an internal combustion engine; and (iii) Combustion of fuel in an internal combustion engine.

43. A method for improving the anti-wear capability of a lubricating oil composition containing less than 1000 ppm phosphorus, The method comprises including in the lubricating oil composition: i) at least 50 mass % of one or more base oils, based on the total mass of the lubricating oil composition; ii) one or more dispersants, wherein the one or more dispersants comprises 2.0 to 6.00 mass % of one or more poly(alkenyl) succinimides, based on the total mass of the lubricating oil composition, wherein the polyalkenyl is derived from polyisobutylene and the imide is derived from a polyamine ("PIBSA-PAM"); wherein the one or more PIBSA-PAMs comprise at least 2.0 mass % of one or more unboronated PIBSA-PAMs; and iii) one or more detergents, wherein the one or more detergents together provide soap to the lubricating oil composition in an amount of 0.1 to 0.9 mass % based on the total mass of the lubricating oil composition; wherein: a) the lubricating oil composition has a ratio of the mass % of the one or more unboronated PIBSA-PAMs to soap, based on the total mass of the lubricating oil composition, of 6.65 or more, and b) the lubricating oil composition has an SAE viscosity grade of 20W-X, 15W-X, 10W-X or 5W-X, wherein X represents any one of 8, 12, 16, 20, 30 and 40, such as 30 or 40, such as 30.

44. A method for improving the antiwear capability of a lubricating oil composition containing less than 1000 ppm phosphorus, The method comprises including in the lubricating oil composition: i) at least 50 mass % of one or more base oils, based on the total mass of the lubricating oil composition; ii) one or more dispersants, wherein the one or more dispersants comprise 2 to 10 mass % of one or more poly(alkenyl) succinimides, based on the total mass of the lubricating oil composition, wherein the polyalkenyl is derived from polyisobutylene and the imide is derived from a polyamine ("PIBSA-PAM"); wherein the one or more PIBSA-PAMs comprise at least 2.0 mass % of one or more unboronated PIBSA-PAMs, based on the total mass of the lubricating oil composition; and iii) one or more detergents, wherein the one or more detergents together provide soap to the lubricating oil composition in an amount of 0.1 to 0.9 mass % based on the total mass of the lubricating oil composition; wherein the one or more detergents comprise 50 mass % or less of calcium salicylate, based on the total mass of detergents present in the lubricating oil composition; wherein: i) the lubricating oil composition has a ratio of the mass % of the one or more unboronated PIBSA-PAM to soap, based on the total mass of the lubricating oil composition, of 6.65 or more, ii) the lubricating oil composition has an SAE viscosity grade of 20W-X, 15W-X, 10W-X or 5W-X, wherein X represents any one of 8, 12, 16, 20, 30 and 40, such as 30 or 40, and iii) optionally, wherein the antiwear capability of the lubricating oil composition is enhanced to provide a valve train rocker arm wear of less than 120 mg as determined by the Ford 6.7L Power Stroke diesel engine test for soot induced wear and viscosity control.

45. A fuel composition comprising the lubricating oil composition according to any one of claims 1 to 20 and one or more of: a hydrocarbon fuel, a renewable fuel, a hydrogen fuel, a natural gas or any blend thereof.

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