Low phosphorus and low sulfated ash lubricant composition

Abstract

To provide the use in a lubricant composition of a dispersant mixture comprising a functionalized polymer, a chloro dispersant, and a heat dispersant that provides robust wear resistance, cleanliness, oxidation performance, and corrosion performance in engine crankcase applications, particularly in compression ignition engine and / or spark ignition applications.SOLUTION: The present invention relates to a lubricating oil composition having a phosphorus content of less than 800 ppm, e.g., less than about 500 ppm, and a SASH content of less than 0.9%, e.g., less than about 0.5%, and including a dispersant mixture, wherein the dispersant mixture comprises: (1) 0.01 to 15 mass%, based on the total weight of the dispersant mixture, of an amide-, imide-, and / or ester-functionalized partially or fully saturated polymer comprising a C4-5 olefin, the amide-, imide-, and / or ester-functionalized partially or fully saturated polymer having i) a Mw / Mn of less than 2, ii) a functionality distribution (Fd) value of 3.5 or less, and iii) a Mn of the polymer before functionalization of 10,000 g / mol or more (GPC-PS); and (2) 50 to 90 mass%, based on the total weight of the dispersant mixture, of one or more poly(alkenyl)succinimides derived from polyalkenyl-substituted succinic anhydrides and polyamines prepared using a chlorine-assisted alkylation process; and (3) 10 to 30 mass%, based on the total weight of the dispersant mixture, of one or more poly(alkenyl)succinimides derived from polyalkenyl-substituted succinic anhydrides and polyamines prepared using a halogen-free thermal alkylation process.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to the use of a dispersant mixture comprising a functionalized polymer, a chloro dispersant, and a thermal dispersant in a lubricant composition that provides robust wear resistance, cleanliness, oxidation performance, and corrosion performance in engine crankcase applications, particularly in compression ignition engines and / or spark ignition applications.

Background Art

[0002] The present invention relates to a lubricating oil composition that exhibits improved performance against turbochargers and piston deposits. More particularly, the present invention relates to an automotive crankcase lubricating oil composition for use in gasoline (spark ignition) and diesel (compression ignition) internal combustion engines, such a composition being referred to as a crankcase lubricating oil. The present invention also relates to the use of additives in such lubricating oil compositions to improve the performance of engines lubricated with the lubricating oil composition, particularly with respect to piston cleanliness, liner wear, wear of gear train wheels, turbocharger housing deposits, and degree of oxidation. In recent years, there has been an increasing trend towards emphasizing fuel efficiency. One way to improve the fuel efficiency of vehicles is to design new lubricant oils that reduce friction while maintaining a good film thickness for durability and provide wear protection while preventing soot-induced viscosity increase. In attempts to improve fuel efficiency, the use and requirements of low viscosity grades by original equipment manufacturer (OEM) customers are becoming increasingly widespread. One of the challenges in providing engine and / or drive train transmission oils with such reduced viscosity grades is to maintain cleanliness and wear protection. Such oils must be able to provide the desired fuel efficiency benefits while reducing sludge, providing good soot handling, and providing wear protection. These goals should be achieved while maintaining low levels of sulfuric acid ash (SASH) and phosphorus and ensuring seal compatibility. There is a need to provide new engine oils with low viscosity grades that meet these requirements.

[0003] Engine durability is an important consideration when selecting lubricants, especially for large diesel (HDD) engine applications. Original equipment manufacturers (OEMs) have been continuously increasing oil change intervals, and the average life of vehicles has steadily increased over the past few decades. Similarly, ashless anti-wear agents that have less impact on aftertreatment systems such as diesel particulate filters in large diesel vehicles are increasingly being used. In addition, due to environmental and regulatory requirements, there is a growing desire to improve the efficiency of internal combustion engines. Lower viscosity lubricants can improve fuel economy because they require less energy to pump into the engine. However, lower viscosity lubricants can result in thinner oil films between contacting engine components (e.g., valve train, piston zone, and bearings), which can lead to higher wear rates, reduced friction modulation, etc. Conventionally, zinc dialkyldithiophosphate (ZDDP) has often been used as a lubricant additive to prevent engine wear and / or reduce friction in the boundary lubrication regime.

[0004] In parallel with the drive to improve fuel economy, there is also a desire to reduce emissions from vehicles. Control of exhaust emissions is typically achieved by aftertreatment devices such as catalytic converters that generally use precious metal catalysts to convert combustion products into less harmful substances. However, such catalysts are poisoned, especially by phosphorus and sulfur, which affects their catalytic activity. In particular, SASH and phosphorus accumulate in the diesel aftertreatment system of HDD vehicles, specifically in the diesel particulate filter (DPF). Exhaust backpressure due to DPF SASH and phosphorus accumulation can shorten the life of the DPF, reduce fuel economy, and negatively impact the catalyst, hindering the overall effectiveness of the aftertreatment system of HDD vehicles. Typically, HDD formulations contain 800 - 1200 ppm of phosphorus and more than 0.9% SASH to achieve the required wear and cleanliness performance defined by various industrial and OEM engine tests and specific requirements. The present invention aims to provide a lubricant composition that still maintains robust wear and cleanliness performance in major engine tests while reducing SASH and phosphorus, particularly targeting 500 ppm of phosphorus and 0.5% SASH. However, the reduction of SASH and phosphorus leads to a reduction in detergents and antiwear agents in the lubricant composition, which play a very important role in achieving the robust performance of HDD lubricants.

[0005] During engine operation, oil-insoluble oxidation by-products, such as soot, are generated. Dispersants assist in suspending or holding these by-products in solution and thus reduce the deposition of by-products on metal surfaces. Common dispersants include (poly)alkenyl succinic acid derivatives, such as hydrocarbyl-substituted succinic anhydrides, such as polyisobutylene succinic anhydride (PIBSA), and hydrocarbyl-substituted succinimides, such as polyisobutylene succinimide (PIBSA-PAM), such as those derived from the reaction of maleated polyisobutylene and N-phenyl-p-phenylenediamine. U.S. Patent Application No. 18 / 480,571, filed on October 4, 2023, claiming the priority of U.S. Patent Application No. 63 / 379,006, filed on October 11, 2022, discloses the use of amides, imides, and / or ester-functionalized polymers containing specific C 4~5 olefins as additives in lubricating oil compositions for reducing wear. U.S. Patent Application No. 63 / 584,675, filed on September 22, 2023, further discloses a lubricant composition containing a functionalized polymer containing a specific olefin homopolymer or copolymer backbone, but with a reduced or absent polyalkenyl succinimide dispersant, which is a conventional polyalkenyl succinimide dispersant where the polyalkenyl is derived from polyisobutylene and the imide is derived from polyamine.

[0006] Now, the inventors have surprisingly found that, for the specific C described above 4~5 amides, imides, and / or ester-functionalized polymers containing olefins, and polyalkenyl-substituted succinic anhydrides prepared using a chlorine-assisted alkylation process and poly(alkenyl)succinimides (chloro dispersants) derived from polyamines, and polyalkenyl succinic anhydrides prepared using a halogen-free thermal alkylation process and poly(alkenyl)succinimides (thermal dispersants) derived from polyamines, when used in a lubricant composition such as an internal combustion engine lubricant composition, can provide improved wear performance and cleanliness performance. Furthermore, the inventors have surprisingly found that by using the dispersant mixture in the lubricant composition, even when the phosphorus content is less than 800 ppm, for example less than 500 ppm, and the SASH content is less than 0.9%, for example less than 0.5%, it is possible to pass the Daimler OM471 FE1 performance test. In addition, strong performance in the Daimler OM471 FE1 performance test has been observed in a semi-synthetic base stock system, and the present invention promotes a more sustainable and effective solution. SUMMARY OF THE INVENTION

[0007] The present invention is an additive concentrate or additive package containing a dispersant mixture, wherein the dispersant mixture is (1) 0.01 to 15% by mass, based on the total mass of the dispersant mixture, of an amide, imide, and / or ester-functionalized partially or fully saturated polymer containing C 4~5 olefins, and i) having an Mw / Mn of less than 2, ii) having a functionality distribution (Fd) value of 3.5 or less, and iii) having an Mn of 10,000 g / mol or more (GPC-PS) for the polymer before functionalization An amide, imide, and / or ester functionalized partially or fully saturated polymer having, and (2) One or more poly(alkenyl) succinimides (the "chloro dispersant") derived from polyalkenyl succinic anhydride and polyamine prepared using a chlorine-assisted alkylation process, based on 50 to 90% by mass of the total mass of the dispersant mixture; and (3) One or more poly(alkenyl) succinimides (the "thermal dispersant") derived from polyalkenyl succinic anhydride and polyamine prepared using a halogen-free thermal alkylation process, based on 10 to 30% by mass of the total mass of the dispersant mixture Relating to an additive concentrate or additive package comprising.

[0008] The present disclosure relates to a lubricating oil composition, A) At least 50% by mass of one or more base oils, based on the total mass of the lubricating oil composition, and (B) An additive concentrate comprising a dispersant mixture, the dispersant mixture comprising (1) Based on the total mass of the dispersant mixture, 0.01 to 15% by mass of an amide, imide, and / or ester functionalized partially or fully saturated polymer containing C 4~5 olefin, i) having an Mw / Mn of less than 2, ii) a functionality distribution (Fd) value of 3.5 or less, and iii) an Mn of the polymer before functionalization of 10,000 g / mol or more (GPC-PS) An amide, imide, and / or ester functionalized partially or fully saturated polymer having, and (2) One or more poly(alkenyl) succinimides (the "chloro dispersant") derived from polyalkenyl succinic anhydride and polyamine prepared using a chlorine-assisted alkylation process, based on 50 to 90% by mass of the total mass of the dispersant mixture; and (3) One or more poly(alkenyl) succinimides (the "thermal dispersant") derived from polyalkenyl succinic anhydride and polyamine prepared using a halogen-free thermal alkylation process, based on 10 to 30% by mass of the total mass of the dispersant mixture An additive concentrate comprising Further relates to a lubricating oil composition obtained by comprising or mixing.

[0009] Typically, one or more poly(alkenyl) succinimide dispersants are one or more PIBSA-PAM dispersants derived from polyisobutylene-substituted succinic anhydride and polyamine prepared using either a chlorine-assisted alkylation method or a halogen-free thermal alkylation method.

[0010] According to another aspect of the present disclosure, there is provided the use of the dispersant mixture described above to increase the piston cleanliness and / or wear resistance of a lubricating oil composition.

[0011] According to still a further aspect of the present invention, there is provided the use of the lubricating oil composition described above, wherein the lubricating oil composition a) An average piston cleanliness of 70% or more, such as 73% or more, such as 74% or more, 75% or more, such as 76% or more, 78% or more, such as 80% or more, such as 80.5% or more, as determined by Daimler OM471 FE1 (CEC L-118-21), and / or b) An average wear of the gear train wheels of 75% or more, 80% or more, such as 81% or more, 82% or more, such as 82.5% or more, such as 83% or more, as determined by Daimler OM471 FE1 (CEC L-118-21), and / or c) An average liner wear of 8 μm or less, 5 μm or less, 3 μm or less, such as 2 μm or less, such as 1 μm or less, as determined by Daimler OM471 FE1 (CEC L-118-21), and / or d) An oxidation degree of 65 A / cm or less, 55 A / cm or less, such as 51 A / cm or less, such as 49 A / cm or less, such as 45 A / cm or less, such as 40 A / cm or less, as determined by Daimler OM471 FE1 (CEC L-118-21) is provided.

[0012] According to still a further aspect of the present invention, (i) A large amount of one or more base oils, (ii) The dispersant mixture described above A crankcase lubricating oil composition is provided that is made by including or mixing the above.

[0013] In another aspect, the lubricating oil composition described herein 1) A phosphorus content of less than 800 ppm, such as less than 550 ppm, such as less than 500 ppm, such as less than 490 ppm, based on the total mass of the lubricating oil composition, and 2) A sulfuric acid ash (SASH) content of less than 0.9% by mass, such as less than 0.6% by mass, such as less than 0.5% by mass, based on the total mass of the lubricating oil composition is included.

[0014] Also, the present invention is a lubricating oil composition obtained by including or mixing (i) one or more base oils, (ii) one or more poly(alkenyl) succinimide chloro dispersants and one or more poly(alkenyl) succinimide thermal dispersants, (iii) one or more detergents, and (iv) one or more antiwear agents, (v) one or more antioxidants, and (vi) one or more functionalized polymers described herein, which contains the chloro dispersant and the thermal dispersant in a ratio of at least 4:1, a) An SAE viscosity grade of 20W-X, 15W-X, 10W-X, 5W-X, or 0W-X (for example, 10W-X or 5W-X), where X represents any one of 8, 12, 16, 20, 30, 40, and 50 (for example, 30), an SAE viscosity grade, and b) A mean piston cleanliness of 70% or more, such as 73% or more, such as 74% or more, 75% or more, such as 76% or more, 78% or more, such as 80% or more, such as 80.5% or more, as determined by Daimler OM471 FE1 (CEC L-118-21), and c) A mean wear of the gear train wheel of 75% or more, 80% or more, such as 81% or more, 82% or more, such as 82.5% or more, such as 83% or more, as determined by Daimler OM471 FE1 (CEC L-118-21), and d) As determined by Daimler OM471 FE1 (CEC L-118-21), an average liner wear of 8 μm or less, 5 μm or less, 3 μm or less, for example 2 μm or less, for example 1 μm or less, and e) As determined by Daimler OM471 FE1 (CEC L-118-21), an oxidation degree of 65 A / cm or less, 55 A / cm or less, for example 51 A / cm or less, for example 49 A / cm or less, for example 45 A / cm or less, for example 40 A / cm or less The present invention also relates to a lubricating oil composition having the above properties.

[0015] Definition For all purposes of this specification and the claims of the present invention, the following words and expressions have the meanings described below when used and as used. For the purposes of this specification, the Periodic Table of the Elements in the new numbering scheme shown in CHEMICAL AND ENGINEERING NEWS, Vol. 63 (No. 5), page 27 (1985) is used. That is, 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.).

[0016] With respect to the lubricating oil compositions described herein and the components or active ingredients included in the claims thereto, the term "absent" (or "free of") means that a particular component or active ingredient is present at 0.000% by mass based on the mass of the lubricating oil composition, or in the case of "substantially absent", the component or active ingredient is present at a level that does not affect the properties of the lubricating oil composition, for example less than 100 ppm, for example 10 ppm, or less than 1 ppm, or less than 0.001 ppm. The term "absent" when used with respect to monomer reactants and / or repeat units in the (co)polymers described herein means 0% by mass based on the mass of all (co)monomers in the (co)polymer, or at a level so low that even if present, it does not substantially affect the physical properties of the (co)polymer, for example 0.2% by mass or less or 0.1% by mass or less.

[0017] The term "about" means approximately and includes values obtained by rounding. As used herein, the term "about" modifying an amount of a component, constituent, or reactant of the present invention refers to the variability in numerical amounts that may arise, for example, from typical measurement and liquid handling procedures used in making concentrates or lubricating oil compositions. Further, the variability may arise from accidental errors in the measurement procedure, differences in manufacture, source, or purity of the components used in making the composition or carrying out the method. 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. Further, in another aspect, the term "about" means within 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1% of the reported numerical value.

[0018] The term "LOC" means a lubricating oil composition (which term is used synonymously herein with the terms "lubricating agent oil composition", or "lubricating composition", or "lubricating agent composition"). The term "a large amount" means more than 50% by mass of the composition, for example more than 60% by mass of the composition, for example more than 70% by mass of the composition, for example 80 to 99.009% by mass of the composition, for example 80 to 99.9, 80 to 99.009% by mass of the composition, based on the mass of the composition. The term "a small amount" means 50% by mass or less of the composition, for example 40% by mass or less of the composition, for example 30% by mass or less of the composition, for example 20 to 0.001% by mass, for example 20 to 0.1% by mass, based on the mass of the composition. The term "mass%" means, unless otherwise indicated, the mass percentage of a component based on the mass of the composition measured in grams, and is alternatively (alternately) also referred to as weight percentage ("weight%", wt%, or "weight(w) / weight(w)%"). The term "active ingredient" (also referred to as "a.i." or "A.I.") refers to an additive substance that is neither a diluent nor a solvent. Unless otherwise indicated, the amounts in this specification are described as active ingredients. As an example, a particular component in a lubricating oil composition may contain the functionalized polymers and diluent oil described herein. The content of the functionalized polymer itself is the active ingredient content (expressed, for example, as mass % based on the total mass of the component including the diluent oil). Unless otherwise indicated, all amounts, ranges, and ratios in this specification and the claims refer to the active ingredient.

[0019] As used herein, the terms "oil-soluble" and "oil-dispersible" or cognate terms do not necessarily indicate that a compound or additive is soluble, dissolvable, miscible, or suspendable in oil in all proportions. However, such terms mean that the compound or additive is soluble or stably dispersible in oil to an extent sufficient to, for example, exert the intended effect in an environment where oil is used. Further, if desired, higher levels of incorporation of a particular additive can be enabled by further incorporating other additives. As used herein, the terms "group" and "radical" are used synonymously. The term "hydrocarbon" means a compound of hydrogen and carbon atoms. A "heteroatom" is an atom other than carbon or hydrogen. When "hydrocarbon" is referred to, particularly "refined hydrocarbon", the hydrocarbon may contain small amounts (e.g., amounts that do not substantially alter the hydrocarbon character of the hydrocarbon compound) of one or more heteroatoms or heteroatom-containing groups (such as halo, particularly chloro and fluoro, amino, alkoxyl, mercapto, alkylmercapto, nitro, nitroso, sulfoxy, etc.).

[0020] The term "hydrocarbyl" means a radical containing hydrogen and carbon atoms. Preferably, this group consists essentially of, and more preferably consists only of, hydrogen and carbon atoms, unless otherwise specified. Preferably, the hydrocarbyl group includes an aliphatic hydrocarbyl group. The term "hydrocarbyl" includes "alkyl", "alkenyl", "alkynyl", and "aryl" as defined herein. A hydrocarbyl group may contain one or more atoms / groups other than carbon and hydrogen, provided that such atoms / groups do not substantially affect the essentially hydrocarbyl nature of the hydrocarbyl group. Those skilled in the art will recognize such atoms / groups (e.g., halo, especially chloro and fluoro, amino, alkoxyl, mercapto, alkylmercapto, nitro, nitroso, sulfoxy, etc.).

[0021] The term "alkyl" means a radical of carbon and hydrogen (e.g., C1 - C 30 group, e.g., C1 - C 12 group). An alkyl group in a compound is typically directly bonded to the compound through a carbon atom. Unless otherwise specified, an alkyl group may be straight-chain (i.e., unbranched) or branched-chain, and may be cyclic, acyclic, or partially cyclic / acyclic. Preferably, the alkyl group includes a straight-chain or branched-chain acyclic alkyl group. Representative examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, dimethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, and triacontyl.

[0022] The term "alkenyl" means a radical of carbon and hydrogen having at least one double bond (e.g., C2 - C 30 radical, e.g., C2 - C 12means "(radical)". The alkenyl group in the compound is typically directly bonded to the compound via a carbon atom. Unless otherwise specified, the alkenyl group may be linear (i.e., unbranched) or branched, and may be cyclic, acyclic, or partially cyclic / acyclic. The term "alkylene" means a C1-C which may be linear or branched 20 , preferably C1-C 10 divalent saturated aliphatic radical. Representative examples of alkylene include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, 1-methylethylene, 1-ethylethylene, 1-ethyl-2-methylethylene, 1,1-dimethylethylene, and 1-ethylpropylene.

[0023] "Olefin", alternatively referred to as "alkene", is a straight-chain, branched-chain, or cyclic compound of carbon and hydrogen having at least one double bond. 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 in a polymerized form of the olefin. For example, when a copolymer is said to have an "isoprene" content of 55% to 95% by mass, the monomer units of the copolymer are derived from isoprene in the polymerization reaction, and such derived units are understood to be present at 55% to 95% by mass based on the mass of the copolymer. A "polymer" has two or more same or different monomer units. A "homopolymer" is a polymer having the same monomer units. A "copolymer" is a polymer having two or more different monomer units that are different from each other. "Different" as used to refer to monomer units indicates that the monomer units are different from each other by at least one atom or are isomerically different. An "isoprene polymer" or "isoprene copolymer" is a polymer or copolymer containing at least 50 mol% of units derived from isoprene, a "butadiene polymer" or "butadiene copolymer" is a polymer or copolymer containing at least 50 mol% of units derived from butadiene, and so on. Similarly, when a polymer is said to be a "partially or fully saturated polymer containing C 4~5 olefin", the C 4~5 olefin present in such polymer or copolymer is in a polymerized form of the olefin, and the polymer is partially or fully saturated (e.g., by hydrogenation) after polymerization of the monomer. The polymer "skeleton" is the polymer main chain containing the monomer units of the monomer and is in a state before any (subsequent) functionalization has been carried out.

[0024] The term "alkynyl" means a C2 - C 30 (C2 - C 12 etc.) radical containing at least one carbon-carbon triple bond. The term "aryl" means a group containing at least one aromatic ring such as cyclopentadienyl, phenyl, naphthyl, and anthracenyl. An aryl group is typically a C5-C 40 (e.g., C5-C 18 , e.g., C6-C 14 ) aryl group. Preferred aryl groups include phenyl and naphthyl groups and substituted derivatives thereof, particularly phenyl and alkyl-substituted derivatives of phenyl.

[0025] The term "substituted" means that a hydrogen atom is replaced by a hydrocarbon group, a heteroatom, or a heteroatom-containing group. An alkyl-substituted derivative means that a hydrogen atom is replaced by an alkyl group. "Alkyl-substituted phenyl" means that a hydrogen atom is replaced by an alkyl group, e.g., a C1-C 20 alkyl group, e.g., 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, icosyl, and / or triacontyl-substituted phenyl group.

[0026] The term "halogen" or "halo" means a Group 17 atom or a radical of a Group 17 atom, e.g., fluoro, chloro, bromo, and iodo. The term "ashless" with respect to an additive means that the composition does not contain a metal. The term "ash-containing" with respect to an additive means that the composition contains a metal. The term "ppm" means parts per million by mass based on the total mass of the lubricating oil composition, unless otherwise indicated. The term "metal content" of a lubricant composition or an additive component, e.g., magnesium content, molybdenum content, or total metal content (i.e., the sum of all individual metal contents) is measured by ASTM D5185.

[0027] The term "aliphatic hydrocarbyl fatty acid" means a monocarboxylic acid having an aliphatic C7 - C 29 , preferably C9 - C 27 , most preferably C 11 - C 23 hydrocarbyl chain. Such compounds are herein sometimes referred to as aliphatic (C7 - C 29 ), more preferably (C9 - C 27 ), most preferably (C 11 - C 23 ) hydrocarbyl monocarboxylic acids or hydrocarbyl fatty acids (wherein Cx - Cy refers to the total number of carbon atoms in the aliphatic hydrocarbyl chain of the fatty acid, and the fatty acid itself contains a total of Cx + 1 - Cy + 1 carbon atoms due to the presence of the carboxyl carbon atom). Preferably, the aliphatic hydrocarbyl fatty acid has an even number of carbon atoms including the carboxyl carbon atom. The aliphatic hydrocarbyl chain of the fatty acid may be saturated or unsaturated (i.e., contains at least one carbon - carbon double bond). Preferably, the aliphatic hydrocarbyl chain is unsaturated and contains at least one carbon - carbon double bond, and such fatty acids can be obtained from natural sources (e.g., derived from animal or vegetable oils) and / or by reduction of the corresponding saturated fatty acids. It will be understood that a portion of the aliphatic hydrocarbyl chain of the corresponding aliphatic hydrocarbyl fatty acid ester is unsaturated (i.e., contains at least one carbon - carbon double bond) and can react with other agents, e.g., sulfur, to form the corresponding functionalized, e.g., sulfided, aliphatic hydrocarbyl fatty acid ester.

[0028] The term "aliphatic hydrocarbyl fatty acid ester" means an ester that can be obtained by converting the monocarboxylic acid functional group of the corresponding aliphatic hydrocarbyl fatty acid into an ester group. Preferably, the monocarboxylic acid functional group of the aliphatic hydrocarbyl fatty acid is converted into a hydrocarbyl ester, preferably a C1-C 30 aliphatic hydrocarbyl ester, such as an alkyl ester, preferably a C1-C6 alkyl ester, particularly a methyl ester. Alternatively or in addition, the monocarboxylic acid functional group of the aliphatic hydrocarbyl fatty acid may be in the form of a natural glycerol ester. Thus, the term "aliphatic hydrocarbyl fatty acid ester" includes aliphatic hydrocarbyl fatty acid glycerol esters and aliphatic hydrocarbyl fatty acid C1-C 30 aliphatic hydrocarbyl esters [e.g., aliphatic hydrocarbyl fatty acid alkyl esters, more preferably aliphatic hydrocarbyl fatty acid C1-C6 alkyl esters, particularly aliphatic hydrocarbyl fatty acid methyl esters]. Preferably, the term "aliphatic hydrocarbyl fatty acid ester" refers to aliphatic (C7-C 29 ) hydrocarbyl, more preferably aliphatic (C9-C 27 ) hydrocarbyl, most preferably aliphatic (C 11 -C 23 ) hydrocarbyl fatty acid glycerol esters and aliphatic (C7-C 29 ) hydrocarbyl, more preferably aliphatic (C9-C 27 ) hydrocarbyl, most preferably aliphatic (C 11 -C 23 ) hydrocarbyl fatty acid C1-C 30 aliphatic hydrocarbyl esters. Preferably, in order to enable functionalization of the aliphatic hydrocarbyl fatty acid ester, such as sulfurization, a part of the aliphatic hydrocarbyl chain of the fatty acid ester is unsaturated and contains at least one carbon-carbon double bond.

[0029] The term "sulfurized aliphatic hydrocarbyl fatty acid ester" means a compound obtained by sulfurizing the aliphatic hydrocarbyl fatty acid ester as defined herein. 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 referred to as the polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise stated, all molecular weight units (e.g., Mw, Mn, Mz) are reported in g / mol. For additive components or for a lubricating oil composition (i.e., an unused lubricating oil composition), the total base number, also referred to as "TBN", means the total base number measured according to ASTM D2896 and is reported in units of mg KOH / g. The total acid number ("TAN") is determined according to ASTM D664. The contents of phosphorus, boron, calcium, zinc, molybdenum, sodium, silicon, and magnesium are measured according to ASTM D5185.

[0030] The sulfur content in the oil formulation is measured according to ASTM D5185. The sulfuric acid ash ("SASH") content is measured according to ASTM D874. The kinematic viscosity (KV100, KV40) is determined in accordance with ASTM D445-19a and is reported in units of cSt unless otherwise specified. The viscosity index is determined in accordance with ASTM D2270. The saponification value is determined according to ASTM D94 and is reported in units of mg KOH / g. HTCBT, the high-temperature corrosion bench test, is determined in accordance with ASTM D6594. The average functionality [also referred to as the average functionality value (Fv)] and the functionality distribution (Fd) values are determined by gel permeation chromatography using polystyrene standards as described in the experimental sections of U.S. Patent Application No. 18 / 480,571, filed October 4, 2023, which claims priority to U.S. Patent Application No. 63 / 379,006, filed October 11, 2022, and in the experimental section of this specification.

[0031] Unless otherwise indicated, all percentages reported are weight percentages based on the active ingredient, i.e., are not related to carrier oil or diluent oil unless otherwise indicated. Unless otherwise indicated, "weight %" has the same meaning as "weight %" or "wt %" in this specification. Also, it is understood that the various components, essential components, and optional and conventional components used may react under the conditions of formulation, storage, or use, and the present disclosure also provides any products that can be obtained or are obtained as a result of any such reaction. Furthermore, it is understood that any upper and lower limits, ranges, and ratio limits shown herein can be combined independently. Also, it will be understood that the preferred features of each aspect of the present disclosure are considered to be the preferred features of any other aspect of the present disclosure. Accordingly, the preferred and more preferred features of one aspect of the present disclosure can be combined independently with the other preferred and / or more preferred features of the same or different aspects of the present disclosure.

Mode for Carrying Out the Invention

[0032] Hereinafter, the features of the present disclosure regarding each and all aspects of the present disclosure will be described in more detail as necessary. The lubricating oil compositions and additive concentrates of the present disclosure may contain components that may or may not remain chemically the same before and after mixing with an oily carrier (e.g., base oil) and / or other additives. The present disclosure encompasses compositions containing such components before mixing, or after mixing, or both before and after mixing.

[0033] Lubricating oil composition The present disclosure is a lubricating oil composition (also referred to as "LOC", "lubricant composition", "lubricating composition", or "lubricant oil composition"), and the lubricating oil composition (a) One or more base oils in an amount of 1 to 99% by mass (alternatively 30 to 95% by mass, alternatively 50 to 90% by mass, alternatively 60 to 95% by mass, alternatively 70 to 85% by mass) based on the mass of the lubricating composition, or alternatively, one or more base oils in an amount of 50% by mass or more based on the mass of the lubricating composition, (b) A functionalized polymer containing a partially or fully saturated olefin homopolymer or copolymer backbone and at least one functional group (e.g., a group derived from an amine group or a hydroxyl group) in an amount of 0.1 to 20% by mass (in particular 0.15 to 10% by mass, alternatively 0.2 to 5% by mass, alternatively 0.25 to 2% by mass, alternatively 0.5 to 1% by mass) based on the mass of the lubricating composition, having an Mn of the polymer before functionalization of 10,000 g / mol or more (GPC-PS), preferably functionalized with an acylating agent and then reacted with a compound containing an amino group and / or a hydroxyl group (e.g., C 2~5 One or more amide, imide, and / or ester-functionalized partially or fully saturated polymers containing olefins), i) an Mw / Mn of less than 2, ii) optionally a functionality distribution (Fd) value of 3.5 or less (GPC-PS), and iii) an Mn of the polymer before functionalization of 10,000 g / mol or more (GPC-PS), provided that when the polymer before functionalization is a copolymer of isoprene and butadiene, it has an Mn of the copolymer greater than 25,000 g / mol (GPC-PS), a functionalized polymer, c) One or more poly(alkenyl) succinimide dispersants (e.g., a blend of poly(alkenyl) succinimide dispersants) derived from polyalkenyl-substituted succinic anhydride and polyamine prepared using a chlorine-assisted alkylation method in an amount of 0.1 to 20% by mass (alternatively 0.1 to 12% by mass, alternatively 0.25 to 10% by mass, alternatively 0.5 to 8% by mass, alternatively 1 to 7% by mass, alternatively 3 to 6% by mass) based on the mass of the lubricating composition; and d) One or more poly(alkenyl) succinimide dispersants (e.g., a blend of poly(alkenyl) succinimide dispersants) derived from polyalkenyl succinic anhydride and polyamine prepared using a halogen-free thermal alkylation process, in an amount of 0.1 to 10% by mass (alternatively 0.1 to 6% by mass, alternatively 0.25 to 4% by mass, alternatively 0.5 to 3% by mass, alternatively 0.8 to 1.5% by mass, alternatively 1 to 1.25% by mass) based on the mass of the lubricating composition (the "thermal dispersant"), present in an amount such that the mass ratio of the chloro dispersant (c) to the thermal dispersant is at least 4:1, e) Optionally, one or more antioxidants (e.g., a blend of antioxidants) in an amount of 0 to 20% by mass based on the mass of the lubricating oil composition (e.g., not present or substantially absent in the lubricating oil composition, alternatively 0.1 to 12% by mass, alternatively 0.25 to 8% by mass, alternatively 0.5 to 6% by mass, alternatively 0.05 to 5% by mass, alternatively 3.5 to 5% by mass), and when present, optionally one or more antioxidants are preferably a mixture of one or more amine antioxidants and one or more phenolic antioxidants in a ratio of at least 2:1, one or more antioxidants obtained by including or mixing, The lubricating oil composition preferably 1) has an SAE viscosity grade of 20W-X, 15W-X, 10W-X, 5W-X, or 0W-X (e.g., 10W-X or 5W-X), where X represents any one of 8, 12, 16, 20, 30, 40, and 50 (e.g., 30), an SAE viscosity grade, and 2) Optionally, as determined by Daimler OM471 FE1 (CEC L-118-21), an average piston cleanliness of 70% or more, e.g., 73% or more, e.g., 74% or more, 75% or more, e.g., 76% or more, 78% or more, e.g., 80% or more, e.g., 80.5% or more, and / or 3) Optionally, determined by Daimler OM471 FE1 (CEC L-118-21), an average wear of the gear train wheels of 75% or more, 80% or more, for example 81% or more, 82% or more, for example 82.5% or more, for example 83% or more, and / or 4) Optionally, determined by Daimler OM471 FE1 (CEC L-118-21), an average liner wear of 8 μm or less, 5 μm or less, 3 μm or less, for example 2 μm or less, for example 1 μm or less, and / or 5) Optionally, determined by Daimler OM471 FE1 (CEC L-118-21), an oxidation degree of 65 A / cm² or less, 55 A / cm² or less, for example 51 A / cm² or less, for example 49 A / cm² or less, for example 45 A / cm² or less, for example 40 A / cm² or less The present invention relates to a lubricating oil composition which may exhibit the above properties.

[0034] Furthermore, the present disclosure relates to a lubricating oil composition comprising: (i) one or more base oils in an amount of 1 to 99% by mass (alternatively 30 to 95% by mass, alternatively 50 to 90% by mass, alternatively 60 to 95% by mass, alternatively 70 to 85% by mass) based on the mass of the lubricating composition, or alternatively, the lubricating oil composition comprises one or more base oils in an amount of 50% by mass or more based on the mass of the lubricating composition, (ii) Based on the mass of the lubricating composition, 0.1 to 20% by mass (in particular, 0.1 to 12% by mass, alternatively 0.1 to 10% by mass, alternatively 1 to 8% by mass) of one or more poly(alkenyl) succinimide dispersants derived from polyalkenyl-substituted succinic anhydride and polyamine prepared using the chlorine-assisted alkylation method (for example, a blend of poly(alkenyl) succinimide dispersants) (the "chloro dispersant") and one or more poly(alkenyl) succinimide dispersants derived from polyalkenyl succinic anhydride and polyamine prepared using the halogen-free alkylation method (for example, a blend of poly(alkenyl) succinimide dispersants) (the "thermal dispersant"), wherein the thermal dispersant is present in an amount such that the mass ratio of the chloro dispersant to the thermal dispersant is at least 4:1, one or more poly(alkenyl) succinimide dispersants (for example, a blend of poly(alkenyl) succinimide dispersants), and (iii) Based on the mass of the composition, 0.01 to 20% by mass (in particular 0.1 to 10% by mass, alternatively 0.15% to 5% by mass, alternatively 0.2 to 2% by mass) of one or more detergents (for example, a blend of detergents), (iv) Based on the mass of the lubricating composition, 0.001 to 10% by mass (in particular 0.01 to 5% by mass, alternatively 0.1 to 3% by mass, alternatively 0.15 to 1.5% by mass, alternatively 0.2 to 1% by mass) of one or more antiwear agents (for example, a blend of antiwear agents, for example, zinc dialkyldithiophosphate), v) Based on the mass of the lubricating composition, 0.1 to 20% by mass (in particular 0.1 to 12% by mass, alternatively 0.25 to 8% by mass, alternatively 0.5 to 6% by mass, alternatively 0.05 to 5% by mass, alternatively 3.5 to 5% by mass) of one or more antioxidants (for example, a blend of antioxidants, for example, preferably a mixture of one or more amine antioxidants and one or more phenolic antioxidants in a ratio of at least 2:1), (vi) 0.10 to 20% by mass (particularly 0.15 to 10% by mass, alternatively 0.20% to 5% by mass, alternatively 0.25 to 2% by mass, alternatively 0.5 to 1% by mass), based on the mass of the lubricating composition, of C 4~5 one or more amide, imide, and / or ester functionalized partially or fully saturated polymers containing olefins, i) an Mw / Mn of less than 2, ii) a functionality distribution (Fd) value of 3.5 or less (GPC-PS), and i) having an Mn of the polymer before functionalization of 10,000 g / mol or more (GPC-PS), provided that when the polymer before functionalization is a copolymer of isoprene and butadiene, it has a copolymer Mn greater than 25,000 g / mol (GPC-PS), one or more amide, imide, and / or ester functionalized partially or fully saturated polymers, obtained from including or mixing, The lubricating oil composition preferably is, 1) an SAE viscosity grade of 20W-X, 15W-X, 10W-X, 5W-X, or 0W-X (e.g., 10W-X or 5W-X), where X represents any one of 8, 12, 16, 20, 30, 40, and 50 (e.g., 30), an SAE viscosity grade, and 2) Optionally, determined by Daimler OM471 FE1 (CEC L-118-21), an average piston cleanliness of 70% or more, e.g., 73% or more, e.g., 74% or more, 75% or more, e.g., 76% or more, 78% or more, e.g., 80% or more, e.g., 80.5% or more, and / or 3) Optionally, determined by Daimler OM471 FE1 (CEC L-118-21), an average wear of the gear train wheel of 75% or more, 80% or more, e.g., 81% or more, 82% or more, e.g., 82.5% or more, e.g., 83% or more, and / or 4) Optionally, determined by Daimler OM471 FE1 (CEC L-118-21), an average liner wear of 8 μm or less, 5 μm or less, 3 μm or less, e.g., 2 μm or less, e.g., 1 μm or less, and / or 5) Optionally, as determined by Daimler OM471 FE1 (CEC L-118-21), an oxidation degree of 65 A / cm or less, 55 A / cm or less, for example 51 A / cm or less, for example 49 A / cm or less, for example 45 A / cm or less, for example 40 A / cm or less relates to a lubricating oil composition exhibiting the same.

[0035] Also, the present disclosure relates to a lubricant composition of an oil having a lubricating viscosity, comprising a dispersant mixture of 0.1 to 30% by mass (particularly 0.1 to 20% by mass, alternatively 0.1 to 12% by mass, alternatively 3 to 10% by mass, alternatively 6 to 8% by mass) based on the mass of the lubricant composition, and the dispersant mixture comprises (1) C 4~5 an amide, imide, and / or ester functionalized partially or fully saturated polymer containing olefins, i) an Mw / Mn of less than 2, ii) a functionality distribution (Fd) value of 3.5 or less, and iii) an Mn of the polymer before functionalization of 10,000 g / mol or more (GPC-PS) having an amide, imide, and / or ester functionalized partially or fully saturated polymer, and (2) one or more poly(alkenyl)succinimide dispersants (e.g., a blend of poly(alkenyl)succinimide dispersants) derived from polyalkenyl-substituted succinic anhydride and polyamine prepared using a chlorine-assisted alkylation method (a "chloro dispersant"), and (3) one or more poly(alkenyl)succinimide dispersants (e.g., a blend of poly(alkenyl)succinimide dispersants) derived from polyalkenyl succinic anhydride and polyamine prepared using a halogen-free thermal alkylation method (a "thermal dispersant"), wherein the mass ratio of the chloro dispersant (2) to the thermal dispersant is at least 4:1, and / or the mass ratio of the functionalized polymer (1) to the thermal dispersant is at least 0.5:1, and the one or more poly(alkenyl)succinimide dispersants are present in such amounts relates to a lubricant composition of an oil having a lubricating viscosity.

[0036] Also, the present disclosure A) One or more base oils in an amount of 1 to 99% by mass (alternatively 30 to 95% by mass, alternatively 50 to 90% by mass, alternatively 60 to 95% by mass, alternatively 70 to 85% by mass) based on the mass of the lubricating oil composition, or alternatively, one or more base oils in an amount of 50% by mass or more based on the mass of the lubricating composition, B) One or more of the amides, imides, and / or ester-functionalized partially or fully saturated polymers described herein in an amount of 0.1 to 20% by mass (in particular 0.15 to 10% by mass, alternatively 0.2% by mass to 5% by mass, alternatively 0.25 to 2% by mass, alternatively 0.5 to 1% by mass, alternatively 0.2 to 1% by mass) based on the mass of the lubricating oil composition, C) One or more detergents (e.g., a blend of detergents) in an amount of 0.01 to 20% by mass (in particular 0.1 to 10% by mass, alternatively 0.15% by mass to 5% by mass, alternatively 0.2 to 2% by mass, alternatively 0.2 to 0.6% by mass) based on the mass of the lubricating oil composition, D) Optionally, one or more friction modifiers (e.g., a blend of friction modifiers) in an amount of 0.001 to 5% by mass (in particular 0.01 to 4% by mass, alternatively 0.015 to 3% by mass, alternatively 0.02 to 0.04% by mass) based on the mass of the lubricating oil composition, E) One or more antioxidants (e.g., a blend of antioxidants) in an amount of 0.1 to 20% by mass (in particular 0.1 to 12% by mass, alternatively 0.25 to 8% by mass, alternatively 0.5 to 6% by mass, alternatively 0.05 to 5% by mass, alternatively 3.5 to 5% by mass) based on the total mass of the lubricating oil composition, F) Optionally, one or more pour point depressants (e.g., a blend of pour point depressants) in an amount of 0.01 to 5% by mass (in particular 0.01 to 3% by mass, alternatively 0.02 to 1.5% by mass, alternatively 0.025 to 0.2% by mass) based on the mass of the lubricating oil composition, G) Optionally, one or more anti-foaming agents (e.g., a blend of anti-foaming agents) in an amount of 0.001 to 5% by mass (in particular 0.001 to 3% by mass, alternatively 0.005 to 1.5% by mass, alternatively 0.005 to 0.01% by mass) based on the mass of the lubricating oil composition, H) Optionally, one or more friction modifiers (e.g., a blend of friction modifiers) in an amount of 0.001 to 10% by mass (particularly 0.01 to 6% by mass, alternatively 0.01 to 5% by mass, alternatively 0.1 to 4% by mass, alternatively 0.1 to 2% by mass, alternatively 0.1 to 0.22% by mass) based on the mass of the lubricating oil composition, I) One or more poly(alkenyl) succinimide dispersants (e.g., a blend of poly(alkenyl) succinimide dispersants) derived from polyalkenyl-substituted succinic anhydride and polyamine prepared using a chlorine-assisted alkylation process (referred to as "chloro dispersants") and one or more poly(alkenyl) succinimide dispersants (e.g., a blend of poly(alkenyl) succinimide dispersants) derived from polyalkenyl succinic anhydride and polyamine prepared using a halogen-free thermal alkylation process (referred to as "thermal dispersants") in an amount of 0.1 to 20% by mass (particularly 0.1 to 12% by mass, alternatively 0.1 to 10% by mass, alternatively 1 to 8% by mass) based on the mass of the lubricating composition, especially consisting of, one or more dispersants (e.g., a blend of dispersants), wherein the thermal dispersant is present in an amount such that the mass ratio of the chloro dispersant to the thermal dispersant is at least 4:1, and J) Optionally, one or more inhibitors and / or rust inhibitors (e.g., a blend of inhibitors and / or rust inhibitors) in an amount of 0.01 to 5% by mass (particularly 0.01 to 3% by mass, alternatively 0.05 to 1.5% by mass, alternatively 0.05 to 0.1% by mass) based on the mass of the lubricating oil composition, K) One or more antiwear agents (e.g., a blend of antiwear agents, e.g., ZDDP) in an amount of 0.001 to 10% by mass (particularly 0.01 to 5% by mass, alternatively 0.1 to 3% by mass, alternatively 0.15 to 1.5% by mass, alternatively 0.2 to 1% by mass, alternatively 0.06 to 0.6% by mass) based on the mass of the lubricating composition, M) Optionally, one or more seal compatibility agents, e.g., seal swell agents, in an amount of 0.01 to 5% by mass (particularly 0.05 to 2% by mass, alternatively 0.1 to 1% by mass) based on the mass of the lubricating oil composition, and / or (O) Optionally, based on the mass of the lubricating oil composition, one or more unsaturated C 12 ~C 60 hydrocarbons (e.g., C 12 ~C 24 linear alpha-olefins (LAO), oligomers / polymers of polyisobutylene, and / or blends thereof) relating to a lubricating oil composition obtained by including or mixing the same.

[0037] Alternatively, the lubricating oil composition of the present invention (including but not limited to those disclosed above) may contain at least 50% by mass, e.g., 50 - 90% by mass, alternatively 60 - 95% by mass, alternatively 70 - 85% by mass of one or more base oils based on the mass of the lubricating oil composition. In particular, the lubricating oil composition of the present invention (including but not limited to those disclosed above) may contain at least 30% by mass, e.g., 30 - 55% by mass, alternatively 35 - 50% by mass of one or more Group III base oils, and at least 25% by mass, e.g., 25 - 45% by mass, alternatively 30 - 40% by mass of one or more Group II base oils based on the mass of the lubricating oil composition.

[0038] For the purposes of the present disclosure, component B) the functionalized polymer is not added to elements C, D, E, F, G, H, I, J, K, M, and / or O for the purpose of determining the mass percentage, even if they may exhibit similar properties. For example, component B) the functionalized polymer may have a positive effect on wear, but is not added to element K) for the purpose of determining the mass percentage of the antiwear agent. In particular, the compositions according to the present disclosure may also contain additives having different notation functions that are similarly aminated (e.g., the dispersant components PIBSA-PAM and others described in the dispersant section below). Such additives are not included in the functionalized polymer for the purpose of determining the amount of the functionalized polymer in the lubricating oil composition or additive concentrate herein. However, component B) the functionalized polymer constitutes the dispersant mixture described herein together with component I) the poly(alkenyl) succinimide dispersant.

[0039] In embodiments, in addition to the base oil, the detergent, and one or more functionalized polymers described herein, all of elements D, E, F, G, H, I, J, K, M, and O are present. In embodiments, in addition to the base oil, the detergent, and one or more functionalized polymers described above, elements D, E, F, G, H, I, J, and K are present. In embodiments, in addition to the base oil, the detergent, and one or more functionalized polymers described herein, elements I and E are present. In embodiments, in addition to the base oil, the detergent, and one or more functionalized polymers described herein, element K is present. Preferably, the lubricant composition may have a total base number (TBN) of 4 to 15 mg KOH / g, preferably 5 to 12 mg KOH / g, such as 7 to 12 mg KOH / g, such as 8 to 11 mg KOH / g, as measured by ASTM D2896.

[0040] The lubricating composition of the present disclosure may contain phosphorus at a particularly low level, i.e., 1000 ppm or less, preferably 800 ppm or less, more preferably 500 ppm or less, e.g., 1 to 1000 ppm, e.g., 50 to 800 ppm, e.g., 100 to 500 ppm, expressed as atoms of phosphorus, based on the total mass of the lubricating composition, as measured by ASTM D5185. Preferably, the lubricant composition may have a phosphorus level of 1000 ppm or less, alternatively 800 ppm or less, alternatively 500 ppm or less, as measured by ASTM D5185. The lubricating composition of the present disclosure may contain a ratio of magnesium atoms to calcium atoms of at least up to 0.5, preferably at least 0.6, more preferably at least 0.65, based on the total mass of the lubricating composition, as measured by ASTM D5185.

[0041] Typically, the lubricating composition may contain a low level of sulfur. Preferably, the lubricating composition contains sulfur at a maximum of 0.4, more preferably at a maximum of 0.3, most preferably at a maximum of 0.2, e.g., 0.1 to 0.4% by mass, based on the total mass of the lubricating oil composition, as measured by ASTM D5185. Typically, the lubricating composition has a low level of sulfuric acid ash, e.g., 1.0% by mass or less, e.g., 0.9% by mass or less, preferably 0.6% by mass or less, preferably 0.5% by mass or less, alternatively 0.0001 to 0.5% by mass or less, based on the total mass of the lubricating composition, as measured by ASTM D874-13a(2018). Generally, the kinematic viscosity of the lubricating composition at 100 °C (“KV100”) may be in the range of 2 to 30 cSt, e.g., 2 to 20 cSt, e.g., 5 to 15 cSt, as determined in accordance with ASTM D445-19a. In an embodiment, the kinematic viscosity of the lubricating composition at 100 °C (“KV100”) may be in the range of 6 to 17 cSt, e.g., 9 to 16.3 cSt, e.g., less than 9.3 to 12.5 cSt, e.g., less than 12.5 to 16.3 cSt, as determined in accordance with ASTM D445-19a. Generally, the total base number of the lubricating composition ranges from 1 to 30, for example, from 5 to 15 mg KOH / g (determined in accordance with ASTM D2896).

[0042] Preferably, the lubricating composition of the present disclosure may be a multigrade oil specified by the viscosity description symbols 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 various viscosity grades can be found in the SAE J300 classification. Alternatively, the lubricating composition may be in the form of a viscosity grade SAE 15W-X, SAE 10W-X, SAE 5W-X, or SAE 0W-X, for example, in the form of SAE 5W-X, where X represents any one of 8, 12, 16, 20, 30, 40, and 50. Preferably, X is 8, 12, 16, 20, or 30. Alternatively, the lubricating composition of the present disclosure may be a multigrade oil specified by the viscosity description symbols SAE 10W-30, 15W-40, 5W-30, 5W-40, 10W-40, 5W-50, for example, SAE 5W-30 (see the standard SAE J300 published by SAE International in January 2015, formerly known as the Society of Automotive Engineers).

[0043] Optionally, the lubricating composition may not contain a phenate detergent. Optionally, the lubricating composition may not contain a PIBSA ester dispersant. Optionally, the lubricating composition may not contain a phenolic antioxidant. Alternatively, the lubricating composition may contain a phenolic antioxidant. Optionally, the lubricating composition may not contain a methyl ester sulfide antioxidant. In an embodiment, the lubricating oil composition may contain less than 1000 ppm of boron, alternatively less than 600 ppm of boron, alternatively 80 to 350 ppm of boron. Alternatively, the LOC may not contain boron.

[0044] In an embodiment, the lubricating oil composition may contain a functionalized (e.g., aminated) polybutene (e.g., polyisobutylene), such as PIBSA-PAM, of less than 20% by mass (e.g., less than 15% by mass, e.g., less than 10% by mass, e.g., less than 6% by mass). In an embodiment, the lubricating oil composition contains a functionalized (e.g., aminated) polybutene (e.g., polyisobutylene), such as PIBSA-PAM, of more than 0.1% by mass (e.g., 0.1 to 10% by mass, e.g., 0.5 to 8% by mass). In an embodiment, the lubricating oil composition contains a functionalized (e.g., aminated) polybutene (e.g., polyisobutylene), such as PIBSA-PAM, of more than 0.5% by mass (e.g., 0.5 to 8% by mass, e.g., 2 to 8% by mass), which is derived from polyisobutylene succinic anhydride and polyamine prepared using a chlorine-assisted alkylation method.

[0045] In an embodiment, the lubricating oil composition contains a functionalized (e.g., aminated) polybutene (e.g., polyisobutylene), such as PIBSA-PAM, of more than 0.5% by mass (e.g., 0.5 to 8% by mass, e.g., 0.5 to 2% by mass), which is derived from polyisobutylene succinic anhydride and polyamine prepared using a halogen-free thermal alkylation method. In an embodiment, the lubricating oil composition contains a functionalized (e.g., aminated) polybutene (e.g., polyisobutylene), such as PIBSA-PAM, of more than 0.1% by mass (e.g., 0.1 to 5% by mass, e.g., 0.1 to 3% by mass, e.g., 0.5 to 2% by mass), which has a high vinylidene content at the end. In an embodiment, the lubricating oil composition may contain an acylated polymer, such as polyisobutylene succinic acid (PIBSA), having an Mn of 500 to 50,000 g / mol, e.g., 600 to 5,000 g / mol, e.g., 700 to 3000 g / mol, optionally. In an embodiment, the lubricating oil composition may contain an acylated polymer, such as polyisobutylene succinic acid, having an Mn of 500 to 1600 g / mol, e.g., 700 to 1200 g / mol.

[0046] In an embodiment, the lubricating oil composition may contain 20 (for example, 15, for example, 10, for example, 5, for example, 3, for example, 1) mass% or less of a block copolymer, such as a block, star, random, and / or tapered block copolymer. In an embodiment, the lubricating oil composition may not substantially contain a block copolymer, such as a block, star, random, and / or tapered block copolymer, or the lubricating oil composition may not contain a block copolymer, such as a block, star, random, and / or tapered block copolymer. In an embodiment, the lubricating oil composition may contain 20 (for example, 15, for example, 10, for example, 5, for example, 3, for example, 1) mass% or less of a styrenic copolymer, such as a block, star, random, and / or tapered styrenic copolymer. In an embodiment, the lubricating oil composition may not substantially contain a styrenic copolymer, such as a block, star, random, and / or tapered styrenic copolymer, or the lubricating oil composition may not contain a styrenic copolymer, such as a block, star, random, and / or tapered styrenic copolymer.

[0047] In an embodiment, the lubricating oil composition may contain less than 20 mass% (for example, less than 15 mass%, for example, less than 10 mass%, for example, less than 5 mass%, for example, less than 3 mass%, for example, less than 1 mass%) of a functionalized diluent, such as a functionalized oil. In an embodiment, the lubricating oil composition may contain a functionalized diluent, such as a functionalized oil, may not substantially contain it, or the lubricating oil composition may not contain a functionalized diluent, such as a functionalized oil. In an embodiment, the lubricating oil composition may contain less than 20 mass% (for example, less than 15 mass%, for example, less than 10 mass%, for example, less than 5 mass%, for example, less than 3 mass%, for example, less than 1 mass%) of a solvent, such as an aromatic solvent. In an embodiment, the lubricating oil composition may not substantially contain a solvent, such as a functionalized solvent, or the lubricating oil composition may not contain a solvent, such as a functionalized solvent.

[0048] In an embodiment, the lubricating oil composition may have a total saponification value (SAP) of 25 (e.g., 28, e.g., 30, e.g., 32) mg KOH / g or more as determined by ASTM 94. In an embodiment, the lubricating oil composition may have a total saponification value (SAP) of 25 (e.g., 28, e.g., 30, e.g., 32) mg KOH / g or more as determined by ASTM 94, and the functionalized polymer may have a functionality distribution (Fd) value of 3.5 or less (as determined by GPC-PS described in the following experimental section, e.g., 3.4 or less, e.g., 1 to 3.3, e.g., 1.1 to 3.2, e.g., 1.2 to 3.0, e.g., 1.4 to 2.9). In an embodiment, the lubricating oil composition may have a total saponification value (SAP) of 25 (e.g., 28, e.g., 30, e.g., 32) mg KOH / g or more as determined by ASTM 94, and the functionalized polymer may have an average functionality of 1.4 to 20 FG grafts / polymer chain (e.g., 1.4 to 15 FG grafts / polymer chain, e.g., 3 to 12.5 FG grafts / polymer chain, e.g., 4 to 10 FG grafts / polymer chain) as determined by GPC-PS described in the following experimental section. In an embodiment, the lubricating oil composition may contain less than 0.5% by mass (e.g., 0.4% by mass, e.g., less than 0.3% by mass, e.g., less than 0.2% by mass, e.g., less than 0.1% by mass, substantially absent, or 0% by mass) of secondary hydrocarbylamine compounds and tertiary hydrocarbylamine compounds based on the mass of the LOC.

[0049] In an embodiment, the secondary hydrocarbylamine compound and the tertiary hydrocarbylamine compound may be substantially absent from the lubricating oil composition, or the lubricating oil composition may not contain the secondary hydrocarbylamine compound and the tertiary hydrocarbylamine compound. In an embodiment, the lubricating composition of the present disclosure may be a heavy-duty diesel oil (e.g., for use in the engine of a heavy-duty diesel vehicle, i.e., a heavy-duty diesel vehicle having a total vehicle weight rating of 4535.9 kg (10,000 pounds) or more). In an embodiment, the lubricating composition of the present disclosure may be a motor oil for passenger cars. In an embodiment, the lubricating composition of the present disclosure may be a diesel oil for passenger cars.

[0050] In an embodiment, the lubricating composition of the present disclosure is an oil having a lubricating viscosity having more than 50% by mass of Group I, II, III, IV, and / or V oils (for example, one or more Group II base oils, one or more Group III base oils, or a mixture thereof); first and second PIB succinimide dispersants derived from PIB having a Mn of 1800 to 2500 Mn, a third PIB succinimide dispersant and a fourth PIB succinimide dispersant derived from PIB having a Mn of less than 1600, wherein at least one of the first PIB succinimide dispersant and the second PIB succinimide dispersant has a high terminal vinylidene content, and the third PIB succinimide dispersant and the fourth PIB succinimide dispersant do not contain boron (optionally, at least one of the third PIB succinimide dispersant and the fourth PIB succinimide dispersant is boronated), the first and second PIB succinimide dispersants and the third and fourth PIB succinimide dispersants; C 4~5 An amide, imide, and / or ester functionalized partially or fully saturated polymer containing olefins; one or more alkaline earth metal sulfonate detergents; and a phosphorus antiwear agent present in an amount to deliver 100 to 500 ppm of phosphorus to a lubricating composition having a total sulfur ash of 0.1 to 0.5% by mass may be a diesel engine lubricating composition.

[0051] The lubricating composition disclosed herein, for example, a diesel engine lubricating composition, may have a kinematic viscosity of 2.0 to 12.5, for example, 5.0 to 12.5, for example 7.5 to 12.0 (for example 9.0 to 12.0, or 9.7 to 11.7, or 9.7 to 11.5) cSt (mm 2 / s) as measured by ASTM D-445 at 100°C. The lubricating compositions disclosed herein, such as diesel engine lubricating compositions, may have a high temperature high shear viscosity (HTHS) of less than 3.6 mPa·s, or less than 3.5 mPa·s, or less than 3.4 mPa·s, or less than 3.3 mPa·s, or less than 3.2 mPa·s, or less than 3.1 mPa·s, as measured by ASTM D4683 at 150 °C. In another embodiment, the HTHS of the lubricating composition is from 2.4 to 3.5 mPa·s, or from 2.6 to 3.1 mPa·s, or from 2.8 to 3.1 mPa·s. The lubricating composition, such as a diesel engine lubricating composition, may have an SAE viscosity grade of 5W-X, where Y may be 8, 12, 16, 20, or 30. In certain embodiments, the lubricating oil composition has an SAE viscosity grade of 5W-30.

[0052] The lubricating compositions disclosed herein, such as diesel engine lubricating compositions, have 1) a kinematic viscosity of 7.5 to 12.0 (e.g., 9.0 to 12.0, or 9.7 to 11.7, or 9.7 to 11.5) cSt (mm 2 / s) as measured by ASTM D-445 at 100 °C, 2) a high temperature shear viscosity (HTHS) of less than 3.6 mPa·s, or less than 3.5 mPa·s, or less than 3.4 mPa·s, or less than 3.3 mPa·s, or less than 3.2 mPa·s, or less than 3.1 mPa·s (alternatively from 2.4 to 3.5 mPa·s, or from 2.6 to 3.1 mPa·s, or from 2.8 to 3.1 mPa·s) as measured by ASTM D4683 at 150 °C, and 3) may have an SAE viscosity grade of 5W-30.

[0053] Additive concentrate An additive concentrate, also referred to as an additive package, adpak, or addpack, has less than 50 wt% (e.g., less than 40 wt%, e.g., less than 30 wt%, e.g., less than 25 wt%, e.g., less than 20 wt%) base oil and lubricant composition additives (e.g., those described herein) and is typically a (concentrate) composition that is then further blended with additional base oil to form a lubricating oil product.

[0054] The present disclosure relates to a concentrate composition comprising (a) one or more base oils in an amount of less than 1 to 50% by mass (alternatively 5 to 45% by mass, alternatively 7 to 40% by mass, alternatively 10 to 35% by mass, alternatively 10 to 25% by mass) based on the mass of the concentrate composition, (b) 0.1 to 40% by mass (in particular 0.15 to 20% by mass, alternatively 0.2 to 10% by mass, alternatively 0.25 to 5% by mass, alternatively 0.5 to 4% by mass) based on the mass of the concentrate composition, of a functionalized polymer comprising a partially or fully saturated olefin homopolymer or copolymer backbone and at least one functional group (e.g., a group derived from an amine group or a hydroxyl group), having an Mn of the polymer before functionalization of 10,000 g / mol or more (GPC-PS), preferably functionalized with an acylating agent and then reacted with a compound containing an amino group and / or a hydroxyl group (e.g., C 2~5 one or more amides, imides, and / or esters functionalized with olefins of a partially or fully saturated polymer), having i) an Mw / Mn of less than 2, ii) a functionality distribution (Fd) value of 3.5 or less (GPC-PS), and iii) an Mn of the polymer before functionalization of 10,000 g / mol or more (GPC-PS), provided that when the polymer before functionalization is a copolymer of isoprene and butadiene, it has an Mn of the copolymer greater than 25,000 g / mol (GPC-PS), a functionalized polymer, c) 0.1 to 60% by mass (alternatively 0.1 to 40% by mass, alternatively 0.5 to 30% by mass, alternatively 1 to 25% by mass, alternatively 15 to 25% by mass) based on the mass of the concentrate composition, of one or more poly(alkenyl) succinimide dispersants (e.g., a blend of poly(alkenyl) succinimide dispersants) derived from polyalkenyl-substituted succinic anhydride and polyamine prepared using a chlorine-assisted alkylation method (a "chloro dispersant"); and d) 0.1 to 20% by mass (alternatively 0.1 to 12% by mass, alternatively 0.25 to 10% by mass, alternatively 0.5 to 8% by mass, alternatively 1.5 to 7% by mass, alternatively 3 to 6% by mass) based on the mass of the concentrate composition of one or more poly(alkenyl)succinimide dispersants derived from polyalkenyl succinic anhydride and polyamine prepared using a halogen-free thermal alkylation process (e.g., a blend of poly(alkenyl)succinimide dispersants) ("thermal dispersant"), present in an amount such that the mass ratio of the chloro dispersant (c) to the thermal dispersant is at least 4:1, one or more poly(alkenyl)succinimide dispersants e) Optionally, 0 to 50% by mass (e.g., not present or substantially not present in the lubricating oil composition, alternatively 0.1 to 35% by mass, alternatively 0.25 to 25% by mass, alternatively 0.5 to 22% by mass, alternatively 0.05 to 20% by mass, alternatively 14 to 20% by mass) based on the mass of the concentrate composition of one or more antioxidants (e.g., a blend of antioxidants), and when present, optionally one or more antioxidants are preferably a mixture of one or more amine antioxidants and one or more phenolic antioxidants in a ratio of at least 2:1, one or more antioxidants relates to a concentrate composition obtained by including or mixing.

[0055] The present disclosure is a concentrate composition, (i) one or more base oils in an amount less than 1 to 50% by mass (alternatively 5 to 45% by mass, alternatively 7 to 40% by mass, alternatively 10 to 35% by mass, alternatively 10 to 25% by mass) based on the mass of the concentrate composition (ii) Based on the mass of the concentrate composition, 0.1 to 70% by mass (particularly 0.1 to 50% by mass, alternatively 0.1 to 40% by mass, alternatively 1 to 30% by mass) of one or more poly(alkenyl) succinimide dispersants (e.g., blends of poly(alkenyl) succinimide dispersants) derived from polyalkenyl-substituted succinic anhydride and polyamine prepared using a chlorine-assisted alkylation method (hereinafter referred to as "chloro dispersant") and one or more poly(alkenyl) succinimide dispersants (e.g., blends of poly(alkenyl) succinimide dispersants) derived from polyalkenyl succinic anhydride and polyamine prepared using a halogen-free alkylation method (hereinafter referred to as "thermal dispersant"), wherein the thermal dispersant is present in an amount such that the mass ratio of the chloro dispersant to the thermal dispersant is at least 4:1, and one or more poly(alkenyl) succinimide dispersants (e.g., blends of poly(alkenyl) succinimide dispersants), and (iii) 0.01 to 30% by mass (particularly 0.1 to 20% by mass, alternatively 0.5% to 10% by mass, alternatively 0.5 to 5% by mass) of one or more detergents (e.g., blends of detergents) based on the mass of the concentrate composition, (iv) 0.001 to 20% by mass (particularly 0.01 to 10% by mass, alternatively 0.1 to 5% by mass, alternatively 0.5 to 5% by mass, alternatively 1 to 3% by mass) of one or more antiwear agents (e.g., blends of antiwear agents, e.g., zinc dialkyldithiophosphate) based on the mass of the concentrate composition, (v) 0.1 to 50% by mass (particularly 0.1 to 35% by mass, alternatively 0.25 to 25% by mass, alternatively 0.5 to 22% by mass, alternatively 0.05 to 20% by mass, alternatively 14 to 20% by mass) of one or more antioxidants (e.g., blends of antioxidants, e.g., preferably a mixture of one or more amine antioxidants and one or more phenolic antioxidants in a ratio of at least 2:1) based on the mass of the concentrate composition, (vi) 0.1 to 40% by mass (particularly 0.15 to 20% by mass, alternatively 0.2% to 10% by mass, alternatively 0.25 to 5% by mass, alternatively 0.5 to 4% by mass) of C based on the mass of the composition 4~5One or more amide, imide, and / or ester functionalized partial or fully saturated polymers containing olefins, i) Mw / Mn less than 2, ii) functionality distribution (Fd) value of 3.5 or less (GPC-PS), and ii) having a Mn of the polymer before functionalization of 10,000 g / mol or more (GPC-PS), provided that when the polymer before functionalization is a copolymer of isoprene and butadiene, it has a copolymer Mn greater than 25,000 g / mol (GPC-PS), one or more amide, imide, and / or ester functionalized partial or fully saturated polymers, (vii) Optional additional components, pour point depressants, defoamers, viscosity modifiers, corrosion inhibitors, extreme pressure additives, demulsifiers, seal compatibility agents, additive diluent base oils, friction modifiers (e.g., organic FMs, e.g., organic esters, e.g., fatty acid esters), etc. relates to a concentrate composition obtained by including or mixing them.

[0056] Also, the present disclosure relates to a concentrate composition comprising 0.1 to 50% by mass (particularly 0.1 to 40% by mass, alternatively 15 to 40% by mass, alternatively 20 to 32% by mass, alternatively 25 to 30% by mass) of a dispersant mixture based on the mass of the concentrate composition, and the dispersant mixture comprises (1) C 4~5 an amide, imide, and / or ester functionalized partial or fully saturated polymer containing olefins, i) Mw / Mn less than 2, ii) functionality distribution (Fd) value of 3.5 or less, and iii) Mn of the polymer before functionalization of 10,000 g / mol or more (GPC-PS) having, an amide, imide, and / or ester functionalized partial or fully saturated polymer, and (2) one or more poly(alkenyl) succinimide dispersants (e.g., a blend of poly(alkenyl) succinimide dispersants) derived from polyalkenyl-substituted succinic anhydride and polyamine prepared using a chlorine-assisted alkylation method ("chloro dispersants"), and (3) One or more poly(alkenyl) succinimide dispersants (e.g., blends of poly(alkenyl) succinimide dispersants) derived from polyalkenyl succinic anhydride and polyamine prepared using a halogen-free thermal alkylation method (the "thermal dispersant"), wherein the mass ratio of the chloro dispersant (2) to the thermal dispersant is at least 4:1, and / or the functionalized polymer (1) is present in an amount such that the mass ratio to the thermal dispersant is at least 0.5:1. Relates to a concentrate composition comprising.

[0057] In embodiments, the dispersant mixture in the concentrate compositions disclosed herein (1) 0.01 to 15% by mass (particularly 1 to 12% by mass, alternatively 5% to 11% by mass, alternatively 7.5 to 10.5% by mass, alternatively 8.5 to 10% by mass) based on the total mass of the dispersant mixture of the C 4~5 Olefin-containing amide, imide, and / or ester functionalized or fully saturated polymers as described herein, and (2) 50 to 90% by mass (particularly 55 to 85% by mass, alternatively 62 to 82% by mass, alternatively 68 to 80% by mass, alternatively 70 to 76% by mass) based on the total mass of the dispersant mixture of one or more chloro dispersants, and (3) 10 to 30% by mass (particularly 12 to 25% by mass, alternatively 14 to 22% by mass, alternatively 15 to 20% by mass, alternatively 15.5 to 17.5% by mass) based on the total mass of the dispersant mixture of one or more thermal dispersants is included.

[0058] In embodiments, the concentrate compositions disclosed herein may optionally include one or more antioxidants.

[0059] In embodiments, the concentrate compositions disclosed herein may further include one or more additional additives selected from the group consisting of detergents, friction modifiers, defoamers, corrosion inhibitors / rust preventives, and antiwear agents.

[0060] Also, the present disclosure is a concentrate composition, A) one or more base oils of less than 1 to 50% by weight (alternatively 5 to 45% by weight, alternatively 7 to 40% by weight, alternatively 10 to 35% by weight, alternatively 10 to 25% by weight) based on the weight of the concentrate composition, B) 0.1 to 40% by weight (in particular 0.15 to 20% by weight, alternatively 0.2% by weight to 10% by weight, alternatively 0.25 to 5% by weight, alternatively 0.5 to 4% by weight) of one or more of the amide, imide, and / or ester functionalized partially or fully saturated polymers described herein, based on the weight of the concentrate composition, C) 0.01 to 30% by weight (in particular 0.1 to 20% by weight, alternatively 0.5% by weight to 10% by weight, alternatively 0.5 to 5% by weight) of one or more detergents (e.g., a blend of detergents), based on the weight of the concentrate composition, D) Optionally, 0.001 to 10% by weight (in particular 0.01 to 8% by weight, alternatively 0.05 to 5% by weight, alternatively 0.05 to 0.2% by weight) of one or more friction modifiers (e.g., a blend of friction modifiers), based on the weight of the concentrate composition, E) 0.1 to 50% by weight (in particular 0.1 to 35% by weight, alternatively 0.25 to 25% by weight, alternatively 0.5 to 22% by weight, alternatively 0.05 to 20% by weight, alternatively 14 to 20% by weight) of one or more antioxidants (e.g., a blend of antioxidants), based on the total weight of the concentrate composition, G) Optionally, 0.001 to 8% by weight (in particular 0.001 to 5% by weight, alternatively 0.005 to 2% by weight, alternatively 0.01 to 0.1% by weight) of one or more antifoaming agents (e.g., a blend of antifoaming agents), based on the weight of the concentrate composition, I) One or more poly(alkenyl) succinimide dispersants (e.g., blends of poly(alkenyl) succinimide dispersants) derived from polyalkenyl-substituted succinic anhydrides and polyamines prepared using a chlorine-assisted alkylation process (e.g., "chloro dispersants") and one or more poly(alkenyl) succinimide dispersants (e.g., blends of poly(alkenyl) succinimide dispersants) derived from polyalkenyl succinic anhydrides and polyamines prepared using a halogen-free thermal alkylation process (e.g., "thermal dispersants"), present in an amount based on the mass of the concentrate composition of 0.1 to 70% by mass (especially 0.1 to 50% by mass, alternatively 0.1 to 40% by mass, alternatively 1 to 30% by mass), and the thermal dispersants are present in an amount such that the mass ratio of the chloro dispersants to the thermal dispersants is at least 4:1, especially about 9:2, and J) Optionally, one or more inhibitors and / or rust inhibitors (e.g., blends of inhibitors and / or rust inhibitors) in an amount based on the mass of the concentrate composition of 0.01 to 10% by mass (especially 0.01 to 5% by mass, alternatively 0.05 to 3% by mass, alternatively 0.1 to 0.5% by mass), K) One or more antiwear agents (e.g., blends of antiwear agents, e.g., ZDDP) in an amount based on the mass of the lubricating composition of 0.001 to 20% by mass (especially 0.01 to 10% by mass, alternatively 0.1 to 5% by mass, alternatively 0.5 to 5% by mass, alternatively 1 to 3% by mass), relating to a concentrate composition obtained by including or mixing the same.

[0061] The concentrate composition may be present in the lubricating oil composition in an amount of 0.5% to 35% by mass, e.g., 5% to 30% by mass, e.g., 7.5% to 25% by mass, e.g., 10% to 22.5% by mass, e.g., 15% to 20% by mass, based on the mass of the lubricating oil composition. Optionally, the concentrate composition may be free of functionalized oil. In embodiments, the concentrate composition may optionally be free of a solvent (e.g., an aliphatic or aromatic solvent) and / or free of a functionalized base oil. Optionally, the concentrate composition may not contain a phenate detergent. Optionally, the concentrate composition may not contain a PIBSA ester dispersant.

[0062] Optionally, the concentrate composition may not contain a phenolic antioxidant. Alternatively, the concentrate composition may contain a phenolic antioxidant. Optionally, the concentrate composition may not contain a methyl sulfide ester antioxidant. In embodiments, the concentrate composition may contain less than 1000 ppm of boron, alternatively less than 600 ppm of boron, alternatively 80 - 350 ppm of boron. Alternatively, the concentrate may not contain boron. In embodiments, the concentrate composition may contain less than 40 wt% (e.g., less than 35 wt%, e.g., less than 30 wt%, e.g., less than 26 wt%) of a functionalized (e.g., aminated) polybutene (e.g., polyisobutylene), such as PIBSA - PAM. In embodiments, the lubricating oil composition contains more than 0.1 wt% (e.g., 0.1 - 30 wt%, e.g., 0.5 - 26 wt%) of a functionalized (e.g., aminated) polybutene (e.g., polyisobutylene), such as PIBSA - PAM.

[0063] In embodiments, the concentrate composition contains more than 0.5 wt% (e.g., 0.5 - 25 wt%, e.g., 10 - 25 wt%) of a functionalized (e.g., aminated) polybutene (e.g., polyisobutylene) derived from polyisobutylene - substituted succinic anhydride and polyamine prepared using a chlorine - assisted alkylation process, such as PIBSA - PAM. In embodiments, the concentrate composition contains more than 0.5 wt% (e.g., 0.5 - 25 wt%, e.g., 0.5 - 10 wt%) of a functionalized (e.g., aminated) polybutene (e.g., polyisobutylene) derived from polyisobutylene - substituted succinic anhydride and polyamine prepared using a halogen - free thermal alkylation process, such as PIBSA - PAM. In an embodiment, the concentrate composition comprises a functionalized (e.g., aminated) polybutene (e.g., polyisobutylene) having a high terminal vinylidene content of more than 0.1% by mass (e.g., 0.1 - 10% by mass, e.g., 0.1 - 8% by mass, e.g., 0.5 - 5% by mass), such as HR - PIBSA - PAM.

[0064] In an embodiment, the concentrate composition may optionally contain an acylated polymer, such as polyisobutylene succinic acid (PIBSA), having an Mn of 500 - 50,000 g / mol, e.g., 600 - 5,000 g / mol, e.g., 700 - 3000 g / mol. In an embodiment, the lubricating oil composition may contain an acylated polymer, such as polyisobutylene succinic acid, having an Mn of 500 - 1600 g / mol, e.g., 700 - 1200 g / mol. In an embodiment, the concentrate composition may contain up to 20 (e.g., 15, e.g., 10, e.g., 5, e.g., 3, e.g., 1) % by mass of a block copolymer, such as a block, star, random, and / or tapered block copolymer. In an embodiment, the concentrate composition may not substantially contain a block copolymer, such as a block, star, random, and / or tapered block copolymer, or the concentrate may not contain a block copolymer, such as a block, star, random, and / or tapered block copolymer.

[0065] In an embodiment, the concentrate composition may contain up to 20% by mass (e.g., 15% by mass or less, e.g., 10% by mass or less, e.g., 5% by mass or less, e.g., 3% by mass or less, e.g., 1% by mass or less) of a styrenic copolymer, such as a block, star, random, and / or tapered styrenic block copolymer. In an embodiment, the concentrate composition may not substantially contain a styrenic copolymer, such as a block, star, random, and / or tapered styrenic block copolymer, or the concentrate composition may not contain a styrenic copolymer, such as a block, star, random, and / or tapered styrenic block copolymer. In an embodiment, the concentrate composition may contain less than 20% by mass (e.g., less than 15% by mass, e.g., 10% by mass, e.g., less than 5% by mass, e.g., less than 3% by mass, e.g., 1% by mass) of a functionalized diluent, such as a functionalized oil. In an embodiment, the concentrate composition may not substantially contain a functionalized diluent, such as a functionalized oil, or the concentrate composition may not contain a functionalized diluent, such as a functionalized oil.

[0066] In an embodiment, the concentrate composition may contain less than 0.5% by mass (e.g., less than 0.4% by mass, e.g., less than 0.3% by mass, e.g., less than 0.2% by mass, e.g., 0.1% by mass, substantially absent, or zero mass%) of a secondary hydrocarbylamine compound and a tertiary hydrocarbylamine compound based on the mass of the concentrate composition. In an embodiment, the concentrate composition may not substantially contain a secondary hydrocarbylamine compound and a tertiary hydrocarbylamine compound, or the concentrate composition may not contain a secondary hydrocarbylamine compound and a tertiary hydrocarbylamine compound. In an embodiment, the concentrate composition may have a kinematic viscosity at 100 °C of less than 1000 cSt, e.g., less than 500 cSt, e.g., less than 200 cSt.

[0067] A. Base oil Base oils useful herein (also referred to as "base stocks", "lubricating oil base stocks", or "oils of lubricating viscosity") may be a single oil or a blend of oils and are typically the major liquid component of a lubricating composition, also called a lubricant, into which additives and optionally additional oils are blended to produce, for example, a lubricating composition such as a final lubricant composition, a concentrate, or other lubricating composition. Base oils can be selected from vegetable oils, animal oils, mineral oils, and synthetic lubricating oils, and mixtures thereof. Base oils can vary widely in terms of viscosity, from light distillate mineral oils to heavy lubricating oils such as those for gas engine oils, mineral lubricating oils, motor vehicle oils, and large diesel oils. Generally, the kinematic viscosity of the base oil at 100 °C ("KV100") is determined in accordance with ASTM D445-19a and ranges from 1 to 30, for example 2 to 25 cSt, for example 5 to 20 cSt, particularly in the range of 1.0 cSt to 10 cSt, 1.5 cSt to 3.3 cSt, 2.7 cSt to 8.1 cSt, 3.0 cSt to 7.2 cSt, or 2.5 cSt to 6.5 cSt. Generally, the high temperature high shear viscosity (HTHS) of the base oil at 150 °C is determined in accordance with ASTM D4683-20 and ranges from 0.5 to 20 cP, for example 1 to 10 cP, for example 2 to 5 cP.

[0068] Typically, when making a concentrate using a lubricating oil base stock, the lubricating oil base stock may be present in an amount that advantageously results in a concentrate containing 5 wt% to 80 wt%, 10 wt% to 70 wt%, or 5 wt% to 50 wt% active ingredient, based on the mass of the concentrate. Common oils useful as base oils include animal and vegetable oils (e.g., castor oil and lard oil), liquid petroleum, and paraffinic, naphthenic, and paraffinic-naphthenic mixed type hydrotreated and / or solvent-treated mineral lubricating oils. Oils derived from coal or shale are also useful base oils. Base stocks can be produced using a variety of different methods including, but not limited to, distillation, solvent refining, hydrotreating, oligomerization, esterification, and re-refining.

[0069] Synthetic lubricating oils useful herein as base oils include hydrocarbon oils such as polyalphaolefins or PAO, also known as Group IV base oils, including homopolymers and copolymers of olefins [see API EOLCS 1509 definition (API Publication 1509, Section E.1.3, 19th Edition, January 2021, www.API.org)]. Examples of PAO useful as base oils include poly(ethylene), copolymers of ethylene and propylene, polybutylene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutylene, poly(1-hexene), poly(1-octene), poly(1-decene), C8-C 20 Homopolymers or copolymers of alkenes, C8 and / or C 10 And / or C 12 Homopolymers or copolymers of alkenes, C8 / C 10 Copolymers, C8 / C 10 / C 12 Copolymers, and C 10 / C 12 Copolymers, and derivatives, analogs, and homologs thereof. In another embodiment, the base oil may include a polyalphaolefin containing oligomers of linear olefins having a kinematic viscosity at 100 °C (measured by ASTM D445) of 10 or more, preferably having a viscosity index ("VI") of 100 or more, preferably 110 or more, more preferably 120 or more, more preferably 130 or more, more preferably 140 or more as determined by ASTM D2270, and / or a pour point (measured by ASTM D97) of -5 °C or less, more preferably -10 °C or less, more preferably -20 °C or less, having 6 to 14 carbon atoms, more preferably 8 to 12 carbon atoms, more preferably 10 carbon atoms.

[0070] In another embodiment, the polyalphaolefin oligomers useful in the present disclosure are C 20 ~C 1500 Paraffins, preferably C 40 ~C 1000 Paraffins, preferably C 50 ~C 750Paraffin, preferably C 50 ~C 500 may contain paraffin. The PAO oligomer, in one embodiment, is C5~C 14 alpha-olefin, and in another embodiment is C6~C 12 alpha-olefin, and in another embodiment is C8~C 12 alpha-olefin dimers, trimers, tetramers, pentamers, etc. Suitable olefins include 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene. In one embodiment, the olefin is a combination of 1-octene, 1-decene, and 1-dodecene, or alternatively may be substantially 1-decene, and the PAO is a mixture of these dimers, trimers, tetramers, and pentamers (and higher order species). Useful PAOs are described in more detail, for example, in U.S. Patent Nos. 5,171,908 and 5,783,531, and on pages 1 to 52 of Synthetic Lubricants and High-Performance Functional Fluids (edited by Leslie R. Rudnick & Ronald L. Shubkin, Marcel Dekker, Inc., 1999).

[0071] The PAOs useful in the present disclosure typically have a number average molecular weight of 100 to 21,000 g / mol in one embodiment, 200 to 10,000 g / mol in another embodiment, 200 to 7,000 g / mol in yet another embodiment, 200 to 2,000 g / mol in yet another embodiment, and 200 to 500 g / mol in yet another embodiment. Desirable PAOs are commercially available as SpectraSyn™ Hi-Vis, SpectraSyn™ Low-Vis, SpectraSyn™ plus, SpectraSyn™ Elite PAO (ExxonMobil Chemical Company, Houston, Texas) and Durasyn PAO from Ineos Oligomers USA LLC.

[0072] Synthetic lubricating oils useful as base oils include hydrocarbon oils such as homopolymerized and copolymerized alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2-ethylhexyl)benzene); polyphenols (e.g., biphenyl, terphenyl, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides; as well as derivatives, analogs, and homologs thereof. Another suitable type of synthetic lubricating oil useful as a base oil includes esters of dicarboxylic acids (e.g., 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) reacted with various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of such esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, 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.

[0073] Esters useful as synthetic oils herein include those made from C5 - C 12 monocarboxylic acids and polyols, as well as polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol. Desirable ester base oils are commercially available as Esterex (trademark) esters (ExxonMobil Chemical Company, Houston, Texas).

[0074] Silicon-based oils, such as polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxysilicone oils and silicate oils, constitute another useful type of synthetic lubricant useful herein. Such oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) silicate, tetra-(p-tert-butyl-phenyl) silicate, hexa-(4-methyl-2-ethylhexyl) disiloxane, poly(methyl) siloxane, and poly(methylphenyl)-siloxane. Other synthetic lubricating oils useful herein include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid), and polymeric tetrahydrofuran.

[0075] Unrefined oils, refined oils, and re-refined oils can be used in the lubricating compositions of the present disclosure. Unrefined oils are oils obtained directly from natural or synthetic sources without further refining treatment. For example, shale oil obtained directly from a retorting operation, petroleum obtained directly from distillation, or ester oil obtained directly from an esterification process and used without further treatment is considered an unrefined oil. Refined oils are similar to unrefined oils except that they have been further processed in one or more refining steps to improve one or more properties. Many such refining techniques, such as distillation, solvent extraction, acid or base extraction, filtration, and percolation, are used by those skilled in the art. Re-refined oils are oils obtained by a method similar to the method used to obtain refined oils, to which a refining method is applied to previously used refined oils. Such re-refined oils are also called regenerated oils or reprocessed oils and are often additionally treated to remove spent additives and oil decomposition products. Re-refined base oils preferably contain substantially no substances introduced by manufacture, contamination, or previous use.

[0076] Other examples of useful base oils are gas-to-liquid (GTL) base oils, i.e., base oils that are derived from hydrocarbons produced from synthesis gas (''syngas'') containing H2 and CO using a Fischer-Tropsch catalyst. Such hydrocarbons typically require further processing to make them useful as base oils. For example, such hydrocarbons may be hydroisomerized, hydrocracked and hydroisomerized, dewaxed, or hydroisomerized and dewaxed by methods known in the art. Further information regarding useful GTL base oils and blends thereof can be found in 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). In particular, herein, renewable resources, i.e., oils that are at least partially based on carbon and energy captured from the environment, such as biological resources, are useful.

[0077] Various base oils are often classified into groups I, II, III, IV, or V according to the API EOLCS 1509 definition (American Petroleum Institute Publication 1509, Section E.1.3, 19th Edition, January 2021, www.API.org). Generally speaking, group I base stocks have a viscosity index of about 80 - 120 and contain more than about 0.03% sulfur and / or less than about 90% saturates. Group II base stocks have a viscosity index of about 80 - 120 and contain up to about 0.03% sulfur and at least about 90% saturates. Group III base stocks have a viscosity index higher than about 120 and contain up to about 0.03% sulfur and more than about 90% saturates. Group IV base stocks include polyalphaolefins (PAOs). Group V base stocks include base stocks not included in groups I - IV. (The viscosity index is measured by ASTM D2270, saturates are measured by ASTM D2007, and sulfur is measured by ASTM D2622, ASTM D4294, ASTM D4927, and ASTM D3120).

[0078] The base oils for use in the formulated lubricating compositions useful in the present disclosure are any one, two, three, or more of the various oils described herein. In a desirable embodiment, the base oils for use in the formulated lubricating compositions useful in the present disclosure are oils of API Group I (including Group I+), Group II (including Group II+), Group III (including Group III+), Group IV, and Group V, and mixtures thereof, preferably those described as oils of API Group II, Group III, Group IV, and Group V, and mixtures thereof. The base oils may be Group III, Group III+, IV, and Group V base oils because of their excellent volatility, stability, viscosity, and cleanliness characteristics. Small amounts of Group I base stock, for example, the amount used to dilute additives for blending into formulated lubricating oil products, can be tolerated but are typically minimized, for example, to the amount only relevant to its use as a diluent / carrier oil for the additives used on a "received" basis. With respect to Group II stock, it is often more useful for the Group II base stock to be in a higher quality range in relation to that stock, i.e., a Group II stock having a viscosity index in the range of 100 - 120.

[0079] The base oils useful herein can be selected from either synthetic oils, natural oils, or re-refined oils (such as those typically used as crankcase lubricants for spark-ignition engines and compression-ignition engines). Optionally, mixtures of synthetic base oils and / or natural base oils and / or re-refined base oils may be used. Optionally, multimodal mixtures (e.g., bimodal or trimodal mixtures) of Group I, II, III, IV, and / or V base stocks may be used. The base oil or base oil blend used herein is conveniently about 2 to about 40 cSt, alternatively 3 to 30 cSt, alternatively 4 to 20 cSt at 100 °C, alternatively 5 to 10 cSt kinematic viscosity at 100 °C (KV100, measured in accordance with ASTM D445-19a, in centistokes (cSt) or the equivalent in mm 2(reported in units of / s), or alternatively, 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 from about 2.5 cSt to about 9 cSt.

[0080] The base oil or base oil blend preferably has a saturation content of at least 65% by mass, more preferably at least 75% by mass, such as at least 85% by mass, such as at least 90% by mass, as determined by ASTM D2007. Preferably, the base oil or base oil blend will have a sulfur content of less than 1% by mass, preferably less than 0.6% by mass, most preferably less than 0.4% by mass, such as less than 0.3% by mass, based on the total mass of the lubricating composition, as measured by ASTM D5185.

[0081] In an embodiment, the volatility of the base oil or base oil blend is measured by the Noack test (ASTM D5800, Procedure B) and is 30% by mass or less, such as 25% by mass or less, such as 20% by mass or less, such as 16% by mass or less, such as 12% by mass or less, such as 10% by mass or less, based on the total mass of the lubricating composition. In an embodiment, the viscosity index (VI) of the base oil is at least 95, preferably at least 110, more preferably at least 120, even more preferably at least 125, most preferably from about 130 to 240, particularly from about 105 to 140 (determined by ASTM D2270). The base oil may be provided in large amounts in combination with one or more additive components in small amounts as described hereinafter that make up the lubricant. This preparation can be achieved by adding the additives directly to the oil or by adding one or more additives in the form of these 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, either before, simultaneously with, or after the addition of other additives.

[0082] The base oil may be provided in small amounts in combination with one or more minor additive components as described hereinafter that make up the additive concentrate. This preparation can be accomplished by adding the additive directly to the oil or by adding one or more additives in the form of these solutions, slurries, or suspensions to disperse or dissolve the additive in the oil. The additive can be added to the oil by any method known to those skilled in the art, either before, simultaneously with, or after the addition of other additives. The base oil typically constitutes the major component of the engine oil lubricant composition of the present disclosure and is typically present in an amount in the range of at least about 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.

[0083] Typically, one or more base oils are present in the lubricating composition in an amount of 32% by weight or more, alternatively 55% by weight or more, alternatively 60% by weight or more, alternatively 65% by weight or more, based on the total weight of the lubricating composition. Typically, one or more base oils are present in the lubricating composition in an amount of 98% by weight or less, more preferably 95% by weight or less, even more preferably 90% by weight or less. Alternatively, one or more base oils are present in the lubricating composition in an amount of 1 to 99% by weight, alternatively 50 to 97% by weight, alternatively 60 to 95% by weight, alternatively 70 to 95% by weight, based on the weight of the lubricating composition. The base oils and blends thereof described above are useful for making concentrates as well as for making lubricants therefrom. The concentrate is a convenient means for facilitating the handling of additives prior to use and the dissolution or dispersion of the additives in the lubricant. When preparing a lubricant containing more than one type of additive (sometimes referred to as "additive components"), each additive can be separately incorporated 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 "add pack") that contains one or more additives / cosmetics as described hereinafter in a single concentrate.

[0084] Typically, one or more base oils are present in the concentrate composition in an amount of less than 50% by weight, alternatively 40% by weight or less, alternatively 30% by weight or less, alternatively 20% by weight or less, based on the total weight of the concentrate composition. Typically, one or more base oils are present in the concentrate composition in an amount of 0.1 to 49% by weight, alternatively 5 to 40% by weight, alternatively 10 to 30% by weight, alternatively 15 to 25% by weight, based on the weight of the concentrate composition. In embodiments, the acylation / functionalization reactions described herein may occur in the presence of a base oil diluent. As a byproduct, a functionalized base oil may be produced. The oil itself may be acylated and / or functionalized. After the functionalization reactions described herein, for example, a maleated base oil or an aminated base oil may be present. It is contemplated that the functionalized base oil may include an acylated oil. It is contemplated that the functionalized base oil may include a reaction product of an acylated oil and an amine that forms an amide, imide, or a combination thereof. It is contemplated that the functionalized base oil may include both an acylated oil and a reaction product of an acylated oil and an amine that forms an amide, imide, or a combination thereof.

[0085] In embodiments, the lubricating oil composition and / or additive concentrate may include a functionalized base oil, e.g., an acylated oil, and / or a reaction product of an acylated oil and an amine or alcohol that forms an amide, imide, ester, or a combination thereof, in an amount of 40% by weight or less, alternatively 20% by weight or less, alternatively 10% by weight or less, alternatively 5% by weight or less, based on the total weight of the concentrate composition. Typically, one or more functionalized base oils, e.g., an acylated oil, and / or a reaction product of an acylated oil and an amine or alcohol that forms an amide, imide, ester, or a combination thereof, are present in the concentrate in an amount of 0.01 to 40% by weight, alternatively 0.1 to 20% by weight, alternatively 1 to 10% by weight, alternatively 1.5 to 5% by weight, based on the weight of the concentrate composition.

[0086] Typically, one or more functionalized base oils, such as acylated oils, and / or reaction products of acylated oils with amines or alcohols that form amides, imides, esters, or combinations thereof, are present in the lubricating oil composition in an amount of from 0.01 to 40 wt%, alternatively from 0.1 to 20 wt%, alternatively from 1 to 10 wt%, alternatively from 1.5 to 5 wt%, based on the mass of the lubricating oil composition. In embodiments, the functionalized oil may be present in the lubricating oil composition at 3 wt% or less, preferably 2 wt% or less, preferably 1 wt% or less, preferably 0.1 wt% or less, preferably 0 wt%, based on the mass of the lubricating oil composition. In embodiments, the functionalized oil may be present in the additive concentrate at 3 wt% or less, preferably 2 wt% or less, preferably 1 wt% or less, preferably 0.1 wt% or less, preferably 0 wt%, based on the mass of the concentrate composition. In embodiments, the acylation / functionalization reactions described herein may occur in a solvent-containing medium. As a by-product, a functionalized solvent may be produced. The solvent itself may be acylated and / or functionalized. In embodiments, the acylated and / or functionalized solvent may be present in the concentrate composition at 3 wt% or less, preferably 2 wt% or less, preferably 1 wt% or less, preferably 0.1 wt% or less, preferably 0 wt%, based on the mass of the concentrate composition. In embodiments, the functionalized solvent may be present in the lubricating oil composition at 3 wt% or less, preferably 2 wt% or less, preferably 1 wt% or less, preferably 0.1 wt% or less, preferably 0 wt%, based on the mass of the lubricating oil composition.

[0087] In the lubricating oil composition and additive concentrate of the present invention, the base oil may be composed of only one or more Group II base oils, may be composed of only one or more Group III base oils, or may be composed of only a mixture of one or more Group II base oils and one or more Group III base oils. In certain embodiments, the base oil contained in the lubricating oil composition and additive concentrate of the present invention is only one or more Group III base oils. Alternatively, in certain embodiments, the base oil contained in the lubricating oil composition and additive concentrate of the present invention is a mixture of one or more Group II base oils and one or more Group III base oils. In certain embodiments where the base oil is a mixture of one or more Group II base oils and one or more Group III base oils, the base oil contains at least 20% by mass, for example at least 30% by mass, for example at least 50% by mass of one or more Group II base oils (based on the total mass of the base oil present in the lubricating oil composition). In certain embodiments, the lubricating oil composition of the present invention contains, based on the total mass of the lubricating oil composition, 25 to 65% by mass, for example 30 to 55% by mass, for example 34 to 48% by mass of one or more Group III base oils, and, based on the total mass of the lubricating oil composition, 20 to 60% by mass, for example 28 to 48% by mass, for example 30 to 38% by mass of one or more Group II base oils.

[0088] In certain embodiments, regardless of whether the Group III base oil is used alone or as a mixture with a Group II base oil, it contains at least 25%, for example at least 50%, for example at least 75%, for example at least 80%, up to 100% of a Group III base oil having a viscosity of 6 cSt or less and / or a Group III base oil of 4 cSt or less (based on the total mass of the Group III base oil present in the lubricating oil composition).

[0089] In certain embodiments, the base oils used in the lubricant compositions and additive concentrates of the present invention are a mixture of one or more Group II base oils and one or more Group III base oils, and the one or more Group III base oils and the one or more Group II base oils are present in a ratio of about 70:30 to about 30:70, such as about 65:35 to about 40:60, such as about 60:40 to about 45:55, such as about 55:45 to about 50:50. In the present disclosure, for the sake of clarity, any additive package diluent (used to dilute the active ingredient in the components of the lubricant composition or additive concentrate of the present invention) is not considered to be a "base oil" in the meaning of the separate components described herein.

[0090] B. Functionalized Polymer The present disclosure relates to a functionalized polymer comprising a polymer having an Mn of about 10,000 g / mol or more, such as 20,000 g / mol or more, such as 25,000 g / mol or more, such as 30,000 g / mol or more, such as 35,000 g / mol or more (GPC-PS) prior to functionalization. Alternatively, the functionalized polymer comprises a polymer having an Mn of 10,000 to 300,000 g / mol, such as 20,000 to about 150,000 g / mol, such as 30,000 to about 125,000 g / mol, such as 35,000 to about 100,000 g / mol, such as 40,000 to 80,000 g / mol (GPC-PS) prior to functionalization. The polymer prior to functionalization may have an Mw / Mn of less than 2 (determined by GPC-PS, such as less than 1.6, such as less than 1.5, such as less than 1.4, 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). The polymer prior to functionalization may contain repeat units of one or more olefins having 4 to 5 carbon atoms (preferably, conjugated dienes having 4 to 5 carbon atoms). Prior to functionalization, the polymer (e.g., C 4~5The polymer) is preferably fully or partially saturated (e.g., fully or partially hydrogenated). The functionalized polymer can be obtained by reacting the polymer with an acylating agent to form an acylated polymer and then reacting the acylated polymer with an amine or alcohol to form an amide, imide, ester, or a combination thereof. The functionalized polymer can be obtained by reacting an acylated polymer (e.g., a commercially available maleated fully or partially hydrogenated C 4~5 polymer) with an amine to form an amide, imide, or a combination thereof.

[0091] This disclosure relates to a C having an Mw / Mn of less than 2 4~5 A fully or partially saturated (e.g., fully or partially hydrogenated) polymer of a conjugated diene is reacted with an acylating agent, such as maleic acid or maleic anhydride, and then the acylated polymer is reacted with an amine (e.g., a polyamine) to form an imide, amide, or a combination thereof, the C described herein 4~5 Further relates to amide, imide, and / or ester functionalized saturated (e.g., hydrogenated) polymers of conjugated dienes. This disclosure relates to a C containing one or more pendant amine groups and at least partially (preferably fully) hydrogenated 4~5 An olefin polymer is mixed with an acylating agent, such as maleic acid or maleic anhydride, and then the acylated polymer is reacted with a polyamine to form an imide, amide, or a combination thereof, or a polymer resulting therefrom.

[0092] In embodiments, the functionalized polymer is not prepared in an aromatic solvent (e.g., benzene or toluene), or the aromatic solvent is present at 2 wt% or less (e.g., 1 wt% or less, e.g., 0.5 wt% or less) based on the mass of the solvent, diluent, and polymer. In embodiments, the functionalized polymer is not prepared in an alkylated naphthalene-based solvent, or the alkylated naphthalene-based solvent is present at 5 wt% or less (e.g., 3 wt% or less, e.g., 1 wt% or less) based on the mass of the solvent, diluent, and polymer.

[0093] Polymers useful herein for preparing the functionalized polymer may be homopolymers such as butadiene or isoprene. In embodiments, polymers useful herein for preparing the functionalized polymer may be homopolymers of isoprene or copolymers of isoprene with less than 5 mol% (e.g., less than 3 mol%, e.g., less than 1 mol%, e.g., less than 0.1 mol%) of comonomer. In some embodiments, the polymer backbone prior to functionalization comprises at least 90% isoprene repeat units. In certain embodiments, the functionalized polymer has a homo-polyisoprene or essentially homo-polyisoprene backbone.

[0094] Polymers useful herein for preparing the functionalized polymer may be copolymers of isoprene with one or more of styrene, methyl-styrene, 2,3-dimethyl-butadiene, 2-methyl-1,3-pentadiene, myrcene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, 2-phenyl-1,3-pentadiene, 3-phenyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2-hexyl-1,3-butadiene, 3-methyl-1,3-hexadiene, 2-benzyl-1,3-butadiene, 2-p-tolyl-1,3-butadiene 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2,4-heptadiene, 1,3-octadiene, 2,4-octadiene, 3,5-octadiene, 1,3-nonadiene, 2,4-nonadiene, 3,5-nonadiene, 1,3-decadiene, 2,4-decadiene, and 3,5-decadiene (optionally, the comonomer is present at less than 20 mol%, less than 5 mol%, e.g., less than 3 mol%, e.g., less than 1 mol%, e.g., less than 0.1 mol%).

[0095] Generally, the polymerized conjugated diene polymers useful herein for preparing 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). The polymerized conjugated diene polymers useful herein for preparing functionalized polymers contain, as measured by 1H NMR, at least about 50% 1,4-insertion, for example at least about 75% 1,4-insertion, for example at least about 80% 1,4-insertion, for example at least about 90% 1,4-insertion, for example at least about 95% 1,4-insertion, for example at least 98% 1,4-insertion, based on the sum 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.

[0096] Optionally, the polymer backbone includes repeat units of one or more polar monomers, such as, but not limited to, those selected from the group consisting of fumarate, acrylate, and combinations thereof. Optionally, the polymers useful herein for preparing functionalized polymers may be free of styrene repeat units. Optionally, the functionalized hydrogenated / saturated polymers may be free of styrene repeat units.

[0097] Optionally, the polymers useful herein for preparing functionalized polymers may be free of butadiene repeat units. Optionally, the functionalized hydrogenated / saturated polymers may be free of butadiene repeat units. Optionally, the polymers useful herein for preparing functionalized polymers may not be homopolybutylene. Optionally, the functionalized hydrogenated / saturated polymers may not be homopolybutylene. Optionally, the polymers useful herein for preparing functionalized polymers may not be homopolyisobutylene. Optionally, the functionalized hydrogenated / saturated polymers may not be homopolyisobutylene. 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.

[0098] The polymers and / or functionalized polymers useful herein for preparing functionalized polymers may be homopolymers or copolymers. The copolymers may be random copolymers, tapered block copolymers, star copolymers, or block copolymers. The block copolymer is formed from a monomer mixture comprising one or more first monomers (e.g., isobutylene), and for example, the first monomer forms an individual block of the polymer joined to a second individual block of the polymer formed from a second monomer (e.g., butadiene). The block copolymer has substantially distinct blocks formed from monomers, while the tapered block copolymer may be composed of a relatively pure first monomer at one end and a relatively pure second monomer at the other end. The middle portion of the tapered block copolymer may have an increasing gradient composition of the two monomers.

[0099] The polymers useful herein for preparing functionalized polymers typically have an Mn (i.e., before functionalization) of 10,000 - 150,000 g / mol, alternatively about 10,000 - about 100,000 g / mol, or 20,000 - about 150,000 g / mol, alternatively 30,000 - about 125,000 g / mol, such as about 30,000 - about 50,000 g / mol, such as about 30,000 - about 40,000 g / mol, alternatively 35,000 - about 100,000 g / mol, alternatively 40,000 - 80,000 g / mol (GPC-PS). Alternatively, the polymer before functionalization may have an Mn of at least 25,000 g / mol, such as at least 30,000 g / mol (GPC-PS).

[0100] Polymers useful herein for preparing functionalized polymers may typically have an Mw / Mn (determined by GPC-PS) of 1 to 2, alternatively greater than 1 and less than 2, alternatively 1.1 to 1.8, alternatively 1.2 to 1.5. Alternatively, polymers useful herein for preparing functionalized polymers may typically have an Mw / Mn of 1 or greater than 1 and less than 2 (e.g., less than 1.8, e.g., less than 1.7, e.g., less than 1.6, e.g., less than 1.5, e.g., less than 1.4, e.g., less than 1.3, e.g., 1.25 or less, e.g., less than 1.2, e.g., less than 1.15, e.g., less than 1.12, e.g., less than 1.10).

[0101] Polymers used to prepare functionalized polymers may have an Mz (determined by GPC-PS) of 20,000 to 150,000 g / mol, alternatively 30,000 to about 125,000 g / mol, alternatively 35,000 to about 100,000 g / mol, alternatively 40,000 to 80,000 g / mol, e.g., about 50,000 to about 60,000 g / mol, alternatively 40,000 to 60,000 g / mol (GPC-PS). Polymers useful herein for preparing functionalized polymers may have a glass transition temperature (Tg) of -25°C or less, e.g., -40°C or less, e.g., -50°C or less, 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, holding at 210°C for 5 minutes, then cooling to -40°C at 10°C / min and holding for 5 minutes).

[0102] Polymers useful herein for preparing functionalized polymers typically have less than 3%, e.g., less than 2%, e.g., less than 1%, e.g., less than 0.5%, e.g., less than 0.25% residual unsaturation, based on the number of double bonds in the non-hydrogenated polymer. Polymers useful herein for preparing functionalized polymers typically have a residual metal (e.g., Li, Co, and Al) content of less than 100 ppm, such as less than 50 ppm, such as less than 25 ppm, such as less than 10 ppm, such as less than 5 ppm.

[0103] Hydrogenation C useful herein for preparing functionalized polymers 4~5 The polymers can be partially or fully hydrogenated with any hydrogenating agent known to those skilled in the art. For example, saturated or partially saturated polymers can be prepared by: (a) hydrogenating a C 1 -C 2 -C ... 4~5 The method can be prepared by (b) providing a polymer, and (b) hydrogenating at least some or all of the unsaturation (e.g., double or triple bonds) of the polymer in the presence of a hydrogenation reagent. In some embodiments, the polymer is fully hydrogenated. In some embodiments, the polymer is partially hydrogenated. In some embodiments, the polymer is 50% or more saturated (hydrogenated), such as 60% or more, such as 70% or more, such as 80% or more, such as 90% or more, such as 95% or more, such as 98% or more, such as 99% or more, such as 50-100% saturated (hydrogenated), as determined by the ozone adsorption method described in Martino N. Smits and Dirkman Hoefman, Quantitative Determination of Olefinic Unsaturation by Measurement of Ozone Absorption Analytical Chemistry, Vol. 44, No. 9, p. 1688, 1972, Martino N. Smits.

[0104] In an embodiment, the hydrogenation reagent may be hydrogen in the presence of a hydrogenation catalyst. In some embodiments, the hydrogenation catalyst is Pd, Pd / C, Pt, PtO2, Ru(PPh3)2Cl2, Raney nickel, or a combination thereof. In an embodiment, the catalyst is a Pd catalyst. In another embodiment, the catalyst is 5% Pd / C. In a further embodiment, the catalyst may contain 10% Pd / C or be 10% Pd / C in a high-pressure reaction vessel, and the hydrogenation reaction can proceed until completion. Generally, after completion, the reaction mixture can be washed, concentrated, and dried to obtain the corresponding hydrogenated product. Alternatively, any reducing agent capable of reducing a C=C double bond to a C-C single bond can also be used. For example, an olefin polymer can be hydrogenated by hydrazine treatment in the presence of a catalyst under an oxygen atmosphere, such as 5-ethyl-3-methylrhodanine perchlorate, to obtain the corresponding hydrogenated product. The reduction reaction with hydrazine is disclosed in Imada et al., J Am. Chem. Soc., Vol. 127, pp. 14544-14545 (2005). This document is incorporated herein by reference.

[0105] Acylation A fully or partially saturated (hydrogenated) polymer can be chemically modified (functionalized) to provide a polymer having at least one polar functional group, such as, but not limited to, halogen, epoxy, hydroxy, amino, nitrilo, mercapto, imide, carboxy, and sulfonic acid groups, or a combination thereof. The functionalized polymer can be further modified to impart a more desirable type of functionality. Preferably, the fully or partially hydrogenated polymer is functionalized by a method that includes reacting the fully or partially hydrogenated polymer with an unsaturated carboxylic acid (or a derivative thereof, such as maleic anhydride) to provide an acylated polymer (which can then be further functionalized as described below).

[0106] In some embodiments, a carboxylic acid functionality or a reactive equivalent thereof is grafted onto the polymer to form an acylated polymer. Typically, an ethylenically unsaturated carboxylic acid substance is grafted onto the polymer backbone. Such substances attached to the polymer typically contain at least one ethylene bond (before reaction) and at least one, for example two, carboxylic acid (or its anhydride) groups, or a polar group convertible to said carboxyl group by oxidation or hydrolysis. Maleic anhydride or its derivatives are suitable. Grafting such substances onto the polymer imparts two carboxylic acid functionalities. Examples of additional unsaturated carboxylic acid substances include itaconic anhydride, or the corresponding dicarboxylic acids, such as maleic acid, fumaric acid, and their esters, as well as cinnamic acid and its esters. In certain embodiments, the acylating agent is maleic anhydride.

[0107] The ethylenically unsaturated carboxylic acid substance can be grafted onto the polymer in a number of ways. The ethylenically unsaturated carboxylic acid substance can be grafted onto the polymer in solution or in an essentially pure (molten) form, with or without using a radical initiator. Free radical induced grafting of the ethylenically unsaturated carboxylic acid substance can also be carried out in a solvent, such as hexane or mineral oil. Free radical induced grafting of the ethylenically unsaturated carboxylic acid substance can be carried out at elevated temperatures in the range of 100 °C to 250 °C, for example 120 °C to 190 °C or 150 °C to 180 °C, such as above 160 °C.

[0108] Free radical initiators that can be used include peroxides, hydroperoxides, and azo compounds, typically those having a boiling point higher than about 100° C. and thermally decomposing within the grafting temperature range to provide free radicals. Representative examples of such free radical initiators include azobisisobutyronitrile and 2,5-dimethyl-hexa-3-yne-2,5-bis-tert-butylperoxide. The initiator can be used in an amount of 0.005% to 1% by weight based on the weight of the reaction mixture solution. The grafting may be carried out in an inert atmosphere, for example, under a nitrogen blanket. The resulting acylated polymer intermediate is characterized by having carboxylic acid acylation functional groups as part of its structure.

[0109] In embodiments, the acylated polymer may have two or more anhydride groups per polymer molecule and less than 10% may be in the form of a gel. Alternatively, the acylated polymer may have less than two anhydride groups per polymer molecule and less than 10% may be in the form of a gel. (See also column 17, line 14 to column 18, line 11 of U.S. Patent No. 5,429,758).

[0110] Alternatively, in some embodiments, the acylated polymer may have a gel content of less than about 5%, less than 3%, less than 2%, less than 1%, less than 0.5%, less than 0.1%, or 0% by weight, and the gel content is measured by determining the amount of material extractable from the polymer using boiling xylene (or cyclohexane) as the extractant. The percentages of soluble and insoluble (gel) materials in the polymer composition are determined by immersing a polymer film specimen having a nominal thickness of 0.5 mm in cyclohexane at 23° C. for 48 hours or refluxing the film specimen in boiling xylene for 30 minutes, removing the solvent, weighing the dry residue, and calculating the amounts of soluble and insoluble (gel) materials. This method is outlined in U.S. Patent No. 4,311,628, which is incorporated herein by reference. For the purposes of the present disclosure, the gel content is measured using boiling xylene, and if the sample does not dissolve in xylene, the cyclohexane method is used.

[0111] In an embodiment, the saponification value (SAP) of the acylated polymer may be 5 g / KOH or more, for example 10 g / KOH or more, for example 20 g / KOH or more, for example 30 g / KOH, for example 50 g / KOH or more, for example 10 to 60 g / KOH, for example 20 to 40 g / KOH, as determined by ASTM D94.

[0112] In an embodiment, the acylated polymer composition may have less than 5% by mass, for example less than 4% by mass, for example less than 3% by mass, for example less than 1% by mass, for example less than 0.5% by mass, for example less than 0.25% by mass, for example less than 0.1% by mass of unreacted acylating agent (e.g., maleic anhydride), based on the mass of the acylated polymer composition (i.e., polymer, acylating agent, and diluent).

[0113] In an embodiment, the acylation reaction described herein may occur in a base oil diluent. As a by-product, a functionalized base oil may be produced. The oil itself may be acylated. After the acylation reaction described herein, for example, maleated base oil may be present. It is contemplated that the functionalized base oil may include an acylated oil and / or a reaction product of an acylated oil and an amine that forms an amide, imide, or a combination thereof. Preferably, the acylated oil and / or the reaction product of an acylated oil and an amine or alcohol that forms an amide, imide, ester, or a combination thereof may be present in the concentrate composition in an amount of 40% by mass or less, alternatively 20% by mass or less, alternatively 10% by mass or less, alternatively 5% by mass or less, alternatively 3% by mass or less, preferably 2% by mass or less, preferably 1% by mass or less, preferably 0.1% by mass or less, preferably 0% by mass (e.g., 0 to 40% by mass, alternatively 0.01 to 40% by mass, alternatively 0.1 to 20% by mass, alternatively 1 to 10% by mass, alternatively 1.5 to 5% by mass), based on the mass of the concentrate composition.

[0114] Preferably, one or more functionalized base oils, such as acylated oils, and / or reaction products of acylated oils with amines or alcohols that form amides, imides, esters, or combinations thereof, may be present in the lubricating oil composition in an amount of 0.01 to 40% by weight, alternatively 0.1 to 20% by weight, alternatively 1 to 10% by weight, alternatively 1.5 to 5% by weight (e.g., 3% by weight or less, preferably 2% by weight or less, preferably 1% by weight or less, preferably 0.1% by weight or less, preferably 0% by weight) based on the mass of the lubricating oil composition.

[0115] In embodiments, the acylation reactions described herein occur in a solvent-containing medium. As a by-product, an acylated / functionalized solvent may be formed. In embodiments, the acylated and / or functionalized solvent may be present in the concentrate composition in an amount of 3% by weight or less, preferably 2% by weight or less, preferably 1% by weight or less, preferably 0.1% by weight or less, preferably 0% by weight based on the mass of the concentrate composition. In embodiments, the functionalized solvent may be present in the lubricating oil composition in an amount of 3% by weight or less, preferably 2% by weight or less, preferably 1% by weight or less, preferably 0.1% by weight or less, preferably 0% by weight based on the mass of the lubricating oil composition. In embodiments, the acylating agent can be added to minimize side reactions (e.g., reactions with the base oil or other diluents present in the reaction vessel).

[0116] In an embodiment, the acylation reaction can be caused by adding an acylating agent (e.g., maleic acid or maleic anhydride) in a continuous or semi - continuous (e.g., intermittent) flow (e.g., controlled to be in relatively equal amounts over the reaction time or in larger and / or smaller amounts at various points in the reaction) to minimize functionalized base oil and other side reactions. As an example, the acylating agent can be added in a continuous manner where the amounts of the polymer and the acylating agent are added in a controlled stoichiometric amount. As another example, the polymer can be added to the reaction vessel in a batch manner and the acylating agent can be added slowly or in a semi - continuous manner (e.g., the acylating agent is added in separate amounts or portions more than 2 times, e.g., more than 5 times, e.g., more than 10 times, e.g., more than 20 times, e.g., more than 30 times, e.g., more than 40 times, e.g., more than 50 times, e.g., more than 60 times). Alternatively, the polymer can be added to the reaction vessel in X portions and the acylating agent can be added in more than 1.5X portions (e.g., more than 2X portions, e.g., more than 5X portions, e.g., more than 10X portions, e.g., more than 20X portions, e.g., more than 30X portions, e.g., more than 40X portions, e.g., more than 50X portions, e.g., more than 60X portions). The same effect can also be achieved by diluting or concentrating the polymer solution and / or the acylating agent solution to the same or different extents.

[0117] Preferably, the acylating agent may be added, for example, in a continuous or semi - continuous manner so as to minimize side reactions. The reaction can also be carried out to minimize side reactions by using a high concentration of polymer in a diluent, such as 45% by mass or more, or 50% by mass or more, or 55% by mass or more, or 60% by mass, in batch, semi - continuous, or continuous reactor operation. For example, a polymer (such as a hydrogenated isoprene polymer, such as hydrogenated homo - polyisoprene) can be introduced into a batch, semi - continuous, or continuous reactor operation as a solution or suspension (such as a slurry) in a diluent (such as an oil (such as a base oil, such as Group I, II, III, IV, and / or V base oil, such as Group II and / or Group III base oil) or an alkane solvent or diluent, or a combination thereof), and the polymer may be present in the solution or suspension at 45% by mass or more (or 50% by mass or more, or 55% by mass or more, or 60% by mass or more) based on the mass of the polymer and the diluent.

[0118] In embodiments, side reactions can be minimized by 1) adding the acylating agent in a continuous or semi - continuous manner and / or 2) introducing the polymer as a solution or suspension in a diluent in which the polymer is present at 45% by mass or more based on the mass of the polymer and the diluent, in batch, semi - continuous, or continuous reactor operation. In embodiments, optionally, by adding the acylating agent in a continuous or semi - continuous manner and / or introducing a fully or partially hydrogenated polymer (such as an isoprene polymer) as a solution or suspension in a diluent containing 45% by mass or more (or 50% by mass or more, or 55% by mass or more, or 60% by mass or more) of the fully or partially hydrogenated polymer based on the mass of the fully or partially hydrogenated polymer and the diluent, in batch, semi - continuous, or continuous reactor operation, side reactions are minimized.

[0119] In an embodiment, optionally, by adding the acylating agent in a continuous or semi - continuous manner and introducing a fully or partially hydrogenated polymer (such as an isoprene polymer), as a solution or suspension in a diluent containing 45% by mass or more (or 50% by mass or more, or 55% by mass or more, or 60% by mass or more) of the fully or partially hydrogenated polymer based on the mass of the fully or partially hydrogenated polymer and the diluent, into a batch, semi - continuous, or continuous reactor operation, side reactions are minimized.

[0120] Functionalization In an embodiment, the acylated polymer can be reacted with an alcohol or an amine to form an amide, imide, ester, or a combination thereof. This reaction may consist of a condensation to form an imide, amide, semi - amide, amide - ester, diester, or amine salt. Typically, a primary amino group will condense to form an amide or, in the case of maleic anhydride, an imide will be formed. It should be noted that the amine may have a single primary amino group or multiple primary amino groups.

[0121] Suitable amines can include one or more aromatic amines, for example, amines in which a carbon atom of the aromatic ring structure is directly attached to the amino nitrogen. Also, the amine may be aliphatic. The amine may be a monoamine or a polyamine. In an embodiment, the aliphatic amines can be used alone, in combination with each other, or in combination with aromatic amines. The amount of the aromatic amine may be large, small, or in some embodiments, the composition may not substantially contain an aromatic amine compared to the amount of the non - aromatic amine. Alternatively, the composition may not substantially contain an aliphatic amine.

[0122] Examples of aromatic amines that can be used herein include the following formula:

Chemical formula

[0123] Suitable N-aryl phenylenediamines include N-phenyl phenylenediamine (NPPDA), for example, N-phenyl-4,4-phenylenediamine, N-phenyl-1,3-phenylenediamine, and N-phenyl-1,2-phenylenediamine, and N-naphthyl-1,4-phenylenediamine. Other derivatives of NPPDA, such as N-propyl-N'-phenyl phenylenediamine, may also be included.

[0124] In an embodiment, the amine reacted with the acylated polymer is an amine having at least 3 or 4 aromatic groups, of the following formula:

Chemical formula

[0125] Other examples of aromatic amines include the following: aniline, N-alkyl aniline such as N-methyl aniline and N-butyl aniline, di-(para-methylphenyl)amine, naphthylamine, 4-aminodiphenylamine, N,N-dimethylphenylenediamine, 4-(4-nitro-phenylazo)aniline (Disperse Orange 3), sulfamethazine, 4-phenoxyaniline, 3-nitroaniline, 4-aminoacetanilide, 4-amino-2-hydroxy-benzoic acid phenyl ester (phenylaminosalicylate), N-(4-amino-5-methoxy-2-methyl-phenyl)-benzamide (Fast Violet B), N-(4-amino-2,5-dimethoxy-phenyl)-benzamide (Fast Blue RR), N-(4-amino-2,5-diethoxy-phenyl)-benzamide (Fast Blue BB), N-(4-amino-phenyl)-benzamide, and 4-phenylazoaniline. Suitable amines are referred to in U.S. Patent No. 7,790,661, which is incorporated herein by reference.

[0126] In an embodiment, the compound to be condensed with the acylated polymer can be represented by the following formula.

Chemical formula

Chemical formula

[0127] Alternatively, the amine may be an amine having at least 4 aromatic groups and an aldehyde (e.g., formaldehyde). The aromatic amine has the following formula:

Chemical formula

[0064] to

[0070] , and European Patent No. 2 401 348.

[0128] It can be condensed with an acylating agent. Examples of compounds further having a tertiary amino group include, but are not limited to, the following: dimethylaminopropylamine, N,N-dimethyl-aminopropylamine, N,N-diethyl-aminopropylamine, N,N-dimethyl-aminoethylamine, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, isomeric butylenediamine, pentanediamine, hexanediamine, heptanediamine, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, triethylenetetraamine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenetetramine, and bis(hexamethylene)triamine, diaminobenzene, diaminopyridine, or mixtures thereof. Examples of compounds that can be condensed with an acylating agent and further have a tertiary amino group include aminoalkyl-substituted heterocyclic compounds, such as 1-(3-aminopropyl)imidazole and 4-(3-aminopropyl)morpholine, 1-(2-aminoethyl)piperidine, 3,3-di-amino-N-methyldipropylamine, 3’,3-aminobis(N,N-dimethylpropylamine). Another example of a compound that can be condensed with an acylating agent and has a tertiary amino group includes, but is not limited to, alkanolamines such as triethanolamine, trimethanolamine, N,N-dimethylaminopropanol, N,N-di-ethylaminopropanol, N,N-diethylaminobutanol, N,N,N-tris(hydroxyethyl)amine, N,N,N-tris(hydroxymethyl)amine.

[0129] In an embodiment, the polymer may be reacted with a polyether aromatic compound. Typically, the polyether aromatic compound will have at least two functional groups each capable of reacting with a monocarboxylic acid or its ester, or a dicarboxylic acid, its anhydride or ester, or a mixture thereof. In an embodiment, the polyether aromatic compound is derived from an aromatic compound containing at least one amine group, and the polyether is capable of reacting with a monocarboxylic acid or its ester, or a dicarboxylic acid, its anhydride or ester.

[0130] Examples of suitable polyether aromatic amines include the following structures:

Chemical formula

[0131] The acylated polymer may be reacted with a polyetheramine or a polyether polyamine. Typical polyetheramine compounds contain at least one ether unit and are chain-terminated with at least one amine moiety. The polyether polyamine may be based on a polymer derived from C2 - C6 epoxides, such as ethylene oxide, propylene oxide, and butylene oxide. Examples of polyether polyamines are sold under the Jeffamine (trademark) brand and are commercially available from Huntsman Corporation.

[0132] Amines useful herein for combination with acyl polymers include one or more of the following: N - phenyldiamines (e.g., N - phenyl - 1,4 - phenylenediamine, N - phenyl - p - phenylenediamine (also known as 4 - aminodiphenylamine, ADPA), N - phenyl - 1,3 - phenylenediamine, N - phenyl - 1,2 - phenylenediamine), nitroanilines (e.g., 3 - nitroaniline), N - phenylethane - diamines (e.g., N1 - phenylethane - 1,2 - diamine), N - aminophenylacetamides (e.g., N - (4 - aminophenyl)acetamide), morpholinopropanamines (e.g., 3 - morpholinopropan - 1 - amine), and aminoethylpiperazines (e.g., 1 - (2 - aminoethyl)piperazine). In certain embodiments of the invention, the amine is 4 - aminodiphenylamine, ADPA.

[0133] In embodiments, the functionalization (e.g., amination) reactions described herein may occur in a diluent (e.g., base oil or alkane solvent). As a by - product, a functionalized diluent (e.g., functionalized base oil) may be produced. It is contemplated that the functionalized diluent (e.g., functionalized base oil) may include the reaction product of an acylating diluent (e.g., acylating base oil) and an amine that forms an amide, imide, or a combination thereof. Preferably, the reaction product of an acylating diluent (e.g., acylating oil) and an amine or alcohol that forms an amide, imide, ester, or a combination thereof may be present in the concentrate in an amount of 40 wt% or less, alternatively 20 wt% or less, alternatively 10 wt% or less, alternatively 5 wt% or less, alternatively 3 wt% or less, preferably 2 wt% or less, preferably 1 wt% or less, preferably 0.1 wt% or less, preferably 0 wt% (e.g., 0 - 40 wt%, alternatively 0.01 - 40 wt%, alternatively 0.1 - 20 wt%, alternatively 1 - 10 wt%, alternatively 1.5 - 5 wt%) based on the mass of the concentrate composition.

[0134] Preferably, the reaction product of an acylating diluent (such as an acylated base oil) and an amine or an alcohol that forms one or more functionalized base oils, such as amides, imides, esters, or combinations thereof, may be present in the lubricating oil composition in an amount of 0.01 to 40% by weight, alternatively 0.1 to 20% by weight, alternatively 1 to 10% by weight, alternatively 1.5 to 5% by weight (such as 3% by weight or less, preferably 2% by weight or less, preferably 1% by weight or less, preferably 0.1% by weight or less, preferably 0% by weight), based on the weight of the lubricating oil composition.

[0135] In embodiments, the functionalization (such as amination) reaction described herein may occur in a solvent-containing medium. As a byproduct, a functionalized solvent may be produced. In embodiments, the functionalized solvent may be present in the concentrate composition in an amount of 3% by weight or less, preferably 2% by weight or less, preferably 1% by weight or less, preferably 0.1% by weight or less, preferably 0% by weight, based on the weight of the concentrate composition. In embodiments, the functionalized solvent may be present in the lubricating oil composition in an amount of 3% by weight or less, preferably 2% by weight or less, preferably 1% by weight or less, preferably 0.1% by weight or less, preferably 0% by weight, based on the weight of the lubricating oil composition. In embodiments, the acylated base oil / solvent may be removed prior to functionalization.

[0136] Conjugated diene functionalized polymer The functionalized polymer may be a homopolymer of a C4 or C5 olefin, such as butadiene, or a homopolymer of isoprene. In embodiments, the functionalized polymer may be a homopolymer of isoprene, or a copolymer of isoprene and a comonomer in an amount less than 5 mol% (such as less than 3 mol%, such as less than 1 mol%, such as less than 0.1 mol%).

[0137] The functionalized polymer may or may not include a copolymer with isoprene and one or more of styrene, methyl-styrene, 2,3-dimethyl-butadiene, 2-methyl-1,3-pentadiene, myrcene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, 2-phenyl-1,3-pentadiene, 3-phenyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2-hexyl-1,3-butadiene, 3-methyl-1,3-hexadiene, 2-benzyl-1,3-butadiene, 2-p-tolyl-1,3-butadiene, 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2,4-heptadiene, 1,3-octadiene, 2,4-octadiene, 3,5-octadiene, 1,3-nonadiene, 2,4-nonadiene, 3,5-nonadiene, 1,3-decadiene, 2,4-decadiene, and 3,5-decadiene (optionally, the comonomer is present at less than 20 mol%, less than 5 mol%, such as less than 3 mol%, such as less than 1 mol%, such as less than 0.1 mol%).

[0138] In embodiments, the functionalized polymer includes styrene monomer at 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) mass% or less based on the mass of the functionalized polymer. In embodiments, the functionalized polymer may not have styrene repeat units. In embodiments, the functionalized polymer may be a block or tapered block copolymer that does not include a styrene block. In embodiments, the functionalized polymer may be a block or tapered block copolymer that includes (or consists of or consists essentially of) isoprene. In embodiments, the functionalized polymer may be a block or tapered block copolymer that includes 50 mass% or more of isoprene based on the mass of the copolymer. In embodiments, the functionalized polymer is C 4~5A (or consisting of or consisting essentially of) conjugated diene, preferably at least 50 (e.g., 60, e.g., 70, e.g., 80, e.g., 90, e.g., 95, e.g., 98) mass % of C based on the mass of the copolymer 4~5 It may be a block or tapered block copolymer containing a conjugated diene. In an embodiment, the functionalized polymer may be a copolymer containing at least 50 (e.g., 60, e.g., 70, e.g., 80, e.g., 90, e.g., 95, e.g., 98) mass % of isoprene based on the mass of the copolymer. In an embodiment, the functionalized polymer may be a copolymer containing at least 50 (e.g., 60, e.g., 70, e.g., 80, e.g., 90, e.g., 95, e.g., 98) mass % of butadiene based on the mass of the copolymer.

[0139] In an embodiment, the functionalized polymer may be a copolymer containing at least 50 (e.g., 60, e.g., 70, e.g., 80, e.g., 90, e.g., 95, e.g., 98) mass % of butadiene and isoprene based on the mass of the copolymer. In an embodiment, the functionalized polymer may be a diblock copolymer containing at least one block of an isoprene homopolymer or copolymer. Optionally, the functionalized polymer may not have butadiene repeat units. Optionally, the functionalized polymer may not be homopolyisobutylene. Optionally, the functionalized polymer may not be a copolymer of isoprene and butadiene. Generally, the polymerized conjugated diene in the functionalized polymer includes monomer units inserted into the growing polymer chain by conjugate addition and non-conjugate addition. In an embodiment, the functionalized polymer is 13 As measured by C NMR, based on the total number of conjugate addition and non-conjugate insertions, it includes at least about 50% conjugate addition insertions, e.g., at least about 75% conjugate addition insertions, e.g., about 80% conjugate addition insertions, e.g., about 85% - about 100% conjugate addition insertions.

[0140] Isoprene insertion most often occurs by 2,1 insertion, 1,4 insertion (trans and cis), and 3,4 insertion of isoprene. (Measurement of the insertion geometry is 1 determined by 1H NMR.) Functionalized isoprene polymers have, 1 as measured by 1H NMR, 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 sum 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.

[0141] The functionalized polymer may be a homopolymer or a copolymer. Optionally, the functionalized polymer includes a homopolymer or copolymer of isoprene. The copolymer may be a random copolymer, a tapered block copolymer, a star copolymer, or a block copolymer. The functionalized polymer may typically have an Mn of 20,000 - 150,000 g / mol, alternatively 20,000 - about 150,000 g / mol, alternatively 30,000 - about 125,000 g / mol, alternatively 35,000 - about 100,000 g / mol, alternatively 40,000 - 80,000 g / mol (GPC-PS). The polymer before functionalization may typically have an Mn / Mw (GPC-PS) of 1.0 - 2, such as 1.1 - 1.5, such as 1.1 - 1.3, such as 1.1 - 1.2. As functionalization occurs, there may be Mw / Mn broadening.

[0142] The functionalized polymer may typically have an Mw / Mn (GPC-PS) of 1 to 3, alternatively 1 to 2, alternatively greater than 1 and less than 2, alternatively 1.05 to 1.9, alternatively 1.10 to 1.8, alternatively 1.10 to 1.7, alternatively 1.12 to 1.6, alternatively 1.13 to 1.5, alternatively 1.15 to 1.4, alternatively 1.15 to 1.3. Alternatively, the functionalized polymer may typically have an Mw / Mn greater than 1 or greater than 1 and less than 2 (e.g., less than 1.8, e.g., less than 1.7, e.g., less than 1.6, e.g., less than 1.4, e.g., less than 1.2, e.g., less than 1.15, e.g., less than 1.12, e.g., less than 1.10).

[0143] In an embodiment, the functionalized polymer may have a saponification value (SAP) of 25 (e.g., 28, e.g., 30, e.g., 32, e.g., 34) mg KOH / g or more as determined by ASTM D94. In an embodiment, the functionalized polymer can contribute 17% or more (e.g., 20% or more, e.g., 17 - 40%, e.g., 20 - 30%) to the saponification value of the lubricating oil composition. In an embodiment, the functionalized polymer may have an average functionality of 1.4 to 20 FG grafts / polymer chain, e.g., 1.4 to 15 FG grafts / polymer chain, e.g., 3 to 12.5 FG grafts / polymer chain, e.g., 4 to 10 FG grafts / polymer chain, e.g., 7, 8, or 9 FG grafts / polymer chain as determined by GPC-PS.

[0144] The functionalized polymer may have an average functionality of 15 (e.g., 14, 13, 12, 11, 10, 9, 8, 7, or 6) FG grafts / polymer chain or less as determined by GPC-PS.

[0145] The functionalized polymer may have an average functionality of 1 (e.g., 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, or 4.0) FG grafts / polymer chain or more as determined by GPC-PS. The functionalized polymer may have an average functionality of 1 (e.g., 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, or 4.0) to 15 (e.g., 14, 13, 12, 11, 10, 9, 8, 7, or 6) FG grafts / polymer chain as determined by GPC-PS.

[0146] In embodiments, the functionalized polymer may have an aromatic content of 5% or less, e.g., 3% or less, e.g., 1% or less, e.g., 0% based on the mass of the polymer. In embodiments, the functionalized polymer has a Mn of 20,000 to 500,000 g / mol as determined by GPC-PS and an Mw / Mn of 2 or less, e.g., 1 to 2.0, and is a branched-chain C 4~5 It may contain an acylated polymer of the monomer. In embodiments, the functionalized polymer may have a number average molecular weight (Mn) of 15,000 (e.g., 20,000, e.g., 25,000, e.g., 30,000, e.g., 35,000, e.g., 40,000) g / mol or more 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).

[0147] In embodiments, the functionalized polymer may have a weight average molecular weight (Mw) of 50,000 (e.g., 40,000, e.g., 35,000) g / mol or less as determined by GPC-PS. In embodiments, the functionalized polymer may have a weight average molecular weight (Mw) of 1000 to 50,000 g / mol, e.g., 5000 to 40,000 g / mol as determined by GPC-PS. In an embodiment, 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, alternatively 20,000 to about 150,000 g / mol, alternatively 30,000 to about 125,000 g / mol, alternatively 35,000 to about 100,000 g / mol, alternatively 40,000 to 80,000 g / mol, alternatively 40,000 to 60,000 g / mol (GPC-PS).

[0148] In an embodiment, the functionalized polymer may have a gel content of less than about 5 wt%, less than 3 wt%, less than 2 wt%, less than 1 wt%, less than 0.5 wt%, less than 0.1 wt%, or 0 wt%, and the gel content is measured by determining the amount of material extractable from the polymer using boiling xylene (or cyclohexane) as an extractant. The percentages of soluble and insoluble (gel) materials in the polymer composition are determined as described herein. In an embodiment, the functionalized polymer has a functionality distribution (Fd) value of 3.5 or less (determined by GPC-PS, 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), 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 (the functionality distribution (Fd) value is determined as shown in the following Examples section).

[0149] This disclosure relates to C having an Mw / Mn of less than 2 and a functionality distribution (Fd) value of 3.5 or less (determined by GPC-PS, 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). 4~5An amide, imide, and / or ester functionalized hydrogenated / saturated polymer containing (or consisting essentially of or consisting of) an olefin, wherein the polymer before functionalization is a C4 olefin polymer such as polyisobutylene, polybutadiene, or a copolymer thereof (preferably polyisobutylene or a copolymer of isobutylene and butadiene), the C4 olefin polymer has an Mn of 10,000 g / mol or more (GPC-PS), and when the polymer before functionalization is a C4 / C5 copolymer of isoprene and butadiene, the Mn of the copolymer is greater than 25,000 Mn (GPC-PS), relating to an amide, imide, and / or ester functionalized hydrogenated / saturated polymer.

[0150] The present disclosure also relates to an amide, imide, and / or ester functionalized hydrogenated / saturated polymer containing 90 mol% or more of isoprene repeat units and having a functionality distribution (Fd) value of less than 2, for example less than 3.5 (determined by GPC-PS, for example less than 3.4, for example 1 to 3.3, for example 1.1 to 3.2, for example 1.2 to 3.0, for example 1.4 to 2.9), and the polymer before functionalization has an Mn of 10,000 g / mol or more, for example 30,000 g / mol or more (GPC-PS).

[0151] The present disclosure also relates to an amide, imide, and / or ester functionalized hydrogenated / saturated homopolymer of isoprene having an Mw / Mn of less than 2, for example less than 1.8, a functionality distribution (Fd) value of less than 3.5 (determined by GPC-PS, for example less than 3.4, for example less than 2.5, or 1 to 3.3, for example 1.1 to 3.2, for example 1.2 to 3.0, for example 1.4 to 2.9), and an average functionality (Fv) of 4 to 10 functional groups per polymer chain, and the polymer before functionalization has an Mn of 20,000 g / mol or more, for example 20,000 to 50,000 g / mol (determined by GPC-PS).

[0152] In certain embodiments, the functionalized polymers used in the lubricant compositions and additive 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 as disclosed herein; an average functionality (Fv) of 4 to 10, such as 6 to 8 (determined as disclosed herein); an Mn of 20,000 to 50,000 g / mol, such as 30,000 to 40,000 g / mol (GPC-PS); and / or an Mz of 40,000 to 70,000 g / mol, such as 50,000 to 60,000 g / mol (GPC-PS); and / or are functionalized with maleic anhydride and further reacted with a polyamine such as N-phenyl-p-phenylenediamine (NPPDA), such as 4-amino-diphenylamine (ADPA), and have a backbone of homo-polyisoprene.

[0153] In the compositions according to the present disclosure, component B) is considered to constitute, together with the (poly)alkenyl succinic acid dispersant of component I), the dispersant mixture disclosed herein. Thus, component B), and the (poly)alkenyl succinic acid dispersant of component I) are considered together for the purpose of determining the amount of the dispersant mixture in the lubricant compositions or additive concentrates disclosed herein. In certain embodiments, the dispersant mixture comprises 0.01 to 15% by weight, such as 1 to 12% by weight, such as 5 to 11% by weight, such as 7.5 to 10.5% by weight, such as 8.5 to 10% by weight, of the functionalized polymer, based on the total weight of the dispersant mixture. The lubricating compositions and additive concentrates according to the present disclosure may further comprise one or more additives, such as detergents, friction modifiers, antioxidants, pour point depressants, antifoaming agents, viscosity modifiers, dispersants, corrosion inhibitors, antiwear agents, extreme pressure additives, demulsifiers, seal compatibility agents, additive diluent base oils, 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 some are discussed in more detail below.

[0154] C. Detergent The lubricating composition may contain one or more metal detergents (e.g., the friend of metal detergents), also called "detergent additives". Metal detergents typically function both as detergents for reducing or removing deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life. Detergents generally contain a polar head having a long-chain hydrophobic tail, and the polar head contains a metal salt of an acidic organic compound. Such salts may contain substantially stoichiometric amounts of metal, in which case such salts are usually described as normal or neutral salts and typically will have a total base number (TBN, measured by ASTM D2896) of up to 150 mg KOH / g, e.g., 0 - 80 (or 5 - 30) mg KOH / g. By reacting an excess metal compound (e.g., an oxide or hydroxide) with an acidic gas (e.g., carbon dioxide), a large amount of metal base can be incorporated. Such detergents may also be called overbased and may have a TBN of 100 mg KOH / g or more (e.g., 200 mg KOH / g or more), typically 250 mg KOH / g or more, e.g., 300 mg KOH / g or more, e.g., 200 - 800 mg KOH / g, 225 - 700 mg KOH / g, 250 - 650 mg KOH / g, or 300 - 600 mg KOH / g, e.g., 150 - 650 mg KOH / g.

[0155] 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, for example, oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, naphthenates, and other oil-soluble carboxylates of Ca and / or Mg. Further, the detergent may include a hybrid detergent containing any combination of sodium salts, potassium salts, lithium salts, calcium salts, or magnesium salts of sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and naphthenates, or other oil-soluble carboxylates of Group 1 and / or Group 2 metals.

[0156] Preferably, the detergent additives useful in the present disclosure include calcium and / or magnesium metal salts. The detergent may be calcium and / or magnesium carboxylate (such as salicylic acid), calcium and / or magnesium sulfonate, or calcium and / or magnesium phenate detergent. More preferably, the detergent additive is selected from magnesium salicylate, calcium salicylate, magnesium sulfonate, calcium sulfonate, magnesium phenate, calcium phenate, and hybrid detergents containing two, three, four, or more of such detergents and / or combinations thereof.

[0157] In addition, examples of the metal-containing detergent include "hybrid" detergents formed of a mixed surfactant system containing a phenate and / or sulfonate component, such as a phenate / salicylate, sulfonate / phenate, sulfonate / salicylate, or sulfonate / phenate / salicylate, as described in U.S. Patent Nos. 6,429,178, 6,429,179, 6,153,565, and 6,281,179. For example, when a hybrid sulfonate / phenate detergent is used, the hybrid detergent is considered to be in the same amount as the amounts of the separate phenate detergent and sulfonate detergent that introduce similar amounts of the phenate saponified product and the sulfonate saponified product, respectively.

[0158] The overbased metal-containing detergent may be a sodium salt, calcium salt, magnesium salt, or a mixture thereof of phenate, sulfur-containing phenate, sulfonate, salixarate, and salicylate. The overbased phenate and salicylate typically have a total base number of 180 to 650 mg KOH / g, for example 200 to 450 TBN mg KOH / g. The overbased sulfonate typically has a total base number of 250 to 600 mg KOH / g, or 300 to 500 mg KOH / g. In an embodiment, the sulfonate detergent may be mainly a linear alkylbenzene sulfonate detergent having a metal ratio of at least 8, as described in paragraphs

[0026] to

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

[0159] The detergent additive may contain one or more magnesium sulfonate detergents. The magnesium detergent may be a neutral salt or a overbased salt. Preferably, the magnesium detergent is an overbased magnesium sulfonate having a TBN of 80 to 650 mg KOH / g (ASTM D2896), for example 200 to 500 mg KOH / g, for example 240 to 450 mg KOH / g. Alternatively, the detergent additive is magnesium salicylate. Preferably, the magnesium detergent is magnesium salicylate having a TBN of 30 to 650 mg KOH / g (ASTM D2896), for example 50 to 500 mg KOH / g, for example 200 to 500 mg KOH / g, for example 240 to 450 mg KOH / g, or alternatively having a TBN of 150 mg KOH / g or less, for example 100 mg KOH / g or less.

[0160] Alternatively, the detergent additive is a combination of magnesium salicylate and magnesium sulfonate. The magnesium detergent provides 200 to 4000 ppm of magnesium atoms, preferably 200 to 2000 ppm, 300 to 1500 ppm, or 450 to 1200 ppm of magnesium atoms to the lubricating composition (ASTM D5185). The detergent composition may comprise (or consist of) a combination of one or more magnesium sulfonate detergents and one or more calcium salicylate detergents. The combination of one or more magnesium sulfonate detergents and one or more calcium salicylate detergents provides to these lubricating compositions 1) 200 to 4000 ppm of magnesium atoms, preferably 200 to 2000 ppm, 300 to 1500 ppm, or 450 to 1200 ppm of magnesium atoms (ASTM D5185), and 2) at least 500 ppm, preferably at least 750 ppm, more preferably at least 900 ppm of atomic calcium, for example 500 to 4000 ppm, preferably 750 to 3000 ppm, more preferably 900 to 2000 ppm of atomic calcium (ASTM D5185).

[0161] The detergent may contain one or more calcium detergents, such as calcium carboxylate (e.g., salicylic acid) calcium, calcium sulfonate, or calcium phenate detergent. Preferably, the calcium detergent has a TBN of 30 - 700 mg KOH / g (ASTM D2896), such as 50 - 650 mg KOH / g, such as 200 - 500 mg KOH / g, such as 240 - 450 mg KOH / g, or alternatively 150 mg KOH / g or less, such as 100 mg KOH / g or less, or 200 mg KOH / g or more, or 300 mg KOH / g or more, or 350 mg KOH / g or more. Preferably, the calcium detergent is calcium salicylate, calcium sulfonate, or calcium phenate having a TBN of 30 - 700 mg KOH / g, 30 - 650 mg KOH / g (ASTM D2896), such as 50 - 650 mg KOH / g, such as 200 - 500 mg KOH / g, such as 240 - 450 mg KOH / g, or alternatively 150 mg KOH / g or less, such as 100 mg KOH / g or less, or 200 mg KOH / g or more, or 300 mg KOH / g or more, or 350 mg KOH / g or more.

[0162] The calcium detergent is typically present in an amount sufficient to provide at least 500 ppm, preferably at least 750, more preferably at least 900 ppm of atomic calcium to the lubricating oil composition (ASTM D5185). If present, any calcium detergent is preferably present in an amount sufficient to provide 4000 ppm or less, preferably 3000 ppm or less, more preferably 2000 ppm or less of atomic calcium to the lubricating oil composition (ASTM D5185). If present, any calcium detergent is preferably present in an amount sufficient to provide 500 - 4000 ppm, preferably 750 - 3000 ppm, more preferably 900 - 2000 ppm of atomic calcium to the lubricating oil composition (ASTM D5185).

[0163] Suitably, the total atomic weight of the metal derived from the detergent in the lubricating composition according to all aspects of the present disclosure is 5000 ppm or less, preferably 4000 ppm or less, more preferably 2000 ppm or less (ASTM D5185). The total amount of metal atoms derived from the detergent in the lubricating oil composition according to all aspects of the present disclosure is preferably at least 500 ppm, preferably at least 800 ppm, more preferably at least 1000 ppm (ASTM D5185). The total amount of metal atoms derived from the detergent in the lubricating oil composition according to all aspects of the present disclosure is preferably 500 to 5000 ppm, preferably 500 to 3000 ppm, more preferably 500 to 2000 ppm (ASTM D5185).

[0164] Sulfonate detergents can typically be prepared from sulfonic acids obtained by sulfonation of alkyl-substituted aromatic hydrocarbons such as those obtained from the fractional distillation of petroleum, or by alkylation of aromatic hydrocarbons. Examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl, or halogen derivatives thereof, such as chlorobenzene, chlorotoluene, and chloronaphthalene. The alkylation can be carried out in the presence of a catalyst with an alkylating agent having from about 3 to more than 70 carbon atoms. Alkaryl sulfonates usually contain from about 9 to about 80 or more carbon atoms, preferably from about 16 to about 60 carbon atoms per alkyl-substituted aromatic moiety. The oil-soluble 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 desired TBN of the final product, but is typically in the range of about 100 to 220% by mass (preferably at least 125% by mass) of the stoichiometrically required amount.

[0165] Metal salts of phenol and sulfurized phenol are prepared by reaction 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. Sulfurized phenol can be prepared by reacting phenol with sulfur or a sulfur-containing compound such as hydrogen sulfide, monohalogenated sulfur, or dihalogenated sulfur to form a product that is generally a mixture of compounds in which two or more phenols are bridged by sulfur-containing linkages.

[0166] Carboxylate detergents, such as salicylates, can be prepared by reacting an aromatic carboxylic acid (e.g., C 5~100 , C 9~30 , C 14~24 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 portion of the aromatic carboxylic acid may contain heteroatoms such as nitrogen and oxygen. Preferably, this portion contains only carbon atoms, and more preferably, this portion contains 6 or more carbon atoms. For example, a preferred portion is benzene. The aromatic carboxylic acid may contain one or more aromatic portions, such as one or more benzene rings, which are either condensed or connected via an alkylene bridge.

[0167] Preferred substituents in oil-soluble salicylic acid are alkyl substituents. In alkyl-substituted salicylic acid, the alkyl group preferably contains 5 to 100, more preferably 9 to 30, and particularly 14 to 20 carbon atoms. When more than one alkyl group is present, the average number of carbon atoms in all alkyl groups is preferably at least 9 to ensure adequate oil solubility. In an embodiment, the ratio of detergent metal to atomic molybdenum in the lubricating oil composition may be less than 3:1, such as less than 2:1. Furthermore, since the metal organic and inorganic base salts used as detergents may contribute to the sulfuric acid ash content of the lubricating oil composition, in embodiments of the present disclosure, the amount of such additives is minimized. To maintain a low sulfur level, 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 in the range of 0.05 to 20.0% by weight, more preferably 1.0 to 10.0% by weight, most preferably 2.0 to 5.0% by weight based on the total weight of the lubricating composition).

[0168] The total sulfuric acid ash content of the lubricating compositions herein, as determined by ASTM D874, is typically 2.0% by weight or less, alternatively 1.0% by weight or less, alternatively 0.8% by weight or less, alternatively 0.5% by weight or less based on the total weight of the lubricating composition. Furthermore, each of the detergents independently advantageously has a TBN (total base number) value in the range of 10 to 700 mg KOH / g, 10 to 500 mg KOH / g, alternatively in the range of 100 to 650, alternatively in the range of 10 to 500 mg KOH / g, alternatively in the range of 30 to 350 mg KOH / g, alternatively in the range of 50 to 300 mg KOH / g as measured by ISO3771. Sulfonate detergents (e.g., Ca and / or Mg sulfonate detergents) may be present in an amount that delivers 0.1% to 1.5% by weight, or 0.15 to 1.2% by weight, or 0.2% to 0.9% by weight of the sulfonate saponified product to the lubricant composition. Salicylate detergents (e.g., Ca and / or Mg salicylate detergents) are present in an amount that delivers 0.3% to 1.4% by weight, or 0.35% to 1.2% by weight, or 0.4% to 1.0% by weight of the salicylate saponified product to the lubricant composition.

[0169] The sulfonate saponified product may be present in an amount of 0.2% to 0.8% by weight of the lubricant composition, and the salicylate saponified product may be present in an amount of 0.3% to 1.0% by weight of the lubricant composition. The total amount of all alkaline earth metal detergent soaps may be present in an amount of 0.6% to 2.1% by mass, or 0.7% to 1.4% by mass, of the lubricant composition. Typically, a lubricating composition formulated for use in a large diesel engine contains from about 0.1 to about 10% by mass, alternatively from about 0.5 to about 7.5% by mass, alternatively from about 1 to about 6.5% by mass, of a detergent, based on the lubricating composition. Typically, a lubricating composition formulated for use in a passenger car engine contains from about 0.1 to about 10% by mass, alternatively from about 0.5 to about 7.5% by mass, alternatively from about 1 to about 6.5% by mass, of a detergent, based on the lubricating composition.

[0170] Typically, a lubricating composition formulated for use in a drive train (e.g., a transmission) contains from about 0.1 to about 10% by mass, alternatively from about 0.5 to about 7.5% by mass, alternatively from about 2 to about 6.5% by mass, of a detergent, based on the lubricating composition. In embodiments, one or more detergents used in the lubricating oil compositions and additive concentrates of the present invention are present at 0.01 to 3% by mass, such as 0.1 to 1% by mass, such as 0.2 to 0.6% by mass, based on the total mass of the lubricating oil composition, and / or at 0.1 to 5% by mass, such as 0.5 to 4% by mass, such as 1 to 3% by mass, based on the total mass of the additive concentrate. In embodiments, the detergents used in the lubricating oil compositions and additive concentrates of the present invention are selected from the group consisting of oil-soluble neutral or overbased sulfonates and phenates of alkali metals or alkaline earth metals, and in particular are selected from the group consisting of oil-soluble neutral or overbased sulfonates of calcium or magnesium (e.g., calcium sulfonate and / or magnesium sulfonate).

[0171] In certain embodiments, the lubricating oil compositions and additive concentrates of the present invention do not contain phenate detergents and / or do not contain salicylate detergents. Preferably, the lubricating oil compositions and additive concentrates of the present invention do not contain phenate detergents, or are substantially free of, for example, less than 1.2% by mass, less than 1.0% by mass, less than 0.5% by mass, etc., based on the total mass of the lubricating oil composition or additive concentrate, and / or do not contain salicylate detergents, or are substantially free of, for example, less than 1.2% by mass, less than 1.0% by mass, less than 0.5% by mass, etc., 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 are a mixture of calcium sulfonate and magnesium sulfonate, and particularly consist of.

[0172] D. Friction Modifiers A friction modifier is any one or more substances that can change the coefficient of friction of a surface lubricated by any lubricant or a fluid containing such a substance. Friction modifiers, also known as friction reducers or lubricity agents or oiliness agents, and other such agents that can change the ability of a base oil, formulated lubricating composition, or functional fluid to adjust 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, as needed. It is particularly advantageous to combine friction modifiers that lower the coefficient of friction with the base oils and lubricating compositions of the present disclosure. Exemplary friction modifiers can include, for example, organometallic compounds or substances or mixtures thereof. Exemplary organometallic friction modifiers useful in the lubricating oil formulations of the present disclosure can include, for example, tungsten and / or molybdenum compounds, such as molybdenum amines, molybdenum diamines, organotungstenates, molybdenum dithiocarbamate, molybdenum dithiophosphate, molybdenum amine complexes, and molybdenum carboxylates, etc., and mixtures thereof. Examples of useful molybdenum-containing compounds can conveniently include molybdenum dithiocarbamate, such as the trinuclear molybdenum compound described in WO 98 / 26030 pamphlet, molybdenum sulfide, and molybdenum dithiophosphate.

[0173] Other known friction modifiers include oil-soluble organomolybdenum compounds. Such organomolybdenum friction modifiers can also provide antioxidant and antiwear credits to lubricating oil compositions. Examples of such oil-soluble organomolybdenum compounds include dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, and sulfides, among others, and mixtures thereof. Particularly preferred are molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, molybdenum alkylxanthate, and molybdenum alkylthioxanthate. In addition, the molybdenum compound may be an acidic molybdenum compound. Such compounds will react with basic nitrogen compounds and are typically hexavalent as measured by the ASTM test D664 or D2896 titration procedure. Molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates, and other molybdenum salts, such as sodium hydrogen molybdate, MoOC l4 , MoO2Br2, Mo2O3C l6 , molybdenum trioxide, or similar acidic molybdenum compounds are included.

[0174] 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 generally selected from the group consisting of alkyl, aryl, aralkyl, and alkoxyalkyl having from 1 to 30 carbon atoms, preferably from 2 to 12 carbon atoms, and most preferably alkyl having from 2 to 12 carbon atoms. Particularly preferred are molybdenum dialkyldithiocarbamates. Another group of organomolybdenum compounds useful in the lubricating compositions of the present disclosure are trinuclear molybdenum compounds, particularly those of the formula Mo3SkLnQz, and mixtures thereof, where L is an independently selected ligand having an organic group having a sufficient number of carbon atoms to render the compound soluble or dispersible in oil, n is from 1 to 4, k is in the range of 4 to 7, Q is selected from the group of neutral electron donor compounds such as water, amines, alcohols, phosphines, and ethers, z is in the range of 0 to 5, including non-stoichiometric values. All ligands / organic groups should have at least 21 carbon atoms, such as at least 25, at least 30, or at least 35 carbon atoms.

[0175] Lubricating oil compositions useful in all aspects of the present disclosure preferably contain at least 10 ppm, at least 30 ppm, at least 40 ppm, more preferably at least 50 ppm of molybdenum. Suitably, lubricating oil compositions useful in all aspects of the present disclosure contain 1000 ppm or less, 750 ppm or less, or 500 ppm or less of molybdenum. Lubricating oil compositions useful in all aspects of the present disclosure preferably contain 10 to 1000 ppm, such as 30 to 750 ppm, or 40 to 500 ppm of molybdenum (measured as molybdenum atoms). For further information regarding useful friction modifiers containing Mo, see U.S. Patent No. 10,829,712 (column 8, line 58 to column 11, line 31).

[0176] The lubricating oil composition of the present disclosure may contain an ashless friction modifier, which is generally known and includes esters and amine-based friction modifiers formed by reacting carboxylic acids and anhydrides with alkanols. Other useful friction modifiers generally include polar end groups (e.g., carboxyl or hydroxyl) covalently bonded to a lipophilic hydrocarbon chain. Esters of carboxylic acids and anhydrides with alkanols are described in U.S. Patent No. 4,702,850. Examples of other conventional organic friction modifiers are described in M. Belzer, "Journal of Tribology" (1992), Vol. 114, pp. 675 - 682, and M. Belzer and S. Jahanmir, "Lubrication Science" (1988), Vol. 1, pp. 3 - 26. Typically, the total amount of the organic ashless friction modifier in the lubricant according to the present disclosure does not exceed 5% by mass, preferably does not exceed 2% by mass, and more preferably does not exceed 0.5% by mass based on the total mass of the lubricating oil composition.

[0177] Exemplary friction modifiers useful in the lubricating compositions described herein include, for example, alkoxylated fatty acid esters, alkanolamides, polyol fatty acid esters, glycerol borate fatty acid esters, fatty alcohol ethers, and mixtures thereof. Exemplary alkoxylated fatty acid esters include, for example, polyoxyethylene stearate and fatty acid polyglycol esters. Examples of such include polyoxypropylene stearate, polyoxybutylene stearate, polyoxyethylene isostearate, polyoxypropylene isostearate, and polyoxyethylene palmitate.

[0178] Exemplary alkanolamides include, for example, diethyl alkanolamide laurate and diethyl alkanolamide palmitate (palmic acid), etc. Such examples include diethyl alkanolamide oleate, diethyl alkanolamide stearate, diethyl alkanolamide oleate, polyethoxylated hydrocarbylamide, and polypropoxylated hydrocarbylamide, etc. Exemplary polyol fatty acid esters include, for example, glycerol monooleate, saturated mono-, di-, and triglyceride esters, and glycerol monostearate, etc. Such examples include polyol esters and hydroxyl-containing polyol esters, etc.

[0179] Exemplary glycerol borate fatty acid esters include, for example, glycerol monooleate borate, saturated mono-, di-, and triglyceride ester borates, and glycerol monostearate borate, etc. In addition to glycerol polyols, such examples include trimethylolpropane, pentaerythritol, and sorbitan, etc. Such esters may be polyol monocarboxylic acid esters, polyol dicarboxylic acid esters, and in some cases polyol tricarboxylic acid esters. Preferred are glycerol monooleate, glycerol dioleate, glycerol trioleate, glycerol monooleate, glycerol distearate, and glycerol tristearate, and the corresponding glycerol monopalmitate, glycerol dipalmitate, and glycerol tripalmitate, and the corresponding isostearates and linoleates, etc. In this specification, in particular, ethoxylated, propoxylated, and / or butoxylated fatty acid esters of polyols in which glycerol is used as the base polyol are useful.

[0180] Exemplary aliphatic alcohol ethers include, for example, stearyl ether and myristyl ether, etc. C3 - C50 Alcohols having a carbon number of 11 ~ 13 hydrocarbons, oleyl, and isostearyl, etc. may also be used.

[0181] Useful concentrations of the friction modifier may range from 0.01% to 5% by mass, or from about 0.001% to about 2.5% by mass, or from about 0.05% to about 1.5% by mass, or from about 0.051% to about 1% by mass. The concentration of the molybdenum-containing substance is often described in terms of the Mo metal concentration. Advantageous concentrations of Mo may range from 25 ppm to 700 ppm or higher, and in many cases, the preferred range is 50 - 200 ppm. Any type of friction modifier may be used alone or in combination with the substances of the present disclosure. In many cases, mixtures of two or more friction modifiers, or mixtures of friction modifiers and alternative surfactants are also desirable. In this specification, for example, combinations of Mo-containing compounds and polyol fatty acid esters, such as glycerol monooleate, are useful.

[0182] In an embodiment, one or more detergents used in the lubricating oil composition and additive concentrate of the present invention are present at 0.001 to 0.2% by mass, such as 0.01 to 0.06% by mass, such as 0.02 to 0.04% by mass, based on the total mass of the lubricating oil composition, and / or at 0.01 to 1% by mass, such as 0.02 to 0.5% by mass, such as 0.05 to 0.2% by mass, based on the total mass of the additive concentrate. In certain embodiments, the lubricating oil compositions and additive concentrates of the present invention do not contain alkoxylated fatty acid esters, alkanolamides, polyol fatty acid esters, boronated glycerol fatty acid esters, and / or fatty alcohol ethers. Preferably, the friction modifiers used in the lubricating oil compositions and additive concentrates of the present invention include at least one oil-soluble organic molybdenum compound, such as at least one molybdenum dithiocarbamate compound, such as a trimer molybdenum dithiocarbamate compound, and particularly so.

[0183] E. Antioxidants Antioxidants retard the oxidative degradation of the base oil during service. Such degradation can lead to deposits on metal surfaces, the presence of sludge, and an increase in the viscosity of the lubricant. A wide variety of oxidation inhibitors are useful in lubricating oil compositions. See, for example, Lubricants and Related Products, Klamann, Wiley VCH, 1984; U.S. Patent Nos. 4,798,684 and 5,084,197.

[0184] Useful antioxidants include hindered phenols. Such phenolic antioxidants may be ashless (metal-free) phenolic compounds or neutral or basic metal salts of certain phenolic compounds. Typical phenolic antioxidant compounds are hindered phenolic substances containing sterically hindered hydroxyl groups, and examples of such substances include derivatives of dihydroxyaryl compounds in which the hydroxyl groups are in the ortho or para positions to each other. Typical phenolic antioxidants include C 6+Examples include hindered phenols substituted with an alkyl group and alkylene coupling derivatives of such hindered phenols. Examples of this type of phenolic substance include 2-t-butyl-4-heptylphenol, 2-t-butyl-4-octylphenol, 2-t-butyl-4-dodecylphenol, 2,6-di-t-butyl-4-heptylphenol, 2,6-di-t-butyl-4-dodecylphenol, 2-methyl-6-t-butyl-4-heptylphenol, and 2-methyl-6-t-butyl-4-dodecylphenol. Other useful hindered monophenolic antioxidants include, for example, hindered 2,6-di-alkyl-phenolic propionate esters derivatives. In this specification, bis-phenolic antioxidants can also be advantageously used. Examples of ortho-coupling phenols include 2,2'-bis(4-heptyl-6-t-butyl-phenol), 2,2'-bis(4-octyl-6-t-butyl-phenol), and 2,2'-bis(4-dodecyl-6-t-butyl-phenol). Examples of para-coupling bisphenols include, for example, 4,4'-bis(2,6-di-t-butyl-phenol) and 4,4'-methylene-bis(2,6-di-t-butyl-phenol).

[0185] Also, an effective amount of one or more catalytic antioxidants can be used. The catalytic antioxidant comprises an effective amount of a) one or more oil-soluble 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 both b) and c). The catalytic antioxidants useful herein are described in more detail in U.S. Patent No. 8,048,833. Examples of non-phenolic antioxidants that can be used include aromatic amine antioxidants, which can be used either as such or in combination with phenolic substances. Typical examples of non-phenolic antioxidants include alkylated and non-alkylated aromatic amines, such as the formula R8R9R 10Examples of aromatic monoamines of N include, in the formula, R8 is an aliphatic group, an aromatic group, or a substituted aromatic group, R9 is an aromatic group or a substituted aromatic group, and R 10 is H, alkyl, aryl, or R 11 S(O)XR 12 wherein, in the formula, R 11 is an alkylene group, an alkenylene group, or an aralkylene group, R 12 is an alkyl group, or an alkenyl group, an aryl group, or an alkaryl group, and x is 0, 1, or 2. The aliphatic group R8 may contain 1 to about 20 carbon atoms, preferably about 6 to 12 carbon atoms. The aliphatic group is typically a saturated aliphatic group. Preferably, both R8 and R9 are aromatic groups or substituted aromatic groups, and the aromatic group may be a condensed ring aromatic group, such as naphthyl. The aromatic groups R8 and R9 may be joined together with other groups, such as S.

[0186] Typical aromatic amine antioxidants have an alkyl substituent of at least about 6 carbon atoms. Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl, and decyl. Generally, the aliphatic group will not contain more than about 14 carbon atoms. General types of amine antioxidants useful in this composition include diphenylamine, phenylnaphthylamine, phenothiazine, imidodibenzyl, and diphenylphenylenediamine. Mixtures of two or more aromatic amines are also useful. Polymeric amine antioxidants can also be used. Specific examples of aromatic amine antioxidants useful in this disclosure include p,p'-dioctyldiphenylamine, t-octylphenyl-alpha-naphthylamine, phenyl-alpha-naphthylamine, and p-octylphenyl-alpha-naphthylamine.

[0187] In this specification, sulfur-containing antioxidants are also useful. In particular, one or more oil-soluble or oil-dispersible sulfur-containing antioxidants can be used as antioxidant additives. For example, alkylphenol sulfides and their alkali metal salts or alkaline earth metal salts are also useful antioxidants in this specification. Preferably, the lubricating oil composition of the present disclosure contains one or more sulfur-containing antioxidants in an amount that provides 0.02 to 0.2, preferably 0.02 to 0.15, more preferably 0.02 to 0.1, and even more preferably 0.04 to 0.1% by mass of sulfur based on the total mass of the lubricating oil composition. Optionally, the oil-soluble or oil-dispersible sulfur-containing antioxidant is a sulfurized C4-C 25 olefin, sulfurized aliphatic (C7-C 29 ) hydrocarbyl fatty acid ester, ashless sulfurized phenolic antioxidant, sulfur-containing organic molybdenum compound, and combinations thereof. For further information on sulfide substances useful as antioxidants in this specification, see U.S. Patent No. 10,731,101, columns 15, line 55 to column 22, line 12.

[0188] Antioxidants useful in this specification include hindered phenols and / or arylamines. These antioxidants can be used individually or in combination with each other for each type. Typical antioxidants include Irganox (trademark) L67, Irganox (trademark) L135, Ethanox (trademark) 4702, Lanxess Additin (trademark) RC7110; Ethanox (trademark) 4782J; Irganox (trademark) 1135, Irganox (trademark) 5057, sulfurized lard oil, and palm oil fatty acid methyl ester.

[0189] The antioxidant additive can be used in an amount of about 0.01 to 10 (alternatively 0.01 to 5, alternatively 0.01 to 3% by mass, alternatively about 0.03 to 5% by mass, alternatively less than 0.05 to 3% by mass) based on the mass of the lubricating composition. In an embodiment, the antioxidant used in the lubricating oil composition and the additive concentrate of the present invention is present in an amount of 0.1 to 10% by mass, for example 3 to 8% by mass, for example 3.5 to 5% by mass, based on the total mass of the lubricating oil composition, and / or in an amount of 5 to 25% by mass, for example 10 to 22% by mass, for example 14 to 20% by mass, based on the total mass of the additive concentrate. In an embodiment, the antioxidant used in the lubricating oil composition and the additive concentrate of the present invention is at least one or more amine antioxidants and / or at least one or more phenolic antioxidants. Preferably, the antioxidant used in the lubricating oil composition and the additive concentrate of the present invention is more preferably a mixture of one or more amine antioxidants and one or more phenolic antioxidants in a ratio of about 5:2 to about 9:5, for example about 2:1.

[0190] In a particular embodiment, the lubricating oil composition and the additive concentrate of the present invention do not contain a sulfur-containing antioxidant. Preferably, the lubricating oil composition and the additive concentrate of the present invention do not contain a methyl ester sulfide antioxidant, or are substantially free of it, such as less than 2.5% by mass, less than 2.2% by mass, less than 1.5% by mass, less than 0.5% by mass, etc., based on the total mass of the additive concentrate. More preferably, the antioxidant used in the lubricating oil composition and the additive concentrate of the present invention is, in particular, a mixture of an alkylated diphenylamine antioxidant and a hindered phenolic antioxidant, and consists particularly of. The composition according to the present disclosure may include additives having various notational functions that also have a secondary effect as an antioxidant (for example, a phosphorus-containing antiwear agent (for example, ZDDP) can also exhibit an antioxidant effect). Such additives are not included in the antioxidant for the purpose of determining the amount of antioxidant in the lubricating oil composition or the additive concentrate herein.

[0191] F. Pour Point Depressant Conventional pour point depressants (also known as lubricating oil flow improvers) can be added to the compositions of the present disclosure as needed. Adding such pour point depressants to the lubricating compositions of the present disclosure can lower the minimum temperature at which the fluid will flow or can be poured. Examples of suitable pour point depressants include polymethacrylates, polyacrylates, polyaryl amides, condensation products of haloparaffin waxes and aromatic compounds, vinyl carboxylate polymers, and terpolymers of dialkyl fumarate, vinyl esters of fatty acids, 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 amounts 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.

[0192] In embodiments, the pour point depressant used in the lubricating oil compositions and additive concentrates of the present invention is present in an amount of 0.001 to 1% by weight, such as 0.01 to 0.5% by weight, such as 0.05 to 0.2% by weight, based on the total weight of the lubricating oil composition. In certain embodiments, the pour point depressant used in the lubricating oil compositions of the present invention is C 12~18 a dialkyl fumarate / vinyl acetate copolymer (which is commercially available as Infineum V387™).

[0193] G. Antifoaming Agents Advantageously, an antifoaming agent can be added to the lubricant compositions described herein. Such agents prevent or delay the formation of stable bubbles. Silicones and / or organic polymers are typical antifoaming agents. For example, polysiloxanes, such as silicone oil or polydimethylsiloxane, provide antifoaming properties. Defoamers are commercially available and can be used in small amounts, for example, 5% by mass or less, 3% by mass or less, 1% by mass or less, 0.1% by mass or less, for example, 5% by mass to 0.1 ppm, for example, 3% by mass to 0.5 ppm, for example, 1% by mass to 10 ppm.

[0194] For example, the lubricating oil composition is a defoamer containing a polyalkylsiloxane, for example, a polydialkylsiloxane, and for example, the alkyl is C1 - C 10 It may be an alkyl group, and the defoamer may contain polydimethylsiloxane (PDMS), also known as silicone oil. Alternatively, the siloxane is a poly(R 3 ) siloxane, and R 3 is typically one or more identical or different linear, branched, or cyclic hydrocarbyls having 1 to 20 carbon atoms, such as alkyl or aryl. For example, the lubricating oil composition may contain a polymeric siloxane compound according to the following formula 1, where R 1 and R 2 are independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl, phenyl, naphthyl, alkyl-substituted phenyl, or isomers thereof (e.g., methyl, phenyl), and n may be 2 to 1000, for example, 50 to 450, or alternatively, for example, 40 to 100.

[0195] In addition or alternatively, the lubricating oil composition may contain an organically modified siloxane (OMS), for example, a polyether (e.g., an ethylene-propylene oxide copolymer), a long-chain hydrocarbyl (e.g., C 11 -C 100 alkyl), or a siloxane modified with an organic group such as aryl (e.g., C6 - C 14 aryl). For example, the lubricating oil composition may contain an organically modified siloxane compound according to formula 1, where n may be 2 to 2000, for example, 50 to 450 (alternatively, for example, 40 to 100), and R 1 and R 2 may be the same or different, and optionally, R1 and R 2 Each of which is independently an organic group, such as a polyether (e.g., ethylene - propylene oxide copolymer), a long - chain hydrocarbyl (e.g., C 11 ~C100 alkyl), or an aryl (e.g., C6~C 14 aryl), which may be an organic group selected therefrom. Preferably, one of R 1 and R 2 is CH3.

Chemical formula

[0196] Based on the total mass of the lubricant composition, the siloxane according to Formula 1 is incorporated to provide about 0.1 to less than about 30 ppm of Si, or about 0.1 to about 25 ppm of Si, or about 0.1 to about 20 ppm of Si, or about 0.1 to about 15 ppm of Si, or about 0.1 to about 10 ppm of Si. More preferably, it is in the range of about 3 to 10 ppm of Si. In embodiments, silicone defoamers useful herein, such as Dow Corning FS - 1265 (1000 centistokes), Dow Corning DC - 20, and Union Carbide UC - L45, etc., are available from Dow Corning Corporation and Union Carbide Corporation. Silicone defoamers useful herein include polydimethylsiloxane, phenyl - methylpolysiloxane, linear, cyclic, or branched siloxanes, silicone polymers and copolymers, and / or organosilicone copolymers. Also, a siloxane polyether copolymer defoamer available from OSI Specialties, Inc., Farmington Hills, Michigan, can be substituted for or included. One such substance is sold as SILWET - L - 7220.

[0197] Acrylate polymer defoamers can also be used in this specification. Typical acrylate defoamers include polyacrylate defoamers available from Monsanto Polymer Products Co., known as PC-1244. Preferred acrylate polymer defoamers useful in this specification are commercially available from Dorf Ketl and are PX(™) 3841 (i.e., an alkyl acrylate polymer), also called Mobilad(™) C402. In embodiments, a combination of silicone defoamer and acrylate defoamer can be used, for example, at a mass ratio of silicone defoamer to acrylate defoamer of about 5:1 to about 1:5. See, for example, U.S. Patent Application Publication No. 2021 / 0189283.

[0198] In embodiments, the defoamer used in the lubricating oil composition and additive concentrate of the present invention is present at 0.001 to 0.1% by mass, such as 0.003 to 0.03% by mass, such as 0.005 to 0.01% by mass, based on the total mass of the lubricating oil composition, and / or at 0.001 to 0.5% by mass, such as 0.01 to 0.1% by mass, such as 0.02 to 0.04% by mass, based on the total mass of the additive concentrate. In certain embodiments, the defoamer used in the lubricating oil composition and additive concentrate of the present invention does not contain an acrylate defoamer. In certain embodiments, the defoamer used in the lubricating oil composition and additive concentrate of the present invention consists essentially of, or particularly consists of, a silicone defoamer, such as polydimethylsiloxane.

[0199] H. Viscosity Modifier A viscosity modifier (also referred to as a viscosity index improver or a viscosity increaser) can be included in the lubricating composition described herein. The viscosity modifier provides high and low temperature operating performance to the lubricant. Such additives impart shear stability at high temperatures and an acceptable viscosity at low temperatures. Suitable viscosity modifiers include high molecular weight hydrocarbons, polyesters, and viscosity modifier dispersants that can function as both a viscosity modifier and a dispersant. The typical molecular weight of such polymers is from about 10,000 to 1,500,000 g / mol, more typically from about 20,000 to 1,200,000 g / mol, and even more typically from about 50,000 to 1,000,000 g / mol.

[0200] Examples of suitable viscosity modifiers are linear or star polymers and copolymers of methacrylate, butadiene, olefin, or alkylated styrene. Polyisobutylene is a commonly used viscosity modifier. Another suitable viscosity modifier is polymethacrylate (e.g., a copolymer of alkyl methacrylates of various chain lengths), some formulations of which also serve as pour point depressants. Other suitable viscosity modifiers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (e.g., copolymers of acrylates of various chain lengths). Specific examples include styrene-isoprene or styrene-butadiene base polymers having a molecular weight of 50,000 to 200,000 g / mol.

[0201] Useful copolymers as viscosity modifiers include those commercially available under the trade name "PARATONE (trademark)" from Chevron Oronite Company LLC (e.g., "PARATONE (trademark) 8921", "PARATONE (trademark) 68231, and "PARATONE (trademark) 8941"); those commercially available under the trade name "HiTEC (trademark)" from Afton Chemical Corporation (e.g., HiTEC (trademark) 5850B and HiTEC (trademark) 5777); and those commercially available under the trade name "Lubrizol (trademark) 7067C" from The Lubrizol Corporation. Examples of hydrogenated polyisoprene star polymers useful as viscosity modifiers in this specification include those commercially available from Infineum International Limited under, for example, the trade names "SV200 (trademark)" and "SV600 (trademark)". Hydrogenated diene-styrene block copolymers useful as viscosity modifiers in this specification are commercially available from Infineum International Limited under, for example, the trade name "SV50 (trademark)".

[0202] Polymers useful as viscosity modifiers in this specification include polymethacrylate or polyacrylate polymers, such as linear polymethacrylate or polyacrylate polymers, for example, those available under the trade name "Viscoplex (trademark)" (e.g., Viscoplex (trademark) 6-954) from Evnoik Industries, or star polymers available under the trade name Asteric (trademark) (e.g., Lubrizol (trademark) 87708 and Lubrizol (trademark) 87725) from Lubrizol Corporation. The vinyl aromatic-containing polymers useful as viscosity modifiers in this specification can be derived from vinyl aromatic hydrocarbon monomers, such as styrenic monomers like styrene. Exemplary vinyl aromatic-containing copolymers useful in this specification can be represented by the following 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).

[0203] The vinyl aromatic-containing polymers useful as viscosity modifiers may have a kinematic viscosity at 100 °C of 20 cSt or less, such as 15 cSt or less, such as 12 cSt or less, but may be diluted to a higher kinematic viscosity at 100 °C, such as 40 cSt or more, such as 100 cSt or more, such as 1000 cSt or more, such as 1000 - 2000 cSt (e.g., with Group I, II, and / or III base stocks). Typically, the viscosity modifier can be used in an amount of about 0.01 to about 10 mass%, such as about 0.1 to about 7 mass%, such as 0.1 to about 4 mass%, such as about 0.2 to about 2 mass%, such as about 0.2 to about 1 mass%, and such as about 0.2 to about 0.5 mass% based on the total mass of the formulated lubricant composition.

[0204] In embodiments, the viscosity modifier used in the lubricating oil composition of the present invention is present as one or more viscosity modifiers in an amount of 0.001 to 0.5 mass%, such as 0.05 to 0.3 mass%, such as 0.1 to 0.22 mass% based on the total mass of the lubricating oil composition. The viscosity modifier is typically added as a concentrate to a large amount of diluent oil. The "as-received" viscosity modifier typically contains 20 mass% - 75 mass% active polymer in the case of polymethacrylate or polyacrylate polymers, or 8 mass% - 20 mass% active polymer in the case of olefin copolymers, hydrogenated polyisoprene star polymers, or hydrogenated diene-styrene block copolymers in the "as-received" polymer concentrate. In certain embodiments, the "as-received" viscosity modifier used in the lubricating oil compositions of the present invention is an olefin copolymer viscosity modifier, which is commercially available as Oronite Paratone® 24EX.

[0205] I. Dispersants During engine operation, oil-insoluble oxidation by-products are generated. Dispersants assist in keeping such by-products in solution and thus reduce the deposition of by-products on metal surfaces. The dispersants used in formulating the lubricating compositions herein may be ashless in nature or ash-forming. Preferably, the dispersants are ashless. So-called ashless dispersants are organic substances that do not substantially form ash upon combustion. For example, non-metal-containing dispersants or boronated metal-free dispersants are considered ashless. In contrast, metal-containing detergents tend to form ash upon combustion.

[0206] Dispersants useful in the present invention typically include a polar group attached to a relatively high molecular weight hydrocarbon chain. The polar group typically contains at least one element of nitrogen, oxygen, or phosphorus. Typical hydrocarbon chains contain from 40 to 500, for example 50 to 400, carbon atoms.

[0207] Dispersant of (poly) alkenyl succinic acid derivative Particularly useful types of dispersants typically include long-chain hydrocarbyl-substituted succinic compounds, usually (poly)alkenyl succinic derivatives produced by the reaction of hydrocarbyl-substituted succinic anhydrides with polyhydroxy or polyamino compounds. The long-chain hydrocarbyl groups that constitute the lipophilic portion of the molecule imparting solubility in the oil are often polyisobutylene groups (typically, long-chain hydrocarbyl groups, such as polyisobutylene groups, have a Mn of 400 to 3000 g / mol, for example 450 to 2500 g / mol). Many examples of this type of dispersant are well known commercially and in the literature. Exemplary U.S. patents in which such dispersants are described include U.S. Patent Nos. 3,172,892; 3,214,5707; 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; and 5,705,458. Further descriptions of dispersants useful herein can be found, for example, in European Patent Applications Nos. 0 471 071 and 0 451 380, which are hereby incorporated by reference for this purpose.

[0208] Hydrocarbyl-substituted succinic acids and hydrocarbyl-substituted succinic anhydride derivatives are useful dispersants. In particular, succinimides, succinic esters, or succinic ester amides prepared by reacting a hydrocarbon-substituted succinic acid or anhydride compound (typically having at least 25 carbon atoms, e.g., 28 to 400 carbon atoms in the hydrocarbon substituent) with at least 1 equivalent of a polyhydroxy or polyamino compound (e.g., an alkylene amine) are particularly useful herein. Hydrocarbyl-substituted succinic acids and hydrocarbyl-substituted succinic anhydride derivatives may have a number average molecular weight of at least 400 g / mol, e.g., at least 900 g / mol, e.g., at least 1500 g / mol, e.g., 400 to 4000 g / mol, e.g., 800 to 3000, e.g., 2000 to 2800 g / mol, e.g., about 2100 to 2500 g / mol, e.g., about 2200 to about 2400 g / mol.

[0209] The succinimides that are particularly useful herein are formed by the condensation reaction of 1) a hydrocarbyl-substituted succinic anhydride, such as polyisobutylene succinic anhydride (PIBSA), and 2) a polyamine (PAM). Examples of suitable polyamines include polyhydrocarbyl polyamines, polyalkylene polyamines, hydroxy-substituted polyamines, polyoxyalkylene polyamines, and combinations thereof. Examples of polyamines include tetraethylene pentamine, pentaethylene hexamine, tetraethylene pentamine (TEPA), pentaethylene hexamine (PEHA), N-phenyl-p-phenylenediamine (ADPA), and other polyamines having an average of 5, 6, 7, 8, or 9 nitrogen atoms per molecule. Mixtures in which the average number of nitrogen atoms per polyamine molecule is greater than 7 are generally referred to as heavy polyamines or H-PAM and may be commercially available under trade names such as HPA™ and HPA-X™ from The Dow Chemical Company and E-100™ from Huntsman Chemical Company et al. 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 commercially available under the trade name Jeffamine™. 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.

[0210] The polyalkenyl-substituted mono- or dicarboxylic acid anhydrides or esters derived therefrom of the succinimide dispersant can be prepared using a halogen (e.g., chlorine) assisted alkylation process ("chloro dispersant") or may be prepared using a halogen-free thermal or "ene" reaction process ("thermal dispersant"). When using "conventional" Lewis acid catalyzed polyalkenes, high functionality carboxylic acid acylating agents, particularly polyisobutylene succinic anhydride ("PIBSA"), cannot be provided by the halogen-free thermal reaction process. However, PIBSA having a higher functionality (e.g., a functionality greater than 1.3) can be prepared by heat treatment using polyalkenes (particularly polyisobutylene) having a high terminal vinylidene content (more than 65%, e.g., more than 70%, 80%, or 85%). Methods for producing high terminal vinylidene content polyisobutylene products (referred to as high reactivity polyisobutylene or "HR-PIB") are described, for example, in U.S. Patent No. 4,152,499, and HR-PIB products are commercially available from TPC or BASF under the trade name Glissopal™. PIBSA having a functionality greater than 1.3, prepared by heat treatment using polyisobutylene having a high terminal vinylidene content, together with the succinimide dispersants derived therefrom, are described in European Patent No. 0 355 895.

[0211] The chloro dispersant or thermal dispersant may contain one or more succinimides of higher molecular weight (Mn 1600 g / mol or more, for example 1800 - 3000 g / mol) which may be boronated, and one or more succinimides of lower molecular weight (Mn less than 1600 g / mol) which may be boronated. The higher molecular weight may be 1600 - 3000 g / mol, for example 1700 - 2800 g / mol, for example 1800 - 2500 g / mol, for example 1850 - 2300 g / mol. The lower molecular weight may be less than 600 - 1600 g / mol, for example 650 - 1500 g / mol, for example 700 - 1400 g / mol, for example 800 - 1300 g / mol, for example 850 - 1200 g / mol, for example 900 - 1150 g / mol, for example 900 - 1000 g / mol. The higher molecular weight succinimide dispersant may be present in the lubricating composition in an amount of 0.5 - 10% by mass, or 0.8 - 6% by mass, or 1.0 - 5% by mass, or 1.5 - 5% by mass, or 1.5 - 4.0% by mass. The lower molecular weight succinimide dispersant may be present in the lubricating composition in an amount of 1 - 5% by mass, or 1.5 - 4.8% by mass, or 1.8 - 4.6% by mass, or 1.9 - 4.6% by mass, or 2% by mass or more, for example 2 - 5% by mass. The lower molecular weight succinimide may differ from the higher molecular weight succinimide by 500 g / mol or more, for example 750 g / mol or more, for example 1000 g / mol or more, for example 1200 g / mol, for example 500 - 3000 g / mol, for example 750 - 2000 g / mol, for example 1000 - 1500 g / mol.

[0212] Useful succinic esters as dispersants include those formed by the condensation reaction of a hydrocarbyl-substituted succinic anhydride with an alcohol or polyol. For example, the condensation product of a hydrocarbyl-substituted succinic anhydride and pentaerythritol is a useful dispersant. The succinic ester amides useful herein are formed by the condensation reaction of a hydrocarbyl-substituted succinic anhydride with an alkanolamine. Suitable alkanolamines include ethoxylated polyalkylpolyamines, propoxylated polyalkylpolyamines, and polyalkenylpolyamines such as polyethylene polyamines and / or propoxylated hexamethylenediamine. Representative examples are shown in U.S. Patent No. 4,426,305.

[0213] Hydrocarbyl-substituted succinic (e.g., PIBSA) esters of hydrocarbyl-bridged aryloxy alcohols are also useful as dispersants herein. Information regarding such dispersants can be found in 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 naphthyloxyethanol (i.e., 2-hydroxyethyl-1-naphthol ether (or a hydroxy-terminated ethylene oxide oligomer ether of naphthol)) is useful herein. The molecular weight of the hydrocarbyl-substituted succinic anhydride used in the preceding paragraphs will typically range from 350 to 4000 g / mol, such as 400 to 3000 g / mol, such as 450 to 2800 g / mol, such as 800 to 2500 g / mol. The above (poly)alkenyl succinic derivatives may be post-reacted with various reagents such as sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid.

[0214] The chloro-dispersant or heat-dispersant may be present in the lubricant in an amount of 0.1 wt% to 20 wt% of the composition, such as 0.2 wt% to 15 wt%, such as 0.25 wt% to 10 wt%, such as 0.3 wt% to 5 wt%, such as 1.0 wt% to 3.0 wt% of the lubricating oil composition. The above (poly)alkenyl succinic derivatives may be post-reacted with a boron compound such as boric acid, boric acid ester, or a borated dispersant to form a borated dispersant having from about 0.1 to about 5 moles of boron per mole of dispersant reaction product.

[0215] Useful dispersants in this specification include borated succinimides containing derivatives derived from monosuccinimide, bis-succinimide, and / or mixtures of monosuccinimide and bis-succinimide. Hydrocarbyl succinimide is derived from a hydrocarbylene group, such as polyisobutylene having an Mn of about 300 to about 5000 g / mol, or about 500 to about 3000 g / mol, or about 1000 to about 2000 g / mol, or a mixture of such hydrocarbylene groups that often have a high terminal vinyl group. The boron-containing dispersant may be present in the lubricating composition at 0.01% to 20% by mass, or 0.1% to 15% by mass, or 0.1% to 10% by mass, or 0.5% to 8% by mass, or 1.0% to 6.5% by mass, or 0.5% to 2.2% by mass. The boron-containing dispersant may be present in an amount that delivers 15 ppm to 2000 ppm, or 25 ppm to 1000 ppm, or 40 ppm to 600 ppm, or 80 ppm to 350 ppm of boron to the composition.

[0216] The borated dispersant can be used in combination with a non-borated dispersant, which may be the same compound or a different compound as the non-borated dispersant. In one embodiment, the lubricating composition may contain one or more boron-containing dispersants and one or more non-borated dispersants, and the total amount of the dispersant may be 0.01% to 20% by mass, or 0.1% to 15% by mass, or 0.1% to 10% by mass, or 0.5% to 8% by mass, or 1.0% to 6.5% by mass, or 0.5% to 2.2% by mass of the lubricating composition. The ratio of the borated dispersant to the non-borated dispersant may be 1:10 to 10:1 (mass:mass), or 1:5 to 3:1, or 1:3 to 2:1.

[0217] The dispersant may contain one or more boricated or non-boricated poly(alkenyl) succinimides, wherein the polyalkyenyl is derived from polyisobutylene and the imide is derived from a polyamine.

[0218] The dispersant may contain one or more PIBSA-PAMs, wherein the PIB is derived from polyisobutylene 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 tetraethylene pentamine, pentaethylene hexamine, tetraethylene pentamine (TEPA), pentaethylene hexamine (PEHA), N-phenyl-p-phenylenediamine (ADPA), and other polyamines having an average of 5, 6, 7, 8, or 9 nitrogen atoms per molecule. The dispersant may typically be boricated at a level of up to 4% by weight, such as 1 to 3% by weight. The dispersant may contain one or more boricated PIBSA-PAMs and one or more non-boricated PIBSA-PAMs. The dispersant may contain one or more boricated 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-boricated PIBSA-PAMs derived from PIB having a Mn greater than 1800 and up to 5000 g / mol (such as 2000 to 3000 g / mol). The dispersant may contain one or more non-boricated 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 boricated PIBSA-PAMs derived from PIB having a Mn greater than 1800 and up to 5000 g / mol (such as 2000 to 3000 g / mol).

[0219] The dispersant may include PIBSA derived from PIB having an Mn of 700 to 5000 g / mol (for example, 800 to 3000 g / mol) and one or more boric acidated or non-boric acidated PIBSA-PAMs derived from PIB having an Mn of 700 to 5000 g / mol. The dispersant may include PIBSA derived from PIB having an Mn of 700 to 5000 g / mol (for example, 800 to 3000 g / mol), and one or more boric acidated PIBSA-PAMs derived from PIB having an Mn of 700 to 1800 g / mol (for example, 800 to 1500 g / mol), and one or more non-boric acidated PIBSA-PAMs derived from PIB having an Mn greater than 1800 and up to 5000 g / mol (for example, 2000 to 3000 g / mol). The dispersant may include PIBSA derived from PIB having an Mn of 700 to 5000 g / mol (for example, 800 to 3000 g / mol), one or more non-boric acidated PIBSA-PAMs derived from PIB having an Mn of 700 to 1800 g / mol (for example, 800 to 1500 g / mol), and one or more boric acidated PIBSA-PAMs derived from PIB having an Mn greater than 1800 and up to 5000 g / mol (for example, 2000 to 3000 g / mol).

[0220] The dispersant may include one or more boric acidated or non-boric acidated PIBSA-PAMs, and one or more PIBSA-esters of hydrocarbyl cross-linked aryloxy alcohols. The dispersant may include one or more boric acidated PIBSA-PAMs and one or more non-boric acidated PIBSA-PAMs. The dispersant may contain one or more PIBSA-PAMs with a higher molecular weight (Mn 1600 g / mol or more, for example 1800 - 3000 g / mol), which may be boronated, and one or more PIBSA-PAMs with a lower molecular weight (less than Mn 1600 g / mol), which may be boronated. The higher molecular weight may be 1600 - 3000 g / mol, for example 1700 - 2800 g / mol, for example 1800 - 2500 g / mol, for example 1850 - 2300 g / mol. The lower molecular weight may be less than 600 - 1600 g / mol, for example 650 - 1500 g / mol, for example 700 - 1400 g / mol, for example 800 - 1300 g / mol, for example 850 - 1200 g / mol, for example 900 - 11500 g / mol, for example 900 - 100 g / mol. The PIBSA-PAM dispersant with a higher molecular weight may be present in the lubricating composition in an amount of 0.5 - 10% by mass, or 0.8 - 6% by mass, or 1.0 - 5% by mass, or 1.5 - 5% by mass, or 1.5 - 4.0% by mass. The PIBSA-PAM dispersant with a lower molecular weight may be present in the lubricating composition in an amount of 1 - 5% by mass, or 1.5 - 4.8% by mass, or 1.8 - 4.6% by mass, or 1.9 - 4.6% by mass, or 2% by mass or more, for example 2 - 5% by mass.

[0221] According to the present invention, the lubricating oil composition and the additives concentrate of the present invention (other than the dispersant (component B)) used contain, in particular consist of, a mixture of one or more chloro-dispersants and one or more thermal dispersants. In an embodiment, the one or more chloro-dispersants and the one or more thermal dispersants are present in a ratio of about 9:1 to about 3:2, for example about 6:1 to about 3:1, for example about 5:1 to about 4:1, in particular in a ratio of about 9:2.

[0222] In certain embodiments, one or more chloro dispersants used in the lubricating oil compositions and additive concentrates of the present invention are one or more boro-oxidized or non-boro-oxidized poly(alkenyl) succinimides, wherein the polyalkenyl is derived from polyisobutylene and the imide is derived from a polyamine, one or more boro-oxidized or non-boro-oxidized poly(alkenyl) succinimides (“PIBSA-PAM”), particularly including one or more boro-oxidized PIBSA-PAM and one or more non-boro-oxidized PIBSA-PAM, and particularly consisting of. In certain embodiments, one or more chloro dispersants used in the lubricating oil compositions and additive concentrates of the present invention are one or more PIBSA-PAM of higher molecular weight (Mn 1600 g / mol or more, for example 1800 - 3000 g / mol), and one or more PIBSA-PAM of lower molecular weight (Mn less than 1600 g / mol) which may be boro-oxidized, particularly the first higher molecular weight PIBSA-PAM and the second and third lower molecular weight PIBSA-PAM (optionally, one of them is boro-oxidized), particularly consisting of, and 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.

[0223] In certain embodiments, one or more thermal dispersants used in the lubricating oil compositions and additive concentrates of the present invention are one or more poly(alkenyl) succinimides, wherein the polyalkenyl is derived from polyisobutylene and the imide is derived from a polyamine, one or more poly(alkenyl) succinimides (referred to as "PIBSA-PAM", particularly one or more poly(alkenyl) succinimides (referred to as "HR-PIBSA-PAM") wherein the polyalkenyl is derived from high vinylidene content polyisobutylene and the imide is derived from a polyamine. In certain embodiments, one or more thermal dispersants used in the lubricating oil compositions and additive concentrates of the present invention include, particularly consist of, one or more PIBSA-PAMs having a higher molecular weight (Mn of 1000 g / mol or more, such as 1200 to 3000 g / mol, such as 1500 to 2800 g / mol, such as 1800 to 2500 g / mol, such as 2200 to 2300 g / mol), particularly having an Mn of at least 1200 g / mol, such as at least 1500 g / mol, such as at least 1800 g / mol, such as at least 2200 g / mol, or at least 2300 g / mol.

[0224] Dispersant of Mannich base Mannich base dispersants useful herein are typically made from the reaction of an amine component, a hydroxyaromatic compound (substituted or unsubstituted, such as alkyl-substituted), such as an alkylphenol, with an aldehyde, such as formaldehyde. See U.S. Patent Nos. 4,767,551 and 10,899,986. Also, processing aids and catalysts, such as oleic acid and sulfonic acid, may 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 International Publication No. 01 / 42399 Pamphlet.

[0225] Dispersant of polymethacrylate or polyacrylate derivative Polymethacrylates or polyacrylate derivatives are another type of dispersant useful herein. Such dispersants are typically prepared by reacting a nitrogen-containing monomer with a methacrylic acid ester or acrylic acid ester containing 5 to 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 typically have a lower molecular weight.

[0226] The lubricating compositions of the present disclosure typically contain 0.1 wt% to 20 wt% of the composition, for example, 0.2 to 15 wt% of a lubricating oil composition, for example 0.25 to 10 wt%, for example 0.3 to 5 wt%, for example 2.0 wt% to 4.0 wt% of a dispersant. Alternatively, the dispersant may be present at 0.1 wt% to 5 wt% or 0.01 wt% to 4 wt% of the lubricating composition. In embodiments, the dispersants used in the lubricating oil compositions and additive concentrates of the present invention are present at 1 to 12 wt%, for example 3 to 10 wt%, for example 6 to 8 wt% based on the total weight of the lubricating oil composition, and at 15 to 40 wt%, for example 20 to 32 wt%, for example 25 to 30 wt% based on the total weight of the additive concentrate.

[0227] In certain embodiments, the dispersants used in the lubricating oil compositions and additive concentrates of the present invention do not include Mannich base dispersants and / or poly(meth)acrylate dispersants. In certain embodiments, the dispersants used in the lubricating oil compositions and additive concentrates of the present invention do not include hydrocarbyl-substituted succinic anhydrides, such as esters of hydrocarbyl-bridged aryloxy alcohols. Preferably, the dispersants used in the lubricating oil compositions and additive concentrates of the present invention include, particularly consist of, poly(alkylene) succinimide dispersants, especially PIBSA-PAM dispersants. More preferably, the dispersants used in the lubricating oil compositions and additive concentrates of the present invention include, particularly consist of, first and second PIBSA-PAM dispersants derived from PIBs having 1800 - 2500 Mn, and third and fourth PIBSA-PAM dispersants derived from PIBs having a Mn of less than 1600, and at least one of the first PIBSA-PAM dispersant and the second PIBSA-PAM dispersant has a high terminal vinylidene content, and at least one of the third PIBSA-PAM dispersant and the fourth PIBSA-PAM dispersant does not contain boron (optionally, at least one of the third PIBSA-PAM dispersant and the fourth PIBSA-PAM dispersant is boronated). Particularly preferably, the dispersants used in the lubricating oil compositions and additive concentrates of the present invention include, particularly consist of, a first boron-free PIBSA-PAM dispersant derived from 2200 Mn PIB, a second boron-free PIBSA-PAM dispersant derived from 2300 Mn PIB with a high terminal vinylidene content, a third boron-free PIBSA-PAM dispersant derived from 950 Mn PIB, and a fourth boronated PIBSA-PAM dispersant derived from 950 Mn PIB.

[0228] For further information regarding dispersants useful herein, see columns 13, line 36 to column 16, line 67 of U.S. Patent No. 10,829,712, and columns 2, line 65 to column 6, line 22, columns 8, line 25 to column 14, line 53, and columns 23, line 40 to column 26, line 46 of U.S. Patent No. 7,485,603.

[0229] The compositions according to the present disclosure may include additives having various notational functions that also have a secondary effect as a dispersant (for example, the component B functionalized polymer described above can also exhibit a dispersant effect). Such additives are not included in the dispersant for the purpose of determining the amount of dispersant in the lubricating oil composition or concentrate herein. However, the (poly)alkenyl succinic acid dispersant of component I) is considered to constitute the dispersant mixture disclosed herein together with component B). Therefore, the (poly)alkenyl succinic acid dispersants of component I) and component B) are considered together for the purpose of determining the amount of the dispersant mixture in the lubricating oil composition or additive concentrate disclosed herein.

[0230] In certain embodiments, the detergent mixture comprises one or more chloro-dispersants in an amount of 50 to 90% by weight, such as 55 to 85% by weight, such as 62 to 82% by weight, such as 68 to 80% by weight, such as 70 to 76% by weight, based on the total weight of the dispersant mixture, and / or one or more thermal dispersants in an amount of 10 to 30% by weight, such as 12 to 25% by weight, such as 14 to 22% by weight, such as 15 to 20% by weight, such as 15.5 to 17.5% by weight, based on the total weight of the dispersant mixture. Preferably, the dispersant mixture comprises one or more chloro-dispersants and one or more thermal dispersants in a ratio of about 9:1 to about 3:2, such as about 6:1 to about 3:1, such as about 5:1 to about 4:1. More preferably, the dispersant mixture comprises one or more chloro-dispersants and one or more thermal dispersants in a ratio of about 9:2.

[0231] J. Corrosion Inhibitor / Rust Preventive Corrosion inhibitors can be used to reduce the corrosion of metals and are alternatively often referred to as metal deactivators or metal passivators. Some corrosion inhibitors may alternatively be characterized as antioxidants.

[0232] Suitable corrosion inhibitors 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 of these. Useful triazoles include 1H-1,2,4-triazole-1-methanamine, N,N-bis(2-ethylhexyl), Irgamet™ 30, which is commercially available from BASF in Ludwigshafen, Germany, and is represented by the following formula. [Chemical formula] 1H-1,2,4-triazole-1-methanamine, N,N-bis(2-ethylhexyl)

[0233] A specific corrosion inhibitor has the following structure: [Chemical formula] is benzotriazole represented by wherein R 8 is absent (hydrogen) or is a linear or branched, saturated or unsaturated C1-C 20It is a hydrocarbyl group or a substituted hydrocarbyl group, which may have alkyl or aromatic properties and / or contain a ring structure containing heteroatoms such as N, O, or S. Examples of suitable compounds include benzotriazole, alkyl-substituted benzotriazole (such as tolyltriazole, ethylbenzotriazole, hexylbenzotriazole, octylbenzotriazole, etc.), aryl-substituted benzotriazole, and alkylaryl-substituted or arylalkyl-substituted benzotriazole, etc., and combinations thereof. For example, the triazole may include benzotriazole and / or an alkylbenzotriazole having 1 to about 20 carbon atoms or 1 to about 8 carbon atoms in the alkyl group or may be thereof. Non-limiting examples of such corrosion inhibitors include benzotriazole, tolyltriazole, and / or optionally substituted benzotriazole, such as (n,n-bis(2-ethylhexyl)-4-methyl-1h-benzotriazole-1-methanamine), and may include or be Irgamet™ 39 commercially available from BASF, Ludwigshafen, Germany. Preferred corrosion inhibitors may include benzotriazole and / or tolyltriazole or may be benzotriazole and / or tolyltriazole.

[0234] In addition or alternatively, the corrosion inhibitor has the following structure:

Chemical formula

[0235] Further, in addition to or alternatively, the corrosion inhibitor may include one or more other derivatives of DMTD, such as R 15 and R 16 may include carboxylic acid esters in which are bonded to the sulfide sulfur atoms via a carbonyl group. The preparation of such thioester-containing DMTD derivatives is described, for example, in U.S. Patent No. 2,760,933. DMTD derivatives produced by condensation of DMTD with an alpha-halogenated aliphatic carboxylic acid having at least 10 carbon atoms are described, for example, in U.S. Patent No. 2,836,564. By this process, DMTD derivatives in which R 15 and R 16 are HOOC-CH(R 19 )-(R 19 is a hydrocarbyl group) are produced. DMTD derivatives further produced by amidation or esterification of such terminal carboxylic acid groups may also be useful.

[0236] The preparation of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazole is described, for example, in U.S. Patent No. 3,663,561. Examples of DMTD derivatives include mixtures of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazole and 2,5-bis-hydrocarbyldithio-1,3,4-thiadiazole. Such mixtures may be sold under the trade name HiTEC™ 4313 and are commercially available from Afton Chemical Company. The preparation of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazole is described, for example, in U.S. Patent No. 3,663,561. Examples of DMTD derivatives include mixtures of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazole and 2,5-bis-hydrocarbyldithio-1,3,4-thiadiazole. Such mixtures may be sold under the trade name HiTEC™ 4313 and are commercially available from Afton Chemical Company.

[0237] Still further, in addition or in the alternative, the corrosion inhibitor may include a trifunctional borate having Structure B(OR 46 )3, wherein each R 46 may be the same or different. Since the borate is typically desirably compatible with the non-aqueous medium of the composition, each R 46 may in particular include a hydrocarbyl C1-C8 moiety or be a hydrocarbyl C1-C8 moiety. For example, in the case of a composition in which the non-aqueous medium comprises or is a lubricating oil base stock, typically better compatibility can be achieved when the hydrocarbyl moieties are each at least C4. Thus, non-limiting examples of such corrosion inhibitors include, but are not limited to, triethyl borate, tripropyl borate, such as triisopropyl borate, tributyl borate, such as tri-tert-butyl borate, tripentyl borate, trihexyl borate, trioctyl borate, such as tri-(2-ethylhexyl) borate, and monohexyl dibutyl borate, etc., and combinations thereof.

[0238] When used, the corrosion inhibitor may include a substituted thiadiazole, a substituted benzotriazole, a substituted triazole, a trisubstituted borate, or a combination thereof. Optionally, the corrosion inhibitor can be used in any effective amount, but when used, it is typically 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 mass of the composition. Alternatively, such an additive can be used in an amount of about 0.01 to 5 wt%, preferably about 0.01 to 1.5 wt% based on the mass of the lubricating composition. In embodiments, the corrosion inhibitor / rust inhibitor used in the lubricating oil composition and additive concentrate of the present invention is present at 0.001 to 1 wt%, such as 0.01 to 0.5 wt%, such as 0.05 to 0.1 wt% based on the total mass of the lubricating oil composition, and / or at 0.01 to 2 wt%, such as 0.05 to 1.5 wt%, such as 0.1 to 0.5 wt% based on the total mass of the additive concentrate.

[0239] In certain embodiments, the corrosion inhibitor / rust inhibitor used in the lubricating oil composition and additive concentrate of the present invention is selected from the group consisting of liquid triazole derivatives, such as liquid triazole amines. Preferably, the corrosion inhibitor / rust inhibitor used in the lubricating oil composition and additive concentrate of the present invention comprises, particularly consists of, N,N-bis(2-ethylhexyl)-((1,2,4)-triazol-1-yl)methyl)amine (which is commercially available as Irgamet™ 30). In an alternative embodiment, the 3,4-oxypyridinone-containing composition may be substantially free of triazole, benzotriazole, substituted thiadiazole, imidazole, thiazole, tetrazole, hydroxyquinoline, oxazoline, imidazoline, thiophene, indole, indazole, quinoline, benzoxazine, dithiol, oxazole, oxatriazole, pyridine, piperazine, triazine, their derivatives, their combinations, or any corrosion inhibitor (e.g., 0, or less than 0.001 wt%, 0.0005 wt% or less, intentionally not added, and / or not contained at all).

[0240] The compositions according to the present disclosure may include additives having various notational functions that also have a secondary effect as corrosion inhibitors (e.g., the component B functionalized polymers described above can also exhibit a corrosion inhibitor effect). Such additives are not included in the corrosion inhibitor for the purpose of determining the amount of corrosion inhibitor in the lubricating oil composition or concentrate herein.

[0241] K. Antiwear Agents The lubricating oil compositions of the present disclosure may include one or more antiwear agents that can reduce friction and excessive wear. Any antiwear agent known to those skilled in the art can be used in the lubricating oil composition. Non-limiting examples of suitable antiwear agents include zinc dithiophosphate, metal salts of dithiophosphates (e.g., salts of Pb, Sb, and Mo, etc.), metal salts of dithiocarbamates (e.g., salts of Zn, Pb, Sb, and Mo, etc.), metal salts of fatty acids (e.g., salts of Zn, Pb, and Sb, etc.), boron compounds, phosphate esters, phosphite esters, amine salts of phosphate esters or thiophosphate esters, reaction products of dicyclopentadiene and thiophosphoric acid, and combinations thereof. The amount of the antiwear agent may range from about 0.01 wt% to about 5 wt%, about 0.05 wt% to about 3 wt%, or about 0.1 wt% to about 1 wt% based on the total mass of the lubricating oil composition. In an embodiment, the antiwear agent used in the lubricating oil composition and the additive concentrate of the present invention is present in one or more antiwear agents in an amount of 0.01 to 1.5% by mass, for example 0.05 to 1% by mass, for example 0.06 to 0.6% by mass, based on the total mass of the lubricating oil composition, and / or is present in an amount of 0.1 to 5% by mass, for example 1 to 2.4% by mass, for example 1.5 to 2.2% by mass, based on the total mass of the additive concentrate.

[0242] In a particular embodiment, the antiwear agent used in the lubricating oil composition and the additive concentrate of the present invention is present in the lubricating oil composition and / or the additive concentrate in an amount that delivers 900 ppm or less of phosphorus, for example 800 ppm or less of phosphorus, for example 700 ppm or less of phosphorus, for example 600 ppm or less of phosphorus, for example 500 ppm or less of phosphorus, for example 490 ppm or less of phosphorus. In an embodiment, the antiwear agent is or comprises a metal dihydrocarbyl dithiophosphate, such as a zinc dialkyldithiophosphate compound. The metal of the metal dihydrocarbyl dithiophosphate may 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 dihydrocarbyl dithiophosphate has about 3 to about 22 carbon atoms, about 3 to about 18 carbon atoms, about 3 to about 12 carbon atoms, or about 3 to about 8 carbon atoms. In a further embodiment, the alkyl group is linear or branched. Also, useful antiwear agents include substituted or unsubstituted thiophosphoric acids, and salts thereof include zinc-containing compounds such as zinc dithiophosphate compounds selected from zinc dialkyldithiophosphate, zinc diaryldithiophosphate, and / or zinc alkylaryldithiophosphate.

[0243] Metal alkyl thiophosphates and more particularly zinc dialkyldithiophosphates or zinc dialkyldithiophosphates (ZDDP) where the metal component is zinc can be useful components of the lubricating compositions 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)(OR1)(OR2)]2, where R1 and R2 are C1-C 18 alkyl groups, preferably C2-C 12 alkyl groups. Such alkyl groups may be straight-chain or branched-chain. Alcohols used in ZDDP can be 2-propanol, butanol, secondary butanol, pentanol, hexanol, for example, 4-methyl-2-pentanol, n-hexanol, n-octanol, 2-ethylhexanol, and alkylated phenols, etc. Mixtures of secondary alcohols, or mixtures of primary alcohols and secondary alcohols may be used. Alkylaryl groups can also be used. Useful zinc dithiophosphates include secondary zinc dithiophosphates, for example, those available from The Lubrizol Corporation under the trade names "LZ 677A", "LZ 1095", and "LZ 1371", those available from Chevron Oronite under the trade name "OLOA 262", and those available from Afton Chemical under the trade name "HiTEC™ 7169".

[0244] In an embodiment, the zinc compound is a zinc dithiocarbamate complex, for example, of the following formula:

Chemical formula

[0245] Antiwear additives, such as ZDDP and / or zinc carbamate, are typically used in amounts 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 mass of the lubricating composition, but in many cases, more or less amounts can be advantageously used. Preferably, the antiwear additive is ZDDP, preferably secondary ZDDP, and is present in an amount of about 0.6 to 1.0 wt% of the total mass of the lubricating composition. In certain embodiments, the antiwear agent used in the lubricating oil compositions and additive concentrates of the present invention comprises, and in particular consists of, ZDDP.

[0246] Also useful as antiwear additives herein are boron-containing compounds such as boric esters, boronated aliphatic amines, boronated epoxides, alkali metal (or mixed alkali metal or alkaline earth metal) borates, and boronated overbased metal salts. The compositions according to the present disclosure may include additives having various notational functions that also have a secondary effect as antiwear agents (e.g., the component B-functionalized polymers described above can also exhibit an antiwear effect). Such additives are not included in the antiwear agents for the purpose of determining the amount of antiwear agent in the lubricating oil composition or concentrate herein.

[0247] L. Demulsifier Useful anti-emulsifiers in this specification include those described in U.S. Patent No. 10,829,712 (column 20, lines 34 to 40). In this specification, typically, a small amount of anti-emulsifying component can be used. Preferred anti-emulsifying components are described in European Patent No. 330,522. This is obtained by reacting an alkylene oxide with an adduct obtained by reacting a bis-epoxide with a polyhydric alcohol. Such additives can be used in an amount of about 0.001 to 5% by mass, preferably about 0.01 to 2% by mass.

[0248] M. Seal compatibility agent Other optional additives include seal compatibility agents such as organic phosphates, aromatic esters, aromatic hydrocarbons, esters (e.g., butyl benzyl phthalate), and polybutenyl succinic anhydride. Such additives can be used in an amount of about 0.001 to 5% by mass, preferably about 0.01 to 2% by mass. In an embodiment, the seal compatibility agent is a sea swell agent, such as PIBSA (polyisobutenyl succinic anhydride). In certain embodiments, PIBSA may be present in the lubricating oil composition or additive concentrate of the present invention in an amount of 0.01 to 5% by mass, such as 0.02 to 3% by mass, such as 0.05 to 1% by mass, such as 0.1 to 0.5% by mass, based on the mass of the lubricating oil composition, and / or in an amount of 0.01 to 10% by mass, such as 0.05 to 5% by mass, such as 0.1 to 3% by mass, such as 0.5 to 1.5% by mass, based on the mass of the additive concentrate.

[0249] N. Extreme pressure agent The lubricating oil composition of the present disclosure may contain one or more extreme pressure agents capable of preventing seizure of a sliding metal surface under extreme pressure conditions. Any extreme pressure agent known to those skilled in the art can be used in the lubricating oil composition. Generally, an extreme pressure agent is a compound that can chemically combine with a metal to form a surface film that prevents welding of the unevenness of the opposing metal surfaces under high loads. Non-limiting examples of suitable extreme pressure agents include the following: sulfurized animal or vegetable fats or oils, sulfurized animal or vegetable fatty acid esters, complete or partially esterified esters of trivalent or pentavalent acids of phosphorus, sulfurized olefins, dihydrocarbyl polysulfides, sulfurized Diels-Alder adducts, sulfurized dicyclopentadiene, sulfurized or co-sulfurized mixtures of fatty acid esters and mono-unsaturated olefins, co-sulfurized blends of fatty acids, fatty acid esters, and alpha-olefins, functional group-substituted dihydrocarbyl polysulfides, thia-aldehydes, thia-ketones, episulfide compounds, sulfur-containing acetal derivatives, co-sulfurized blends of terpenes and acyclic olefins, and polysulfide olefin products, amine salts of phosphoric esters or thiophosphoric esters, and combinations thereof. The amount of the extreme pressure agent may range from about 0.01% by mass to about 5% by mass, from about 0.05% by mass to about 3% by mass, or from about 0.1% by mass to about 1% by mass based on the total mass of the lubricating oil composition.

[0250] O. Non-base stock unsaturated hydrocarbons The lubricating oil composition of the present disclosure may contain one or more unsaturated hydrocarbons. Such unsaturated hydrocarbons are different from any base oil (lubricating oil base stocks of Groups I, II, III, IV, and / or V) and / or viscosity modifier that may be present in the composition, and always have at least one unsaturation per molecule (typically only one in the case of linear alpha-olefins or LAOs). Without being bound by theory, the unsaturation can provide antioxidant functionality and / or sulfur scavenging functionality that can complement and / or replace one or more antioxidant additives and / or one or more corrosion inhibitor additives, but unsaturated hydrocarbons (LAOs) will typically not be the sole antioxidant or the sole corrosion inhibiting functionality provider in the lubricating oil composition. Non-limiting examples of unsaturated hydrocarbons include one or more unsaturated C 12 ~C 60 hydrocarbons (e.g., C 12 ~C 48 hydrocarbons, C 12 ~C 36 hydrocarbons, C 12 ~C 30 hydrocarbons, or C 12 ~C 24 hydrocarbons). When there is only one unsaturation, the unsaturated hydrocarbon may be referred to as a linear alpha-olefin (LAO). Other non-limiting examples of unsaturated hydrocarbons include oligomers / polymers of polyisobutylene that retain (or are post-polymerization modified to exhibit) terminal (near) unsaturation, and / or blends thereof. Unsaturated hydrocarbons (LAOs), when present, may be present in an amount of 0.01 to 5% by mass, particularly 0.1 to 3% by mass, alternatively 0.1 to 1.5% by mass, based on the total mass of the lubricating oil composition.

[0251] When the lubricating oil composition contains one or more of the additives discussed above, the additives are typically blended into the composition in an amount sufficient to perform their intended function. Typical amounts of such additives useful in the present disclosure, particularly for use in crankcase lubricants, are shown in the table below.

[0252] Note that many additives are shipped from the additive manufacturer as concentrates containing one or more additives together with a certain amount of base oil or other diluent. Therefore, the amounts by mass in the tables below, as well as the other amounts referred to herein, refer to the amount of the active ingredient (i.e., the undiluted portion of the component). The mass percentages (mass %) shown below are based on the total mass of the lubricating oil composition. [Table 1]

[0253] The above additives are typically commercially available substances. These additives may be added independently, but are usually pre-mixed in packages that can be obtained from suppliers of lubricating oil additives. Additive packages with various components, ratios, and characteristics are available, and the appropriate package will be selected considering the use of the final composition.

[0254] Fuel The present disclosure is a method for lubricating an automotive internal combustion engine during engine operation, comprising: (i) supplying the lubricating composition described herein to the crankcase of the automotive internal combustion engine; (ii) supplying a hydrocarbon fuel to the automotive internal combustion engine; and (iii) combusting the fuel in the automotive internal combustion engine, such as a spark-ignition or compression-ignition two-stroke or four-stroke reciprocating engine, such as a diesel engine or a passenger vehicle engine (e.g., a spark-ignition combustion engine). The present disclosure also relates to a method comprising these steps.

[0255] The present disclosure also relates to a fuel composition comprising the lubricating oil composition and hydrocarbon fuel described herein, wherein the fuel may be derived from petroleum and / or biological sources (“biofuel” or “renewable fuel”). In embodiments, the fuel comprises from 0.1 to 100 wt%, alternatively from 1 to 75 wt%, alternatively from 5 to 50 wt% renewable fuel, based on the total weight of the renewable fuel and petroleum-derived fuel of 1 to 50 wt%.

[0256] Renewable fuel components are typically produced from vegetable oils (e.g., palm oil, rapeseed oil, soybean oil, jatropha oil), microbial oils (e.g., algal oil), animal fats (e.g., cooking oils, animal fats, and / or fish fats), and / or biogas. Renewable fuel refers to biofuels produced from biological resources formed by modern biological processes. In one embodiment, the renewable fuel component is produced by a hydrotreating process. Hydrotreating includes various reactions in which molecular hydrogen reacts with other components or components undergo molecular transformation in the presence of molecular hydrogen and a solid catalyst. Reactions include, but are not limited to, hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrocracking, and isomerization. The renewable fuel component may have various distillation ranges that provide desired properties to the component depending on the intended use.

[0257] Use The lubricating compositions of the present disclosure can be used for lubricating mechanical engine parts of internal combustion engines, particularly spark-ignition or compression-ignition two-stroke or four-stroke reciprocating engines, by adding lubricants thereto. Typically, the lubricating compositions of the present disclosure are crankcase lubricants, such as passenger car motor oils or large diesel engine lubricants. In particular, the lubricating compositions of the present disclosure are preferably used for lubricating the crankcase of a compression-ignition internal combustion engine, such as a large diesel engine. In particular, the lubricating compositions of the present disclosure are preferably used for lubricating the crankcase of a spark-ignition turbocharged internal combustion engine.

[0258] 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 ignition internal combustion engine, the lubricating oil composition of the present disclosure is useful for lubricating a high compression spark ignition engine. In an embodiment, the lubricating composition of the present disclosure is preferably used for lubricating the crankcase of an engine of a large diesel vehicle (i.e., a large diesel vehicle having a vehicle gross weight rating of 4535.9 kg (10,000 pounds) or more). In an embodiment, the lubricating composition of the present disclosure is preferably used for lubricating the crankcase of a passenger car diesel engine.

[0259] In particular, the lubricating oil formulation of the present disclosure is particularly useful for compression ignition internal combustion engines that use low viscosity oils such as API FA-4 and future oil classifications where wear protection of the valve train is difficult, i.e., large diesel engines.

[0260] The present disclosure further relates to the following. 1. An additive concentrate (or additive package) containing a dispersant mixture, wherein the dispersant mixture is (1) Based on the total mass of the dispersant mixture, 0.01 to 15% by mass of an amide, imide, and / or ester-functionalized partial or fully saturated polymer containing C 4~5 olefin, i) having an Mw / Mn of less than 2, ii) a functionality distribution (Fd) value of 3.5 or less, and iii) an Mn of the polymer before functionalization of 10,000 g / mol or more (GPC-PS) of an amide, imide, and / or ester-functionalized partial or fully saturated polymer, and (2) One or more poly(alkenyl) succinimides (''chloro dispersants'') derived from polyalkenyl-substituted succinic anhydride and polyamine prepared using a chlorine-assisted alkylation method, 50 to 90% by mass based on the total mass of the dispersant mixture; and (3) Based on the total mass of the dispersant mixture, 10 to 30% by mass of one or more poly(alkenyl) succinimides (the "thermal dispersant") derived from polyalkenyl succinic anhydride and polyamine prepared using a halogen-free thermal alkylation method An additive concentrate comprising 2. The one or more thermal dispersants are the additive concentrate according to paragraph 1, derived from polyisobutylene succinic anhydride ("PIBSA") and polyamine ("PAM"). 3. The PIBSA is the additive concentrate according to paragraph 2, based on high terminal vinylidene content polyisobutylene (highly reactive polyisobutylene, "HR-PIB"). 4. The PIBSA is the additive concentrate according to paragraph 2 or 3, based on polyisobutylene having a Mn of at least 1200 g / mol, for example at least 1500 g / mol, for example at least 1800 g / mol, for example at least 2200 g / mol, or at least 2300 g / mol. 5. The one or more thermal dispersants are PIBSA-PAM based on polyisobutylene having a Mn of about 2300 g / mol, which is the additive concentrate according to the preceding paragraph. 6. The dispersant mixture contains 1 to 12% by mass, for example 5 to 11% by mass, for example 7.5 to 10.5% by mass, for example 8.5 to 10% by mass of a functionalized polymer based on the total mass of the dispersant mixture, which is the additive concentrate according to the preceding paragraph. 7. The dispersant mixture contains 55 to 85% by mass, for example 62 to 82% by mass, for example 68 to 80% by mass, for example 70 to 76% by mass of one or more chloro-dispersants based on the total mass of the dispersant mixture, which is the additive concentrate according to the preceding paragraph. 8. The dispersant mixture contains 12 to 25% by mass, for example 14 to 22% by mass, for example 15 to 20% by mass, for example 15.5 to 17.5% by mass of one or more thermal dispersants based on the total mass of the dispersant mixture, which is the additive concentrate according to the preceding paragraph. 9. The dispersant mixture contains one or more chloro-dispersants and one or more thermal dispersants in a ratio of about 9:1 to about 3:2, for example about 6:1 to about 3:1, for example about 5:1 to about 4:1, which is the additive concentrate according to the preceding paragraph. 10. The dispersant mixture is the additive concentrate described in the preceding paragraph, comprising one or more chloro dispersants and one or more thermal dispersants in a ratio of about 9:2. 11. The functionalized polymer is (i) an Mw / Mn of less than 1.8, (ii) a functionality distribution (Fd) value of 2.5 or less, (iii) an average functionality (Fv) of 4 to 10 functional groups grafted / polymer chain, and (iv) an Mn of the polymer before functionalization of 20,000 g / mol to 50,000 g / mol (GPC-PS) which is an amide or imide functionalized partial or fully saturated homo-polyisoprene, of the additive concentrate described in the preceding paragraph. 12. The functionalized polymer is (i) an Mw / Mn of less than 1.5, (ii) a functionality distribution (Fd) value of 2.1 or less, (iii) an average functionality (Fv) of 6 to 8 functional groups grafted / polymer chain, and (iv) an Mn of the polymer before functionalization of 30,000 g / mol to 40,000 g / mol (GPC-PS) which is an amide or imide functionalized partial or fully saturated homo-polyisoprene, of the additive concentrate described in the preceding paragraph. 13. The functionalized polymer is (i) an Mw / Mn of about 1.2, (ii) a functionality distribution (Fd) value of about 1.9, (iii) an average functionality (Fv) of about 7 functional groups grafted / polymer chain, and (iv) an Mn of the polymer before functionalization of about 35,140 g / mol (GPC-PS) which is an amide or imide functionalized partial or fully saturated homo-polyisoprene, of the additive concentrate described in the preceding paragraph. 14. The functionalized polymer is derived from a homo-polyisoprene acylated with maleic anhydride or maleic acid and further reacted with N-phenyl-p-phenylenediamine (NPPDA), such as 4-amino-diphenylamine (ADPA), of the additive concentrate described in the preceding paragraph. 15. The additive concentrate according to the preceding paragraph, further comprising one or more antioxidants. 16. The additive concentrate according to paragraph 15, wherein the one or more antioxidants are at least one or more amine antioxidants. 17. The additive concentrate according to paragraph 15 or 16, wherein the one or more antioxidants are a mixture of one or more amine antioxidants and one or more phenolic antioxidants. 18. The additive concentrate according to paragraphs 15 to 17, wherein the one or more amine antioxidants and the one or more phenolic antioxidants are present in a ratio of about 5:2 to about 9:5, such as about 2:1. 19. The additive concentrate according to the preceding paragraph, which does not contain a methyl ester sulfide antioxidant or is substantially free of, such as less than 2.5% by mass, such as less than 2.2% by mass, such as less than 1.5% by mass, such as less than 0.5% by mass, based on the total mass of the additive concentrate. 20. (a) The dispersant mixture is present at 15 to 40% by mass, such as 20 to 32% by mass, such as 25 to 30% by mass, based on the total mass of the additive concentrate. (b) The one or more antioxidants are optionally present at 5 to 25% by mass, such as 10 to 22% by mass, such as 14 to 20% by mass, based on the total mass of the additive concentrate. The additive concentrate according to the preceding paragraph. 21. The additive concentrate according to the preceding paragraph, further comprising one or more additional additives selected from the group consisting of detergents, friction modifiers, defoamers, corrosion inhibitors / rust preventives, and antiwear agents. 22. The additive concentrate according to the preceding paragraph, further comprising one or more detergents selected from the group consisting of oil-soluble neutral or overbased sulfonates and phenates of alkali metals or alkaline earth metals. 23. The additive concentrate according to the preceding paragraph, further comprising one or more detergents selected from the group consisting of oil-soluble neutral or overbased sulfonates of calcium or magnesium. 24. An additive concentrate as described in the preceding paragraph that does not contain a fenate detergent or contains less than 1.2% by mass, such as less than 1.0% by mass, such as less than 0.5% by mass, and is substantially free of it, based on the total mass of the additive concentrate. 25. Further comprising one or more detergents, (c) The one or more detergents are present at 0.1 to 5% by mass, such as 0.5 to 4% by mass, such as 1 to 3% by mass, based on the total mass of the additive concentrate. The additive concentrate as described in the preceding paragraph. 26. Further comprising one or more friction modifiers, (d) The one or more friction modifiers are present at 0.01 to 1% by mass, such as 0.02 to 0.5% by mass, such as 0.05 to 0.2% by mass, based on the total mass of the additive concentrate. The additive concentrate as described in the preceding paragraph. 27. Further comprising one or more antifoaming agents, (e) The one or more antifoaming agents are present at 0.001 to 0.5% by mass, such as 0.01 to 0.1% by mass, such as 0.02 to 0.04% by mass, based on the total mass of the additive concentrate. The additive concentrate as described in the preceding paragraph. 28. The additive concentrate as described in the preceding paragraph, further comprising one or more corrosion inhibitors / rust preventives selected from the group consisting of liquid triazole derivatives, such as liquid triazole amine. 29. Further comprising one or more corrosion inhibitors / rust preventives, (f) The one or more corrosion inhibitors / rust preventives are present at 0.01 to 2% by mass, such as 0.05 to 1.5% by mass, such as 0.1 to 0.5% by mass, based on the total mass of the additive concentrate. The additive concentrate as described in the preceding paragraph. 30. Further comprising one or more antiwear agents, (g) The one or more antiwear agents are present at 0.1 to 5% by mass, such as 1 to 2.4% by mass, such as 1.5 to 2.2% by mass, based on the total mass of the additive concentrate. The additive concentrate as described in the preceding paragraph. 31. A lubricating oil composition, (A) At least 50% by mass, based on the total mass of the lubricating oil composition, of one or more base oils, and (B) The additive concentrate described in the preceding paragraph A lubricating oil composition obtained by including or mixing. 32. The lubricating oil composition according to paragraph 31, wherein the one or more base oils include one or more Group III base oils and optionally one or more Group II base oils. 33. The lubricating oil composition according to paragraph 31 or 32, wherein the one or more base oils include a mixture of one or more Group III base oils and one or more Group II base oils. 34. The lubricating oil composition according to paragraphs 31 to 33, wherein the one or more Group III base oils and the one or more Group II base oils are present in a ratio of about 70:30 to about 30:70, such as about 65:35 to about 40:60, such as about 60:40 to about 45:55, such as about 55:45 to about 50:50. 35. The lubricating oil composition according to paragraphs 31 to 34, including 50 to 95% by mass, such as 60 to 90% by mass, such as 65 to 85% by mass, of one or more base oils based on the total mass of the lubricating oil composition. 36. (A)(a) Based on the total mass of the lubricating oil composition, 25 to 65% by mass, such as 30 to 55% by mass, such as 34 to 48% by mass, of one or more Group III base oils, and (b) Based on the total mass of the lubricating oil composition, 20 to 60% by mass, such as 28 to 48% by mass, such as 30 to 38% by mass, of one or more Group II base oils The lubricating oil composition according to paragraphs 31 to 35, including. 37. (B)(a) Based on the total mass of the lubricating oil composition, 1 to 12% by mass, such as 3 to 10% by mass, such as 6 to 8% by mass, of a dispersant mixture, (b) Optionally, based on the total mass of the lubricating oil composition, 0.1 to 10% by mass, such as 3 to 8% by mass, such as 3.5 to 5% by mass, of one or more antioxidants, (c) Optionally, based on the total mass of the lubricating oil composition, 0.01 to 3% by mass, such as 0.1 to 1% by mass, such as 0.2 to 0.6% by mass, of one or more detergents, (d) Optionally, based on the total mass of the lubricating oil composition, one or more friction modifiers in an amount of 0.001 to 0.2% by mass, for example 0.01 to 0.06% by mass, for example 0.02 to 0.04% by mass, (e) Optionally, based on the total mass of the lubricating oil composition, one or more anti-foaming agents in an amount of 0.001 to 0.1% by mass, for example 0.003 to 0.03% by mass, for example 0.005 to 0.01% by mass, (f) Optionally, based on the total mass of the lubricating oil composition, one or more corrosion inhibitors / rust preventives in an amount of 0.001 to 1% by mass, for example 0.01 to 0.5% by mass, for example 0.05 to 0.1% by mass, (g) Optionally, based on the total mass of the lubricating oil composition, one or more anti-wear agents in an amount of 0.01 to 1.5% by mass, for example 0.05 to 1% by mass, for example 0.06 to 0.6% by mass The lubricating oil composition according to paragraphs 31 to 36, comprising 38. (C)(a) One or more pour point depressants in an amount of 0.001 to 1% by mass, for example 0.01 to 0.5% by mass, for example 0.05 to 0.2% by mass, based on the total mass of the lubricating oil composition The lubricating oil composition according to paragraphs 31 to 37, further comprising 39. (C)(b) One or more viscosity modifiers in an amount of 0.001 to 0.5% by mass, for example 0.05 to 0.3% by mass, for example 0.1 to 0.22% by mass, based on the total mass of the lubricating oil composition The lubricating oil composition according to paragraphs 31 to 38, further comprising 40. The lubricating oil composition according to paragraph 39, wherein the one or more viscosity modifiers are selected from olefin copolymer viscosity modifiers. 41. (A)(a) One or more Group III base oils are present in an amount of 38 to 42% by mass based on the total mass of the lubricating oil composition, (b) One or more Group II base oils are present in an amount of 33 to 37% by mass based on the total mass of the lubricating oil composition, (B)(a)(1) The functionalized polymer is present in an amount of 0.2 to 1% by mass based on the total mass of the lubricating oil composition, (2) One or more chloro dispersants are present in an amount of 4 to 6% by mass based on the total mass of the lubricating oil composition, (3) One or more heat dispersants are present at 0.5 to 2% by mass based on the total mass of the lubricating oil composition, (b) One or more antioxidants are present at 3.5 to 5% by mass based on the total mass of the lubricating oil composition, (c) One or more detergents are present at 0.2 to 0.6% by mass based on the total mass of the lubricating oil composition, (d) One or more friction modifiers are present at 0.02 to 0.04% by mass based on the total mass of the lubricating oil composition, (e) One or more defoamers are present at 0.005 to 0.01% by mass based on the total mass of the lubricating oil composition, (f) One or more corrosion inhibitors / rust preventives are present at 0.05 to 0.1% by mass based on the total mass of the lubricating oil composition, (g) One or more antiwear agents are present at 0.06 to 0.6% by mass based on the total mass of the lubricating oil composition, (C)(a) One or more pour point depressants are present at 0.05 to 0.2% by mass based on the total mass of the lubricating oil composition, (b) One or more viscosity modifiers are present at 0.1 to 0.22% by mass based on the total mass of the lubricating oil composition. The lubricating oil composition described in paragraphs 31 to 40. 42. The lubricating oil composition described in paragraphs 31 to 41, having a phosphorus content of less than 800 ppm, for example less than 550 ppm, for example less than 500 ppm, for example less than 490 ppm, based on the total mass of the lubricating oil composition. 43. The lubricating oil composition described in paragraphs 31 to 42, having a sulfuric acid ash (SASH) content of less than 0.9% by mass, for example less than 0.6% by mass, for example less than 0.5% by mass, based on the total mass of the lubricating oil composition. 44. The lubricating oil composition described in paragraphs 31 to 43, having a phosphorus content of less than 550 ppm or about 550 ppm, and a SASH content of less than 0.5% by mass or about 0.5% by mass. 45. The lubricating oil composition described in paragraphs 31 to 44, exhibiting an SAE viscosity grade of 5W-X, where X represents any one of 8, 12, 16, 20, or 30. 46. The lubricating oil composition described in paragraphs 31 to 45, exhibiting an SAE viscosity grade of 5W-30. 47. The lubricating oil composition according to paragraphs 31 to 46, which is a large diesel engine oil. 48. The lubricating oil composition according to paragraphs 31 to 47, wherein the average piston cleanliness is at least 70%, such as at least 75%, such as at least 78%, as determined by CEC L-118-21. 49. The lubricating oil composition according to paragraphs 31 to 48, wherein the average wear of the gear train wheel is at least 75%, such as at least 80%, such as at least 82%, as determined by CEC L-118-21. 50. The lubricating oil composition according to paragraphs 31 to 49, wherein the average liner wear is less than 8 μm, such as less than 5 μm, such as less than 3 μm, as determined by CEC L-118-21. 51. The lubricating oil composition according to paragraphs 31 to 50, wherein the average turbocharger housing deposit is at least 30%, such as at least 45%, such as at least 75%, as determined by CEC L-118-21. 52. The lubricating oil composition according to paragraphs 31 to 47, wherein the oxidation is less than 65 A / cm, such as less than 60 A / cm, such as less than 55 A / cm, as determined by CEC L-118-21. 53. A method for lubricating an internal combustion engine during operation of the engine, comprising: (i) supplying the lubricating composition according to paragraphs 31 to 52 to the crankcase of the internal combustion engine; (ii) supplying a hydrocarbon fuel to the internal combustion engine; and (iii) burning the fuel in the internal combustion engine. A method comprising the above steps. 64. The method according to paragraph 53, wherein the fuel is one or more of a hydrocarbon fuel, a renewable fuel, a hydrogen fuel, or any blend thereof. 55. The method according to paragraph 52 or 54, wherein the fuel is a hydrocarbon fuel. 56. The method according to paragraphs 53 to 55, wherein the engine is a diesel engine, such as a large diesel engine. 57. A lubricating oil composition as described in paragraphs 31 to 52, and a fuel composition comprising one or more of a hydrocarbon fuel, a renewable fuel, a hydrogen fuel, or any blend thereof. 58. A method for increasing the piston cleanliness of a lubricating oil composition, comprising the step of including a dispersant mixture in the lubricating oil composition, the dispersant mixture comprising (1) 0.01 to 15% by mass, based on the total mass of the dispersant mixture, of an amide, imide, and / or ester-functionalized partially or fully saturated polymer containing C 4~5 olefins, i) having an Mw / Mn of less than 2, ii) a functionality distribution (Fd) value of 3.5 or less, and iii) an Mn of the polymer before functionalization of 10,000 g / mol or more (GPC-PS), an amide, imide, and / or ester-functionalized partially or fully saturated polymer having the above properties, and (2) 50 to 90% by mass, based on the total mass of the dispersant mixture, of one or more poly(alkenyl)succinimides ( "chloro-dispersants") derived from polyalkenyl-substituted succinic anhydrides and polyamines prepared using a chlorine-assisted alkylation method, and (3) 10 to 30% by mass, based on the total mass of the dispersant mixture, of one or more poly(alkenyl)succinimides ( "thermal dispersants") derived from polyalkenyl succinic anhydrides and polyamines prepared using a halogen-free thermal alkylation method A method comprising the above components. 59. The method according to paragraph 58, wherein the average piston cleanliness increases to at least 70%, such as at least 75%, such as at least 78%, as determined by CEC L-118-21. 60. A method for improving the wear resistance of a lubricating oil composition, comprising the step of including a dispersant mixture in the lubricating oil composition, the dispersant mixture comprising (1) 0.01 to 15% by mass, based on the total mass of the dispersant mixture, of an amide, imide, and / or ester-functionalized partially or fully saturated polymer containing C 4~5 olefins, i) An Mw / Mn of less than 2, ii) A functionality distribution (Fd) value of 3.5 or less, and iii) An Mn of the polymer before functionalization of 10,000 g / mol or more (GPC-PS) having an amide, imide, and / or ester functionalized partially or fully saturated polymer, and (2) One or more poly(alkenyl) succinimides (''chloro dispersants'') derived from polyalkenyl-substituted succinic anhydride and polyamine prepared using a chlorine-assisted alkylation process, in an amount of 50 to 90% by mass based on the total mass of the dispersant mixture, and (3) One or more poly(alkenyl) succinimides (''thermal dispersants'') derived from polyalkenyl succinic anhydride and polyamine prepared using a halogen-free thermal alkylation process, in an amount of 10 to 30% by mass based on the total mass of the dispersant mixture A method comprising. 61. The method according to paragraph 58, wherein the average wear of the gear train wheel is at least 75%, such as at least 80%, such as at least 82%, determined by CEC L-118-21. 62. The method according to paragraph 58 or 59, wherein the average liner wear is less than 8 μm, such as less than 5 μm, such as less than 3 μm, determined by CEC L-118-21.

[0261] The present invention further relates to the following. A1. An additive concentrate (or additive package) comprising a dispersant mixture, the dispersant mixture comprising (1) 0.01 to 15% by mass, based on the total mass of the dispersant mixture, of a C 4~5 amide, imide, and / or ester functionalized partially or fully saturated polymer containing olefins, i) An Mw / Mn of less than 2, ii) A functionality distribution (Fd) value of 3.5 or less, and iii) An Mn of the polymer before functionalization of 10,000 g / mol or more (GPC-PS) having an amide, imide, and / or ester functionalized partially or fully saturated polymer, and (2) 50 to 90% by mass, based on the total mass of the dispersant mixture, of one or more poly(alkenyl) succinimides derived from polyalkenyl-substituted succinic anhydride and polyamine prepared using a chlorine-assisted alkylation method ("chloro dispersant"); and (3) 10 to 30% by mass, based on the total mass of the dispersant mixture, of one or more poly(alkenyl) succinimides derived from polyalkenyl succinic anhydride and polyamine prepared using a halogen-free thermal alkylation method ("thermal dispersant") An additive concentrate comprising. A2. One or more thermal dispersants are derived from polyisobutylene succinic anhydride ("PIBSA") and polyamine ("PAM"), preferably PIBSA is based on high vinylidene content polyisobutylene (highly reactive polyisobutylene, "HR-PIB"), and / or PIBSA is based on polyisobutylene having a Mn of at least 1200 g / mol, such as at least 1500 g / mol, such as at least 1800 g / mol, such as at least 2200 g / mol, or at least 2300 g / mol, the additive concentrate according to paragraph A1. A3. The dispersant mixture comprises 1 to 12% by mass, such as 5 to 11% by mass, such as 7.5 to 10.5% by mass, such as 8.5 to 10% by mass of a functionalized polymer, based on the total mass of the dispersant mixture, and / or the dispersant mixture comprises 55 to 85% by mass, such as 62 to 82% by mass, such as 68 to 80% by mass, such as 70 to 76% by mass of one or more chloro dispersants, based on the total mass of the dispersant mixture, and / or the dispersant mixture comprises 12 to 25% by mass, such as 14 to 22% by mass, such as 15 to 20% by mass, such as 15.5 to 17.5% by mass of one or more thermal dispersants, based on the total mass of the dispersant mixture, the additive concentrate according to paragraph A1 or A2. A4. The dispersant mixture comprises one or more chloro dispersants and one or more thermal dispersants in a ratio of about 9:1 to about 3:2, such as about 6:1 to about 3:1, such as about 5:1 to about 4:1, especially about 9:2, the additive concentrate according to the preceding paragraphs A1 - A3. A5. Further comprising one or more antioxidants, preferably, the one or more antioxidants are at least one or more amine antioxidants, more preferably, the one or more antioxidants are a mixture of one or more amine antioxidants and one or more phenolic antioxidants, in particular, the one or more amine antioxidants and the one or more phenolic antioxidants are present in a ratio of about 5:2 to about 9:5, such as about 2:1, the additive concentrate described in the preceding paragraphs A1 - A4. A6. (a) The dispersant mixture is present at 15 - 40% by mass, such as 20 - 32% by mass, such as 25 - 30% by mass, based on the total mass of the additive concentrate. (b) The one or more antioxidants are optionally present at 5 - 25% by mass, such as 10 - 22% by mass, such as 14 - 20% by mass, based on the total mass of the additive concentrate. The additive concentrate described in the preceding paragraphs A1 - A5. A7. Further comprising one or more additional additives selected from the group consisting of detergents, friction modifiers, defoamers, corrosion inhibitors / rust preventives (e.g., one or more triazole amine corrosion inhibitors), and antiwear agents, in particular further comprising one or more detergents, the additive concentrate described in the preceding paragraphs A1 - A6. 8. i. The one or more detergents are present at 0.1 - 5% by mass, such as 0.5 - 4% by mass, such as 1 - 3% by mass, based on the total mass of the additive concentrate, and / or further comprising one or more friction modifiers, preferably, ii. The one or more friction modifiers are present at 0.01 - 1% by mass, such as 0.02 - 0.5% by mass, such as 0.05 - 0.2% by mass, based on the total mass of the additive concentrate, and / or further comprising one or more defoamers, preferably, iii. The one or more defoamers are present at 0.001 - 0.5% by mass, such as 0.01 - 0.1% by mass, such as 0.02 - 0.04% by mass, based on the total mass of the additive concentrate, and / or further comprising one or more corrosion inhibitors / rust preventives, preferably, iv. One or more corrosion inhibitors / rust preventives are present at 0.01 to 2% by mass, such as 0.05 to 1.5% by mass, such as 0.1 to 0.5% by mass, based on the total mass of the additive concentrate, and / or further contain one or more antiwear agents, preferably, v. One or more antiwear agents are present at 0.1 to 5% by mass, such as 1 to 2.4% by mass, such as 1.5 to 2.2% by mass, based on the total mass of the additive concentrate, The additive concentrate described in paragraph A7. A9. A lubricating oil composition, (A) At least 50% by mass of one or more base oils, based on the total mass of the lubricating oil composition, and (B) The additive concentrate described in any one of paragraphs A1 to A8 A lubricating oil composition obtained by including or mixing them. A10. One or more base oils include one or more Group III base oils and optionally one or more Group II base oils, preferably a mixture of one or more Group III base oils and one or more Group II base oils. In particular, one or more Group III base oils and one or more Group II base oils are present in a ratio of about 70:30 to about 30:70, such as about 65:35 to about 40:60, such as about 60:40 to about 45:55, such as about 55:45 to about 50:50, for the lubricating oil composition described in paragraph A9. A11. Includes 50 to 95% by mass, such as 60 to 90% by mass, such as 65 to 85% by mass of one or more base oils, based on the total mass of the lubricating oil composition, preferably, (A)(a) 25 to 65% by mass, such as 30 to 55% by mass, such as 34 to 48% by mass of one or more Group III base oils, based on the total mass of the lubricating oil composition, and (b) 20 to 60% by mass, such as 28 to 48% by mass, such as 30 to 38% by mass of one or more Group II base oils For the lubricating oil composition described in paragraph A9 or A10. A12. (B)(a) A dispersant mixture of 1 to 12% by mass, such as 3 to 10% by mass, such as 6 to 8% by mass, based on the total mass of the lubricating oil composition, (b) Optionally, based on the total mass of the lubricating oil composition, one or more antioxidants in an amount of 0.1 to 10% by mass, for example 3 to 8% by mass, for example 3.5 to 5% by mass, (c) Optionally, based on the total mass of the lubricating oil composition, one or more detergents in an amount of 0.01 to 3% by mass, for example 0.1 to 1% by mass, for example 0.2 to 0.6% by mass, (d) Optionally, based on the total mass of the lubricating oil composition, one or more friction modifiers in an amount of 0.001 to 0.2% by mass, for example 0.01 to 0.06% by mass, for example 0.02 to 0.04% by mass, (e) Optionally, based on the total mass of the lubricating oil composition, one or more antifoaming agents in an amount of 0.001 to 0.1% by mass, for example 0.003 to 0.03% by mass, for example 0.005 to 0.01% by mass, (f) Optionally, based on the total mass of the lubricating oil composition, one or more corrosion inhibitors / rust preventives in an amount of 0.001 to 1% by mass, for example 0.01 to 0.5% by mass, for example 0.05 to 0.1% by mass, (g) Optionally, based on the total mass of the lubricating oil composition, the lubricating oil composition contains one or more antiwear agents in an amount of 0.01 to 1.5% by mass, for example 0.05 to 1% by mass, for example 0.06 to 0.6% by mass, preferably, (C) (a) Based on the total mass of the lubricating oil composition, one or more pour point depressants in an amount of 0.001 to 1% by mass, 0.01 to 0.5% by mass, for example 0.05 to 0.2% by mass, and / or (b) Based on the total mass of the lubricating oil composition, one or more viscosity modifiers in an amount of 0.001 to 0.5% by mass, for example 0.05 to 0.3% by mass, for example 0.1 to 0.22% by mass The lubricating oil composition according to paragraphs 9 to 11, further comprising. A13. Having a phosphorus content of less than 800 ppm, for example less than 550 ppm, for example less than 500 ppm, for example less than 490 ppm, based on the total mass of the lubricating oil composition, and / or having a sulfuric acid ash ("SASH") content of less than 0.9% by mass, for example less than 0.6% by mass, for example less than 0.5% by mass, based on the total mass of the lubricating oil composition, in particular, having a phosphorus content of less than 550 ppm or about 550 ppm and a SASH content of less than 0.5% by mass or about 0.5% by mass, the lubricating oil composition according to paragraphs A9 to A12. The average piston cleanliness is at least 70%, for example at least 75%, for example at least 78%, as determined by CEC L-118-21, and / or the average wear of the gear train wheels is at least 75%, for example at least 80%, for example at least 82%, as determined by CEC L-118-21, and / or the average wear of the liner is less than 8 μm, for example less than 5 μm, for example less than 3 μm, as determined by CEC L-118-21, and / or the average turbocharger housing deposits are at least 30%, for example at least 45%, for example at least 75%, as determined by CEC L-118-21, and / or the oxidation is less than 65 A / cm, for example less than 60 A / cm, for example less than 55 A / cm, as determined by CEC L-118-21, the lubricating oil composition according to paragraphs A9 to A13. A15. A method for lubricating an internal combustion engine during operation of the engine, (i) supplying the lubricating composition according to paragraphs A9 to A14 to the crankcase of the internal combustion engine, (ii) supplying fuel to the internal combustion engine, and (iii) combusting the fuel in the internal combustion engine comprising preferably, the fuel is one or more of a hydrocarbon fuel (e.g., a petroleum-derived fuel and / or a renewable fuel), and / or a hydrogen fuel, or any mixture thereof, particularly a hydrocarbon fuel, and / or the engine is a diesel engine, e.g., a large diesel engine, method. A16. A fuel composition comprising the lubricating composition according to paragraphs A9 to A14 and one or more of a hydrocarbon fuel, a hydrogen fuel, or any blend thereof (preferably the hydrocarbon fuel comprises a petroleum-derived fuel and / or a renewable fuel). A17. A method for increasing the piston cleanliness of a lubricating oil composition, comprising the step of including a dispersant mixture in the lubricating oil composition, the dispersant mixture being (1) 0.01 to 15% by mass, based on the total mass of the dispersant mixture, of C 4~5An amide, imide, and / or ester functionalized partially or fully saturated polymer containing olefins, i) an Mw / Mn of less than 2, ii) a functionality distribution (Fd) value of 3.5 or less, and iv) an Mn of the polymer before functionalization of 10,000 g / mol or more (GPC-PS), an amide, imide, and / or ester functionalized partially or fully saturated polymer, and (2) one or more poly(alkenyl) succinimides ( "chloro dispersants") derived from polyalkenyl substituted succinic anhydride and polyamine prepared using a chlorine assisted alkylation process, 50 to 90% by mass based on the total mass of the dispersant mixture, and (3) one or more poly(alkenyl) succinimides ( "thermal dispersants") derived from polyalkenyl succinic anhydride and polyamine prepared using a halogen-free thermal alkylation process, 10 to 30% by mass based on the total mass of the dispersant mixture comprising, preferably, the average piston cleanliness increases to at least 70%, such as at least 75%, such as at least 78% as determined by CEC L-118-21. A18. A method for improving the wear resistance of a lubricating oil composition, comprising the step of including a dispersant mixture in the lubricating oil composition, the dispersant mixture comprising (1) 0.01 to 15% by mass based on the total mass of the dispersant mixture of a C 4~5 an amide, imide, and / or ester functionalized partially or fully saturated polymer containing olefins, i) an Mw / Mn of less than 2, ii) a functionality distribution (Fd) value of 3.5 or less, and v) an Mn of the polymer before functionalization of 10,000 g / mol or more (GPC-PS), an amide, imide, and / or ester functionalized partially or fully saturated polymer, and (2) 50 to 90% by mass, based on the total mass of the dispersant mixture, of one or more poly(alkenyl) succinimides derived from polyalkenyl-substituted succinic anhydride and polyamine prepared using a chlorine-assisted alkylation method (the "chloro dispersant"); and (3) 10 to 30% by mass, based on the total mass of the dispersant mixture, of one or more poly(alkenyl) succinimides derived from polyalkenyl succinic anhydride and polyamine prepared using a halogen-free thermal alkylation method (the "thermal dispersant") comprising Preferably, the average wear of the gear train wheel is increased by at least 75%, such as at least 80%, such as at least 82%, as determined by CEC L-118-21, and / or the average liner wear is reduced to less than 8 μm, such as less than 5 μm, such as less than 3 μm, as determined by CEC L-118-21.

[0262] The following non-limiting examples are provided to illustrate the present disclosure. Experiment All molecular weights are number average molecular weights (Mn) determined by gel permeation chromatography using polystyrene standards and reported in g / mol, unless otherwise stated. "A.I.", "ai", "a.i.", and "ai" are active ingredients in mass %, unless otherwise indicated.

[0263] Test procedure The viscosity index is measured according to ASTM D2270. The high-temperature high-shear viscosity ("HTHS" or "HTHS150") is determined at 150 °C according to ASTM D4683 and reported in cPs. KV100 is the kinematic viscosity measured at 100 °C according to ASTM D445-19a. Unless otherwise indicated, the cold cranking simulator ("CCS") at -25 °C is a measure of the cold cranking properties of a crankcase lubricant and is determined as described in ASTM D5293-92. The Noack volatility ("Noack") is determined by the Noack test (ASTM D5800, Procedure B). The phosphorus content is measured by ASTM D4951. The sulfuric acid ash ("SASH") content is measured by ASTM D874.

[0264] The Mack T11 test for soot-induced viscosity control, ASTM D7156-19, was performed on a Mack E-TECH V-MAC III diesel engine with an exhaust gas recirculation device. Oil flushing for 30 minutes was carried out twice, followed by operation at a constant speed of 1800 rpm for 252 hours. The fuel injection timing was adjusted according to the soot level (thermos-gravimetric analysis (TGA), ASTM D5967) targets at 96 hours, 192 hours, and 228 hours. Specifically, the TGA soot level was 2.75% + / - 0.25% at 96 hours, 5.50% + / - 0.35% at 192 hours, and 6.53% + / - 0.44% at 228 hours. Oil samples were taken every 12 hours, and the soot level (TGA, ASTM D5967) and kinematic viscosity at 100 °C were measured. The performance of the oil was determined by comparing the soot levels at which the specified viscosity increases (4 cSt, 12 cSt, and 15 cSt) were observed. Also, the oil consumption was measured.

[0265] The Caterpillar 1N test for piston deposits was performed according to ASTM D6750-19. Also, the oil consumption was measured. The test was performed on a single-cylinder Caterpillar 1Y540 diesel engine (this engine was operated under the conditions detailed in Table A14.1 of ASTM D6750-19 for a 60-minute conditioning period, followed by 252 hours of test conditions). The piston was then removed and evaluated according to the procedure outlined in the ASTM Deposit Evaluation Manual 20. Note that ASTM D6750 covers both the 1K procedure with 0.4% fuel sulfur and the 1N procedure with 0.04% fuel sulfur.

[0266] Cummins ISM Engine Test. Valve train wear protection was determined in a Cummins ISM engine test in a 10.8L six-cylinder diesel engine equipped with an exhaust gas recirculation device, according to ASTM D7468-21. The Cummins ISB test covers a large diesel engine test procedure conducted under high soot conditions to evaluate oil performance regarding valve train wear, top ring wear, sludge deposition, and oil filter plugging. The engine is operated for 200 hours in four stages of 50 hours each. Under the stage A and B test conditions, the fuel injection timing is retarded to generate soot and the engine is operated at 1800 RPM at rated output. Under the stage B and D test conditions, the engine is operated at 1600 RPM at instantaneous maximum torque to promote and evaluate the wear of injector adjustment screws, crossheads, and upper piston rings. Oil performance was evaluated by assessing injector adjustment screws, crossheads, top ring wear, oil filter plugging, oil pans, and valve cover sludge formation. By combining these parameters, an overall merit result compliant with ASTM D7468 was established.

[0267] Cummins ISB Engine Test. Valve train wear protection was determined in a Cummins ISB engine test in a 5.9L six-cylinder diesel engine equipped with an exhaust gas recirculation device, according to ASTM D7484-21. The Cummins ISB test is a two-stage test. In stage A, the engine was operated for 100 hours with the fuel injection timing retarded to generate excessive soot according to the ASTM protocol. In stage B, the engine was operated for 250 hours under cycle conditions according to the ASTM protocol to induce valve train wear. Oil performance was determined by evaluating the crosshead mass loss (mg) measured as detailed in section 8.1.5 of ASTM D7484-21, the tappet mass loss (mg) measured as detailed in section 8.1.6 of ASTM D7484-21, and the camshaft wear (μm) averaged over 12 lobes measured using a Mitutoyo snap gauge and a Mitutoyo digital indicator as detailed in section 8.1.7 of ASTM D7484-21.

[0268] The Daimler OM471 FE1 performance test was carried out in Germany in accordance with CEC L-118-21 using APL (Oil D, Oil E, Comparative Oil B1) or ISP (Oil F) based on the Daimler / Mercedes-Benz in-house test method. The OM471 is a EURO VI 12.8L 6-cylinder engine that generates a maximum output of 375 kilowatts and an instantaneous maximum torque of 2500 Newton meters. This test is designed to test the performance of lubricating oil against piston deposits. This is an extensive (over 600 hours) HDD engine test required to meet various OEM and industry specifications, including DTFR 15C130. At the end of this test, there are several important test parameters that need to meet the limit values set by Daimler to pass the test. Such parameters include sludge in the oil mist separator (≧95%), piston cleanliness, grooves (average ≧74%), liner wear (average ≦8 μm), turbocharger housing deposits (average ≧30%), wear of the gear train wheels (single ≧70%, average ≧75%), oxidation (≦65 A / cm μm), and specific oil consumption (≦8 g / hour).

[0269] The moments of molecular weight (Mw, Mn, Mz) were determined as follows by gel permeation chromatography (“GPC-PS”) using polystyrene standards (Acquity™ APC Polystyrene High Molecular Weight Calibration Kit, 266 - 1,760,000 Da) and software (Empower™ 3, version 7.41.00.00) provided by the vendor. Molecular weight [number average molecular weight (Mn), mass average molecular weight (Mw), and z average molecular weight (Mz)] is determined using an Agilent Acuity P-SM-FTN and P-15m high temperature GPC-SEC (gel permeation / size exclusion chromatograph) equipped with an online differential refractive index (DRI) detector and PDA UV detectors at wavelengths of 215, 254, and 304. In GPC, three Agilent PLgel 10 micron Mixed B LS columns are used. Column separation is carried out using a flow rate of 0.25 mL / min and a nominal injection volume of 10 microliters. The detector and columns are maintained at 30 °C in low flow mode (idle) and heated to 35 °C in preparation for sample runs. The flow emerging from the SEC column is sent to an optical flow cell and then to the DRI detector. The solvent for the SEC experiment is un-inhibited THF (tetrahydrofuran). The polymer solution is prepared by placing the dry polymer in a glass container and adding the desired amount of THF. After adding the sample to the machine, wait until it reaches 35 °C before starting the run. GPC performs the programmed equilibration before the run for approximately 1.5 hours. The sample is stirred for 2 - 15 hours depending on solubility. The sample is filtered after stirring and before the run. All amounts are measured by gravimetry. 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, purge the DRI detector and injector. Then increase the flow rate of the apparatus from 0.01 to 0.25 mL / min and stabilize the DRI for 4 - 5 hours before injecting the first sample. The software used to run GPC and prepare the report is Empower™ 3, version 7.41.00.00.

[0270] "FG" means a functional group. The average functionality [also called the average functionality value (Fv)] and functionality distribution (Fd) values are determined as follows. A simple non-polymeric substance having an ADPA-imide functional group (ODSA-ADPA) was prepared according to the following procedure and then used as a reference substance and calibration substance for functional group GPC analysis as further described below.

[0271] 268 g of octadecenyl succinic anhydride (isomer mixture, 0.094 mol) was added to a four-necked round-bottom flask equipped with an air-driven stirrer, a temperature controller, a thermocouple connected to an electric heating mantle, and a nitrogen inlet. This substance was continuously stirred while flowing nitrogen continuously from the reactor headspace and heated to 170 °C. 17.2 g of 4-aminodiphenylamine (ADPA, 0.094 mol) was added to the hot reaction mixture in several portions and allowed time until the bubbles ceased completely when continuing the amine addition. The mixture was heated until the reaction was determined to be complete by FTIR analysis of the anhydride peak and imide peak at approximately 1780 and 1700 cm-1, respectively (the anhydride peak was completely consumed and the imide peak did not increase any further for approximately 2 to 3 hours). The substance was cooled partially (below 100 °C) before discharging from the reactor. It was used directly as a GPC calibration substance without further purification.

[0272] A GPC calibration curve (shown in Figure 1 of U.S. Patent Application No. 18 / 480,571, filed October 4, 2023, claiming priority to U.S. Patent Application No. 63 / 379,006, filed October 11, 2022) was created from ODSA-ADPA samples of 0.01, 0.02, 0.03, 0.04, and 0.05 mg / ml according to the GPC procedure described above, and the UV 304 nm channel was integrated.

[0273] A sample of the functional polymer was prepared and subjected to GPC analysis as described above. The chromatogram was integrated by drawing a flat baseline along the solvent baseline across the base of each peak. If the chromatogram peaks were not separated to the baseline (the baseline indicated by triangles on the horizontal axis of Figure 2), they were vertically cut at the minimum point between them (indicated by diamonds on the horizontal axis of Figure 2 of U.S. Patent Application No. 18 / 480,571, filed October 4, 2023, claiming priority to U.S. Patent Application No. 63 / 379,006, filed October 11, 2022). The minimum point is the inflection point of the GPC trace, the point at which the sign of the second derivative of the curve changes (e.g., from negative to positive, or vice versa). For the purposes of calculating the average functionality value (Fv) and functionality distribution (Fd), any chain coupling polymers and chain fragmentation polymers separated from the main polymer peak should be included as part of the main peak in all calculations (Mn, Mw, PDI (Mw / Mn), and any subsequent calculations). A representative chromatogram of the GPC analysis is shown in Figure 2 of U.S. Patent Application No. 18 / 480,571, filed October 4, 2023, claiming priority to the specification of U.S. Patent Application No. 63 / 379,006, filed October 11, 2022).

[0274] The average functionality value (Fv) of the sample is defined as the average number of functional groups per polymer chain across the entire sample and is calculated by Equation 1.

Equation

[0275] The functionality distribution (Fd) value represents the range of functionality across the MW distribution in the sample (i.e., the diffe...

Claims

Claim 1 An additive concentrate comprising a dispersant mixture, wherein the dispersant mixture (1) 0.01 to 15% by mass, based on the total mass of the dispersant mixture, of a C 4~5 amide, imide, and / or ester functionalized partially or fully saturated polymer containing olefins, i) has an Mw / Mn of less than 2, ii) has a functionality distribution (Fd) value of 3.5 or less, and iii) has an Mn of the polymer before functionalization of 10,000 g / mol or more (GPC-PS) and is an amide, imide, and / or ester functionalized partially or fully saturated polymer, and (2) one or more poly(alkenyl) succinimides ( "chloro dispersants") derived from polyalkenyl-substituted succinic anhydride and polyamine prepared using a chlorine-assisted alkylation method, which is 50 to 90% by mass based on the total mass of the dispersant mixture, and (3) one or more poly(alkenyl) succinimides ( "thermal dispersants") derived from polyalkenyl-substituted succinic anhydride and polyamine prepared using a halogen-free thermal alkylation method, which is 10 to 30% by mass based on the total mass of the dispersant mixture An additive concentrate comprising the same. Claim 2 The one or more thermal dispersants are derived from polyisobutylene succinic anhydride ( "PIBSA") and polyamine ( "PAM"), and the PIBSA is based on high terminal vinylidene content polyisobutylene (highly reactive polyisobutylene, "HR-PIB"), and the PIBSA is based on polyisobutylene having an Mn of at least 1200 g / mol. The additive concentrate according to Claim 1. Claim 3 The dispersant mixture comprises 1) 1 to 12% by mass of the functionalized polymer based on the total mass of the dispersant mixture, 2) one or more chloro dispersants of 55 to 85% by mass based on the total mass of the dispersant mixture, and 3) one or more thermal dispersants of 12 to 25% by mass based on the total mass of the dispersant mixture. The additive concentrate according to Claim 1. Claim 4 The dispersant mixture comprises the one or more chloro dispersants and the one or more thermal dispersants in a ratio of about 9:1 to about 3:

2. The additive concentrate according to Claim 1. Claim 5 Further comprising one or more antioxidants, wherein (1) the one or more antioxidants are at least one or more amine antioxidants, or (2) the one or more antioxidants are a mixture of one or more amine antioxidants and one or more phenolic antioxidants, and the one or more amine antioxidants and the one or more phenolic antioxidants are present in a ratio of about 5:2 to about 9:

5. The additive concentrate according to claim 1.

6. (a) The dispersant mixture is present at 15 to 40% by mass based on the total mass of the additive concentrate, (b) One or more antioxidants are optionally present at 5 to 25% by mass based on the total mass of the additive concentrate. The additive concentrate according to claim 1.

7. The additive concentrate according to claim 1, further comprising one or more additional additives selected from the group consisting of detergents, friction modifiers, defoamers, corrosion inhibitors / rust preventives, and antiwear agents.

8. The additive concentrate according to claim 1, further comprising one or more triazole amine corrosion inhibitors.

9. i. One or more detergents are present at 0.1 to 5% by mass based on the total mass of the additive concentrate, ii. Optionally, one or more friction modifiers are present at 0.01 to 1% by mass based on the total mass of the additive concentrate, and / or iii. Optionally, one or more defoamers are present at 0.001 to 0.5% by mass based on the total mass of the additive concentrate, and / or iv. One or more corrosion inhibitors / rust preventives are present at 0.01 to 2% by mass based on the total mass of the additive concentrate, and / or v. Optionally, one or more antiwear agents are present at 0.1 to 5% by mass based on the total mass of the additive concentrate. The additive concentrate according to claim 7.

10. A lubricating oil composition comprising: (A) at least 50% by mass of one or more base oils based on the total mass of the lubricating oil composition, and (B) the additive concentrate according to any one of claims 1 to 9 A lubricating oil composition obtained by including or mixing.

11. The lubricating oil composition according to claim 10, wherein the one or more base oils include one or more Group III base oils and optionally one or more Group II base oils.

12. Comprising 50 to 95% by mass of one or more base oils based on the total mass of the lubricating oil composition, (a) at least 25 to 65% by mass, based on the total mass of the lubricating oil composition, of one or more Group III base oils, and (b) at least 20 to 60% by mass, based on the total mass of the lubricating oil composition, of one or more Group II base oils The lubricating oil composition according to claim 10, comprising

13. (a) 1 to 12% by mass of a dispersant mixture, based on the total mass of the lubricating oil composition, (b) optionally, one or more antioxidants in an amount of 0.1 to 10% by mass, based on the total mass of the lubricating oil composition, (c) optionally, one or more detergents in an amount of 0.01 to 3% by mass, based on the total mass of the lubricating oil composition, (d) optionally, one or more friction modifiers in an amount of 0.001 to 0.2% by mass, based on the total mass of the lubricating oil composition, (e) optionally, one or more antifoaming agents in an amount of 0.001 to 0.1% by mass, based on the total mass of the lubricating oil composition, (f) optionally, one or more corrosion inhibitors / rust preventives in an amount of 0.001 to 1% by mass, based on the total mass of the lubricating oil composition, (g) optionally, one or more antiwear agents in an amount of 0.01 to 1.5% by mass, based on the total mass of the lubricating oil composition, (h) optionally, one or more pour point depressants in an amount of 0.001 to 1% by mass, based on the total mass of the lubricating oil composition, and / or (i) one or more viscosity modifiers in an amount of 0.001 to 0.5% by mass, based on the total mass of the lubricating oil composition The lubricating oil composition according to claim 10, comprising

14. Having a phosphorus content of less than 800 ppm, alternatively less than 550 ppm, and / or a sulfuric acid ash ("SASH") content of less than 0.9% by mass, alternatively less than 0.5% by mass, based on the total mass of the lubricating oil composition, the lubricating oil composition according to claim 10.

15. 1) The average piston cleanliness is at least 70% as determined by CEC L-118-21, and / or 2) The average wear of the gear train wheels is greater than 75% as determined by CEC L-118-21, and / or 3) The average liner wear is less than 8 μm as determined by CEC L-118-21, and / or 4) The average turbocharger housing deposits are at least 30% as determined by CEC L-118-21, and / or 5) The oxidation is less than 65 A / cm as determined by CEC L-118-21, The lubricating oil composition according to claim 10.

16. A method for lubricating an internal combustion engine during operation of the engine, comprising: (i) supplying the lubricating composition according to any one of claims 10 to 15 to the crankcase of the internal combustion engine; (ii) supplying fuel to the internal combustion engine; and (iii) burning the fuel in the internal combustion engine wherein the fuel is one or more of a hydrocarbon fuel, a renewable fuel, a hydrogen fuel, or any blend thereof. **Claim 17** The method according to claim 16, wherein the fuel comprises a hydrocarbon fuel and / or the engine is a diesel engine. **Claim 18** A lubricating composition according to any one of claims 10 to 15 and a fuel composition comprising a hydrocarbon fuel, a hydrogen fuel, or one or more of any blend thereof. **Claim 19** The fuel composition according to claim 18, wherein the hydrocarbon fuel comprises a petroleum-derived fuel and / or a renewable fuel. **Claim 20** A method for increasing the piston cleanliness of a lubricating oil composition, comprising including the additive concentrate according to any one of claims 1 to 9 in the lubricating oil composition, preferably, the average piston cleanliness is increased to at least 70% as determined by CEC L-118-21. **Claim 21** A method for improving the wear resistance of a lubricating oil composition, comprising including the additive concentrate according to any one of claims 1 to 9 in the lubricating oil composition, preferably, the average wear of the gear train wheel is at least 75% as determined by CEC L-118-21 and / or the average liner wear is less than 8 μm as determined by CEC L-118-21.

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