Lubricant compositions containing low phosphorous and low sulfate ash

Abstract

The present invention relates to a lubricating oil composition having a phosphorus content of less than 800 ppm, such as less than or about 500 ppm, and an SASH content of less than 0.9%, such as less than or about 0.5%, comprising a dispersant mixture, the dispersant mixture comprises (1) 0.01-15 mass%, based on the total mass of the dispersant mixture, of an amide, imide and / or ester-functionalized, partially or fully saturated C4-5 olefin-containing 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 (GPC-PS) of the pre-functionalized polymer of 10,000 g / mol or more; and (2) 50-90 mass%, based on the total mass 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) 10-30 mass%, based on the total mass of the dispersant mixture, of one or more poly (alkenyl) succinimides derived from polyalkenyl succinic anhydrides and polyamines prepared using a halogen-free thermal alkylation process.

Description

Field of the Invention

[0001] The present disclosure relates to the use of a dispersant mixture comprising a functionalized polymer, a chlorine dispersant, and a thermal dispersant in a lubricant composition for engine crankcase applications, particularly in compression ignition engines and / or spark ignition applications, to provide robust wear, cleanliness, oxidation, and corrosion properties. Background of the Invention

[0002] The present invention relates to lubricating oil compositions that exhibit improved anti-turbocharger and piston deposit performance. More specifically, the present invention relates to automotive crankcase lubricating oil compositions for gasoline (spark ignition) and diesel (compression ignition) internal combustion engines, such compositions being referred to as crankcase lubricants; and to the use of additives in such lubricating oil compositions to improve the performance of an engine lubricated with the lubricating oil composition, particularly with respect to piston cleanliness, bushing wear, wear on gear train wheels, turbocharger housing deposits, and oxidation.

[0003] The importance placed on fuel economy has increased in recent years. One way to improve vehicle fuel economy is to design new lubricating oils that reduce friction while maintaining a good film thickness for durability and wear protection, and also prevent soot-induced viscosity increases. In the attempt to improve fuel economy, the use and specification of lower viscosity grades by original equipment manufacturers (OEMs) have become increasingly common. One of the challenges in providing engine oils and / or drivetrain lubricants with these reduced viscosity grades is to maintain cleanliness and wear protection. Such oils must be able to reduce sludging, provide good soot handling, and provide wear protection while providing the desired fuel economy benefits. These objectives should be achieved while maintaining low levels of sulfated 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.

[0004] Engine durability is an important consideration in the selection of lubricants, particularly for heavy-duty diesel (HDD) engine applications. OEMs are increasing their oil change intervals, and the average vehicle life has increased steadily over the past few decades. Similarly, there is a trend towards using ashless anti-wear agents that have a lower impact on aftertreatment systems such as diesel particulate filters in heavy-duty diesel vehicles.

[0005] In addition, environmental and regulatory requirements drive the need to improve the efficiency of internal combustion engines. Lower viscosity lubricants require less energy to pump around the engine and can thus improve its fuel economy. However, lower viscosity lubricants result in thinner oil films between the engine's contacting components (such as in the valvetrain, piston area, and bearings), which can lead to higher wear rates, reduced friction improvement, etc. Conventionally, zinc dialkyldithiophosphate (ZDDP) is often used as a lubricant additive to prevent engine wear and / or reduce friction in boundary lubrication conditions.

[0006] In addition to driving improved fuel economy, it is also desirable to reduce emissions from vehicles. Control of exhaust emissions is typically achieved through aftertreatment devices, such as catalytic converters, which commonly use noble metal catalysts to convert combustion products into less objectionable species. However, these catalysts are particularly poisoned by phosphorus and sulfur, which affects their catalytic activity. In particular, SASH and phosphorus accumulate in the diesel aftertreatment systems of HDD vehicles, especially in diesel particulate filters (DPFs). The exhaust backpressure caused by DPF SASH and phosphorus accumulation can shorten the life of the DPF, reduce fuel economy, and have a harmful effect on the catalyst, hindering the overall effectiveness of the aftertreatment system in HDD vehicles.

[0007] Typically, HDD formulations contain 800 to 1200 ppm of phosphorus and greater than 0.9% SASH to provide the required wear and cleanliness performance determined by various industry and OEM engine tests and specific requirements. The present invention now aims to provide a lubricant composition targeted at reducing SASH and phosphorus, particularly having 500 ppm of phosphorus and 0.5% SASH, while still maintaining strong wear and cleanliness performance in critical engine tests. However, the reduction of SASH and phosphorus means a reduction in the detergents and antiwear agents in the lubricant composition, which play a key role in providing strong performance in HDD lubricants.

[0008] During engine operation, oil-insoluble oxidation by-products, such as soot, are generated. Dispersants help keep these by-products suspended or dissolved, thereby reducing their deposition on metal surfaces. Common dispersants include (poly)alkenyl succinic derivatives, such as hydrocarbon-substituted succinic anhydrides, such as polyisobutylene succinic anhydride (PIBSA), and hydrocarbon-substituted succinimides, such as polyisobutylene succinimide (PIBSA-PAM), such as those derived from the reaction of maleated polyisobutylene with N-phenyl-p-phenylenediamine.

[0009] U.S. Patent Application USSN 18 / 480,571, filed October 4, 2023 (which claims priority to USSN 63 / 379,006, filed October 11, 2022), discloses amide-, imide-, and / or ester-functionalized containing specific C 4-5Use of polymers of olefins as additives in lubricant compositions to reduce wear. U.S. Patent Application USSN 63 / 584,675, filed on September 22, 2023, further discloses a lubricant composition comprising a functionalized polymer containing a specific olefin homopolymer or copolymer backbone, while conventional polyalkenyl succinimide dispersants (wherein the polyalkenyl is derived from polyisobutene and the imide is derived from polyamine (PIBSA - PAM)) are reduced or completely absent.

[0010] The inventors of the present invention have now surprisingly found that a dispersant mixture comprising the above amide, imide, and / or ester - functionalized polymers containing specific C 4-5 olefins, and poly(alkenyl) succinimides (chlorine dispersants) derived from polyalkenyl - substituted succinic anhydrides and polyamines prepared using a chlorine - assisted alkylation method and poly(alkenyl) succinimides (thermal dispersants) derived from polyalkenyl succinic anhydrides and polyamines prepared using a halogen - free thermal alkylation method can be used in lubricant compositions, such as in internal combustion engines, to provide improved wear and cleanliness performance. Furthermore, the inventors of the present invention have surprisingly found that using the said dispersant mixture in a lubricant composition enables passing the Daimler OM471FE1 performance test even at a phosphorus content of less than 800 ppm, such as less than 500 ppm, and a SASH content of less than 0.9%, such as less than 0.5%. Additionally, due to the more sustainable but effective solution proposed by the said invention, strong performance in the Daimler OM471 FE1 performance test has been observed in a semi - synthetic base oil system. SUMMARY OF THE INVENTION

[0011] The present invention relates to an additive concentrate or additive package comprising a dispersant mixture, the dispersant mixture comprising (1) 0.01 - 15% by mass, based on the total mass of the dispersant mixture, of amide, imide, and / or ester - functionalized partially or fully saturated polymers containing C 4-5 olefins, having: i) an Mw / Mn of less than 2, ii) a functionality distribution (Fd) value of 3.5 or less, and iii) an Mn (GPC - PS) of the polymer before functionalization of 10,000 g / mol or more; and (2) 50 - 90% by mass, based on the total mass of the dispersant mixture, of one or more poly(alkenyl) succinimides (“chlorine dispersants”) derived from polyalkenyl - substituted succinic anhydrides and polyamines prepared using a chlorine - assisted alkylation method; and (3) One or more poly(alkenyl)succinimides (“thermal dispersants”) derived from polyalkenyl succinic anhydrides and polyamines prepared using a halogen-free thermal alkylation method, accounting for 10-30% by mass based on the total mass of the dispersant mixture.

[0012] This disclosure further relates to a lubricating oil composition comprising the following components or obtained by mixing the following components: (A) At least 50% by mass of one or more base oils based on the total mass of the lubricating oil composition; and (B) An additive concentrate comprising a dispersant mixture, the dispersant mixture comprising (1) Amide, imide, and / or ester-functionalized partially or fully saturated polymers containing C 4-5 alkenes, accounting for 0.01-15% by mass based on the total mass of the dispersant mixture, having: i) Mw / Mn less than 2, ii) A functionality distribution (Fd) value of 3.5 or less, and iii) Mn (GPC-PS) of the polymer before functionalization of 10,000 g / mol or more; and (2) One or more poly(alkenyl)succinimides (“chlorine dispersants”) derived from polyalkenyl-substituted succinic anhydrides and polyamines prepared using a chlorine-assisted alkylation method, accounting for 50-90% 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 anhydrides and polyamines prepared using a halogen-free thermal alkylation method, accounting for 10-30% by mass based on the total mass of the dispersant mixture.

[0013] Generally, the one or more poly(alkenyl)succinimide dispersants are one or more PIBSA-PAM dispersants, i.e., those derived from polyisobutene-substituted succinic anhydrides and polyamines prepared using a chlorine-assisted alkylation method or a halogen-free thermal alkylation method.

[0014] According to another aspect of the present disclosure, there is provided the use of the above dispersant mixture for improving the piston cleanliness and / or wear resistance of a lubricating oil composition.

[0015] According to still another aspect of the present invention, there is provided the use of the above lubricating oil composition, wherein the lubricating oil composition has: a) An average piston cleanliness of more than 70%, such as more than 73%, such as more than 74%, more than 75%, such as more than 76%, more than 78%, such as more than 80%, such as more than 80.5% as measured by Daimler OM471 FE1 (CEC L-118-21), and / or b) An average wear on the gear drive wheel of more than 75%, more than 80%, such as more than 81%, more than 82%, such as more than 82.5%, such as more than 83% as measured by Daimler OM471 FE1 (CEC L-118-21), and / or c) An average bushing 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 measured by Daimler OM471 FE1 (CEC L-118-21), and / or d) Oxidation 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 measured by Daimler OM471 FE1 (CEC L-118-21).

[0016] According to a further aspect of the present invention, there is provided a crankcase lubricating oil composition comprising the following components or made by mixing the following components: (i) A major amount of one or more base oils; (ii) The above dispersant mixture.

[0017] In another aspect, the lubricating oil composition described herein contains: 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 sulfate 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.

[0018] The present invention also relates to a lubricating oil composition comprising the following components or made by mixing the following components: (i) one or more base oils, (ii) one or more poly(alkenyl) succinimide chlorine dispersants and one or more poly(alkenyl) succinimide thermal dispersants, (iii) one or more detergents, (iv) one or more antiwear agents, (v) one or more antioxidants, and (vi) one or more functionalized polymers described herein, wherein the lubricating oil composition comprises a ratio of the chlorine dispersant to the thermal dispersant of at least 4:1, and wherein the lubricating oil composition has: a) An SAE viscosity grade of 20W-X, 15W-X, 10W-X, 5W-X or 0W-X (such as 10W-X or 5W-X), where X represents any one of 8, 12, 16, 20, 30, 40 and 50 (such as 30); and b) An average piston cleanliness of more than 70%, such as more than 73%, such as more than 74%, more than 75%, such as more than 76%, more than 78%, such as more than 80%, such as more than 80.5%, as determined by Daimler OM471 FE1 (CEC L-118-21), and c) An average wear on the gear drive wheel of more than 75%, more than 80%, such as more than 81%, more than 82%, such as more than 82.5%, such as more than 83%, as determined by Daimler OM471 FE1 (CEC L-118-21), and d) An average bushing 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 e) Oxidation 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). Definition

[0019] For the purposes of this specification and all claims of the present invention, the following words and expressions have the meanings given below.

[0020] For the purposes of this text, the new numbering scheme of the periodic table of the elements as described in CHEMICAL AND ENGINEERING NEWS, 63(5), 27 (1985) is used, i.e., the alkali metals are Group 1 metals (e.g., Li, Na, K, etc.) and the alkaline earth metals are Group 2 metals (e.g., Mg, Ca, Ba, etc.).

[0021] The term "absent" (or "free of") when referring to a component or active ingredient included within a lubricating oil composition described herein and in the claims thereof means that the particular component or active ingredient is present at 0.000% by weight based on the weight of the lubricating oil composition, or if "substantially absent", the component or active ingredient is present in an amount that does not affect the properties of the lubricating oil composition, such as less than 100 ppm, such as 10 ppm, or less than 1 ppm or less than 0.001 ppm. When the term "absent" is used with respect to a monomeric reactant and / or with respect to a repeating unit in a (co)polymer described herein, it means present at 0% by weight based on the weight of all (co)monomers in the (co)polymer, or if present, in an amount so low that they do not substantially affect the physical properties of the (co)polymer, such as 0.2% by weight or less or 0.1% by weight or less.

[0022] The term "about" means approximate and includes values obtained by rounding. As used herein, the term "about" modifying the amount of a component, ingredient or reactant of the present invention being used refers to variations in numerical amounts that may occur, for example, through typical measurement and liquid handling procedures used in making concentrates or lubricating oil compositions. In addition, deviations may occur due to inadvertent errors in the measurement procedures, differences in the manufacture, source or purity of the ingredients used to make the composition or carry out the method, etc. In one aspect, the term "about" means within 10% of the reported numerical value. In another aspect, the term "about" means within 5% of the reported numerical value. In yet another aspect, the term "about" means within 10, 9, 8, 7, 6, 5, 4, 3, 2 or 1% of the reported numerical value.

[0023] The term "LOC" refers to a lubricating oil composition (this term is used interchangeably herein with the terms "lubricant oil composition" or "lubricating composition" or "lubricant composition").

[0024] The term "major amount" means more than 50% by mass of the composition, such as more than 60% by mass of the composition, such as more than 70% by mass of the composition, such as 80 to 99.009% by mass of the composition, such as 80 to 99.9% by mass of the composition, such as 80 to 99.009% by mass of the composition, based on the mass of the composition.

[0025] The term "minor amount" means 50% by mass or less of the composition; such as 40% by mass or less of the composition; such as 30% by mass or less of the composition, such as 20 to 0.001% by mass, such as 20 to 0.1% by mass, based on the mass of the composition.

[0026] Unless otherwise specified, the term "mass %" refers to the mass percentage of a component based on the mass of the composition measured in grams and is alternatively referred to as weight percentage ("weight %", "wt %" or "% w / w").

[0027] The term "active ingredient" (also referred to as "a.i." or "A.I.") refers to an additive material that is neither a diluent nor a solvent. Unless otherwise specified, amounts herein are described in terms of active ingredient. For example, a certain component in a lubricating oil composition may contain a functionalized polymer and a diluent oil as described herein. The content of the functionalized polymer itself is the active ingredient content (e.g., expressed as mass % based on the mass of the entire component including the diluent oil). Unless otherwise specified, all amounts, ranges and ratios in the present specification and claims refer to the active ingredient, unless otherwise specified.

[0028] As used herein, the terms "oil-soluble" and "oil-dispersible" or cognate terms do not necessarily mean that the compound or additive is soluble, dissolvable, miscible or capable of being suspended in oil at all ratios. However, these mean that they are soluble or stably dispersible in oil, for example, to an extent sufficient to exert their intended effects in the environment of use of the oil. In addition, if desired, the additional incorporation of other additives may also permit the incorporation of higher amounts of a particular additive.

[0029] The terms "group" and "radical" are used interchangeably herein.

[0030] The term "hydrocarbon" refers to a compound of hydrogen and carbon atoms. "Heteroatom" is an atom other than carbon or hydrogen. When referred to as a "hydrocarbon", particularly as a "refined hydrocarbon", the hydrocarbon may also contain minor amounts (such as those in which the heteroatoms do not substantially change the hydrocarbon nature of the hydrocarbon compound) of one or more heteroatoms or heteroatom-containing groups (such as halogens, especially chlorine and fluorine, amino groups, alkoxy groups, mercapto groups, alkyl mercapto groups, nitro groups, nitroso groups, sulfoxy groups, etc.).

[0031] The term "hydrocarbyl group" refers to a group containing hydrogen and carbon atoms. Preferably, unless otherwise specified, the group consists essentially of hydrogen and carbon atoms, and more preferably consists only of hydrogen and carbon atoms. Preferably, the hydrocarbyl group comprises an aliphatic hydrocarbyl group. The term "hydrocarbyl group" includes "alkyl group", "alkenyl group", "alkynyl group" and "aryl group" as defined herein. The hydrocarbyl group may contain one or more atoms / groups other than carbon and hydrogen, provided that they do not affect the basic hydrocarbyl nature of the hydrocarbyl group. Those skilled in the art are aware of such atoms / groups (such as halogens, especially chlorine and fluorine, amino groups, alkoxy groups, mercapto groups, alkyl mercapto groups, nitro groups, nitroso groups, sulfoxy groups, etc.).

[0032] The term "alkyl group" refers to a group of carbon and hydrogen (such as C1 to C 30 , such as C1 to C 12 group). The alkyl group in a compound is usually directly bonded to the compound via a carbon atom. Unless otherwise specified, the alkyl group may be straight-chain (i.e., unbranched) or branched, cyclic, acyclic or partially cyclic / acyclic. Preferably, the alkyl group comprises a straight-chain or branched acyclic alkyl group. Representative examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, dimethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and triacontyl.

[0033] The term "alkenyl group" refers to a group of carbon and hydrogen having at least one double bond (such as C2 to C 30 group, such as C2 to C12 (group). An alkenyl group in a compound is usually directly bonded to the compound via a carbon atom. Unless otherwise specified, an alkenyl group can be straight-chain (i.e., unbranched) or branched, cyclic, acyclic, or partially cyclic / acyclic.

[0034] The term "alkylene" refers to a C1 to C 20 , preferably C1 to C 10 divalent saturated aliphatic group, which can be straight-chain or branched. Representative examples of alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, 1-methylethylene, 1-ethylethylene, 1-ethyl-2-methylethylene, 1,1-dimethylethylene, and 1-ethylpropylene.

[0035] "Olefin", also known as "alkene", is a straight-chain, branched, or cyclic hydrocarbon 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 a polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an "isoprene" content of 55% to 95% by weight, it is to be understood that the monomer units in the copolymer are derived from isoprene in a polymerization reaction, and the derived units are present in an amount of 55% to 95% by weight based on the weight of the copolymer. A "polymer" has two or more identical or different monomer units. A "homopolymer" is a polymer having the same monomer units. A "copolymer" is a polymer having two or more monomer units that are different from each other. The "different" used to denote monomer units means that the monomer units differ from each other by at least one atom or are isomerically different. An "isoprene polymer" or "isoprene copolymer" is a polymer or copolymer containing at least 50 mol% of isoprene-derived units, a "butadiene polymer" or "butadiene copolymer" is a polymer or copolymer containing at least 50 mol% of butadiene-derived units, and so on. Similarly, when a polymer is referred to as a "partially or fully saturated polymer containing C 4-5 olefins", the C 4-5 olefins present in such a polymer or copolymer are the polymerized form of the olefin, and the polymer has been partially or fully saturated (such as by hydrogenation) after monomer polymerization. The "main chain" of a polymer is the polymer main chain containing the monomer units of the monomer, without any (subsequent) functionalization / before any (subsequent) functionalization.

[0036] The term "alkynyl" refers to a C2 to C containing at least one carbon-carbon triple bond 30 (such as C2 to C 12 ) group.

[0037] The term "aryl" refers to a group containing at least one aromatic ring, such as cyclopentadiene, phenyl, naphthyl, anthracenyl, etc. An aryl group is typically C5 to C 40 (such as C5 to C 18 , such as C6 to C 14 ) aryl, optionally substituted by one or more hydrocarbyl groups, heteroatoms or heteroatom-containing groups (such as halogen, hydroxy, alkoxy and amino). Preferred aryl groups include phenyl and naphthyl and their substituted derivatives, especially phenyl and alkyl-substituted derivatives of phenyl.

[0038] The term "substituted" means that a hydrogen atom has been replaced by a hydrocarbyl group, a heteroatom or a heteroatom-containing group. An alkyl-substituted derivative means that a hydrogen atom has been replaced by an alkyl group. "Alkyl-substituted phenyl" is one in which a hydrogen atom has been replaced by an alkyl group, such as a C1 to C 20 alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, dimethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and / or triacontyl-substituted phenyl.

[0039] The term "halogen" or "halo group" refers to a Group 17 atom or a group of Group 17 atoms, such as fluorine, chlorine, bromine and iodine.

[0040] The term "ashless" with respect to an additive means that the composition does not contain a metal.

[0041] The term "ash-containing" with respect to an additive means that the composition contains a metal.

[0042] Unless otherwise specified, the term "ppm" refers to parts per million by mass based on the total mass of the lubricating oil composition.

[0043] The "metal content" of a lubricating oil composition or an additive component, such as magnesium content, molybdenum content or total metal content (i.e., the sum of all individual metal contents) is measured by ASTM D5185.

[0044] The term "aliphatic hydrocarbon-based fatty acid" refers to a monocarboxylic acid having an aliphatic C7 to C 29 , preferably C9 to C 27 , most preferably C 11 to C 23 hydrocarbon chain. Such compounds may be referred to herein as aliphatic (C7 to C 29 ), more preferably (C9 to C 27 ), most preferably (C 11 to C 23)Hydrocarbyl monocarboxylic acids or hydrocarbyl fatty acids (where Cx to Cy represent the total number of carbon atoms in the aliphatic hydrocarbon radical chain of the fatty acid, and the fatty acid itself includes a total of Cx + 1 to Cy + 1 carbon atoms due to the presence of the carboxyl carbon atom). Preferably, the aliphatic hydrocarbon radical fatty acid, including the carboxyl carbon atom, has an even number of carbon atoms. The aliphatic hydrocarbon radical chain of the fatty acid can be saturated or unsaturated (i.e., includes at least one carbon-carbon double bond); preferably, the aliphatic hydrocarbon radical chain is unsaturated and includes at least one carbon-carbon double bond - such fatty acids can be obtained from natural sources (e.g., derived from animal or vegetable oils) and / or obtained by reduction of the corresponding saturated fatty acids. It should be recognized that a certain proportion of the aliphatic hydrocarbon radical chains of the corresponding aliphatic hydrocarbon radical fatty acid esters are unsaturated (i.e., include at least one carbon-carbon double bond) to allow reaction with other reagents, such as sulfur, to form the corresponding functionalized (e.g., sulfided) aliphatic hydrocarbon radical fatty acid esters.

[0045] The term "aliphatic hydrocarbon radical fatty acid ester" refers to an ester that can be obtained by converting the monocarboxylic acid functional group of the corresponding aliphatic hydrocarbon radical fatty acid into an ester group. Suitably, the monocarboxylic acid functional group of the aliphatic hydrocarbon radical fatty acid is converted into a hydrocarbyl ester, preferably a C1 to C 30 aliphatic hydrocarbyl ester, such as an alkyl ester, preferably a C1 to C6 alkyl ester, especially a methyl ester. Alternatively or additionally, the monocarboxylic acid functional group of the aliphatic hydrocarbon radical fatty acid can be in the form of a natural glyceride. Accordingly, the term "aliphatic hydrocarbon radical fatty acid ester" includes aliphatic hydrocarbon radical fatty acid glycerides and aliphatic hydrocarbon radical fatty acid C1 to C 30 aliphatic hydrocarbyl esters, [such as aliphatic hydrocarbon radical fatty acid alkyl esters, more preferably aliphatic hydrocarbon radical fatty acid C1 to C6 alkyl esters, especially aliphatic hydrocarbon radical fatty acid methyl esters]. Suitably, the term "aliphatic hydrocarbon radical fatty acid ester" includes aliphatic (C7 to C 29 ) hydrocarbyl, more preferably aliphatic (C9 to C 27 ) hydrocarbyl, most preferably aliphatic (C 11 to C 23 ) hydrocarbyl fatty acid glycerides and aliphatic (C7 to C 29 ) hydrocarbyl, more preferably aliphatic (C9 to C 27 ) hydrocarbyl, most preferably aliphatic (C 11 to C 23 ) hydrocarbyl fatty acid C1 to C 30 aliphatic hydrocarbyl esters. Suitably, in order to allow functionalization of the aliphatic hydrocarbon radical fatty acid ester, such as sulfidation, a certain proportion of the aliphatic hydrocarbon radical chains of the fatty acid ester are unsaturated and include at least one carbon-carbon double bond.

[0046] The term "sulfided aliphatic hydrocarbon radical fatty acid ester" refers to a compound obtained by sulfiding the aliphatic hydrocarbon radical fatty acid ester as defined herein.

[0047] As used herein, Mn is the number average molecular weight, Mw is the weight average molecular weight, and Mz is the z average molecular weight. The molecular weight distribution (MWD), also known as the polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise specified, all molecular weight units (e.g., Mw, Mn, Mz) are reported in g / mol.

[0048] Regarding the additive component or the lubricating oil composition (i.e., the unused lubricating oil composition), the total base number, also known as "TBN", refers to the total base number measured by ASTM D2896 and reported in mgKOH / g.

[0049] The total acid number ("TAN") is determined by ASTM D664.

[0050] The phosphorus, boron, calcium, zinc, molybdenum, sodium, silicon, and magnesium contents are measured by ASTM D5185.

[0051] The sulfur content in the oil formulation is measured by ASTM D5185.

[0052] The sulfate ash ("SASH") content is measured by ASTM D874.

[0053] Unless otherwise specified, the kinematic viscosities (KV100, KV40) are determined according to ASTM D445-19a and reported in cSt.

[0054] The viscosity index is determined by ASTM D2270.

[0055] The saponification value is determined by ASTM D94 and reported in mgKOH / g.

[0056] HTCBT, the high temperature corrosion bench test, is determined according to ASTM D6594.

[0057] The average functionality [also known as the average functionality value (Fv)] and the functionality distribution (Fd) values are determined by gel permeation chromatography using polystyrene standards as described in the experimental section of USSN 18 / 480,571 filed on October 4, 2023 (which claims the priority of USSN 63 / 379,006 filed on October 11, 2022) and the experimental section herein.

[0058] Unless otherwise specified, all percentages reported are mass % based on the active ingredient, i.e., without considering the carrier or diluent oil, unless otherwise specified. Unless otherwise specified, "mass %" has the same meaning as "weight %" or "wt %" herein.

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

[0060] In addition, it is to be understood that any upper and lower limits of the amounts, ranges and ratios listed herein can be combined independently.

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

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

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

[0064] The present disclosure relates to lubricating oil compositions (also referred to as "LOCs", "lubricant compositions", "lubricating compositions" or "lubricant oil compositions") which comprise the following components or are obtained by mixing the following components: (a) One or more base oils in an amount of 1 to 99% by mass (or 30 to 95% by mass, or 50 to 90% by mass, or 60 to 95% by mass, or 70 to 85% by mass) based on the weight of the lubricating composition; or one or more base oils in an amount of more than 50% by mass based on the weight of the lubricating composition; (b) A functionalized polymer in an amount of 0.1 to 20% by mass (especially 0.15 to 10% by mass, or 0.2 to 5% by mass, or 0.25 to 2% by mass, or 0.5 to 1% by mass) based on the weight of the lubricating composition, which comprises a partially or fully saturated olefin homopolymer or copolymer backbone and at least one functional group (such as a group derived from an amine or a hydroxyl group), the backbone having: an Mn (GPC-PS) of the polymer before functionalization of more than 10,000 g / mol, and preferably having been functionalized with an acylating agent and subsequently reacted with a compound containing an amino group and / or a hydroxyl group, (such as one or more amide, imide and / or ester functionalized partially or fully saturated C 2-5a polymer of an olefin) having: i) an Mw / Mn of less than 2, ii) optionally, a functionality distribution (Fd) value (GPC-PS) of 3.5 or less, and iii) an Mn (GPC-PS) of the polymer before functionalization of 10,000 g / mol or more, provided that if the polymer before functionalization is a copolymer of isoprene and butadiene, the Mn of the copolymer is greater than 25,000 g / mol (GPC-PS); c) from 0.1 to 20% by mass (or from 0.1 to 12% by mass, or from 0.25 to 10% by mass, or from 0.5 to 8% by mass, or from 1 to 7% by mass, or from 3 to 6% by mass), based on the weight of the lubricating composition, of one or more poly(alkenyl)succinimide dispersants derived from polyalkenyl-substituted succinic anhydrides and polyamines prepared using a chlorine-assisted alkylation process (such as blends of poly(alkenyl)succinimide dispersants) ("chlorine dispersants"); and d) from 0.1 to 10% by mass (or from 0.1 to 6% by mass, or from 0.25 to 4% by mass, or from 0.5 to 3% by mass, or from 0.8 to 1.5% by mass, or from 1 to 1.25% by mass), based on the weight of the lubricating composition, of one or more poly(alkenyl)succinimide dispersants derived from polyalkenyl succinic anhydrides and polyamines prepared using a halogen-free thermal alkylation process (such as blends of poly(alkenyl)succinimide dispersants) ("thermal dispersants"), present in an amount such that the weight ratio of the chlorine dispersant (c) to the thermal dispersant is at least 4:1; e) optionally, from 0 to 20% by mass (such as absent or substantially absent from the lubricating oil composition, or from 0.1 to 12% by mass, or from 0.25 to 8% by mass, or from 0.5 to 6% by mass, or from 0.05 to 5% by mass, or from 3.5 to 5% by mass), based on the weight of the lubricating composition, of one or more antioxidants (such as blends of antioxidants), wherein if present, optionally the one or more antioxidants are a mixture of one or more amine antioxidants and one or more phenolic antioxidants, preferably in a ratio of at least 2:1; wherein the lubricating composition may preferably exhibit: 1) an SAE viscosity grade of 20W-X, 15W-X, 10W-X, 5W-X or 0W-X (such as 10W-X or 5W-X), where X represents any one of 8, 12, 16, 20, 30, 40 and 50 (such as 30); and 2) optionally, 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 3) Optionally, an average wear on the gear drive wheel measured by Daimler OM471 FE1 (CEC L-118-21) of more than 75%, more than 80%, such as more than 81%, more than 82%, such as more than 82.5%, such as more than 83%, and / or 4) Optionally, an average bushing wear measured by Daimler OM471 FE1 (CEC L-118-21) 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, and / or 5) Optionally, an oxidation measured by Daimler OM471 FE1 (CEC L-118-21) 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.

[0065] The present disclosure also relates to a lubricating oil composition comprising the following components or obtained by mixing the following components: (i) One or more base oils in an amount of 1 to 99% by mass (or 30 to 95% by mass, or 50 to 90% by mass, or 60 to 95% by mass, or 70 to 85% by mass) based on the weight of the lubricating composition; or the lubricating oil composition comprises one or more base oils in an amount of more than 50% by mass based on the weight of the lubricating composition; (ii) One or more poly(alkenyl)succinimide dispersants (such as a blend of poly(alkenyl)succinimide dispersants) in an amount of 0.1 to 20% by mass (especially 0.1 to 12% by mass, or 0.1 to 10% by mass, or 1 to 8% by mass) based on the weight of the lubricating composition, which comprises one or more poly(alkenyl)succinimide dispersants (such as a blend of poly(alkenyl)succinimide dispersants) derived from polyalkenyl-substituted succinic anhydrides and polyamines prepared by a chlorine-assisted alkylation method (“chlorine dispersants”) and one or more poly(alkenyl)succinimide dispersants (such as a blend of poly(alkenyl)succinimide dispersants) derived from polyalkenyl succinic anhydrides and polyamines prepared by a halogen-free thermal alkylation method (“thermal dispersants”), and the thermal dispersant is present in an amount such that the weight ratio of the chlorine dispersant to the thermal dispersant is at least 4:1; and (iii) One or more detergents (such as a blend of detergents) in an amount of 0.01 to 20% by mass (especially 0.1 to 10% by mass, or 0.15% to 5% by mass, or 0.2 to 2% by mass) based on the weight of the composition; (iv) from 0.001 to 10% by mass, particularly from 0.01 to 5% by weight, or from 0.1 to 3% by mass, or from 0.15 to 1.5% by mass, or from 0.2 to 1% by mass, of one or more antiwear agents, such as a blend of antiwear agents, such as zinc dialkyldithiophosphate, based on the weight of the lubricating composition; v) from 0.1 to 20% by mass, particularly from 0.1 to 12% by mass, or from 0.25 to 8% by mass, or from 0.5 to 6% by mass, or from 0.05 to 5% by mass, or from 3.5 to 5% by mass, of one or more antioxidants, such as a blend of antioxidants, such as a mixture of one or more amine antioxidants and one or more phenolic antioxidants, preferably in a ratio of at least 2:1, based on the weight of the lubricating composition; (vi) from 0.10 to 20% by mass, particularly from 0.15 to 10% by mass, or from 0.20% by mass to 5% by mass, or from 0.25 to 2% by mass, or from 0.5 to 1% by mass, of one or more amide-, imide- and / or ester-functionalized partially or fully saturated polymers comprising C 4-5 olefins, having: i) an Mw / Mn of less than 2, ii) a functionality distribution (Fd) value (GPC-PS) of 3.5 or less, and iii) an Mn (GPC-PS) of the polymer before functionalization of 10,000 g / mol or more, provided that if the polymer before functionalization is a copolymer of isoprene and butadiene, the Mn of the copolymer is greater than 25,000 g / mol (GPC-PS), wherein the lubricating oil composition may preferably exhibit: 1) an SAE viscosity grade of 20W-X, 15W-X, 10W-X, 5W-X or 0W-X, such as 10W-X or 5W-X, where X represents any one of 8, 12, 16, 20, 30, 40 and 50, such as 30; and 2) optionally, an average piston cleanliness of more than 70%, such as more than 73%, such as more than 74%, more than 75%, such as more than 76%, more than 78%, such as more than 80%, such as more than 80.5%, as determined by Daimler OM471 FE1 (CEC L-118-21), and / or 3) optionally, an average wear on the gear drive wheels of more than 75%, more than 80%, such as more than 81%, more than 82%, such as more than 82.5%, such as more than 83%, as determined by Daimler OM471 FE1 (CEC L-118-21), and / or 4) Optionally, an average bushing wear measured by Daimler OM471 FE1 (CEC L-118-21) 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, and / or 5) Optionally, an oxidation measured by Daimler OM471 FE1 (CEC L-118-21) 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.

[0066] The present disclosure also relates to a lubricant composition of an oil having a lubricating viscosity, which comprises 0.1 to 30% by mass (in particular 0.1 to 20% by mass, or 0.1 to 12% by mass, or 3 to 10% by mass, or 6 to 8% by mass) of a dispersant mixture based on the weight of the lubricating composition, and the dispersant mixture comprises (1) An amide-, imide- and / or ester-functionalized partially or fully saturated polymer comprising C 4-5 olefins, which has: i) an Mw / Mn of less than 2, ii) a functionality distribution (Fd) value of 3.5 or less, and iii) an Mn (GPC-PS) of the polymer before functionalization of 10,000 g / mol or more; and (2) One or more poly(alkenyl)succinimide dispersants (such as blends of poly(alkenyl)succinimide dispersants) derived from polyalkenyl-substituted succinic anhydrides and polyamines prepared using a chlorine-assisted alkylation method ("chlorine dispersants"); and (3) One or more poly(alkenyl)succinimide dispersants (such as blends of poly(alkenyl)succinimide dispersants) derived from polyalkenyl succinic anhydrides and polyamines prepared using a halogen-free thermal alkylation method ("thermal dispersants"), which are present in an amount such that the weight ratio of the chlorine dispersant (2) to the thermal dispersant is at least 4:1 and / or such that the weight ratio of the functionalized polymer (1) to the thermal dispersant is at least 0.5:1.

[0067] The present disclosure also relates to a lubricating oil composition, which comprises the following components or is obtained by mixing the following components: A) One or more base oils of 1 to 99% by mass (or 30 to 95% by mass, or 50 to 90% by mass, or 60 to 95% by mass, or 70 to 85% by mass) based on the weight of the lubricating oil composition, or one or more base oils of more than 50% by mass based on the weight of the lubricating composition; B) One or more of the amide-, imide- and / or ester-functionalized partially or fully saturated polymers described herein, in an amount of 0.1 to 20% by mass, based on the weight of the lubricating oil composition (in particular 0.15 to 10% by mass, or 0.2 to 5% by mass, or 0.25 to 2% by mass, or 0.5 to 1% by mass, or 0.2 to 1% by mass); C) One or more detergents (such as blends of detergents), in an amount of 0.01 to 20% by mass, based on the weight of the lubricating oil composition (in particular 0.1 to 10% by mass, or 0.15% to 5% by mass, or 0.2 to 2% by mass, or 0.2 to 0.6% by mass); D) Optionally, one or more friction improvers (such as blends of friction improvers), in an amount of 0.001 to 5% by mass, based on the weight of the lubricating oil composition (in particular 0.01 to 4% by mass, or 0.015 to 3% by mass, or 0.02 - 0.04% by mass); E) One or more antioxidants (such as blends of antioxidants), in an amount of 0.1 to 20% by mass, based on the total weight of the lubricating oil composition (in particular 0.1 to 12% by mass, or 0.25 to 8% by mass, or 0.5 to 6% by mass, or 0.05 to 5% by mass, or 3.5 to 5% by mass); F) Optionally, one or more pour point depressants (such as blends of pour point depressants), in an amount of 0.01 to 5% by mass, based on the weight of the lubricating oil composition (in particular 0.01 to 3% by mass, or 0.02 to 1.5% by mass, or 0.025 to 0.2% by mass); G) Optionally, one or more antifoaming agents (such as blends of antifoaming agents), in an amount of 0.001 to 5% by mass, based on the weight of the lubricating oil composition (in particular 0.001 to 3% by mass, or 0.005 to 1.5% by mass, or 0.005 to 0.01% by mass); H) Optionally, one or more viscosity improvers (such as blends of viscosity improvers), in an amount of 0.001 to 10% by mass, based on the weight of the lubricating oil composition (in particular 0.01 to 6% by weight, or 0.01 to 5% by mass, or 0.1 to 4% by mass, or 0.1 to 2% by mass, or 0.1 to 0.22% by mass); I) Based on the weight of the lubricating composition, 0.1 to 20% by mass (especially 0.1 to 12% by mass, or 0.1 to 10% by mass, or 1 to 8% by mass) of one or more dispersants (such as a blend of dispersants), which comprise the following components, especially consist of the following components: one or more poly(alkenyl)succinimide dispersants derived from polyalkenyl-substituted succinic anhydrides and polyamines prepared using a chlorine-assisted alkylation method (such as a blend of poly(alkenyl)succinimide dispersants) ("chlorine dispersants") and one or more poly(alkenyl)succinimide dispersants derived from polyalkenyl succinic anhydrides and polyamines prepared using a halogen-free thermal alkylation method (such as a blend of poly(alkenyl)succinimide dispersants) ("thermal dispersants"), and the thermal dispersant is present in an amount such that the weight ratio of the chlorine dispersant to the thermal dispersant is at least 4:1, especially about 9:2; J) Optionally, based on the weight of the lubricating oil composition, 0.01 to 5% by weight (especially 0.01 to 3% by mass, or 0.05 to 1.5% by mass, or 0.05 to 0.1% by mass) of one or more inhibitors and / or rust inhibitors (such as a blend of inhibitors and / or rust inhibitors); K) Based on the weight of the lubricating composition, 0.001 to 10% by mass (especially 0.01 to 5% by weight, or 0.1 to 3% by mass, or 0.15 to 1.5% by mass, or 0.2 to 1% by mass, or 0.06 to 0.6% by mass) of one or more antiwear agents (such as a blend of antiwear agents, such as ZDDP); M) Optionally, based on the weight of the lubricating oil composition, 0.01 to 5% by weight (especially 0.05 to 2% by mass, or 0.1 to 1% by mass) of one or more seal compatibilizers, such as seal swelling agents, and / or O) Optionally, based on the weight of the lubricating composition, 0.01 to 5% by mass (especially 0.1 to 3% by mass, or 0.1 to 1.5% by mass) of one or more unsaturated C 12 -C 60 hydrocarbons (such as C 12 -C 24 linear alpha-olefins (LAO), oligomers / polymers of polyisobutene, and / or blends thereof).

[0068] Alternatively, the lubricating oil compositions of the present invention (including but not limited to those disclosed above) may contain at least 50% by mass, such as 50 to 90% by mass, or 60 to 95% by mass, or 70 to 85% by mass, of one or more base oils based on the weight of the lubricating oil composition. In particular, the lubricating oil compositions of the present invention (including but not limited to those disclosed above) may contain at least 30% by mass, such as 30 to 55% by mass, or 35 to 50% by mass, of one or more Group III base oils based on the weight of the lubricating oil composition, and at least 25% by mass, such as 25 to 45% by mass, or 30 to 40% by mass, of one or more Group II base oils based on the weight of the lubricating oil composition.

[0069] For the purposes of the present disclosure, component B) the functionalized polymer is not counted towards components C, D, E, F, G, H, I, J, K, M, and / or O above to determine weight percentages, although they may exhibit similar properties. For example, component B) the functionalized polymer may positively affect wear, but is not counted towards component K) to determine the weight percentage of the anti-wear agent. Specifically, the compositions according to the present disclosure may contain aminated additives (such as the dispersant component PIBSA-PAM etc. described below in the dispersant section) having different recited functions. For determining the amount of the functionalized polymer in the lubricating oil compositions or additive concentrates herein, these additives are not counted as functionalized polymers. However, component B) the functionalized polymer and component I) the poly(alkenyl) succinimide dispersant together constitute the dispersant mixture described herein.

[0070] In embodiments, all components D, E, F, G, H, I, J, K, M, and O are present in addition to the base oil, the detergent, and the one or more functionalized polymers described herein.

[0071] In embodiments, components D, E, F, G, H, I, J, and K are present in addition to the base oil, the detergent, and the one or more functionalized polymers described herein.

[0072] In embodiments, components I and E are present in addition to the base oil, the detergent, and the one or more functionalized polymers described herein.

[0073] In embodiments, component K is present in addition to the base oil, the detergent, and the one or more functionalized polymers described herein.

[0074] Suitably, 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, measured by ASTM D2896.

[0075] The lubricating composition of the present disclosure may contain a particularly low phosphorus content, that is, not more than 1000, preferably not more than 800, more preferably not more than 500, such as 1 to 1000, such as 50 to 800, such as 100 to 500 parts per million by mass (ppm) of phosphorus, expressed as phosphorus atoms, based on the total mass of the lubricating composition as measured by ASTM D5185.

[0076] Suitably, the lubricant composition may have a phosphorus content of 1000 ppm or less, or 800 ppm or less, or 500 ppm or less as measured by ASTM D5185.

[0077] The lubricating composition of the present disclosure may contain a magnesium atom / calcium atom ratio of at least 0.5, preferably at least 0.6, more preferably at least 0.65, based on the total mass of the lubricating composition as measured by ASTM D5185.

[0078] Generally, the lubricating composition may contain a low sulfur content. Preferably, the lubricating composition contains at most 0.4, more preferably at most 0.3, most preferably at most 0.2, such as 0.1 to 0.4% by mass of sulfur, based on the total mass of the lubricating oil composition as measured by ASTM D5185.

[0079] Generally, the lubricating composition may contain a particularly low sulfate ash content, not more than 1.0% by mass, such as not more than 0.9% by mass, preferably not more than 0.6% by mass, preferably not more than 0.5% by mass, or 0.0001 to 0.5% by mass or less of sulfate ash, based on the total mass of the lubricating composition as measured by ASTM D874-13a(2018).

[0080] Generally, the kinematic viscosity ("KV100") of the lubricating composition at 100 °C may be 2 to 30 cSt, such as 2 to 20 cSt, such as 5 to 15 cSt (measured according to ASTM D 445-19a).

[0081] In an embodiment, the kinematic viscosity ("KV100") of the lubricating composition at 100 °C may be 6 to 17 cSt, such as 9 to 16.3 cSt, such as 9.3 to less than 12.5 cSt, such as 12.5 to less than 16.3 cSt (measured according to ASTM D 445-19a).

[0082] Generally, the total base number of the lubricating composition may be 1 to 30, such as 5 to 15 mgKOH / g (measured according to ASTM D2896).

[0083] Preferably, the lubricating composition of the present disclosure can be a multigrade oil specified by the viscosity descriptors SAE 20W-X, SAE 15W-X, SAE 10W-X, SAE 5W-X or SAE 0W-X, where X represents any one of 8, 12, 16, 20, 30, 40 and 50; the characteristics of different viscosity grades can be found in the SAE J300 classification. Alternatively, the lubricating composition can be in the form of viscosity grades SAE 15W-X, SAE 10W-X, SAE 5W-X or SAE 0W-X, such as in the form of SAE 5W-X, where X represents any one of 8, 12, 16, 20, 30, 40 and 50. X is preferably 8, 12, 16, 20 or 30. Alternatively, the lubricating composition of the present disclosure can be a multigrade oil specified by the viscosity descriptors SAE 10W-30, 15W-40, 5W-30, 5W-40, 10W-40, 5W-50, such as SAE 5W-30. (See Standard SAE J300 issued by SAE International, formerly known as the Society of Automotive Engineers, in January 2015).

[0084] Optionally, the lubricating composition may be free of phenate detergents.

[0085] Optionally, the lubricating composition may be free of PIBSA ester dispersants.

[0086] Optionally, the lubricating composition may be free of phenolic antioxidants. Alternatively, the lubricating composition may contain phenolic antioxidants.

[0087] Optionally, the lubricating composition may be free of methyl sulfide antioxidants.

[0088] In an embodiment, the lubricating oil composition may contain less than 1000 ppm boron, or less than 600 ppm boron, or 80 to 350 ppm boron. Alternatively, the LOC may be free of boron.

[0089] In an embodiment, the lubricating oil composition may contain less than 20 (such as less than 15, such as less than 10, such as less than 6) mass% of functionalized (such as aminated) polybutene (such as polyisobutene), such as PIBSA-PAM. In an embodiment, the lubricating oil composition contains more than 0.1 (such as 0.1 to 10, such as 0.5 to 8) mass% of functionalized (such as aminated) polybutene (such as polyisobutene), such as PIBSA-PAM.

[0090] In an embodiment, the lubricating oil composition comprises greater than 0.5 (such as 0.5 to 8, such as 2 to 8) mass % of a functionalized (such as aminated) polybutene (such as polyisobutene), such as PIBSA-PAM, derived from a polyisobutene-substituted succinic anhydride and a polyamine prepared using a chlorine-assisted alkylation process.

[0091] In an embodiment, the lubricating oil composition comprises greater than 0.5 (such as 0.5 to 8, such as 0.5 to 2) mass % of a functionalized (such as aminated) polybutene (such as polyisobutene), such as PIBSA-PAM, derived from a polyisobutene-substituted succinic anhydride and a polyamine prepared using a halogen-free thermal alkylation process.

[0092] In an embodiment, the lubricating oil composition comprises greater than 0.1 (such as 0.1 to 5, such as 0.1 to 3, such as 0.5 to 2) mass % of a functionalized (such as aminated) polybutene (such as polyisobutene) having a high terminal vinylidene content, such as HR-PIBSA-PAM.

[0093] In an embodiment, the lubricating oil composition may comprise an acylated polymer, such as polyisobutene succinic acid (PIBSA), which optionally has a Mn of 500 to 50,000 g / mol, such as 600 to 5,000 g / mol, such as 700 to 3,000 g / mol. In an embodiment, the lubricating oil composition may comprise an acylated polymer, such as polyisobutene succinic acid, having a Mn of 500 to 1,600 g / mol, such as 700 to 1,200 g / mol.

[0094] In an embodiment, the lubricating oil composition may comprise 20 (such as 15, such as 10, such as 5, such as 3, such as 1) mass % or less of a block copolymer, such as a block, star, random, and / or gradient block copolymer.

[0095] In an embodiment, the lubricating oil composition may be substantially free of or may not contain a block copolymer, such as a block, star, random, and / or gradient block copolymer.

[0096] In an embodiment, the lubricating oil composition may comprise 20 (such as 15, such as 10, such as 5, such as 3, such as 1) mass % or less of a styrenic copolymer, such as a block, star, random, and / or gradient styrenic block copolymer.

[0097] In an embodiment, the lubricating oil composition may be substantially free of or may not contain a styrenic copolymer, such as a block, star, random, and / or gradient styrenic block copolymer.

[0098] In an embodiment, the lubricating oil composition may comprise less than 20 (such as less than 15, such as less than 10, such as less than 5, such as less than 3, such as less than 1) mass % of a functionalized diluent, such as a functionalized oil.

[0099] In embodiments, the lubricating oil composition may comprise, may be substantially free of, or may be devoid of a functionalized diluent, such as a functionalized oil.

[0100] In embodiments, the lubricating oil composition may comprise less than 20 (such as less than 15, such as less than 10, such as less than 5, such as less than 3, such as less than 1) mass % of a solvent, such as an aromatic solvent.

[0101] In embodiments, the lubricating oil composition may be substantially free of or devoid of a solvent, such as a functionalized solvent.

[0102] In embodiments, the lubricating oil composition may have a total saponification value (SAP) of greater than 25 (such as 28, such as 30, such as 32) mgKOH / g as determined by ASTM 94.

[0103] In embodiments, the lubricating oil composition may have a total saponification value (SAP) of greater than 25 (such as 28, such as 30, such as 32) mgKOH / g as determined by ASTM 94, and the functionalized polymer may have a functionality distribution (Fd) value of 3.5 or less (such as 3.4 or less, such as 1 to 3.3, such as 1.1 to 3.2, such as 1.2 to 3.0, such as 1.4 to 2.9) as determined by GPC-PS as described in the Experimental section below.

[0104] In embodiments, the lubricating oil composition may have a total saponification value (SAP) of greater than 25 (such as 28, such as 30, such as 32) mgKOH / g as determined by ASTM 94, and the functionalized polymer may have an average functionality of 1.4 to 20 FG grafts / polymer chain, such as 1.4 to 15 FG grafts / polymer chain, such as 3 to 12.5 FG grafts / polymer chain, such as 4 to 10 FG grafts / polymer chain as determined by GPC-PS as described in the Experimental section below.

[0105] In embodiments, the lubricating oil composition may comprise less than 0.5 (such as less than 0.4, such as less than 0.3, such as less than 0.2, such as less than 0.1, substantially absent or 0) weight % of secondary and tertiary hydrocarbylamine compounds based on the weight of the LOC.

[0106] In embodiments, the lubricating oil composition may be substantially absent or may be free of secondary and tertiary hydrocarbylamine compounds.

[0107] In embodiments, the lubricating composition of the present disclosure may be a heavy-duty diesel engine oil (e.g., for a heavy-duty diesel vehicle, i.e., an engine of a heavy-duty diesel vehicle having a gross vehicle weight rating of more than 10,000 pounds).

[0108] In embodiments, the lubricating composition of the present disclosure may be a passenger car motor oil.

[0109] In an embodiment, the lubricating composition of the present disclosure can be a passenger car diesel fuel.

[0110] In an embodiment, the lubricating composition of the present disclosure can be a diesel engine lubricating composition comprising: an oil having lubricating viscosity, which has greater than 50 wt% of Group I, II, III, IV, and / or V oils (such as 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 1800 to 2500 Mn PIB; third and fourth PIB succinimide dispersants 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 at least one of the third PIB succinimide dispersant and the fourth PIB succinimide dispersant is boron-free (optionally, at least one of the third PIB succinimide dispersant and the fourth PIB succinimide dispersant is borated); amide, imide, and / or ester-functionalized partially or fully saturated polymers comprising C 4-5 olefins; one or more alkaline earth metal sulfonate detergents; and a phosphorus antiwear agent present in an amount to provide 100 to 500 ppm of phosphorus to the lubricating composition, the lubricating composition having a total sulfate ash between 0.1 and 0.5 wt%.

[0111] The lubricating compositions disclosed herein (such as diesel engine lubricating compositions) can have a kinematic viscosity at 100 °C measured by ASTM D-445 of 2.0 to 12.5, such as 5.0 to 12.5, such as 7.5 to 12.0 (such as 9.0 to 12.0, or 9.7 to 11.7, or 9.7 to 11.5) cSt (mm 2 / s).

[0112] The lubricating compositions disclosed herein (such as diesel engine lubricating compositions) can have a high temperature high shear viscosity (HTHS) measured by ASTM D4683 at 150 °C 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. In another embodiment, the HTHS of the lubricating composition is 2.4 to 3.5 mPa·s, or 2.6 to 3.1 mPa·s, or 2.8 to 3.1 mPa·s.

[0113] The lubricating composition (such as a diesel engine lubricating composition) may have an SAE viscosity grade of 5W-X, where Y can be 8, 12, 16, 20, or 30. In a specific embodiment, the lubricating oil composition has an SAE viscosity grade of 5W-30.

[0114] The lubricating compositions disclosed herein (such as diesel engine lubricating compositions) may have: 1) a kinematic viscosity at 100 °C measured by ASTM D-445 of 7.5 to 12.0 (such as 9.0 to 12.0, or 9.7 to 11.7, or 9.7 to 11.5) cSt (mm 2 / s); 2) a high temperature high shear viscosity (HTHS) measured by ASTM D4683 at 150 °C 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 (or 2.4 to 3.5 mPa·s, or 2.6 to 3.1 mPa·s, or 2.8 to 3.1 mPa·s); and 3) an SAE viscosity grade of 5W-30. Additive concentrate

[0115] An additive concentrate, also known as an additive package, adpak, or addpack, is a (concentrate) composition having less than 50% by mass (such as less than 40% by mass, such as less than 30% by mass, such as less than 25% by mass, such as less than 20% by mass) base oil and lubricant composition additives (as described herein), which is typically subsequently further blended with additional base oil to form a lubricating oil product.

[0116] This disclosure relates to a concentrate composition comprising the following components or obtained by mixing the following components: (a) One or more base oils in an amount of 1 to less than 50% by mass (or 5 to 45% by mass, or 7 to 40% by mass, or 10 to 35% by mass, or 10 to 25% by mass) based on the weight of the concentrate composition; (b) A functionalized polymer in an amount of 0.1 to 40% by mass (especially 0.15 to 20% by mass, or 0.2 to 10% by mass, or 0.25 to 5% by mass, or 0.5 to 4% by mass) based on the weight of the concentrate composition, which comprises a partially or fully saturated olefin homopolymer or copolymer backbone and at least one functional group (such as a group derived from an amine or a hydroxyl group), the backbone having: an Mn (GPC-PS) of the polymer before functionalization of more than 10,000 g / mol, and preferably having been functionalized with an acylating agent and subsequently reacted with a compound containing an amino group and / or a hydroxyl group (such as one or more amide, imide, and / or ester functionalized partially or fully saturated C 2-5Polymers of olefins), having: i) an Mw / Mn of less than 2, ii) optionally, a functionality distribution (Fd) value (GPC-PS) of 3.5 or less, and iii) an Mn (GPC-PS) of the polymer before functionalization of 10,000 g / mol or more, provided that if the polymer before functionalization is a copolymer of isoprene and butadiene, the Mn of the copolymer is greater than 25,000 g / mol (GPC-PS); c) From 0.1 to 60% by mass (or from 0.1 to 40% by mass, or from 0.5 to 30% by mass, or from 1 to 25% by mass, or from 15 to 25% by mass) of one or more poly(alkenyl)succinimide dispersants (such as blends of poly(alkenyl)succinimide dispersants) derived from polyalkenyl-substituted succinic anhydrides and polyamines prepared using a chlorine-assisted alkylation process ("chlorine dispersants"), based on the weight of the concentrate composition; and d) From 0.1 to 20% by mass (or from 0.1 to 12% by mass, or from 0.25 to 10% by mass, or from 0.5 to 8% by mass, or from 1.5 to 7% by mass, or from 3 to 6% by mass) of one or more poly(alkenyl)succinimide dispersants (such as blends of poly(alkenyl)succinimide dispersants) derived from polyalkenyl succinic anhydrides and polyamines prepared using a halogen-free thermal alkylation process ("thermal dispersants"), present in an amount such that the weight ratio of the chlorine dispersant (c) to the thermal dispersant is at least 4:1; e) Optionally, from 0 to 50% by mass (such as absent or substantially absent from the lubricating oil composition, or from 0.1 to 35% by mass, or from 0.25 to 25% by mass, or from 0.5 to 22% by mass, or from 0.05 to 20% by mass, or from 14 to 20% by mass) of one or more antioxidants (such as blends of antioxidants), based on the weight of the concentrate composition, wherein if present, optionally the one or more antioxidants is a mixture of one or more amine antioxidants and one or more phenolic antioxidants, preferably in a ratio of at least 2:1.

[0117] The present disclosure relates to a concentrate composition comprising the following components or obtained by mixing the following components: (i) From 1 to less than 50% by mass (or from 5 to 45% by mass, or from 7 to 40% by mass, or from 10 to 35% by mass, or from 10 to 25% by mass) of one or more base oils, based on the weight of the concentrate composition; (ii) Based on the weight of the concentrate composition, 0.1 to 70% by mass (especially 0.1 to 50% by mass, or 0.1 to 40% by mass, or 1 to 30% by mass) of one or more poly(alkenyl) succinimide dispersants (such as blends of poly(alkenyl) succinimide dispersants), which comprise one or more poly(alkenyl) succinimide dispersants (such as blends of poly(alkenyl) succinimide dispersants) derived from polyalkenyl-substituted succinic anhydrides and polyamines prepared using a chlorine-assisted alkylation method (“chlorine dispersants”) and one or more poly(alkenyl) succinimide dispersants (such as blends of poly(alkenyl) succinimide dispersants) derived from polyalkenyl succinic anhydrides and polyamines prepared using a halogen-free thermal alkylation method (“thermal dispersants”), and the thermal dispersant is present in an amount such that the weight ratio of the chlorine dispersant to the thermal dispersant is at least 4:1; and (iii) Based on the weight of the concentrate composition, 0.01 to 30% by mass (especially 0.1 to 20% by mass, or 0.5% to 10% by mass, or 0.5 to 5% by mass) of one or more detergents (such as blends of detergents); (iv) Based on the weight of the concentrate composition, 0.001 to 20% by mass (especially 0.01 to 10% by weight, or 0.1 to 5% by mass, or 0.5 to 5% by mass, or 1 to 3% by mass) of one or more antiwear agents (such as blends of antiwear agents, such as zinc dialkyldithiophosphate); v) Based on the weight of the concentrate composition, 0.1 to 50% by mass (especially 0.1 to 35% by mass, or 0.25 to 25% by mass, or 0.5 to 22% by mass, or 0.05 to 20% by mass, or 14 to 20% by mass) of one or more antioxidants (such as blends of antioxidants, such as a mixture of one or more amine antioxidants and one or more phenolic antioxidants, preferably a mixture in a ratio of at least 2:1); (vi) Based on the weight of the composition, 0.1 to 40% by mass (especially 0.15 to 20% by mass, or 0.2 to 10% by mass, or 0.25 to 5% by mass, or 0.5 to 4% by mass) of one or more amide-, imide- and / or ester-functionalized partially or fully saturated polymers containing C 4-5 alkenes, which have: i) Mw / Mn less than 2, ii) a functionality distribution (Fd) value (GPC-PS) of 3.5 or less, and iii) Mn (GPC-PS) of the polymer before functionalization of 10,000 g / mol or more, provided that if the polymer before functionalization is a copolymer of isoprene and butadiene, the Mn of the copolymer is greater than 25,000 g / mol (GPC-PS), (vii) Optional additional components, pour point depressants, defoamers, viscosity improvers, corrosion inhibitors, extreme pressure additives, demulsifiers, seal compatibility agents, additive diluents base oils, friction improvers (such as organic FMs, such as organic esters, such as fatty acid esters), etc.

[0118] The present disclosure also relates to a concentrate composition comprising 0.1 to 50% by mass (in particular 0.1 to 40% by mass, or 15 to 40% by mass, or 20 to 32% by mass, or 25 to 30% by mass) of a dispersant mixture based on the weight of the concentrate composition, the dispersant mixture comprising: (1) Amide-, imide- and / or ester-functionalized partially or fully saturated polymers comprising C 4-5 olefins, having: i) an Mw / Mn of less than 2, ii) a functionality distribution (Fd) value of 3.5 or less, and iii) an Mn (GPC-PS) of the polymer before functionalization of 10,000 g / mol or more; and (2) One or more poly(alkenyl)succinimide dispersants (such as blends of poly(alkenyl)succinimide dispersants) derived from polyalkenyl-substituted succinic anhydrides and polyamines prepared using a chlorine-assisted alkylation process ("chlorine dispersants"); and (3) One or more poly(alkenyl)succinimide dispersants (such as blends of poly(alkenyl)succinimide dispersants) derived from polyalkenyl succinic anhydrides and polyamines prepared using a halogen-free thermal alkylation process ("thermal dispersants"), present in an amount such that the weight ratio of the chlorine dispersant (2) to the thermal dispersant is at least 4:1 and / or such that the weight ratio of the functionalized polymer (1) to the thermal dispersant is at least 0.5:1.

[0119] In an embodiment, the dispersant mixture in the concentrate composition disclosed herein comprises: (1) 0.01 to 15% by mass (in particular 1 to 12% by mass, or 5 to 11% by mass, or 7.5 to 10.5% by mass, or 8.5 to 10% by mass) of the amide-, imide- and / or ester-functionalized partially or fully saturated polymers comprising C 4-5 olefins based on the total mass of the dispersant mixture; and (2) 50 to 90% by mass (in particular 55 to 85% by mass, or 62 to 82% by mass, or 68 to 80% by mass, or 70 to 76% by mass) of one or more chlorine dispersants based on the total mass of the dispersant mixture; and (3) One or more thermal dispersants in an amount of 10 to 30% by mass (in particular 12 to 25% by mass, or 14 to 22% by mass, or 15 to 20% by mass, or 15.5 to 17.5% by mass) based on the total mass of the dispersant mixture.

[0120] In an embodiment, the concentrate composition disclosed herein may optionally contain one or more antioxidants.

[0121] In an embodiment, the concentrate composition disclosed herein may further contain one or more additional additives selected from detergents, friction modifiers, defoamers, corrosion inhibitors / rust inhibitors, and antiwear agents.

[0122] The present disclosure also relates to a concentrate composition comprising the following components or obtained by mixing the following components: A) One or more base oils in an amount of 1 to less than 50% by mass (or 5 to 45% by mass, or 7 to 40% by mass, or 10 to 35% by mass, or 10 to 25% by mass) based on the weight of the concentrate composition; B) One or more amide-, imide- and / or ester-functionalized partially or fully saturated polymers as described herein in an amount of 0.1 to 40% by mass (in particular 0.15 to 20% by mass, or 0.2 to 10% by mass, or 0.25 to 5% by mass, or 0.5 to 4% by mass) based on the weight of the concentrate composition; C) One or more detergents (such as a blend of detergents) in an amount of 0.01 to 30% by mass (in particular 0.1 to 20% by mass, or 0.5% to 10% by mass, or 0.5 to 5% by mass) based on the weight of the concentrate composition; D) Optionally, one or more friction modifiers (such as a blend of friction modifiers) in an amount of 0.001 to 10% by mass (in particular 0.01 to 8% by mass, or 0.05 to 5% by mass, or 0.05 - 0.2% by mass) based on the weight of the concentrate composition; E) One or more antioxidants (such as a blend of antioxidants) in an amount of 0.1 to 50% by mass (in particular 0.1 to 35% by mass, or 0.25 to 25% by mass, or 0.5 to 22% by mass, or 0.05 to 20% by mass, or 14 to 20% by mass) based on the total weight of the concentrate composition; G) Optionally, one or more defoamers (such as a blend of defoamers) in an amount of 0.001 to 8% by mass (in particular 0.001 to 5% by mass, or 0.005 to 2% by mass, or 0.01 to 0.1% by mass) based on the weight of the concentrate composition; I) Based on the weight of the concentrate composition, 0.1 to 70% by mass (especially 0.1 to 50% by mass, or 0.1 to 40% by mass, or 1 to 30% by mass) of one or more dispersants (such as blends of dispersants), which comprise one or more poly(alkenyl) succinimide dispersants derived from polyalkenyl-substituted succinic anhydrides and polyamines prepared using a chlorine-assisted alkylation process (such as blends of poly(alkenyl) succinimide dispersants) ("chlorine dispersants") and one or more poly(alkenyl) succinimide dispersants derived from polyalkenyl succinic anhydrides and polyamines prepared using a halogen-free thermal alkylation process (such as blends of poly(alkenyl) succinimide dispersants) ("thermal dispersants"), and the thermal dispersant is present in an amount such that the weight ratio of the chlorine dispersant to the thermal dispersant is at least 4:1, especially about 9:2; J) Optionally, based on the weight of the lubricating oil composition, 0.01 to 10% by weight (especially 0.01 to 5% by mass, or 0.05 to 3% by mass, or 0.1 to 0.5% by mass) of one or more inhibitors and / or rust inhibitors (such as blends of inhibitors and / or rust inhibitors); K) Based on the weight of the lubricating composition, 0.001 to 20% by mass (especially 0.01 to 10% by weight, or 0.1 to 5% by mass, or 0.5 to 5% by mass, or 1 to 3% by mass) of one or more antiwear agents (such as blends of antiwear agents, such as ZDDP).

[0123] The concentrate composition can be present in the lubricating oil composition in an amount of 0.5% to 35% by mass, such as 5% to 30% by mass, such as 7.5% to 25% by mass, such as 10 to 22.5% by mass, such as 15 to 20% by mass, based on the mass of the lubricating oil composition.

[0124] Optionally, the concentrate composition can be free of functionalized oil.

[0125] In an embodiment, the concentrate composition can optionally be free of solvents (such as aliphatic or aromatic solvents) and / or free of functionalized base oil.

[0126] Optionally, the concentrate composition can be free of phenate detergents.

[0127] Optionally, the concentrate composition can be free of PIBSA ester dispersants.

[0128] Optionally, the concentrate composition can be free of phenolic antioxidants. Alternatively, the concentrate composition can contain phenolic antioxidants.

[0129] Optionally, the concentrate composition can be free of methyl sulfide antioxidants.

[0130] In an embodiment, the concentrate composition may comprise less than 1000 ppm boron, or less than 600 ppm boron, or 80 to 350 ppm boron. Alternatively, the concentrate may be boron-free.

[0131] In an embodiment, the concentrate composition may comprise less than 40 (such as less than 35, such as less than 30, such as less than 26) mass % of a functionalized (such as aminated) polybutene (such as polyisobutene), such as PIBSA-PAM. In an embodiment, the lubricating oil composition comprises greater than 0.1 (such as 0.1 to 30, such as 0.5 to 26) mass % of a functionalized (such as aminated) polybutene (such as polyisobutene), such as PIBSA-PAM.

[0132] In an embodiment, the concentrate composition comprises greater than 0.5 (such as 0.5 to 25, such as 10 to 25) mass % of a functionalized (such as aminated) polybutene (such as polyisobutene), such as PIBSA-PAM, derived from polyisobutene-substituted succinic anhydride and polyamine prepared using a chlorine-assisted alkylation process.

[0133] In an embodiment, the concentrate composition comprises greater than 0.5 (such as 0.5 to 25, such as 0.5 to 10) mass % of a functionalized (such as aminated) polybutene (such as polyisobutene), such as PIBSA-PAM, derived from polyisobutene-substituted succinic anhydride and polyamine prepared using a halogen-free thermal alkylation process.

[0134] In an embodiment, the concentrate composition comprises greater than 0.1 (such as 0.1 to 10, such as 0.1 to 8, such as 0.5 to 5) mass % of a functionalized (such as aminated) polybutene (such as polyisobutene) with a high terminal vinylidene content, such as HR-PIBSA-PAM.

[0135] In an embodiment, the concentrate composition may comprise an acylated polymer, such as polyisobutene succinic acid (PIBSA), optionally having a Mn of 500 to 50,000 g / mol, such as 600 to 5,000 g / mol, such as 700 to 3000 g / mol. In an embodiment, the lubricating oil composition may comprise an acylated polymer, such as polyisobutene succinic acid, having a Mn of 500 to 1600 g / mol, such as 700 to 1200 g / mol.

[0136] In an embodiment, the concentrate composition may comprise 20 (such as 15, such as 10, such as 5, such as 3, such as 1) mass % or less of a block copolymer, such as a block, star, random, and / or gradient block copolymer.

[0137] In an embodiment, the concentrate composition may be substantially free of or may not contain a block copolymer, such as a block, star, random, and / or gradient block copolymer.

[0138] In an embodiment, the concentrate composition may comprise up to 20% by mass (such as up to 15% by mass, such as up to 10% by mass, such as up to 5% by mass, such as up to 3% by mass, such as up to 1% by mass) of a styrenic copolymer, such as a block, star, random, and / or tapered styrenic block copolymer.

[0139] In an embodiment, the concentrate composition may be substantially free or devoid of a styrenic copolymer, such as a block, star, random, and / or tapered styrenic block copolymer.

[0140] In an embodiment, the concentrate composition may comprise less than 20 (such as less than 15, such as 10, such as less than 5, such as less than 3, such as 1) % by mass of a functionalized diluent, such as a functionalized oil.

[0141] In an embodiment, the concentrate composition may be substantially free or devoid of a functionalized diluent, such as a functionalized oil.

[0142] In an embodiment, the concentrate composition may comprise less than 0.5 (such as less than 0.4, such as less than 0.3, such as less than 0.2, such as 0.1, substantially absent, 0) % by weight, based on the weight of the concentrate composition, of secondary hydrocarbyl amine compounds and tertiary hydrocarbyl amine compounds.

[0143] In an embodiment, the concentrate composition may be substantially absent or may be devoid of secondary hydrocarbyl amine compounds and tertiary hydrocarbyl amine compounds.

[0144] In an embodiment, the concentrate composition may have a kinematic viscosity at 100 °C of less than 1000 cSt, such as less than 500 cSt, such as less than 200 cSt. A. Base Oil

[0145] The base oil useful herein (also referred to as "base stock", "lubricating oil base stock", or "oil having lubricating viscosity") can be a single oil or a blend of oils and is typically the major liquid component of a lubricating composition (also referred to as a lubricant), into which additives and optionally additional oils are incorporated to, for example, make a lubricating composition, such as a final lubricant composition, a concentrate, or other lubricating composition.

[0146] The base oil can be selected from vegetable oils, animal oils, mineral oils, synthetic lubricating oils, and mixtures thereof. Its viscosity ranges from light distillate mineral oils to heavy lubricating oils, such as those used in gas engine oils, mineral lubricating oils, motor vehicle oils, and heavy diesel engine oils. Generally, the kinematic viscosity of the base oil at 100 °C ("KV100") is 1 to 30, such as 2 to 25 cSt, such as 5 to 20 cSt (measured according to ASTM D445-19a), especially 1.0 cSt to 10 cSt, 1.5 cSt to 3.3 cSt, 2.7 cSt to 8.1 cSt, 3.0 cSt to 7.2 cSt, or 2.5 cSt to 6.5 cSt. Generally, the high-temperature high-shear (HTHS) viscosity of the base oil at 150 °C is 0.5 to 20 cP, such as 1 to 10 cP, such as 2 to 5 cP (measured according to ASTM D4683-20).

[0147] Generally, when the lubricating oil base stock is used to manufacture the concentrate, it can advantageously be present in an amount to form a concentrate to obtain a concentrate containing 5 wt% to 80 wt%, 10 wt% to 70 wt%, or 5 wt% to 50 wt% of the active ingredient based on the weight of the concentrate.

[0148] Common oils that can be used as base oils include animal oils and vegetable oils (such as castor oil and lard), liquid petroleum, and hydrorefined and / or solvent-treated paraffinic, naphthenic, and mixed paraffin-naphthenic mineral lubricating oils. Oils derived from coal or shale are also available as base oils. The base stock can be manufactured using a variety of different methods, including but not limited to distillation, solvent refining, hydroprocessing, oligomerization, esterification, and re-refining.

[0149] Synthetic lubricating oils that can be used as base oils in this article include hydrocarbon oils, such as homopolymers and copolymers of olefins, known as polyalphaolefins or PAO or Group IV base oils [defined according to API EOLCS1509 (American Petroleum Institute Publication 1509, see Section E.1.3, 19th Edition, January 2021, www.API.org)]. Examples of PAO that can be used as base oils include: poly(ethylene), ethylene-propylene copolymer, polybutene, polypropylene, propylene-isobutylene copolymer, chlorinated polybutene, poly(1-hexene), poly(1-octene), poly(1-decene), C8 to C 20 homopolymers or copolymers of olefins, C8 and / or C 10 and / or C 12 homopolymers or copolymers of olefins, C8 / C 10 copolymer, C8 / C 10 / C 12 copolymer, and C 10 / C 12Copolymers, and their derivatives, analogs, and homologs.

[0150] In another embodiment, the base oil can comprise a polyalphaolefin, including oligomers of linear olefins having 6 to 14 carbon atoms, more preferably 8 to 12 carbon atoms, and more preferably 10 carbon atoms, having a kinematic viscosity at 100 °C (measured by ASTM D445) of greater than 10; preferably having a viscosity index ("VI") measured by ASTM D2270 of greater than 100, preferably greater than 110, more preferably greater than 120, more preferably greater than 130, more preferably greater than 140; and / or having a pour point of less than -5 °C (measured by ASTM D97), more preferably less than -10 °C, more preferably less than -20 °C.

[0151] In another embodiment, the polyalphaolefin oligomers useful in the present disclosure can comprise C 20 to C 1500 alkanes, preferably C 40 to C 1000 alkanes, preferably C 50 to C 750 alkanes, preferably C 50 to C 500 alkanes. PAO oligomers are in one embodiment C5 to C 14 alpha-olefins, and in another embodiment C6 to C 12 alpha-olefins, and in another embodiment C8 to C 12 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 can be substantially 1-decene, and the PAO is a mixture of its dimers, trimers, tetramers, and pentamers (and higher). Available PAOs are more particularly described, for example, in U.S. Patent Nos. 5,171,908 and 5,783,531 and Synthetic Lubricants and High-Performance Functional Fluids 1-52 (Leslie R. Rudnick & Ronald L. Shubkin, eds. Marcel Dekker, Inc. 1999).

[0152] 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 available as SpectraSyn TM Hi-Vis, SpectraSyn TM Low-Vis, SpectraSyn TM plus, SpectraSyn TM ElitePAO's (ExxonMobil Chemical Company, Houston Texas) and Durasyn PAO's from Ineos Oligomers USA LLC were purchased.

[0153] Synthetic lubricating oils that can be used as base oils also include hydrocarbon oils such as homopolymers and copolymers of: alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, bis(2-ethylhexyl)benzene); polyphenyls (biphenyls) (e.g., biphenyl, terphenyl, alkylated polyphenyls); and alkylated diphenyl ethers and alkylated diphenyl sulfides; and their derivatives, analogs, and homologs.

[0154] Another class of suitable synthetic lubricating oils that can be used as base oils includes esters formed by reacting 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) with various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of these esters include dibutyl adipate, bis(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, didocosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, and a complex ester formed by reacting 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid.

[0155] The esters that can be used as synthetic oils herein also include those made from C5 to C 12 monocarboxylic acids and polyols and polyol ethers (such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol).

[0156] Desirable ester base oils are available as Esterex TMPurchased from Esters (ExxonMobil Chemical Company, Houston, Texas).

[0157] Silicone oils, such as polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-silicone oils and silicate oils, constitute another class of useful synthetic lubricants that can be used herein; such oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) silicate, tetra-(p-tert-butylphenyl) silicate, hexa-(4-methyl-2-ethylhexyl) disiloxane, poly(methyl) siloxane, and poly(methylphenyl)-siloxane.

[0158] Other synthetic lubricating oils useful herein include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl decylphosphonate) and polymeric tetrahydrofuran.

[0159] Unrefined oils, refined oils, and re-refined oils can be used in the lubricating compositions of the present disclosure. Unrefined oils are those obtained directly from natural or synthetic sources without further purification treatment. For example, shale oil obtained directly from a retorting operation, petroleum obtained directly from distillation, or ester oils obtained directly from an esterification process and used without further treatment are considered unrefined oils. Refined oils are similar to unrefined oils, except that they have been further processed in one or more purification steps to improve one or more properties. Many such purification techniques are used by those skilled in the art, such as distillation, solvent extraction, acid or base extraction, filtration, and percolation. Re-refined oils are oils obtained by a process similar to the process used to obtain refined oils, where the refining process is applied to a refined oil that has been previously put into use. Such re-refined oils are also known as regenerated oils or reprocessed oils and are typically further processed to remove spent additives and oil cracking products. The re-refined base oils are preferably substantially free of materials introduced through manufacture, contamination, or previous use.

[0160] Some other examples of available base oils are gas-to-liquid ("GTL") base oils, i.e., the base oils are derived from hydrocarbons made from synthesis gas ("syn gas") containing H2 and CO using a Fischer-Tropsch catalyst. These hydrocarbons usually require further processing to be used as base oils. For example, they can be hydroisomerized; hydrocracked and hydroisomerized; dewaxed; or hydroisomerized and dewaxed by methods known in the art. For further information on available GTL base oils and their blends, see U.S. Patent No. 10,913,916 (column 4, line 62 to column 5, line 60) and U.S. Patent No. 10,781,397 (column 14, line 54 to column 15, line 5, and column 16, line 44 to column 17, line 55).

[0161] In particular, oils from renewable sources, i.e., partially based on carbon and energy captured from the environment, such as biogenic sources, are available herein.

[0162] Various base oils are generally classified as Group I, Group II, Group III, Group IV, or Group V according to the API EOLCS 1509 definition (American Petroleum Institute Publication 1509, see Section E.1.3, 19th Edition, January 2021, www.API.org). Generally speaking, Group I base stocks have a viscosity index between approximately 80 and 120 and contain more than approximately 0.03% sulfur and / or less than approximately 90% saturates. Group II base stocks have a viscosity index between approximately 80 and 120 and contain less than or equal to approximately 0.03% sulfur and greater than or equal to approximately 90% saturates. Group III base stocks have a viscosity index greater than approximately 120 and contain less than or equal to approximately 0.03% sulfur and greater than approximately 90% saturates. Group IV base stocks include polyalphaolefins (PAOs). Group V base stocks include base stocks not included in Groups I - IV. (The viscosity index is measured by ASTM D 2270, saturates are measured by ASTM D2007, and sulfur is measured by ASTM D5185, D2622, ASTM D4294, ASTM D4927, and ASTM D3120).

[0163] The base oils useful in the formulated lubricating compositions of the present disclosure can be any one, two, three, or more of the various oils described herein. In an ideal embodiment, the base oils useful in the formulated lubricating compositions of the present disclosure are those described as API Group I (including Group I+), Group II (including Group II+), Group III (including Group III+), Group IV, and Group V oils and mixtures thereof, preferably Group II, Group III, Group IV, and Group V oils and mixtures thereof. Due to their excellent volatility, stability, viscosity, and cleanliness characteristics, the base oils can be Group III, Group III+, Group IV, and Group V base oils. Small amounts of Group I base stocks are admissible, such as the amounts used to dilute additives for incorporation into formulated lubricating oil products, but are generally kept to a minimum, e.g., only the amounts associated with their use as diluent / carrier oils for additives used on an "as-received" basis. With respect to Group II stocks, it is generally more useful for the Group II base stocks to be in the higher quality range associated with that stock, i.e., Group II stocks having a viscosity index of 100 to 120.

[0164] The base oils useful herein can be selected from any synthetic oil, natural oil, or re-refined oil (such as those commonly used as crankcase lubricants for spark-ignition and compression-ignition engines). If desired, mixtures of synthetic oils and / or natural oils and / or re-refined base oils can be used. If desired, multi-modal mixtures (such as bimodal or trimodal mixtures) of Group I, II, III, IV, and / or V base stocks can be used.

[0165] The base oil or base oil blend used herein conveniently has a kinematic viscosity at 100 °C (KV100, measured according to ASTM D445-19a and reported in centistokes (cSt) or its equivalent unit mm2 / s) of from about 2 to about 40 cSt, or from 3 to 30 cSt, or from 4 to 20 cSt, or from 5 to 10 cSt at 100 °C, or the base oil or base oil blend can have a kinematic viscosity at 100 °C of from 2 to 20 cSt, from 2.5 to 2 cSt, preferably from about 2.5 cSt to about 9 cSt.

[0166] The base oil or base oil blend preferably has a saturate content of at least 65 mass%, more preferably at least 75 mass%, such as at least 85 mass%, such as at least 90 mass% as determined by ASTM D2007.

[0167] Preferably, the base oil or base oil blend has a sulfur content of less than 1 mass%, preferably less than 0.6 mass%, most preferably less than 0.4 mass%, such as less than 0.3 mass% based on the total mass of the lubricating composition as measured by ASTM D5185.

[0168] In an embodiment, the volatility of the base oil or base oil blend as measured by the Noack test (ASTM D5800, Procedure B) is less than or equal to 30 mass%, such as less than or equal to 25 mass%, such as less than or equal to 20 mass%, such as less than or equal to 16 mass%, such as less than or equal to 12 mass%, such as less than or equal to 10 mass% based on the total mass of the lubricating composition.

[0169] In an embodiment, the viscosity index (VI) of the base oil is at least 95, preferably at least 110, more preferably at least 120, still more preferably at least 125, most preferably from about 130 to 240, especially from about 105 to 140 (determined by ASTM D2270).

[0170] Base oil can be provided in a major amount and combined with a minor amount of one or more additive components as described below to form a lubricant. This preparation can be achieved by adding the additives directly to the oil or by adding the one or more additives in the form of their concentrates to disperse or dissolve the additives. The additives can be added to the oil by any method known to those skilled in the art before, simultaneously with, or after adding other additives.

[0171] Base oil can be provided in a minor amount and combined with a minor amount of one or more additive components as described below to form an additive concentrate. This preparation can be achieved by adding the additives directly to the oil or by adding the one or more additives in the form of their solutions, slurries, or suspensions to disperse or dissolve the additives in the oil. The additives can be added to the oil by any method known to those skilled in the art before, simultaneously with, or after adding other additives.

[0172] Base oil generally constitutes the major component of the engine oil lubricant composition disclosed herein and is generally present in an amount of at least about 50% by weight, such as about 50 to about 99% by weight, preferably about 70 to about 95% by weight, more preferably about 80 to about 95% by weight, based on the total weight of the composition.

[0173] Generally, one or more base oils are present in the lubricant composition in an amount of more than 32% by weight, or more than 55% by weight, or more than 60% by weight, or more than 65% by weight, based on the total weight of the lubricating composition. Generally, one or more base oils are present in the lubricant composition in an amount of 98% by weight or less, more preferably 95% by weight or less, still more preferably 90% by weight or less. Alternatively, one or more base oils are present in the lubricant composition in an amount of 1 to 99% by mass, or 50 to 97% by mass, or 60 to 95% by mass, or 70 to 95% by weight, based on the weight of the lubricating composition.

[0174] The above base oils and their blends can also be used to manufacture concentrates and to manufacture lubricants therefrom.

[0175] Concentrates constitute a convenient means of handling additives before their use and facilitating the dissolution or dispersion of additives in lubricants. When preparing a lubricant containing more than one type of additive (sometimes referred to as "additive components"), each additive can be incorporated separately in the form of a concentrate. However, in many cases, it is convenient to provide a so-called additive "package" (also referred to as "addpack") that contains one or more of the additives / coconut additives as described below in a single concentrate.

[0176] Typically, one or more base oils are present in the concentrate composition in an amount of 50 wt% or less, or 40 wt% or less, or 30 wt% or less, or 20 wt% or less, based on the total weight of the concentrate composition. Typically, one or more base oils are present in the concentrate composition in an amount of 0.1 to 49 mass%, or 5 to 40 mass%, or 10 to 30 mass%, or 15 to 25 mass%, based on the weight of the concentrate composition.

[0177] In an embodiment, the acylation / functionalization reaction described herein can be carried out in the presence of a base oil diluent. As a by-product, a functionalized base oil can be produced. The oil itself may be acylated and / or functionalized. For example, a maleated base oil or an aminated base oil may be present after the functionalization reaction described herein.

[0178] It is contemplated that the functionalized base oil can comprise an acylated oil.

[0179] It is contemplated that the functionalized base oil can comprise a reaction product of an acylated oil and an amine to form an amide, imide, or a combination thereof.

[0180] It is contemplated that the functionalized base oil can comprise an acylated oil and a reaction product of an acylated oil and an amine to form an amide, imide, or a combination thereof.

[0181] In an embodiment, the lubricating oil composition and / or additive concentrate can comprise a functionalized base oil, such as an acylated oil and / or a reaction product of an acylated oil and an amine or alcohol to form an amide, imide, ester, or a combination thereof, in an amount of 40 wt% or less, or 20 wt% or less, or 10 wt% or less, or 5 wt% or less, based on the total weight of the concentrate composition. Typically, one or more functionalized base oils, such as an acylated oil and / or a reaction product of an acylated oil and an amine or alcohol to form an amide, imide, ester, or a combination thereof, are present in the concentrate in an amount of 0.01 to 40 mass%, or 0.1 to 20 mass%, or 1 to 10 mass%, or 1.5 to 5 mass%, based on the weight of the concentrate composition.

[0182] Typically, one or more functionalized base oils, such as an acylated oil and / or a reaction product of an acylated oil and an amine or alcohol to form an amide, imide, ester, or a combination thereof, are present in the lubricating oil composition in an amount of 0.01 to 40 mass%, or 0.1 to 20 mass%, or 1 to 10 mass%, or 1.5 to 5 mass%, based on the weight of the lubricating oil composition.

[0183] In an embodiment, the functionalized oil can be present in the lubricating oil composition in an amount of 3 wt% or less, preferably 2 wt% or less, preferably 1 wt% or less, preferably 0.1 wt% or less, preferably 0 wt%, based on the weight of the lubricating oil composition.

[0184] In an embodiment, the functionalized oil may be present in the additive concentrate at 3 mass% or less, preferably 2 mass% or less, preferably 1 mass% or less, preferably 0.1 mass% or less, preferably 0 mass% based on the weight of the concentrate composition.

[0185] In an embodiment, the acylation / functionalization reaction described herein may be carried out 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 an embodiment, the acylated and / or functionalized solvent may be present in the concentrate composition at 3 mass% or less, preferably 2 mass% or less, preferably 1 mass% or less, preferably 0.1 mass% or less, preferably 0 mass% based on the weight of the concentrate composition. In an embodiment, the functionalized solvent may be present in the lubricating oil composition at 3 mass% or less, preferably 2 mass% or less, preferably 1 mass% or less, preferably 0.1 mass% or less, preferably 0 mass% based on the weight of the lubricating oil composition.

[0186] In the lubricating oil compositions and additive concentrates of the present invention, the base oil may consist entirely of one or more Group II base oils, one or more Group III base oils, or a mixture of one or more Group II base oils and one or more Group III base oils. In a particular embodiment, the base oil contained in the lubricating oil compositions and additive concentrates of the present invention is entirely one or more Group III base oils. Alternatively, in a particular embodiment, the base oil contained in the lubricating oil compositions and additive concentrates 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 mass%, such as at least 30 mass%, such as at least 50 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 a particular embodiment, the lubricating oil composition of the present invention contains 25 to 65 mass%, such as 30 to 55 mass%, such as 34 to 48 mass% of one or more Group III base oils based on the total mass of the lubricating oil composition; and 20 to 60 mass%, such as 28 to 48 mass%, such as 30 to 38 mass% of one or more Group II base oils based on the total mass of the lubricating oil composition.

[0187] In certain embodiments, the Group III base oil, whether used alone or in combination with a Group II base oil, contains at least 25%, such as at least 50%, such as at least 75%, such as at least 80%, up to 100% of the Group III base oil having a viscosity of 6 cSt or less and / or the Group III base oil having a viscosity of 4 cSt or less (based on the total mass of the Group III base oil present in the lubricating oil composition).

[0188] In certain embodiments, the base oils used in the lubricating oil 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 from about 70:30 to about 30:70, such as from about 65:35 to about 40:60, such as from about 60:40 to about 45:55, such as from about 55:45 to about 50:50.

[0189] In the present disclosure, for clarity, any additive package diluent (used to dilute the active ingredients in the components of the lubricating oil compositions or additive concentrates of the present invention) is not considered to be a "base oil" in the sense of a separate component as described herein. B. Functionalized Polymer

[0190] The present disclosure relates to a functionalized polymer comprising a polymer having an Mn (GPC-PS) of greater than about 10,000 g / mol, such as greater than 20,000 g / mol, such as greater than 25,000 g / mol, such as greater than 30,000 g / mol, such as greater than 35,000 g / mol before functionalization. Alternatively, the functionalized polymer comprises a polymer having an Mn (GPC-PS) of from 10,000 to 300,000 g / mol, such as from 20,000 to about 150,000 g / mol, such as from 30,000 to about 125,000 g / mol, such as from 35,000 to about 100,000 g / mol, such as from 40,000 to 80,000 g / mol before functionalization. The polymer before functionalization may have an Mw / Mn of less than 2 (such as less than 1.6, such as less than 1.5, such as 1.4 or less, such as from 1 to 1.3, such as from 1.0 to 1.25, such as from 1.0 to 1.2, such as from 1.0 to 1.15, such as from 1.0 to 1.1, as determined by GPC-PS). The polymer before functionalization may comprise repeating units of one or more olefins having 4 to 5 carbon atoms (preferably conjugated dienes having 4 to 5 carbon atoms). Before functionalization, the polymer (such as C 4-5 polymer) is preferably fully or partially saturated (such as 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 an alcohol to form an amide, an imide, an ester, or a combination thereof. The functionalized polymer can also be obtained by reacting an acylated polymer (such as a commercially available maleated fully or partially hydrogenated C 4-5 polymer) with an amine to form an amide, an imide, or a combination thereof.

[0191] The present disclosure further relates to the C described herein 4-5Amide-, imide- and / or ester-functionalized saturated (such as hydrogenated) polymers of conjugated dienes, which are obtained by reacting a completely or partially saturated (such as completely or partially hydrogenated) polymer of a conjugated diene with an acylating agent such as maleic acid or maleic anhydride and thereafter reacting the acylated polymer with an amine (such as a polyamine) to form an imide, an amide or a combination thereof, starting from a C with an Mw / Mn of less than 2 4-5 conjugated diene with an acylating agent such as maleic acid or maleic anhydride and thereafter reacting the acylated polymer with an amine (such as a polyamine) to form an imide, an amide or a combination thereof

[0192] The present disclosure relates to polymers containing one or more amine side groups and comprising or consisting of a mixture of the following components: at least partially (preferably completely) hydrogenated C 4-5 olefin polymers with an acylating agent such as maleic acid or maleic anhydride and thereafter reacting the acylated polymer with a polyamine to form an imide, an amide or a combination thereof

[0193] In an embodiment, the functionalized polymer is not prepared in an aromatic solvent (such as benzene or toluene), or the aromatic solvent is present in an amount of 2 wt% or less (such as 1 wt% or less, such as 0.5 wt% or less) based on the weight of the solvent, diluent and polymer

[0194] In an embodiment, the functionalized polymer is not prepared in an alkylated naphthylenic solvent, or the alkylated naphthylenic solvent is present in an amount of 5 wt% or less (such as 3 wt% or less, such as 1 wt% or less) based on the weight of the solvent, diluent and polymer

[0195] The polymers that can be used herein to prepare the functionalized polymers can be homopolymers of butadiene, isoprene, etc

[0196] In an embodiment, the polymers that can be used herein to prepare the functionalized polymers can be homopolymers of isoprene, or copolymers of isoprene and less than 5 mol% (such as less than 3 mol%, such as less than 1 mol%, such as less than 0.1 mol%) of comonomers. In some embodiments, the polymer backbone before functionalization comprises at least 90% isoprene repeat units. In a particular embodiment, the functionalized polymer has a backbone of homopolyisoprene or substantially homopolyisoprene

[0197] The polymers useful herein for preparing functionalized polymers can be copolymers of isoprene and one or more of the following: styrene, methyl-styrene, 2,3-dimethyl-butadiene, 2-methyl-1,3-pentadiene, myrcene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, 2-phenyl-1,3-pentadiene, 3-phenyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2-hexyl-1,3-butadiene, 3-methyl-1,3-hexadiene, 2-benzyl-1,3-butadiene, 2-p-tolyl-1,3-butadiene, 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2,4-heptadiene, 1,3-octadiene, 2,4-octadiene, 3,5-octadiene, 1,3-nonadiene, 2,4-nonadiene, 3,5-nonadiene, 1,3-decadiene, 2,4-decadiene, and 3,5-decadiene, (optionally, the comonomer is present in 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%).

[0198] 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). By 1 1H NMR measurement, the polymerized conjugated diene polymers useful herein for preparing functionalized polymers contain at least about 50% 1,4-insertion, such as at least about 75% 1,4-insertion, such as at least about 80% 1,4-insertion, such as at least about 90% 1,4-insertion, such as at least about 95% 1,4-insertion, such as at least 98% 1,4-insertion, based on the total amount of 2,1-insertion, 1,4-insertion, and 3,4-insertion based on isoprene. For the present disclosure: 1) the phrase "1,4-insertion" includes 1,4- and 4,1-insertions, 2) the phrase "2,1-insertion" includes 2,1- and 1,2-insertions, and 3) the phrase "3,4-insertion" includes 3,4- and 4,3-insertions.

[0199] Optionally, the polymer backbone contains one or more polar monomers, such as (but not limited to) repeat units selected from those of fumarates, acrylates, and combinations thereof.

[0200] Optionally, styrene repeat units may be absent in the polymers useful herein for preparing functionalized polymers. Optionally, styrene repeat units may be absent in the functionalized hydrogenated / saturated polymers.

[0201] Optionally, butadiene repeat units may be absent in the polymers useful herein for preparing functionalized polymers. Optionally, butadiene repeat units may be absent in the functionalized hydrogenated / saturated polymers.

[0202] Optionally, the polymer useful herein for preparing the functionalized polymer may not be homopolybutene. Optionally, the functionalized hydrogenated / saturated polymer may not be homopolybutene.

[0203] Optionally, the polymer useful herein for preparing the functionalized polymer may not be homopolyisobutene. Optionally, the functionalized hydrogenated / saturated polymer may not be homopolyisobutene.

[0204] Optionally, the polymer useful herein for preparing the functionalized polymer may not be a copolymer of isoprene and butadiene. Optionally, the functionalized hydrogenated / saturated polymer may not be a copolymer of isoprene and butadiene.

[0205] The polymer and / or the functionalized polymer useful herein for preparing the functionalized polymer may be a homopolymer or a copolymer. The copolymer may be a random copolymer, a gradient block copolymer, a star copolymer or a block copolymer. The block copolymer is formed from a monomer mixture comprising one or more first monomers (such as isobutene), wherein, for example, the first monomer forms discrete blocks of the polymer, which are linked to second discrete blocks of the polymer formed from a second monomer (such as butadiene). Although the block copolymer has substantially discrete blocks formed from the monomers, the gradient block copolymer may consist of a relatively pure first monomer at one end and a relatively pure second monomer at the other end. The middle of the gradient block copolymer may be more of a gradient combination of these two monomers.

[0206] The polymer useful herein for preparing the functionalized polymer may generally have an Mn (i.e., before functionalization) (GPC-PS) of 10,000 to 150,000 g / mol, or about 10,000 to about 100,000 g / mol, or 20,000 to about 150,000 g / mol, or 30,000 to about 125,000 g / mol, such as about 30,000 to about 50,000 g / mol, such as about 30,000 to about 40,000 g / mol, or 35,000 to about 100,000 g / mol, or 40,000 to 80,000 g / mol. Alternatively, the polymer before functionalization may have an Mn (GPC-PS) of at least 25,000 g / mol, such as at least 30,000 g / mol.

[0207] The polymers useful herein for preparing functionalized polymers can generally have an Mw / Mn (determined by GPC-PS) of from 1 to 2, or greater than 1 to less than 2, or from 1.1 to 1.8, or from 1.2 to 1.5. Alternatively, the polymers useful herein for preparing functionalized polymers can generally have an Mw / Mn of 1 or greater than 1 to less than 2 (such as less than 1.8, such as less than 1.7, such as less than 1.6, such as less than 1.5, such as less than 1.4, such as less than 1.3, such as below 1.25, such as less than 1.2, such as less than 1.15, such as less than 1.12, such as less than 1.10).

[0208] The polymers useful for preparing functionalized polymers can have a Mz (determined by GPC-PS) (GPC-PS) of from 20,000 to 150,000 g / mol, or from 30,000 to about 125,000 g / mol, or from 35,000 to about 100,000 g / mol, or from 40,000 to 80,000 g / mol, such as from about 50,000 to about 60,000 g / mol, or from 40,000 to 60,000 g / mol.

[0209] The polymers useful herein for preparing functionalized polymers can have a glass transition temperature (Tg) below -25 °C, such as below -40 °C, such as below -50 °C, determined by differential scanning calorimetry (DSC) using a Perkin Elmer or TA Instrument Thermal Analysis System (heating the sample from ambient temperature to 210 °C at 10 °C / min and holding at 210 °C for 5 minutes, then cooling to -40 °C at 10 °C / min and holding for 5 minutes).

[0210] The polymers useful herein for preparing functionalized polymers generally have a residual unsaturation of less than 3%, such as less than 2%, such as less than 1%, such as less than 0.5%, such as less than 0.25%, based on the number of double bonds in the non-hydrogenated polymer.

[0211] The polymers useful herein for preparing functionalized polymers generally have a residual metal (such as Li, Co, and Al) content of less than 100 ppm, such as less than 50 ppm, such as less than 25 ppm, such as less than 10 ppm, such as less than 5 ppm. Hydrogenation

[0212] The C polymers useful herein for preparing functionalized polymers 4-5 The polymers can be partially or fully hydrogenated with any hydrogenating agent known to those of ordinary skill in the art. For example, a saturated or partially saturated polymer can be prepared as follows: (a) providing a C containing unsaturation (such as double or triple bonds) 4-5a polymer; and (b) hydrogenating at least a portion or all of the unsaturations (such as double or triple bonds) in the polymer in the presence of a hydrogenating reagent. In some embodiments, the polymer is fully hydrogenated. In some embodiments, the polymer is partially hydrogenated. In some embodiments, the polymer is saturated (hydrogenated) at greater than 50%, such as greater than 60%, such as greater than 70%, such as greater than 80%, such as greater than 90%, such as greater than 95%, such as greater than 98%, such as greater than 99%, such as 50 to 100% saturation (hydrogenation), as determined by the ozone absorption method described by Martino N. Smits and Dirkman Hoefman, Quantitative Determination of Olefinic Unsaturation by Measurement of Ozone Absorption Analytical Chemistry Vol 44, No. 9, page 1688, 1972, Martino N. Smits.

[0213] In an embodiment, the hydrogenating reagent can be hydrogen in the presence of a hydrogenation catalyst. In some embodiments, the hydrogenation catalyst is Pd, Pd / C, Pt, PtO2, Ru(PPh3)2Cl2, Raney nickel, or a combination thereof. In an embodiment, the catalyst is a Pd catalyst. In another embodiment, the catalyst is 5% Pd / C. In a further embodiment, the catalyst can comprise or be 10% Pd / C in a high-pressure reaction vessel and the hydrogenation reaction is allowed to proceed to completion. Typically, after completion, the reaction mixture can be washed, concentrated, and dried to obtain the corresponding hydrogenated product. Alternatively, any reducing agent that can reduce a C═C double bond to a C-C single bond can also be used. For example, an olefin polymer can be hydrogenated by treatment with hydrazine in an oxygen atmosphere in the presence of a catalyst such as 5-ethyl-3-methyllumiflavinium perchlorate to obtain the corresponding hydrogenated product. The reduction reaction with hydrazine is disclosed in Imada et al., J Am. Chem. Soc., 127, pages 14544-14545, (2005), which is incorporated herein by this reference. Acylation

[0214] Fully or partially saturated (hydrogenated) polymers can be chemically modified (functionalized) to provide polymers having at least one polar functional group, such as, but not limited to, halogen, epoxy, hydroxyl, amino, imino, mercapto, imido, carboxyl, and sulfonic acid groups, or combinations thereof. The functionalized polymers can be further modified to provide more desired functional types. In a preferred case, the fully or partially hydrogenated polymer is functionalized by a method including reacting the fully or partially hydrogenated polymer with an unsaturated carboxylic acid (or its derivative, such as maleic anhydride) to provide an acylated polymer (which can then be further functionalized as described below).

[0215] In some embodiments, a carboxylic acid functionality or its reactive equivalent is grafted onto the polymer to form an acylated polymer. Generally, an ethylenically unsaturated carboxylic acid material is grafted onto the polymer backbone. These materials attached to the polymer typically contain at least one double bond (before reaction) and at least one, such as two carboxylic acid (or its anhydride) groups or polar groups that can be converted to the carboxyl group by oxidation or hydrolysis. Maleic anhydride or its derivatives are suitable. It is grafted onto the polymer to provide two carboxylic acid functionalities. Examples of additional unsaturated carboxylic acid materials include itaconic anhydride or the corresponding dicarboxylic acids, such as maleic acid, fumaric acid, and their esters, and cinnamic acid and its esters. In certain embodiments, the acylating agent is maleic anhydride.

[0216] The ethylenically unsaturated carboxylic acid material can be grafted onto the polymer in a variety of ways. It can be grafted onto the polymer in solution or in a substantially pure (molten) form, with or without a free radical initiator. The free radical-initiated grafting of the ethylenically unsaturated carboxylic acid material can also be carried out in a solvent, such as hexane or mineral oil. It can be carried out at an elevated temperature of 100 °C to 250 °C, such as 120 °C to 190 °C, or 150 °C to 180 °C, for example, above 160 °C.

[0217] Free radical initiators that can be used include peroxides, hydroperoxides, and azo compounds, typically those having a boiling point greater than about 100 °C and thermally decomposing within the grafting temperature range to provide free radicals. Representatives of these free radical initiators include azobisisobutyronitrile and 2,5-dimethyl-hex-3-yne-2,5-bis(tert-butylperoxide). The initiator can be used in an amount of 0.005 wt% to 1 wt% based on the weight of the reaction mixture solution. The grafting can be carried out in an inert atmosphere, such as under a nitrogen blanket. The resulting acylated polymer intermediate is characterized by having a carboxylic acid acylation functionality as part of its structure.

[0218] In an embodiment, the acylated polymer may have two or more anhydride groups per polymer molecule and may exhibit less than 10% gel. Alternatively, the acylated polymer may have less than two anhydride groups per polymer molecule and may exhibit less than 10% gel. (See also columns 17, line 14 - column 18, line 11 of U.S. Patent No. 5,429,758).

[0219] Alternatively, in some embodiments, the acylated polymer may have a gel content of less than about 5 wt%, less than 3 wt%, less than 2 wt%, less than 1 wt%, less than 0.5 wt%, less than 0.1 wt% or 0 wt%, where the gel content is measured by determining the amount of material extractable from the polymer using boiling xylene (or cyclohexane) as an extractant. The percentage of soluble and insoluble (gel) material in the polymer composition is determined by soaking a nominally 0.5 mm thick polymer film specimen in cyclohexane at 23 °C for 48 hours or refluxing the film specimen in boiling xylene for half an hour, removing the solvent, weighing the dry residue and calculating the amount of soluble and insoluble (gel) material. This method is generally described in U.S. Patent No. 4,311,628, which is hereby incorporated by reference. For the purposes of this disclosure, the gel content is measured using boiling xylene, unless the sample is insoluble in xylene, in which case the cyclohexane method is used.

[0220] In an embodiment, the acylated polymer may have a saponification value (SAP) of more than 5 g / KOH as determined by ASTM D94, such as more than 10 g / KOH, such as more than 20 g / KOH, such as more than 30 g / KOH, such as more than 50 g / KOH, such as from 10 to 60 g / KOH, such as from 20 to 40 g / KOH.

[0221] In an embodiment, the acylated polymer composition may have less than 5 wt% of unreacted acylating agent (such as maleic anhydride) based on the weight of the acylated polymer composition (i.e., polymer, acylating agent and diluent), such as less than 4 wt%, such as less than 3 wt%, such as less than 1 wt%, such as less than 0.5 wt%, such as less than 0.25 wt%, such as less than 0.1 wt%.

[0222] In an embodiment, the acylation reaction described herein may be carried out in a base oil diluent. As a by - product, a functionalized base oil may be produced. The oil itself may be acylated. For example, a maleated base oil may be present after the acylation reaction described herein.

[0223] It is contemplated that the functionalized base oil may comprise an acylated oil and / or a reaction product of an acylated oil with an amine to form an amide, imide or a combination thereof.

[0224] Preferably, the acylated oil and / or the reaction product of the acylated oil with an amine or an alcohol to form an amide, imide, ester, or a combination thereof may be present in the concentrate in an amount of 40% by weight or less, or 20% by weight or less, or 10% by weight or less, or 5% by weight or less, or 3% by 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 (such as 0 to 40% by mass, or 0.01 to 40% by mass, or 0.1 to 20% by mass, or 1 to 10% by mass, or 1.5 to 5% by mass) based on the weight of the concentrate composition.

[0225] Preferably, one or more functionalized base oils, such as the acylated oil and / or the reaction product of the acylated oil with an amine or an alcohol to form an amide, imide, ester, or a combination thereof may be present in the lubricating oil composition in an amount of 0.01 to 40% by mass, or 0.1 to 20% by mass, or 1 to 10% by mass, or 1.5 to 5% by mass (such as 3% by mass or less, preferably 2% by mass or less, preferably 1% by mass or less, preferably 0.1% by mass or less, preferably 0% by mass) based on the weight of the lubricating oil composition.

[0226] In an embodiment, the acylation reaction described herein is carried out in a solvent-containing medium. As a by-product, an acylated / functionalized solvent may be produced. In an embodiment, the acylated and / or functionalized solvent may be present in the concentrate composition in an amount of 3% by mass or less, preferably 2% by mass or less, preferably 1% by mass or less, preferably 0.1% by mass or less, preferably 0% by mass based on the weight of the concentrate composition. In an embodiment, the functionalized solvent may be present in the lubricating oil composition in an amount of 3% by mass or less, preferably 2% by mass or less, preferably 1% by mass or less, preferably 0.1% by mass or less, preferably 0% by mass based on the weight of the lubricating oil composition.

[0227] In an embodiment, the acylating agent may be added in a manner that minimizes side reactions (such as reactions with the base oil or other diluents present in the reaction vessel).

[0228] In an embodiment, an acylation reaction can occur where an acylating agent (such as maleic acid or maleic anhydride) is added in a continuous or semi - continuous (such as batch) feed stream (e.g., added in controlled relatively equal portions over the reaction time, or in larger and / or smaller portions at different points during 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 controlled stoichiometric amounts. As another example, the polymer can be added to the reaction vessel in a batch manner while the acylating agent is added slowly or in a semi - continuous manner (such as in more than 2, such as more than 5, such as more than 10, such as more than 20, such as more than 30, such as more than 40, such as more than 50, such as more than 60 discrete amounts or portions). Alternatively, the polymer can be divided into X portions and added to the reaction vessel while the acylating agent is divided into more than 1.5X (such as more than 2X, such as more than 5X, such as more than 10X, such as more than 20X, such as more than 30X, such as more than 40X, such as more than 50X, such as 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.

[0229] Preferably, the acylating agent can be added in a manner that minimizes side reactions, such as in a continuous or semi - continuous manner.

[0230] The reaction can also be run to minimize side reactions by using a high - concentration polymer (such as more than 45 wt%, or more than 50 wt%, or more than 55 wt%, or more than 60 wt%) in a diluent in a batch, semi - continuous, or continuous reactor operation. For example, a polymer (such as a hydrogenated isoprene polymer, such as a hydrogenated homopolyisoprene) can be introduced as a solution or suspension (such as a slurry) in a diluent (such as an oil (e.g., a base oil, such as Group I, II, III, IV, and / or V base oils, such as Group II and / or Group III base oils) or an alkane solvent or diluent or a combination thereof) into a batch, semi - continuous, or continuous reactor operation, where the polymer can be present in the solution or suspension at more than 45 wt% (such as more than 50 wt%, or more than 55 wt%, or more than 60 wt%) based on the weight of the polymer and the diluent.

[0231] In an embodiment, side reactions can be minimized as follows: 1) adding the acylating agent in a continuous or semi - continuous manner, and / or 2) introducing the polymer as a solution or suspension in a diluent into a batch, semi - continuous, or continuous reactor operation, where the polymer is present at more than 45 wt% based on the weight of the polymer and the diluent.

[0232] In an embodiment, side reactions are minimized, optionally by adding the acylating agent in a continuous or semi - continuous manner, and / or by introducing a fully or partially hydrogenated polymer (such as an isoprene polymer) as a solution or suspension in a diluent into a batch, semi - continuous or continuous reactor operation to minimize side reactions, the solution or suspension comprising more than 45 wt% (such as more than 50 wt%, or more than 55 wt%, or more than 60 wt%) of the fully or partially hydrogenated polymer based on the weight of the fully or partially hydrogenated polymer and the diluent.

[0233] In an embodiment, side reactions are minimized, optionally by adding the acylating agent in a continuous or semi - continuous manner, and by introducing a fully or partially hydrogenated polymer (such as an isoprene polymer) as a solution or suspension in a diluent into a batch, semi - continuous or continuous reactor operation to minimize side reactions, the solution or suspension comprising more than 45 wt% (such as more than 50 wt%, or more than 55 wt%, or more than 60 wt%) of the fully or partially hydrogenated polymer based on the weight of the fully or partially hydrogenated polymer and the diluent. Functionalization

[0234] In an embodiment, the acylated polymer can react with an alcohol or an amine to form an amide, an imide, an ester, or a combination thereof. The reaction can consist of condensations to form imides, amides, semi - amides, amide - esters, diesters, or amine salts. A primary amino group will generally condense to form an amide, or an imide in the case of maleic anhydride. It should be noted that the amine can have a single primary amino group or multiple primary amino groups.

[0235] Suitable amines can include one or more aromatic amines, such as amines in which a carbon atom of the aromatic ring structure is directly attached to the amino nitrogen. The amine can also be aliphatic. The amine can be a monoamine or a polyamine. In an embodiment, the aliphatic amines can be used alone, or in combination with each other or with aromatic amines. In some embodiments, the amount of aromatic amine can be a major or minor amount compared to the amount of non - aromatic amine, or in some cases, the composition can be substantially free of aromatic amines. Alternatively, the composition can be substantially free of aliphatic amines.

[0236] Examples of aromatic amines useful herein include one or more N - aryl - p - phenylenediamines represented by the following formula: wherein R7 is H, —NHaryl, —NHalkaryl, or a branched or straight - chain hydrocarbon group having from about 4 to about 24 carbon atoms selected from alkyl, alkenyl, alkoxy, aralkyl, or alkaryl; R9 is —NH2, —(NH(CH2) n ) mNH2, —NH-alkyl, —NH-arylalkyl or —CH2-aryl-NH2, where n and m each have a value of from about 1 to about 10; and R8 is hydrogen, or an alkyl, alkenyl, alkoxy, arylalkyl or alkaryl group having from about 4 to about 24 carbon atoms.

[0237] Suitable N-aryl phenylenediamines include N-phenyl phenylenediamine (NPPDA), such as N-phenyl-4,4-phenylenediamine, N-phenyl-1,3-phenylenediamine and N-phenyl-1,2-phenylenediamine and N-naphthyl-1,4-phenylenediamine. Other derivatives of NPPDA may also be included, such as N-propyl-N'-phenyl phenylenediamine.

[0238] In an embodiment, the amine reacting with the acylated polymer is an amine having at least 3 or 4 aryl groups and may be represented by the following formula: wherein, independently of each variable, R 1 may be hydrogen or C l to C5 alkyl (usually hydrogen); R 2 may be hydrogen or C l to C5 alkyl (usually hydrogen); U may be an aliphatic, alicyclic or aromatic group, provided that when U is aliphatic, the aliphatic group may be a straight-chain or branched alkylene group containing 1 to 5, or 1 to 2 carbon atoms; and w may be from 1 to 10, or from 1 to 4, or from 1 to 2 (usually 1).

[0239] Other examples of aromatic amines include aniline, N-alkyl anilines such as N-methyl aniline and N-butyl aniline, di-(p-methylphenyl)amine, naphthylamine, 4-aminodiphenylamine, N,N-dimethyl phenylenediamine, 4-(4-nitro-phenylazo)aniline (Disperse Orange 3), sulfamethazine, 4-phenoxyaniline, 3-nitroaniline, 4-aminoacetanilide, 4-amino-2-hydroxy-benzoic acid phenyl ester (phenyl salicylate), N-(4-amino-5-methoxy-2-methyl-phenyl)-benzamide (Fast Violet B), N-(4-amino-2,5-dimethoxy-phenyl)-benzamide (Fast Blue RR), N-(4-amino-2,5-diethoxy-phenyl)-benzamide (Fast Blue BB), N-(4-amino-phenyl)-benzamide and 4-phenylazoaniline. Suitable amines are mentioned in U.S. Patent No. 7,790,661 and incorporated herein by reference.

[0240] In an embodiment, the compound condensed with the acylated polymer may be represented by the following formula: wherein X is an alkylene group containing from about 1 to about 4 carbon atoms; R 2 , R 3 and R 4 are hydrocarbon groups. wherein X is an alkylene group containing from about 1 to about 4 carbon atoms; R 3 and R 4 are hydrocarbon groups.

[0241] Alternatively, the amine can be an amine having at least 4 aromatic groups and an aldehyde (such as formaldehyde). The aromatic amine can be represented by the following formula: wherein, R 1 is hydrogen or C 1-5 alkyl (usually hydrogen); R 2 is hydrogen or C 1-5 alkyl (usually hydrogen); U is an aliphatic, alicyclic or aromatic group, provided that when U is aliphatic, the aliphatic group can be a straight-chain or branched alkylene group containing 1, 2, 3, 4 or 5, or 1 to 2 carbon atoms; and w is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, such as 0, 1, 2 or 3, or 0 or 1 (usually 0). For further information on such amines, see, for example, US2017 / 0073606, page 5, paragraphs

[0064] -

[0070] and European Patent No. 2401 348.

[0242] Examples of compounds capable of condensing with an acylating agent and further having a tertiary amino group may include, but are not limited to: dimethylaminopropylamine, N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, N,N-dimethylaminoethylamine, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, isobutylenediamine, pentanediamine, hexanediamine, heptanediamine, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenetetramine and bis(hexamethylene)triamine, diaminobenzene, diaminopyridine or mixtures thereof. Compounds capable of condensing with an acylating agent and further having a tertiary amino group may further include aminoalkyl-substituted heterocyclic compounds such as 1-(3-aminopropyl)imidazole and 4-(3-aminopropyl)morpholine, 1-(2-aminoethyl)piperidine, 3,3-diamino-N-methyldipropylamine, 3',3-aminobis(N,N-dimethylpropylamine). Another example of a compound capable of condensing with an acylating agent and having a tertiary amino group includes alkanolamines, including but not limited to triethanolamine, trimethanolamine, N,N-dimethylaminopropanol, N,N-diethylaminopropanol, N,N-diethylaminobutanol, N,N,N-tris(hydroxyethyl)amine, N,N,N-tris(hydroxymethyl)amine.

[0243] In an embodiment, the polymer can react with a polyether aromatic compound. Generally, the polyether aromatic compound has 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 wherein the polyether is capable of reacting with a monocarboxylic acid or its ester, or a dicarboxylic acid, its anhydride or ester.

[0244] Examples of suitable polyether aromatic amines include compounds having the following structures: wherein A represents an aromatic amine structural moiety, wherein the ether group is linked via at least one amine group on the aromatic structural moiety; R1 and R6 are independently hydrogen, alkyl, alkaryl, aralkyl or aryl or a mixture thereof; R2, R3, R4 and R5 are independently hydrogen or an alkyl group containing from about 1 to about 6 carbon atoms or a mixture thereof; a and x are independently integers from about 1 to about 50.

[0245] The acylated polymer can react 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 structural moiety. The polyether polyamine can be based on polymers derived from C2-C6 epoxides such as ethylene oxide, propylene oxide and butylene oxide. Examples of polyether polyamines are sold under the Jeffamine TM brand and are available from Huntsman Corporation.

[0246] Amines that can be used in combination with the acylated polymer herein include one or more of the following: N-phenylenediamines (such as 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 (such as 3-nitroaniline), N-phenylethylenediamines (such as N1-phenylethane-1,2-diamine), N-aminophenylacetamides (such as N-(4-aminophenyl)acetamide), morpholinopropylamines (such as 3-morpholinopropan-1-amine) and aminoethylpiperazines (such as 1-(2-aminoethyl)piperazine). In a particular embodiment of the invention, the amine is 4-aminodiphenylamine, ADPA.

[0247] In an embodiment, the functionalization (such as amination) reaction described herein can be carried out in a diluent (such as a base oil or an alkane solvent). As a by-product, a functionalized diluent (such as a functionalized base oil) can be produced. It is contemplated that the functionalized diluent (such as a functionalized base oil) can comprise the reaction product of an acylated diluent (such as an acylated base oil) with an amine to form an amide, an imide or a combination thereof.

[0248] Preferably, the reaction product of an acylation diluent (such as an acylated oil) with an amine or an alcohol (to form an amide, imide, ester, or a combination thereof) may be present in the concentrate in an amount of 40 wt% or less, or 20 wt% or less, or 10 wt% or less, or 5 wt% or less, or 3 wt% or less, preferably 2 wt% or less, preferably 1 wt% or less, preferably 0.1 wt% or less, preferably 0 wt% (such as 0 to 40 wt%, or 0.01 to 40 wt%, or 0.1 to 20 wt%, or 1 to 10 wt%, or 1.5 to 5 wt%) based on the weight of the concentrate composition.

[0249] Preferably, one or more functionalized base oils, such as the reaction product of an acylation diluent (such as an acylated base oil) with an amine or an alcohol to form an amide, imide, ester, or a combination thereof, may be present in the lubricating oil composition in an amount of 0.01 to 40 wt%, or 0.1 to 20 wt%, or 1 to 10 wt%, or 1.5 to 5 wt% (such as 3 wt% or less, preferably 2 wt% or less, preferably 1 wt% or less, preferably 0.1 wt% or less, preferably 0 wt%) based on the weight of the lubricating oil composition.

[0250] In an embodiment, the functionalization (such as amination) reaction described herein may be carried out in a solvent-containing medium. As a by-product, a functionalized solvent may be produced. In an embodiment, the functionalized solvent may be present in the concentrate composition in an amount of 3 wt% or less, preferably 2 wt% or less, preferably 1 wt% or less, preferably 0.1 wt% or less, preferably 0 wt% based on the weight of the concentrate composition. In an embodiment, the functionalized solvent may be present in the lubricating oil composition in an amount of 3 wt% or less, preferably 2 wt% or less, preferably 1 wt% or less, preferably 0.1 wt% or less, preferably 0 wt% based on the weight of the lubricating oil composition.

[0251] In an embodiment, the acylated base oil / solvent may be removed prior to functionalization. Conjugated diene functionalized polymer

[0252] The functionalized polymer may be a homopolymer of a C4 or C5 olefin, such as a homopolymer of butadiene or a homopolymer of isoprene.

[0253] In an embodiment, 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%).

[0254] The functionalized polymer can comprise or be a copolymer of isoprene and one or more of the following: styrene, methyl-styrene, 2,3-dimethyl-butadiene, 2-methyl-1,3-pentadiene, myrcene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, 2-phenyl-1,3-pentadiene, 3-phenyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2-hexyl-1,3-butadiene, 3-methyl-1,3-hexadiene, 2-benzyl-1,3-butadiene, 2-p-tolyl-1,3-butadiene, 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2,4-heptadiene, 1,3-octadiene, 2,4-octadiene, 3,5-octadiene, 1,3-nonadiene, 2,4-nonadiene, 3,5-nonadiene, 1,3-decadiene, 2,4-decadiene, and 3,5-decadiene, (optionally, the comonomer is present in 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%).

[0255] In an embodiment, the functionalized polymer comprises 10 (such as 9, such as 8, such as 7, such as 6, such as 5, such as 4, such as 3, such as 2, such as 1) wt% or less of styrene monomer based on the weight of the functionalized polymer.

[0256] In an embodiment, styrene repeating units may be absent in the functionalized polymer.

[0257] In an embodiment, the functionalized polymer can be a block copolymer or a gradient block copolymer that does not contain a styrene block.

[0258] In an embodiment, the functionalized polymer can be a block copolymer or a gradient block copolymer that comprises isoprene (or consists of or consists essentially of isoprene).

[0259] In an embodiment, the functionalized polymer can be a block copolymer or a gradient block copolymer that comprises 50 wt% or more of isoprene based on the weight of the copolymer.

[0260] In an embodiment, the functionalized polymer can be a block copolymer or a gradient block copolymer that comprises C 4-5 conjugated diene (or consists of or consists essentially of C 4-5 conjugated diene), preferably a block copolymer or a gradient block copolymer that comprises 50 (such as 60, such as 70, such as 80, such as 90, such as 95, such as 98) wt% or more of C 4-5 conjugated diene based on the weight of the copolymer. 4-5 conjugated diene.

[0261] In an embodiment, the functionalized polymer can be a copolymer comprising greater than 50 (such as 60, such as 70, such as 80, such as 90, such as 95, such as 98) weight percent isoprene based on the weight of the copolymer.

[0262] In an embodiment, the functionalized polymer can be a copolymer comprising greater than 50 (such as 60, such as 70, such as 80, such as 90, such as 95, such as 98) weight percent butadiene based on the weight of the copolymer.

[0263] In an embodiment, the functionalized polymer can be a copolymer comprising greater than 50 (such as 60, such as 70, such as 80, such as 90, such as 95, such as 98) weight percent butadiene and isoprene based on the weight of the copolymer.

[0264] In an embodiment, the functionalized polymer can be a diblock copolymer comprising at least one isoprene homopolymer or copolymer block.

[0265] Optionally, there may be no butadiene repeat units in the functionalized polymer.

[0266] Optionally, the functionalized polymer may not be homopolyisobutene.

[0267] Optionally, the functionalized polymer may not be a copolymer of isoprene and butadiene.

[0268] Typically, the polymerized conjugated dienes in the functionalized polymer include monomer units that have been inserted into the growing polymer chain by both conjugate addition and non-conjugate addition. In an embodiment, by 13 13C NMR measurement, based on the total number of conjugate additions and non-conjugate insertions, the functionalized polymer contains at least about 50% of the insertions by conjugate addition, such as at least about 75% of the insertions by conjugate addition, such as about 80% of the insertions by conjugate addition, such as about 85% to about 100% of the insertions by conjugate addition.

[0269] Insertion of isoprene most commonly occurs by 2,1 insertion, 1,4 insertion (trans and cis), and 3,4 insertion of isoprene. (By 1 1H NMR measurement of the insertion geometry). By 1For ¹H NMR measurements, the functionalized isoprene polymer contains at least about 50% 1,4 - insertions, based on the total of 2,1 - insertions, 1,4 - insertions, and 3,4 - insertions based on isoprene, such as at least about 75% 1,4 - insertions, such as at least about 80% 1,4 - insertions, such as at least about 90% 1,4 - insertions, such as at least about 95% 1,4 - insertions, such as at least 98% 1,4 - insertions. For the present disclosure: 1) the phrase “1,4 - insertion” includes 1,4 - and 4,1 - insertions, 2) the phrase “2,1 - insertion” includes 2,1 - and 1,2 - insertions, and 3) the phrase “3,4 - insertion” includes 3,4 - and 4,3 - insertions.

[0270] The functionalized polymer can be a homopolymer or a copolymer. Optionally, the functionalized polymer comprises a homopolymer or copolymer of isoprene. The copolymer can be a random copolymer, a gradient block copolymer, a star copolymer, or a block copolymer.

[0271] The functionalized polymer can generally have a Mn (GPC - PS) of from 20,000 to 150,000 g / mol, or from 20,000 to about 150,000 g / mol, or from 30,000 to about 125,000 g / mol, or from 35,000 to about 100,000 g / mol, or from 40,000 to 80,000 g / mol.

[0272] The polymer before functionalization can generally have a Mn / Mw (GPC - PS) of from 1.0 to 2, such as from 1.1 to 1.5, such as from 1.1 to 1.3, such as from 1.1 to 1.2. As functionalization proceeds, Mw / Mn broadening may occur.

[0273] The functionalized polymer can generally have a Mw / Mn (GPC - PS) of from 1 to 3, or from 1 to 2, or greater than 1 to less than 2, or from 1.05 to 1.9, or from 1.10 to 1.8, or from 1.10 to 1.7, or from 1.12 to 1.6, or from 1.13 to 1.5, or from 1.15 to 1.4, or from 1.15 to 1.3. Alternatively, the functionalized polymer can generally have a Mw / Mn of 1 or greater than 1 to less than 2 (such as less than 1.8, such as less than 1.7, such as less than 1.6, such as less than 1.4, such as less than 1.2, such as less than 1.15, such as less than 1.12, such as less than 1.10).

[0274] In an embodiment, the functionalized polymer can have a saponification value (SAP) of greater than 25 (such as 28, such as 30, such as 32, such as 34) mgKOH / g as determined by ASTM D94.

[0275] In an embodiment, the functionalized polymer can contribute more than 17% (such as more than 20%, such as from 17 to 40%, such as from 20 to 30%) of the saponification value of the lubricating oil composition.

[0276] In embodiments, the functionalized polymer may have an average functionality of from 1.4 to 20 FG grafts / polymer chain as determined by GPC-PS, such as from 1.4 to 15 FG grafts / polymer chain, such as from 3 to 12.5 FG grafts / polymer chain, such as from 4 to 10 FG grafts / polymer chain, for example 7, 8 or 9 FG grafts / polymer chain.

[0277] The functionalized polymer may have an average functionality of 15 (such as 14, 13, 12, 11, 10, 9, 8, 7 or 6) or fewer FG grafts / polymer chain as determined by GPC-PS.

[0278] The functionalized polymer may have an average functionality of 1 (such as 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9 or 4.0) or more FG grafts / polymer chain as determined by GPC-PS.

[0279] The functionalized polymer may have an average functionality of 1 (such as 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9 or 4.0) to 15 (such as 14, 13, 12, 11, 10, 9, 8, 7 or 6) FG grafts / polymer chain as determined by GPC-PS.

[0280] In embodiments, the functionalized polymer may have an aromatic content of 5% or less, such as 3% or less, such as 1% or less, such as 0% based on the weight of the polymer.

[0281] In embodiments, the functionalized polymer may comprise a branched C monomer acylated polymer having an Mw / Mn of 2 or less, such as from 1 to 2.0 as determined by GPC-PS and having a Mn of from 20,000 to 500,000 g / mol. 4-5 monomer

[0282] In an embodiment, the functionalized polymer may have a number average molecular weight (Mn) of 15,000 (such as 20,000, such as 25,000, such as 30,000, such as 35,000, such as 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) (GPC-PS) of 20,000 to 60,000, particularly 30,000 to 40,000 g / mol.

[0283] In an embodiment, the functionalized polymer may have a weight average molecular weight (Mw) of 50,000 (such as 40,000, such as 35,000) g / mol or less as determined by GPC-PS. In an embodiment, the functionalized polymer may have a weight average molecular weight (Mw) of 1000 to 50,000 g / mol, such as 5000 to 40,000 g / mol as determined by GPC-PS.

[0284] In an embodiment, the functionalized polymer may have a z-average molecular weight (Mz) (GPC-PS) of 5000 to 150,000 g / mol, such as 10,000 to 150,000 g / mol, such as 15,000 to 70,000 g / mol, such as 20,000 to 150,000 g / mol, or 20,000 to about 150,000 g / mol, or 30,000 to about 125,000 g / mol, or 35,000 to about 100,000 g / mol, or 40,000 to 80,000 g / mol, or 40,000 to 60,000 g / mol.

[0285] 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%, wherein the gel content is measured by determining the amount of material extractable from the polymer using boiling xylene (or cyclohexane) as an extractant. The percentages of soluble and insoluble (gel) materials in the polymer composition are determined as described herein.

[0286] In an embodiment, the functionalized polymer can have a functionality distribution (Fd) value of 3.5 or less (such as 3.4 or less, such as 1 to 3.3, such as 1.1 to 3.2, such as 1.2 to 3.0, such as 1.4 to 2.9, such as 1.7 to 1.9, determined by GPC-PS (the functionality distribution (Fd) value is determined as described in the Examples section below)) and from 1.4 to 20 FG grafts / polymer chain, such as from 1.4 to 15 FG grafts / polymer chain, such as from 3 to 12.5 FG grafts / polymer chain, such as from 4 to 10 FG grafts / polymer chain, such as an average functionality of 7, 8, or 9 FG grafts / polymer chain, determined by GPC-PS.

[0287] This disclosure relates to amide-, imide-, and / or ester-functionalized hydrogenated / saturated polymers comprising C 4-5 olefins (consisting essentially of C 4-5 olefins or consisting of C 4-5 olefins) having an Mw / Mn of less than 2 and a functionality distribution (Fd) value of 3.5 or less (such as 3.4 or less, such as 1 to 3.3, such as 1.1 to 3.2, such as 1.2 to 3.0, such as 1.4 to 2.9, determined by GPC-PS), and wherein if the polymer before functionalization is a C4 olefin polymer, such as polyisobutylene, polybutadiene, or a copolymer thereof (preferably polyisobutylene or a copolymer of isobutylene and butadiene), the C4 olefin polymer has an Mn (GPC-PS) of 10,000 g / mol or more, and if the polymer before functionalization is a copolymer of C4 / C5 isoprene and butadiene, the copolymer has an Mn greater than 25,000 Mn (GPC-PS).

[0288] This disclosure also relates to amide-, imide-, and / or ester-functionalized hydrogenated / saturated polymers comprising more than 90 mole% isoprene repeat units having an Mw / Mn of less than 2 and a functionality distribution (Fd) value of 3.5 or less (such as 3.4 or less, such as 1 to 3.3, such as 1.1 to 3.2, such as 1.2 to 3.0, such as 1.4 to 2.9, determined by GPC-PS), and wherein the polymer before functionalization has an Mn (GPC-PS) of 10,000 g / mol or more, such as 30,000 g / mol or more.

[0289] The present disclosure also relates to amide-, imide- and / or ester-functionalized hydrogenated / saturated isoprene homopolymers having an Mw / Mn of less than 2, such as less than 1.8, a functionality distribution (Fd) value of 3.5 or less (such as 3.4 or less, such as 2.5 or less, or from 1 to 3.3, such as from 1.1 to 3.2, such as from 1.2 to 3.0, such as from 1.4 to 2.9, as determined by GPC-PS), an average functionality (Fv) of 4 to 10 functional groups grafted / polymer chain, and wherein the polymer before functionalization has an Mn of 20,000 g / mol or more, such as from 20,000 to 50,000 g / mol (as determined by GPC-PS).

[0290] In certain embodiments, the functionalized polymers used in the lubricating oil 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, as determined as disclosed herein; an Mn (GPC-PS) of 20,000 to 50,000 g / mol, such as 30,000 to 40,000 g / mol; and / or an Mz (GPC-PS) of 40,000 to 70,000 g / mol, such as 50,000 to 60,000 g / mol; and / or having a backbone of homopolyisoprene that has been functionalized with maleic anhydride and further reacted with a polyamine (such as N-phenyl-p-phenylenediamine (NPPDA), such as 4-aminodiphenylamine (ADPA)).

[0291] In the compositions according to the present disclosure, component B) is considered to form a dispersant mixture as disclosed herein together with the poly(alkenyl) succinic acid dispersant of component I). Accordingly, component B) and the poly(alkenyl) succinic acid dispersant of component I) are used together to determine the amount of the dispersant mixture in the lubricating oil compositions or additive concentrates disclosed herein. In certain embodiments, the dispersant mixture comprises 0.01 to 15% by mass, such as 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 the functionalized polymer, based on the total mass of the dispersant mixture.

[0292] The lubricating oil 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, defoamers, viscosity improvers, 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 several will be discussed in more detail below. C. Detergent

[0293] The lubricating composition may comprise one or more metal detergents (such as blends of metal detergents), also known as "detergent additives". Metal detergents generally act both as detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life.

[0294] Detergents generally comprise a polar head and a long hydrophobic tail, and the polar head comprises a metal salt of an acidic organic compound. The salt may contain stoichiometric amounts of metal, in which case they are generally described as normal or neutral salts and generally have a total base number ("TBN", measured by ASTM D2896) of at most 150 mg KOH / g, such as 0 to 80 (or 5 - 30) mg KOH / g. A large amount of metal base can be introduced by reacting an excess metal compound (such as an oxide or hydroxide) with an acidic gas (such as carbon dioxide). Such detergents, sometimes referred to as overbased, may have a TBN of more than 100 mg KOH / g (such as more than 200 mg KOH / g), and generally have a TBN of more than 250 mg KOH / g, such as more than 300 mg KOH / g, such as 200 to 800 mg KOH / g, 225 to 700 mg KOH / g, 250 to 650 mg KOH / g, or 300 to 600 mg KOH / g, such as 150 to 650 mg KOH / g.

[0295] Suitable detergents include metals, especially alkali metals (Group 1 metals, such as Li, Na, K, Rb) or alkaline earth metals (Group 2 metals, such as Be, Mg, Ca, Sr, Ba), especially sodium, potassium, lithium, calcium, and magnesium, such as oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, naphthenates, and other oil-soluble carboxylates of Ca and / or Mg. In addition, the detergent may include hybrid detergents containing any combination of sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and naphthenates of sodium, potassium, lithium, calcium, or magnesium or other oil-soluble carboxylates of Group 1 and / or 2 metals.

[0296] Preferably, the detergent additives useful in the present disclosure include calcium and / or magnesium metal salts. The detergent can be a calcium and / or magnesium carboxylate (such as salicylate), sulfonate or phenate detergent. More preferably, the detergent additive is selected from magnesium salicylate, calcium salicylate, magnesium sulfonate, calcium sulfonate, magnesium phenate, calcium phenate and hybrid detergents containing two, three, four or more of these detergents and / or combinations thereof.

[0297] The metal-containing detergents can also include "hybrid" detergents formed with mixed surfactant systems including phenate and / or sulfonate components such as phenate / salicylate, sulfonate / phenate, sulfonate / salicylate, sulfonate / phenate / salicylate as described in, for example, U.S. Patent Nos. 6,429,178; 6,429,179; 6,153,565; and 6,281,179. When, for example, a hybrid sulfonate / phenate detergent is used, the hybrid detergent is considered equivalent to the amount of separate phenate and sulfonate detergents introducing similar amounts of phenate and sulfonate soaps, respectively.

[0298] The overbased metal-containing detergents can be sodium salts, calcium salts, magnesium salts or mixtures thereof of phenates, sulfur-containing phenates, sulfonates, salixarates and salicylates. Overbased phenates and salicylates generally have a total base number of 180 to 650 mg KOH / g, such as 200 to 450 TBN mg KOH / g. Overbased sulfonates generally have a total base number of 250 to 600 mg KOH / g, or 300 to 500 mg KOH / g. In an embodiment, the sulfonate detergent can be a linear alkylbenzene sulfonate detergent having a metal ratio of at least 8 as described in paragraphs

[0026] to

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

[0299] The detergent additive can comprise one or more magnesium sulfonate detergents. The magnesium detergent can be a neutral salt or an overbased salt. Suitably, the magnesium detergent is an overbased magnesium sulfonate having a TBN of 80 to 650 mg KOH / g (ASTM D2896), such as 200 to 500 mg KOH / g, such as 240 to 450 mg KOH / g.

[0300] Alternatively, the detergent additive is magnesium salicylate. Suitably, the magnesium detergent has a TBN of 30 to 650 mg KOH / g (ASTM D2896), such as 50 to 500 mg KOH / g, such as 200 to 500 mg KOH / g, such as 240 to 450 mg KOH / g, or 150 mg KOH / g or less, such as 100 mg KOH / g or less, of magnesium salicylate.

[0301] Alternatively, the detergent additive is a combination of magnesium salicylate and magnesium sulfonate.

[0302] The magnesium detergent provides 200 - 4000 ppm of magnesium atoms, suitably 200 - 2000 ppm, 300 to 1500 ppm or 450 - 1200 ppm of magnesium atoms (ASTM D5185) to its lubricating composition.

[0303] The detergent composition may comprise (or consist of) a combination of one or more magnesium sulfonate detergents and one or more calcium salicylate detergents.

[0304] A combination of one or more magnesium sulfonate detergents and one or more calcium salicylate detergents provides to its lubricating composition: 1) 200 - 4000 ppm of magnesium atoms, suitably 200 - 2000 ppm, 300 to 1500 ppm or 450 - 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, such as 500 - 4000 ppm, preferably 750 - 3000 ppm, more preferably 900 - 2000 ppm of atomic calcium (ASTM D5185).

[0305] The detergent may comprise one or more calcium detergents, such as calcium carboxylates (e.g., salicylates), sulfonates or phenates detergents.

[0306] Suitably, the calcium detergent has a TBN of 30 to 700 mg KOH / g (ASTM D2896), such as 50 to 650 mg KOH / g, such as 200 to 500 mg KOH / g, such as 240 to 450 mg KOH / g, or 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.

[0307] Suitably, the calcium detergent is calcium salicylate, calcium sulfonate or calcium phenate having a TBN of 30 to 700 mg KOH / g, 30 to 650 mg KOH / g (ASTM D2896), such as 50 to 650 mg KOH / g, such as 200 to 500 mg KOH / g, such as 240 to 450 mg KOH / g, or 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.

[0308] 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 atomic calcium to the lubricating oil composition (ASTM D5185). If present, any calcium detergent is suitably present in an amount sufficient to provide no greater than 4000 ppm, preferably no greater than 3000 ppm, more preferably no greater than 2000 ppm atomic calcium to the lubricating oil composition (ASTM D5185). If present, any calcium detergent is suitably present in an amount sufficient to provide 500 - 4000 ppm, preferably 750 - 3000 ppm, more preferably 900 - 2000 ppm atomic calcium to the lubricating oil composition (ASTM D5185).

[0309] Suitably, the total atomic weight of the metals of the detergents in the lubricating compositions from all aspects according to the present disclosure is no greater than 5000 ppm, preferably no greater than 4000 ppm, more preferably no greater than 2000 ppm (ASTM D5185). The total atomic metal content of the detergents in the lubricating oil compositions from all aspects according to the present disclosure is suitably at least 500 ppm, preferably at least 800 ppm, more preferably at least 1000 ppm (ASTM D5185). The total atomic metal content of the detergents in the lubricating oil compositions from all aspects according to the present disclosure is suitably 500 to 5000 ppm, preferably 500 to 3000 ppm, more preferably 500 to 2000 ppm (ASTM D5185).

[0310] Sulfonate detergents can be prepared from sulfonic acids, which are typically obtained by sulfonation of alkyl-substituted aromatics (such as those obtained by fractional distillation of petroleum or by alkylation of aromatics). Examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, biphenyl, or halogen derivatives thereof, such as chlorobenzene, chlorotoluene, and chloronaphthalene. Alkylation can be carried out with an alkylating agent having from about 3 to more than 70 carbon atoms in the presence of a catalyst. The alkaryl sulfonates generally contain from about 9 to about 80 or more carbon atoms per alkyl-substituted aromatic structural moiety, preferably from about 16 to about 60 carbon atoms. The oil-soluble sulfonate or alkaryl sulfonic acid can be neutralized with metal oxides, hydroxides, alkoxides, carbonates, carboxylates, sulfides, hydrosulfides, nitrates, borates, and ethers. The amount of the metal compound is selected considering the desired TBN of the final product, but is generally about 100 to 220 mass% (preferably at least 125 mass%) of the stoichiometrically required amount.

[0311] Metal salts of phenols and sulfurized phenols 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 phenols can be prepared by reacting a phenol with sulfur or a sulfur-containing compound (such as hydrogen sulfide, sulfur monohalide, or sulfur dihalide) to form a product that is generally a mixture of compounds in which two or more phenols are bridged by sulfur-containing bridges.

[0312] Carboxylate detergents (such as salicylates) can be prepared by reacting an aromatic carboxylic acid (such as a 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 structural moiety of the aromatic carboxylic acid can contain heteroatoms, such as nitrogen and oxygen. The structural moiety preferably contains only carbon atoms; the structural moiety more preferably contains six or more carbon atoms; for example, benzene is a preferred structural moiety. The aromatic carboxylic acid can contain one or more aromatic structural moieties fused or linked by an alkylene bridge, such as one or more benzene rings.

[0313] Preferred substituents in the oil-soluble salicylic acid are alkyl substituents. In alkyl-substituted salicylic acids, the alkyl advantageously contains from 5 to 100, preferably from 9 to 30, especially from 14 to 20 carbon atoms. If there is more than one alkyl, the average number of carbon atoms in all alkyls is preferably at least 9 to ensure sufficient oil solubility.

[0314] In an embodiment, the ratio of the detergent atomic metal to atomic molybdenum in the lubricating oil composition can be less than 3:1, such as less than 2:1.

[0315] In addition, since the metal organic and inorganic base salts used as detergents can contribute to the sulfate ash content of the lubricating oil composition, in the embodiments of the present disclosure, the amount of such additives is minimized. To maintain a low sulfur content, salicylate detergents can be used and the lubricating compositions herein can contain one or more salicylate detergents (the detergents are preferably used in an amount of 0.05 to 20.0% by weight, more preferably 1.0 to 10.0% by weight, and most preferably 2.0 to 5.0% by weight based on the total weight of the lubricating composition).

[0316] As determined by ASTM D874, based on the total weight of the lubricating composition, the total sulfate ash content of the lubricating compositions herein is generally not greater than 2.0% by weight, or at a level not greater than 1.0% by weight, or at a level not greater than 0.8% by weight, or at a level not greater than 0.5% by weight.

[0317] In addition, it is useful that each detergent independently has a TBN value (total base number) in the range of 10 to 700 mg KOH / g, 10 to 500 mg KOH / g, or in the range of 100 to 650 mg KOH / g, or in the range of 10 to 500 mg KOH / g, or in the range of 30 to 350 mg KOH / g, or in the range of 50 to 300 mg KOH / g as measured by ISO 3771.

[0318] Sulfonate detergents (such as Ca and / or Mg sulfonate detergents) can be present in an amount that provides 0.1% to 1.5% by weight, or 0.15 to 1.2% by weight, or 0.2% to 0.9% by weight of sulfonate soap to the lubricant composition.

[0319] Salicylate detergents (such as Ca and / or Mg salicylate detergents) are present in an amount that provides 0.3% to 1.4% by weight, or 0.35% to 1.2% by weight, or 0.4% to 1.0% by weight of salicylate soap to the lubricant composition.

[0320] The sulfonate soap can be present in an amount of 0.2% to 0.8% by weight of the lubricant composition, and the salicylate soap can be present in an amount of 0.3% to 1.0% by weight of the lubricant composition.

[0321] All alkaline earth metal detergent soaps in total can be present in an amount of 0.6% to 2.1% by weight, or 0.7% to 1.4% by weight of the lubricant composition.

[0322] Typically, lubricating compositions formulated for heavy-duty diesel engines contain about 0.1 to about 10 mass%, or about 0.5 to about 7.5 mass%, or about 1 to about 6.5 mass% of detergents based on the lubricating composition.

[0323] Typically, a lubricating composition formulated for a passenger car engine comprises from about 0.1 to about 10% by mass, or from about 0.5 to about 7.5% by mass, or from about 1 to about 6.5% by mass of a detergent, based on the lubricating composition.

[0324] Typically, a lubricating composition formulated for a driveline (e.g., a transmission) comprises from about 0.1 to about 10% by mass, or from about 0.5 to about 7.5% by mass, or from about 2 to about 6.5% by mass of a detergent, based on the lubricating composition.

[0325] In an embodiment, the one or more detergents used in the lubricating oil composition and additive concentrate of the present invention are present in an amount of 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 in an amount of 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.

[0326] In an embodiment, the detergents used in the lubricating oil composition and additive concentrate of the present invention are selected from oil-soluble neutral or overbased sulfonates and phenates of alkali metals or alkaline earth metals, particularly oil-soluble neutral or overbased sulfonates of calcium or magnesium (such as calcium sulfonate and / or magnesium sulfonate).

[0327] In a particular embodiment, the lubricating oil composition and additive concentrate of the present invention are free of phenate detergents and / or free of salicylate detergents. Preferably, the lubricating oil composition and additive concentrate of the present invention do not contain or substantially do not contain phenate detergents, such as less than 1.2% by mass, such as less than 1.0% by mass, such as less than 0.5% by mass, based on the total mass of the lubricating oil composition or additive concentrate, and / or do not contain or substantially do not contain salicylate detergents, such as less than 1.2% by mass, such as less than 1.0% by mass, such as less than 0.5% by mass, based on the total mass of the lubricating oil composition or additive concentrate. More preferably, the detergents used in the lubricating oil composition and additive concentrate of the present invention are a mixture of calcium sulfonate and magnesium sulfonate, particularly consisting of a mixture of calcium sulfonate and magnesium sulfonate. D. Friction modifier

[0328] A friction modifier is any material that can change the coefficient of friction of a surface lubricated with any lubricant or fluid containing such a material. If desired, friction modifiers, also known as friction reducers or lubricity agents or oiliness agents, and other such reagents that alter the ability of a base oil, formulated lubricating composition, or functional fluid to condition the coefficient of friction of a lubricated surface can be effectively used in combination with the base oils or lubricating compositions of the present disclosure. Friction modifiers that reduce the coefficient of friction are particularly advantageously combined with the base oils and lubricating compositions of the present disclosure.

[0329] Exemplary friction modifiers can include, for example, organometallic compounds or materials or mixtures thereof. Exemplary organometallic friction modifiers useful in the lubricating oil formulations of the present disclosure include, for example, tungsten and / or molybdenum compounds such as molybdenum amines, molybdenum diamines, organotungstates, molybdenum dithiocarbamates, molybdenum dithiophosphates, molybdenum amine complexes, molybdenum carboxylates, etc., and mixtures thereof. Examples of available molybdenum-containing compounds can conveniently include molybdenum dithiocarbamate, trinuclear molybdenum compounds such as those described in PCT Publication No. WO 98 / 26030, sulfides of molybdenum, and molybdenum dithiophosphates.

[0330] Other known friction modifiers include oil-soluble organomolybdenum compounds. Such organomolybdenum friction modifiers can also provide antioxidant and antiwear benefits to lubricating oil compositions. Examples of such oil-soluble organomolybdenum compounds include dithiocarbamates, dithiophosphates, dithiophosphites, xanthates, thioxanthates, sulfides, etc., and mixtures thereof. Particularly preferred are molybdenum dithiocarbamate, dialkyldithiophosphate molybdenum, alkylxanthate molybdenum, and alkylthioxanthate molybdenum.

[0331] In addition, the molybdenum compound can be an acidic molybdenum compound. These compounds react with basic nitrogen compounds as measured by ASTM test D664 or D2896 titration procedures and are generally hexavalent. Include molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts such as sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide, or similar acidic molybdenum compounds.

[0332] Molybdenum compounds useful in the compositions of the present disclosure include organomolybdenum compounds of the formula Mo(R"OCS2)4 and Mo(R"SCS2)4, where R" is an organic group selected from alkyl, aryl, aralkyl, and alkoxyalkyl groups generally having from 1 to 30 carbon atoms, preferably from 2 to 12 carbon atoms, and most preferably an alkyl group having from 2 to 12 carbon atoms. Particularly preferred are dialkyldithiocarbamates of molybdenum.

[0333] Another class of organomolybdenum compounds useful in the lubricating compositions of the present disclosure is trinuclear molybdenum compounds, particularly of the formula Mo3S kL n Q z and mixtures thereof, where L is an independently selected ligand having an organic group with a sufficient number of carbon atoms to render the compound soluble or dispersible in oil, n is from 1 to 4, k varies from 4 to 7, Q is selected from neutral electron-donating compounds such as water, amines, alcohols, phosphines, and ethers, and z is from 0 to 5 and includes non-stoichiometric values. There should be at least 21 carbon atoms present in all ligands / organic groups, such as at least 25, at least 30, or at least 35 carbon atoms.

[0334] The 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, and more preferably at least 50 ppm of molybdenum. Suitably, the lubricating oil compositions useful in all aspects of the present disclosure contain no more than 1000 ppm, no more than 750 ppm, or no more than 500 ppm of molybdenum. The lubricating oil compositions useful in all aspects of the present disclosure preferably contain 10 to 1000, such as 30 to 750 or 40 to 500 ppm of molybdenum (measured as molybdenum atoms).

[0335] For more information on available Mo-containing friction modifiers, see U.S. Patent No. 10,829,712 (column 8, line 58 to column 11, line 31).

[0336] Ashless friction modifiers can be present in the lubricating oil compositions of the present disclosure and are well-known and include esters formed by reacting carboxylic acids and acid anhydrides with alkanols and amine-based friction modifiers. Other available friction modifiers generally include polar end groups (such as carboxyl or hydroxyl groups) covalently bonded to a lipophilic hydrocarbon chain. Esters of carboxylic acids and acid anhydrides with alkanols are described in U.S. Patent No. 4,702,850. Examples of other conventional organic friction modifiers are described by M. Belzer in "Journal of Tribology" (1992), volume 114, pages 675 - 682 and by M. Belzer and S. Jahanmir in "Lubrication Science" (1988), volume 1, pages 3 - 26. Generally, the total amount of organic ashless friction modifiers in the lubricants according to the present disclosure is not more than 5% by mass, preferably not more than 2% by mass, and more preferably not more than 0.5% by mass based on the total mass of the lubricating oil composition.

[0337] Exemplary friction modifiers useful in the lubricating compositions described herein include, for example, alkoxylated fatty acid esters, alkanolamides, polyol fatty acid esters, borated glycerol fatty acid esters, fatty alcohol ethers, and mixtures thereof.

[0338] Exemplary alkoxylated fatty acid esters include, for example, polyoxyethylene stearate, fatty acid polyglycol esters, etc. These may include polyoxypropylene stearate, polyoxybutylene stearate, polyoxyethylene isostearate, polyoxypropylene isostearate, polyoxyethylene palmitate, etc.

[0339] Exemplary alkanolamides include, for example, diethyl alkanolamide laurate, diethyl alkanolamide palmitate, etc. These may include diethyl alkanolamide oleate, diethyl alkanolamide stearate, diethyl alkanolamide oleate, polyethoxylated alkylamides, polypropoxylated alkylamides, etc.

[0340] Exemplary polyol fatty acid esters include, for example, glycerol monooleate, saturated mono-, di- and triglycerides, glycerol monostearate, etc. These may include polyol esters, hydroxy-containing polyol esters, etc.

[0341] Exemplary borated glycerol fatty acid esters include, for example, borated glycerol monooleate, borated saturated mono-, di- and triglycerides, borated glycerol monostearate, etc. In addition to glycerol polyols, these may also include trimethylolpropane, pentaerythritol, sorbitan, etc. These esters may be polyol monocarboxylic acid esters, polyol dicarboxylic acid esters and sometimes, polyol tricarboxylic acid esters. Preferred may be glycerol monooleate, glycerol dioleate, glycerol trioleate, glycerol monostearate, glycerol distearate and glycerol tristearate and the corresponding glycerol monopalmate, glycerol dipalmitate and glycerol tripalmitate, as well as the respective isostearates, linoleates, etc. Ethoxylated, propoxylated and / or butoxylated fatty acid esters of polyols (especially using glycerol as the base polyol) can be used herein.

[0342] Exemplary fatty alcohol ethers include, for example, stearyl ether, myristyl ether, etc. Alcohols, including those having C3 to C 50 carbon atoms, can be ethoxylated, propoxylated or butoxylated to form the corresponding fatty alkyl ethers. The base alcohol moiety may preferably be stearyl, myristyl, C 11 -C 13 hydrocarbons, oleyl, isostearyl, etc.

[0343] Useful concentrations of friction modifiers can be from 0.01 wt% to 5 wt%, or from about 0.001 wt% to about 2.5 wt%, or from about 0.05 wt% to about 1.5 wt%, or from about 0.051 wt% to about 1 wt%. The concentration of the molybdenum-containing material is typically described as the Mo metal concentration. A favorable concentration of Mo can be from 25 ppm to 700 ppm or more, with a generally preferred range of 50 - 200 ppm. All types of friction modifiers can be used alone or in combination with the materials of the present disclosure. Mixtures of two or more friction modifiers or mixtures of friction modifiers with alternative surface-active materials are generally also desirable. For example, a combination of a Mo-containing compound and a polyol fatty acid ester, such as glycerol monooleate, can be used for this purpose.

[0344] In an embodiment, the one or more friction modifiers used in the lubricating oil compositions and additive concentrates of the present invention are present in an amount of 0.001 to 0.2 mass%, such as 0.01 to 0.06 mass%, such as 0.02 to 0.04 mass%, based on the total mass of the lubricating oil composition, and / or in an amount of 0.01 to 1 mass%, such as 0.02 to 0.5 mass%, such as 0.05 to 0.2 mass%, based on the total mass of the additive concentrate.

[0345] In a particular embodiment, the lubricating oil compositions and additive concentrates of the present invention are free of alkoxylated fatty acid esters, alkanolamides, polyol fatty acid esters, borated 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 comprise at least one oil-soluble organomolybdenum compound, such as at least one molybdenum dithiocarbamate compound, such as tris(molybdenum dithiocarbamate) compound, particularly the foregoing substances. E. Antioxidants

[0346] Antioxidants retard the oxidative degradation of the base oil during use. Such degradation can lead to the presence of deposits on metal surfaces, the presence of sludges, an increase in viscosity in the lubricant, etc. A wide variety of oxidation inhibitors can be used in lubricating oil compositions. See, for example, Lubricants and Related Products, Klamann, Wiley VCH, 1984; U.S. Patent Nos. 4,798,684 and 5,084,197.

[0347] Available antioxidants include hindered phenols. These phenolic antioxidants can be ashless (metal-free) phenolic compounds or neutral or basic metal salts of certain phenolic compounds. Typical phenolic antioxidant compounds are hindered phenols containing sterically hindered hydroxyl groups, which include derivatives of dihydroxyaryl compounds, where the hydroxyl groups are in the ortho or para positions to each other. Typical phenolic antioxidants include those substituted by C 6+Alkyl-substituted hindered phenols and alkylene-coupled derivatives of these hindered phenols. Examples of phenolic materials of this type include 2-tert-butyl-4-heptylphenol; 2-tert-butyl-4-octylphenol; 2-tert-butyl-4-dodecylphenol; 2,6-di-tert-butyl-4-heptylphenol; 2,6-di-tert-butyl-4-dodecylphenol; 2-methyl-6-tert-butyl-4-heptylphenol; and 2-methyl-6-tert-butyl-4-dodecylphenol. Other available hindered mono-phenolic antioxidants can include, for example, hindered 2,6-di-alkyl-phenol propionate derivatives. Bisphenolic antioxidants can also be advantageously used herein. Examples of ortho-coupled phenols include: 2,2'-bis(4-heptyl-6-tert-butyl-phenol); 2,2'-bis(4-octyl-6-tert-butyl-phenol); and 2,2'-bis(4-dodecyl-6-tert-butyl-phenol). Para-coupled bisphenols include, for example, 4,4'-bis(2,6-di-tert-butyl-phenol) and 4,4'-methylene-bis(2,6-di-tert-butyl-phenol).

[0348] An effective amount of one or more catalytic antioxidants can also be used. The catalytic antioxidant comprises an effective amount of a) one or more oil-soluble polymetallic organic compounds; and an effective amount of b) one or more substituted N,N'-diaryl-o-phenylenediamine compounds, or c) one or more hindered phenol compounds; or a combination of b) and c). The catalytic antioxidants available herein are more fully described in U.S. Patent No. 8,048,833.

[0349] Non-phenolic oxidation inhibitors that can be used include aromatic amine antioxidants, which can be used as such or in combination with phenolic types. Typical examples of non-phenolic antioxidants include: alkylated and non-alkylated aromatic amines, such as the aromatic monoamine of the formula R8R9R 10 N, where R8 is an aliphatic, aromatic or substituted aromatic group, R9 is an aromatic or substituted aromatic group, and R 10 is H, alkyl, aryl or R 11 S(O)XR 12 where R 11 is alkylene, alkenylene or aralkylene, R 12 is alkyl or alkenyl, aryl or alkaryl, and x is 0, 1 or 2. The aliphatic group R8 can contain from 1 to about 20 carbon atoms, preferably about 6 to 12 carbon atoms. The aliphatic group is usually a saturated aliphatic group. Preferably, both R8 and R9 are aromatic or substituted aromatic groups, and the aromatic group can be a fused-ring aromatic group such as naphthyl. The aromatic groups R8 and R9 can be linked together with other groups such as S.

[0350] Typical aromatic amine antioxidants have an alkyl substituent containing at least about 6 carbon atoms. Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl, and decyl. Generally, the aliphatic group contains no more than about 14 carbon atoms. General types of amine antioxidants useful in the present composition include diphenylamine, phenylnaphthylamine, phenothiazine, imidodibenzyls, and diphenylbenzidine. Mixtures of two or more aromatic amines may also be used. Polymer amine antioxidants may also be used. Specific examples of aromatic amine antioxidants useful in the present disclosure include: p,p'-dioctyldiphenylamine; tert-octylphenyl-α-naphthylamine; phenyl-α-naphthylamine; and p-octylphenyl-α-naphthylamine.

[0351] Sulfur-containing antioxidants can also be used herein. In particular, one or more oil-soluble or oil-dispersible sulfur-containing antioxidants can be used as antioxidant additives. For example, sulfurized alkylphenols and their alkali metal or alkaline earth metal salts are also antioxidants useful herein. Suitably, the lubricating oil composition of the present disclosure may include the one or more sulfur-containing antioxidants in an amount providing 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 mass % sulfur based on the total mass of the lubricating oil composition. Optionally, the oil-soluble or oil-dispersible sulfur-containing antioxidant is selected from sulfurized C4 to C 25 olefins, sulfurized aliphatic (C7 to C 29 ) hydrocarbon-based fatty acid esters, ashless sulfurized phenolic antioxidants, sulfur-containing organomolybdenum compounds, and combinations thereof. For further information on sulfurized materials useful as antioxidants herein, see U.S. Patent No. 10,731,101 (column 15, line 55 to column 22, line 12).

[0352] Antioxidants useful herein include hindered phenols and / or arylamines. These antioxidants can be used independently by type or in combination with each other.

[0353] Typical antioxidants include: Irganox TM L67, Irganox TM L135, Ethanox TM 4702, LanxessAdditin TM RC 7110; Ethanox TM 4782J; Irganox TM 1135, Irganox TM 5057, sulfurized lard and palm oil fatty acid methyl ester.

[0354] The antioxidant additive can be used in an amount of about 0.01 to 10 (or 0.01 to 5, or 0.01 to 3) wt%, or about 0.03 to 5 wt%, or 0.05 to less than 3 wt% based on the weight of the lubricating composition.

[0355] In an embodiment, the antioxidant used in the lubricating oil composition and additive concentrate of the present invention is present in an amount of 0.1 to 10% by mass, such as 3 to 8% by mass, such as 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, such as 10 to 22% by mass, such as 14 to 20% by mass, based on the total mass of the additive concentrate.

[0356] In an embodiment, the antioxidant used in the lubricating oil composition and 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 additive concentrate of the present invention is a mixture of one or more amine antioxidants and one or more phenolic antioxidants, more preferably in a ratio of about 5:2 to about 9:5, such as about 2:1.

[0357] In a specific embodiment, the lubricating oil composition and additive concentrate of the present invention do not contain sulfur-containing antioxidants. Preferably, the lubricating oil composition and additive concentrate of the present invention do not contain or substantially do not contain methyl ester sulfide antioxidants, 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. More preferably, the antioxidant used in the lubricating oil composition and additive concentrate of the present invention is a mixture of alkylated diphenylamine antioxidants and hindered phenolic antioxidants, particularly consisting of a mixture of alkylated diphenylamine antioxidants and hindered phenolic antioxidants.

[0358] The composition according to the present disclosure may contain additives having different recited functions and also having a secondary effect as an antioxidant (for example, a phosphorus-containing antiwear agent (such as ZDDP) may also have an antioxidant effect). For determining the amount of antioxidant in the lubricating oil composition or additive concentrate herein, these additives are not counted as antioxidants. F. Pour Point Depressant

[0359] If desired, conventional pour point depressants (also known as lubricating oil flow improvers) can be added to the compositions of the present disclosure. These pour point depressants can be added to the lubricating compositions of the present disclosure to lower the minimum temperature at which the fluid can flow or be poured. Examples of suitable pour point depressants include polymethacrylates, polyacrylates, polyacrylamides, condensation products of halogenated paraffins and aromatic compounds, carboxylic acid vinyl ester polymers, and terpolymers of dialkyl fumarates, fatty acid vinyl esters, and allyl vinyl ethers. U.S. Patent Nos. 1,815,022; 2,015,748; 2,191,498; 2,387,501; 2,655,479; 2,666,746; 2,721,877; 2,721,878; and 3,250,715 describe available pour point depressants and / or their preparation. Such additives can be used in an amount of about 0.01 to 5 wt%, preferably about 0.01 to 1.5 wt%, based on the weight of the lubricating composition.

[0360] In an embodiment, the pour point depressant used in the lubricating oil composition and additive concentrate of the present invention is present in an amount of 0.001 to 1 wt%, such as 0.01 to 0.5 wt%, such as 0.05 to 0.2 wt%, based on the total mass of the lubricating oil composition.

[0361] In a specific embodiment, the pour point depressant used in the lubricating oil composition of the present invention is a C 12-18 dialkyl fumarate / vinyl acetate copolymer (which is available as Infineum V387 TM and can be purchased). G. Antifoaming Agents

[0362] Antifoaming agents can be advantageously added to the lubricant compositions described herein. These agents prevent or delay the formation of stable foams. Silicones and / or organic polymers are typical antifoaming agents. For example, polysiloxanes, such as silicone oils or polydimethylsiloxane, provide antifoaming properties.

[0363] Antifoaming agents are commercially available and can be used in minor amounts, such as below 5 wt%, below 3 wt%, below 1 wt%, below 0.1 wt%, such as from 5 wt% to 0.1 ppm, such as from 3 wt% to 0.5 ppm, such as from 1 wt% to 10 ppm.

[0364] For example, it is possible that the lubricating oil composition contains an antifoaming agent containing polyalkylsiloxane, such as polydialkylsiloxane, where the alkyl is C1-C 10 alkyl, such as polydimethylsiloxane (PDMS), also known as silicone oil. Alternatively, the siloxane is poly(R 3 ) siloxane, where R 3is one or more identical or different straight-chain, branched or cyclic hydrocarbon groups, such as alkyl or aryl groups, which generally have from 1 to 20 carbon atoms. It is possible that, for example, the lubricating oil composition comprises a polymeric siloxane compound according to formula 1 below, wherein R 1 and R 2 are independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl, phenyl, naphthyl, alkyl-substituted phenyl or an isomer thereof (such as methyl, phenyl), and n is from 2 to 1000, such as from 50 to 450, or such as from 40 to 100.

[0365] Additionally or alternatively, it is possible that the lubricating oil composition comprises an organically modified siloxane (OMS), such as a siloxane modified with an organic group such as a polyether (e.g., ethylene oxide-propylene oxide copolymer), a long-chain hydrocarbon group (e.g., C 11 -C 100 alkyl) or an aryl group (e.g., C6-C 14 aryl). It is possible that, for example, the lubricating oil composition comprises an organically modified siloxane compound according to formula 1, wherein n is from 2 to 2000, such as from 50 to 450 (or such as from 40 to 100), and wherein R 1 and R 2 are the same or different, and optionally wherein R 1 and R 2 are each independently an organic group, such as an organic group selected from polyethers (e.g., ethylene oxide-propylene oxide copolymer), long-chain hydrocarbon groups (e.g., C 11 -C 100 alkyl) or aryl groups (e.g., C6-C 14 aryl). Preferably, one of R 1 and R 2 is CH3.

[0366] Based on the total weight of the lubricant composition, a siloxane according to formula 1 is incorporated to provide from about 0.1 to less than about 30 ppm Si, or from about 0.1 to about 25 ppm Si, or from about 0.1 to about 20 ppm Si, or from about 0.1 to about 15 ppm Si, or from about 0.1 to about 10 ppm Si. More preferably, it is in the range of about 3 - 10 ppm Si.

[0367] In embodiments, the silicone defoamers useful herein can be obtained from Dow Corning Corporation and Union Carbide Corporation, such as Dow Corning FS-1265 (1000 centistokes), Dow Corning DC-200, and Union Carbide UC-L45. The silicone defoamers useful herein include polydimethylsiloxane, phenyl-methyl polysiloxane, linear, cyclic, or branched siloxanes, silicone polymers and copolymers, and / or organo-silicone copolymers. Silicone polyether copolymer defoamers available from OSI Specialties, Inc. of Farmington Hills, Michigan can also be used in place of or in addition to. One such material is sold as SILWET-L-7220.

[0368] Acrylate polymer defoamers can also be used herein. Typical acrylate defoamers include the polyacrylate defoamer designated PC-1244 available from Monsanto Polymer Products Co. A preferred acrylate polymer defoamer useful herein is PX TM 3841 (i.e., an alkyl acrylate polymer), also known as Mobilad TM C402.

[0369] In embodiments, a combination of a silicone defoamer and an acrylate defoamer can be used, such as at a silicone defoamer / acrylate defoamer weight ratio of from about 5:1 to about 1:5, see for example U.S. Patent Application Publication No. 2021 / 0189283.

[0370] In embodiments, the defoamer used in the lubricating oil compositions and additive concentrates of the present invention is present in an amount of 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 in an amount of 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.

[0371] In certain embodiments, the defoamer used in the lubricating oil compositions and additive concentrates of the present invention does not contain an acrylate defoamer. In certain embodiments, the defoamer used in the lubricating oil compositions and additive concentrates of the present invention consists of, particularly, a silicone defoamer, such as polydimethylsiloxane. H. Viscosity Improver

[0372] Viscosity modifiers (also known as viscosity index improvers or viscosity improvers) can be included in the lubricating compositions described herein. Viscosity improvers provide high and low temperature operability to lubricants. These additives provide shear stability at elevated temperatures and acceptable viscosities at low temperatures. Suitable viscosity improvers include high molecular weight hydrocarbons, polyesters, and viscosity improver dispersants that can act as both viscosity improvers and dispersants. The typical molecular weights of these polymers are between about 10,000 and 1,500,000 g / mol, more typically about 20,000 and 1,200,000 g / mol, and even more typically about 50,000 and 1,000,000 g / mol.

[0373] Examples of suitable viscosity improvers are linear or star polymers and copolymers of methacrylates, butadiene, olefins, or alkylated styrenes. Polyisobutene is a commonly used viscosity improver. Another suitable viscosity improver is polymethacrylate (e.g., a copolymer of alkyl methacrylates of various chain lengths), some formulations of which also act as pour point depressants. Other suitable viscosity improvers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (e.g., a copolymer of acrylates of various chain lengths). Specific examples include styrene-isoprene or styrene-butadiene type polymers with molecular weights of 50,000 to 200,000 g / mol.

[0374] Copolymers that can be used as viscosity improvers include those available under the trade name "PARATONE" TM [[ID=8"]](such as "PARATONE" TM 8921", "PARATONE" TM 68231" and "PARATONE" TM 8941") purchased from Chevron Oronite Company LLC; those available under the trade name "HiTEC" TM [[ID=16"]](such as HiTEC TM 5850B and HiTEC TM 5777) purchased from Afton Chemical Corporation; and those available under the trade name "Lubrizol" TM 7067C" purchased from The Lubrizol Corporation. Hydrogenated polyisoprene star polymers that can be used as viscosity improvers in this article include those available from Infineum International Limited, such as those available under the trade names "SV200" TM [[ID=24"]]" and "SV600" TM". The hydrogenated diene-styrene block copolymer that can be used as a viscosity improver herein is commercially available from Infineum International Limited, for example, under the trade name "SV 50 TM ".

[0375] Polymers that can be used as viscosity improvers herein include polymethacrylate or polyacrylate polymers, such as linear polymethacrylate or polyacrylate polymers, such as those that can be obtained under the trade name "Viscoplex TM "(e.g., Viscoplex TM 6-954) from Evonik Industries, or those that can be obtained under the trade name Asteric TM (e.g., Lubrizol TM 87708 and Lubrizol TM 87725) star polymers from Lubrizol Corporation.

[0376] Vinyl aromatic-containing polymers that can be used as viscosity improvers herein can be derived from vinyl aromatic monomers, such as styrenic monomers, such as styrene. Exemplary vinyl aromatic-containing copolymers useful herein can be represented by the general formula: A-B, where A is a polymeric block mainly derived from vinyl aromatic monomers (such as styrene), and B is a polymeric block mainly derived from conjugated diene monomers (such as isoprene).

[0377] Vinyl aromatic-containing polymers that can be used as viscosity improvers can have a kinematic viscosity at 100 °C of less than 20 cSt, such as less than 15 cSt, such as less than 12 cSt, but can be diluted (such as in Group I, II, and / or III base oils) to a higher kinematic viscosity at 100 °C, such as to more than 40 cSt, such as more than 100 cSt, such as more than 1000 cSt, such as 1000 to 2000 cSt.

[0378] Generally, the viscosity improver can be used in an amount of about 0.01 to about 10% by weight, such as about 0.1 to about 7% by weight, such as 0.1 to about 4% by weight, such as about 0.2 to about 2% by weight, such as about 0.2 to about 1% by weight, and such as about 0.2 to about 0.5% by weight, based on the total weight of the formulated lubricant composition.

[0379] In an embodiment, one or more viscosity improvers are present in the lubricating oil composition of the present invention in an amount of 0.001 to 0.5% by mass, such as 0.05 to 0.3% by mass, such as 0.1 to 0.22% by mass, based on the total mass of the lubricating oil composition.

[0380] Viscosity improvers are typically added as concentrates to a large amount of diluent oil. The "as delivered" viscosity improver typically contains 20 wt% to 75 wt% of active polymer (for polymethacrylate or polyacrylate polymers) or 8 wt% to 20 wt% of active polymer (for olefin copolymers, hydrogenated polyisoprene star polymers, or hydrogenated diene-styrene block copolymers) in the "as delivered" polymer concentrate.

[0381] In certain embodiments, the "as delivered" viscosity improver used in the lubricating oil compositions of the present invention is an olefin copolymer viscosity improver (which is available as Oronite 24EX). I. Dispersants

[0382] During engine operation, oil-insoluble oxidation by-products are produced. Dispersants help keep these by-products in solution, thereby reducing their deposition on metal surfaces. The dispersants used in the formulation of the lubricating compositions herein can be ashless or ash-forming in nature. The dispersant is preferably ashless. So-called ashless dispersants are organic materials that form essentially no ash upon combustion. For example, metal-free dispersants or borated metal-free dispersants are considered ashless. In contrast, metal-containing detergents tend to form ash upon combustion.

[0383] Dispersants useful herein typically contain a polar group attached to a relatively high molecular weight hydrocarbon chain. The polar group typically contains at least one element of nitrogen, oxygen, or phosphorus. Typical hydrocarbon chains contain from 40 to 500, such as 50 to 400 carbon atoms. (Poly)alkenyl succinic acid derivative dispersants

[0384] One particularly useful class of dispersants includes (poly)alkenyl succinic derivatives typically made by the reaction of a succinic compound (typically a hydrocarbyl-substituted succinic anhydride) usually substituted by a long-chain hydrocarbyl group with a polyhydroxy or polyamino compound. The long-chain hydrocarbyl group that constitutes the lipophilic portion of the molecule (which provides oil solubility) is typically a polyisobutene group (such long-chain hydrocarbyl groups, such as polyisobutene groups, typically have a Mn of from 400 to 3000 g / mol, such as from 450 to 2500 g / mol). Many examples of this type of dispersant are known commercially and in the literature. Exemplary U.S. patents describing such dispersants 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; 5,705,458. Further descriptions of dispersants useful herein can be found, for example, in European Patent Application Nos. 0 471 071 and 0 451 380, to which reference is made therefor.

[0385] Hydrocarbyl-substituted succinic acids and hydrocarbyl-substituted succinic anhydride derivatives are useful dispersants. In particular, succinimides, succinate esters or succinate amides prepared by the reaction of a hydrocarbyl-substituted succinic acid or anhydride compound (usually having at least 25 carbon atoms, such as from 28 to 400 carbon atoms in the hydrocarbyl substituent) with at least 1 equivalent of a polyhydroxy or polyamino compound (such as an alkylene amine) are particularly useful herein. Hydrocarbyl-substituted succinic acids and hydrocarbyl-substituted succinic anhydride derivatives can have a number average molecular weight of at least 400 g / mol, such as at least 900 g / mol, such as at least 1500 g / mol, such as from 400 to 4000 g / mol, such as from 800 to 3000, such as from 2000 to 2800 g / mol, such as about 2100 to 2500 g / mol, and such as about 2200 to about 2400 g / mol.

[0386] The succinimides particularly useful herein are formed by the condensation reaction between 1) a hydrocarbyl-substituted succinic anhydride, such as polyisobutylene succinic anhydride (PIBSA); and 2) a polyamine (PAM). Examples of suitable polyamines include: polyhydrocarbyl polyamines, polyalkylene polyamines, hydroxy-substituted polyamines, polyoxyalkylene polyamines, and combinations thereof. Examples of polyamines include tetraethylenepentamine, pentaethylenehexamine, tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), N-phenyl-p-phenylenediamine (ADPA), and other polyamines having an average of 5, 6, 7, 8, or 9 nitrogen atoms per molecule. Mixtures in which the average number of nitrogen atoms per polyamine molecule is greater than 7 are generally referred to as heavy polyamines or H-PAMs and can be obtained under trade names such as HPA TM and HPA-X TM available from Dow Chemical under the name E-100 TM available from Huntsman Chemical, etc. Examples of hydroxy-substituted polyamines include N-hydroxyalkyl-alkylene polyamines, such as N-(2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)piperazine, and / or N-hydroxyalkylated alkylene diamines of the type described, for example, in U.S. 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 from about 200 to about 5000 g / mol. Products of this type are available under the trade name Jeffamine TM and may be obtained. Representative examples of available 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.

[0387] The polyalkenyl-substituted monocarboxylic or dicarboxylic acids, anhydrides or esters that are the source of the succinimide dispersants can be prepared using halogen (e.g., chlorine)-assisted alkylation methods (“chlorine dispersants”), or by halogen-free thermal or “ene” reaction methods (“thermal dispersants”). When using “conventional” Lewis acid-catalyzed polyalkenes, halogen-free thermal reaction methods do not provide highly functional carboxylic acylating agents, especially polyisobutylene succinic anhydride (“PIBSA”). However, PIBSA with a relatively high functionality (e.g., functionality greater than 1.3) can be prepared thermally using polyalkenes (especially polyisobutylene) with a high terminal vinylidene content (greater than 65%, such as greater than 70%, 80% or 85%). Methods for producing polyisobutylene products with a high terminal vinylidene content (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 available from TPC or under the trade name Glissopal TM from BASF. PIBSA with a functionality greater than 1.3 prepared thermally using polyisobutylene with a high terminal vinylidene content, along with the succinimide dispersants derived therefrom, are described in EP 0 355 895.

[0388] The chlorine dispersant or heat dispersant may comprise one or more optionally borated higher molecular weight succinimides (Mn above 1600 g / mol, such as 1800 to 3000 g / mol) and one or more optionally borated lower molecular weight succinimides (Mn less than 1600 g / mol), wherein the higher molecular weight may be 1600 to 3000 g / mol, such as 1700 to 2800 g / mol, such as 1800 to 2500 g / mol, such as 1850 to 2300 g / mol; the lower molecular weight may be 600 to less than 1600 g / mol, such as 650 to 1500 g / mol, such as 700 to 1400 g / mol, such as 800 to 1300 g / mol, such as 850 to 1200 g / mol, such as 900 to 1150 g / mol, such as 900 to 1000 g / mol. The higher molecular weight succinimide dispersant may be present in the lubricating composition in an amount of 0.5 to 10 wt%, or 0.8 to 6 wt%, or 1.0 to 5 wt%, or 1.5 to 5 wt%, or 1.5 to 4.0 wt%; the lower molecular weight succinimide dispersant may be present in the lubricating composition in an amount of 1 to 5 wt%, or 1.5 to 4.8 wt%, or 1.8 to 4.6 wt%, or 1.9 to 4.6 wt%, or more than 2 wt%, such as 2 to 5 wt%. The lower molecular weight succinimide may differ from the higher molecular weight succinimide by more than 500 g / mol, such as more than 750 g / mol, such as more than 1000 g / mol, such as more than 1200 g / mol, such as 500 to 3000 g / mol, such as 750 to 2000 g / mol, such as 1000 to 1500 g / mol.

[0389] Succinic esters useful as dispersants include those formed by the condensation reaction between a hydrocarbyl-substituted succinic anhydride and an alcohol or polyol. For example, the condensation product of a hydrocarbyl-substituted succinic anhydride and pentaerythritol is a useful dispersant.

[0390] The succinic ester amides useful herein are formed by the condensation reaction between a hydrocarbyl-substituted succinic anhydride and an alkanolamine. Suitable alkanolamines include ethoxylated polyalkyl polyamines, propoxylated polyalkyl polyamines, and polyalkenyl polyamines, such as polyethylenepolyamines and / or propoxylated hexamethylenediamine. Representative examples are shown in U.S. Patent No. 4,426,305.

[0391] Hydrocarbyl-substituted succinic anhydride (such as PIBSA) esters of hydrocarbyl-bridged aryloxy alcohols can also be used as dispersants herein. For information on such dispersants, see U.S. Patent No. 7,485,603, particularly columns 2, line 65 to column 6, line 22 and column 23, line 40 to column 26, line 46. In particular, the PIBSA ester of methylene-bridged naphthoxy ethanol (i.e., 2-hydroxyethyl-1-naphthyl ether (or hydroxy-terminated naphthol ethylene oxide oligomeric ether)) can be used herein.

[0392] The molecular weight of the hydrocarbyl-substituted succinic anhydride used in the preceding paragraphs is generally 350 to 4000 g / mol, such as 400 to 3000 g / mol, such as 450 to 2800 g / mol, such as 800 to 2500 g / mol. The above (poly)alkenyl succinic derivatives can be post-reacted with various reagents such as sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid.

[0393] The chlorine dispersant or heat dispersant can be present in the lubricant in an amount of 0.1% to 20% by mass of the composition, such as 0.2 to 15% by mass, such as 0.25 to 10% by mass, such as 0.3 to 5% by mass, such as 1.0% to 3.0% by mass of the lubricating oil composition.

[0394] The above (poly)alkenyl succinic derivatives can also be post-reacted with boron compounds such as boric acid, borate esters or highly borated dispersants to form borated dispersants that generally have about 0.1 to about 5 moles of boron / mole of dispersant reaction product.

[0395] Dispersants useful herein include borated succinimides, including those derivatives from mono-succinimides, bis-succinimides and / or mixtures of mono-succinimides and bis-succinimides, wherein the hydrocarbyl succinimide is derived from a hydrocarbylene group having a Mn of about 300 to about 5000 g / mol, or about 500 to about 3000 g / mol, or about 1000 to about 2000 g / mol, such as polyisobutene, or mixtures of such hydrocarbylene groups that generally have high terminal vinyl groups.

[0396] The boron-containing dispersant can be present in the lubricating composition in an amount of 0.01% to 20% by weight, or 0.1% to 15% by weight, or 0.1% to 10% by weight, or 0.5% to 8% by weight, or 1.0% to 6.5% by weight, or 0.5% to 2.2% by weight.

[0397] The boron-containing dispersant may be present in an amount that provides 15 ppm to 2000 ppm, or 25 ppm to 1000 ppm, or 40 ppm to 600 ppm, or 80 ppm to 350 ppm of boron to the composition.

[0398] The borated dispersant may be used in combination with a non-borated dispersant and may be the same or a different compound from the non-borated dispersant. In one embodiment, the lubricating composition may comprise one or more boron-containing dispersants and one or more non-borated dispersants, wherein the total amount of the dispersant may be 0.01 wt% to 20 wt%, or 0.1 wt% to 15 wt%, or 0.1 wt% to 10 wt%, or 0.5 wt% to 8 wt%, or 1.0 wt% to 6.5 wt%, or 0.5 wt% to 2.2 wt% of the lubricating composition, and wherein the ratio of the borated dispersant to the non-borated dispersant may be from 1:10 to 10:1 (weight:weight) or 1:5 to 3:1 or 1:3 to 2:1.

[0399] The dispersant may comprise one or more borated or unborated poly(vinyl) succinimides, wherein the polyvinyl is derived from polyisobutene and the imide is derived from a polyamine ("PIBSA-PAM").

[0400] The dispersant may comprise one or more PIBSA-PAMs, wherein the PIB is derived from polyisobutene having a Mn of 600 to 5000, such as 700 to 4000, such as 800 to 3000, such as 900 to 2500 g / mol, and the polyamine is derived from a hydrocarbyl-substituted polyamine, such as tetraethylenepentamine, pentaethylenehexamine, tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), N-phenyl-p-phenylenediamine (ADPA) and other polyamines having an average of 5, 6, 7, 8 or 9 nitrogen atoms per molecule. The dispersant may be borated, typically at a level of up to 4 mass%, such as 1 to 3 mass%. The dispersant may comprise one or more borated PIBSA-PAMs and one or more non-borated PIBSA-PAMs. The dispersant may comprise one or more borated PIBSA-PAMs derived from PIB having a Mn of 700 to 1800 g / mol (such as 800 to 1500 g / mol) and one or more non-borated PIBSA-PAMs derived from PIB having a Mn of greater than 1800 to 5000 g / mol (such as 2000 to 3000 g / mol). The dispersant may comprise one or more non-borated PIBSA-PAMs derived from PIB having a Mn of 700 to 1800 g / mol (such as 800 to 1500 g / mol) and one or more borated PIBSA-PAMs derived from PIB having a Mn of greater than 1800 to 5000 g / mol (such as 2000 to 3000 g / mol).

[0401] The dispersant may comprise PIBSA derived from PIB having a Mn of 700 to 5000 g / mol (such as 800 to 3000 g / mol) and one or more borated or non-borated PIBSA-PAMs derived from PIB having a Mn of 700 to 5000 g / mol.

[0402] The dispersant may comprise PIBSA derived from PIB having a Mn of 700 to 5000 g / mol (such as 800 to 3000 g / mol), one or more borated PIBSA-PAMs derived from PIB having a Mn of 700 to 1800 g / mol (such as 800 to 1500 g / mol), and one or more non-borated PIBSA-PAMs derived from PIB having a Mn greater than 1800 to 5000 g / mol (such as 2000 to 3000 g / mol). The dispersant may comprise PIBSA derived from PIB having a Mn of 700 to 5000 g / mol (such as 800 to 3000 g / mol), one or more non-borated PIBSA-PAMs derived from PIB having a Mn of 700 to 1800 g / mol (such as 800 to 1500 g / mol), and one or more borated PIBSA-PAMs derived from PIB having a Mn greater than 1800 to 5000 g / mol (such as 2000 to 3000 g / mol).

[0403] The dispersant may comprise one or more borated or non-borated PIBSA-PAMs and one or more PIBSA esters of hydrocarbon group-bridged aryloxy alcohols.

[0404] The dispersant may comprise one or more borated PIBSA-PAMs and one or more non-borated PIBSA-PAMs.

[0405] The dispersant may comprise one or more optionally borated higher molecular weight (Mn above 1600 g / mol, such as 1800 to 3000 g / mol) PIBSA-PAMs and one or more optionally borated lower molecular weight (Mn less than 1600 g / mol) PIBSA-PAMs, wherein the higher molecular weight may be from 1600 to 3000 g / mol, such as from 1700 to 2800 g / mol, such as from 1800 to 2500 g / mol, such as from 1850 to 2300 g / mol; the lower molecular weight may be from 600 to less than 1600 g / mol, such as from 650 to 1500 g / mol, such as from 700 to 1400 g / mol, such as from 800 to 1300 g / mol, such as from 850 to 1200 g / mol, such as from 900 to 1150 g / mol, such as from 900 to 1000 g / mol. The higher molecular weight PIBSA-PAM dispersant may be present in the lubricating composition in an amount of 0.5 to 10 wt%, or 0.8 to 6 wt%, or 1.0 to 5 wt%, or 1.5 to 5 wt% or 1.5 to 4.0 wt%; the lower molecular weight PIBSA-PAM dispersant may be present in the lubricating composition in an amount of 1 to 5 wt%, or 1.5 to 4.8 wt%, or 1.8 to 4.6 wt%, or 1.9 to 4.6 wt%, or more than 2 wt%, such as 2 to 5 wt%.

[0406] According to the present invention, the dispersant (different from component B) used in the lubricating oil composition and additive concentrate of the present invention comprises a mixture of one or more chlorine dispersants and one or more thermal dispersants, especially consisting of a mixture of one or more chlorine dispersants and one or more thermal dispersants. In an embodiment, the one or more chlorine dispersants and the one or more thermal dispersants are present 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 in a ratio of about 9:2.

[0407] In certain embodiments, the one or more chlorine dispersants used in the lubricant compositions and additive concentrates of the present invention comprise one or more borated or non-borated poly(alkenyl) succinimides, particularly consisting of one or more borated or unborated poly(alkenyl) succinimides, wherein the polyalkenyl is derived from polyisobutene and the imide is derived from a polyamine (“PIBSA-PAM”), particularly one or more borated PIBSA-PAMs and one or more non-borated PIBSA-PAMs. In certain embodiments, the one or more chlorine dispersants used in the lubricant compositions and additive concentrates of the present invention comprise one or more higher molecular weight (Mn above 1600 g / mol, such as 1800 to 3000 g / mol) PIBSA-PAMs and one or more optionally borated lower molecular weight (Mn less than 1600 g / mol) PIBSA-PAMs, particularly a first higher molecular weight PIBSA-PAM; and second and third lower molecular weight PIBSA-PAMs (optionally, one of which is borated), wherein preferably, the ratio of the higher molecular weight PIBSA PAM to the lower molecular weight PIBSA-PAM is from about 1:1 to about 2:3, particularly consisting of the foregoing substances.

[0408] In certain embodiments, the one or more thermal dispersants used in the lubricant compositions and additive concentrates of the present invention comprise one or more poly(alkenyl) succinimides as follows, particularly consisting of one or more poly(alkenyl) succinimides as follows, wherein the polyalkenyl is derived from polyisobutene and the imide is derived from a polyamine (“PIBSA-PAM”), particularly wherein the polyalkenyl is derived from polyisobutene with a high terminal vinylidene content and the imide is derived from a polyamine (“HR-PIBSA-PAM”). In certain embodiments, the one or more thermal dispersants used in the lubricant compositions and additive concentrates of the present invention comprise one or more higher molecular weight (Mn above 1000 g / mol, 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) PIBSA-PAMs, particularly those 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, particularly consisting of the foregoing higher molecular weight PIBSA-PAMs. Mannich base dispersant

[0409] The Mannich base dispersants useful herein are generally made by the reaction of an amine component, a hydroxyaromatic compound (substituted or unsubstituted, such as alkyl-substituted), such as an alkylphenol, and an aldehyde, such as formaldehyde. See U.S. Patent Nos. 4,767,551 and 10,899,986. Processing aids and catalysts, such as oleic acid and sulfonic acid, can also be part of the reaction mixture. Representative examples are shown in U.S. Patent Nos. 3,697,574; 3,703,536; 3,704,308; 3,751,365; 3,756,953; 3,798,165; 3,803,039; 4,231,759; 9,938,479; 7,491,248; and 10,899,986 and PCT Publication No. WO 01 / 42399. Polymethacrylate or polyacrylate derivative dispersants

[0410] Polymethacrylate or polyacrylate derivatives are another class of dispersants useful herein. These dispersants are generally prepared by reacting a nitrogen-containing monomer with a methacrylate or acrylate containing 5 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 are generally of lower molecular weight.

[0411] The lubricating compositions of the present disclosure generally contain from 0.1% to 20% by mass, such as from 0.2% to 15% by mass, such as from 0.25% to 10% by mass, such as from 0.3% to 5% by mass, such as from 2.0% to 4.0% by mass of the lubricating oil composition, of the dispersant. Alternatively, the dispersant can be present at from 0.1% to 5% by weight, or from 0.01% to 4% by weight of the lubricating composition.

[0412] In embodiments, the dispersants used in the lubricating oil compositions and additive concentrates of the present invention are present at from 1% to 12% by mass, such as from 3% to 10% by mass, such as from 6% to 8% by mass, based on the total mass of the lubricating oil composition, and at from 15% to 40% by mass, such as from 20% to 32% by mass, such as from 25% to 30% by mass, based on the total mass of the additive concentrate.

[0413] In certain embodiments, the dispersants used in the lubricant oil compositions and additive concentrates of the present invention are free of Mannich base dispersants and / or poly(meth)acrylate dispersants. In certain embodiments, the dispersants used in the lubricant oil compositions and additive concentrates of the present invention are free of hydrocarbyl-substituted succinic anhydrides, such as esters of hydrocarbyl-bridged aryloxy alcohols. Preferably, the dispersants used in the lubricant oil compositions and additive concentrates of the present invention comprise poly(alkenyl)succinimide dispersants, particularly PIBSA-PAM dispersants, particularly consisting of the foregoing. More preferably, the dispersants used in the lubricant oil compositions and additive concentrates of the present invention comprise the following, particularly consisting of the following: a first and a second PIBSA-PAM dispersant derived from 1800 to 2500 Mn PIB; a third and a fourth PIBSA-PAM dispersant derived from PIB having a Mn of less than 1600, wherein 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 is boron-free (optionally, at least one of the third PIBSA-PAM dispersant and the fourth PIBSA-PAM dispersant is borated). Particularly preferably, the dispersants used in the lubricant oil compositions and additive concentrates of the present invention comprise the following, particularly consisting of the following: 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 borated PIBSA-PAM dispersant derived from 950 Mn PIB.

[0414] For further information regarding the dispersants available herein, see U.S. Patent No. 10,829,712, column 13, line 36 to column 16, line 67, and U.S. Patent No. 7,485,603, column 2, line 65 to column 6, line 22, column 8, line 25 to column 14, line 53, and column 23, line 40 to column 26, line 46.

[0415] The compositions according to the present disclosure may contain additives having different recited functions and also having a secondary effect as a dispersant (e.g., the component B functionalized polymers described above may also have a dispersant effect). For determining the amount of dispersant in the lubricating oil compositions or concentrates herein, these additives are not counted as dispersants. However, the poly(alkenyl) succinic acid dispersants of component I) are considered to form, together with component B), a dispersant mixture as disclosed herein. Thus, the poly(alkenyl) succinic acid dispersants of component I) and component B) are used together to determine the amount of the dispersant mixture in the lubricating oil compositions or additive concentrates disclosed herein.

[0416] In certain embodiments, the detergent mixture comprises 50 to 90 mass%, such as 55 to 85 mass%, such as 62 to 82 mass%, such as 68 to 80 mass%, such as 70 to 76 mass% of said one or more chlorine dispersants based on the total mass of the dispersant mixture and / or 10 to 30 mass%, such as 12 to 25 mass%, such as 14 to 22 mass%, such as 15 to 20 mass%, such as 15.5 to 17.5 mass% of said one or more thermal dispersants based on the total mass of the dispersant mixture. Preferably, the dispersant mixture comprises the one or more chlorine dispersants and the one or more thermal dispersants in a ratio of from about 9:1 to about 3:2, such as from about 6:1 to about 3:1, such as from about 5:1 to about 4:1. More preferably, the dispersant mixture comprises the one or more chlorine dispersants and the one or more thermal dispersants in a ratio of about 9:2. J. Corrosion Inhibitors / Rust Inhibitors

[0417] Corrosion inhibitors can be used to mitigate the corrosion of metals and are often also referred to as metal deactivators or metal passivators. Some corrosion inhibitors can also be characterized as antioxidants.

[0418] Suitable corrosion inhibitors can include nitrogen- and / or sulfur-containing heterocyclic compounds such as triazoles (e.g., benzotriazole), substituted thiadiazoles, imidazoles, thiazoles, tetrazoles, hydroxyquinolines, oxazolines, imidazolines, thiophenes, indoles, indazoles, quinolines, benzoxazines, dithiols, oxazoles, oxatriazoles, pyridines, piperazines, triazines and derivatives of any one or more thereof. Available triazoles include N,N-bis(2-ethylhexyl)-1H-1,2,4-triazole-1-methanamine, Irgamet TM 30, which is available from BASF, Ludwigshafen, Germany and is represented by the following formula: N,N-bis(2-ethylhexyl)-1H-1,2,4-triazole-1-methanamine.

[0419] A specific corrosion inhibitor is benzotriazole represented by the following structure: wherein R 8 is absent (hydrogen) or can be a straight-chain or branched, saturated or unsaturated C1 to C 20 hydrocarbyl or substituted hydrocarbyl group. It can contain a ring structure that is alkyl or aryl in nature and / or contain heteroatoms such as N, O, or S. Examples of suitable compounds can include benzotriazole, alkyl-substituted benzotriazoles (such as tolyltriazole, ethylbenzotriazole, hexylbenzotriazole, octylbenzotriazole, etc.), aryl-substituted benzotriazoles, alkylaryl- or arylalkyl-substituted benzotriazoles, etc., and combinations thereof. For example, the triazole can comprise or be benzotriazole and / or alkylbenzotriazole, wherein the alkyl contains from 1 to about 20 carbon atoms, or from 1 to about 8 carbon atoms. Non-limiting examples of such corrosion inhibitors can comprise or be benzotriazole, tolyltriazole, and / or optionally, substituted benzotriazole, such as (N,N-bis(2-ethylhexyl)-4-methyl-1H-benzotriazole-1-methanamine), available as Irgamet TM 39 from BASF, Ludwigshafen, Germany. Preferred corrosion inhibitors can comprise or be benzotriazole and / or tolyltriazole.

[0420] Additionally or alternatively, the corrosion inhibitor can include one or more substituted thiadiazoles of the following structures: wherein R 15 and R 16 are independently hydrogen or a hydrocarbyl group, which can be aliphatic or aromatic, including cyclic, cycloaliphatic, aralkyl, aryl, and alkaryl, and wherein each w is independently 1, 2, 3, 4, 5, or 6 (preferably 2, 3, or 4, such as 2). These substituted thiadiazoles are derived from 2,5-dimercapto-1,3,4-thiadiazole (DMTD) molecules. Many derivatives of DMTD have been described in the art, and any such compounds can be included in the fluids used in the present disclosure. For example, U.S. Patent Nos. 2,719,125; 2,719,126; and 3,087,937 describe the preparation of various 2,5-bis-(hydrocarbyldithio)-1,3,4-thiadiazoles.

[0421] Still additionally or alternatively, the corrosion inhibitor can include one or more other DMTD derivatives, such as carboxylic acid esters, wherein R 15 and R 16It can be connected to the sulfur atom of the sulfide via a carbonyl group. The preparation of these sulfur - ester - containing DMTD derivatives is described, for example, in U.S. Patent No. 2,760,933. DMTD derivatives made by the condensation of DMTD with α - haloaliphatic carboxylic acids having at least 10 carbon atoms are described, for example, in U.S. Patent No. 2,836,564. This method yields DMTD derivatives in which R 15 and R 16 are HOOC - CH(R 19 )(R 19 is a hydrocarbon group). DMTD derivatives further made by amidation or esterification of these terminal carboxylic acid groups are also available.

[0422] The preparation of 2 - alkyldithio - 5 - mercapto - 1,3,4 - thiadiazole is described, for example, in U.S. Patent No. 3,663,561.

[0423] A class of DMTD derivatives can include a mixture of 2 - alkyldithio - 5 - mercapto - 1,3,4 - thiadiazole and 2,5 - bis - alkyldithio - 1,3,4 - thiadiazole. Such a mixture can be sold under the trade name HiTEC TM 4313 and is available from Afton Chemical Company.

[0424] The preparation of 2 - alkyldithio - 5 - mercapto - 1,3,4 - thiadiazole is described, for example, in U.S. Patent No. 3,663,561.

[0425] A class of DMTD derivatives can include a mixture of 2 - alkyldithio - 5 - mercapto - 1,3,4 - thiadiazole and 2,5 - bis - alkyldithio - 1,3,4 - thiadiazole. Such a mixture can be sold under the trade name HiTEC TM 4313 and is available from Afton Chemical Company.

[0426] Additionally or alternatively, the corrosion inhibitor can include a trifunctional borate having the structure B(OR 46 )3, where each R 46 can be the same or different. Since this borate can generally be ideally compatible with the non - aqueous medium of the composition, each R 46 can particularly comprise or be a C1 - C8 hydrocarbon - based moiety. For compositions in which the non - aqueous medium comprises or is a lubricating oil base stock, for example, better compatibility can generally be achieved when the hydrocarbon - based moieties are each at least C4. Non - limiting examples of such corrosion inhibitors thus include, but are not limited to, triethyl borate, tripropyl borate such as tri - isopropyl borate, tributyl borate such as tri - tert - butyl borate, tripentyl borate, trihexyl borate, trioctyl borate such as tri - (2 - ethylhexyl) borate, mono - hexyl dibutyl borate, etc., and combinations thereof.

[0427] When in use, the corrosion inhibitor may comprise a substituted thiadiazole, a substituted benzotriazole, a substituted triazole, a trisubstituted borate ester, or a combination thereof.

[0428] When desired, the corrosion inhibitor can be used in any effective amount, but when in use, it can generally be used in an amount of about 0.001 wt% to 5.0 wt%, such as 0.005 wt% to 3.0 wt% or 0.01 wt% to 1.0 wt%, based on the weight of the composition. Alternatively, such 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 weight of the lubricating composition.

[0429] In an embodiment, the corrosion inhibitor / rust inhibitor used in the lubricating oil composition and additive concentrate of the present invention is present in an amount of 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 in an amount of 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.

[0430] In a specific embodiment, the corrosion inhibitor / rust inhibitor used in the lubricating oil composition and additive concentrate of the present invention is selected from liquid triazole derivatives, such as liquid triazoleamine. Preferably, the corrosion inhibitor / rust inhibitor used in the lubricating oil composition and additive concentrate of the present invention comprises N,N-bis(2-ethylhexyl)-((1,2,4)-triazol-1-yl)methyl)amine (which can be obtained as Irgamet TM 30), and in particular consists of it.

[0431] In an alternative embodiment, the composition containing 3,4-oxypyridone can be substantially free (e.g., 0, or less than 0.001 wt%, less than 0.0005 wt%, not intentionally added, and / or absolutely free) of triazole, benzotriazole, substituted thiadiazole, imidazole, thiazole, tetrazole, hydroxyquinoline, oxazoline, imidazoline, thiophene, indole, indazole, quinoline, benzoxazine, dithiol, oxazole, oxatriazole, pyridine, piperazine, triazine, their derivatives, their combinations, or all corrosion inhibitors.

[0432] The composition according to the present disclosure may contain additives having different listed functions and also having a second effect as a corrosion inhibitor (e.g., the component B functionalized polymer described above may also have a corrosion inhibitor effect). For determining the amount of the corrosion inhibitor in the lubricating oil composition or concentrate herein, these additives are not counted as corrosion inhibitors. K. Antiwear agent

[0433] The lubricating oil composition of the present disclosure may contain one or more anti-wear agents that can reduce friction and excessive wear. Any anti-wear agent known to those of ordinary skill in the art can be used in the lubricating oil composition. Non-limiting examples of suitable anti-wear agents include zinc dialkyl dithiophosphates, metal (such as Pb, Sb, Mo, etc.) salts of dithiophosphoric acid, metal (such as Zn, Pb, Sb, Mo, etc.) salts of dithiocarbamic acid, metal (such as Zn, Pb, Sb, etc.) salts of fatty acids, boron compounds, phosphate esters, phosphite esters, amine salts of phosphate esters or thiophosphate esters, reaction products of dicyclopentadiene and dithiophosphoric acid, and combinations thereof. Based on the total weight of the lubricating oil composition, the amount of the anti-wear agent can be from about 0.01 wt% to about 5 wt%, from about 0.05 wt% to about 3 wt%, or from about 0.1 wt% to about 1 wt%.

[0434] In an embodiment, the anti-wear agent used in the lubricating oil composition and additive concentrate of the present invention is present as one or more anti-wear agents in an amount of 0.01 to 1.5% by mass, such as 0.05 to 1% by mass, such as 0.06 to 0.6% by mass, based on the total mass of the lubricating oil composition, and / or in an amount of 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.

[0435] In a specific embodiment, the anti-wear agent used in the lubricating oil composition and additive concentrate of the present invention is present in an amount that provides no more than 900 ppm of phosphorus, such as no more than 800 ppm of phosphorus, such as no more than 700 ppm of phosphorus, such as no more than 600 ppm of phosphorus, such as no more than 500 ppm of phosphorus, such as no more than 490 ppm of phosphorus, to the lubricating oil composition and / or additive concentrate.

[0436] In an embodiment, the anti-wear agent is or comprises a metal salt of a dihydrocarbyl dithiophosphate, such as a zinc dialkyl dithiophosphate compound. The metal of the metal salt of the dihydrocarbyl dithiophosphate can be an alkali metal or an alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper. In some embodiments, the metal is zinc. In other embodiments, the alkyl group of the metal salt of the dihydrocarbyl dithiophosphate has from about 3 to about 22 carbon atoms, from about 3 to about 18 carbon atoms, from about 3 to about 12 carbon atoms, or from about 3 to about 8 carbon atoms. In a further embodiment, the alkyl group is straight-chain or branched.

[0437] Available anti-wear agents also include substituted or unsubstituted thiophosphoric acids, the salts of which include zinc-containing compounds, such as zinc dithiophosphate compounds selected from dialkyl-, diaryl- and / or alkylaryl-dithiophosphates.

[0438] Metal alkyl thiophosphates, and more particularly metal dialkyldithiophosphates where the metal component is zinc, or zinc dialkyldithiophosphates (ZDDP) 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)(OR 1 )(OR 2 )]2, where R 1 and R 2 are C1-C 18 alkyls, preferably C2-C 12 alkyls. These alkyls can be straight-chain or branched. The alcohols used in ZDDP can be 2-propanol, butanol, sec-butanol, pentanol, hexanol such as 4-methyl-2-pentanol, n-hexanol, n-octanol, 2-ethylhexanol, alkylated phenols, etc. Mixtures of secondary alcohols or mixtures of primary and secondary alcohols can be used. Alkyl aryls can also be used. Available zinc dialkyldithiophosphates include secondary zinc dialkyldithiophosphates such as those available from The Lubrizol Corporation under the trade names "LZ 677A", "LZ 1095", and "LZ 1371", from Chevron Oronite under the trade name "OLOA 262", and from Afton Chemical under the trade name "HiTEC TM 7169".

[0439] In an embodiment, the zinc compound can be a zinc dithiocarbamate complex, a zinc dithiocarbamate as shown by the following formula: where each R I is independently a straight-chain, cyclic or branched, saturated or unsaturated aliphatic hydrocarbon moiety having 1 to about 10 carbon atoms, n is 0, 1 or 2, L is a ligand that saturates the zinc coordination layer, and x is 0, 1, 2, 3 or 4. In certain embodiments, the ligand L is selected from water, hydroxide, ammonia, amino, amido, alkylthiolate, halide, and combinations thereof.

[0440] Antiwear additives such as ZDDP and / or zinc carbamate are generally 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 weight of the lubricating composition, although more or less can generally be used advantageously. 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 weight of the lubricating composition. In a particular embodiment, the antiwear agent used in the lubricating oil compositions and additive concentrates of the present invention comprises ZDDP, particularly consists of ZDDP.

[0441] The antiwear additives useful herein also include boron-containing compounds such as borate esters, boronated fatty amines, boronated epoxides, alkali metal (or mixed alkali metals or alkaline earth metals) borates, and boronated overbased metal salts.

[0442] The compositions according to the present disclosure may contain additives having different recited functions and also having a secondary effect as an antiwear agent (e.g., the component B functionalized polymers described above may also have an antiwear effect). For determining the amount of antiwear agent in the lubricating oil compositions or concentrates herein, these additives are not counted as antiwear agents. L. Demulsifiers

[0443] The demulsifiers useful herein include those described in U.S. Patent No. 10,829,712 (column 20, lines 34 to 40). Generally, small amounts of demulsifying components may be used herein. Preferred demulsifying components are described in European Patent No. 330 522. It is obtained by reacting an alkylene oxide with an adduct obtained by reacting a diepoxide with a polyol. Such additives may be used in an amount of about 0.001 to 5 wt%, preferably about 0.01 to 2 wt%. M. Seal compatibilizers

[0444] Other optional additives include seal compatibilizers such as organic phosphates, aromatic esters, aromatic hydrocarbons, esters (e.g., butyl benzyl phthalate), and polybutenyl succinic anhydride. Such additives may be used in an amount of about 0.001 to 5 wt%, preferably about 0.01 to 2 wt%. In an embodiment, the seal compatibilizer is a seal swelling agent such as PIBSA (polyisobutenyl succinic anhydride). In certain embodiments, PIBSA may be present in the lubricating oil compositions or additive concentrates of the present invention in an amount of 0.01 to 5 mass%, such as 0.02 to 3 mass%, such as 0.05 to 1 mass%, such as 0.1 to 0.5 mass%, based on the weight of the lubricating oil composition, and / or in an amount of 0.01 to 10 mass%, such as 0.05 to 5 mass%, such as 0.1 to 3 mass%, such as 0.5 to 1.5 mass%, based on the weight of the additive concentrate. N. Extreme pressure agents

[0445] The lubricating oil composition of the present disclosure may contain one or more extreme pressure agents that can prevent seizure of sliding metal surfaces under extreme pressure conditions. Any extreme pressure agent known to those of ordinary skill in the art can be used in the lubricating oil composition. Generally, an extreme pressure agent is a compound that can chemically bond with a metal to form a surface film, which prevents welding of asperities in opposing metal surfaces under high loads. Non-limiting examples of suitable extreme pressure agents include sulfurized animal or vegetable fats or oils, sulfurized animal or vegetable fatty acid esters, fully or partially esterified esters of trivalent or pentavalent phosphorus-containing acids, sulfurized olefins, 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 α-olefins, functionally substituted dihydrocarbyl polysulfides, thioaldehydes, thioketones, episulfide compounds, sulfur-containing acetal derivatives, co-sulfurized blends of terpenes and acyclic olefins, polysulfide olefin products, amine salts of phosphate esters or thiophosphate esters, and combinations thereof. Based on the total weight of the lubricating oil composition, the amount of the extreme pressure agent can range from about 0.01 wt% to about 5 wt%, from about 0.05 wt% to about 3 wt%, or from about 0.1 wt% to about 1 wt%. O. Non - base oil unsaturated hydrocarbons

[0446] The lubricating oil composition of the present disclosure may contain one or more unsaturated hydrocarbons. These unsaturated hydrocarbons are different from any base oils (Group I, II, III, IV, and / or V lubricating oil base stocks) and / or viscosity improvers that may be present in the composition and always have at least one unsaturation per molecule (usually only one in the case of linear α - olefins or LAOs). Without being bound by theory, the unsaturation can provide antioxidant functionality and / or sulfur capture functionality, which can supplement and / or replace one or more antioxidant additives and / or one or more corrosion inhibitor additives, but unsaturated hydrocarbons (LAOs) generally do not provide the only antioxidant functionality and the only corrosion inhibition functionality in the lubricating oil composition. Non - limiting examples of unsaturated hydrocarbons may include one or more unsaturated C 12 -C 60 hydrocarbons (such as C 12 -C 48 hydrocarbons, C 12 -C 36 hydrocarbons, C 12 -C 30 hydrocarbons or C 12 -C 24Hydrocarbons). When there is only one unsaturation, the unsaturated hydrocarbon can be referred to as a linear alpha-olefin (LAO). Other non-limiting examples of unsaturated hydrocarbons can include polyisobutene oligomers / polymers and / or blends thereof that retain (or are modified after polymerization to exhibit) (near) terminal unsaturation. When present, the unsaturated hydrocarbon (LAO) can be present in an amount of 0.01 to 5 wt% (especially 0.1 to 3 mass%, or 0.1 to 1.5 mass%) based on the total weight of the lubricating oil composition.

[0447] When the lubricating oil composition contains one or more of the additives discussed above, the additives are typically incorporated into the composition in an amount sufficient to enable them to perform their intended functions. Typical amounts of such additives useful in the present disclosure, particularly for crankcase lubricants, are shown in the table below.

[0448] It should be noted that many additives are shipped by additive manufacturers as concentrates containing one or more additives together with a certain amount of base oil or other diluent. Accordingly, the weights in the table below and other amounts mentioned herein relate to the amount of the active ingredient (i.e., the undiluted portion of the ingredient). The weight percentages (mass%) shown below are based on the total weight of the lubricating oil composition. Typical amounts of optional lubricating oil components

[0449] The above additives are generally commercially available materials. These additives can be added independently, but are typically pre-blended in additive packages available from lubricating oil additive suppliers. Additive packages with various compositions, ratios, and properties are available and the selection of the appropriate additive package will take into account the intended use of the final composition. Fuel

[0450] The present disclosure also relates to a method of lubricating an automotive internal combustion engine during engine operation, which includes: (i) providing the lubricating composition described herein to the crankcase of the automotive internal combustion engine; (ii) providing a hydrocarbon fuel in 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 (such as a spark-ignition internal combustion engine).

[0451] The present disclosure also relates to a fuel composition that includes the lubricating oil composition described herein and a hydrocarbon fuel, where the fuel may be derived from petroleum and / or biological sources ("biofuel" or "renewable fuel"). In an embodiment, the fuel includes 0.1 to 100 mass% renewable fuel, or 1 to 75 mass% renewable fuel, or 5 to 50 mass% renewable fuel, based on the total mass of the renewable fuel and the petroleum-derived fuel.

[0452] Renewable fuel components are typically made from vegetable oils (such as palm oil, rapeseed oil, soybean oil, jatropha oil), microbial oils (such as algal oil), animal fats (such as edible oils, animal fats, and / or fish fats), and / or biogas. Renewable fuels refer to biofuels made from biological resources formed through contemporary biological processes. In one embodiment, the renewable fuel component is made by a hydrotreating process. Hydrotreating involves various reactions in which molecular hydrogen reacts with other components or components undergo molecular transformation in the presence of molecular hydrogen and a solid catalyst. The reactions include but are not limited to hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrocracking, and isomerization. The renewable fuel component can have different distillation ranges to provide the desired properties for the component according to the intended use. Use

[0453] The lubricating compositions of the present disclosure can be used to lubricate mechanical engine components by adding a lubricant thereto, particularly in internal combustion engines, such as spark-ignition or compression-ignition two-stroke or four-stroke reciprocating engines. Generally, they are crankcase lubricants, such as passenger car motor oils or heavy-duty diesel engine lubricants.

[0454] In particular, the lubricating compositions of the present disclosure are suitably used for lubricating the crankcase of a compression-ignition internal combustion engine, such as a heavy-duty diesel engine.

[0455] In particular, the lubricating compositions of the present disclosure are suitably used for lubricating the crankcase of a spark-ignition turbocharged internal combustion engine.

[0456] 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 can be used to lubricate the high-compression spark-ignition engine.

[0457] In an embodiment, the lubricating compositions of the present disclosure are suitably used for lubricating the crankcase of an engine of a heavy-duty diesel vehicle (i.e., a heavy-duty diesel vehicle having a gross vehicle weight rating of more than 10,000 pounds).

[0458] In an embodiment, the lubricating compositions of the present disclosure are suitably used for lubricating the crankcase of a passenger car diesel engine.

[0459] In particular, the lubricating oil formulations of the present disclosure are particularly useful for compression-ignition internal combustion engines, i.e., heavy-duty diesel engines, using low-viscosity oils, such as API FA-4 and future oil categories where wear protection of the valve train becomes challenging.

[0460] The present disclosure further relates to: 1. An additive concentrate (or additive package) comprising a dispersant mixture, the dispersant mixture comprising (1) 0.01 - 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 comprising C 4-5 olefins, having: i) Mw / Mn less than 2, ii) a functionality distribution (Fd) value of 3.5 or less, and iii) Mn (GPC - PS) of the polymer before functionalization of 10,000 g / mol or more; and (2) 50 - 90% by mass, based on the total mass of the dispersant mixture, of one or more poly(alkenyl)succinimides (“chlorine dispersants”) derived from polyalkenyl-substituted succinic anhydrides and polyamines prepared using a chlorine-assisted alkylation process; and (3) 10 - 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 process. 2. The additive concentrate of paragraph 1, wherein the one or more thermal dispersants are derived from polyisobutene succinic anhydride (“PIBSA”) and polyamine (“PAM”). 3. The additive concentrate of paragraph 2, wherein the PIBSA is based on polyisobutene with a high terminal vinylidene content (highly reactive polyisobutene, “HR - PIB”). 4. The additive concentrate of paragraph 2 or 3, wherein the PIBSA is based on polyisobutene 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. 5. The additive concentrate of the foregoing paragraphs, wherein the one or more thermal dispersants are PIBSA - PAM based on polyisobutene having a Mn of approximately 2300 g / mol. 6. The additive concentrate of the foregoing paragraphs, wherein the dispersant mixture comprises 1 - 12% by mass, such as 5 - 11% by mass, such as 7.5 - 10.5% by mass, such as 8.5 - 10% by mass, of the functionalized polymer based on the total mass of the dispersant mixture. 7. The additive concentrate of the foregoing paragraphs, wherein the dispersant mixture comprises 55 - 85% by mass, such as 62 - 82% by mass, such as 68 - 80% by mass, such as 70 - 76% by mass, of the one or more chlorine dispersants based on the total mass of the dispersant mixture. 8. The additive concentrate of the preceding paragraph, wherein the dispersant mixture comprises 12-25% by mass, such as 14-22% by mass, such as 15-20% by mass, such as 15.5-17.5% by mass, based on the total mass of the dispersant mixture, of the one or more thermal dispersants. 9. The additive concentrate of the preceding paragraph, wherein the dispersant mixture comprises the one or more chlorine dispersants and the 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. 10. The additive concentrate of the preceding paragraph, wherein the dispersant mixture comprises the one or more chlorine dispersants and the one or more thermal dispersants in a ratio of about 9:2. 11. The additive concentrate of the preceding paragraph, wherein the functionalized polymer is an amide- or imide-functionalized partially or fully saturated homopolyisoprene having: (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 per polymer chain, and (iv) an Mn (GPC-PS) of the polymer before functionalization of 20,000 g / mol to 50,000 g / mol. 12. The additive concentrate of the preceding paragraph, wherein the functionalized polymer is an amide- or imide-functionalized partially or fully saturated homopolyisoprene having: (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 per polymer chain, and (iv) an Mn (GPC-PS) of the polymer before functionalization of 30,000 g / mol to 40,000 g / mol. 13. The additive concentrate of any of the preceding paragraphs, wherein the functionalized polymer is an amide- or imide-functionalized partially or fully saturated homopolyisoprene having: (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 per polymer chain, and (iv) an Mn (GPC-PS) of the polymer before functionalization of about 35,140 g / mol. 14. The additive concentrate of the preceding paragraph, wherein the functionalized polymer is derived from a homopolyisoprene that has been acylated with maleic anhydride or maleic acid and further reacted with N-phenyl-p-phenylenediamine (NPPDA), such as 4-aminodiphenylamine (ADPA). 15. The additive concentrate of the preceding paragraph, which further comprises one or more antioxidants. 16. The additive concentrate of paragraph 15, wherein the one or more antioxidants are at least one or more amine antioxidants. 17. The additive concentrate of 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 of paragraphs 15-17, 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 of the preceding paragraph, which does not contain or substantially does not contain methyl sulfide antioxidants, 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. The additive concentrate of the preceding paragraph, wherein: (a) the dispersant mixture is present in an amount of 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; and (b) one or more antioxidants are optionally present in an amount of 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. 21. The additive concentrate of the preceding paragraph, which further comprises one or more additional additives selected from detergents, friction modifiers, defoamers, corrosion inhibitors / rust inhibitors, and antiwear agents. 22. The additive concentrate of the preceding paragraph, which further comprises one or more detergents selected from oil-soluble neutral or overbased sulfonates and phenates of alkali metals or alkaline earth metals. 23. The additive concentrate of the preceding paragraph, which further comprises one or more detergents selected from oil-soluble neutral or overbased sulfonates of calcium or magnesium. 24. The additive concentrate of the preceding paragraph, which does not contain or substantially does not contain phenolic detergent, such as less than 1.2% by mass, such as less than 1.0% by mass, such as less than 0.5% by mass, based on the total mass of the additive concentrate. 25. The additive concentrate of the preceding paragraph, which further comprises one or more detergents, wherein: (c) The one or more detergents are present in an amount of 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. 26. The additive concentrate of the preceding paragraph, which further comprises one or more friction modifiers, wherein: (d) The one or more friction modifiers are present in an amount of 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. 27. The additive concentrate of the preceding paragraph, which further comprises one or more defoamers, wherein: (e) The one or more defoamers are present in an amount of 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. 28. The additive concentrate of the preceding paragraph, which further comprises one or more corrosion inhibitors / rust preventives selected from liquid triazole derivatives, such as liquid triazole amine. 29. The additive concentrate of the preceding paragraph, which further comprises one or more corrosion inhibitors / rust preventives, wherein: (f) The one or more corrosion inhibitors / rust preventives are present in an amount of 0.01 - 2% by mass, such as 0.05 - 1.5% by mass, such as 0.1 - 0.5% by mass, based on the total mass of the additive concentrate. 30. The additive concentrate of the preceding paragraph, which further comprises one or more antiwear agents, wherein: (g) The one or more antiwear agents are present in an amount of 0.1 - 5% by mass, such as 1 - 2.4% by mass, such as 1.5 - 2.2% by mass, based on the total mass of the additive concentrate. 31. A lubricating oil composition, which comprises the following components or is obtained by mixing the following components: (A) At least 50% by mass of one or more base oils, based on the total mass of the lubricating oil composition; and (B) The additive concentrate of the preceding paragraph. 32. The lubricating oil composition of paragraph 31, wherein the one or more base oils comprise one or more Group III base oils and optionally one or more Group II base oils. 33. The lubricating oil composition of paragraph 31 or 32, wherein the one or more base oils comprise a mixture of one or more Group III base oils and one or more Group II base oils. 34. The lubricating oil composition of paragraphs 31 - 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 of paragraphs 31 - 34, which comprises 50 - 95% by mass, such as 60 - 90% by mass, such as 65 - 85% by mass, of one or more base oils based on the total mass of the lubricating oil composition. 36. The lubricating oil composition of paragraphs 31 - 35, which comprises: (A)(a) 25 - 65% by mass, such as 30 - 55% by mass, such as 34 - 48% by mass, of one or more Group III base oils based on the total mass of the lubricating oil composition; and (b) 20 - 60% by mass, such as 28 - 48% by mass, such as 30 - 38% by mass, of one or more Group II base oils based on the total mass of the lubricating oil composition. 37. The lubricating oil composition of paragraphs 31 - 36, which comprises: (B)(a) 1 - 12% by mass, such as 3 - 10% by mass, such as 6 - 8% by mass, of a dispersant mixture based on the total mass of the lubricating oil composition; (b) Optionally, 0.1 - 10% by mass, such as 3 - 8% by mass, such as 3.5 - 5% by mass, of one or more antioxidants based on the total mass of the lubricating oil composition; (c) Optionally, 0.01 - 3% by mass, such as 0.1 - 1% by mass, such as 0.2 - 0.6% by mass, of one or more detergents based on the total mass of the lubricating oil composition; (d) Optionally, 0.001 - 0.2% by mass, such as 0.01 - 0.06% by mass, such as 0.02 - 0.04% by mass, of one or more friction modifiers based on the total mass of the lubricating oil composition; (e) Optionally, 0.001 - 0.1% by mass, such as 0.003 - 0.03% by mass, such as 0.005 - 0.01% by mass, of one or more antifoaming agents based on the total mass of the lubricating oil composition; (f) Optionally, 0.001 - 1% by mass, such as 0.01 - 0.5% by mass, such as 0.05 - 0.1% by mass, of one or more corrosion inhibitors / rust preventives based on the total mass of the lubricating oil composition; (g) Optionally, 0.01 - 1.5% by mass, such as 0.05 - 1% by mass, such as 0.06 - 0.6% by mass, of one or more antiwear agents based on the total mass of the lubricating oil composition. 38. The lubricating oil composition of paragraphs 31 - 37, further comprising: (C)(a) One or more pour point depressants in an amount of 0.001 - 1% by mass, such as 0.01 - 0.5% by mass, such as 0.05 - 0.2% by mass, based on the total mass of the lubricating oil composition. 39. The lubricating oil composition of paragraphs 31 - 38, further comprising: (C)(b) One or more viscosity improvers in an amount of 0.001 - 0.5% by mass, such as 0.05 - 0.3% by mass, such as 0.1 - 0.22% by mass, based on the total mass of the lubricating oil composition. 40. The lubricating oil composition of paragraph 39, wherein the one or more viscosity improvers are selected from olefin copolymer viscosity improvers. 41. The lubricating oil composition of paragraphs 31 - 40, comprising: (A)(a) The one or more Group III base oils are present in an amount of 38 - 42% by mass based on the total mass of the lubricating oil composition; (b) The one or more Group II base oils are present in an amount of 33 - 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 - 1% by mass based on the total mass of the lubricating oil composition; (2) The one or more chlorine dispersants are present in an amount of 4 - 6% by mass based on the total mass of the lubricating oil composition; (3) The one or more thermal dispersants are present in an amount of 0.5 - 2% by mass based on the total mass of the lubricating oil composition; (b) The one or more antioxidants are present in an amount of 3.5 - 5% by mass based on the total mass of the lubricating oil composition; (c) The one or more detergents are present in an amount of 0.2 - 0.6% by mass based on the total mass of the lubricating oil composition; (d) The one or more friction improvers are present in an amount of 0.02 - 0.04% by mass based on the total mass of the lubricating oil composition; (e) The one or more antifoaming agents are present in an amount of 0.005 - 0.01% by mass based on the total mass of the lubricating oil composition; (f) The one or more corrosion inhibitors / rust preventives are present in an amount of 0.05 - 0.1% by mass based on the total mass of the lubricating oil composition; (g) The one or more antiwear agents are present in an amount of 0.06 - 0.6% by mass based on the total mass of the lubricating oil composition; (C)(a) The one or more pour point depressants are present in an amount of 0.05 - 0.2% by mass based on the total mass of the lubricating oil composition; and (b) The one or more viscosity improvers are present in an amount of 0.1-0.22% by mass based on the total mass of the lubricating oil composition. 42. The lubricating oil composition of paragraphs 31-41, which has 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. 43. The lubricating oil composition of paragraphs 31-42, which has a sulfated 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. 44. The lubricating oil composition of paragraphs 31-43, which has a phosphorus content of less than or about 550 ppm and a SASH content of less than or about 0.5% by mass. 45. The lubricating oil composition of paragraphs 31-44, which exhibits an SAE viscosity grade of 5W-X, where X represents any one of 8, 12, 16, 20, or 30. 46. The lubricating oil composition of paragraphs 31-45, which exhibits an SAE viscosity grade of 5W-30. 47. The lubricating oil composition of paragraphs 31-46, wherein the lubricating oil composition is a heavy-duty diesel engine oil. 48. The lubricating oil composition of paragraphs 31-47, wherein the average piston cleanliness determined by CEC L-118-21 is at least 70%, such as at least 75%, such as at least 78%. 49. The lubricating oil composition of paragraphs 31-48, wherein the average wear on the gear drive wheels determined by CEC L-118-21 is at least 75%, such as at least 80%, such as at least 82%. 50. The lubricating oil composition of paragraphs 31-49, wherein the average bushing wear determined by CEC L-118-21 is less than 8 μm, such as less than 5 μm, such as less than 3 μm. 51. The lubricating oil composition of paragraphs 31-50, wherein the average turbocharger housing deposits determined by CEC L-118-21 are at least 30%, such as at least 45%, such as at least 75%. 52. The lubricating oil composition of paragraphs 31-47, wherein the oxidation determined by CEC L-118-21 is less than 65 A / cm, such as less than 60 A / cm, such as less than 55 A / cm. 53. A method of lubricating an internal combustion engine during engine operation, which comprises: (i) providing the lubricating composition of paragraphs 31-52 to the crankcase of the internal combustion engine; (ii) providing a hydrocarbon fuel in the internal combustion engine; and (iii) Combust fuel in an internal combustion engine. 54. The method of 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 of paragraph 53 or 54, wherein the fuel is a hydrocarbon fuel. 56. The method of paragraphs 53 - 55, wherein the engine is a diesel engine, such as a heavy - duty diesel engine. 57. A fuel composition comprising the lubricating composition of paragraphs 31 - 52, and one or more of a hydrocarbon fuel, a renewable fuel, a hydrogen fuel, or any blend thereof. 58. A method of improving piston cleanliness of a lubricating oil composition, the method comprising including in the lubricating oil composition a dispersant mixture, the dispersant mixture comprising (1) 0.01 - 15% by mass of an amide, imide, and / or ester - functionalized partially or fully saturated polymer comprising C 4-5 olefins, based on the total mass of the dispersant mixture, having: i) an Mw / Mn of less than 2, ii) a functionality distribution (Fd) value of 3.5 or less, and iii) an Mn (GPC - PS) of the polymer before functionalization of 10,000 g / mol or more; and (2) 50 - 90% by mass of one or more poly(alkenyl)succinimides (“chlorine dispersants”) derived from polyalkenyl - substituted succinic anhydrides and polyamines prepared using a chlorine - assisted alkylation process, based on the total mass of the dispersant mixture; and (3) 10 - 30% by mass of one or more poly(alkenyl)succinimides (“thermal dispersants”) derived from polyalkenyl succinic anhydrides and polyamines prepared using a halogen - free thermal alkylation process, based on the total mass of the dispersant mixture. 59. The method of paragraph 58, wherein the average piston cleanliness determined by CEC L - 118 - 21 is increased to at least 70%, such as at least 75%, such as at least 78%. 60. A method of improving the wear resistance of a lubricating oil composition, the method comprising including in the lubricating oil composition a dispersant mixture, the dispersant mixture comprising (1) 0.01 - 15% by mass of an amide, imide, and / or ester - functionalized partially or fully saturated polymer comprising C 4-5 olefins, based on the total mass of the dispersant mixture, having: i) an Mw / Mn of less than 2, ii) a functionality distribution (Fd) value of 3.5 or less, and iii) The Mn (GPC-PS) of the polymer before functionalization that is 10,000 g / mol or more; and (2) 50 - 90% by mass, based on the total mass of the dispersant mixture, of one or more poly(alkenyl)succinimides (“chlorine dispersants”) derived from polyalkenyl-substituted succinic anhydrides and polyamines prepared using a chlorine-assisted alkylation method; and (3) 10 - 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. The method of paragraph 58, wherein the average wear on the gear drive wheel measured by CEC L-118-21 is increased to at least 75%, such as at least 80%, such as at least 82%. The method of paragraph 58 or 59, wherein the average bushing wear measured by CEC L-118-21 is reduced to less than 8 μm, such as less than 5 μm, such as less than 3 μm.

[0461] The present disclosure further relates to: A1. An additive concentrate (or additive package) comprising a dispersant mixture, the dispersant mixture comprising (1) 0.01 - 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 comprising C 4-5 alkenes, which has: i) an Mw / Mn of less than 2, ii) a functionality distribution (Fd) value of 3.5 or less, and iii) an Mn (GPC-PS) of the polymer before functionalization that is 10,000 g / mol or more; and (2) 50 - 90% by mass, based on the total mass of the dispersant mixture, of one or more poly(alkenyl)succinimides (“chlorine dispersants”) derived from polyalkenyl-substituted succinic anhydrides and polyamines prepared using a chlorine-assisted alkylation method; and (3) 10 - 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. A2. An additive concentrate according to paragraph A1, wherein said one or more heat dispersants are derived from polyisobutylene succinic anhydride ("PIBSA") and polyamine ("PAM"), wherein preferably, said PIBSA is based on polyisobutylene with a high terminal vinylidene content (highly reactive polyisobutylene, "HR-PIB"), and / or said 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. A3. An additive concentrate according to paragraph A1 or A2, wherein said dispersant mixture comprises 1-12% by mass, such as 5-11% by mass, such as 7.5-10.5% by mass, such as 8.5-10% by mass of said functionalized polymer based on the total mass of the dispersant mixture, and / or wherein said dispersant mixture comprises 55-85% by mass, such as 62-82% by mass, such as 68-80% by mass, such as 70-76% by mass of said one or more chlorine dispersants based on the total mass of the dispersant mixture, and / or wherein said dispersant mixture comprises 12-25% by mass, such as 14-22% by mass, such as 15-20% by mass, such as 15.5-17.5% by mass of said one or more heat dispersants based on the total mass of the dispersant mixture. A4. An additive concentrate according to any one of paragraphs A1 to A3 above, wherein said dispersant mixture comprises a ratio of said one or more chlorine dispersants to said one or more heat dispersants of from about 9:1 to about 3:2, such as from about 6:1 to about 3:1, such as from about 5:1 to about 4:1, especially a ratio of about 9:2. A5. An additive concentrate according to any one of paragraphs A1 to A4 above, which further comprises one or more antioxidants, wherein preferably, said one or more antioxidants are at least one or more amine antioxidants, and wherein more preferably, said one or more antioxidants are a mixture of one or more amine antioxidants and one or more phenolic antioxidants, wherein in particular, said one or more amine antioxidants and said one or more phenolic antioxidants are present in a ratio of from about 5:2 to about 9:5, such as about 2:1. A6. An additive concentrate according to any one of paragraphs A1 to A5 above, wherein: (a) said 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; and (b) 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. An additive concentrate according to paragraphs A1 to A6 above, further comprising one or more additional additives selected from detergents, friction modifiers, antifoaming agents, corrosion inhibitors / rust inhibitors (such as one or more triazoleamine corrosion inhibitors), and antiwear agents, particularly further comprising one or more detergents. An additive concentrate according to paragraph A7, wherein: i. based on the total mass of the additive concentrate, the one or more detergents are present in an amount of 0.1 - 5% by mass, such as 0.5 - 4% by mass, such as 1 - 3% by mass, and / or further comprises one or more friction modifiers, wherein preferably: ii. based on the total mass of the additive concentrate, the one or more friction modifiers are present in an amount of 0.01 - 1% by mass, such as 0.02 - 0.5% by mass, such as 0.05 - 0.2% by mass, and / or further comprises one or more antiwear agents, wherein preferably: iii. based on the total mass of the additive concentrate, the one or more antifoaming agents are present in an amount of 0.001 - 0.5% by mass, such as 0.01 - 0.1% by mass, such as 0.02 - 0.04% by mass, and / or further comprises one or more corrosion inhibitors / rust inhibitors, wherein preferably: iv. based on the total mass of the additive concentrate, the one or more corrosion inhibitors / rust inhibitors are present in an amount of 0.01 - 2% by mass, such as 0.05 - 1.5% by mass, such as 0.1 - 0.5% by mass, and / or further comprises one or more antiwear agents, wherein preferably: v. based on the total mass of the additive concentrate, the one or more antiwear agents are present in an amount of 0.1 - 5% by mass, such as 1 - 2.4% by mass, such as 1.5 - 2.2% by mass. A lubricating oil composition comprising the following components or obtained by mixing the following components: (A) at least 50% by mass of one or more base oils based on the total mass of the lubricating oil composition; and (B) an additive concentrate according to any one of paragraphs A1 to A8. A lubricating oil composition according to paragraph A9, wherein the one or more base oils comprise 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, wherein in particular, 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. The lubricating oil composition of paragraph A9 or A10, which comprises 50 - 95% by mass, such as 60 - 90% by mass, such as 65 - 85% by mass of one or more base oils based on the total mass of the lubricating oil composition, and preferably comprises: (A)(a) 25 - 65% by mass, such as 30 - 55% by mass, such as 34 - 48% by mass of one or more Group III base oils based on the total mass of the lubricating oil composition; and (b) 20 - 60% by mass, such as 28 - 48% by mass, such as 30 - 38% by mass of one or more Group II base oils based on the total mass of the lubricating oil composition. The lubricating oil composition of paragraphs 9 - 11, which comprises: (B)(a) 1 - 12% by mass, such as 3 - 10% by mass, such as 6 - 8% by mass of a dispersant mixture based on the total mass of the lubricating oil composition; (b) Optionally, 0.1 - 10% by mass, such as 3 - 8% by mass, such as 3.5 - 5% by mass of one or more antioxidants based on the total mass of the lubricating oil composition; (c) Optionally, 0.01 - 3% by mass, such as 0.1 - 1% by mass, such as 0.2 - 0.6% by mass of one or more detergents based on the total mass of the lubricating oil composition; (d) Optionally, 0.001 - 0.2% by mass, such as 0.01 - 0.06% by mass, such as 0.02 - 0.04% by mass of one or more friction modifiers based on the total mass of the lubricating oil composition; (e) Optionally, 0.001 - 0.1% by mass, such as 0.003 - 0.03% by mass, such as 0.005 - 0.01% by mass of one or more antifoaming agents based on the total mass of the lubricating oil composition; (f) Optionally, 0.001 - 1% by mass, such as 0.01 - 0.5% by mass, such as 0.05 - 0.1% by mass of one or more corrosion inhibitors / rust preventives based on the total mass of the lubricating oil composition; (g) Optionally, 0.01 - 1.5% by mass, such as 0.05 - 1% by mass, such as 0.06 - 0.6% by mass of one or more antiwear agents, and preferably further comprises: (C)(a) 0.001 - 1% by mass, such as 0.01 - 0.5% by mass, such as 0.05 - 0.2% by mass of one or more pour point depressants, and / or (b) 0.001 - 0.5% by mass, such as 0.05 - 0.3% by mass, such as 0.1 - 0.22% by mass of one or more viscosity improvers based on the total mass of the lubricating oil composition. The lubricating oil composition of paragraphs A9 - A12, which has 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 / or has a sulfate 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, and particularly has a phosphorus content of less than or about 550 ppm and a SASH content of less than or about 0.5% by mass. The lubricating oil composition of paragraphs A9 - A13, wherein the average piston cleanliness measured by CEC L - 118 - 21 is at least 70%, such as at least 75%, such as at least 78%, and / or wherein the average wear on the gear drive wheels measured by CEC L - 118 - 21 is at least 75%, such as at least 80%, such as at least 82%, and / or wherein the average bushing wear measured by CEC L - 118 - 21 is less than 8 μm, such as less than 5 μm, such as less than 3 μm, and / or wherein the average turbocharger housing deposits measured by CEC L - 118 - 21 is at least 30%, such as at least 45%, such as at least 75%, and / or wherein the oxidation measured by CEC L - 118 - 21 is less than 65 A / cm, such as less than 60 A / cm, such as less than 55 A / cm. A15. A method of lubricating an internal combustion engine during engine operation, which includes: (i) providing the lubricating composition of paragraphs A9 - A14 to the crankcase of the internal combustion engine; (ii) providing fuel in the internal combustion engine; and (iii) burning the fuel in the internal combustion engine, wherein preferably, the fuel is one or more of a hydrocarbon fuel (such as a petroleum - derived fuel, and / or a renewable fuel) and / or a hydrogen fuel or any blend thereof, particularly a hydrocarbon fuel, and / or the engine is a diesel engine, such as a heavy - duty diesel engine. A16. A fuel composition, which contains the lubricating composition of paragraphs A9 - A14, and one or more of a hydrocarbon fuel, a hydrogen fuel or any blend thereof (preferably, the hydrocarbon fuel contains a petroleum - derived fuel and / or a renewable fuel). A17. A method of improving the piston cleanliness of a lubricating oil composition, the method includes including a dispersant mixture in the lubricating oil composition, the dispersant mixture containing (1) 0.01 - 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, which has: i) an Mw / Mn of less than 2, ii) A functionality distribution (Fd) value of 3.5 or less, and iii) A Mn (GPC-PS) of the polymer before functionalization of 10,000 g / mol or more; and (2) 50 - 90% by mass, based on the total mass of the dispersant mixture, of one or more poly(alkenyl)succinimides (“chlorine dispersants”) derived from polyalkenyl-substituted succinic anhydrides and polyamines prepared using a chlorine-assisted alkylation process; and (3) 10 - 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 process, wherein preferably, the average piston cleanliness measured by CEC L-118-21 is increased to at least 70%, such as at least 75%, such as at least 78%. A18. A method of improving the antiwear properties of a lubricating oil composition, the method comprising including in the lubricating oil composition a dispersant mixture comprising (1) 0.01 - 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 comprising C 4-5 olefins, having: i) An Mw / Mn of less than 2, ii) A functionality distribution (Fd) value of 3.5 or less, and iii) A Mn (GPC-PS) of the polymer before functionalization of 10,000 g / mol or more; and (2) 50 - 90% by mass, based on the total mass of the dispersant mixture, of one or more poly(alkenyl)succinimides (“chlorine dispersants”) derived from polyalkenyl-substituted succinic anhydrides and polyamines prepared using a chlorine-assisted alkylation process; and (3) 10 - 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 process, wherein preferably, the average wear on the gear drive wheels measured by CEC L-118-21 is increased to at least 75%, such as at least 80%, such as at least 82%, and / or the average bushing wear measured by CEC L-118-21 is reduced to less than 8 μm, such as less than 5 μm, such as less than 3 μm.

[0462] The following non-limiting examples are provided to illustrate the disclosure. Experiments

[0463] Unless otherwise indicated, all molecular weights are number average molecular weights (Mn) reported in g / mol determined by gel permeation chromatography using polystyrene standards. Unless otherwise specified, "A.I.", "ai", "a.i.", and "ai" are weight % active ingredient. Test Procedures

[0464] The viscosity index is measured according to ASTM D2270.

[0465] The high temperature high shear viscosity ("HTHS" or "HTHS150") is determined at 150 °C according to ASTM D4683 and reported in cPs.

[0466] KV100 is the kinematic viscosity measured at 100 °C according to ASTM D445-19a.

[0467] Unless otherwise indicated, the Cold Crank Simulator ("CCS") at -25 °C is a measure of the cold start characteristics of a crankcase lubricant and is determined as described in ASTM D5293-92.

[0468] The Noack volatility ("Noack") is determined by the Noack test (ASTM D5800, Procedure B).

[0469] The phosphorus content is measured by ASTM D4951.

[0470] The sulfate ash ("SASH") content is measured by ASTM D874.

[0471] The Mack T11 test for soot-induced viscosity control is conducted in a Mack E-TECH V-MAC III diesel engine with exhaust gas recirculation, ASTM D7156-19. Two 30-minute oil flushes are followed by 252 hours at a constant speed of 1800 rpm. The fuel injection timing is adjusted to the soot level target values (thermogravimetric analysis (TGA), ASTM D5967) at 96 hours, 192 hours, and 228 hours, specifically a TGA soot level of 2.75% + / - 0.25% at 96 hours, 5.50% + / - 0.35% at 192 hours, and 6.53% + / - 0.44% at 228 hours. Oil samples are taken every 12 hours to measure the soot level (TGA, ASTM D5967) and the kinematic viscosity at 100 °C. The performance of the oil is determined by comparing the soot levels at which specified viscosity increases (4 cSt, 12 cSt, and 15 cSt) are observed. Oil consumption is also measured.

[0472] The Caterpillar 1N test for piston deposits is conducted in accordance with ASTM D6750-19. Oil consumption is also measured. The test is conducted in a single-cylinder Caterpillar 1Y540 diesel engine (the engine is run for a 60-minute break-in period under the conditions detailed in Table A14.1 of ASTM D6750-19, and then for 252 hours under the test conditions). The piston is then removed and rated according to the procedure outlined in the ASTM Deposit Rating Manual 20. It should be noted that ASTM D6750 covers the 1K procedure with 0.4% fuel sulfur and the 1N procedure with 0.04% fuel sulfur.

[0473] Cummins ISM engine test. According to the Cummins ISM engine test, ASTM D7468-21 determines valve train wear protection in a 10.8L 6-cyl diesel engine equipped with exhaust gas recirculation. The Cummins ISB test covers heavy-duty diesel engine test procedures conducted under high soot conditions to evaluate oil performance in terms of valve train wear, top ring wear, sludge deposits, and filter plugging. The engine is run for 200 hours in 4, 50-hour phases. The test conditions for Phases A and B are run at 1800 RPM at rated power with a retarded fuel injection timing to generate soot, and the test conditions for Phases B and D are run at 1600 RPM at peak torque to promote and evaluate wear on the injector adjustment screw, crosshead, and top piston ring. Oil performance is evaluated by assessing the injector adjustment screw, crosshead, top piston ring, filter plugging, oil sludge formation in the oil pan and valve cover. These parameters are combined to establish the total merit result according to ASTM D7468.

[0474] Cummins ISB engine test. According to the Cummins ISB engine test, ASTM D7484-21 determines valve train wear protection in a 5.9L 6-cyl diesel engine equipped with exhaust gas recirculation. The Cummins ISB test is a two-phase test. In Phase A, for 100 hours, the engine is run with a retarded fuel injection timing according to the ASTM procedure to generate excessive soot. In Phase B, over a 250-hour period, the engine is run under cyclic conditions according to the ASTM procedure to induce valve train wear. Oil performance is determined by evaluating the crosshead weight loss (mg) measured as detailed in Section 8.1.5 of ASTM D7484-21, the tappet weight 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 caliper and Mitutoyo digital indicator as detailed in Section 8.1.7 of ASTM D7484-21.

[0475] The Daimler OM471 FE1 performance test is carried out in Germany according to this Daimler / Mercedes-Benz In-House test method at APL (oil D, oil E and reference oil B1) or ISP (oil F) in accordance with CEC L-118-21. The OM471 is a EURO VI, 12.8L 6-cyl engine that produces a peak power of 375 kW and a peak torque of 2500 Nm. This test is designed to test the performance of the lubricating oil against piston deposits. It is a long-duration (600 hours) HDD engine test that needs to meet various OEM and industrial specifications (including DTFR 15C130). At the end of the test, several key test parameters need to meet the limits set by Daimler to pass the test, including: sludge in the oil mist separator (≥95%), piston cleanliness, grooves (average ≥74%), bushing wear (average ≤8 μm), deposits on the turbocharger housing (average ≥30%), wear on the gear drive wheels (single time ≥70%, average ≥75%), oxidation (≤65 A / cmμm), and oil consumption rate (≤8 g / h).

[0476] The values of the molecular weight moments (Mw, Mn, Mz) are determined by gel permeation chromatography ("GPC-PS") using polystyrene standards (Acquity TM APC polystyrene high MW calibration kit, 266 - 1,760,000 Da) and the software provided by the vendor (Empower TM 3, version 7.41.00.00) as follows. Molecular weight [number average molecular weight (Mn), weight average molecular weight (Mw), and z-average molecular weight (Mz)] was 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 215, 254, and 304 wavelengths. The GPC used three Agilent PLgel 10 micron Mixed B LS columns. Column separation was carried out with a flow rate of 0.25 mL / min and a nominal injection volume of 10 microliters. When in the low flow mode (idle), the detector and columns were maintained at 30 °C and heated to 35 °C when preparing to run the sample. The stream leaving the SEC column was introduced into an optical flow cell and then into the DRI detector. The solvent used for the SEC experiment was inhibitor-free THF (tetrahydrofuran). The polymer solution was prepared by placing the dried polymer in a glass container and adding the required amount of THF. Once the sample was added to the machine, a certain time was allowed to elapse before the run began to reach 35 °C. The GPC was programmed to run a pre-run equilibration for approximately 1.5 hours. Depending on solubility, the sample was stirred for 2 to 15 hours. The sample was filtered after stirring and before running. All amounts were measured by gravimetric analysis. The density of THF used to express the polymer concentration in mass / volume units was 0.887 g / mL at 68 °C. The injected sample concentration was 3 mg / mL. Before running each sample, the DRI detector and syringe were purged. Then the flow rate in the device was increased from 0.01 to 0.25 mL / min, and the DRI was allowed to stabilize for 4 to 5 hours before injecting the first sample. The software used to run the GPC and prepare the report was Empower TM version 7.41.00.00.

[0477] "FG" refers to the functional group.

[0478] The average functionality [also known as the average functionality value (Fv)] and the functionality distribution (Fd) values were determined as follows.

[0479] A simplified non-polymeric material with ADPA-imide functional groups (ODSA-ADPA) was prepared according to the following procedure; it was subsequently used as a reference material and calibrant for the functional group GPC analysis described further below.

[0480] 268 grams of octadecenyl succinic anhydride (a mixture of isomers, 0.094 moles) was added to a four-necked round-bottom flask equipped with an aerodynamic stirrer, a thermocouple connected to a temperature controller and an electric heating mantle, and a nitrogen inlet. The material was heated to 170 °C under constant stirring and under a continuous nitrogen purge through the reactor headspace.

[0481] 17.2 g of 4-aminodiphenylamine (ADPA, 0.094 moles) was added portionwise to the hot reaction mixture, allowing time for any foaming to subside as the amine addition continued. The mixture was heated until the reaction was complete as determined by FTIR analysis of the anhydride and imide peaks at approximately 1780 and 1700 cm-1 respectively (anhydride peak completely consumed, imide peak no longer increasing - approximately 2 - 3 hours). The material was allowed to cool partially (below 100 °C) before discharging from the reactor. It was used directly as a GPC calibrant without further purification.

[0482] According to the above GPC procedure, a GPC calibration curve was prepared from the ODSA - ADPA sample at 0.01, 0.02, 0.03, 0.04, and 0.05 mg / ml (as shown in Figure 1 of USSN 18 / 480,571 filed on October 4, 2023, which claims priority from USSN 63 / 379,006 filed on October 11, 2022), and integrated in the UV 304 nm channel.

[0483] Samples of the functional polymer were prepared and GPC analyzed as described above. The chromatogram was integrated by drawing a flat baseline that aligned with the solvent baseline and passed through the bottom of each peak. When the peaks of the chromatogram were not resolved to the baseline (the baseline is represented by the triangles in the x-axis of Figure 2), a vertical cut was made at the lowest point between them (shown as diamonds in the x-axis of Figure 2 in USSN 18 / 480,571 filed on October 4, 2023, which claims priority from USSN 63 / 379,006 filed on October 11, 2022). The lowest point is the inflection point in the GPC trace where the sign of the second derivative of the curve changes (e.g., from negative to positive or vice versa). For the calculation of the average functionality value (Fv) and functionality distribution (Fd), any chain - coupled and chain - fragmented polymers resolved 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 USSN 18 / 480,571 filed on October 4, 2023, which claims priority from USSN 63 / 379,006 filed on October 11, 2022.

[0484] The average functionality value (Fv) of the sample is defined as the average number of functional groups per polymer chain in the entire sample and is calculated by Equation 1: where Fv = average functionality calculated in the entire sample in units of FG grafted / polymer chain, UV304 int 总 = Total polymer peak integration in the UV 304 channel, FG Cal slope = Slope of the UV304 calibration curve from ODSA - ADPA, Mn = Number - average molecular weight of the polymer peak (using polystyrene standards), and Poly mg / ml = Polymer concentration in the total sample in mg / ml measured gravimetrically during sample preparation (excluding functional groups).

[0485] The functionality distribution (Fd) value represents the range of functionality across the MW distribution in the sample (i.e., the functionality difference between the high - MW and low - MW fractions in the sample). Fd is calculated by Equation 2: where PDI = Polydispersity index of the total polymer peak, calculated as Mn / Mw, F max = Maximum functionality value between the 10th and 90th cumulative percentiles (by RI) of the polymer peak, F min = Minimum functionality value between the 10th and 90th cumulative percentiles (by RI) of the polymer peak, and Fv = Average functionality value of the entire sample.

[0486] To calculate the individual functionalities in the sample, a detailed GPC slice report is output for the polymer peaks in the refractive index (RI) and UV 304 channel chromatograms (output at equal time intervals in each slice, approximately 0.003 minutes / slice), which contains data on slice retention time, MW, slice area, and cumulative %.

[0487] The output data from the two channels are aligned at the same retention time and then offset by 6.0 seconds based on the retention time difference measured between the RI and UV detectors (i.e., the time it takes for the material to travel from one detector to the other - this is determined by the retention time (RT) difference of the polystyrene (PS) peak in the calibration curve).

[0488] To verify that the output slice data match the original data adequately, for the RI and UV 304 channel polymer peaks, the sum of the peak slice areas should be within ±5% of the total integrated peak area.

[0489] The polymer concentration in each slice of the RI channel data is determined by Equation 3: (No knowledge of the functional polymer dn / dc is required, but the assumption here is that dn / dc does not vary with MW) Wherein, Poly mol / L 片 = the polymer concentration in mol / L (excluding functional groups) calculated in a single MW slice of the RI chromatogram, Poly mg / ml = the polymer concentration in the total sample in mg / ml measured gravimetrically during sample preparation (excluding functional groups), RI int 片 = the integrated area of an individual slice in the RI chromatogram, RI int 总 = the total polymer peak integration in the RI chromatogram, and Mn 片 = the MW of the polymer peak slice in the RI chromatogram.

[0490] The amine concentration in each slice of the UV304 channel data is determined by Equation 4: Wherein amine FG mo / L 片 = the concentration of amine functional groups in mol / L calculated in a single slice of the UV 304 chromatogram, UV304 int 片 = the integrated area of an individual slice in the UV304 chromatogram, and FG Cal slope = the slope of the UV304 calibration curve from ODSA - ADPA.

[0491] From the polymer and amine FG slice concentrations calculated above, the functionality of individual chromatogram slices can be calculated according to Equation 5: Wherein, F 片 = the functionality in units of FG grafts / polymer chain calculated for an individual slice of the RI / UV304 chromatogram, Poly mol / L 片 = the polymer concentration in mol / L (excluding functional groups) calculated in a single MW slice of the RI chromatogram, and amine FG mo / L 片 = the concentration of amine functional groups in mol / L calculated in a single slice of the UV 304 chromatogram.

[0492] The calculation is completed for each slice of the output chromatogram. The maximum and minimum functionality values between the 10th and 90th cumulative percentiles of the polymer peak are selected as Fmax and Fmin, respectively, and are used to calculate Fd as described above. Material

[0493] F-H-PI is 7.0-F-H-polyisoprene-A. Using SA-H-polyisoprene-A (succinate functionality 7.0), an amine-functionalized hydrogenated isoprene polymer with an average functionality (Fv) of 7.0 was prepared by adding 1 equivalent of amine (4-aminodiphenylamine, ADPA) per succinate unit (determined by SAP, ASTM D94) under nitrogen at 170 °C. Allow the reaction to continue and heat soak for up to 2 hours, after which it is diluted with additional oil (Group III, 4 cSt (Yubase TM 4)) and cooled to ambient temperature. During cooling, the material is combined with an ethoxylated alcohol such as Berol TM 1214 or Surfonic TM L24-4, Huntsman) at 10 wt% of the reaction mixture. 7.15-F-H-polyisoprene-A has a functionality distribution (Fd) value of 1.76, an Mw / Mn of 1.239, an Mn of 31629 g / mol, an Mz of 47835 g / mol and is used as an admixture in oil with ai = 0.5 wt% unless otherwise stated.

[0494] PIB is polyisobutene.

[0495] PIBSA is polyisobutene succinic anhydride.

[0496] PIBSA-PAM is polyisobutene succinic anhydride-polyalkyleneamine. Component Table

[0497] In the following table of the examples, the amounts indicated for each material refer to the amounts of the components (as shown in the component table above, which contains a certain amount of active ingredients in the oil). For example, the component F-H-PI has an active ingredient (a.i.) content of approximately 27.7 wt%, and the balance of this component is the diluent oil (see the component table above). This means that, for example, the active ingredient content of the functionalized polymer in oil F (see Table 2.1 below, which indicates that the content of the F-H-PI component is 2.150 mass%) is 0.596 mass% (i.e., 2.150 mass% × 0.277). Similarly, the active ingredient content of the thermal dispersant in oil F (which indicates that the content of the HR-PIBS-PAM component is 2 mass%) is 1.08 mass% (i.e., 2 mass% × 0.54), and the active ingredient content of the chlorine dispersant in oil F (which indicates that the content of the borated PIBSA-PAM component is 2 mass%, the content of the PIBSA-PAM 950Mn component is 3 mass%, and the content of the PIBSA-PAM 2200Mn component is 4 mass%) is 4.85 mass% (i.e., 2 mass% × 0.5+(3 + 4 mass%)×0.55). In this oil F, the ratio of the chlorine dispersant to the thermal dispersant is thus 4.85 / 1.08 = 4.49. The ratios of the chlorine dispersant to the thermal dispersant for the other oils can be calculated similarly based on the mass% of each component indicated in the example table below and the active ingredient content (%) indicated for each component in the component table above. Examples Example 1: Preliminary test

[0498] Oil A, comparative oils B1 and B2, and comparative oils C1 to C4 were prepared as shown in Table 1.1 below. Table 1.1

[0499] Oil A is characterized by a dispersant mixture containing approximately 10.5 mass% of a functionalized polymer, approximately 73 mass% of a chlorine dispersant, and approximately 16.5 mass% of a thermal dispersant, while comparative oils B1 and B2 do not contain a thermal dispersant, and comparative oils C1 to C4 c...

Claims

1. An additive concentrate comprising a dispersant mixture, said dispersant mixture comprising (1) Amides, imides and / or ester-functionalized partially or fully saturated polymers containing C 4-5 olefins, based on the total mass of the dispersant mixture, in an amount of 0.01-15% by mass, having: i) an Mw / Mn of less than 2, ii) a functionality distribution (Fd) value of 3.5 or less, and iii) an Mn (GPC-PS) of the polymer before functionalization of 10,000 g / mol or more; and (2) 50 - 90% by mass, based on the total mass of the dispersant mixture, of one or more poly(alkenyl)succinimides ("chlorine dispersants") derived from polyalkenyl-substituted succinic anhydrides and polyamines prepared using a chlorine-assisted alkylation process; and (3) 10 - 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 process.

2. The additive concentrate according to claim 1, wherein said one or more thermal dispersants are derived from polyisobutylene succinic anhydride ("PIBSA") and polyamine ("PAM"), wherein said PIBSA is based on polyisobutylene with a high terminal vinylidene content (highly reactive polyisobutylene, "HR-PIB"), and said PIBSA is based on polyisobutylene having an Mn of at least 1200 g / mol.

3. The additive concentrate according to claim 1, wherein said dispersant mixture comprises: 1) 1 to 12% by mass, based on the total mass of the dispersant mixture, of said functionalized polymer, 2) 55 to 85% by mass, based on the total mass of the dispersant mixture, of one or more chlorine dispersants, and 3) 12 to 25% by mass, based on the total mass of the dispersant mixture, of one or more thermal dispersants.

4. The additive concentrate according to claim 1, wherein said dispersant mixture comprises a ratio of said one or more chlorine dispersants to said one or more thermal dispersants of from about 9:1 to about 3:

2.

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

5.

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

7. The additive concentrate according to claim 1, which further comprises one or more additional additives selected from detergents, friction modifiers, defoamers, corrosion inhibitors / rust inhibitors, and antiwear agents.

8. The additive concentrate according to claim 1, which further comprises one or more triazoleamine corrosion inhibitors.

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

10. A lubricating oil composition comprising the following components or obtained by mixing the following components: (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 according to any one of claims 1 to 9.

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

12. The lubricating oil composition according to claim 10, which comprises 50 - 95% by mass, based on the total mass of the lubricating oil composition, of one or more base oils, which comprise: (a) 25 - 65% by mass, based on the total mass of the lubricating oil composition, of one or more Group III base oils; and (b) 20 - 60% by mass, based on the total mass of the lubricating oil composition, of one or more Group II base oils.

13. The lubricating oil composition according to claim 10, which comprises: (a) A dispersant mixture in an amount of 1 - 12% by mass, based on the total mass of the lubricating oil composition; (b) Optionally, one or more antioxidants in an amount of 0.1 - 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 - 3% by mass, based on the total mass of the lubricating oil composition; (d) Optionally, one or more friction improvers in an amount of 0.001 - 0.2% by mass, based on the total mass of the lubricating oil composition; (e) Optionally, one or more defoamers in an amount of 0.001 - 0.1% by mass, based on the total mass of the lubricating oil composition; (f) Optionally, one or more corrosion inhibitors / rust inhibitors in an amount of 0.001 - 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 - 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 - 1% by mass, based on the total mass of the lubricating oil composition, and / or (i) Optionally, one or more viscosity improvers in an amount of 0.001 - 0.5% by mass, based on the total mass of the lubricating oil composition.

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

15. The lubricating oil composition according to claim 10, wherein: 1) The average piston cleanliness determined by CEC L-118-21 is at least 70%, and / or 2) wherein the average wear on the gear drive wheel determined by CEC L-118-21 is greater than 75%, and / or wherein 3) the average bushing wear determined by CEC L-118-21 is less than 8 μm, and / or 4) wherein the average turbocharger housing deposits determined by CEC L-118-21 is at least 30%, and / or 5) wherein the oxidation determined by CEC L-118-21 is less than 65 A / cm².

16. A method of lubricating an internal combustion engine during engine operation, comprising: (i) providing to the crankcase of the internal combustion engine a lubricating composition according to any one of claims 10 to 15; (ii) providing fuel in the internal combustion engine; and (iii) combusting 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.

17. The method according to claim 16, wherein the fuel comprises a hydrocarbon fuel and / or the engine is a diesel engine.

18. A fuel composition comprising a lubricating composition according to any one of claims 10 to 15, and one or more of a hydrocarbon fuel, a hydrogen fuel, or any blend thereof.

19. The fuel composition according to claim 18, wherein the hydrocarbon fuel comprises a petroleum-derived fuel and / or a renewable fuel.

20. A method of improving the piston cleanliness of a lubricating oil composition, the method comprising including in the lubricating oil composition an additive concentrate according to any one of claims 1 to 9, wherein preferably the average piston cleanliness determined by CEC L-118-21 is increased to at least 70%.

21. A method of improving the wear resistance of a lubricating oil composition, the method comprising including in the lubricating oil composition an additive concentrate according to any one of claims 1 to 9, wherein preferably the average wear on the gear drive wheel determined by CEC L-118-21 is at least 75%, and / or the average bushing wear determined by CEC L-118-21 is less than 8 μm.

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