Flat oil viscosity lubricant composition

Abstract

The present invention relates to a lubricating oil composition comprising or being obtained by mixing (i) at least 50 mass%, based on the weight of the lubricating oil composition, of a base oil, (ii) at least one blocked dispersant having a number average molecular weight (Mn) of less than 1600 g / mol, (iii) at least one magnesium-containing detergent, (iv) at least one calcium-containing detergent, (v) at least one lubricant, (v) at least one lubricant, (v) at least one lubricant, (v) at least one lubricant, (v) at least one lubricant, (v) at least one lubricant, (v) at least one lubricant, and (v) at least one lubricant. (v) at least one copolymer viscosity improver having: 1) a ratio of relative KV140 / relative KV20 of 1.9 or more when measured on a blend of the copolymer viscosity improver and a Group III base oil having a KV100 of about 4 cSt (ASTM D445) and a viscosity index of about 120 (ASTM D2270) with a KV100 of about 8 cSt (1), 2) and 3); 2) a ratio of relative KV100 / relative KV70 of 1.30 or more; and 3) a viscosity index (ASTM 2270D) of 320 or more.

Description

Priority declaration

[0001] This application claims priority to and the benefit of U.S. Provisional Patent Application No. USSN 63 / 514,687, filed on July 20, 2023. Field of the Invention

[0002] The present disclosure relates to the use of a combination of a comb copolymer viscosity modifier, a capped lower molecular weight dispersant, and a combination of calcium and magnesium detergents as additives in lubricant compositions having flat viscosity properties in engine crankcase applications, especially in compression ignition engines and / or spark ignition applications. Background of the Invention

[0003] The present invention relates to lubricating oil compositions exhibiting improved viscosity characteristics. More particularly, the present invention relates to driveline and automotive crankcase lubricating oil compositions for gasoline (spark ignition) and diesel (compression ignition, spark assisted compression ignition) internal combustion engines, such compositions being referred to as crankcase lubricants, and to the use of additives in such lubricating oil compositions for improving the fuel economy performance of engines lubricated with said lubricating oil compositions.

[0004] The importance of fuel economy has been growing in recent years. One way to improve vehicle fuel economy is to design new lower viscosity lubricants to reduce friction in the engine. In order to improve fuel economy and optimally reduce CO2 emissions, the use and regulation of low viscosity grades by original equipment manufacturers (OEMs) has become increasingly common. One of the challenges of providing engine and / or transmission gearbox oils with reduced SAE viscosity grades is to maintain engine lubrication benefits within a higher temperature range of use. As engine temperature increases, lubricants tend to become thinner and loosen kinematic viscosity. This is not ideal because thin oils provide lower lubrication and protection effects, especially in engines designed for thicker lubricants. Achieving a balance between fuel efficiency and reliability is challenging for existing low viscosity engine oils (such as SAE 0W-8 grades). For example, lower viscosity (at high temperatures) increases the amount of oil leakage in various components of the lubrication system, so that the oil pressure is lower, and the engine hardware needs to be adjusted to compensate for the leakage, which reduces the fuel economy effect.

[0005] One approach to improving vehicle fuel economy is to design new lubricating oils that reduce friction while maintaining a "flat" viscosity throughout the engine temperature usage range. Such oils ideally provide good soot handling and / or provide enhanced anti-wear protection while providing the desired fuel economy benefits. There is a need to provide new engine oils with lower viscosity grades that meet these requirements.

[0006] "Flat Viscosity Oils" are engine oils in which the viscosity change with increasing temperature is significantly lower than that of conventional oils. Flat viscosity oils vary less over the temperature usage range and therefore still perform their intended lubrication function over a wider engine operating range. One proposed method for obtaining flat oils is to increase the contribution of low viscosity base oils and add a viscosity improver with a high viscosity index, which can reduce the kinematic viscosity in the medium and low temperature ranges while enhancing the thickening effect in the high temperature state.

[0007] Flat viscosity engine oils are required to have improved fuel efficiency (by further reducing the viscosity in the medium and low temperature range (about 20 to 70° C.)) and reliability (by maintaining the viscosity in the high temperature range within the range of conventional standards). See also "Research on Ultra-High Viscosity Index Engine Oil Part 1-'Flat Viscosity' Concept and Contribution to Carbon Neutrality" Yamamori, K. et al. SAE Technical Paper 2022-01-0525, 2022, doi: 10.4271 / 2022-01-0525; and "Research on Ultra-High Viscosity Index Engine Oil: Part 2-Influence of Engine Oil Evaporation Characteristics on Oil Consumption of Internal Combustion Engines" Koyama, T. et al. SAE Technical Paper 2022-01-0524, 2022, doi: 10.4271 / 2022-01-0524.

[0008] Major engine manufacturers aim to replace their current SAE 0W-8, 0W-12, 0W-16 (and possibly 0W-20) factory fill and original oil with flat viscosity engine oils by 2025. Therefore, new lower SAE viscosity grade lubricants with flat oil characteristics are needed as soon as possible.

[0009] US2021 / 0189281, US2021 / 0179961, US2021 / 0179960, US 11,384,311, US2021 / 0179965 and US 11,365,273 disclose various comb copolymer viscosity improvers and their use in lubricating oil compositions.

[0010] JP2023 / 004932A discloses a lubricant blend containing a polymethacrylate comb copolymer, a GTL base oil, a detergent, a dispersant, an antioxidant, and having a HTHS150 of 2.25 to 2.54 MPa·s, a KV of 8.5 to 9.5 cSt. 80 , KV of 13.0 to 14.2 cSt 60 and having NOACK evaporation of 15 to 25 wt % of the composition.

[0011] JP2022 / 120328A discloses a lubricant blend containing a comb copolymer, an ester base stock, and having a NOACK evaporation amount of 15% by mass to less than 25% by mass.

[0012] JP2022 / 022996A discloses a lubricant blend containing a comb copolymer, a base oil, having a NOACK evaporation amount of 15% by mass to less than 25% by mass and a KV of 6.1 to 9.3 cSt. 100 .

[0013] JP2022 / 022491A discloses a lubricant blend containing a comb copolymer, a base oil, having a NOACK evaporation amount of 25% by mass to less than 40% by mass and a KV of 2.5 to 3.5 cSt. 100 .

[0014] WO2022210065A1 discloses a lubricant blend containing a comb copolymer, a base oil, and an oxidized synthetic oil.

[0015] WO2022201845A1 discloses a lubricant blend containing a magnesium detergent and optionally a calcium boride detergent in a specific ratio.

[0016] Dispersants terminated with organic carbonates or similar end-capping agents (epoxides, lactones, hydroxyaliphatic carboxylic acids) are common technology, see, for example, U.S. publication US2010 / 0160192, which describes a succinimide dispersant that has been post-treated in two steps; succinimide is first reacted with phthalic anhydride or naphthalic anhydride to produce an initial post-treated succinimide, which is then reacted with a cyclic carbonate to form a final post-treated succinimide in which at least one basic nitrogen is retained.

[0017] Likewise, U.S. Pat. No. 8,901,050 describes a method of improving the copper corrosion performance of a lubricating oil composition by using a dispersant mixture including a boronated disuccinimide, an ethylene carbonate post-treated disuccinimide, and a polysuccinimide copolymer-based dispersant together with a silane-based corrosion inhibitor.

[0018] U.S. Patent No. 10,407,640 is directed to a marine diesel engine cylinder lubricating oil composition comprising (a) a major amount of a Group II base oil of lubricating viscosity, and (b) a non-boronated, post-treated polybutene bis-succinimide dispersant present in an amount of about 1.5 to about 8.0 weight percent on an active basis based on the total weight of the marine diesel engine cylinder lubricating oil composition, wherein the polybutene substituent is derived from a polybutene radical having a number average molecular weight of about 1500 to about 2500, the marine diesel engine cylinder lubricating oil composition having a TBN of about 5 to about 20, and further wherein the non-boronated, post-treated polybutene bis-succinimide is a cyclic carbonate (e.g., ethylene carbonate) post-treated polybutene bis-succinimide dispersant.

[0019] Other relevant references include: J. Bartz, Additive für Schmierstoffe [Additives for Lubricants], Expert-Verlag, Renningen-Malmsheim 1994, pp. 197-252); U.S. Patent 3,702,300; U.S. Patent No. 8,324,139; U.S. Patent No. 8,455,568; U.S. Patent No. 8,901,050; U.S. Patent No. 8,927,469; U.S. Patent No. 10,179,886; U.S. Patent No. 8,927,469; U.S. Patent No. 10,407,640; U.S. Patent No. 10,174,272; U.S. Patent No. 8,927,469; U.S. Patent No. 10,179,886; and U.S. Patent No. 11,390,825; U.S. Patent Publication No. US2010 / 0160192; and U.S. 2018 / 0334635; European Patent Office publications EP 0 969 077; EP 0 637 332, EP 0 937 769 and EP 0 979 834.

[0020] The present inventors have now surprisingly found that certain comb copolymers used in combination with a capped dispersant can be used in lubricant compositions, such as in internal combustion engines, to provide desirable flat viscosity oil characteristics in addition to improved fuel economy and / or wear properties.

[0021] The present disclosure also provides use of a capped low viscosity dispersant according to the present disclosure in combination with a comb copolymer viscosity improver to provide a fuel efficient lubricant composition having flat oil viscosity characteristics according to the present disclosure. Summary of the invention SUMMARY OF THE INVENTION

[0022] The present invention relates to a lubricating oil composition, which comprises the following components or is obtained by mixing the following components: (i) at least 50% by mass, based on the weight of the lubricating oil composition, of a base oil, (ii) at least one capped dispersant having a number average molecular weight (Mn) of less than 1600 g / mol, (iii) at least one magnesium-containing detergent, (iv) at least one calcium-containing detergent, (v) at least one copolymer viscosity improver having, when 1), 2) and 3) are measured on a blend of said copolymer viscosity improver and a Group III base oil having a KV100 of about 4 cSt (ASTM D445) and a viscosity index of about 120 (ASTM D2270) having a KV100 of about 8 cSt: 1) A relative KV140 / relative KV20 ratio of 1.9 or higher; 2) a relative KV100 / relative KV70 ratio of 1.30 or higher; and 3) Viscosity index of 320 or higher (ASTM 2270D).

[0023] The present invention relates to a lubricating oil composition, which comprises the following components or is obtained by mixing the following components: (i) at least 50% by mass, based on the weight of the lubricating oil composition, of a base oil, (ii) at least one end-capped dispersant having a number average molecular weight (Mn) of less than 1600 g / mol, preferably wherein the end-capped dispersant is represented by the formula: Among them, each R 11 and R 12 may be independently hydrogen or a hydrocarbon group, provided that R 11 and R 12 are not all hydrogen; z may be an integer from 0 to 10; and each R 13 may be independently acetyl, or wherein the two closest R 13 Groups can be linked together; (iii) at least one magnesium-containing detergent, (iv) at least one calcium-containing detergent, (v) at least one copolymer viscosity improver having a kinematic viscosity (Kv) of about 4 cSt 100 , ASTM D445) and a Group III base oil with a viscosity index (VI, ASTM D2270) of about 120 to obtain a KV100 of about 8 cSt, has: 1) a relative KV140 / relative KV20 ratio of 1.9 or higher (e.g., 2.1 or higher); 2) a relative KV100 / relative KV70 ratio of 1.30 or higher (e.g., 1.35 or higher); and 3) Viscosity index (ASTM 2270D) of 320 or higher (eg, 340 or higher).

[0024] The present invention further relates to a lubricating oil composition, which comprises the following components or is obtained by mixing the following components: (i) at least 50% by mass, based on the weight of the lubricating oil composition, of a base oil, (ii) at least one end-capped dispersant having a number average molecular weight (Mn) of less than 1600 g / mol, preferably wherein the end-capped dispersant is represented by the formula: Among them, each R 11 and R 12 may be independently hydrogen or a hydrocarbon group, provided that R 11 and R 12 are not all hydrogen; z may be an integer from 0 to 10, such as from 1 to 8; and each R 13 may be independently acetyl, or wherein the two closest R 13 The groups may be linked together, for example using an ethylene bridge to form a piperazinyl group; (iii) at least one magnesium-containing detergent, (iv) at least one calcium-containing detergent, (v) at least one comb copolymer viscosity modifier comprising the reaction product of at least the following monomers: (a) hydrogenated polybutadiene-based (alk) acrylate ester macromonomer; (b) (Alkyl) acrylic acid C3-C8 alkyl ester monomer; (c) (Alkyl) acrylic acid C 12 -C 24 Alkyl ester monomers; and (d)C1-C 18 Alkyl-terminated or C6-C 20 Aryl-, aralkyl- or alkaryl-terminated C2-C6 oxyalkyl or C2-C6 oligo(alkyleneglycol)-based(alk)acrylate ester monomer and / or hydroxyalkyl or H-endcapped oligo(alkylene glycol)-based(alk)acrylate monomer having the following structure (II): Where R 2 represents hydrogen or C1-C2 alkyl, and m is 2 to 6, such that -(CH2) m - represents a linear, branched and / or cyclic alkyl group between oxygen, n is 1 to 10, and R 1 Represents H, C1-C 18 Linear, branched and / or cyclic alkyl end groups or C6-C 20 aryl, aralkyl or alkaryl end groups, wherein the combination of (c) and (d) together constitute greater than 20.0 weight percent of the repeating units of the comb copolymer viscosity modifier, based on the weight of all repeating units in the copolymer; vi) optionally, a metal alkylthiophosphate, wherein the alkyl group is derived from at least one secondary alcohol (e.g., a zinc dialkyl dithiophosphate, wherein the alkyl group is at least partially (e.g., completely) derived from a secondary alcohol or a mixture of a primary alcohol and a secondary alcohol, such as a compound of the formula Zn[SP(S)(OR1)(OR2)]2, wherein R1 and R2 are C1-C 18 Alkyl, preferably at least one of R1 and R2, if both are secondary C2-C 12 alkyl); The lubricating oil composition preferably has: a) less than or equal to 30 mass % (e.g., 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 from 15 to 25 mass %, such as from 15 to 30 mass %, such as from 19 to 28 mass %) volatility as measured by the Noack test (ASTM D5800, Procedure B), based on the total mass of the lubricating composition; and / or b) a ratio of calcium from the detergent to magnesium from the detergent of from 10:1 to 2:1 (e.g., from 10:1 to 3:1, such as from 8:1 to 4:1, such as about 6:1 to about 5:1); and / or c) a total soap content of less than 30 mmol (such as less than 25 mmol, such as less than 20 mmol, such as less than 16 mmol, such as less than 10 mmol, such as less than 8 mmol, such as less than 7 mmol, such as 0.5 to 10 mmol, such as 1 to 8 mmol, such as 2 to 7 mmol).

[0025] According to another aspect of the present invention, there is provided a use of the above lubricating oil composition for providing flat oil viscosity properties to a lubricating oil composition of relatively low viscosity (such as SAE 0W-20, 0W-16, 0W-12, 0W-8).

[0026] According to another aspect of the present invention, there is provided a lubricating oil composition comprising a first PIBSA-PAM dispersant composition derived from a first polyamine and a first PIB having a number average molecular weight of 1200 to 1400 g / mol (e.g., 1250 to 1350 g / mol, such as about 1300 g / mol), the viscosity (Pa.s) of which is reduced at 100 sec. compared to an otherwise identical lubricating oil composition except that the first PIBSA-PAM composition is replaced by a physical mixture of two different PIBSA-PAM dispersants. -1 At least about 30% lower (e.g., 35% lower) at a shear rate of -1 The shear rate is at least about 55% lower (e.g., at least 65% lower) at a shear rate of 1.5 % (Haake carbon black test - 9 wt. % carbon black, 1 to 10 s -1 and 10 to 1000s -1 The invention relates to a method for preparing a dispersion of a first PIB having a plurality of PIBs, wherein the first and second PIBs are dispersants of the type described herein ...

[0027] According to another aspect of the present invention, there is provided an end-capped (e.g., ethylene carbonate end-capped) dispersant having a number average molecular weight (Mn) and / or derived from a polymer (e.g., polyisobutylene) having an Mn of less than 1600 g / mol or less (e.g., 800 to 1500, such as 900 to 1450 g / mol, such as 1000 to 1400 g / mol, such as 1100 to 1400 g / mol, such as 1200 to 1400 g / mol, such as about 1300 g / mol). The end-capped dispersant may be an ethylene carbonate end-capped 1200 to 1400 g / mol PIBSA-PAM, such as an Mn 1300Mn PIBSA-PAM. The capped dispersant may be an ethylene carbonate capped PIBSA PAM composition derived from a polyamine and PIB having a number average molecular weight of 1200 to 1400 g / mol, such as 1250 to 1350 g / mol, such as about 1300 g / mol.

[0028] According to another aspect of the present invention, there is provided a polymethacrylate comb copolymer viscosity improver, which is prepared by polymerization of at least the following monomers: (a) hydrogenated polybutadiene-based (alk) acrylate ester macromonomer; (b) (Alkyl) acrylic acid C3-C8 alkyl ester monomer (such as butyl methacrylate); (c) (Alkyl) acrylic acid C 12 -C 24 Alkyl ester monomers (such as dodecyl methacrylate); and (d)C6-C 20 Aryl-, aralkyl- or alkaryl-terminated C2-C6 oxyalkyl or C2-C6 oligo(alkylene glycol)-based(alk)acrylate ester monomer having the following structure (II): Where R 2 represents hydrogen or C1-C2 alkyl, and m is 2 to 6, such that -(CH2) m - represents a linear, branched and / or cyclic alkyl group between oxygen, n is 1 to 10, and R 1 Represents C6-C 20 an aryl, aralkyl or alkaryl terminal group, in: 1) Based on the weight of all repeating units in the copolymer, the (c) (alkyl) acrylic acid C 12 -C 24 The alkyl ester monomer repeating units are present in 16 to less than 21 weight percent (e.g., 16.5 to less than 20.0 weight percent, such as 17 to less than 19.5 weight percent), 2) based on the weight of all repeating units in the copolymer, the (d) C6-C 20 Aryl-, aralkyl- or alkaryl-terminated C2-C6 oxyalkyl or C2-C6 oligo(alkylene glycol) type (alkyl)acrylate monomer repeating units are present in 3 to 7 weight percent, and 3) The combination of (c) and (d) together constitute greater than 20.0 weight percent of the repeating units of the comb copolymer viscosity modifier, based on the weight of all repeating units in the copolymer.

[0029] According to another aspect of the present invention, there is provided a polymethacrylate comb copolymer viscosity improver having: 1) a relative KV140 / relative KV20 ratio of 1.9 or higher (e.g., 2.1 or higher); 2) a relative KV100 / relative KV70 ratio of 1.30 or higher (e.g., 1.35 or higher); and 3) Viscosity index (ASTM D 2270) of 320 or higher (eg, 340 or higher).

[0030] Typically, it has a VI of 120 and a Kv of 4 cSt 100 The Group III base oil also has a Kv of 2 cSt 140 、Kv of 44cSt 20 and Kv of 19cSt 70 (All kinematic viscosities are measured according to ASTM D445).

[0031] According to another aspect of the present invention, there is provided a concentrate comprising: (i) less than 50% by mass, based on the weight of the lubricating oil composition, of a base oil, (ii) at least one end-capped dispersant having a number average molecular weight (Mn) of less than 1600 g / mol, preferably wherein the end-capped dispersant is represented by the formula: Among them, each R 11 and R 12 may be independently hydrogen or a hydrocarbon group, provided that R 11 and R 12 are not all hydrogen; z may be an integer from 0 to 10, such as from 1 to 8; and each R 13 may be independently acetyl, or wherein the two closest R 13 The groups may be linked together, for example using an ethylene bridge to form a piperazinyl group; (iii) at least one magnesium-containing detergent and at least one calcium-containing detergent, wherein the ratio of calcium from the detergent to magnesium from the detergent is from 10:1 to 2:1 (e.g., from 10:1 to 3:1, such as from 8:1 to 4:1, such as about 6:1 to about 5:1); and (iv) at least one comb copolymer viscosity modifier comprising the reaction product of at least the following monomers: (a) hydrogenated polybutadiene-based (alk) acrylate ester macromonomer; (b) (Alkyl) acrylic acid C3-C8 alkyl ester monomer; (c) (Alkyl) acrylic acid C12 -C 24 Alkyl ester monomers; (d)C1-C 18 Alkyl-terminated or C6-C 20 Aryl-, aralkyl- or alkaryl-terminated C2-C6 oxyalkyl or C2-C6 oligo(alkyleneglycol)-based(alk)acrylate ester monomer and / or hydroxyalkyl or H-endcapped oligo(alkylene glycol)-based(alk)acrylate monomer having the following structure (II): Where R 2 represents hydrogen or C1-C2 alkyl, and m is 2 to 6, such that -(CH2) m - represents a linear, branched and / or cyclic alkyl group between oxygen, n is 1 to 10, and R 1 Represents H, C1-C 18 Linear, branched and / or cyclic alkyl end groups or C6-C 20 aryl, aralkyl or alkaryl end groups, wherein the combination of (c) and (d) together constitute greater than 20.0 weight percent of the repeating units of the comb copolymer viscosity modifier, based on the weight of all repeating units in the copolymer; (v) optionally, a metal alkylthiophosphate, wherein the alkyl group is derived from at least one secondary alcohol (e.g., a zinc dialkyl dithiophosphate, wherein the alkyl group is at least partially (e.g., completely) derived from a secondary alcohol or a mixture of a primary alcohol and a secondary alcohol, such as a compound of the formula Zn[SP(S)(OR1)(OR2)]2, wherein R1 and R2 are C1-C 18 Alkyl, preferably at least one of R1 and R2, if both are secondary C2-C 12 alkyl); (vi) optionally, a molybdenum-containing compound (such as dimerized or trimerized MoDTC), and (vii) optionally, an antioxidant (such as an aminic antioxidant).

[0032] According to a still further aspect of the present invention, there is provided a use of the above-mentioned lubricating oil composition for providing improved fuel economy, for example a FEI (Fuel Economy Improvement) difference of greater than 10% (such as 15% or higher, such as 20% or higher) compared to Toyota 0W-8GLV-1 lubricating oil, which comprises introducing the lubricating oil composition described herein into an internal combustion engine and operating the engine. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 (Fig.1) is a graph of the data in Table 2.

[0034] Figure 2 (Fig.2) is a graph of the data in Table 9.

[0035] Figure 3 (Fig.3) is a graph of the relative viscosity data in Table X.

[0036] Figure 4 (Fig. 4) is a graph of Kv40 vs. m%N for selected PIBSA-PAM's in Table A.

[0037] Figure 5 (Fig. 5) is a graph of the soot control properties of selected blends in Table A2. definition

[0038] For the purposes of this specification and all claims hereof, if used or lower words and expressions shall have the meanings given below.

[0039] For purposes herein, the new numbering scheme of the periodic table is used as described in CHEMICAL AND ENGINEERING NEWS, 63(5), 27 (1985), i.e., alkali metals are Group 1 metals (e.g., Li, Na, K, etc.) and alkaline earth metals are Group 2 metals (e.g., Mg, Ca, Ba, etc.).

[0040] The term "comprising" or any cognates specifies the presence of stated elements, steps or integers or components, but does not exclude the presence or addition of one or more other elements, steps, integers, components or combinations thereof. The expression "consisting of" or "consisting essentially of" or cognates may be encompassed within "comprising" or cognates, wherein "consisting essentially of" allows the inclusion of substances that do not substantially affect the characteristics of the composition to which it is applied.

[0041] The term "approximately" refers to approximation, which includes values ​​obtained by rounding. As used herein, the term "approximately" to modify the amount of the ingredients, components or reactants of the present invention used refers to changes in the numerical amount that may occur, for example, by typical measurements and liquid handling procedures for making concentrates or lubricating oil compositions. In addition, changes may be made by unintentional errors in the measurement procedures, differences in the manufacture, source or purity of the ingredients used to make the composition or to carry out the method, etc. In one aspect, the term "approximately" refers to within 10% of the reported numerical value. In another aspect, the term "approximately" refers to within 5% of the reported numerical value. In yet another aspect, the term "approximately" refers to within 10, 9, 8, 7, 6, 5, 4, 3, 2 or 1% of the reported numerical value.

[0042] The term "LOC" refers to a lubricating oil composition.

[0043] The term "major amount" means more than 50 mass % of the composition, such as more than 60 mass % of the composition, such as more than 70 mass % of the composition, such as 80 to 99.009 mass % of the composition, such as 80 to 99.9 mass %, such as 80 to 99.009 mass % of the composition, based on the mass of the composition.

[0044] The term "minor amount" means 50 mass % or less of the composition; such as 40 mass % or less of the composition; such as 30 mass % or less of the composition, such as 20 to 0.001 mass %, such as 20 to 0.1 mass %, based on the mass of the composition.

[0045] Unless otherwise indicated, the term "mass %" refers to the mass percentage of a component based on the mass of the composition measured in grams, and is alternatively referred to as weight percent ("weight %", "wt %", "wt. %" or "% w / w").

[0046] The term "active ingredient" (also referred to as "ai" or "AI") refers to an additive material that is neither a diluent nor a solvent. Unless otherwise indicated, amounts herein are described as active ingredients.

[0047] As used herein, the terms "oil-soluble" and "oil-dispersible" or cognate terms do not necessarily mean that the compound or additive is soluble, dissolvable, miscible or capable of being suspended in the oil in all proportions. However, these mean that they are soluble or stably dispersible in the oil, for example, to an extent sufficient to exert their intended effect in the environment in which the oil is used. In addition, the additional incorporation of other additives may also allow the incorporation of higher amounts of a particular additive, if desired.

[0048] The terms "group" and "radical" are used interchangeably herein.

[0049] The term "hydrocarbon" refers to a compound of hydrogen and carbon atoms. A "heteroatom" is an atom other than carbon or hydrogen. When referred to as a "hydrocarbon", especially as a "refined hydrocarbon", the hydrocarbon may also contain a minor amount (e.g., wherein the heteroatom does not substantially change the hydrocarbon nature of the hydrocarbon compound) of one or more heteroatoms or heteroatom-containing groups (e.g., halogens, especially chlorine and fluorine, amino, alkoxy, mercapto, alkylmercapto, nitro, nitroso, sulfoxy, etc.).

[0050] The term "hydrocarbyl" refers to a group containing hydrogen and carbon atoms. Preferably, unless otherwise specified, the group consists essentially of hydrogen and carbon atoms, more preferably consists only of hydrogen and carbon atoms. Preferably, the hydrocarbyl comprises an aliphatic hydrocarbyl. The term "hydrocarbyl" includes "alkyl", "alkenyl", "alkynyl" and "aryl" as defined herein. The hydrocarbyl may contain one or more atoms / groups other than carbon and hydrogen, as long as they do not affect the basic hydrocarbyl nature of the hydrocarbyl. Such atoms / groups (e.g., halogens, especially chlorine and fluorine, amino, alkoxy, mercapto, alkylthiol, nitro, nitroso, sulfoxy, etc.) are known to those skilled in the art.

[0051] The term "alkyl" refers to a carbon and hydrogen radical (e.g., C1 to C 30 , such as C1 to C 12 The alkyl group in the compound is usually directly bonded to the compound via a carbon atom. Unless otherwise specified, the alkyl group can be linear (linear) (i.e., unbranched) or branched, cyclic, acyclic or partially cyclic / acyclic. Preferably, the alkyl group comprises a linear or branched acyclic alkyl group. Representative examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, 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.

[0052] The term "alkenyl" refers to a carbon and hydrogen group (e.g., C2 to C 30 Groups such as C2 to C 12 The alkenyl group in a compound is usually directly bonded to the compound via a carbon atom. Unless otherwise specified, the alkenyl group may be linear (ie, unbranched) or branched, cyclic, acyclic or partially cyclic / acyclic.

[0053] The term "alkylene" refers to a C1 to C 20 , preferably C1 to C 10A divalent saturated aliphatic group which may be linear 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.

[0054] "Olefins," also referred to as "alkenes," are linear, branched, or cyclic hydrocarbons having at least one double bond. For purposes of this specification and the claims thereto, when a polymer or copolymer is referred to as comprising a monomer (such as an olefin), the monomeric unit present in such a polymer or copolymer is the polymerized form of that monomer. For example, when a copolymer is said to have an "isoprene" content of 55% to 95% by weight, it is understood that the monomeric units in the copolymer are derived from isoprene in the polymerization reaction, the derived units being present at 55% to 95% by weight based on the weight of the copolymer. A "polymer" has two or more monomeric units that are the same or different. A "homopolymer" is a polymer having the same monomeric units. A "copolymer" is a polymer having two or more monomeric units that are different from each other. "Different" as used to refer to monomeric units means that the monomeric units differ from each other by at least one atom or are isomerically different. An "isoprene polymer" or "isoprene copolymer" is a polymer or copolymer that comprises at least 50 mole percent isoprene-derived units, a "butadiene polymer" or "butadiene copolymer" is a polymer or copolymer that comprises at least 50 mole percent butadiene-derived units, and so forth. Likewise, when a polymer is referred to as "comprising C 4-5 When a partially or fully saturated polymer of an olefin is used as a "polymer of a partially or fully saturated olefin", the C 4-5 Olefins are polymerized forms of olefins, and the polymers have been partially or fully saturated (eg, by hydrogenation) after polymerization of the monomers.

[0055] The term "alkynyl" refers to a C2 to C16 radical having at least one carbon-carbon triple bond. 30 (such as C2 to C 12 ) group.

[0056] The term "aryl" refers to a group containing at least one aromatic ring, such as cyclopentadiene, phenyl, naphthyl, anthracenyl, etc. Aryl is usually C5 to C 40 (such as C5 to C 18 , such as C6 to C 14 ) aryl, optionally substituted by one or more hydrocarbon groups, heteroatoms or heteroatom-containing groups (such as halogen, hydroxyl, alkoxy and amino). Preferred aryl groups include phenyl and naphthyl and substituted derivatives thereof, especially phenyl and alkyl substituted derivatives of phenyl.

[0057] The term "substituted" means that the hydrogen atom has been replaced by a hydrocarbon group, a heteroatom or a heteroatom-containing group. Alkyl substituted derivatives mean that the hydrogen atom has been replaced by an alkyl group. "Alkyl substituted phenyl" is a phenyl group in which the hydrogen atom has been replaced by an alkyl group, such as a C1 to C 20 Alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, dimethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and / or triacontyl substituted phenyl.

[0058] The term "halogen" or "halo" refers to a Group 17 atom or a group of a Group 17 atom, such as fluorine, chlorine, bromine and iodine.

[0059] The term "ashless" with respect to additives means that the composition does not include metals.

[0060] The term "ash-containing" with respect to an additive means that the composition includes a metal.

[0061] The term "effective amount" with respect to an additive refers to the amount of such additive in the lubricating oil composition such that the additive provides the desired technical effect.

[0062] The term "effective minor amount" with respect to an additive refers to an amount of such additive that is less than 50 mass % of the lubricating oil composition such that the additive provides the desired technical effect.

[0063] The term "effective major amount" with respect to an additive refers to an amount of such additive constituting 50 mass % or more of the lubricating oil composition such that the additive provides the desired technical effect.

[0064] Unless otherwise indicated, the term "ppm" means parts per million by mass based on the total mass of the lubricating oil composition.

[0065] The term "metal content" of a lubricating oil composition or additive component, such as magnesium content, molybdenum content or total metal content (ie, the sum of all individual metal contents) is measured by ASTM D5185.

[0066] The term "aliphatic hydrocarbon fatty acid" refers to an aliphatic C7 to C 29 , preferably C9 to C 27 , the most preferred 11 To C 23 Such compounds may be referred to herein as aliphatic (C7 to C 29 ), more preferably (C9 to C 27 ), most preferably (C 11 To C23 ) Hydrocarbyl monocarboxylic acid or hydrocarbon fatty acid (wherein C x To C y represents the total number of carbon atoms in the aliphatic hydrocarbyl chain of the fatty acid, the fatty acid itself comprising a total of Cx+1 to Cy+1 carbon atoms due to the presence of the carboxyl carbon atom). Preferably, the aliphatic hydrocarbyl fatty acid, including the carboxyl carbon atom, has an even number of carbon atoms. The aliphatic hydrocarbyl chain of the fatty acid may be saturated or unsaturated (i.e. comprising at least one carbon-carbon double bond); preferably, the aliphatic hydrocarbyl chain is unsaturated and comprises at least one carbon-carbon double bond - such fatty acids may be obtained from natural sources (e.g. derived from animal or vegetable oils) and / or by reduction of the corresponding saturated fatty acids. It will be appreciated that a certain proportion of the aliphatic hydrocarbyl chains of the corresponding aliphatic hydrocarbyl fatty acid esters are unsaturated (i.e. comprising at least one carbon-carbon double bond) to allow reaction with other reagents, such as sulfur, to form the corresponding functionalized (e.g. sulfurized) aliphatic hydrocarbyl fatty acid esters.

[0067] The term "aliphatic hydrocarbon fatty acid ester" refers to an ester obtainable by converting the monocarboxylic acid functional group of the corresponding aliphatic hydrocarbon fatty acid into an ester group. Suitably, the monocarboxylic acid functional group of the aliphatic hydrocarbon fatty acid is converted into a hydrocarbon ester, preferably a C1 to C 30 Aliphatic hydrocarbon esters, such as alkyl esters, preferably C1 to C6 alkyl esters, especially methyl esters. Alternatively or additionally, the monocarboxylic acid functional group of the aliphatic hydrocarbon fatty acid may be in the form of a natural glyceride. Accordingly, the term "aliphatic hydrocarbon fatty acid ester" includes aliphatic hydrocarbon fatty acid glycerides and aliphatic hydrocarbon fatty acid C1 to C6 30 Aliphatic hydrocarbon esters, [e.g., aliphatic hydrocarbon fatty acid alkyl esters, more preferably aliphatic hydrocarbon fatty acid C1 to C6 alkyl esters, especially aliphatic hydrocarbon fatty acid methyl esters]. Suitably, the term "aliphatic hydrocarbon fatty acid esters" includes aliphatic (C7 to C 29 ) hydrocarbon group, more preferably aliphatic (C9 to C 27 ) hydrocarbon group, most preferably aliphatic (C 11 To C 23 ) Hydrocarbyl fatty acid glycerides and aliphatic (C7 to C 29 ) hydrocarbon group, more preferably aliphatic (C9 to C 27 ) hydrocarbon group, most preferably aliphatic (C 11 To C 23 ) Hydrocarbyl fatty acid C1 to C 30 Aliphatic hydrocarbyl esters. Suitably, in order to allow functionalisation, such as sulphurisation, of the aliphatic hydrocarbyl fatty acid esters, a proportion of the aliphatic hydrocarbyl chains of the fatty acid esters are unsaturated and comprise at least one carbon-carbon double bond.

[0068] The term "sulfurized aliphatic hydrocarbyl fatty acid ester" refers to a compound obtained by sulfiding an aliphatic hydrocarbyl fatty acid ester as defined herein.

[0069] The term "absent" when referring to a component included in the lubricating oil composition described herein and in the claims thereto means that the particular component is present at 0 wt% based on the weight of the lubricating oil composition, or if present in the lubricating oil composition, the component is present at an amount that does not affect the properties of the lubricating oil composition, such as less than 10 ppm or less than 1 ppm or less than 0.001 ppm. When the term "absent" is used with respect to monomer reactants and / or with respect to repeating units in the (co)polymers described herein, it means that the components are present at 0 wt% based on the weight of all (co)monomers in the (co)polymer, or if present, the amounts are so low that they do not substantially affect the physical properties of the (co)polymer, such as 0.2 wt% or less or 0.1 wt% or less.

[0070] As used herein, Mn is the number average molecular weight, Mw is the weight average molecular weight, and Mz is the z average molecular weight. Molecular weight distribution (MWD), also known as polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise indicated, all molecular weight units (e.g., Mw, Mn, Mz) are reported in g / mol. When used in the context of functionalized polymers (e.g., dispersants, functionalized styrenic polymers, etc.), the molecular weight is usually reported with respect to the base polymer before modification. For example, in PIBSA-PAM dispersants, the molecular weight of the base isobutylene polymer from which the PIBSA-PAM is derived is usually reported before functionalization with an acylating agent (maleic acid or anhydride) and a functional group (e.g., a polyamine).

[0071] With respect to an additive component or a lubricating oil composition (ie, an unused lubricating oil composition), Total Base Number, also referred to as "TBN," refers to the Total Base Number as measured by ASTM D2896 and reported in units of mgKOH / g.

[0072] Total Acid Number ("TAN") is determined by ASTM D664.

[0073] Phosphorus, boron, calcium, zinc, molybdenum, sodium, silicon and magnesium contents were measured by ASTM 5185.

[0074] The sulfur content in the oil formulations was measured by ASTM D5185.

[0075] Sulfated ash ("SASH") content is measured by ASTM D874.

[0076] Unless otherwise specified, kinematic viscosity (KV 150 , KV 140 , KV 130 , KV 120 , KV 110 , KV 100 , KV 90 , KV 80 , KV70 , KV 60 , KV 50 , KV 40 , KV 30 , KV 20 ) was determined according to ASTM D445-19a and reported in cSt.

[0077] The viscosity index is measured according to ASTM D2270.

[0078] Saponification value is determined by ASTM D94 and is reported in mgKOH / g.

[0079] HTCBT, high temperature corrosion bench test (high temperature corrosion bench test) is measured according to ASTMD6594.

[0080] Unless otherwise stated, all percentages reported are mass % on an active ingredient basis, ie without taking into account carrier or diluent oil, unless otherwise stated.

[0081] It is also understood that the various components used (basic as well as optimal and conventional) may react under the conditions of reaction, formulation, storage or use, and the present disclosure also provides products obtainable or obtained as a result of any such reaction, formulation, storage or use.

[0082] Furthermore, it is to be understood that any upper and lower limits of amounts, ranges, and ratios recited herein are independently combinable.

[0083] It is also to be understood that the preferred features of each aspect of the present disclosure are considered as the preferred features of each other aspect of the present disclosure. Accordingly, the preferred and more preferred features of one aspect of the present disclosure can be independently combined with other preferred and / or more preferred features of the same or different aspects of the present disclosure.

[0084] As used herein, the term "comb copolymer" refers to the presence of relatively long side chains (rather than merely pendant moieties) bonded to the polymer main chain (also often referred to as the polymer "backbone"). In the present disclosure, the comb copolymer viscosity modifier comprises at least one repeating unit derived from a polyalkylene-based macromonomer, the repeating units of which are almost entirely based on the polymerization or oligomerization of olefinic, non-aromatic, pure hydrocarbon monomers (i.e., do not contain or are made from monomers containing in excess of contaminant levels of heteroatoms such as O, N, S, P, Si, halides, metals, etc.). Such monomers may include, but are not necessarily limited to, monoolefins (olefins) with alkyl side groups, such as ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene, vinylcyclohexene, and the like, and combinations thereof, and / or those non-aromatic monomers whose polymerized repeat units still contain at least one unsaturation (typically alkadienes, such as butadiene, isoprene, hexadiene, non-aromatic hexatriene, norbornadiene, and the like, and combinations thereof). In the event that any such monomers polymerized / oligomerized to form macromonomers result in residual unsaturation, such unsaturation is preferably treated, for example by hydrogenation, to remove the unsaturation. The term "backbone" as used herein does not necessarily mean that its chain length is greater than the side chains - it only refers to the polymerization process that has linked the listed comonomers, including the macromonomers, together.

[0085] The term "repeat unit" as used herein is known in the art and is usually associated with the monomers used to make the (co)polymer (although not equivalent). For example, in free radical polymerization, the (olefinic) double bonds within individual monomers or macromonomers are opened to enable covalent bonds to be formed with adjacent monomers, thereby forming a polymer chain. Macromonomers themselves are made by polymerization / oligomerization of monomers, although they are used as "single" (macromolecular) monomers in the polymerization of the comb copolymer viscosity modifiers described herein. Nevertheless, when the term "repeat unit" is called, it refers to any polymerized monomer. However, just because a component can be made by polymerization, it does not mean that it constitutes a "repeat unit". For example, in a linear chain C 18 In the case of methacrylate, although an 18-carbon linear chain could theoretically be made by oligomerization of 9 ethylene units, such a component is more likely to be made by a non-polymeric route (e.g., involving the isolation of stearyl alcohol or some similar natural product) and is therefore not considered a "macromer" for purposes of this disclosure. DETAILED DESCRIPTION DETAILED DESCRIPTION OF THE INVENTION

[0086] The features of the present disclosure are now described in more detail as follows, which pertain to each and all aspects of the present disclosure where appropriate.

[0087] The lubricating oil compositions of the present disclosure include components that may or may not remain chemically identical before and after mixing with an oily carrier (such as a base oil) and / or other additives. The present disclosure encompasses compositions comprising components before mixing, or components after mixing, or components before and after mixing. Lubricating oil composition

[0088] The present disclosure relates to a lubricating oil composition (also referred to as a "LOC", "lubricant composition", "lubricating composition" or "lubricant oil composition") comprising or mixed with the following components: (a) 1 to 99 mass % (or 30 to 95 mass %, or 50 to 90 mass %, or 60 to 95 mass %, or 70 to 85 mass %) of one or more base oils, based on the weight of the lubricating composition; b1) 0.10 to 20 mass % (particularly 0.15 to 10 mass %, or 0.20 to 5 mass %, or 0.25 to 2 mass %, such as about 3.3 mass %) of a carbonate-terminated dispersant, based on the total weight of the lubricating oil composition; and b2) 0.10 to 20 mass % (particularly 0.15 to 10 mass %, or 0.20 to 5 mass %, or 0.25 to 4 mass %) of a comb copolymer viscosity improver as described herein, based on the total weight of the lubricating oil composition.

[0089] The present disclosure also relates to a lubricating oil composition, which comprises the following components or is obtained by mixing the following components: (i) 1 to 99 mass % (or 30 to 95 mass %, or 50 to 90 mass %, or 60 to 95 mass %, or 70 to 85 mass %) of one or more base oils, based on the weight of the lubricating composition; (ii) 0.10 to 20 mass % (particularly 0.15 to 10 mass %, or 0.20 to 5 mass %, or 0.25 to 2 mass %) of one or more detergents, such as Ca and Mg detergents, based on the weight of the composition; iii) 0.10 to 20 mass % (particularly 0.15 to 10 mass %, or 0.20 to 5 mass %, or 0.25 to 2 mass %, such as about 3.3 mass %) of a carbonate-terminated dispersant, based on the total weight of the lubricating oil composition; and iv) 0.10 to 20 mass % (particularly 0.15 to 10 mass %, or 0.20 mass % to 5 mass %, or 0.25 to 4 mass %) of a comb copolymer viscosity improver as described herein, based on the total weight of the lubricating oil composition.

[0090] The present disclosure also relates to a lubricating oil composition, which comprises the following components or is obtained by mixing the following components: A) 1 to 99 mass % (or 30 to 95 mass %, or 50 to 90 mass %, or 60 to 95 mass %, or 70 to 85 mass %) of one or more base oils, based on the weight of the lubricating oil composition; B1) 0.10 to 20 mass % (particularly 0.15 to 10 mass %, or 0.20 to 5 mass %, or 0.25 to 2 mass %, such as about 3.3 mass %) of a carbonate-terminated dispersant, based on the total weight of the lubricating oil composition; and B2) 0.10 to 20 mass % (particularly 0.15 to 10 mass %, or 0.20 to 5 mass %, or 0.25 to 4 mass %) of a comb copolymer viscosity improver as described herein, based on the total weight of the lubricating oil composition; C) 0.10 to 20 mass % (particularly 0.15 to 10 mass %, or 0.20 to 5 mass %, or 0.25 to 2 mass %) of one or more detergents (such as a blend of detergents, such as a combination of Ca and Mg detergents), based on the weight of the lubricating oil composition; D) optionally, based on the total weight of the lubricating oil composition, 0.01 to 5 wt % (particularly 0.1 to 4 wt %, or 0.25 to 3 wt %, or 0.045-0.15 wt %) of one or more friction modifiers (such as a blend of friction modifiers); E) optionally, based on the total weight of the lubricating oil composition, 0.01 to 10 wt. % (particularly 0.01 to 5 wt. %, or 0.01 to 3 wt. %, or 0.1 to 2 wt. %) of one or more antioxidants (such as a blend of antioxidants); F) optionally, based on the total weight of the lubricating oil composition, 0.005 to 5 wt. % (particularly 0.01 to 3 wt. %, or 0.1 to 1.5 wt. %) of one or more pour point depressants (such as a blend of pour point depressants); G) optionally, based on the total weight of the lubricating oil composition, 0.001 to 5 wt. % (particularly 0.01 to 3 wt. %, or 0.1 to 1.5 wt. %) of one or more defoaming agents (such as a blend of defoaming agents); H) optionally, based on the total weight of the lubricating oil composition, 0.001 to 10 wt. % (particularly 0.01 to 6 wt. %, or 0.01 to 5 wt. %, or 0.1 to 4 wt. %, or 0.1 to 2 wt. %) of one or more viscosity improvers other than B2 (such as a blend of viscosity improvers); I) optionally, based on the total weight of the lubricating oil composition, 0.01 to 20 wt. % (particularly 0.1 to 12 wt. %, or 0.1 to 8 wt. %) of one or more dispersants other than B1 (such as a blend of dispersants); J) optionally, based on the total weight of the lubricating oil composition, 0.005 to 5 wt. % (particularly 0.01 to 3 wt. %, or 0.01 to 1.5 wt. %) of one or more inhibitors and / or rust inhibitors (such as a blend of inhibitors and / or rust inhibitors); K) 0.001 to 10 wt. % (particularly 0.01 to 5 wt. %, or 0.1 to 3 wt. %, or 0.1 to 1.5 wt. %) of one or more antiwear agents (such as a blend of antiwear agents, such as one or more ZDDPs), based on the total weight of the lubricating oil composition; M) optionally, based on the total weight of the lubricating oil composition, 0.01 to 5 wt. % (particularly 0.05 to 2 wt. %, or 0.1 to 1 wt. %) of one or more seal compatibilizers, such as seal swell agents, and / or O) Optionally, based on the total weight of the lubricating oil composition, 0.01 to 5% by weight (particularly 0.1 to 3% by weight, or 0.1 to 1.5% by weight) of one or more unsaturated C 12 -C 60 Hydrocarbons (such as C 12 -C 24 Linear α-olefins (LAO), oligomers / polymers of polyisobutylene, and / or blends thereof).

[0091] For the purposes of the present disclosure, components B1 and B2 are not added to the above ingredients C, D, E, F, G, H, I, J, K, M and / or O for determining the weight percentage, although they may exhibit similar properties, for example, ingredient B1) may act as a dispersant but is not added to ingredient I) to determine the weight percentage of the dispersant. Similarly, ingredient B2) may act as a viscosity modifier but is not added to ingredient H) to determine the weight percentage of the viscosity modifier.

[0092] In some embodiments, all of ingredients D, E, F, G, H, I, J, K, M, and O are present in addition to the base oil, detergent, the one or more comb copolymer viscosity modifiers described herein, and the one or more end-capped dispersants described herein.

[0093] In some embodiments, ingredients D, E, F, G, H, I, and J are present in addition to the base oil, detergent, the one or more comb copolymer viscosity modifiers described herein, and the one or more end-capped dispersants described herein.

[0094] In some embodiments, ingredients I, F, and G are present in addition to the base oil, detergent, the one or more comb copolymer viscosity modifiers described herein, and the one or more end-capped dispersants described herein.

[0095] In some embodiments, ingredient K is present in addition to the base oil, detergent, the one or more comb copolymer viscosity modifiers described herein, and the one or more end-capped dispersants described herein.

[0096] Suitably, the lubricant composition may have a total base number (TBN) of 4 to 15 mgKOH / g, preferably 5 to 12 mgKOH / g, such as 6 to 12 mgKOH / g, as measured by ASTM D2896.

[0097] The lubricating composition of the present disclosure may contain a low phosphorus content, i.e. no more than 1600, preferably no more than 1200, more preferably no more than 800, such as 1 to 1600, such as 50 to 1200, such as 100 to 800 mass parts per million (ppm) of phosphorus, expressed as phosphorus atoms, based on the total mass of the lubricating composition as measured by ASTM D5185. Suitably, the lubricant composition may have a phosphorus content of 1200 ppm or less, or 1000 ppm or less, or 800 ppm or less as measured by ASTM D5185.

[0098] The lubricating composition of the present disclosure may contain a calcium atom / magnesium atom ratio of at least 2, preferably at least 2.5, based on the total mass of the lubricating composition as measured by ASTM D5185.

[0099] Typically, the lubricating composition may contain a low sulphur content. Preferably, the lubricating composition contains at most 0.4, preferably at most 0.3, such as 0.1 to 0.4 mass % sulphur based on the total mass of the lubricating oil composition as measured by ASTM D5185.

[0100] Typically, the lubricating composition may contain a low sulfated ash content, for example 1.2% or less, such as 1.0% by mass or less, preferably 0.9% by mass or less, such as 0.7% by mass or less, based on the total mass of the lubricating composition as measured by ASTM D874-13a (2018).

[0101] Typically, the kinematic viscosity ("KV100") of the lubricating composition at 100°C may be 3 to 30 cSt, such as 3.8 to 12.5 cSt, such as 3.8 to 9.3 cSt (determined according to ASTM D 445-19a). In an embodiment, the kinematic viscosity ("KV100") of the lubricating composition at 100°C may be 3 to 17 cSt, such as 9 to 16.3 cSt, such as 3.8 to 10 cSt, such as 4 to 9.3 cSt, such as 5 to 8.5 cSt (determined according to ASTM D 445-19a).

[0102] Typically, the lubricating composition may have a total base number of 1 to 30, such as 5 to 15 mgKOH / g (determined according to ASTM D2896).

[0103] Preferably, the lubricating composition of the present disclosure may be a multigrade oil designated by the viscosity descriptors SAE 20W-X, SAE 15W-X, SAE 10W-X, SAE 5W-X or SAE 0W-X, wherein X represents any one of 8, 12, 16, 20, 30, 40 and 50; the characteristics of the different viscosity grades can be found in the SAE J300 classification. Alternatively, the lubricating composition may be in the form of a viscosity grade SAE 15W-X, SAE 10W-X, SAE 5W-X or SAE 0W-X, such as in the form of SAE 15W-X or SAE 10W-X, wherein X represents any one of 8, 12, 16, 20, 30, 40 and 50. X is preferably 8, 12, 16 or 20. Alternatively, the lubricating composition of the present disclosure may be a multigrade oil designated by the viscosity descriptors SAE 10W-30, 15W-40, 5W-30, 5W-40, 10W-40, 5W-50. (See standard SAE J300 published in January 2015 by SAE International, formerly Society of Automotive Engineers).

[0104] Alternatively, the lubricating composition may have an SAE viscosity grade of 0W-Y, where Y may be 8, 12, 16, or 20. In one embodiment, the lubricating composition has an SAE viscosity grade of 0W-12.

[0105] Optionally, the lubricating composition may be free of phenolic antioxidants.

[0106] Optionally, the lubricating composition may be free of amine antioxidants, such as phenylamines, such as diphenylamines, such as alkylated diphenylamines. Optionally, the lubricating composition contains 0.1 to 3, such as 0.2 to 2, such as less than 0.3 mass % (such as 0.25 mass % or less, such as 0.2 mass % or less, such as 0.1 mass % or less, such as 0.05 mass % or less, such as 0 mass %) of amine antioxidants, such as alkylated phenylamines, such as di(alkyl-phenyl)amines, such as di(nonyl-phenyl)amines, based on the weight of the composition. In some embodiments, the lubricating oil composition may contain, may be substantially free of, or may be free of amine antioxidants, such as phenylamines, such as diphenylamines, such as alkylated diphenylamines, such as di(nonyl-phenyl)amines.

[0107] In some embodiments, the lubricating oil composition may contain less than 75 ppm boron, or less than 60 ppm boron, or from 1 to 70 ppm boron. Alternatively, the LOC may be free of boron.

[0108] In some embodiments, the lubricating oil composition may include less than 20 (e.g., 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 functionalized (e.g., aminated) polybutene (e.g., polyisobutylene), such as PIBSA-PAM. In some embodiments, the lubricating oil composition may include, may be substantially free of, or may be absent of functionalized (e.g., aminated) polybutene (e.g., polyisobutylene), such as PIBSA-PAM.

[0109] In some embodiments, the lubricating oil composition may include an acylated polymer, such as polyisobutylene succinic acid (PIBSA), which optionally has an Mn of 500 to 50,000 g / mol, such as 600 to 5,000 g / mol, such as 700 to 3000 g / mol. In some embodiments, the lubricating oil composition may include an acylated polymer, such as polyisobutylene succinic acid, having an Mn of 500 to 1600 g / mol, such as 700 to 1200 g / mol. In some embodiments, the lubricating oil composition includes greater than 0.1 (such as 0.1 to 10, such as 0.5 to 8) mass % of a functionalized (such as aminated) polybutene (such as polyisobutylene), such as PIBSA-PAM.

[0110] In some embodiments, the lubricating oil composition may include 20 (eg, 15, eg, 10, eg, 5, eg, 3, eg, 1) mass % or less of a block copolymer (eg, a block, star, random and / or tapered block copolymer).

[0111] In some embodiments, the lubricating oil composition may be substantially free of or may be absent block copolymers, such as block, radial, random and / or tapered block copolymers.

[0112] In some embodiments, the lubricating oil composition may include 20 (eg, 15, eg, 10, eg, 5, eg, 3, eg, 1) mass % or less of a styrenic copolymer, such as a block, star, random and / or tapered styrenic block copolymer).

[0113] In some embodiments, the lubricating oil composition may be substantially free of or absent styrenic copolymers, such as block, radial, random, and / or tapered styrenic block copolymers.

[0114] In some embodiments, the lubricating oil composition may include less than 20 (eg, less than 15, such as less than 10, such as less than 5, such as less than 3, such as less than 1) mass % of a functionalized diluent, such as a functionalized oil.

[0115] In some embodiments, the lubricating oil composition may include, may be substantially free of, or may be absent a functionalized diluent, such as a functionalized oil.

[0116] In some embodiments, the lubricating oil composition may include less than 20 (eg, less than 15, such as less than 10, such as less than 5, such as less than 3, such as less than 1) mass % of a solvent, such as an aromatic solvent.

[0117] In some embodiments, the lubricating oil composition may be substantially free of or absent solvents, such as functionalized solvents.

[0118] In some embodiments, the lubricating oil composition may have a total saponification value (SAP) as determined by ASTM 94 of 25 (eg, 28, such as 30, such as 32) mgKOH / g or more.

[0119] In some embodiments, the lubricating oil composition may comprise less than 0.5 (eg, 0.4, such as less than 0.3, such as less than 0.2, such as less than 0.1, substantially absent or 0) weight % of secondary and tertiary hydrocarbyl amine compounds based on the weight of the LOC.

[0120] In some embodiments, the lubricating oil composition may be substantially absent or may be free of secondary and tertiary hydrocarbyl amine compounds.

[0121] In some embodiments, the lubricating composition of the present disclosure may be a heavy-duty diesel engine oil (eg, for use in the engine of a heavy-duty diesel vehicle, ie, a heavy-duty diesel vehicle having a gross vehicle weight of 10,000 pounds or more).

[0122] In some embodiments, the lubricating composition of the present disclosure may be a passenger car motor oil.

[0123] In some embodiments, the lubricating composition of the present disclosure may be a passenger car diesel engine oil.

[0124] In some embodiments, the lubricating composition of the present disclosure may be a diesel engine lubricating composition comprising: an oil of lubricating viscosity having greater than 50 wt. % of a Group I, II, III, IV and / or V oil (e.g., a Group III base oil, a Group IV base oil, a Group V base oil, or a mixture thereof); a first PIB succinimide dispersant derived from a PIB having an Mn of 1800 to 2500; a second PIB succinimide dispersant derived from a PIB having an Mn of less than 1600, wherein at least one of the first PIB succinimide dispersant and the second PIB succinimide dispersant is boron-free (optionally, at least one of the first PIB succinimide dispersant and the second PIB succinimide dispersant is boronized); an amide, imide and / or ester functionalized dispersant comprising C 4-5 A partially or fully saturated polymer of an olefin; an alkaline earth metal salicylate detergent; an alkaline earth metal sulfonate detergent present in an amount to provide 0.1 wt % to 1.2 wt % alkaline earth metal soap to the lubricating composition; and a phosphorus antiwear agent present in an amount to provide 300 to 900 ppm phosphorus to the lubricating composition, the lubricating composition having a total sulfated ash between 0.3 and 1.1 wt %; a kinematic viscosity at 100° C. of less than 8.3 cSt; 0.6 wt % to 2.1 wt % total alkaline earth metal soap and a HTHS150 measured according to ASTM D4683 of less than 2.7 mPa·s.

[0125] The lubricating compositions disclosed herein, such as diesel engine lubricating compositions, may have a viscosity of 3.8 to 9.3 cSt (mm 2 / s) of kinematic viscosity at 100°C as measured by ASTM D-445 and 15 to 30 (e.g., 15 to 28) cSt (mm 2 / s) at 40°C.

[0126] The lubricating compositions disclosed herein, such as diesel engine lubricating compositions, may have a high temperature high shear viscosity (HTHS) measured at 150° C. by ASTM D4683 of greater than 2.6 mPa·s, or greater than 2.5 mPa·s, or greater than 2.4 mPa·s, or greater than 2.3 mPa·s, or greater than 2.2 mPa·s, or greater than 2.0 mPa·s, or greater than 1.7 mPa·s. In another embodiment, the HTHS of the lubricating composition is 2.6 to 2.7 mPa·s, or 2.3 to 2.4 mPa·s, or 2.0 to 2.1 mPa·s, or 1.7 to 1.8 mPa·s.

[0127] The lubricating composition, such as a diesel engine lubricating composition, may have an SAE viscosity grade of 0W-Y, where Y may be 8, 12, 16, or 20. In one embodiment, the lubricating composition has an SAE viscosity grade of 0W-12.

[0128] The lubricating compositions disclosed herein, such as diesel engine lubricating compositions, may have: 1) 3.8 to 9.3 (such as 4.0 to 6.1, or 5.0 to 7.1, or 6.1 to 8.2, or 6.9 to 9.3 cSt (mm 2 / s) at 100°C as measured by ASTM D-445; 2) a high temperature high shear viscosity (HTHS) as measured by ASTM D4683 at 150°C of greater than 2.6 mPa·s, or greater than 2.3 mPa·s, or greater than 2.0 mPa·s, or greater than 1.7 mPa·s; and 3) an SAE viscosity grade of 0W-Y, where Y can be 12, 16 or 20 (such as 0W-12).

[0129] The lubricating composition disclosed herein, such as a diesel engine lubricating composition, may have: 1) a molybdenum-containing material providing 20 to 40, such as 20 to 30 ppm Mo to the lubricating oil composition, 2) a zinc alkylthiophosphate, wherein the alkyl group is derived from at least one secondary alcohol, such as a combination of a primary alcohol and a secondary alcohol, 3) about 3 to 5 mass %, such as about 3 to 4, such as about 3.3 mass % of a blocked dispersant. Concentrates

[0130] A concentrate, also referred to as an additive package, adpack or addpack, is a composition having less than 50 mass % (such as less than 40 mass %, such as less than 30 mass %, such as less than 25 mass %, such as less than 20 mass %) of base oil and lubricant composition additives (as described herein), which is typically subsequently further blended with additional base oil to form a lubricant product.

[0131] The present disclosure relates to a concentrate composition comprising or obtained by mixing the following components: (i) 1 to less than 50 mass % (or 3 to 45 mass %, or 5 to 40 mass %, or 5 to 35 mass %, or 10 to 25 mass %) of one or more base oils, based on the weight of the composition; (ii) 0.10 to 20 mass % (particularly 0.15 to 10 mass %, or 0.20 to 5 mass %, or 0.25 to 2 mass %) of one or more calcium detergents and one or more magnesium detergents described herein, based on the weight of the composition; (iii) 0.10 to 50 mass % (particularly 0.15 to 10 mass %, or 0.20 to 5 mass %, or 0.25 to 2 mass %) of one or more capped dispersants described herein (e.g., ethylene carbonate capped PIBSA-PAM derived from PIB having a Mn of 1600 g / mol or less), based on the weight of the composition; and (iv) 0.10 to 20 mass % (particularly 0.15 to 10 mass %, or 0.20 to 5 mass %, or 0.25 to 4 mass %) of one or more comb copolymer viscosity modifiers described herein, based on the weight of the composition; (v) optional additional components, antioxidants, pour point depressants, defoamers, viscosity improvers, corrosion inhibitors, antiwear agents, extreme pressure additives, demulsifiers, seal compatibility agents, additive diluent base oils, friction modifiers (such as organic FMs, such as organic esters, such as fatty acid esters), etc., such as zinc dialkyl dithiophosphates and / or molybdenum-containing compounds (such as dimer or trimer MoDTC) and / or amine antioxidants.

[0132] In some embodiments, the concentrate composition may optionally be absent of solvents (eg, aliphatic or aromatic solvents) and / or absent of functionalized base oils.

[0133] The present disclosure also relates to a concentrate composition comprising or obtained by mixing the following components: A) 1 to less than 50 mass % (or 5 to 45 mass %, or 7 to 40 mass %, or 10 to 35 mass %, or 10 to 25 mass %) of one or more base oils, based on the weight of the concentrate composition; B1) 0.10 to 20 mass % (particularly 0.15 to 10 mass %, or 0.20 to 5 mass %, or 0.25 to 3 mass %) of one or more blocked dispersants described herein, based on the weight of the concentrate composition; B2) 0.10 to 20 mass % (particularly 0.15 to 10 mass %, or 0.20 to 5 mass %, or 0.25 to 4 mass %) of one or more comb copolymer viscosity modifiers described herein, based on the weight of the concentrate composition; C) 0.1 to 20 wt % (particularly 0.5 to 10 wt %, or 2 to 6 wt %) of one or more calcium detergents and one or more magnesium detergents (such as salicylates, sulfonates, or blends of salicylate and sulfonate detergents), based on the total weight of the concentrate composition; D) optionally, based on the total weight of the concentrate composition, 0.01 to 5 wt % (particularly 0.1 to 4 wt %, or 0.25 to 3 wt %, or 0.25 to 0.75 wt %) of one or more friction modifiers (e.g., organic friction modifiers such as glycerol monooleate); E) optionally, based on the total weight of the concentrate composition, 0.01 to 20 wt % (particularly 0.01 to 15 wt %, or 0.1 to 10 wt %) of one or more antioxidants (such as a blend of antioxidants); F) optionally, based on the total weight of the concentrate composition, 0.005 to 5 wt % (particularly 0.01 to 3 wt %, or 0.1 to 1.5 wt %) of one or more pour point depressants (such as a blend of pour point depressants); G) optionally, based on the total weight of the concentrate composition, 0.001 to 5 wt % (particularly 0.01 to 3 wt %, or 0.02 to 1 wt %) of one or more defoamers (such as a blend of defoamers); I) optionally, based on the total weight of the concentrate composition, 0.01 to 40% by weight (particularly 0.1 to 30% by weight, or 1 to 20% by weight) of one or more dispersants other than the blocked dispersants of B1 above (such as a blend of dispersants); K) Optionally, 0.001 to 10 wt % (particularly 0.1 to 8 wt %, or 1 to 5 wt %, or 0.25 to 0.75 wt %) of one or more antiwear agents (such as a blend of antiwear agents, such as ZDDP), based on the total weight of the composition.

[0134] The concentrate may be present in the lubricating oil composition at 0.5 to 35 mass %, such as 5 to 30 mass %, such as 7.5 to 25 mass %, such as 10 to 22.5 mass %, such as 15 to 20 mass % based on the mass of the lubricating oil composition.

[0135] Optionally, the concentrate may be free of functionalized oil.

[0136] In some embodiments, the concentrate composition may optionally be absent of solvents (eg, aliphatic or aromatic solvents) and / or absent of functionalized base oils.

[0137] Optionally, the concentrate may be free of phenolic antioxidants.

[0138] In some embodiments, the concentrate may contain less than 75 ppm boron, or less than 60 ppm boron, or from 1 to 70 ppm boron. Alternatively, the concentrate may be free of boron.

[0139] In some embodiments, the concentrate may contain less than 20 (e.g., 15, 10, 5, 3, 1) mass % of a functionalized (e.g., aminated) polybutene (e.g., polyisobutylene), such as PIBSA-PAM. In some embodiments, the concentrate contains, is substantially free of, or is absent a functionalized (e.g., aminated) polybutene (e.g., polyisobutylene), such as PIBSA-PAM.

[0140] In some embodiments, the concentrate may include an acylated polymer, such as polyisobutylene succinic acid, optionally having an Mn of 500 to 50,000 g / mol, such as 600 to 5,000 g / mol, such as 700 to 3000 g / mol. In embodiments, the concentrate may include an acylated polymer, such as polyisobutylene succinic acid, having an Mn of 500 to 1600 g / mol, such as 700 to 1200 g / mol.

[0141] In some embodiments, the concentrate may contain 20 (eg, 15, eg, 10, eg, 5, eg, 3, eg, 1) mass % or less of a block copolymer, such as a block, star, random and / or tapered block copolymer.

[0142] In some embodiments, the concentrate may be substantially free of or absent block copolymers, such as block, radial, random, and / or tapered block copolymers.

[0143] In some embodiments, the concentrate may contain 20 mass % or less (e.g., 15 mass % or less, such as 10 mass % or less, such as 5 mass % or less, such as 3 mass % or less, such as 1 mass % or less) of a styrenic copolymer, such as a block, star, random and / or tapered styrenic block copolymer.

[0144] In some embodiments, the concentrate may be substantially free of or absent styrenic copolymers, such as block, radial, random, and / or tapered styrenic block copolymers.

[0145] In some embodiments, the concentrate may contain less than 20 (eg, less than 15, such as 10, such as less than 5, such as less than 3, such as 1) mass % of a functionalized diluent, such as a functionalized oil.

[0146] In some embodiments, the concentrate may be substantially free of or absent functionalized diluents, such as functionalized oils.

[0147] In some embodiments, the concentrate may contain less than 0.5 (eg, less than 0.4, such as less than 0.3, such as less than 0.2, such as 0.1, substantially absent, 0) weight percent of secondary and tertiary hydrocarbyl amine compounds based on the weight of the concentrate.

[0148] In some embodiments, the concentrate may be substantially absent or may be free of secondary and tertiary hydrocarbyl amine compounds.

[0149] In some embodiments, the concentrate may have a kinematic viscosity at 100°C of less than 1000 cSt, such as less than 500 cSt, such as less than 200 cSt.

[0150] Furthermore, the present invention relates to a method of making the concentrate described herein, comprising combining, based on the weight of the concentrate: A) 1 to less than 50 mass % (or 5 to 45 mass %, or 7 to 40 mass %, or 10 to 35 mass %, or 10 to 25 mass %) of one or more base oils, based on the weight of the concentrate composition; B1) 0.10 to 20 mass % (particularly 0.15 to 10 mass %, or 0.20 to 5 mass %, or 0.25 to 3 mass %) of one or more blocked dispersants described herein, based on the weight of the concentrate composition; B2) 0.10 to 20 mass % (particularly 0.15 to 10 mass %, or 0.20 to 5 mass %, or 0.25 to 3 mass %) of one or more comb copolymer viscosity modifiers described herein, based on the weight of the concentrate composition; C) 0.1 to 20 wt % (particularly 0.5 to 10 wt %, or 2 to 6 wt %) of one or more calcium detergents and one or more magnesium detergents (such as salicylates, sulfonates, or blends of salicylate and sulfonate detergents), based on the total weight of the concentrate composition; D) optionally, based on the total weight of the concentrate composition, 0.01 to 5 wt % (particularly 0.1 to 4 wt %, or 0.25 to 3 wt %, or 0.25 to 0.75 wt %) of one or more friction modifiers (e.g., organic friction modifiers such as glycerol monooleate); E) optionally, based on the total weight of the concentrate composition, 0.01 to 20 wt % (particularly 0.01 to 15 wt %, or 0.1 to 10 wt %) of one or more antioxidants (such as a blend of antioxidants); F) optionally, based on the total weight of the concentrate composition, 0.01 to 5 wt % (particularly 0.01 to 3 wt %, or 0.1 to 1.5 wt %) of one or more pour point depressants (such as a blend of pour point depressants); G) optionally, based on the total weight of the concentrate composition, 0.001 to 5 wt % (particularly 0.01 to 3 wt %, or 0.02 to 1 wt %) of one or more defoamers (such as a blend of defoamers); I) optionally, based on the total weight of the concentrate composition, 0.01 to 40% by weight (particularly 0.1 to 30% by weight, or 1 to 20% by weight) of one or more dispersants other than the blocked dispersants of B1 above (such as a blend of dispersants); K) Optionally, 0.001 to 10 wt % (particularly 0.1 to 8 wt %, or 1 to 5 wt %, or 0.25 to 0.75 wt %) of one or more antiwear agents (such as a blend of antiwear agents, such as ZDDP), based on the total weight of the composition. A.Base oil

[0151] The base oils useful herein (also referred to as "base stocks", "lubricating base stocks" or "oils of lubricating viscosity") may be a single oil or a blend of oils, and are generally the major liquid component of lubricating compositions (also referred to as lubricants), into which additives and optional additional oils are mixed, for example, to make lubricating compositions, such as finished lubricant compositions, concentrates or other lubricating compositions.

[0152] The base oil can be selected from vegetable oils, animal oils, mineral oils and synthetic lubricating oils and mixtures thereof. It can range in viscosity from light distillate mineral oils to heavy lubricating oils, such as those used for gas engine oils, mineral lubricating oils, motor vehicle oils and heavy diesel engine oils. Typically, the kinematic viscosity ("KV100") of the base oil at 100°C is 1 to 30, such as 2 to 25 cSt, such as 5 to 20 cSt (measured according to ASTM D445-19a), particularly 1.0 cSt to 10 cSt, 1.5 cSt to 3.3 cSt, 2.7 cSt to 8.1 cSt, 3.0 cSt to 7.2 cSt or 2.5 cSt to 6.5 cSt. Typically, the base oil has a high temperature high shear (HTHS) viscosity at 150° C. of 0.5 to 20 cP, such as 1 to 10 cP, such as 2 to 5 cP (determined according to ASTM D4683-20).

[0153] In general, when the lubricating oil base stock is used to make a concentrate it may advantageously be present in a concentrate-forming amount to provide a concentrate containing from 5 to 80 weight percent, from 10 to 70 weight percent or from 5 to 50 weight percent of the active ingredient, based on the weight of the concentrate.

[0154] Common oils that can be used as base oils include animal oils and vegetable oils (e.g., castor oil and lard), liquid petroleum oils, and hydrorefined and / or solvent treated paraffinic, naphthenic, and mixed paraffinic-naphthenic mineral lubricating oils. Oils derived from coal or shale are also available base oils. Base oil stocks can be manufactured using a variety of methods, including but not limited to distillation, solvent refining, hydroprocessing, oligomerization, esterification, and re-refining.

[0155] Synthetic lubricating oils useful as base oils herein include hydrocarbon oils such as homo- and co-olefins, known as polyalphaolefins or PAOs or Group IV base oils [as defined in API EOLCS 1509 (American Petroleum Institute Publication 1509, see Section E.1.3, 19th Edition, January 2021, www.API.org)]. Examples of PAOs useful as base oils include: poly(ethylene), ethylene-propylene copolymers, polybutene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutene, poly(1-hexene), poly(1-octene), poly(1-decene), C8 to C 20 Homopolymers or copolymers of olefins, C8 and / or C 10 and / or C 12 Homopolymer or copolymer of olefins, C8 / C 10 Copolymer, C8 / C 10 / C 12 Copolymer and C 10 / C 12 Copolymers, and their derivatives, analogs and homologs.

[0156] In another embodiment, the base oil may comprise a polyalphaolefin, including oligomers of linear olefins having from 6 to 14 carbon atoms, more preferably from 8 to 12 carbon atoms, more preferably 10 carbon atoms, having a kinematic viscosity at 100°C (as measured by ASTM D445) of 10 or more; preferably having a viscosity index ("VI") as measured by ASTM D2270 of 100 or more, preferably 110 or more, more preferably 120 or more, more preferably 130 or more, more preferably 140 or more; and / or having a pour point of -5°C or less (as measured by ASTM D97), more preferably -10°C or less, more preferably -20°C or less.

[0157] In another embodiment, the polyalphaolefin oligomers useful in the present disclosure may comprise C 20 To C 1500 Alkanes, preferably C 40 To C 1000 Alkanes, preferably C 50 To C 750 Alkanes, preferably C 50 To C500 In one embodiment, the PAO oligomer is C5 to C 14 α-olefins, and in another embodiment C6 to C 12 α-olefins, and in another embodiment C8 to C 12 The dimer, trimer, tetrapolymer, pentamer etc. of alpha-olefin. Suitable olefins include 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene and 1-dodecene. In one embodiment, olefin is a combination of 1-octene, 1-decene and 1-dodecene, or can be substantially 1-decene, and PAO is a mixture of its dimer, trimer, tetrapolymer and pentamer (and higher). Available PAO is more particularly described in, for example, U.S. Patent No. 5,171,908 and 5,783,531 and Synthetic Lubricants and High-Performance Functional Fluids 1-52 (Leslie R.Rudnick & Ronald L.Shubkin, ed.Marcel Dekker, Inc.1999).

[0158] PAOs useful in the present disclosure typically have a number average molecular weight of 100 to 21,000 g / mol in one embodiment, and 200 to 10,000 g / mol in another embodiment, and 200 to 7,000 g / mol in yet another embodiment, and 200 to 2,000 g / mol in yet another embodiment, and 200 to 500 g / mol in yet another embodiment. TM Hi-Vis, SpectraSyn TM Low-Vis, SpectraSyn TM plus、SpectraSyn TM Elite PAO's (ExxonMobil Chemical Company, Houston Texas) and Durasyn PAO's from Ineos Oligomers USA LLC were purchased.

[0159] Synthetic lubricating oils useful as base oils also include hydrocarbon oils such as homopolymers and copolymers of: alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2-ethylhexyl)benzene); polyphenols (e.g., biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides; and their derivatives, analogs and homologs.

[0160] Another class of suitable synthetic lubricating oils that can be used as base oils comprises esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acid, alkenylmalonic acid) reacted with various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, didecyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, and a complex ester formed by reacting 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid.

[0161] Esters useful as synthetic oils herein also include C5 to C 12 Those made from monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.

[0162] Esterex is an ideal ester base oil. TM Available from Esters (ExxonMobil Chemical Company, Houston, Texas).

[0163] Silicon-based oils, such as polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxy-silicone oils and silicate oils, constitute another class of useful synthetic lubricants for use herein; such oils include tetraethyl silicate, tetraisopropyl silicate, tetrakis-(2-ethylhexyl) silicate, tetrakis-(4-methyl-2-ethylhexyl) silicate, tetrakis-(p-tert-butylphenyl) silicate, hexa-(4-methyl-2-ethylhexyl) disiloxane, poly(methyl)siloxanes and poly(methylphenyl)-siloxanes.

[0164] Other synthetic lubricating oils useful herein include liquid esters of phosphorus-containing acids (eg, tricresyl phosphate, trioctyl phosphate, diethyl decylphosphonate) and polymeric tetrahydrofuran.

[0165] Unrefined oils, refined oils and re-refined oils can be used in lubricating compositions of the present disclosure. Unrefined oils are those obtained directly from natural or synthetic sources without further purification treatment. For example, shale oils obtained directly from retorting operations, petroleum oils obtained directly from distillation, or ester oils obtained directly from esterification processes and used without further treatment are considered to be unrefined oils. Refined oils are similar to unrefined oils, except that they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques are used by those skilled in the art, such as distillation, solvent extraction, acid or base extraction, filtration and percolation. Re-refined oils are oils obtained by processes similar to those used to obtain refined oils, wherein the refining process is applied to refined oils that have previously been put to use. Such re-refined oils are also referred to as regenerated oils or reprocessed oils, and are usually processed in addition to remove waste additives and oil cracking products. Re-refined base oils are preferably substantially free of materials introduced by manufacturing, contamination or previous use.

[0166] Other examples of useful base oils are gas-to-liquid ("GTL") base oils, i.e., oils derived from hydrocarbons made from synthesis gas ("syn gas") containing H2 and CO using a Fischer-Tropsch catalyst. These hydrocarbons generally require further processing before they can be used as base oils. For example, they can be hydroisomerized; hydrocracked and hydroisomerized; dewaxed; or hydroisomerized and dewaxed by methods known in the art. For further information on useful GTL base oils and blends thereof, see U.S. Pat. No. 10,913,916 (column 4, line 62 to column 5, line 60) and U.S. Pat. No. 10,781,397 (column 14, line 54 to column 15, line 5, and column 16, line 44 to column 17, line 55).

[0167] In particular, oils from renewable sources, ie based in part on carbon and energy captured from the environment, such as biogenic sources, are useful herein.

[0168] Various base oils are generally classified as Class I, Class II, Class III, Class IV or Class V according to the API EOLCS1509 definition (American Petroleum Institute Publication 1509, see Section E.1.3, 19th Edition, January 2021, www.API.org). In general, Class I base stocks have a viscosity index between about 80 and 120 and contain more than about 0.03% sulfur and / or less than about 90% saturates. Class II base stocks have a viscosity index between about 80 and 120 and contain less than or equal to about 0.03% sulfur and / or greater than or equal to about 90% saturates. Class III base stocks have a viscosity index greater than about 120 and contain less than or equal to about 0.03% sulfur and greater than about 90% saturates. Class IV base stocks include polyalphaolefins (PAOs). Class V base stocks include base stocks not included in Class I-IV. (Viscosity index is measured by ASTM D 2270, saturates are measured by ASTM D2007, and sulfur is measured by ASTM D5185, D2622, ASTM D4294, ASTM D4927, and ASTM D3120).

[0169] The base oil used in the formulated lubricating composition that can be used in the present disclosure is any one, two, three or more of the various oils described herein. In an ideal embodiment, the base oil used in the formulated lubricating composition that can be used in the present disclosure is described as API Class I (including Class I+), Class II (including Class II+), Class III (including Class III+), Class IV and Class V oils and mixtures thereof, preferably those of API Class II, Class III, Class IV and Class V oils and mixtures thereof. Due to their outstanding volatility, stability, viscosity and cleanliness characteristics, the base oil can be Class III, Class III+, Class IV and Class V base oils. A small amount of Class I base oil stock can be allowed, such as the amount used to dilute additives for incorporation into the formulated lubricating oil product, but is generally kept to a minimum, such as only the amount associated with their use as a diluent / carrier oil for additives used on an "as-received" basis. With respect to Group II oils, it is generally more useful to have Group II base stocks in the higher quality range associated with such oils, ie, Group II oils having a viscosity index of 100 to 120.

[0170] The base oils useful herein may be selected from any synthetic oil, natural oil or re-refined oil (such as those commonly used as crankcase lubricating oils for spark ignition and compression ignition engines). If desired, mixtures of synthetic and / or natural oils and / or re-refined base oils may be used. If desired, multi-modal mixtures (such as bi-modal or tri-modal mixtures) of Group I, II, III, IV and / or V base stocks may be used.

[0171] 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 expressed in centistokes (cSt) or its equivalent units mm at 100° C. of about 2 to about 40 cSt, or 3 to 30 cSt, or 4 to 20 cSt, or 5 to 10 cSt. 2 / s), or the base oil or base oil blend may have a kinematic viscosity at 100°C of 2 to 20 cSt, 2.5 to 20 cSt, preferably about 2.5 cSt to about 9 cSt.

[0172] The base oil or base oil blend preferably has a saturates content of at least 65 mass %, more preferably at least 75 mass %, such as at least 85 mass %, such as at least 90 mass % as determined by ASTM D2007.

[0173] 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.

[0174] In some embodiments, 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 %, such as from 15 to 30 mass %, such as from 19 to 28 mass %, based on the total mass of the lubricating composition.

[0175] In some embodiments, the base oil has a viscosity index (VI) of at least 95, preferably at least 110, more preferably at least 120, even more preferably at least 125, most preferably about 130 to 240, especially about 105 to 140 (determined by ASTM D2270).

[0176] The base oil can be provided in a major amount, which is combined with one or more additive components as described below in a minor amount to form a lubricant. This preparation can be achieved by adding the additive directly to the oil or by adding the one or more additives in the form of its concentrate to disperse or dissolve the additive. The additive can be added to the oil before, simultaneously or after adding other additives by any method known to those skilled in the art.

[0177] Base oil can be provided with minor amount, and it is combined with one or more additive components as described below of minor amount, to constitute additive concentrate.Can realize this preparation by adding additive directly in oil or by adding described one or more additives with additive dispersion or dissolution in oil in the form of its solution, slurry or suspension.Additive can be added in oil before, simultaneously or afterwards adding other additives by any method well known to those skilled in the art.

[0178] Base oil generally constitutes the major component of the engine oil lubricant composition of the present disclosure and is generally present in an amount of about 50 to about 99 weight percent, preferably about 70 to about 95 weight percent, more preferably about 80 to about 95 weight percent, based on the total weight of the composition.

[0179] Typically, the one or more base oils are present in the lubricating composition in an amount of 32 wt % or more, or 55 wt % or more, or 60 wt % or more, or 65 wt % or more, based on the total weight of the lubricating composition. Typically, the one or more base oils are present in the lubricating composition in an amount of 98 wt % or less, more preferably 95 wt % or less, and even more preferably 90 wt % or less. Alternatively, the one or more base oils are present in the lubricating composition in an amount of 1 to 99 mass %, or 50 to 97 mass %, or 60 to 95 mass %, or 70 to 95 mass %, based on the weight of the lubricating composition.

[0180] The above base oils and blends thereof may also be used in making concentrates, and in making lubricants therefrom.

[0181] Concentrates constitute a convenient means of manipulating additives prior to their use and of facilitating their dissolution or dispersion in the lubricant. When preparing a lubricant containing more than one type of additive (sometimes referred to as an "additive component"), each additive may be incorporated separately in the form of a concentrate. However, in many cases it is convenient to provide a so-called additive "kit" (also called an "addpack") containing one or more additives / co-additives as described below in a single concentrate.

[0182] Typically, the one or more base oils are present in the concentrate composition in an amount of 50 wt % or less, or 40 wt % or less, or 30 wt % or less, or 20 wt % or less, based on the total weight of the concentrate composition. Typically, the one or more base oils are present in the concentrate composition in an amount of 0.1 to 49 mass %, or 5 to 40 mass %, or 10 to 30 mass %, or 15 to 25 mass %, based on the weight of the concentrate composition. B1. Carbonate-terminated dispersant

[0183] The lubricating oils and / or concentrates described herein may contain one or more alkyl (e.g., linear, branched or cyclic) carbonate post-treated polyalkenyl succinic acid derivative dispersants, such as polyalkenyl succinimide dispersants, such as polyalkenyl bis-succinimide dispersants;

[0184] The term "succinimide", which includes alkenyl or alkyl monosuccinimides, bis-succinimides and other higher homologues, is the reaction product of a hydrocarbyl (eg alkenyl) substituted succinic acid or anhydride (eg maleic acid or maleic anhydride) and a polyamine.

[0185] The term "bis-succinimide" describes a succinimide dispersant that is predominantly bis-succinimide. Predominantly bis-succinimide dispersants contain a predominant amount of bis-succinimide relative to other compounds that may be present in the succinimide dispersant, such as monosuccinimide. The reaction product of a hydrocarbyl-substituted succinic acylating agent (such as polyisobutylene succinic acid, polyisobutylene succinic anhydride, polyisobutylene succinate, commonly referred to as "PIBSA") with an alkylene polyamine ("PAM") will yield a succinimide dispersant containing a mixture of compounds, including monosuccinimide and bis-succinimide (such as PIBSA-PAM). The amount of monoalkenyl succinimide and bis-alkenyl succinimide produced can depend on the charge mole ratio of alkylene polyamine to succinic group and the specific polyamine used. A charge molar ratio of alkylene polyamine to succinic group of about 1:1 can produce a predominantly monosuccinimide dispersant. A charge molar ratio of alkylene polyamine to succinic group of about 1:2 can produce a predominantly bis-succinimide dispersant.

[0186] The PIBSA and PIBSA-PAM useful herein are typically derived from a butene polymer (preferably polyisobutylene) having a number average molecular weight (Mn) of 1600 g / mol or less, such as 800 to 1500, such as 900 to 1450 g / mol, such as 1000 to 1400 g / mol, such as 1100 to 1400 g / mol, such as 1200 to 1400 g / mol, such as about 1300 g / mol. Preferably, the PIBSA and PIBSA-PAM useful herein are derived from a butene polymer (preferably polyisobutylene) having a number average molecular weight (Mn) of 1200 to 1400 g / mol (such as 1250 to 1350 g / mol, such as about 1300 g / mol).

[0187] PIBSA useful herein typically has a functionality (Fv) of 1.0 to 1.7, such as 1.30 to 1.60, such as 1.35 to 1.55, such as 1.40 to 1.50, such as about 1.45. Functionality is a measure of the average number of acid groups per reaction product of PIB and maleic anhydride. Fv is determined according to the following formula 1: Fv=(SAP×M n ) / ((1122×AI)-(SAP×MW))(1) Wherein SAP is the saponification value (i.e., the number of milligrams of KOH consumed to completely neutralize the acid groups in 1 gram of the succinic-containing reaction product as determined according to ASTM D94); M n is the number average molecular weight of the starting olefin polymer (polybutene); AI is the active ingredient percentage of the reaction product containing succinic acid (the remainder being unreacted polybutene and diluent); and MW is the molecular weight of the dicarboxylic acid-producing moiety (98 for maleic anhydride).

[0188] PIBSA useful herein typically has a saponification value (ASTM D94) of 80 to 105 mgKOH / g, such as 86 to 102 mgKOH / g, such as 90 to 98 mgKOH / g, such as about 92 to about 96 mgKOH / g.

[0189] PIBSA PAMs useful herein typically have a coupling ratio of 0.8 to 1.3, such as 0.9 to 1.0. In this disclosure, "coupling ratio" may be defined as the ratio of succinyl groups in the PIBSA to primary amine groups in the polyamine reactant.

[0190] The PIBSA PAM useful herein typically has a nitrogen content of 0.5 to 2.0 mass %, such as 0.75 to 1.75 mass %, such as 1.0 to 1.5 mass %, such as 1.0 to 1.25 mass %, based on the weight of the PIBSA-PAM.

[0191] Preferably, the PIBSA-PAM useful herein is: i) derived from a polyisobutylene having a number average molecular weight (Mn) of 1600 g / mol or less (e.g., 800 to 1500, such as 900 to 1450 g / mol, such as 1000 to 1400 g / mol, such as 1100 to 1400 g / mol, such as 1200 to 1400 g / mol, such as about 1300 g / mol); and ii) has a functionality (Fv) of from 1.0 to 1.7, such as from 1.30 to 1.60, such as from 1.35 to 1.55, such as from 1.40 to 1.50, such as about 1.45; and iii) having a saponification value (ASTM D94) of 80 to 105 mgKOH / g, such as 86 to 102 mgKOH / g, such as 90 to 98 mgKOH / g, such as about 92 to about 96 mgKOH / g; and iv) has a nitrogen content of 0.5 to 2.0 mass %, such as 0.75 to 1.75 mass %, such as 1.0 to 1.5 mass %, such as 1.0 to 1.25 mass % based on the weight of the PIBSA-PAM.

[0192] The PIBSA-PAM that can be used in the lubricating oil composition of the present invention further includes a cyclic carbonate post-treated polyalkenyl bis succinimide dispersant (such as PIBSA-PAM). The polyalkenyl bis succinimide dispersant of this embodiment can be prepared as described in "Section I. Dispersants" below, i.e., the reaction of a polyalkenyl substituted succinic anhydride with a polyamine.

[0193] The polyalkenyl bis succinimide dispersant is post-treated with a cyclic carbonate to form a carbonate-terminated dispersant, such as a cyclic carbonate-post-treated polyalkenyl bis succinimide dispersant. Suitable cyclic carbonates for use in the present invention include, but are not limited to, 1,3-dioxolane-2-one (ethylene carbonate); 4-methyl-1,3-dioxolane-2-one (propylene carbonate); 4-hydroxymethyl-1,3-dioxolane-2-one: 4,5-dimethyl-1,3-dioxolane-2-one; 4-ethyl-1,3-dioxolane-2-one (butylene carbonate); 4,4-dimethyl-1,3-dioxolane-2-one; 4-methyl-5-ethyl-1,3-dioxolane-2-one; 4,5-diethyl-1,3-dioxolane-2-one; 4,4-diethyl-1,3-dioxolane-2-one; 1,3-dioxane-2-one; 4,5-dimethyl-1,3-dioxane-2-one; 1,3-dioxane-2-one: 5,5-dihydroxymethyl-1,3-dioxane-2-one; 5-methyl-1,3-dioxane-2-one; 4-methyl-1,3-dioxane-2-one, 5-hydroxy-1,3-dioxane-2-one; 5-hydroxymethyl-5-methyl-1,3-dioxane-2-one; 5,5- Diethyl-1,3-dioxane-2-one; 5-methyl-5-propyl-1,3-dioxane-2-one; 4,6-dimethyl-1,3-dioxane-2-one; 4,4,6-trimethyl-1,3-dioxane-2-one, spiro[1,3-oxa-2-cyclohexanone-5,5′-1′,3′-oxa-2′-cyclohexanone], etc. Other suitable cyclic carbonates can be made from sugars such as sorbitol, glucose, fructose, galactose, and vicinal diols (which are C1 to C 30 Olefin preparation) are prepared by methods known in the art.

[0194] Several of these cyclic carbonates are commercially available, such as 1,3-dioxolane-2-one or 4-methyl-1,3-dioxolane-2-one. Alternatively, cyclic carbonates can be easily prepared by known reactions. For example, the reaction of phosgene with suitable α-alkanediol or alkane-1,3-diol produces cyclic carbonates for use in the present invention. See, for example, U.S. Patent No. 4,115,206, the contents of which are incorporated herein by this reference. Similarly, cyclic carbonates that can be used in the present invention can be prepared by the transesterification of suitable α-alkanediol or alkane-1,3-diol with, for example, diethyl carbonate under transesterification conditions, see, for example, U.S. Patent Nos. 4,384,115 and 4,423,205, the contents of which are incorporated herein by this reference.

[0195] Polyalkenyl disuccinimide dispersant can be post-processed with cyclic carbonate according to the common method in this area.For example, the polyalkenyl disuccinimide dispersant of cyclic carbonate post-processing can be prepared by a method including (optionally under nitrogen purge) loading disuccinimide dispersant in a reactor and heating at a temperature of about 80 ℃ to about 170 ℃.Optionally, diluent oil can be loaded under nitrogen purge in the same reactor.(Optionally under nitrogen purge) cyclic carbonate is loaded into the reactor.This mixture is heated to a temperature of about 130 ℃ to about 200 ℃ under nitrogen purge.Optionally, vacuum is applied to the mixture for about 0.5 to about 2.0 hours to remove any water formed in the reaction.

[0196] Particularly useful carbonate-terminated dispersants include ethylene carbonate ("EC")-terminated polyisobutylene succinimide, wherein the one or more polyisobutylenes used to make the succinimide each have a number average molecular weight (Mn) of 1600 g / mol or less (e.g., 800 to 1500, such as 900 to 1450 g / mol, such as 1000 to 1400 g / mol, such as 1100 to 1400 g / mol, such as 1200 to 1400 g / mol, such as about 1300 g / mol). In some embodiments, the carbonate-terminated dispersant can be ethylene carbonate-terminated polyisobutylene succinimide, wherein the one or more polyisobutylenes used to make the succinimide each have a number average molecular weight (Mn) of about 950 to about 2300 g / mol, such as about 950, about 1000, about 1200, about 1300, about 1400, about 1500, about 1600, about 1700, about 1800, about 1900, about 2000, about 2100, about 2200, about 2300, about 2400, about 2500 g / mol.

[0197] Preferably, the carbonate-terminated succinimides useful herein (eg, ethylene carbonate-terminated PIBSA-PAM) are derived from polyisobutylene having a number average molecular weight (Mn) of 1200 to 1400 g / mol (eg, 1250 to 1350 g / mol, such as about 1300 g / mol).

[0198] Preferably, carbonate-terminated succinimides useful herein (eg, ethylene carbonate-terminated PIBSA-PAM) have an ethylene carbonate / nitrogen (EC / N) ratio of 1 to 2, such as 1.25 to 1.75, such as 1.30 to 1.70.

[0199] Preferably, the carbonate-terminated succinimide useful herein (such as ethylene carbonate-terminated PIBSA-PAM) has a total base number (TBN) (ASTM D2896) of 10 to 50 mgKOH / g, such as 25 to 40 mgKOH / g, such as 20 to 30 mgKOH / g; and

[0200] Preferably, the carbonate-terminated succinimide useful herein (e.g., ethylene carbonate-terminated PIBSA-PAM) has a nitrogen content of 0.5 to 5.0 mass %, such as 0.5 to 4.0 mass %, such as 0.75 to 3.0 mass %, such as 0.8 to 2.0 mass %, such as 1.0 to 2.0 mass %, such as about 1.5 to about 1.8 mass %, based on the weight of the PIBSA-PAM.

[0201] Preferably, the carbonate-terminated succinimides useful herein (eg, ethylene carbonate-terminated PIBSA-PAM) have a degree of end-capping of 80% or more, such as 85% or more, such as 85 to 100%.

[0202] Preferably, the carbonate-terminated succinimide (such as ethylene carbonate-terminated PIBSA-PAM) useful herein has a residual amount of alkyl carbonate (such as ethylene carbonate) of 0.5 mass % or less, such as 0.4 mass % or less, such as 0.01 to 0.3 mass % or less, such as 0.1 to 0.1 mass %, such as 0 mass %.

[0203] Preferably, the carbonate-terminated succinimide (such as ethylene carbonate-terminated PIBSA-PAM) that can be used herein is: i) derived from a polyisobutylene having a number average molecular weight (Mn) of 1600 g / mol or less (e.g., 800 to 1500, such as 900 to 1450 g / mol, such as 1000 to 1400 g / mol, such as 1100 to 1400 g / mol, such as 1200 to 1400 g / mol, such as about 1300 g / mol); and ii) having an ethylene carbonate / nitrogen (EC / N) ratio of 1 to 2, such as 1.25 to 1.75, such as 1.30 to 1.70; and iii) having a total base number (TBN) (ASTM D2896) of 10 to 50 mgKOH / g, such as 25 to 40 mgKOH / g, such as 20 to 30 mgKOH / g; and iv) has a nitrogen content of 0.5 to 5.0 mass %, such as 0.5 to 4.0 mass %, such as 0.75 to 3.0 mass %, such as 0.8 to 2.0 mass %, such as 1.0 to 2.0 mass %, such as about 1.5 to about 1.8 mass % based on the weight of the PIBSA-PAM.

[0204] Typically, the one or more cyclic carbonate post-treated polyalkenyl bissuccinimide dispersants are present in the lubricating oil composition of the present invention in an amount greater than about 0.25 wt. %, or greater than about 0.5 wt. %, or greater than about 1.0 wt. %, or greater than about 1.2 wt. %, or greater than about 1.5 wt. %, or greater than about 1.8 wt. %, or greater than about 2.0 wt. %, or greater than about 2.5 wt. %, or greater than about 2.8 wt. % on an active basis, based on the total weight of the lubricating oil composition. In another embodiment, the amount of the one or more cyclic carbonate post-treated polyalkenyl bissuccinimide dispersants present in the lubricating oil composition of the present invention may be from about 0.25 to 10 wt. %, or about 0.25 to 8.0 wt. %, or about 0.25 to 5.0 wt. %, or about 0.25 to 4.0 wt. %, or 0.25 to 3.0 wt. %, or about 0.5 to 10 wt. %, or about 0.5 to 8.0 wt. %, or about 0.5 to 5.0 wt. %, or about 0.5 to 4.0 wt. %, or about 0.25 to 3.0 wt. %, or about 0.5 to 10 wt. %, or about 0.5 to 8.0 wt. %, or about 0.5 to 5.0 wt. %, or about 0.5 to 4.0 wt. %, or about 0.5 to 3.0 wt %, or about 0.5 to 10 wt %, or about 0.5 to 8.0 wt %, or about 1.0 to 5.0 wt %, or about 1.0 to 4.0 wt %, or about 1.0 to 3.0 wt %, or about 1.5 to 10 wt %, or about 1.5 to 8.0 wt %, or about 1.5 to 5.0 wt %, or about 1.5 to 4.0 wt %, or about 1.5 to 3.0 wt %, or about 2.0 to 10 wt %, or about 2.0 to 8.0 wt %, or about 2.0 to 5.0 wt %, or about 2.0 to 4.0 wt %. B2. Comb copolymer viscosity improver

[0205] Comb copolymer viscosity modifiers particularly useful herein include those described in U.S. Pat. No. 11,685,874, incorporated herein by reference, or combinations of these with the commercial comb copolymers described above. Comb copolymer viscosity modifiers useful herein generally comprise or are the reaction product of, i.e., are made by polymerization of, the following monomers, including: (a) polyalkylene (such as hydrogenated polybutadiene)-based (alk) acrylate ester macromonomer (whose repeating units may optionally constitute 7.0 wt. % to 18 wt. % of the repeating units of the comb copolymer viscosity modifier); (b) C3-C8 alkyl (alk)acrylate monomers (whose repeating units may optionally constitute 33 wt % to 64 wt % of the repeating units of the comb copolymer viscosity modifier); (c) (Alkyl) acrylic acid C 12 -C 24 an alkyl ester monomer (whose repeating units may constitute at least 16 wt. % and optionally up to 20.0 wt. % of the repeating units of the comb copolymer viscosity modifier); and (d)C1-C 18 Alkyl-terminated or C6-C 20 Aryl-, aralkyl- or alkaryl-terminated C2-C6 oxyalkyl or C2-C6 oligo(alkyleneglycol)-based(alk)acrylate ester monomers and / or hydroxyalkyl or H-endcapped oligo(alkylene glycol)-based(alk)acrylate monomers (whose repeating units may constitute at least 3.0 wt. % and optionally up to 25 wt. % of the repeating units of the comb copolymer viscosity modifier), preferably having the following structure (II): Where R 2 represents hydrogen or C1-C2 alkyl, and m is 2 to 6, such that -(CH2) m - represents a linear, branched and / or cyclic alkyl group between oxygen, n is 1 to 10, and R 1 Represents H, C1-C 18 Linear, branched and / or cyclic alkyl end groups or C6-C 20 Aryl, aralkyl or alkaryl end groups, wherein: the combination of (c) and (d) together constitute greater than 20.0 weight percent of the repeating units of the comb copolymer viscosity modifier, based on the weight of all repeating units in the copolymer.

[0206] In a preferred embodiment, 1) based on the weight of all repeating units in the copolymer, (c) (alkyl) acrylic acid C 12 -C 24 The alkyl ester monomer repeating units are present in 16 to less than 21 weight percent (e.g., 16.5 to less than 20.0 weight percent, such as 17 to less than 19.5 weight percent), 2) based on the weight of all repeating units in the copolymer, (d) C6-C 20Aryl-, aralkyl- or alkaryl-terminated C2-C6 oxyalkyl or C2-C6 oligo(alkylene glycol) type (alkyl)acrylate monomer repeating units are present in 3 to 7 weight percent, and 3) The combination of (c) and (d) together constitute greater than 20.0 weight percent of the repeating units of the comb copolymer viscosity modifier, based on the weight of all repeating units in the copolymer.

[0207] In some embodiments, monomer units (a), (b), (c) and (d) can be prepared as described in US 2021 / 0189281, in particular paragraphs

[0038] to

[0044] of US 2021 / 0189281.

[0208] In some embodiments, (a) polyalkylene-based (alk) acrylate macromonomers can be prepared by reacting (alk) acrylic acid (or its salt) with polyalkylene-based macro-alcohols, such as HLBH5000m (commercially available from Cray Valley of Exton, PA, a monohydroxyl functionalized hydrogenated polybutadiene) is reacted. Other macroalcohols based on hydrogenated polybutadiene are available, for example, according to British Publication No. GB ​​2270317. Some commercially available macromonomers may include, for example, Liquid L-1253 TM and Liquid L-1203 TM (Kuraray Americas Inc. (formerly Kraton Polymers), Houston, TX), both of which are made from hydrogenated polybutadiene that has been functionalized with methacrylate. Other polyolefin-based macromonomers and their preparation are also described, for example, in European Publication Nos. EP 0 621 293 and EP 0 699 694.

[0209] In some embodiments: Monomer (b) is butyl acrylate and / or butyl methacrylate, and / or monomer (c) comprises dodecyl acrylate, dodecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, heptadecyl acrylate, heptadecyl methacrylate or a combination thereof, and / or monomer (d) comprises ethylene glycol acrylate, ethylene glycol methacrylate, ethylene glycol phenyl ether acrylate, ethylene glycol phenyl ether methacrylate, ethylene glycol benzyl ether acrylate, ethylene glycol benzyl ether methacrylate, Ethylene glycol methyl ether acrylate, ethylene glycol methyl ether methacrylate, ethylene glycol ethyl ether acrylate, ethylene glycol ethyl ether methacrylate, oligo(ethylene glycol) acrylate, oligo(ethylene glycol) methacrylate, oligo(ethylene glycol) phenyl ether acrylate, oligo(ethylene glycol) phenyl ether methacrylate, oligo(ethylene glycol) benzyl ether acrylate, oligo(ethylene glycol) benzyl ether methacrylate, oligo(ethylene glycol) naphthyl ether acrylate, oligo(ethylene glycol) naphthyl ether methacrylate, oligo(ethylene glycol) methyl ether acrylate, oligo(ethylene glycol) methyl propylene glycol acrylate, propylene glycol methacrylate, propylene glycol phenyl ether acrylate, propylene glycol phenyl ether methacrylate, propylene glycol methyl ether acrylate, propylene glycol methyl ether methacrylate, propylene glycol ethyl ether acrylate, propylene glycol ethyl ether methacrylate, oligo(propylene glycol) acrylate, oligo(propylene glycol) methacrylate, oligo(propylene glycol) ethyl ether acrylate, oligo(ethylene glycol) butyl ether acrylate, oligo(ethylene glycol) butyl ether methacrylate, propylene glycol acrylate, propylene glycol methacrylate, propylene glycol phenyl ether acrylate, propylene glycol phenyl ether methacrylate, propylene glycol methyl ether acrylate, propylene glycol methyl ether methacrylate, propylene glycol ethyl ether acrylate, propylene glycol ethyl ether methacrylate, oligo(propylene glycol) acrylate, oligo(propylene glycol) methacrylate, oligo( oligo(propylene glycol)phenyl ether acrylate, oligo(propylene glycol)phenyl ether methacrylate, oligo(propylene glycol)benzyl ether acrylate, oligo(propylene glycol)benzyl ether methacrylate, oligo(propylene glycol)naphthyl ether acrylate, oligo(propylene glycol)naphthyl ether methacrylate, oligo(propylene glycol)methyl ether acrylate, oligo(propylene glycol)methyl ether methacrylate, oligo(propylene glycol)ethyl ether acrylate, oligo(propylene glycol)ethyl ether methacrylate, oligo(propylene glycol)propyl ether acrylate, oligo(propylene glycol)propyl ether methacrylate, or a combination thereof.

[0210] Additionally or alternatively, in some embodiments, repeating units of monomer (c) constitute at least 16.0 wt. %, and may optionally constitute up to 35.0 wt. %, of the repeating units of the comb copolymer viscosity modifier.

[0211] Additionally or alternatively, in some embodiments, repeating units of monomer (c) constitute at least 18.0 weight percent, and may optionally constitute up to 35.0 weight percent, of the repeating units of the comb copolymer viscosity modifier.

[0212] Further additionally or alternatively, in some embodiments, the sum of the repeating units of monomer (c) and monomer (d) together constitute greater than 20 wt. %, and may optionally constitute up to 35.0 wt. %, of the repeating units of the comb copolymer viscosity modifier.

[0213] Still further additionally or alternatively, in some embodiments, the comb copolymer viscosity modifier: (i) is made by polymerization of monomers that are substantially free of styrene and styrenic monomers; and (ii) is substantially free of styrene-based repeat units and styrenic-based repeat units.

[0214] In yet further additional or alternative embodiments, the comb copolymer viscosity modifier is prepared by polymerization of at least one additional olefinic monomer comprising monomers (a), (b), (c), (d) and (e) which is different from monomers (a), (b), (c) and (d) and is not an (alkyl) acrylic acid C6-C 20 Aryl, aralkyl or alkaryl ester monomers.

[0215] The polymerized alkyl (alkyl)acrylate (co)polymers described herein are derived from the polymerization (typically, but not limited to, free radical polymerization) of one or more alkyl (alkyl)acrylate monomers, dimers, trimers, oligomers, macromers and / or the like (collectively abbreviated herein as "monomers" for brevity). Alkyl (alkyl)acrylate monomers generally have the following general chemical structure (I): Where C=C* double bond is olefinic bond, R 1 represents the "alkyl" portion of the nomenclature on the oxygen side of the ester, and R 2 represents the "alkyl" part of the nomenclature in brackets. 2 When R is hydrogen, the monomer is an alkyl acrylate; when R 2 When alkyl is present, the monomer is an alkyl acrylate. When present, the nature of the "alkyl" designation is based on R 2 The number of carbons in the alkyl group - for example, one carbon (methyl) refers to methacrylate, while two carbons (ethyl) refer to ethylacrylate, and so on. Similarly, the properties of "alkyl" nomenclature are based on R 1 The number of carbons in the alkyl group - for example, one carbon (methyl) refers to methyl (alkyl)acrylate, while two carbons (ethyl) refer to ethyl (alkyl)acrylate, and so on. Thus, for example, dodecyl methacrylate refers to R 1 It is C 12The alkyl moiety, and R 2 It is a C1 alkyl moiety.

[0216] In particular, the comb copolymer viscosity modifier according to the present disclosure can be made by polymerization comprising, consisting essentially of, or consisting of at least the following monomers: (a) a polyalkylene-based (alk) acrylate ester macromonomer; (b) a C3-C8 alkyl (alk) acrylate ester monomer; (c) a C3-C8 alkyl (alk) acrylate ester monomer; 12 -C 24 Alkyl ester monomer; and (d) C1-C 18 Alkyl-terminated or C6-C 20 Aryl-, aralkyl- or alkylaryl-terminated C2-C6 oxyalkyl or C2-C6 oligo(alkylene glycol) type (alkyl) acrylate monomers (C1-C 18 Alkyl-endcapped or C6-C 20 In some embodiments, the comb copolymer viscosity improver may further comprise (e) one or more other olefinic comonomers which are different from monomers (a), (b), (c) and (d) and are not C6-C 20 Aryl, aralkyl or alkaryl (alkyl) acrylate monomers. For example, monomer (d) may have the following structure (II):

[0217] Where R 2 represents hydrogen or C1-C2 alkyl (especially hydrogen or methyl); m is 2 to 6 (especially 2 to 4), so that -(CH2) m - may represent a linear, branched and / or cyclic alkyl group between oxygen; n is 1 to 10 (especially 1 to 6); and R 1 Represents H, C1-C 18 Linear, branched and / or cyclic alkyl end groups, or C6-C 20Aryl, aralkyl or alkaryl end groups (especially H, C1-C7 linear, branched and / or cyclic alkyl, or C6-C 11 aryl, aralkyl or alkaryl). 1 When R is hydrogen, such monomers may be considered hydroxyacrylates or hydroxymethacrylates; 1 When other than hydrogen, such monomers may be abbreviated herein as "ether acrylate" (EA) or "ether methacrylate" (EMA).

[0218] In some embodiments, the comb copolymer viscosity modifier may be made by polymerization of monomers that are substantially free of styrene and styrenic monomers, and / or may be substantially free of styrene-based repeating units and styrenic-based repeating units. It is important to note that the polyalkylene-based (alk) acrylate ester macromonomer (a) includes the repeating units formed, and its repeating units are considered to be the repeating units of the comb copolymer viscosity modifier herein, even if these monomers are not specifically mentioned. Therefore, when the comb copolymer herein is substantially free of styrene-based repeating units and styrenic-based repeating units, this includes the repeating units of the macromonomer, as well as the repeating units of other comonomers. As used herein, "styrenic" monomers are defined as those monomers having a styrene (vinylbenzene) core, i.e., a 6-membered all-carbon aromatic moiety (including polycyclic ring systems including a phenyl ring) containing from 8 to 17 carbon atoms, an olefinic double bond and one end directly attached to the olefinic double bond and whose ring hydrogens may be optionally substituted (e.g., a phenyl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, biphenylene or acenaphthylenyl moiety).

[0219] With regard to the amount of (a) polyalkylene-based (alk) acrylate ester macromonomer used to make the comb copolymer viscosity modifier, the repeating units of the polyalkylene-based (e.g. hydrogenated polybutadiene-based) (alk) acrylate ester macromonomer may constitute at least 5.0 wt. % (e.g. at least 6.0 wt. %, at least 7.0 wt. %, at least 8.0 wt. %, at least 9.0 wt. %, at least 10 wt. %, at least 11 wt. %, at least 12 wt. % or at least 13 wt. %) and / or at most 30 wt. % (e.g. at most 28 wt. %, at most 25 wt. %, at most 22 wt. %, at most 20 wt. %, at most 18 wt. % or at most 15 wt. %) of the repeating units of the comb copolymer viscosity modifier.For example, the repeating units based on polyolefin type (e.g. hydrogenated polybutadiene type) (alkyl) acrylate macromonomers may constitute 5.0 wt. % to 30 wt. %, 5.0 wt. % to 28 wt. %, 5.0 wt. % to 25 wt. %, 5.0 wt. % to 22 wt. %, 5.0 wt. % to 20 wt. %, 5.0 wt. % to 18 wt. %, 5.0 wt. % to 15 wt. %, 6.0 wt. % to 30 wt. %, 6.0 wt. % to 28 wt. %, 6.0 wt. % to 25 wt. %, 6.0 wt. % to 22 wt. %, 6.0 wt. % to 2 0 wt %, 6.0 wt % to 18 wt %, 6.0 wt % to 15 wt %, 7.0 wt % to 30 wt %, 7.0 wt % to 28 wt %, 7.0 wt % to 25 wt %, 7.0 wt % to 22 wt %, 7.0 wt % to 20 wt %, 7.0 wt % to 18 wt %, 7.0 wt % to 15 wt %, 8.0 wt % to 30 wt %, 8.0 wt % to 28 wt %, 8.0 wt % to 25 wt %, 8.0 wt % to 22 wt %, 8.0 wt % to 20 wt %, 8.0 wt % to 18 wt %, 8.0 wt % to 15 wt %, 9.0 wt % to 30 wt %, 9.0 wt % to 28 wt %, 9.0 wt % to 25 wt %, 9.0 wt % to 22 %. 9.0% to 30% by weight, 9.0% to 28% by weight, 9.0% to 25% by weight, 9.0% to 22% by weight, 9.0% to 20% by weight, 9.0% to 18% by weight, 9.0% to 15% by weight, 10% to 30% by weight, 10% to 28% by weight, 10% to 25% by weight, 10% to 22% by weight, 10% to 20% by weight, 10% to 18% by weight, 10% to 15% by weight, 11% to 30% by weight, 11% to 28% by weight, 11% to 25% by weight, 11% to 15% by weight % to 22 weight %, 11 weight % to 20 weight %, 11 weight % to 18 weight %, 11 weight % to 15 weight %, 12 weight % to 30 weight %, 12 weight % to 28 weight %, 10 weight % to 25 weight %, 12 weight % to 22 weight %, 12 weight % to 20 weight %, 12 weight % to 18 weight %, 12 weight % to 15 weight %, 13 weight % to 30 weight %, 13 weight % to 28 weight %, 13 weight % to 25 weight %, 13 weight % to 22 weight %, 13 weight % to 20 weight %, 13 weight % to 18 weight %, or 13 weight % to 15 weight %. In particular, repeating units based on polyolefin-type (e.g., hydrogenated polybutadiene-type) (alkyl)acrylate macromonomers may constitute 5.0 to 22 wt %, 6.0 to 20 wt %, 7.0 to 18 wt %, or 9.0 to 15 wt % of the repeating units of the comb copolymer viscosity modifier.

[0220] Regarding the amount of (b) C3-C8 alkyl (alk)acrylate monomer used to make the comb copolymer viscosity improver, the repeating units of the C3-C8 alkyl (alk)acrylate monomer may constitute 30 wt % to 71 wt % of the repeating units of the comb copolymer viscosity improver,For example, 30% to 68%, 30% to 66%, 30% to 64%, 30% to 62%, 30% to 60%, 30% to 58%, 30% to 56%, 30% to 54%, 30% to 52%, 30% to 50%, 30% to 48%, 33% to 71%, 33% to 68%, 33% to 66%, 33% to 64%, 33% to 62%, 33% to 60%, 33% to 58%, 33% to 56%, 33% to 54%, 33% to 52%, 30% to 50%, 30% to 48%, 33% to 71%, 33% to 68%, 33% to 66%, 33% to 64%, 33% to 62%, 33% to 60%, 33% to 58%, 33% to 56%, 33% to 54%, 33% to 52%, 3 wt % to 52 wt %, 33 wt % to 50 wt %, 33 wt % to 48 wt %, 35 wt % to 71 wt %, 35 wt % to 68 wt %, 35 wt % to 66 wt %, 35 wt % to 64 wt %, 35 wt % to 62 wt %, 35 wt % to 60 wt %, 35 wt % to 58 wt %, 35 wt % to 56 wt %, 35 wt % to 54 wt %, 35 wt % to 52 wt %, 35 wt % to 50 wt %, 35 wt % to 48 wt %, 38 wt % to 71 wt %, 38 wt % to 68 wt %, 38 wt % to 66 wt %, 38 wt % to 64 wt %, 38 wt % to 62 wt %, 38 wt % % to 60 wt %, 38 wt % to 58 wt %, 38 wt % to 56 wt %, 38 wt % to 54 wt %, 38 wt % to 52 wt %, 38 wt % to 50 wt %, 38 wt % to 48 wt %, 40 wt % to 71 wt %, 40 wt % to 68 wt %, 40 wt % to 66 wt %, 40 wt % to 64 wt %, 40 wt % to 62 wt %, 40 wt % to 60 wt %, 40 wt % to 58 wt %, 40 wt % to 56 wt %, 40 wt % to 54 wt %, 40 wt % to 52 wt %, 40 wt % to 50 wt %, 40 wt % to 48 wt %, 45 wt % to 71 wt %, 45 wt % to 68 wt %, %, 45 wt % to 66 wt %, 45 wt % to 64 wt %, 45 wt % to 62 wt %, 45 wt % to 60 wt %, 45 wt % to 58 wt %, 45 wt % to 56 wt %, 45 wt % to 54 wt %, 45 wt % to 52 wt %, 45 wt % to 50 wt %, 45 wt % to 48 wt %, 50 wt % to 71 wt %, 50 wt % to 68 wt %, 50 wt % to 66 wt %, 50 wt % to 64 wt %, 50 wt % to 62 wt %, 50 wt % to 60 wt %, 50 wt % to 58 wt %, 50 wt % to 56 wt %, 50 wt % to 54 wt %, or 50 wt % to 52 wt %. In particular,Repeating units based on C3-C8 alkyl (alk)acrylate monomers may constitute 33 wt % to 64 wt %, 35 wt % to 60 wt %, or 38 wt % to 58 wt % of the repeating units of the comb copolymer viscosity modifier.

[0221] About (c) (Alkyl) Acrylic Acid C 12 -C 24 Alkyl ester monomers and referring again to the general formula (I) above for acrylate monomers, the optional "alkyl (alk)" may advantageously represent hydrogen (no "alkyl (alk)") or C1-C2 alkyl (especially hydrogen or methyl) R 2 Therefore, considering the R 1 The structural part of C 12 -C 24 Alkyl range, such monomers may contain either linear, cyclic or branched C 12 Acrylates, linear, cyclic or branched C 12 Methacrylates, linear, cyclic or branched C 14 Acrylates, linear, cyclic or branched C 14 Methacrylates, linear, cyclic or branched C 16 Acrylates, linear, cyclic or branched C 16 Methacrylates, linear, cyclic or branched C 17 Acrylates, linear, cyclic or branched C 17 Methacrylates, linear, cyclic or branched C 18 Acrylates, linear, cyclic or branched C 18 Methacrylate, or a combination or polymerization / oligomerization reaction product thereof. In particular, (alkyl) acrylic acid C 12 -C 24 The alkyl ester monomer can be, comprise, or consist essentially of dodecyl acrylate, dodecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, heptadecyl acrylate, heptadecyl methacrylate, or combinations or polymerization / oligomeric reaction products thereof.

[0222] About (c) (Alkyl) Acrylic Acid C for Making Comb Copolymer Viscosity Improver 12 -C 24 Amount of alkyl ester monomer, based on (alkyl) acrylic acid C 12 -C 24% at least 23.0 wt. %, at least 23.5 wt. %, at least 24.0 wt. %, at least 24.5 wt. % or at least 25.0 wt. %) and optionally also up to 35.0 wt. % (e.g. up to 34.0 wt. %, up to 33.0 wt. %, up to 32.0 wt. %, up to 31.0 wt. %, up to 30.0 wt. %, up to 29.0 wt. %, up to 28.0 wt. % or up to 27.0 wt. %) of the repeating units of the comb copolymer viscosity modifier.

[0223] Or, with respect to (c) (alkyl) acrylic acid C for use in the manufacture of a comb copolymer viscosity improver 12 -C 24 Amount of alkyl ester monomer, based on (alkyl) acrylic acid C 12 -C 24 The repeating units of the alkyl ester monomers may constitute at least 16.0 wt. % (e.g. at least 18.5 wt. %, at least 19.0 wt. %, at least 19.5 wt. %) and optionally but preferably at most less than 20.0 wt. % (e.g. at most 20.9 wt. %, at most 20.5 wt. %, at most 20.0 wt. %) of the repeating units of the comb copolymer viscosity modifier. In particular, the (alkyl) acrylic acid C 12 -C 24 The repeating units of the alkyl ester monomer may constitute 16.0 wt % to less than 21 wt % (eg 16.5 wt % to 20.5 wt %, such as about 17 wt % to about 20 wt %, such as about 19 wt %) of the repeating units of the comb copolymer viscosity modifier.

[0224] Regarding (d) C1-C for the manufacture of comb copolymer viscosity improvers 18 Alkyl-terminated or C6-C 20 Aryl-, aralkyl- or alkaryl-terminated C2-C6 oxyalkyl or C2-C6 oligo(alkylene glycol) type (alkyl) acrylate monomers and / or hydroxyalkyl or H-terminated oligo(alkylene glycol) type (alkyl) acrylate monomers (the C1-C 18 Alkyl-endcappedor C6-C 20aryl-,aralkyl-,or alkaryl-endcapped C2-C6 oxyalkyl or C2-C6 oligo(alkylene glycol)-based(alk)acrylate ester monomer and / or hydroxyalkyl or H-endcapped oligo(alkylene glycol)-based(alk)acrylate %, at least 25 wt %, at most 24 wt %, at most 23 wt %, at most 22 wt %, at most 21 wt %, at most 20 wt %, at most 19 wt %, at most 18 wt %, at most 17 wt % or at most 16 wt % of the repeating units of the comb copolymer viscosity modifier. In particular, repeating units based on monomer (d) may constitute at least 3.0 wt%, up to 28 wt%, up to 20 wt%, 3.0 wt% to 25 wt%, or 8.0 wt% to 18 wt% of the repeating units of the comb copolymer viscosity modifier.

[0225] The comb copolymer viscosity modifiers according to the present disclosure may advantageously exhibit an intermediate weight average molecular weight as measured by gel permeation chromatography (GPC; also known as size exclusion chromatography or SEC). The GPC specifications and analytical conditions used to determine the molecular weight distribution are as follows: Waters Acquity APC with Waters RID and UV215 nm; Software: Empower 3; Columns (3 x 4.6 x 150 mm in series): APC-XT 450 (~2.5μ), APC-XT200 (~2.5μ) and APC-XT45 (~1.7μm); Mobile phase and flow: >99.9% Fisheroptima gold label HPLC grade uninhibited THF; Flow: ~0.25 mL / min, ~35 min retention time; Oven temperature: ~35°C; Sample concentration: ~1 mg (solid polymer) / mL; Sample preparation: essentially complete dissolution overnight (~8-20 hours) followed by filtration through a ~0.45μm PTFE filter; Injection volume: ~10μL;Polystyrene calibration curve. Therefore, in some embodiments, the weight average molecular weight of the comb copolymer viscosity modifier according to the present disclosure measured by GPC can be less than or equal to 1,000,000 g / mol (e.g., less than or equal to 850,000 g / mol, less than or equal to 625,000 g / mol, less than or equal to 613,000 g / mol, less than or equal to 600,000 g / mol, less than or equal to 590,000 g / mol, less than or equal to 580,000 g / mol, 200,000 g / mol to 1,000,000 g / mol, 200,000 g / mol to 850,000 g / mol). , 200,000 g / mol to 625,000 g / mol, 200,000 g / mol to 613,000 g / mol, 200,000 g / mol to 600,000 g / mol, 200,000 g / mol to 590,000 g / mol, 200,000 g / mol to 580,000 g / mol, 250,000 g / mol to 1,000,000 g / mol, 250,000 g / mol to 850,000 g / mol, 250,000 g / mol to 625,000 g / mol, 250,000 g / mol to 610, 000 g / mol, 250,000 g / mol to 600,000 g / mol, 250,000 g / mol to 590,000 g / mol, 250,000 g / mol to 580,000 g / mol, 300,000 g / mol to 1,000,000 g / mol, 300,000 g / mol to 850,000 g / mol, 300,000 g / mol to 625,000 g / mol, 300,000 g / mol to 610,000 g / mol, 300,000 g / mol to 600,000 g / mol, 300,000 g / mol to 1,000,000 g / mol, g / mol to 590,000 g / mol, 300,000 g / mol to 580,000 g / mol, 350,000 g / mol to 1,000,000 g / mol, 350,000 g / mol to 850,000 g / mol, 350,000 g / mol to 625,000 g / mol, 350,000 g / mol to 610,000 g / mol, 350,000 g / mol to 600,000 g / mol, 350,000 g / mol to 590,000 g / mol, or 350,000 g / mol to 580,000 g / mol;In particular, less than or equal to 625,000 g / mol, less than or equal to 600,000 g / mol, 250,000 g / mol to 625,000 g / mol, or 300,000 g / mol to 850,000 g / mol), based on polystyrene standards. The comb copolymer viscosity improver according to the present disclosure can advantageously exhibit relatively high oil solubility or oil dispersibility. The term "oil soluble" as used herein means that a composition comprising at least 0.1 wt. %, preferably at least 0.5 wt. % of a comb copolymer viscosity improver and at least 85 wt. % (preferably the remainder) of a lubricating oil base stock can be combined relatively easily without forming a stable macroscopic phase. Oil solubility and / or oil dispersibility can depend, among other things, on the nature of the base stock and on the polymer chemistry (e.g., the proportion of lipophilic side chains). ; Combination with conventional comb copolymers

[0226] The comb copolymers described herein can be further combined with conventional comb copolymer viscosity modifiers, such as acrylate based branched copolymers, which are typically prepared by (co)polymerizing polyalkyl (meth)acrylate macromonomers with alkyl (meth)acrylates and other optional monomers, such as alkyl (meth)acrylates, styrene, alkylstyrenes, vinyl esters of carboxylic acids, (meth)acrylates and amides and vinyl heterocyclic compounds. Useful comb copolymers and methods for their production are described in US 5,756,433, EP 0 637 332, EP 0 937 769, EP 0 979 834, US 3,702,300, EP 0 969 077, EP 0 744 457, EP 0 621 293 and EP 0 699 694, which are incorporated herein by reference.

[0227] Examples of commercially available conventional comb copolymers may include the following: polymethacrylates, some of which have dispersant properties (such as Viscoplex from RohMax TM Series, Hitec from Afton TM series and LZ 7702 from Lubrizol TM 、LZ 7727 TM 、LZ 7725 TM and LZ 7720C TM ); Olefin-grafted polymethacrylate polymers (such as Viscoplex from Evonik / RohMax TM 2-500 and 2-600); and hydrogenated polyisoprene star polymers (such as Shellvis from Shell TM200 and 260). Conventional comb copolymers also include Asteric TM Polymers (methacrylate polymers having radial or star configurations). Other commercially available conventional polymethacrylate comb copolymers useful herein are available as Viscoplex TM 0-410, Viscoplex TM 10-930, Viscoplex TM 5029、Acryloid TM 1253. Acryloid TM 1265、Acryloid TM 1263. Acryloid TM 1267、Acryloid TM 954 is available from Rohm and Haas Company / Evonik, as TLA 233, TLA 5010 and TC 10124 are available from Texaco. Some of these polymethacrylates may be PMA / OCP (olefin copolymer) type polymers. Combinations of comb copolymer viscosity improvers described herein and conventional comb copolymer viscosity improvers may be used in the lubricating oil composition at concentrations of up to 20 wt %, or 60 wt %, or 70 wt %. Concentrations of 0.1 to 12 wt %, 0.1 to 4 wt %, 0.2 to 3 wt %, 1 to 12 wt %, or 3 to 10 wt % may be used.

[0228] The lubricating composition according to the present disclosure may further comprise one or more additives, such as detergents, friction modifiers, antioxidants, pour point depressants, defoamers, viscosity modifiers, dispersants, corrosion inhibitors, antiwear agents, extreme pressure additives, demulsifiers, seal compatibilizers, additive diluent base oils, etc. Specific examples of such additives are described, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, 3rd Edition, Vol. 14, pp. 477-526, several of which are discussed in more detail below. C. Detergents

[0229] The lubricating composition may include one or more metallic detergents (such as a blend of metallic detergents), also referred to as "detergent additives". Metallic detergents typically act both as detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life. Detergents typically comprise a polar head and a long hydrophobic tail, the polar head comprising a metal salt of an acidic organic compound. The salts may contain substantially stoichiometric amounts of the metal, in which case they are typically described as normal or neutral salts, and typically have a total base number ("TBN", as measured by ASTM D2896) of up to 150 mg KOH / g, such as 0 to 80 (or 5-30) mg KOH / g. Large amounts of metal bases may be incorporated by reacting an excess of a 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 100 mg KOH / g or more, such as 200 mg KOH / g or more, and typically have a TBN of 250 mg KOH / g or more, such as 300 mg KOH / g or more, such as 200 to 800 mg KOH / g, 225 to 700 mg KOH / g, 250 to 650 mg KOH / g, or 300 to 600 mg KOH / g, such as 150 to 650 mg KOH / g.

[0230] Suitable detergents include metals, particularly alkali metals (Group 1 metals, such as Li, Na, K, Rb) or alkaline earth metals (Group 2 metals, such as Be, Mg, Ca, Sr, Ba), particularly sodium, potassium, lithium, calcium and magnesium, such as oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, naphthenates and other oil-soluble carboxylates of Ca and / or Mg. In addition, the detergent may comprise a hybrid detergent containing any combination of sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates and naphthenates or other oil-soluble carboxylates of Group 1 and / or 2 metals of sodium, potassium, lithium, calcium or magnesium.

[0231] Preferably, the detergent additive useful in the present disclosure comprises a calcium and / or magnesium metal salt. The detergent may be a calcium and / or magnesium carboxylate (e.g., salicylate), sulfonate, or phenate detergent. More preferably, the detergent additive is selected from magnesium salicylate, calcium salicylate, magnesium sulfonate, calcium sulfonate, magnesium phenate, calcium phenate, and hybrid detergents comprising two, three, four, or more of these detergents and / or combinations thereof.

[0232] Metal-containing detergents may also include "hybrid" detergents formed with mixed surfactant systems including phenate and / or sulfonate components, such as phenate / salicylate, sulfonate / phenate, sulfonate / salicylate, sulfonate / phenate / salicylate, as described, for example, in U.S. Pat. Nos. 6,429,178; 6,429,179; 6,153,565; and 6,281,179. When, for example, a hybrid sulfonate / phenate detergent is used, the hybrid detergent would be considered equivalent to the amounts of separate phenate and sulfonate detergents incorporating similar amounts of phenate and sulfonate soaps, respectively.

[0233] Overbased metal-containing detergents can be sodium salts, calcium salts, magnesium salts or mixtures thereof of phenates, sulfur-containing phenates, sulfonates, salixarates and salicylates. Overbased phenates and salicylates typically have a total base number of 180 to 650 mg KOH / g, such as 200 to 450 mg KOH / g. Overbased sulfonates typically have a total base number of 250 to 600 mg KOH / g, or 300 to 500 mg KOH / g. In some embodiments, the sulfonate detergent can be primarily a linear alkylbenzene sulfonate detergent having a metal ratio of at least 8 as described in paragraphs

[0026] to

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

[0234] The detergent additive may comprise one or more magnesium sulfonate detergents. The magnesium detergent may be a neutral salt or an overbased salt. Suitably, the magnesium detergent is an overbased magnesium sulfonate having a TBN of 80 to 650 mg KOH / g (ASTM D2896), such as 200 to 500 mg KOH / g, such as 240 to 450 mg KOH / g.

[0235] Alternatively, the detergent additive is magnesium salicylate. Suitably, the magnesium detergent is magnesium salicylate having 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.

[0236] Alternatively, the detergent additive is a combination of magnesium salicylate and magnesium sulfonate.

[0237] The magnesium detergent provides 200-4000 ppm of magnesium atoms, suitably 200-2000 ppm, 300 to 1500 ppm or 450-1200 ppm of magnesium atoms to the lubricating composition thereof (ASTM D5185).

[0238] The detergent composition may comprise (or consist of) a combination of one or more magnesium sulfonate detergents and one or more calcium salicylate detergents.

[0239] The detergent composition may comprise (or consist of) a combination of one or more magnesium sulfonate detergents and one or more calcium sulfonate detergents.

[0240] The detergent composition may comprise (or consist of) a combination of one or more magnesium salicylate detergents and one or more calcium salicylate detergents.

[0241] The combination of one or more magnesium detergents and one or more calcium detergents provides to the lubricating composition thereof: 1) 200-4000 ppm of atomic magnesium, suitably 200-2000 ppm, 300 to 1500 ppm or 450-1200 ppm of atomic magnesium (ASTM D5185), and 2) at least 500 ppm, preferably at least 750 ppm, more preferably at least 900 ppm of atomic calcium, such as 500-4000 ppm, preferably 750-3000 ppm, more preferably 900-2000 ppm of atomic calcium (ASTM D5185).

[0242] The detergent may comprise one or more calcium detergents, such as calcium carboxylate (eg salicylate), sulfonate or phenate detergents.

[0243] 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 lower, such as 100 mg KOH / g or lower, or 200 mg KOH / g or higher, or 300 mg KOH / g or higher, or 350 mg KOH / g or higher.

[0244] Suitably, the calcium detergent is a 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.

[0245] The calcium detergent is typically present in an amount sufficient to provide at least 500 ppm, preferably at least 750, more preferably at least 900 ppm of atomic calcium to the lubricating oil composition (ASTM D5185). If present, any calcium detergent is suitably present in an amount sufficient to provide no more than 4000 ppm, preferably no more than 3000 ppm, more preferably no more than 2000 ppm of atomic calcium to the lubricating oil composition (ASTM D5185). If present, any calcium detergent is suitably present in an amount sufficient to provide 500-4000 ppm, preferably 750-3000 ppm, more preferably 900-2000 ppm of atomic calcium to the lubricating oil composition (ASTM D5185).

[0246] Suitably, the total atomic weight of metals from detergents in lubricating compositions according to all aspects of the present disclosure is no more than 5000 ppm, preferably no more than 4000 ppm, more preferably no more than 2000 ppm (ASTM D5185). The total atomic weight of metals from detergents in lubricating oil compositions according to all aspects of the present disclosure is suitably at least 500 ppm, preferably at least 800 ppm, more preferably at least 1000 ppm (ASTM D5185). The total atomic weight of metals from detergents in lubricating oil compositions according to all aspects of the present disclosure is suitably from 500 to 5000 ppm, preferably from 500 to 3000 ppm, more preferably from 500 to 2000 ppm (ASTM D5185).

[0247] Sulfonate detergents can be prepared from sulfonic acids, which are generally obtained by sulfonation of alkyl-substituted aromatic hydrocarbons (such as those obtained by fractionation of petroleum or by alkylation of aromatic hydrocarbons). Examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, biphenyl or their halogen derivatives, such as chlorobenzene, chlorotoluene and chloronaphthalene. Alkylation can be carried out with an alkylating agent having from about 3 to more than 70 carbon atoms in the presence of a catalyst. Alkaryl sulfonates generally contain from about 9 to about 80 or more carbon atoms per alkyl-substituted aromatic moiety, preferably from about 16 to about 60 carbon atoms. The oil-soluble sulfonates or alkaryl sulfonic acids can be neutralized with metal oxides, hydroxides, alkoxides, carbonates, carboxylates, sulfides, hydrosulfides, nitrates, borates and ethers. The amount of the metal compound is selected in consideration of the desired TBN of the final product, but is generally about 100 to 220 mass % (preferably at least 125 mass %) of the stoichiometrically required amount.

[0248] Metal salts of phenols and sulfurized phenols are prepared by reaction with appropriate metal compounds, such as oxides or hydroxides, and neutral or overbased products can be obtained by methods well known in the art. Sulfurized phenols can be prepared by reacting phenols with sulfur or sulfur-containing compounds, such as hydrogen sulfide, sulfur monohalides or sulfur dihalides, to form a product that is generally a mixture of compounds in which two or more phenols are bridged by sulfur-containing bridges.

[0249] Carboxylate detergents, such as salicylates, can be prepared by reacting aromatic carboxylic acids (such as C 5-100 , C 9-30 , C 14-24 The aromatic carboxylic acid may be prepared by reacting an alkyl-substituted hydroxybenzoic acid) with an appropriate metal compound, such as an oxide or hydroxide, and a neutral or overbased product may be obtained by methods known in the art. The aromatic moiety of the aromatic carboxylic acid may contain heteroatoms, such as nitrogen and oxygen. The moiety preferably contains only carbon atoms; the moiety more preferably contains six or more carbon atoms; for example, benzene is a preferred moiety. The aromatic carboxylic acid may contain one or more aromatic moieties, such as one or more benzene rings, fused or connected via an alkylene bridge.

[0250] Preferred substituents in oil-soluble salicylic acid are alkyl substituents. In alkyl-substituted salicylic acids, the alkyl group advantageously contains 5 to 100, preferably 9 to 30, especially 14 to 20 carbon atoms. If more than one alkyl group is present, the average number of carbon atoms in all alkyl groups is preferably at least 9 to ensure sufficient oil solubility.

[0251] In some embodiments, the ratio of detergent atomic metal to atomic molybdenum in the lubricating oil composition may be less than 3:1, such as less than 2:1.

[0252] In addition, since metal organic and inorganic base salts used as detergents can contribute to the sulfated ash content of the lubricating oil composition, in embodiments of the present disclosure, the amount of such additives is minimized. In order to maintain a low sulfur content, salicylate detergents may be used and the lubricating compositions herein may include one or more salicylate detergents (the detergents are preferably used in an amount of 0.05 to 20.0 wt. %, more preferably 1.0 to 10.0 wt. %, and most preferably 2.0 to 5.0 wt. %, based on the total weight of the lubricating composition).

[0253] The lubricating compositions herein generally have a total sulfated ash content of no greater than 2.0 wt%, or at a level of no greater than 1.0 wt%, or at a level of no greater than 0.8 wt%, based on the total weight of the lubricating composition as determined by ASTM D874.

[0254] Furthermore, it is useful that each detergent independently has a TBN value (Total Base Number) as measured by ISO 3771 in the range of 10 to 700 mg KOH / g, 10 to 500 mg KOH / g, or in the range of 100 to 650 mg KOH / g, or in the range of 10 to 500 mg KOH / g, or in the range of 30 to 350 mg KOH / g, or in the range of 50 to 300 mg KOH / g.

[0255] Sulfonate detergents (such as Ca and / or Mg sulfonate detergents) may be present in amounts to provide the lubricant composition with 0.1 wt % to 1.5 wt %, or 0.15 to 1.2 wt %, or 0.2 wt % to 0.9 wt % sulfonate soap.

[0256] The salicylate detergent (such as a Ca and / or Mg salicylate detergent) is present in an amount to provide the lubricant composition with 0.3 wt % to 1.4 wt %, or 0.35 wt % to 1.2 wt %, or 0.4 wt % to 1.0 wt % salicylate soap.

[0257] The sulfonate soap may be present in an amount from 0.2% to 0.8% by weight of the lubricant composition, and the salicylate soap may be present in an amount from 0.3% to 1.0% by weight of the lubricant composition.

[0258] All alkaline earth metal detergent soaps combined may be present in an amount from 0.6 wt % to 2.1 wt %, or from 0.7 wt % to 1.4 wt % of the lubricant composition.

[0259] Typically, lubricating compositions formulated for heavy duty diesel engines contain from about 0.1 to about 10 mass %, alternatively from about 0.5 to about 7.5 mass %, alternatively from about 1 to about 6.5 mass % detergent based on the lubricating composition.

[0260] Typically, lubricating compositions formulated for passenger-car engines contain from about 0.1 to about 10 mass %, alternatively from about 0.5 to about 7.5 mass %, alternatively from about 1 to about 6.5 mass % detergent based on the lubricating composition.

[0261] Typically, lubricating compositions formulated for use in transmission systems (eg, gearboxes) contain about 0.1 to about 10 mass %, or about 0.5 to about 7.5 mass %, or about 2 to about 6.5 mass % detergent based on the lubricating composition. D. Friction modifier

[0262] Friction modifiers are any materials that can change the coefficient of friction of a surface lubricated with any lubricant or fluid containing such materials. If desired, friction modifiers, also known as friction reducers or lubricity agents or oiliness agents, and other such agents that change the ability of a base oil, formulated lubricating composition, or functional fluid to adjust the coefficient of friction of a lubricated surface can be effectively used in combination with the base oil or lubricating composition of the present disclosure. Friction modifiers that reduce the coefficient of friction are particularly advantageously combined with the base oils and lubricating compositions of the present disclosure.

[0263] Exemplary friction modifiers may include, for example, organometallic compounds or materials or mixtures thereof. Exemplary organometallic friction modifiers that may be used in lubricating oil formulations of the present disclosure include, for example, tungsten and / or molybdenum compounds, such as molybdenum amines, molybdenum diamines, organic tungstates, molybdenum dithiocarbamates, molybdenum dithiophosphates, molybdenum amine complexes, molybdenum carboxylates, and mixtures thereof. Examples of available molybdenum-containing compounds may conveniently include molybdenum dithiocarbamates, trinuclear molybdenum compounds (e.g., as described in PCT Publication No. WO 98 / 26030), sulfides of molybdenum, and molybdenum dithiophosphates.

[0264] Other known friction modifiers include oil-soluble organic molybdenum compounds. Such organic molybdenum friction modifiers can also provide antioxidant and antiwear benefits to the lubricating oil composition. Examples of such oil-soluble organic molybdenum compounds include dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, sulfides, and the like, and mixtures thereof. Particularly preferred are molybdenum dithiocarbamates, molybdenum dialkyl dithiophosphates, molybdenum alkyl xanthates, and molybdenum alkyl thioxanthates.

[0265] In addition, the molybdenum compound can be an acidic molybdenum compound. These compounds react with basic nitrogen compounds as measured by ASTM test D664 or D2896 titration procedures and are generally hexavalent. They include molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate and other alkali metal molybdates and other molybdenum salts, such as sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide or similar acidic molybdenum compounds.

[0266] Molybdenum compounds useful in the compositions of the present disclosure include organic molybdenum compounds of the formula Mo(R"OCS2)4 and Mo(R"SCS2)4, wherein R" is an organic group selected from alkyl, aryl, aralkyl and alkoxyalkyl groups generally having 1 to 30 carbon atoms, preferably 2 to 12 carbon atoms, and most preferably an alkyl group having 2 to 12 carbon atoms. Particularly preferred are dialkyl dithiocarbamates of molybdenum.

[0267] Another class of organic molybdenum compounds useful in the lubricating compositions of the present disclosure are trinuclear molybdenum compounds, particularly those of the formula Mo3S k L n Q z Those and mixtures thereof, wherein L is an independently selected ligand having an organic group having a sufficient number of carbon atoms to render the compound soluble or dispersible in oil, n is 1 to 4, k is 4 to 7, Q is selected from neutral electron donating compounds such as water, amines, alcohols, phosphines and ethers, and z is 0 to 5 and includes non-stoichiometric values. At least 21 carbon atoms should be present in all ligands / organic groups, such as at least 25, at least 30 or at least 35 carbon atoms.

[0268] Lubricating oil compositions useful in all aspects of the present disclosure preferably contain at least 10 ppm, at least 30 ppm, at least 40 ppm, more preferably at least 50 ppm of molybdenum. Suitably, lubricating oil compositions useful in all aspects of the present disclosure contain no more than 1000 ppm, no more than 750 ppm, or no more than 500 ppm of molybdenum. 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). In some embodiments, lubricating oil compositions useful in all aspects of the present disclosure preferably contain at least 20 to 40 ppm, such as 20 to 30, such as about 25 ppm of molybdenum.

[0269] For more information on useful Mo-containing friction modifiers, see US Pat. No. 10,829,712 (column 8, line 58 to column 11, line 31).

[0270] Ashless friction modifiers may be present in the lubricating oil composition of the present disclosure and are well known, and include esters formed by reacting carboxylic acids and anhydrides with alkanols and amine-based friction modifiers. Other available friction modifiers generally include polar end groups (e.g., carboxyl or hydroxyl groups) covalently bonded to lipophilic hydrocarbon chains. Esters of carboxylic acids and anhydrides with alkanols are described in U.S. Patent No. 4,702,850. M. Belzer in "Journal of Tribology" (1992), Vol. 114, pp. 675-682 and M. Belzer and S. Jahanmir in "Lubrication Science" (1988), Vol. 1, pp. 3-26 describe examples of other conventional organic friction modifiers. Typically, the total amount of organic ashless friction modifiers in the lubricant according to the present disclosure is no more than 5% by mass, preferably no more than 2% by mass, and more preferably no more than 0.5% by mass based on the total mass of the lubricating oil composition.

[0271] Exemplary friction modifiers useful in the lubricating compositions described herein include, for example, alkoxylated fatty acid esters, alkanolamides, polyol fatty acid esters, boronated glycerol fatty acid esters, fatty alcohol ethers, and mixtures thereof.

[0272] Exemplary alkoxylated fatty acid esters include, for example, polyoxyethylene stearates, fatty acid polyglycol esters, etc. These may include polyoxypropylene stearate, polyoxybutylene stearate, polyoxyethylene isostearate, polyoxypropylene isostearate, polyoxyethylene palmitate, and the like.

[0273] Exemplary alkanolamides include, for example, lauric acid diethyl alkanolamide, palmitic acid diethyl alkanolamide, etc. These may include oleic acid diethyl alkanolamide, stearic acid diethyl alkanolamide, oleic acid diethyl alkanolamide, polyethoxylated hydrocarbyl amides, polypropoxylated hydrocarbyl amides, and the like.

[0274] Exemplary polyol fatty acid esters include, for example, glycerol monooleate, saturated mono-, di- and triglycerides, glycerol monostearate, etc. These may include polyol esters, hydroxyl-containing polyol esters, and the like.

[0275] Exemplary boronized glycerol fatty acid esters include, for example, boronized glycerol monooleate, boronized saturated mono-, di- and triglycerides, boronized glycerol monostearate, etc. In addition to glycerol polyols, these may also include trimethylolpropane, pentaerythritol, sorbitan, etc. These esters may be polyol monocarboxylates, polyol dicarboxylates and sometimes, polyol tricarboxylates. Preferred may be glycerol monooleate, glycerol dioleate, glycerol trioleate, glycerol monostearate, glycerol distearate and glycerol tristearate and corresponding glycerol monopalmitate, glycerol dipalmitate and glycerol tripalmitate, and respective isostearates, linoleate, etc. Ethoxylated, propoxylated and / or butoxylated fatty acid esters of polyols (especially using glycerol as the base polyol) may be used for this.

[0276] Exemplary fatty alcohol ethers include, for example, stearyl ether, myristic ether, and the like. 50 The alcohol portion of the base alcohol may preferably be stearyl, myristyl, C 11 -C 13 Hydrocarbon, oleyl, isostearyl, etc.

[0277] Useful concentrations of friction modifiers may be 0.01 wt % to 5 wt %, or about 0.01 wt % to about 2.5 wt %, or about 0.05 wt % to about 1.5 wt %, or about 0.051 wt % to about 1 wt %. The concentration of molybdenum-containing materials is usually described as Mo metal concentration. The favorable concentration of Mo may be 25 ppm to 700 ppm or more, with a preferred range of 50-200 ppm. All types of friction modifiers may be used alone or in combination with the materials disclosed herein. A mixture of two or more friction modifiers or a mixture of a friction modifier with an alternative surface active material is also generally desirable. For example, a combination of a Mo-containing compound and a polyol fatty acid ester, such as glycerol monooleate, may be used herein. E. Antioxidants

[0278] Antioxidants delay oxidative degradation of base oils during use. Such degradation may result in deposits on metal surfaces, the presence of sludge, increased viscosity in lubricants, etc. A wide variety of oxidation inhibitors can be used in lubricating oil compositions. See, for example, Lubricants and Related Products, Klamann, Wiley VCH, 1984; U.S. Pat. Nos. 4,798,684 and 5,084,197.

[0279] Useful antioxidants include hindered phenols. These phenolic antioxidants can be ashless (metal-free) phenolic compounds or neutral or alkaline metal salts of certain phenolic compounds. Typical phenolic antioxidant compounds are hindered phenols containing sterically hindered hydroxyl groups. These include derivatives of dihydroxy aromatic compounds in which the hydroxyl groups are in the ortho or para position to each other. Typical phenolic antioxidants include C 6+ Alkyl-substituted hindered phenols and alkylene coupled derivatives of these hindered phenols. Examples of this type of phenolic material include 2-tert-butyl-4-heptylphenol; 2-tert-butyl-4-octylphenol; 2-tert-butyl-4-dodecylphenol; 2,6-di-tert-butyl-4-heptylphenol; 2,6-di-tert-butyl-4-dodecylphenol; 2-methyl-6-tert-butyl-4-heptylphenol; and 2-methyl-6-tert-butyl-4-dodecylphenol. Other useful hindered mono-phenolic antioxidants may include, for example, hindered 2,6-di-alkyl-phenol propionate derivatives. Bis-phenolic antioxidants may also be advantageously used herein. Examples of ortho-coupled phenols include: 2,2'-bis(4-heptyl-6-tert-butyl-phenol); 2,2'-bis(4-octyl-6-tert-butyl-phenol); and 2,2'-bis(4-dodecyl-6-tert-butyl-phenol). Para-coupled bisphenols include, for example, 4,4'-bis(2,6-di-tert-butyl-phenol) and 4,4'-methylene-bis(2,6-di-tert-butyl-phenol).

[0280] An effective amount of one or more catalytic antioxidants may also be used. The catalytic antioxidant comprises an effective amount of a) one or more oil-soluble multimetallic organic compounds; and an effective amount of b) one or more substituted N,N'-diaryl-o-phenylenediamine compounds, or c) one or more hindered phenol compounds; or a combination of b) and c). Catalytic antioxidants useful herein are more fully described in U.S. Pat. No. 8,048,833.

[0281] Non-phenolic oxidation inhibitors that may be used include aromatic amine antioxidants, which may be used as such or in combination with phenolics. Typical examples of non-phenolic antioxidants include: alkylated and non-alkylated aromatic amines, such as those of the formula R8R9R 10 N aromatic monoamine, wherein 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 an alkylene group, an alkenylene group or an aralkylene group, R 12R8 is an alkyl or alkenyl, aryl or alkaryl, and x is 0, 1 or 2. The aliphatic group R8 can contain 1 to about 20 carbon atoms, preferably contains about 6 to 12 carbon atoms. The aliphatic group is a saturated aliphatic group normally. Preferably, R8 and R9 are aromatic or substituted aromatic groups, and the aromatic group can be a condensed ring aromatic group, such as naphthyl. Aromatic groups R8 and R9 can be linked together with other groups such as S.

[0282] Typical aromatic amine antioxidants have an alkyl substituent containing at least about 6 carbon atoms. Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl and decyl. Typically, aliphatic groups do not contain more than about 14 carbon atoms. General types of amine antioxidants that can be used in the present composition include diphenylamine, phenylnaphthylamine, phenothiazine, iminodibenzyls and diphenylphenylenediamine. Mixtures of two or more aromatic amines are also available. Polymeric amine antioxidants can also be used. Specific examples of aromatic amine antioxidants that can be used in the present disclosure include: p, p'-dioctyldiphenylamine; tert-octylphenyl-α-naphthylamine; phenyl-α-naphthylamine; and p-octylphenyl-α-naphthylamine.

[0283] Sulfur-containing antioxidants may also be used herein. In particular, one or more oil-soluble or oil-dispersible sulfur-containing antioxidants may be used as antioxidant additives. For example, sulfurized alkylphenols and alkali metal or alkaline earth metal salts thereof are also antioxidants useful herein. Suitably, the lubricating oil composition of the present disclosure may include the one or more sulfur-containing antioxidants in an amount providing the lubricating oil composition with 0.02 to 0.2, preferably 0.02 to 0.15, even more preferably 0.02 to 0.1, even more preferably 0.04 to 0.1 mass % sulfur based on the total mass of the lubricating oil composition. Optionally, the oil-soluble or oil-dispersible sulfur-containing antioxidant is selected from sulfurized C4 to C 25 Olefins, sulfurized aliphatic (C7 to C 29 ) hydrocarbon fatty acid esters, ashless sulfurized phenolic antioxidants, sulfur-containing organic molybdenum compounds and combinations thereof. For further information on sulfurized materials that can be used as antioxidants herein, see U.S. Pat. No. 10,731,101 (column 15, line 55 to column 22, line 12).

[0284] The antioxidants useful herein include hindered phenols and / or arylamines. These antioxidants can be used independently or in combination with each other according to their type.

[0285] Typical antioxidants include: Irganox TM L67, Irganox TM L135, Ethanox TM 4702、LanxessAdditin TM RC 7110; Ethanox TM4782J; Irganox TM 1135. Irganox TM 5057, Sulphurized lard and palm oil fatty acid methyl esters.

[0286] Antioxidant additives may be used in amounts of about 0.01 to 10 (or 0.01 to 5, or 0.01 to less than 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.

[0287] Optionally, the lubricating composition may be free of phenolic antioxidants.

[0288] Optionally, the lubricating composition may be free of amine antioxidants, such as phenylamines, such as diphenylamines, such as alkylated diphenylamines. Optionally, the lubricating composition contains 0.1 to 3, such as 0.2 to 2, such as less than 0.3 mass % (such as 0.25 mass % or less, such as 0.2 mass % or less, such as 0.1 mass % or less, such as 0.05 mass % or less, such as 0 mass %) of amine antioxidants, such as alkylated phenylamines, such as di(alkyl-phenyl)amines, such as di(nonyl-phenyl)amines, based on the weight of the composition. In some embodiments, the lubricating oil composition may contain, may be substantially free of, or may be free of amine antioxidants, such as phenylamines, such as diphenylamines, such as alkylated diphenylamines, such as di(nonyl-phenyl)amines.

[0289] The compositions according to the present disclosure may contain additives having different listed functions and also having a secondary effect as antioxidants (e.g., phosphorus-containing antiwear agents such as ZDDP may also have an antioxidant effect). These additives are not counted as antioxidants for determining the amount of antioxidant in the lubricating oil compositions or concentrates herein. F. Pour Point Depressants

[0290] If desired, conventional pour point depressants (also known as lubricant flow improvers) may be added to the compositions of the present disclosure. These pour point depressants may be added to the lubricating compositions of the present disclosure to reduce the minimum temperature required for the fluid to flow or pour. Examples of suitable pour point depressants include polymethacrylates, polyacrylates, polyacrylamides, condensation products of halogenated paraffins and aromatic compounds, carboxylic acid vinyl ester polymers, and terpolymers of dialkyl fumarates, fatty acid vinyl esters, and allyl vinyl ethers. U.S. Patent Nos. 1,815,022; 2,015,748; 2,191,498; 2,387,501; 2,655,479; 2,666,746; 2,721,877; 2,721,878; and 3,250,715 describe useful pour point depressants and / or their preparation. Such additives may be used in amounts of about 0.01 to 5 wt %, preferably about 0.01 to 1.5 wt %, based on the weight of the lubricating composition. G. Defoaming agent

[0291] Defoamers can be advantageously added to the lubricant compositions described herein. These agents prevent or delay the formation of stable foam. Silicones and / or organic polymers are typical defoamers. For example, polysiloxanes (such as silicone oil) or polydimethylsiloxanes provide defoaming properties.

[0292] Defoamers are commercially available and can be used in minor amounts, such as 5 wt% or less, 3 wt% or less, 1 wt% or less, 0.1 wt% or less, such as 5 wt% to 0.1 ppm, such as 3 wt% to 0.5 ppm, such as 1 wt% to 10 ppm.

[0293] For example, it is possible that the lubricating oil composition comprises a defoamer comprising a polyalkylsiloxane, such as a polydialkylsiloxane, wherein the alkyl group is C1-C 10 Alkyl, such as polydimethylsiloxane (PDMS), also known as silicone oil. Alternatively, siloxane is poly(R 3 ) siloxane, wherein R 3 is one or more identical or different linear, branched or cyclic hydrocarbon radicals, such as alkyl or aryl radicals, which generally have 1 to 20 carbon atoms. It is possible, for example, that the lubricating oil composition comprises a polymeric siloxane compound according to the following formula 1, wherein R 1 and R 2 are independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl, phenyl, naphthyl, alkyl-substituted phenyl or isomers thereof (such as methyl, phenyl), and n is 2 to 1000, such as 50 to 450, or such as 40 to 100.

[0294] Additionally or alternatively, it is possible that the lubricating oil composition comprises an organo-modified siloxane (OMS), such as a polyether (e.g. ethylene-propylene oxide copolymer), a long-chain hydrocarbon group (e.g. C 11 -C 100 Alkyl) or aryl (e.g. C6-C 14 It is possible, for example, that the lubricating oil composition comprises an organic modified siloxane compound according to Formula 1, wherein n is 2 to 2000, such as 50 to 450 (or such as 40 to 100), and wherein R 1 and R 2 Same or different, any one of R 1 and R 2 Each independently is an organic group, such as selected from polyethers (such as ethylene oxide-propylene oxide copolymers), long-chain hydrocarbon groups (such as C 11 -C 100 Alkyl) or aryl (e.g. C6-C 14 aryl) organic group. Preferably, R 1 and R 2 One of them is CH3.

[0295] The siloxane according to Formula 1 is incorporated to provide about 0.1 to less than about 30 ppm Si, or about 0.1 to about 25 ppm Si, or about 0.1 to about 20 ppm Si, or about 0.1 to about 15 ppm Si, or about 0.1 to about 10 ppm Si, based on the total weight of the lubricant composition. More preferably, it is in the range of about 3-10 ppm Si.

[0296] In some embodiments, silicone anti-foam agents useful herein are available from Dow Corning Corporation and Union Carbide Corporation, such as Dow Corning FS-1265 (1000 centistokes), Dow Corning DC-200, and Union Carbide UC-L45. Silicone anti-foam agents useful herein include polydimethylsiloxanes, phenyl-methylpolysiloxanes, linear, cyclic or branched siloxanes, organosilicon polymers and copolymers, and / or organosilicon copolymers. Silicone polyether copolymer anti-foam agents available from OSI Specialties, Inc. of Farmington Hills, Michigan may also be substituted or included. One such material is sold as SILWET-L-7220.

[0297] Acrylate polymer defoamers may also be used herein. Typical acrylate defoamers include the polyacrylate defoamer known as PC-1244 available from Monsanto Polymer Products Co. A preferred acrylate polymer defoamer useful herein is PX TM 3841 (i.e. alkyl acrylate polymer), also known as Mobilad TM C402.

[0298] In some embodiments, a combination of a silicone defoamer and an acrylate defoamer may be used, such as in a weight ratio of silicone defoamer / acrylate defoamer of about 5:1 to about 1:5, see, for example, U.S. Patent Application Publication No. 2021 / 0189283. H. Viscosity Improver

[0299] Viscosity improvers (also referred to as viscosity index improvers or viscosity modifiers) other than the comb copolymer viscosity improvers described in Section B2 above may be included in the lubricating compositions described herein. Viscosity improvers provide high and low temperature operability to lubricants. These additives provide shear stability at elevated temperatures and acceptable viscosity 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 weight of these polymers is between about 10,000 and 1,500,000 g / mol, more typically about 20,000 to 1,200,000 g / mol, and more typically about 50,000 to 1,000,000 g / mol.

[0300] Examples of suitable viscosity modifiers are linear or star polymers and copolymers of butadiene, olefins or alkylated styrenes. Polyisobutylene is a commonly used viscosity modifier. Another suitable viscosity modifier is a polymethacrylate (e.g., a copolymer of alkyl methacrylates of various chain lengths) that is not included in the description of B2 above, in which some of the preparatons also serve as pour point depressants. Other suitable viscosity modifiers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (e.g., copolymers of acrylates of various chain lengths) that are not included in the description of B2 above. Specific examples include styrene-isoprene or styrene-butadiene based polymers (styrene-isoprene or styrene-butadiene based polymers) of 50,000 to 200,000 g / mol molecular weights.

[0301] Copolymers useful as viscosity modifiers include those available under the trade name "PARATONE TM "(such as "PARATONE TM 8921"、"PARATONE TM 68231" and "PARATONE TM 8941") from Chevron Oronite Company LLC; under the trade name "HiTEC TM "(such as HiTEC TM 5850B and HiTEC TM 5777) from Afton Chemical Corporation; and under the trade name "Lubrizol TM 7067C" available from The Lubrizol Corporation. Hydrogenated polyisoprene star polymers useful as viscosity modifiers herein include those available from Infineum International Limited, such as those sold under the trade designation "SV200 TM "and" SV600 TM ". Hydrogenated diene-styrene block copolymers useful as viscosity modifiers herein are available from Infineum International Limited, for example under the trade name "SV 50 TM ".

[0302] Polymers useful as viscosity modifiers herein include polymethacrylate or polyacrylate polymers, such as linear polymethacrylate or polyacrylate polymers, such as those available under the trade name "Viscoplex TM "(e.g. Viscoplex TM6-954) available from Evonik Industries, or under the trade name Asteric TM (e.g. Lubrizol TM 87708 and Lubrizol TM 87725) is a star polymer available from Lubrizol Corporation.

[0303] Vinyl aromatic-containing polymers useful as viscosity modifiers herein may be derived from vinyl aromatic monomers, such as styrenic monomers, such as styrene. Exemplary vinyl aromatic-containing copolymers useful herein may be represented by the following general formula: AB, wherein A is a polymeric block primarily derived from a vinyl aromatic monomer (such as styrene), and B is a polymeric block primarily derived from a conjugated diene monomer (such as isoprene).

[0304] Vinyl aromatic-containing polymers useful as viscosity improvers may have a kinematic viscosity at 100°C of 20 cSt or less, such as 15 cSt or less, such as 12 cSt or less, but may be diluted (such as in Group I, II and / or III base stocks) to a higher kinematic viscosity at 100°C, such as to 40 cSt or more, such as 100 cSt or more, such as 1000 cSt or more, such as 1000 to 2000 cSt.

[0305] Typically, the viscosity modifier can be used in an amount of about 0.01 to about 10 weight percent, such as about 0.1 to about 7 weight percent, such as 0.1 to about 4 weight percent, such as about 0.2 to about 2 weight percent, such as about 0.2 to about 1 weight percent, and such as about 0.2 to about 0.5 weight percent, based on the total weight of the formulated lubricant composition.

[0306] Viscosity improvers are usually added as concentrates in a large amount of diluent oil. "As delivered" viscosity improvers usually contain 20 to 75 weight percent active polymer for polymethacrylate or polyacrylate polymers, or 8 to 20 weight percent active polymer for olefin copolymers, hydrogenated polyisoprene star polymers or hydrogenated diene-styrene block copolymers in an "as delivered" polymer concentrate. I. Dispersants

[0307] During the operation of the engine, oil-insoluble oxidation byproducts are produced. Dispersants help keep these byproducts dissolved, thereby reducing their deposition on metal surfaces. The dispersants used in the formulation of the lubricating composition herein can be ashless or ash-forming in nature. The dispersant is preferably ashless. So-called ashless dispersants are organic materials that do not form ash substantially when burned. For example, metal-free dispersants or boronized metal-free dispersants are considered ashless. In contrast, metal-containing detergents tend to form ash when burned.

[0308] Dispersants other than those described in B1 above that can be used herein generally contain polar groups connected to relatively high molecular weight hydrocarbon chains. Polar groups generally contain at least one element of nitrogen, oxygen or phosphorus. Typical hydrocarbon chains contain 40 to 500, such as 50 to 400 carbon atoms. When used in the context of functionalized polymers acting as dispersants, molecular weights are generally reported for base polymers before modification. For example, molecular weights of PIBSA-PAM dispersants are generally reported for base polymers before functionalization with acylating agents (maleic acid or anhydride) and functional groups (such as polyamines). Therefore, the molecular weight of the dispersant herein belongs to the molecular weight of the base polymer from which the dispersant is derived. Dispersants of (Poly)alkenylsuccinic acid derivatives derivatives

[0309] One class of dispersants that is particularly useful includes (poly) alkenyl succinic acid derivatives, typically made by the reaction of a long chain hydrocarbyl-substituted succinic acid compound (typically a hydrocarbyl-substituted succinic anhydride) with a polyhydroxy or polyamino compound. The long chain hydrocarbyl group that constitutes the lipophilic portion of the molecule (which provides oil solubility) is typically a polyisobutylene group (the long chain hydrocarbyl group, such as a polyisobutylene group, typically has an Mn of 400 to 3000 g / mol, such as 450 to 2500 g / mol, such as 800 to 2500 g / mol or even 1000 to 1500 g / mol). Many examples of dispersants of this type are well known commercially and in the literature. Exemplary U.S. patents describing such dispersants include U.S. Patent Nos. 3,172,892; 3,2145,707; 3,219,666; 3,316,177; 3,341,542; 3,444,170; 3,454,607; 3,541,012; 3,630,904; 3,632,511; 3,787,374 and 4,234,435. Other types of dispersants are described in U.S. Patent Nos. 3,036,003; 3,200,107; 3,254,025; 3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,413,347; 3,697,574; 3,725,277; 3,725,480; 3,726,882; 4,454,059; 3,329,658; 3,449,250; 3,519,565; 3,666,730; 3,687,849; 3,702,300; 4,100,082; 5,705,458. Further descriptions of dispersants useful herein can be found, for example, in European Patent Application Nos. 0 471 071 and 0 451 380, to which reference is made for this purpose.

[0310] Hydrocarbyl-substituted succinic acid and hydrocarbyl-substituted succinic anhydride derivatives are useful dispersants. In particular, succinimide, succinate or succinate amide prepared by the reaction of a hydrocarbyl-substituted succinic acid or anhydride compound (typically having at least 25 carbon atoms, such as 28 to 400 carbon atoms in the hydrocarbyl substituent) with at least 1 equivalent of a polyhydroxy or polyamino compound (such as an alkyleneamine) are particularly useful for this. Hydrocarbyl-substituted succinic acid and hydrocarbyl-substituted succinic anhydride derivatives can have a number average molecular weight of at least 400 g / mol, such as at least 900 g / mol, such as at least 1500 g / mol, such as 400 to 4000 g / mol, such as 800 to 3000, such as 2000 to 2800 g / mol, such as about 2100 to 2500 g / mol, and such as about 2200 to about 2400 g / mol.

[0311] Succinimides particularly useful herein are typically formed by the condensation reaction between 1) a hydrocarbyl-substituted succinic anhydride, such as polyisobutylene succinic anhydride (PIBSA); and 2) a polyamine (PAM). Examples of suitable polyamines include: polyhydrocarbyl polyamines, polyalkylene polyamines, hydroxy-substituted polyamines, polyoxyalkylene polyamines, and combinations thereof. Examples of polyamines include tetraethylenepentamine, pentaethylenehexamine, tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), n-phenyl-p-phenylenediamine (ADPA), and other polyamines having an average of 5, 6, 7, 8, or 9 nitrogen atoms per molecule. Mixtures in which the average number of nitrogen atoms per polyamine molecule is greater than 7 are generally referred to as heavy polyamines or H-PAMs and may be referred to by trade names such as HPA. TM and HPA-X TM Purchased from Dow Chemical, E-100 TM Available from Huntsman Chemical, etc. Examples of hydroxy substituted polyamines include N-hydroxyalkyl-alkylene polyamines such as N-(2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)piperazine and / or N-hydroxyalkylated alkylene diamines of the type described, for example, in U.S. Pat. No. 4,873,009. Examples of polyoxyalkylene polyamines include polyoxyethylene and / or polyoxypropylene diamines and triamines (and co-oligomers thereof) having an average Mn of from about 200 to about 5000 g / mol. Products of this type are available under the trade name Jeffamine TM Representative examples of useful succinimides are shown in U.S. Patent Nos. 3,087,936; 3,172,892; 3,219,666; 3,272,746; 3,322,670; 3,652,616; 3,948,800; and 6,821,307; and in Canadian Patent No. 1,094,044.

[0312] Succinic acid esters useful as dispersants include those formed by the condensation reaction between a hydrocarbyl-substituted succinic anhydride and an alcohol or polyol. For example, the condensation product of a hydrocarbyl-substituted succinic anhydride and pentaerythritol is a useful dispersant.

[0313] The succinic acid ester amides available herein are formed by the condensation reaction between a hydrocarbyl-substituted succinic anhydride and an alkanolamine. Suitable alkanolamines include ethoxylated polyalkyl polyamines, propoxylated polyalkyl polyamines and polyalkenyl polyamines, such as polyethylene polyamines and / or propoxylated hexamethylene diamine. Representative examples are shown in U.S. Patent No. 4,426,305.

[0314] Hydrocarbyl-substituted succinic anhydride (e.g., PIBSA) esters of hydrocarbyl-bridged aryloxy alcohols can also be used as dispersants herein. For information on such dispersants, see U.S. Patent No. 7,485,603, particularly at column 2, line 65 to column 6, line 22 and column 23, line 40 to column 26, line 46. In particular, the PIBSA esters of methylene-bridged naphthoxyethanols (i.e., 2-hydroxyethyl-1-naphthol ethers (or hydroxy-terminated naphthol ethylene oxide oligomer ethers)) can be used herein.

[0315] The (poly)alkenyl succinic acid derivatives described herein, such as PIBSA, PIBSA-PAM, PIBSA esters, PIBSA ester amides, etc., are typically derived from a (poly)alkenyl material, such as polyisobutylene, having a molecular weight (Mn) of typically 350 to 4000 g / mol, such as 400 to 3000 g / mol, such as 450 to 2800 g / mol, such as 800 to 2500 g / mol or even 1000 to 1500 g / mol, such as 1200 to 1400 g / mol.

[0316] The hydrocarbyl-substituted succinic anhydride used in the preceding paragraphs typically has a molecular weight (Mn) of 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 or even 1000 to 1500 g / mol, such as 1200 to 1400 g / mol.

[0317] The dispersant may comprise one or more PIBSA-PAMs wherein the PIB is derived from polyisobutylene having an Mn of 600 to 5000 (e.g., 700 to 4000, such as 800 to 3000, such as 900 to 2500 g / mol or even 1000 to 1500 g / mol, such as 1200 to 1400 g / mol, such as about 1300 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.

[0318] The dispersant may comprise one or more PIBSA-PAMs wherein the PIB is derived from polyisobutylene having an Mn of 1000 to 1500 g / mol, such as 1200 to 1400 g / mol, such as about 1300 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.

[0319] The dispersant may comprise at least one first PIBSA-PAM wherein the PIB is derived from a polyisobutylene having an Mn of from 1000 to 1500 g / mol, such as from 1200 to 1400 g / mol, such as about 1300 g / mol, and at least one second PIBSA-PAM wherein the PIB is derived from a polyisobutylene having an Mn of from greater than 1500 to 5000 g / mol, such as from 1550 to 5000, such as from 1600 to 4000, such as from 1800 to 3000, such as from 1900 to 3000. The invention relates to a polyisobutylene having an Mn of from 200 to 2500 g / mol or even from 2000 to 2500 g / mol, wherein the polyamines used to prepare the first and second PIBSA-PAMs are the same or different and are typically derived from hydrocarbyl-substituted polyamines 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.

[0320] The above (poly)alkenylsuccinic acid derivatives can be post-reacted with various reagents, such as carbonates, sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid.

[0321] The dispersant may comprise one or more cyclic carbonates other than those described above in B1, such as 1,3-dioxolan-2-one (ethylene carbonate), post-treated (poly)alkenylsuccinic acid derivatives.

[0322] The dispersant may be present in the lubricant in an amount of 0.1 to 20 mass % of the composition, such as 0.2 to 15 mass %, such as 0.25 to 10 mass %, such as 0.3 to 5 mass %, such as 1.0 to 3.0 mass % of the lubricating oil composition.

[0323] The (poly)alkenylsuccinic acid derivatives described above may also be post-reacted with boron compounds such as boric acid, boric esters or highly borated dispersants to form borated dispersants typically having from about 0.1 to about 5 moles of boron per mole of dispersant reaction product.

[0324] Dispersants useful herein include boronated succinimides, including those derivatives from monosuccinimides, bis-succinimides and / or mixtures of mono- and bis-succinimides, wherein the hydrocarbyl succinimide is derived from a hydrocarbylene group, such as polyisobutylene, having an Mn of from about 300 to about 5000 g / mol, or from about 500 to about 3000 g / mol, or from about 1000 to about 2000 g / mol, or a mixture of such hydrocarbylene groups, typically having a high terminal vinyl group.

[0325] The boron-containing dispersant may be present at 0.01 wt % to 20 wt %, or 0.1 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 0.5 wt % to 8 wt %, or 1.0 wt % to 6.5 wt %, or 0.5 wt % to 2.2 wt % of the lubricating composition.

[0326] The boron-containing dispersant may be present in an amount to provide 15 ppm to 2000 ppm, or 25 ppm to 1000 ppm, or 40 ppm to 600 ppm, or 80 ppm to 350 ppm boron to the composition.

[0327] Borated dispersants can be used in combination with non-borated dispersants and can be the same or different compounds as the non-borated dispersants. In one embodiment, the lubricating composition can include one or more boron-containing dispersants and one or more non-borated dispersants, wherein the total amount of dispersants can 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 can be 1:10 to 10:1 (weight:weight) or 1:5 to 3:1 or 1:3 to 2:1. The dispersant can include one or more borated or non-borated poly(alkenyl) succinimides, wherein the polyalkenyl is derived from polyisobutylene and the imide is derived from a polyamine ("PIBSA-PAM").

[0328] The dispersant may comprise one or more boronated PIBSA-PAMs derived from a PIB having an Mn of 700 to 1800 g / mol (e.g., 800 to 1500 g / mol) and one or more non-boronated PIBSA-PAMs derived from a PIB having an Mn of greater than 1800 to 5000 g / mol (e.g., 2000 to 3000 g / mol). The dispersant may comprise one or more non-boronated PIBSA-PAMs derived from a PIB having an Mn of 700 to 1800 g / mol (e.g., 800 to 1500 g / mol) and one or more boronated PIBSA-PAMs derived from a PIB having an Mn of greater than 1800 to 5000 g / mol (e.g., 2000 to 3000 g / mol). The dispersant may comprise a PIBSA derived from a PIB having an Mn of 700 to 5000 g / mol, such as 800 to 3000 g / mol, and one or more boronated or non-boronated PIBSA-PAMs derived from a PIB having an Mn of 700 to 5000 g / mol. The dispersant may comprise a PIBSA-PAM derived from a PIB having an Mn of 700 to 5000 g / mol, such as 800 to 3000 g / mol, and one or more boronated or non-boronated PIBSA-PAMs derived from a PIB having an Mn of 700 to 5000 g / mol.

[0329] The dispersant may comprise a PIBSA derived from a PIB having a Mn of 700 to 5000 g / mol, such as 800 to 3000 g / mol, and one or more boronated or non-boronated PIBSA-PAMs derived from a PIB having a Mn of 700 to 5000 g / mol.

[0330] The dispersant may comprise a PIBSA derived from a PIB having an Mn of 700 to 5000 g / mol, such as 800 to 3000 g / mol, and one or more boronated PIBSA-PAMs derived from a PIB having an Mn of 700 to 1800 g / mol, such as 800 to 1500 g / mol, and one or more non-boronated PIBSA-PAMs derived from a PIB having an Mn of greater than 1800 to 5000 g / mol, such as 2000 to 3000 g / mol. The dispersant may comprise a PIBSA derived from a PIB having an Mn of 700 to 5000 g / mol, such as 800 to 3000 g / mol, one or more non-borated PIBSA-PAMs derived from a PIB having an Mn of 700 to 1800 g / mol, such as 800 to 1500 g / mol, and one or more borated PIBSA-PAMs derived from a PIB having an Mn of greater than 1800 to 5000 g / mol, such as 2000 to 3000 g / mol. The dispersant may comprise one or more optionally boronated higher molecular weight (Mn 1600 g / mol or higher, such as 1800 to 3000 g / mol) succinimides and one or more optionally boronated lower molecular weight (Mn less than 1600 g / mol) succinimides, wherein the higher molecular weight may be 1600 to 3000 g / mol, such as 1700 to 2800 g / mol, such as 1800 to 2500 g / mol, such as 1850 to 2300 g / mol; the lower molecular weight may be 600 to less than 1600 g / mol, such as 650 to 1500 g / mol, such as 700 to 1400 g / mol, such as 800 to 1300 g / mol, such as 850 to 1200 g / mol, such as 900 to 1150 g / mol, such as 900 to 1000 g / mol. The higher molecular weight succinimide dispersant may be present in the lubricating composition in an amount of 0.5 to 10 wt %, or 0.8 to 6 wt %, or 1.0 to 5 wt %, or 1.5 to 5 wt %, or 1.5 to 4.0 wt %; the lower molecular weight succinimide dispersant may be present in the lubricating composition in an amount of 1 to 5 wt %, or 1.5 to 4.8 wt %, or 1.8 to 4.6 wt %, or 1.9 to 4.6 wt %, or 2 wt % or more, such as 2 to 5 wt %. The lower molecular weight succinimide may differ from the higher molecular weight succinimide by 500 g / mol or more, such as by 750 g / mol or more, such as by 1000 g / mol or more, such as by 1200 g / mol or more, such as by 500 to 3000 g / mol, such as by 750 to 2000 g / mol, such as by 1000 to 1500 g / mol.

[0331] The dispersant may comprise one or more boronated or non-boronated PIBSA-PAMs and one or more PIBSA esters of hydrocarbyl-bridged aryloxy alcohols.

[0332] The dispersant may comprise one or more boronated PIBSA-PAMs and one or more non-boronated PIBSA-PAMs.

[0333] The dispersant may comprise one or more optionally boronated higher molecular weight (Mn 1600 g / mol or higher, such as 1800 to 3000 g / mol) PIBSA-PAMs and one or more optionally boronated lower molecular weight (Mn less than 1600 g / mol) PIBSA-PAMs, wherein the higher molecular weight may be 1600 to 3000 g / mol, such as 1700 to 2800 g / mol, such as 1800 to 2500 g / mol, such as 1850 to 2300 g / mol; and 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 1200 g / mol. The higher molecular weight PIBSA-PAM dispersant can be present in the lubricating composition in an amount of 0.5 to 10 wt %, or 0.8 to 6 wt %, or 1.0 to 5 wt %, or 1.5 to 5 wt %, or 1.5 to 4.0 wt %; the lower molecular weight PIBSA-PAM dispersant can be present in the lubricating composition in an amount of 1 to 5 wt %, or 1.5 to 4.8 wt %, or 1.8 to 4.6 wt %, or 1.9 to 4.6 wt %, or 2 wt % or more, such as 2 to 5 wt %. Dispersants of Mannich Bases

[0334] Mannich base dispersants useful herein are typically made by the reaction of an amine component, a hydroxy aromatic compound (substituted or unsubstituted, such as alkyl substituted), such as an alkyl phenol, and an aldehyde, such as formaldehyde. See U.S. Pat. Nos. 4,767,551 and 10,899,986. Processing aids and catalysts, such as oleic acid and sulfonic acid, may also be part of the reaction mixture. Representative examples are shown in U.S. Pat. Nos. 3,697,574; 3,703,536; 3,704,308; 3,751,365; 3,756,953; 3,798,165; 3,803,039; 4,231,759; 9,938,479; 7,491,248; and 10,899,986 and PCT Publication No. WO 01 / 42399. Polymethacrylate or polyacrylate derivative dispersant

[0335] Polymethacrylate or polyacrylate derivatives are another class of dispersants useful herein. These dispersants are typically prepared by reacting nitrogen-containing monomers with methacrylate or acrylate containing 5-25 carbon atoms in the ester group. Representative examples are shown in U.S. Pat. Nos. 2,100,993 and 6,323,164. Polymethacrylate and polyacrylate dispersants are typically of relatively low molecular weight.

[0336] The lubricating composition of the present disclosure typically comprises 0.1 to 20 mass % of the composition, such as 0.2 to 15 mass %, such as 0.25 to 10 mass %, such as 0.3 to 5 mass %, such as 2.0 to 4.0 mass % of the lubricating oil composition of the dispersant. Alternatively, the dispersant may be present at 0.1 to 5 wt %, or 0.01 to 4 wt % of the lubricating composition.

[0337] For further information on dispersants useful herein, see U.S. Pat. No. 10,829,712 at column 13, line 36 to column 16, line 67, and U.S. Pat. No. 7,485,603 at column 2, line 65 to column 6, line 22, column 8, line 25 to column 14, line 53, and column 23, line 40 to column 26, line 46.

[0338] The compositions according to the present disclosure may contain additives having different listed functions and also having a second effect as a dispersant (e.g., the above-mentioned component B functionalized polymers may also have a dispersant effect). For determining the amount of dispersant in the lubricating oil composition or concentrate herein, these additives are not counted as dispersants. J.Corrosion Inhibitors / Anti-rust Agents

[0339] Corrosion inhibitors can be used to reduce the corrosion of metals and are also commonly referred to as metal deactivators or metal passivators. Some corrosion inhibitors can also be characterized as antioxidants.

[0340] Suitable corrosion inhibitors may include nitrogen and / or sulfur containing heterocyclic compounds such as triazoles (e.g., benzotriazole), substituted thiadiazoles, imidazoles, thiazoles, tetrazoles, hydroxyquinolines, oxazolines, imidazolines, thiophenes, indoles, indazoles, quinolines, benzoxazines, dithiols, oxazoles, oxatriazoles, pyridines, piperazines, triazines, and derivatives of any one or more thereof. A specific corrosion inhibitor is benzotriazole as shown in the following structure: Where R 8 There is no (hydrogen) or it may be linear or branched, saturated or unsaturated C1 to C 20Hydrocarbyl or substituted hydrocarbyl. It may contain a ring structure that is alkyl or aryl in nature and / or contain heteroatoms, such as N, O or S. Examples of suitable compounds may include benzotriazole, alkyl-substituted benzotriazoles (e.g., tolyltriazole, ethylbenzotriazole, hexylbenzotriazole, octylbenzotriazole, etc.), aryl-substituted benzotriazoles, alkylaryl- or arylalkyl-substituted benzotriazoles, etc., and combinations thereof. For example, the triazole may include or be benzotriazole and / or an alkylbenzotriazole, wherein the alkyl group contains 1 to about 20 carbon atoms, or 1 to about 8 carbon atoms. Non-limiting examples of such corrosion inhibitors may include or be benzotriazole, tolyltriazole and / or optionally substituted benzotriazoles, such as Irgamet® available from BASF of Ludwigshafen, Germany. TM 39. Preferred corrosion inhibitors may comprise or be benzotriazole and / or tolyltriazole.

[0341] Additionally or alternatively, the corrosion inhibitor may include one or more N-substituted triazoles, such as 1,2,4 triazoles, such as those described in paragraphs

[0020] to

[0044] of WO2019 / 236441. Non-limiting examples of such corrosion inhibitors include compounds of the formula:

[0342] Where R 1 and R 2 are independently H, C1 to C 22 , such as C2 to C 20 , such as C3 to C 18 , such as C3 to C 16 , such as C3 to C 12 Linear, cyclic or branched hydrocarbons, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, ethylhexyl, dimethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, phenyl, benzyl, etc. R 1 and R 2 The corrosion inhibitors may be the same or different and may be linked to form a ring structure. In some embodiments, the corrosion inhibitors that may be used are Irgamet TM 30 1H-1,2,4-Triazole-1-methylamine-N,N-bis(2-ethylhexyl)-1H-1,2,4-triazole-1-methylamine-N,N-bis(2-ethylhexyl)-1H ... Additionally or alternatively, the corrosion inhibitor may include one or more substituted thiadiazoles of the following structures: Where R 15and R 16 is independently hydrogen or a hydrocarbon group, which group can be aliphatic or aromatic, including cyclic, alicyclic, aralkyl, aryl and alkaryl, and wherein each w is independently 1, 2, 3, 4, 5 or 6 (preferably 2, 3 or 4, such as 2). These substituted thiadiazoles are derived from 2,5-dimercapto-1,3,4-thiadiazole (DMTD) molecules. Many derivatives of DMTD have been described in the art, and any such compound may be included in the fluid used in the present disclosure. For example, U.S. Patent Nos. 2,719,125; 2,719,126; and 3,087,937 describe the preparation of various 2,5-bis-(hydrocarbon dithio)-1,3,4-thiadiazoles.

[0343] Additionally or alternatively, the corrosion inhibitor may include one or more other DMTD derivatives, such as carboxylic acid esters, wherein R 15 and R 16 The carbonyl group may be attached to the sulfide sulfur atom. The preparation of these thioester-containing DMTD derivatives is described, for example, in U.S. Pat. No. 2,760,933. DMTD derivatives prepared by condensation of DMTD with an α-halogenated aliphatic carboxylic acid having at least 10 carbon atoms are described, for example, in U.S. Pat. No. 2,836,564. This method produces DMTD derivatives in which R 15 and R 16 It is HOOC-CH(R 19 )-(R 19 DMTD derivatives further prepared by amidation or esterification of these terminal carboxylic acid groups are also useful.

[0344] The preparation of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazoles is described, for example, in US Pat. No. 3,663,561.

[0345] One class of DMTD derivatives may include a mixture of 2-alkyldithio-5-mercapto-1,3,4-thiadiazole and 2,5-bis-alkyldithio-1,3,4-thiadiazole. Such a mixture may be marketed under the trade name HiTEC TM 4313 is sold and available from Afton Chemical Company.

[0346] The preparation of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazoles is described, for example, in US Pat. No. 3,663,561.

[0347] One class of DMTD derivatives may include a mixture of 2-alkyldithio-5-mercapto-1,3,4-thiadiazole and 2,5-bis-alkyldithio-1,3,4-thiadiazole. Such a mixture may be marketed under the trade name HiTEC TM4313 is sold and available from Afton Chemical Company.

[0348] Additionally or alternatively, the corrosion inhibitor may include a compound having the structure B(OR 46 )3 trifunctional borate ester, wherein each R 46 Since the borate ester is generally ideally compatible with the non-aqueous medium of the composition, each R 46 In particular, it may comprise or be a hydrocarbyl C1-C8 moiety. For compositions wherein the non-aqueous medium comprises or is a lubricating oil base stock, for example, when the hydrocarbyl moieties are each at least C4, better compatibility can generally be achieved. Non-limiting examples of such corrosion inhibitors therefore include, but are not limited to, triethyl borate, tripropyl borate such as triisopropyl borate, tributyl borate such as tri-tert-butyl borate, tripentyl borate, trihexyl borate, trioctyl borate such as tri-(2-ethylhexyl) borate, monohexyl dibutyl borate, and the like, and combinations thereof.

[0349] When used, the corrosion inhibitor may comprise a substituted thiadiazole, a substituted benzotriazole, a substituted triazole, a trisubstituted borate, or a combination thereof.

[0350] When desired, corrosion inhibitors may be used in any effective amount, but when used, may generally be used in an amount of about 0.001 wt % to 5.0 wt %, such as 0.005 wt % to 3.0 wt % or 0.01 wt % to 1.0 wt %, based on the weight of the composition. Alternatively, such additives may be used in an amount of about 0.01 to 5 wt %, preferably about 0.01 to 1.5 wt %, based on the weight of the lubricating composition.

[0351] In some embodiments, the 3,4-oxypyridinone-containing composition can be substantially free (e.g., 0, or less than 0.001 wt %, 0.0005 wt % or less, no intentional addition, and / or absolutely free) of triazole, benzotriazole, substituted thiadiazole, imidazole, thiazole, tetrazole, hydroxyquinoline, oxazoline, imidazoline, thiophene, indole, indazole, quinoline, benzoxazine, dithiol, oxazole, oxatriazole, pyridine, piperazine, triazine, derivatives thereof, combinations thereof, or all corrosion inhibitors.

[0352] The compositions according to the present disclosure may contain additives having different listed functions and also having a second effect as corrosion inhibitors (e.g., the above-mentioned component B functionalized polymers may also have a corrosion inhibitor effect). For determining the amount of corrosion inhibitor in the lubricating oil composition or concentrate herein, these additives are not counted as corrosion inhibitors. K. Anti-wear agent

[0353] 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 dithiophosphate, metal (e.g., Pb, Sb, Mo, etc.) salts of dithiophosphoric acid, metal (e.g., Zn, Pb, Sb, Mo, etc.) salts of dithiocarbamic acid, metal (e.g., Zn, Pb, Sb, etc.) salts of fatty acids, boron compounds, phosphates, phosphites, amine salts of phosphates or thiophosphoric acid esters, reaction products of dicyclopentadiene and thiophosphoric acid, and combinations thereof. Based on the gross weight of the lubricating oil composition, the amount of the anti-wear agent may be from about 0.01 wt % to about 5 wt %, from about 0.05 wt % to about 3 wt %, or from about 0.1 wt % to about 1 wt %.

[0354] In some embodiments, the antiwear agent is or comprises a dialkyl dithiophosphate metal salt, such as a dialkyl dithiophosphate zinc compound. The metal of the dialkyl dithiophosphate metal salt can be an alkali metal or an alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper. In some embodiments, the metal is zinc. In other embodiments, the alkyl group of the dialkyl dithiophosphate metal salt has about 3 to about 22 carbon atoms, about 3 to about 18 carbon atoms, about 3 to about 12 carbon atoms, or about 3 to about 8 carbon atoms. In further embodiments, the alkyl group is linear or branched.

[0355] Useful antiwear agents also include substituted or unsubstituted thiophosphoric acids, salts thereof including zinc-containing compounds such as zinc dithiophosphate compounds selected from the group consisting of dialkyl-, diaryl- and / or alkylaryl-zinc dithiophosphates.

[0356] Metal alkylthiophosphates, more particularly metal dialkyl dithiophosphates wherein the metal component is zinc, or zinc dialkyl dithiophosphate (ZDDP) can be useful components of the lubricating compositions of the present disclosure. ZDDP can be derived from a primary alcohol, a secondary alcohol, or a mixture thereof. ZDDP compounds generally have the formula Zn[SP(S)(OR1)(OR2)]2, wherein R1 and R2 are C1-C 18 Alkyl, preferably C2-C 12Alkyl. These alkyl groups can be straight chain or branched. The alcohol used in ZDDP can be 2-propanol, butanol, sec-butanol, amyl alcohol, hexanol, such as 4-methyl-2-pentanol, n-hexanol, n-octanol, 2-ethylhexanol, alkylated phenols, etc. A secondary alcohol mixture or a mixture of a primary alcohol and a secondary alcohol can be used. Alkyl aryl groups can also be used. Available zinc dithiophosphates include secondary zinc dithiophosphates (secondary zinc dithiophosphates), such as the trade names "LZ 677A", "LZ 1095" and "LZ 1371" available from The Lubrizol Corporation, the trade name "OLOA 262" available from Chevron Oronite and the trade name "HITEC TM 7169" from Afton Chemical.

[0357] In some embodiments, the zinc compound can be a zinc dithiocarbamate complex, such as the zinc dithiocarbamate shown in the following formula: Among them, each R I is independently a linear, cyclic or branched, saturated or unsaturated aliphatic hydrocarbon moiety having 1 to about 10 carbon atoms, n is 0, 1 or 2, L is a ligand that saturates the zinc coordination sphere, and x is 0, 1, 2, 3 or 4. In certain embodiments, the ligand L is selected from water, hydroxide, ammonia, amino, amido, alkylthiolate, halide, and combinations thereof.

[0358] Antiwear additives, such as ZDDP and / or zinc carbamate are typically used in an amount of about 0.4 wt % to about 1.2 wt %, preferably about 0.5 wt % to about 1.0 wt %, more preferably about 0.6 wt % to about 0.8 wt %, based on the total weight of the lubricating composition, although more or less may often be used to advantage. Preferably, the antiwear additive is 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.

[0359] Antiwear additives useful herein also include boron-containing compounds such as borate esters, borated fatty amines, borated epoxides, alkali metal (or mixed alkali metal or alkaline earth metal) borates and borated overbased metal salts.

[0360] The compositions according to the present disclosure may contain additives having different listed functions and also having a second effect as corrosion inhibitors (e.g., the above-mentioned component B functionalized polymers may also have an antiwear effect). For determining the amount of antiwear agent in the lubricating oil composition or concentrate herein, these additives are not counted as antiwear agents. L. Demulsifier

[0361] Demulsifiers useful herein include those described in U.S. Patent No. 10,829,712 (column 20, lines 34 to 40). Generally, a small amount of demulsifying components may be used herein. Preferred demulsifying components are described in European Patent No. 330522. They are obtained by reacting an alkylene oxide with an adduct obtained by reacting a diepoxide with a polyol. Such additives may be used in an amount of about 0.001 to 5% by weight, preferably about 0.01 to 2% by weight. M. Seal Compatibility Agents

[0362] 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 some embodiments, the seal compatibilizer is a seal swelling agent, such as PIBSA (polyisobutylenyl succinic anhydride). N. Extreme Pressure Agents

[0363] The lubricating oil composition of the present disclosure may contain one or more extreme pressure agents that can prevent the sliding metal surface from biting under extreme pressure conditions. Any extreme pressure agent known to those of ordinary skill in the art can be used for the lubricating oil composition. Generally, an extreme pressure agent is a compound that can be chemically combined with a metal to form a surface film, which prevents the welding of asperities in the relative metal surface under high load. Non-limiting examples of suitable extreme pressure agents include sulfurized animal or vegetable fats or oils, sulfurized animal or vegetable fatty acid esters, trivalent or pentavalent phosphorus-containing esters that are completely or partially esterified, sulfurized olefins, dialkyl polysulfides, sulfurized Diels-Alder adducts, sulfurized dicyclopentadiene, sulfurized or co-sulfurized mixtures of fatty acid esters and monounsaturated olefins, co-sulfurized blends of fatty acids, fatty acid esters and alpha-olefins, functionally substituted dialkyl polysulfides, thioaldehydes, thioketones, table thio compounds, sulfur-containing acetal derivatives, co-sulfurized blends of terpenes and acyclic olefins, polysulfide olefin products, amine salts of phosphates or thiophosphates, and combinations thereof. The amount of the extreme pressure agent may vary from about 0.01 wt % to about 5 wt %, from about 0.05 wt % to about 3 wt %, or from about 0.1 wt % to about 1 wt %, based on the total weight of the lubricating oil composition. O. Non-basestock Unsaturated Hydrocarbons

[0364] The lubricating oil composition of the present disclosure may contain one or more unsaturated hydrocarbons. These unsaturated hydrocarbons are different from any base oil (Group I, II, III, IV and / or V lubricating oil base stocks) and / or viscosity improvers that may be present in the composition, and always have at least one (usually only one in the case of linear alpha olefins or LAOs) unsaturation per molecule. Without being bound by theory, the unsaturation can provide antioxidant function and / or sulfur capture function, 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 function and the only corrosion inhibition function in the lubricating oil composition. Non-limiting examples of unsaturated hydrocarbons may include one or more unsaturated C 12 -C 60 Hydrocarbons (such as C 12 -C 48 Hydrocarbon, C 12 -C 36 Hydrocarbon, C 12 -C 30 Hydrocarbon or C 12 -C 24 The unsaturated hydrocarbon (LAO) may be referred to as a linear alpha olefin (LAO) when only one unsaturation is present. Other non-limiting examples of unsaturated hydrocarbons may include polyisobutylene oligomers / polymers that retain (or are modified after polymerization to exhibit) (near) terminal unsaturation, and / or blends thereof. When present, the unsaturated hydrocarbon (LAO) may be present in an amount of 0.01 to 5 wt % (particularly 0.1 to 3 wt %, or 0.1 to 1.5 wt %) based on the total weight of the lubricating oil composition.

[0365] When the lubricating oil composition contains one or more of the additives discussed above, the additives are generally blended into the composition in an amount sufficient to enable them to perform their intended function. Typical amounts of such additives useful in the present disclosure, especially for crankcase lubricants, are shown in the following table.

[0366] It is noted that many additives are shipped from additive manufacturers as concentrates containing one or more additives together with a certain amount of base oil or other diluent. Therefore, the weights in the following table and other amounts mentioned herein relate to the amount of active ingredient (i.e., the diluent-free portion of the ingredient). The weight % (mass %) shown below is based on the total weight of the lubricating oil composition. Typical amounts of lubricant components

[0367] Typical Amounts of Lubricant Components in LOC (Continued)

[0368] Typical Amounts of Lubricant Components in LOC (Continued)

[0369] The above-mentioned additives are generally commercially available materials. These additives can be added separately, but are usually pre-combined in packages available from lubricant additive suppliers. Additive packages with various ingredients, proportions and properties are available and the selection of an appropriate package will take into account the use of the final composition. fuel

[0370] The present disclosure also relates to a method for lubricating an automotive internal combustion engine during engine operation, comprising: (i) providing a lubricating composition as described herein to a crankcase of an automotive internal combustion engine; (ii) providing a hydrocarbon fuel in an automotive internal combustion engine; and (iii) combusting the fuel in an 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 car engine (such as a spark ignition internal combustion engine).

[0371] The present disclosure also relates to a fuel composition comprising the lubricating oil composition described herein and a hydrocarbon fuel, wherein the fuel may be derived from petroleum and / or biological sources ("biofuel" or "renewable fuel"). In some embodiments, the fuel comprises 0.1 to 100 mass % renewable fuel, or 1 to 75 mass % renewable fuel, or 5 to 50 mass % renewable fuel, based on the total mass of renewable fuel and petroleum-derived fuel.

[0372] Renewable fuel components are typically made from vegetable oils (such as palm oil, rapeseed oil, soybean oil, jatropha oil), microbial oils (such as algae oil), animal fats (such as edible oils, animal fats and / or fish fats) and / or biogas. Renewable fuel refers to biofuels made from biological resources formed by contemporary biological processes. In one embodiment, the renewable fuel component is made with the aid of a hydrotreatment process. Hydrotreatment involves various reactions in which molecular hydrogen reacts with other components, or components undergo molecular transformations in the presence of molecular hydrogen and a solid catalyst. The reactions include, but are not limited to, hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrocracking and isomerization. Renewable fuel components can have different distillation ranges to provide the component with desired properties according to the intended use. use

[0373] The lubricating compositions of the present disclosure can be used to lubricate mechanical engine components by adding lubricants thereto, particularly in internal combustion engines, such as spark ignition, spark assisted compression ignition or compression ignition two-stroke or four-stroke reciprocating engines. Typically, they are crankcase lubricants, such as passenger car motor oils or heavy-duty diesel engine lubricants.

[0374] In particular, the lubricating composition of the present disclosure is suitably used for lubrication of the crankcase of a compression ignition internal combustion engine, such as a heavy-duty diesel engine.

[0375] In particular, the lubricating composition of the present disclosure is suitably used for lubrication of the crankcase of a spark-ignition turbocharged internal combustion engine.

[0376] In particular, the lubricating compositions of the present disclosure are suitable for lubrication of passenger car crankcases of spark-ignited (optionally turbocharged) internal combustion engines.

[0377] In some embodiments, the lubricating oils of the present disclosure are used in spark-assisted high compression internal combustion engines, and when used in high compression spark-ignition internal combustion engines, the lubricating oil compositions of the present disclosure can be used to lubricate high compression spark-ignition engines.

[0378] In some embodiments, the lubricating compositions of the present disclosure are suitable for lubrication of the crankcase of an engine of a heavy-duty diesel vehicle (ie, a heavy-duty diesel vehicle having a gross vehicle weight of 10,000 pounds or more).

[0379] In some embodiments, the lubricating compositions of the present disclosure are suitably used for lubrication of the crankcase of a passenger car diesel engine.

[0380] In particular, the lubricating oil formulations of the present disclosure are particularly useful in compression ignition internal combustion engines, ie, heavy duty diesel engines, using low viscosity oils such as API FA-4 and future oil classes where valve train wear protection becomes challenging.

[0381] The use of the compositions described herein, especially those having a flat viscosity curve, has improved fuel efficiency. Lubricating oil compositions comprising the comb copolymers described herein, especially in combination with the end-capped dispersants described herein, have enhanced fuel economy improvements compared to Toyota 0W-8 GLV-1 lubricating oil.

[0382] The present disclosure further relates to: 1. A lubricating oil composition comprising the following components or a mixture of the following components: (i) at least 50% by mass, based on the weight of the lubricating oil composition, of a base oil, (ii) at least one end-capped dispersant derived from a polymer having a number average molecular weight (Mn) of less than 1600 g / mol, (iii) at least one magnesium-containing detergent, (iv) at least one calcium-containing detergent, (v) at least one copolymer viscosity improver having, when 1), 2) and 3) are measured on a blend of said copolymer viscosity improver and a Group III base oil having a KV100 of about 4 cSt (ASTM D445) and a viscosity index of about 120 (ASTM D2270) having a KV100 of about 8 cSt: 1) A relative KV140 / relative KV20 ratio of 1.9 or higher; 2) a relative KV100 / relative KV70 ratio of 1.30 or higher; and 3) Viscosity index of 320 or higher (ASTM 2270D). 2. The lubricating oil composition of paragraph 1, wherein the blocked dispersant is represented by the following formula: Among them, each R 11 and R 12 are independently hydrogen or a hydrocarbon group, provided that R 11 and R 12 are not all hydrogen; z is an integer from 0 to 10; and each R 13 is independently acetyl, or wherein the two closest R 13 Groups can be linked together. 3. The lubricating oil composition of paragraph 1 or 2, wherein the copolymer viscosity improver is a comb copolymer having repeating units derived from a hydrogenated polybutadiene-based (alk) acrylate ester macromonomer. 4. The lubricating oil composition of paragraph 1, 2 or 3, wherein the Group III base oil of component (v) has a KV140 of 2 cSt, a KV20 of 44 cSt and a KV70 of 19 cSt (ASTM D445). 5. A lubricating oil composition comprising the following components or a mixture of the following components: (i) at least 50% by mass, based on the weight of the lubricating oil composition, of a base oil, (ii) at least one end-capped dispersant derived from a polymer having a number average molecular weight (Mn) of less than 1600 g / mol, wherein the end-capped dispersant is represented by the formula: Among them, each R11 and R 12 are independently hydrogen or a hydrocarbon group, provided that R 11 and R 12 are not all hydrogen; z is an integer from 0 to 10; and each R 13 is independently acetyl, or wherein the two closest R 13 Groups can be linked together; (iii) at least one magnesium-containing detergent, (iv) at least one calcium-containing detergent, (v) at least one comb copolymer viscosity modifier comprising the reaction product of at least the following monomers: (a) hydrogenated polybutadiene-based (alk) acrylate ester macromonomer; (b) (Alkyl) acrylic acid C3-C8 alkyl ester monomer; (c) (Alkyl) acrylic acid C 12 -C 24 Alkyl ester monomers; and (d)C1-C 18 Alkyl-terminated or C6-C 20 Aryl-, aralkyl- or alkylaryl-terminated C2-C6 oxyalkyl or C2-C6 oligo(alkylene glycol) type (alkyl) acrylate monomers (C1-C 18 Alkyl-endcapped or C6-C 20 aryl-,aralkyl-,or alkaryl-endcapped C2-C6oxyalkyl or C2-C6 oligo(alkylene glycol)-based(alk)acrylate ester monomer) and / or hydroxyalkyl or H-endcapped oligo(alkylene glycol)-based(alk)acrylate monomer having the following structure (II): Where R 2 represents hydrogen or C1-C2 alkyl, and m is 2 to 6, such that -(CH2) m - represents a linear, branched and / or cyclic alkyl group between oxygen, n is 1 to 10, and R 1Represents H, C1-C 18 Linear, branched and / or cyclic alkyl end groups or C6-C 20 Aryl, aralkyl or alkaryl end groups, wherein the combination of (c) and (d) together constitute greater than 20.0 weight percent of the repeating units of the comb copolymer viscosity modifier, based on the weight of all repeating units in the copolymer. 6. The lubricating oil composition of paragraph 1, 2, 3, 4 or 5, further comprising a metal alkylthiophosphate, wherein the alkyl group is derived from at least one secondary alcohol. 7. The lubricating oil composition of paragraphs 1, 2, 3, 4 or 5, wherein the alkyl group of the metal alkylthiophosphate is derived from at least one primary alcohol and at least one secondary alcohol. 8. The lubricating oil composition of paragraphs 1, 2, 3, 4 or 5, wherein the metal alkylthiophosphate comprises one or more zinc dialkyldithiophosphates, wherein the alkyl group is derived at least in part from a secondary alcohol or a mixture of a primary and secondary alcohol. 9. The lubricating oil composition of paragraph 6, 7 or 8, wherein the metal alkylthiophosphate is represented by the formula Zn[SP(S)(OR1)(OR2)]2, wherein R1 and R2 are each independently C1-C 18 Alkyl, preferably wherein one, two, three and / or four of R1 and R2 are secondary C2-C 12 alkyl. 10. The lubricating oil composition of any one of paragraphs 1 to 9, further comprising 1) a molybdenum-containing material providing 20 to 40 ppm Mo to the lubricating oil composition, 2) a zinc alkylthiophosphate wherein the alkyl group is derived from at least one secondary alcohol, 3) about 3.3 mass % of the blocked dispersant. 11. The lubricating oil composition of any one of paragraphs 1 to 10, wherein the lubricating oil composition preferably has: a) less than or equal to 30 mass % (e.g., 15-30 mass %, such as 19-28 mass %) volatility as measured by the Noack test (ASTM D5800, Procedure B), based on the total mass of the lubricating composition; and / or b) a ratio of calcium from detergent to magnesium from detergent of from 10:1 to 2:1; and / or c) A total soap content of less than 30 mmol. 12. The lubricating oil composition of any of paragraphs 1 to 11, wherein the capped dispersant is an ethylene carbonate capped PIBSA PAM composition derived from polyisobutylene having a number average molecular weight of 1200 to 1400 g / mol and a polyamine. 13. The lubricating composition of any of paragraphs 1 to 12, further comprising one or more of the following components: D) one or more friction modifiers; E) one or more antioxidants; F) one or more pour point depressants; G) one or more defoaming agents; H) one or more viscosity improvers other than the comb copolymer of (v); 1) one or more dispersants; J) one or more inhibitors and / or rust inhibitors; and / or K) One or more antiwear agents. 14. The lubricating composition of any of paragraphs 1 to 13, wherein: A) the base oil is present in an amount of 50 to 99 mass % based on the weight of the lubricating oil composition; and B) the blocked dispersant is present in an amount of 0.1 to 10 wt % based on the total weight of the lubricating oil composition; and C1) the detergent is present in an amount of 0.1 to 20 wt % based on the total weight of the lubricating oil composition; and C2) The copolymer viscosity modifier is present at 0.1 to 10 wt %, based on the total weight of the lubricating oil composition. 15. The lubricating composition of paragraph 14, wherein: D) one or more friction modifiers are optionally present at 0.01 to 5 weight percent, based on the total weight of the lubricating composition; E) one or more antioxidants are optionally present at 0.01 to 5 wt % based on the total weight of the lubricating composition; F) optionally, one or more pour point depressants are present at 0.01 to 5 weight percent, based on the total weight of the lubricating composition; G) optionally, one or more defoaming agents are present at 0.001 to 5 wt %, based on the total weight of the lubricating composition; H) optionally, one or more viscosity improvers other than (v) are present at 0.001 to 6 wt %, based on the total weight of the lubricating composition; I) optionally, one or more dispersants are present at 0.01 to 20 wt % based on the total weight of the lubricating composition; J) Optionally, one or more inhibitors and / or rust preventives are present at 0.01 to 5 wt. %, based on the total weight of the lubricating composition. 16. The lubricating composition according to any one of paragraphs 1 to 15, wherein the lubricating composition is a passenger car motor oil, a light duty diesel engine oil or a heavy-duty diesel engine oil. 17. A method of lubricating an internal combustion engine during engine operation, comprising: (i) providing the lubricating composition of any one of paragraphs 1 to 16 to a crankcase of the internal combustion engine; (ii) providing a hydrocarbon fuel, a renewable fuel and / or an alternative fuel in the internal combustion engine; and (iii) combusting the fuel in the internal combustion engine. 18. The method of paragraph 17, wherein the internal combustion engine is an automotive internal combustion engine. 19. The method of paragraph 17 or 18, wherein the internal combustion engine is a gasoline or diesel automotive internal combustion engine. 20. A concentrate composition comprising: (i) less than 50% by mass, based on the weight of the composition, of a base oil, (ii) at least one end-capped dispersant having a number average molecular weight (Mn) of less than 1600 g / mol and represented by the formula: Among them, each R 11 and R 12 are independently hydrogen or a hydrocarbon group, provided that R 11 and R 12 are not all hydrogen; z is an integer from 0 to 10 (e.g., from 1 to 8); and each R 13 is independently acetyl, or wherein the two closest R 13 Groups can be linked together; (iii) at least one magnesium-containing detergent and at least one calcium-containing detergent, wherein the ratio of calcium from the detergent to magnesium from the detergent is from 10:1 to 2:1; and (iv) at least one comb copolymer viscosity modifier comprising the reaction product of at least the following monomers: (a) hydrogenated polybutadiene-based (alk) acrylate ester macromonomer; (b) (Alkyl) acrylic acid C3-C8 alkyl ester monomer; (c) (Alkyl) acrylic acid C 12 -C 24Alkyl ester monomers; (d)C1-C 18 Alkyl-terminated or C6-C 20 Aryl-, aralkyl- or alkylaryl-terminated C2-C6 oxyalkyl or C2-C6 oligo(alkylene glycol) type (alkyl) acrylate monomers (C1-C 18 Alkyl-endcapped or C6-C 20 aryl-,aralkyl-,or alkaryl-endcapped C2-C6oxyalkyl or C2-C6 oligo(alkylene glycol)-based(alk)acrylate ester monomer) and / or hydroxyalkyl or H-endcapped oligo(alkylene glycol)-based(alk)acrylate monomer having the following structure (II): Where R 2 represents hydrogen or C1-C2 alkyl, and m is 2 to 6, such that -(CH2) m - represents a linear, branched and / or cyclic alkyl group between oxygen, n is 1 to 10, and R 1 Represents H, C1-C 18 Linear, branched and / or cyclic alkyl end groups or C6-C 20 aryl, aralkyl or alkaryl end groups, wherein the combination of (c) and (d) together constitute greater than 20.0 weight percent of the repeating units of the comb copolymer viscosity modifier, based on the weight of all repeating units in the copolymer; (v) optionally, a metal alkylthiophosphate, wherein the alkyl group is derived from at least one secondary alcohol; (vi) optionally, a molybdenum-containing compound; and (vii) optionally, an antioxidant. 21. A lubricating oil composition (such as the composition of any of paragraphs 1 to 16), comprising a PIBSA-PAM dispersant composition derived from a first polyamine and a first PIB having a number average molecular weight of 1200 to 1400 g / mol, the PIBSA-PAM dispersant composition having a 100 sec -1 The viscosity at a shear rate of 0.01 to 0.03 Pa.s and at 10 sec -1 Viscosity of 0.15 Pa.s or less at a shear rate (Haake carbon black test 9 wt% carbon black, 1 to 10 s -1and 10 to 1000s -1 shear rate range). 22. A lubricating oil composition (such as the composition of any of paragraphs 1 to 16), comprising a first PIBSA-PAM dispersant composition derived from a first polyamine and a first PIB having a number average molecular weight of 1200 to 1400 g / mol, the viscosity (Pa.s) of the first PIBSA-PAM dispersant composition being 100 sec. t / min as compared to an otherwise identical lubricating oil composition except that the first PIBSA-PAM composition is replaced by a physical mixture of two different PIBSA-PAM dispersants. -1 The shear rate is at least about 30% lower and at 10 sec -1 At least about 55% lower shear rate (Haake carbon black test 9 wt% carbon black, 1 to 10 s -1 and 10 to 1000s -1 The invention relates to a method for preparing a dispersant comprising: preparing a dispersant comprising: preparing a dispersant comprising: a first polyamine and a second polyamine having a plurality of dispersants, wherein the dispersants are selected such that the dispersant has a weighted average molecular weight of at least about 200 g / mol and a plurality of dispersants having ... 23. An ethylene carbonate-terminated dispersant derived from polyisobutylene having an Mn of 800 to 1600 g / mol. 24. The ethylene carbonate end-capped dispersant of paragraph 23, wherein the ethylene carbonate end-capped dispersant is derived from a polymer having an Mn of 1200 to 1400 g / mol. 25. A polymethacrylate comb copolymer viscosity improver made by polymerization of at least the following monomers: (a) hydrogenated polybutadiene-based (alk) acrylate ester macromonomer; (b) (Alkyl) acrylic acid C3-C8 alkyl ester monomer (such as butyl methacrylate); (c) (Alkyl) acrylic acid C 12 -C 24 Alkyl ester monomers (such as dodecyl methacrylate); and (d)C6-C 20Aryl-, aralkyl- or alkylaryl-terminated C2-C6 oxyalkyl or C2-C6 oligo(alkylene glycol) type (alkyl) acrylate monomers (C6-C 20 aryl-,aralkyl-,or alkaryl-endcapped C2-C6 oxyalkyl orC2-C6 oligo(alkylene glycol)-based(alk)acrylate ester monomer), having the following structure (II): Where R 2 represents hydrogen or C1-C2 alkyl, and m is 2 to 6, such that -(CH2) m - represents a linear, branched and / or cyclic alkyl group between oxygen, n is 1 to 10, and R 1 Represents C6-C 20 an aryl, aralkyl or alkaryl terminal group, in: 1) Based on the weight of all repeating units in the copolymer, the (c) (alkyl) acrylic acid C 12 -C 24 The alkyl ester monomer repeating units are present in 16 to less than 21 weight percent (e.g., 16.5 to less than 20.0 weight percent, such as 17 to less than 19.5 weight percent), 2) based on the weight of all repeating units in the copolymer, the (d) C6-C 20 Aryl-, aralkyl- or alkaryl-terminated C2-C6 oxyalkyl or C2-C6 oligo(alkylene glycol) type (alkyl)acrylate monomer repeating units are present in 3 to 7 weight percent, and 3) The combination of (c) and (d) together constitute greater than 20.0 weight percent of the repeating units of the comb copolymer viscosity modifier, based on the weight of all repeating units in the copolymer. 26. The polymethacrylate comb copolymer viscosity improver of paragraph 25, which is prepared by polymerization of at least the following monomers: (a) hydrogenated polybutadiene-based (alk) acrylate ester macromonomer; (b) butyl methacrylate; (c) dodecyl methacrylate; and (d)C6-C 20Aryl-, aralkyl- or alkylaryl-terminated C2-C6 oxyalkyl or C2-C6 oligo(alkylene glycol) type (alkyl) acrylate monomers (C6-C 20 aryl-,aralkyl-,or alkaryl-endcapped C2-C6 oxyalkyl orC2-C6 oligo(alkylene glycol)-based(alk)acrylate ester monomer), having the following structure (II): Where R 2 represents hydrogen or C1-C2 alkyl, and m is 2 to 6, such that -(CH2) m - represents a linear, branched and / or cyclic alkyl group between oxygen, n is 1 to 10, and R 1 Represents C6-C 20 an aryl, aralkyl or alkaryl terminal group, in: 1) the (c) dodecyl methacrylate monomer repeating unit is present in an amount of 16.5 to less than 20 wt % based on the weight of all repeating units in the copolymer, 2) based on the weight of all repeating units in the copolymer, the (d) C6-C 20 Aryl-, aralkyl- or alkaryl-terminated C2-C6 oxyalkyl or C2-C6 oligo(alkylene glycol) type (alkyl)acrylate monomer repeating units are present in 3 to 7 weight percent, and 3) The combination of (c) and (d) together constitute greater than 20.0 weight percent of the repeating units of the comb copolymer viscosity modifier, based on the weight of all repeating units in the copolymer. 27. A polymethacrylate comb copolymer viscosity improver having: 1), 2) and 3) when measured on a blend of said copolymer viscosity improver and a Group III base oil having a KV100 of about 4 cSt and a viscosity index (ASTM D2270) of about 120 having a KV100 of about 8 cSt: 1) A relative KV140 / relative KV20 ratio of 1.9 or higher; 2) a relative KV100 / relative KV70 ratio of 1.30 or higher; and 3) Viscosity index of 320 or higher (ASTM 2270D). 28. The polymethacrylate comb copolymer viscosity improver of paragraph 27, wherein the polymethacrylate comb copolymer having a VI of about 120 and a Kv of about 4 cSt 100 The Group III base oil also has a Kv of approximately 2 cSt.140 、Kv of about 44cSt 20 and Kv of about 19cSt 70 . 29. Use of the lubricating oil composition, method or concentrate of paragraphs 1 to 28 for providing improved fuel economy, which differs in FEI (Fuel Economy Improvement) by greater than 10% (such as greater than 15%, such as greater than 20%, such as greater than 25%) compared to Toyota 0W-8 GLV-1 lubricating oil, which comprises introducing the lubricating oil composition of any one of paragraphs 1 to 16 into an internal combustion engine and operating the engine. 30. Use of the lubricating oil composition of any of paragraphs 1 to 16 for providing flat oil viscosity properties to 0W-20, 0W-16, 0W-12, 0W-8 SAE viscosity formulations of lubricating oil compositions. 31. The lubricating oil composition of paragraphs 1 to 16, further comprising 1) a molybdenum-containing material providing 20 to 30 ppm Mo to the lubricating oil composition, 2) a zinc alkylthiophosphate wherein the alkyl group is derived from at least one secondary alcohol and at least one primary alcohol, 3) about 3.3 mass % of the blocked dispersant.

[0383] The following non-limiting examples are provided to illustrate the present disclosure. experiment

[0384] All molecular weights are reported as number average molecular weight (Mn) in g / mol, except for components based on / derived from polyisobutylene (PIB) polymers, as determined by gel permeation chromatography using polystyrene standards. PIB derived materials are reported as number average molecular weight (Mn) in g / mol using PIB standards (including those sold under the trade name Glissopal TM PIB obtained from BASF, where PIB standards are reported as having been used by the manufacturer). Unless otherwise indicated, "AI", "ai" and "ai" are weight % active ingredient. Testing Procedure

[0385] KV150 is the kinematic viscosity measured at 150°C according to ASTM D445-19a. KV140 is the kinematic viscosity measured at 140°C according to ASTM D445-19a. KV130 is the kinematic viscosity measured at 130°C according to ASTM D445-19a. KV120 is the kinematic viscosity measured at 120°C according to ASTM D445-19a. KV110 is the kinematic viscosity measured at 110°C according to ASTM D445-19a. KV100 is the kinematic viscosity measured at 100°C according to ASTM D445-19a. KV90 is the kinematic viscosity measured at 90°C according to ASTM D445-19a. KV80 is the kinematic viscosity measured at 80°C according to ASTM D445-19a. KV70 is the kinematic viscosity measured at 70°C according to ASTM D445-19a. KV60 is the kinematic viscosity measured at 60°C according to ASTM D445-19a. KV50 is the kinematic viscosity measured at 50°C according to ASTM D445-19a. KV40 is the kinematic viscosity measured at 40°C according to ASTM D445-19a. KV30 is the kinematic viscosity measured at 30°C according to ASTM D445-19a. KV20 is the kinematic viscosity measured at 20°C according to ASTM D445-19a.

[0386] The viscosity index is measured according to ASTM D2270.

[0387] Sulfur content in oil is measured by ASTM D5185.

[0388] Sulfated ash ("SASH") content is measured by ASTM D874.

[0389] Phosphorus, boron, calcium, zinc, molybdenum and magnesium contents were measured by ASTM D5185.

[0390] High Temperature High Shear Viscosity at 150°C ("HTHS150") is measured at 150°C according to ASTM D4683 and is reported in cPs.

[0391] High Temperature High Shear Viscosity at 100°C ("HTHS100") is measured at 100°C according to ASTM D6616 and is reported in cPs.

[0392] Functionality (Fv) is a measure of the average number of acid groups per reaction product of PIB and maleic anhydride. Fv is determined according to the following formula 1: Fv=(SAP×M n ) / ((1122×AI)-(SAP×MW)) (1) Wherein SAP is the saponification value (i.e., the number of milligrams of KOH consumed to completely neutralize the acid groups in 1 gram of the succinic-containing reaction product as determined according to ASTM D94); M n is the number average molecular weight of the starting olefin polymer (polybutene); AI is the active ingredient percentage of the reaction product containing succinic acid (the remainder being unreacted polybutene and diluent); and MW is the molecular weight of the dicarboxylic acid-producing moiety (98 for maleic anhydride).

[0393] Haake Carbon Black Test. The dispersancy of carbon black is determined by blending the base oil and the additive components to provide a formulated oil. 9 wt. % of carbon black powder is added to the formulated oil and the sample is blended overnight at 100°C. The sample is then run in a Haake rheometer for 1 to 10 seconds. -1 and 10 to 1000 sec -1 The viscosity of carbon black dispersions is measured over a range of shear rates.

[0394] Simulated % fuel economy improvement (% FEI) was calculated at JASO M366 operating point and overall based on a 0W-20 reference oil (for Examples 1 and 2, Table 3) or a 0W-8 reference oil (commercially available Toyota 0W-8GLV-1, for Examples 3 to 16, Tables 6 and 9). (Higher simulated % FEI values ​​are considered to indicate better fuel efficiency). The coefficient of variation (relative standard deviation) used was 8.4% based on the reference oil evaluation in the same motored friction rig (Toyota 2ZR-FXE engine). The engine was operated at constant engine speed, temperature (oil and coolant) and variable peak cylinder pressure (PCP). Candidate improvements relative to the reference were used to compare formulations. The test procedure consisted of 6 different oil and coolant temperatures (from 14 to 115°C) and 6 different speeds (700 to 3000rpm). In order not to carry over the effects of additives on friction from one oil candidate to the next candidate, a flushing process was performed before each oil change for another test.The engine was run from high to low temperatures, with a speed sweep at each temperature.

[0395] The torque values ​​(Nm) of the candidate formulation and the reference formulation at 6 JASO M366 operating points were determined from the torque values ​​at the above steady-state points. The torque values ​​(Nm) of the candidate formulation and the reference formulation at each JASO M366 operating point were then converted to work (kW) using the following equation:

[0396] The total work (kW) of the candidate formulation vs. the reference formulation was then calculated using the following equation (according to JASO M366 procedure): achievement i = work done in stage i WTF i = weight factor at stage i The % FEI of the candidate formulation vs. the reference formulation in the motorized 2ZR-FXE friction rig was then calculated using the following equation. stage Temperature(℃) Engine speed (rpm) Coolant temperature (℃) Weighting (%) 1 64 1000 73 20.0420 2 67 1300 67 20.4407 3 64 1570 64 14.2498 4 47 1970 67 13.4313 5 37 1600 37 18.5310 6 35 1300 35 13.3054 Material Component table Example Example A Low Mn PIB for PIBSA-PAM

[0397] Table A summarizes the dispersants prepared by reacting an isobutylene polymer (PIB) with maleic anhydride (to form PIBSA) and then with polyvinylamine (to form PIBSA-PAM) using thermal methods known in the art for the maleation step. It is noted that component A9* is composed of 2300Mn HR-PIB (Glissopal TM 2300, 40.8 wt%) and 1000Mn low molecular weight HR-PIB (Glissopal TM 1000, 59.2 wt%), which obtained an average of 1300 Mn. Both PIBSA-PAMs were made with polyvinylamine (PAM). Table A1.

[0398] Selected dispersants from Table A1 were formulated into 0W-12 lubricating oil compositions as shown in Table A2. Figure 1 Selected KV40 vs %N are shown, where %N is the contribution of each dispersant in the finished oil (Table A1). Figure 1As can be seen in the data series, the 1300 MW medium-high functionality A5 (open circles ○) and A6 (open triangles Δ), (and the 1000 MW medium functionality, A10) all exhibit lower KV40 values ​​at each given unit of nitrogen concentration contributed by the dispersant to the finished formulation. This means that when the N% contribution is related to the dispersing effectiveness of the formulation, A5 and A6, which have lower contributions to the formulation viscosity, will exhibit the same or better dispersing power (as shown on the Y axis, KV40 values). This generally corresponds to the ability of oils formulated with A5 or A6 to exhibit higher or equal dispersing power and improved fuel economy due to reduced formulation viscosity. Table A2 *Oil 1 to Oil 10 each also contained 0.501 m% PmNE, 1.180 m% Magnesium Salicylate 340 TBN; 0.680 m% Calcium Salicylate 350 TBN; 1.030 m% ZDDP-1; 2.0 m% DPA Antioxidant: 0.300 m% PIBSA; 0.007 m% Defoamer; and 1.303 m% Diluent. Table A2 continued Table A2*, continued Oil 11 Oil 12 Oil 13 Oil 14 Oil 15 Oil 16 Oil 17 Oil 18 Oil 19 Oil 20 A6 4.000 6.000 2.800 A5 1.000 2.500 4.000 4.000 A10 1.000 2.500 4.000 Group III oil, 4 cSt 89.0 87.0 90.2 92.0 90.5 89.0 89.0 92.0 90.5 89.0 total 100 100 100 100 100 100 100 100 100 100 Set 11.0 13.0 9.8 8.0 9.5 11.0 11.0 8.0 9.5 11.0 KV100(cSt) 5.67 6.29 5.31 4.7 5.12 5.55 5.58 4.67 5.04 5.39 KV40(cSt) 27.21 31.17 25.04 21.49 24.03 26.56 26.95 21.42 23.88 26.09 CCS@-35C(cP) 3671 4626 3290 2702 3162 3690 2706 3399 3761 HTHS(cP)@100C 4.55 4.98 4.17 3.67 3.98 4.36 HTHS(cP)@150C 2.04 2.24 1.91 1.63 1.76 1.91 1.97 1.72 1.84 1.95 Dispersant in oil, ai% 3.65 5.47 2.55 0.87 2.17 3.47 3.47 0.82 2.05 3.28 Dispersant in oil, N% 0.142 0.213 0.099 0.030 0.074 0.119 0.119 0.034 0.085 0.135 *Oil 11 to Oil 20 each also contained 0.501 m% PmNE, 1.180 m% Magnesium Salicylate 340 TBN; 0.680 m% Calcium Salicylate 350 TBN; 1.030 m% ZDDP-1; 2.0 m% DPA Antioxidant: 0.300 m% PIBSA; 0.007 m% Defoamer; and 1.303 m% Diluent.

[0399] The selected dispersants from Table A1 were then formulated to 0W-12 SAE viscosity to evaluate soot control capabilities and are shown in Table A3. Soot dispersancy was measured using the Haake carbon black test described above and the results are shown in Figure 2 It is noted that a different treat rate (4.244 mass %) was used for the 1000Mn dispersant (A10) in Oil 26 because A10 has a significantly higher active ingredient content than the other dispersants in this series (Table A1).

[0400] In the Haake carbon black test, 9% carbon black (CB) was metered into each formulation to simulate the effect of soot in a field aged lubricant. The lower the viscosity measured over a certain shear rate range, the better the soot dispersibility properties of the formulation. Figure 2It can be observed that the data set represented by the open circles from dispersant A8 shows a trend of lower viscosity in the plotted shear rate range compared to the data trend represented by the solid triangles ▲ from dispersant A9. This proves that the dispersing power of dispersant A8 is better than that of A9. Table A3** **Oil 21 to Oil 26 each also contained 0.540m% B-PIBSA-PAM, 950Mn; 0.500m% PmNE, 1.130m% Magnesium Salicylate 340TBN; 0.680m% Calcium Salicylate 350TBN; 1.030m% ZDDP-1; 0.140m% MoDTC trimer; 2.0m% DPA antioxidant: 0.300m% PIBSA; 0.004m% defoamer; 1.656m% diluent and 1.0m% VM-12. Example B Oils O, P, Q, R, S, T and U were prepared as shown below. O P Q R S T U EC PIBSA-PAM, 1300Mn 3.265 3.265 3.490 3.490 3.490 3.490 3.265 Calcium Salicylate 350TBN 1.300 1.100 1.300 1.100 0.870 0.870 1.100 Magnesium Salicylate 340TBN 0.400 0.500 0.400 0.500 0.590 0.590 0.500 Ca, % 0.163 0.138 0.163 0.138 0.110 0.110 0.138 Mg, % 0.030 0.038 0.030 0.038 0.044 0.044 0.037 soap,% 0.495 0.467 0.495 0.467 0.427 0.427 0.467 Each oil also contains: ZDDP (combination of primary and secondary), MODTC dimer and / or trimer, antioxidant (diphenylamine and / or hindered phenol), corrosion inhibitor, PIBSA, defoamer and diluent) and may optionally contain a commercial comb copolymer or the inventive comb copolymer described herein. Fuel economy performance in JASO M366 is expected to be approximately 0.2-0.4% relative to a 0W-8 base oil. Example C

[0401] The impact of VMs. The suitability of a series of different types of VM for flat viscosity oils was evaluated using the relative viscosity contribution properties at different temperatures. Binary blends of VM were prepared in Yubase4 to the same thickening power (KV100 = 8 cSt), and the viscosities of the binary blends and Yubase4 were measured at different temperatures from 20 to 150°C. The relative viscosity relative to Yubase4 was calculated as the ratio of the KV of the binary blend to the KV of Yubase4 at the same temperature (see the equation below and Table 1 below). The lower the relative viscosity (relative to Yubase4), the smaller the viscosity contribution of VM to Yubase4. The data are reported in Tables 1 and Figure 3 middle.

[0402] like Figure 3As can be seen in the Figures 1 and 2, the comb-shaped PMAs (comparative VMs: VM-1, VM-9, VM-10 and VM-11, and VM-16 of the present invention) exhibit good viscosity profiles suitable for flat viscosity oils: (1) extremely small viscosity contribution to the base oil (low relative KV value relative to the base oil) at low temperature conditions related to the operating temperature of the JASO M366 fuel economy test, especially at 20-70°C; and (2) excellent thickening efficiency or high relative KV value at 100-150°C to ensure reliability and engine durability. Compared with other comb-shaped PMAs in the series, VM-16 in particular has very good low temperature properties and high thickening efficiency - as shown by the lowest relative KV from 70 to 90°C and the highest relative KV from 130 to 150°C.

[0403] As can be observed in Table 1, viscosity improvers useful for flat viscosity oils have one, two, or three of the following: 1. A ratio of relative KV140 to relative KV20 of 1.1.9 or higher, such as 2.1 or higher (this indicates the comparison between very high temperature thickening and very low temperature viscosity contributions); and / or 2. A ratio of Relative KV100 to Relative KV70 of 1.3 or higher, such as 1.35 or higher (this indicates the comparison between high temperature thickening and lower temperature viscosity contributions); and / or 3. Viscosity index (VI) of 320 or higher, such as 340 or higher.

[0404] The influence of detergents. Example Oils 1 and 2 were prepared and tested for simulated % FEI (fuel economy improvement) as described above. The data are reported in Tables 2 and Figure 4 Examples 1 and 2 are SAE viscosity grade 0W-16 oils based on mixed salicylic acid Ca / Mg detergents, using the same viscosity improver, base stock type, and targeting the same NOACK level (-20%) and similar soap content, but with different Ca / Mg ratios. Table 2. Table 3. Simulated %FEI in the electric 2ZR-FXE bench, calculated based on 0W-20 reference oil

[0405] In Table 3 and Figure 4As can be seen in the graph, Example 2 performs slightly worse than Example 1, as expected from the use of a higher dispersant treatment rate (3.1 vs. 2.8%) and a slightly higher KV40. As expected, this performance difference is particularly evident in the lower temperature and higher speed region (mixed lubrication regime). However, surprisingly, Example 2 performs better than Example 1 in Stages 1 and 2 (which operate at the lowest speed and highest temperature of the six stages).

[0406] Therefore, when seeking to achieve the desired performance in stage 1 (oil temperature = 64°C; engine speed = 1000 min -1 ) and stage 2 (oil temperature = 67°C; engine speed = 1300 min -1 ), Example 2 having a salicylate detergent with a Ca / Mg ratio of about 5.4 appears to be advantageous.

[0407] Example 3-17. Example oils 3-17 were prepared and tested for simulated % FEI (fuel economy improvement) as described above. Toyota 0W-8GLV-1 was used as a reference oil. The data are reported in Tables 4-9 and Figure 5 middle.

[0408] According to Table 6, Example 3, which has a mixed salicylate detergent with a Ca / Mg ratio of 5.4, outperforms Examples 4-6 (mixed sulfonate candidates) in Stages 1 and 2 (higher temperature and slow speed operation) and in the overall % FEI relative to the 0W-8 reference oil, despite having similar KV40. This is consistent with previous observations (Example 1 vs. Example 2) and supports the finding that the type of additive affects fuel economy performance even when the same level of KV40 is met (unlike the general teaching in Research on Ultra-High Viscosity Index Engine Oil Part 1-'Flat Viscosity' Concept and Contribution to Carbon Neutrality" Yamamori, K. et al. SAE Technical Paper 2022-01-0525, 2022). Similarly, the examples with a mixed salicylate detergent with a Ca / Mg ratio of 5.4 (Examples 11 and 12) outperform the mixed sulfonate candidates (Examples 9 and 10) in Stages 1 and 2, despite similar KV40 values.

[0409] Effect of dispersantsAs can be seen in Table 6, Examples 9 to 12, EC-capped 1300Mn dispersants, perform better in Stages 1 and 2 than Examples 7 to 8 using uncapped precursors. This suggests that the capped dispersants reduce dispersant-ZDDP interactions, theoretically freeing up ZDDP to increase MoS2 formation, resulting in better friction performance at more marginal conditions (higher temperature and low speed operation). Example 12 (combination of capped low viscosity dispersant, mixed salicylate detergent with a Ca / Mg ratio of 5.4, and secondary ZDDP) exhibits a high simulated %FEI of 0.48% relative to the benchmark Toyota 0W-8GLV-1 reference oil.

[0410] Effects of comb-shaped PMA candidates. In Examples 13 and 14 to 16, the comb copolymer PMAs of the present invention (VM-3, VM-4, VM-5 and VM-16) are compared with commercial comb PMA VMs (VM-1 and VM-2). As can be seen from Table 9, when formulated to the same viscosity grade and NOACK limits using additive technology and base oil type, VM-3, VM-4VM-5 and VM-16PMA produce much better fuel economy performance than commercial comb PMA VMs (VM-1 and VM-2). This is surprising considering the fact that all formulations achieve the same level of KV40. Table 6. Simulated %FEI in the electric 2ZR-FXE bench, calculated against Toyota 0W-8GLV-1 reference oil Table 7 Table 8. Example 13 Embodiment 14 Embodiment 15 Example 16 HTHS150(cP) 2.34 2.31 2.37 2.27 HTHS100(cP) 4.03 3.88 3.96 3.87 Kv100 / D445(cSt) 6.22 6.52 6.33 6.05 Kv40 / D445(cSt) 22.26 21.94 21.87 21.96 B ppm 0 0 0 0 Ca% 0.163 0.163 0.163 0.163 Mg% 0.030 0.030 0.030 0.030 Mo ppm 750 750 750 750 N％ 0.081 0.081 0.081 0.081 P％ 0.071 0.071 0.071 0.071 S％ 0.261 0.261 0.261 0.261 Si ppm 10.942 10.942 10.942 10.942 Zn% 0.079 0.079 0.079 0.079 Mass %N from antioxidants 0.035 0.035 0.035 0.035 Mass %N from dispersant 0.033 0.033 0.033 0.033 Ca / Mg ratio 5.4 5.4 5.4 5.4 Soap Type Salicylates Salicylates Salicylates Salicylates Soap content (mmol) 0.495 0.495 0.495 0.495 Table 9. Simulated %FEI in electric 2ZR-FXE bench, calculated against Toyota 0W-8GLV-1 reference oil Stage / Implementation Example 13 Embodiment 14 Embodiment 15 Example 16 Phase 1 0.66 0.61 0.92 1.31 Phase 2 0.43 0.65 0.87 0.96 Phase 3 0.45 0.78 0.92 0.87 Phase 4 1.06 1.47 1.60 1.55 Phase 5 1.67 1.94 2.18 2.01 Phase 6 1.88 2.12 2.46 2.35 overall 1.1 1.3 1.5 1.5

[0411] All documents described herein are incorporated herein by reference to the extent that they do not contradict this article, including any priority documents and / or test procedures. It is apparent from the above general description and specific embodiments that, although the form of the present invention has been illustrated and described, various modifications can be made without departing from the spirit and scope of the present invention. Accordingly, it is not intended to limit the present invention thereby. The term "comprising" is considered to be synonymous with the term "including". Similarly, as long as the conjunction "comprising" is present before the composition, element or element group, it is to be understood that we also envision the same composition or element group with conjunction "substantially consisting of", "consisting of", "selected from" or "being" before the enumeration of the composition, element or multiple elements, and vice versa.

Claims

1. A lubricating oil composition comprising the following components or a mixture of the following components: (i) at least 50% by mass, based on the weight of the lubricating oil composition, of a base oil, (ii) at least one end-capped dispersant derived from a polymer having a number average molecular weight (Mn) of less than 1600 g / mol, (iii) at least one magnesium-containing detergent, (iv) at least one calcium-containing detergent, (v) at least one copolymer viscosity improver having, when 1), 2) and 3) are measured on a blend of said copolymer viscosity improver and a Group III base oil having a KV100 of about 4 cSt (ASTM D445) and a viscosity index of about 120 (ASTM D2270) having a KV100 of about 8 cSt: 1) A relative KV140 / relative KV20 ratio of 1.9 or higher; 2) a relative KV100 / relative KV70 ratio of 1.30 or higher; and 3) Viscosity index of 320 or higher (ASTM 2270D).

2. The lubricating oil composition according to claim 1, wherein the blocked dispersant is represented by the following formula: Among them, each R 11 and R 12 are independently hydrogen or a hydrocarbon group, provided that R 11 and R 12 are not all hydrogen; z is an integer from 0 to 10; and each R 13 is independently acetyl, or wherein the two closest R 13 Groups can be linked together.

3. The lubricating oil composition according to claim 1, wherein the copolymer viscosity improver is a comb copolymer having repeating units derived from a hydrogenated polybutadiene type (alkyl)acrylate macromonomer.

4. The lubricating oil composition according to claim 1, wherein the Group III base oil of component (v) has a KV140 of 2 cSt, a KV20 of 44 cSt and a KV70 of 19 cSt (ASTM D445).

5. A lubricating oil composition comprising the following components or a mixture of the following components: (i) at least 50% by mass, based on the weight of the lubricating oil composition, of a base oil, (ii) at least one end-capped dispersant derived from a polymer having a number average molecular weight (Mn) of less than 1600 g / mol, wherein the end-capped dispersant is represented by the formula: Among them, each R 11 and R 12 are independently hydrogen or a hydrocarbon group, provided that R 11 and R 12 are not all hydrogen; z is an integer from 0 to 10; and each R 13 is independently acetyl, or wherein the two closest R 13 Groups can be linked together; (iii) at least one magnesium-containing detergent, (iv) at least one calcium-containing detergent, (v) at least one comb copolymer viscosity modifier comprising the reaction product of at least the following monomers: (a) hydrogenated polybutadiene (alkyl) acrylate macromonomer; (b) (Alkyl) acrylic acid C3-C8 alkyl ester monomer; (c) (Alkyl) acrylic acid C 12 -C 24 Alkyl ester monomers; and (d)C1-C 18 Alkyl-terminated or C6-C 20 Aryl-, aralkyl- or alkaryl-terminated C2-C6 oxyalkyl or C2-C6 oligo(alkylene glycol) type (alkyl) acrylate monomers and / or hydroxyalkyl or H-terminated oligo(alkylene glycol) type (alkyl) acrylate monomers having the following structure (II): Where R 2 represents hydrogen or C1-C2 alkyl, and m is 2 to 6, such that -(CH2) m - represents a linear, branched and / or cyclic alkyl group between oxygen, n is 1 to 10, and R 1 Represents H, C1-C 18 Linear, branched and / or cyclic alkyl end groups or C6-C 20 an aryl, aralkyl or alkaryl terminal group, wherein the combination of (c) and (d) together constitute greater than 20.0 weight percent of the repeating units of the comb copolymer viscosity modifier, based on the weight of all repeating units in the copolymer.

6. The lubricating oil composition of claim 5, further comprising a metal alkylthiophosphate, wherein the alkyl group is derived from at least one secondary alcohol.

7. The lubricating oil composition of claim 6, wherein the alkyl group of the metal alkylthiophosphate is derived from at least one primary alcohol and at least one secondary alcohol.

8. The lubricating oil composition of claim 6, wherein the metal alkylthiophosphate comprises one or more zinc dialkyldithiophosphates, wherein the alkyl group is at least partially derived from a secondary alcohol or a mixture of a primary and secondary alcohol.

9. The lubricating oil composition according to claim 6, wherein the metal alkylthiophosphate is represented by the formula Zn[SP(S)(OR1)(OR2)]2, wherein R1 and R2 are each independently C1-C 18 alkyl.

10. The lubricating oil composition according to claim 9, wherein one, two, three and / or four of R1 and R2 are secondary C2-C 12 alkyl.

11. The lubricating oil composition according to claim 1, wherein the lubricating oil composition has: a) less than or equal to 30 mass % volatility as measured by the Noack test (ASTM D5800, Procedure B), based on the total mass of the lubricating composition; and / or b) a ratio of calcium from detergent to magnesium from detergent of from 10:1 to 2:1; and / or c) A total soap content of less than 30 mmol.

12. The lubricating oil composition of claim 1, wherein the end-capped dispersant is an ethylene carbonate-capped PIBSA PAM composition derived from polyisobutylene having a number average molecular weight of 1200 to 1400 g / mol and polyamines.

13. The lubricating composition according to claim 1, further comprising one or more of the following components: D) one or more friction modifiers; E) one or more antioxidants; F) one or more pour point depressants; G) one or more defoaming agents; H) one or more viscosity improvers other than the comb copolymer of (v); 1) one or more dispersants; J) one or more inhibitors and / or rust preventives; and / or K) One or more antiwear agents.

14. The lubricating composition of claim 1, wherein: A) the base oil is present in an amount of 50 to 99 mass % based on the weight of the lubricating oil composition; and B) the blocked dispersant is present in an amount of 0.1 to 10 wt % based on the total weight of the lubricating oil composition; and C1) the detergent is present in an amount of 0.1 to 20 wt % based on the total weight of the lubricating oil composition; and C2) The copolymer viscosity modifier is present at 0.1 to 10 wt %, based on the total weight of the lubricating oil composition.

15. The lubricating composition according to claim 14, wherein: D) one or more friction modifiers are optionally present at 0.01 to 5 weight percent, based on the total weight of the lubricating composition; E) one or more antioxidants are optionally present at 0.01 to 5 wt % based on the total weight of the lubricating composition; F) optionally, one or more pour point depressants are present at 0.01 to 5 weight percent, based on the total weight of the lubricating composition; G) optionally, one or more defoaming agents are present at 0.001 to 5 wt %, based on the total weight of the lubricating composition; H) optionally, one or more viscosity improvers other than (v) are present at 0.001 to 6 wt %, based on the total weight of the lubricating composition; I) optionally, one or more dispersants are present at 0.01 to 20 wt % based on the total weight of the lubricating composition; J) Optionally, one or more inhibitors and / or rust preventives are present at 0.01 to 5 wt. %, based on the total weight of the lubricating composition.

16. The lubricating composition of claim 1, wherein the lubricating composition is a passenger car motor oil, a light-duty diesel engine oil, or a heavy-duty diesel engine oil.

17. A method of lubricating an internal combustion engine during engine operation, comprising: (i) providing the lubricating composition according to claim 1 to a crankcase of an internal combustion engine; (ii) providing hydrocarbon fuels, renewable fuels and / or alternative fuels in internal combustion engines; and (iii) combusting the fuel in an internal combustion engine.

18. The method of claim 17, wherein the internal combustion engine is an automotive internal combustion engine.

19. The method of claim 17, wherein the internal combustion engine is a gasoline or diesel automotive internal combustion engine.

20. A concentrate composition comprising: (i) less than 50% by mass, based on the weight of the composition, of a base oil, (ii) at least one end-capped dispersant having a number average molecular weight (Mn) of less than 1600 g / mol and represented by the formula: Among them, each R 11 and R 12 are independently hydrogen or a hydrocarbon group, provided that R 11 and R 12 are not all hydrogen; z is an integer from 0 to 10; and each R 13 is independently acetyl, or wherein the two closest R 13 Groups can be linked together; (iii) at least one magnesium-containing detergent and at least one calcium-containing detergent, wherein the ratio of calcium from the detergent to magnesium from the detergent is from 10:1 to 2:1; and (iv) at least one comb copolymer viscosity modifier comprising the reaction product of at least the following monomers: (a) hydrogenated polybutadiene (alkyl) acrylate macromonomer; (b) (Alkyl) acrylic acid C3-C8 alkyl ester monomer; (c) (Alkyl) acrylic acid C 12 -C 24 Alkyl ester monomers; (d)C1-C 18 Alkyl-terminated or C6-C 20 Aryl-, aralkyl- or alkaryl-terminated C2-C6 oxyalkyl or C2-C6 oligo(alkylene glycol) type (alkyl) acrylate monomers and / or hydroxyalkyl or H-terminated oligo(alkylene glycol) type (alkyl) acrylate monomers having the following structure (II): Where R 2 represents hydrogen or C1-C2 alkyl, and m is 2 to 6, such that -(CH2) m - represents a linear, branched and / or cyclic alkyl group between oxygen, n is 1 to 10, and R 1 Represents H, C1-C 18 Linear, branched and / or cyclic alkyl end groups or C6-C 20 an aryl, aralkyl or alkaryl terminal group, wherein the combination of (c) and (d) together constitute greater than 20.0 weight percent of the repeating units of the comb copolymer viscosity modifier, based on the weight of all repeating units in the copolymer; (v) optionally, a metal alkylthiophosphate, wherein the alkyl group is derived from at least one secondary alcohol; (vi) optionally, a molybdenum-containing compound; and (vii) optionally, an antioxidant.

21. A lubricating oil composition comprising a PIBSA-PAM dispersant composition derived from a first polyamine and a first PIB having a number average molecular weight of 1200 to 1400 g / mol, the PIBSA-PAM dispersant composition having a -1 The viscosity at a shear rate of 0.01 to 0.03 Pa.s and at 10 sec -1 Viscosity of 0.15 Pa.s or less at a shear rate (Haake carbon black test 9 wt% carbon black, 1 to 10 s -1 and 10 to 1000s -1 shear rate range).

22. A lubricating oil composition comprising a first PIBSA-PAM dispersant composition derived from a first polyamine and a first PIB having a number average molecular weight of 1200 to 1400 g / mol, the viscosity (Pa.s) of the first PIBSA-PAM dispersant composition being 100 sec. lower than that of an otherwise identical lubricating oil composition except that the first PIBSA-PAM composition is replaced by a physical mixture of two different PIBSA-PAM dispersants. -1 The shear rate is at least about 30% lower and at 10 sec -1 The shear rate is at least about 55% lower (Haake carbon black test 9 wt% carbon black, 1 to 10 s -1 and 10 to 1000s -1 The invention relates to a method for preparing a dispersant comprising: preparing a dispersant comprising: preparing a dispersant comprising: a first polyamine and a second polyamine having a plurality of dispersants, wherein the dispersants are selected such that the dispersant has a weighted average molecular weight of at least about 200 g / mol and a plurality of dispersants having ...

23. An ethylene carbonate-terminated dispersant derived from polyisobutylene having an Mn of 800 to 1600 g / mol.

24. The ethylene carbonate-terminated dispersant of claim 23, wherein the ethylene carbonate-terminated dispersant is derived from a polymer having an Mn of 1200 to 1400 g / mol.

25. A polymethacrylate comb copolymer viscosity improver made by polymerization of at least the following monomers: (a) hydrogenated polybutadiene (alkyl) acrylate macromonomer; (b) (Alkyl) acrylic acid C3-C8 alkyl ester monomer; (c) (Alkyl) acrylic acid C 12 -C 24 Alkyl ester monomers; and (d)C6-C 20 Aryl-, aralkyl- or alkaryl-terminated C2-C6 oxyalkyl or C2-C6 oligo(alkylene glycol) type (alkyl) acrylate monomer having the following structure (II): Where R 2 represents hydrogen or C1-C2 alkyl, and m is 2 to 6, such that -(CH2) m - represents a linear, branched and / or cyclic alkyl group between oxygen, n is 1 to 10, and R 1 Represents C6-C 20 an aryl, aralkyl or alkaryl terminal group, in: 1) Based on the weight of all repeating units in the copolymer, the (c) (alkyl) acrylic acid C 12 -C 24 The alkyl ester monomer repeating units are present in 16 to less than 21 weight percent, 2) based on the weight of all repeating units in the copolymer, the (d) C6-C 20 Aryl-, aralkyl- or alkaryl-terminated C2-C6 oxyalkyl or C2-C6 oligo(alkylene glycol) type (alkyl)acrylate monomer repeating units are present in 3 to 7 weight percent, and 3) The combination of (c) and (d) together constitute greater than 20.0 weight percent of the repeating units of the comb copolymer viscosity modifier, based on the weight of all repeating units in the copolymer.

26. The polymethacrylate comb copolymer viscosity modifier according to claim 25, which is prepared by polymerization of at least the following monomers: (a) hydrogenated polybutadiene (alkyl) acrylate macromonomer; (b) butyl methacrylate; (c) dodecyl methacrylate; and (d)C6-C 20 Aryl-, aralkyl- or alkaryl-terminated C2-C6 oxyalkyl or C2-C6 oligo(alkylene glycol) type (alkyl) acrylate monomer having the following structure (II): Where R 2 represents hydrogen or C1-C2 alkyl, and m is 2 to 6, such that -(CH2) m - represents a linear, branched and / or cyclic alkyl group between oxygen, n is 1 to 10, and R 1 Represents C6-C 20 an aryl, aralkyl or alkaryl terminal group, in: 1) the (c) dodecyl methacrylate monomer repeating unit is present in an amount of 16.5 to less than 20 wt % based on the weight of all repeating units in the copolymer, 2) based on the weight of all repeating units in the copolymer, the (d) C6-C 20 Aryl-, aralkyl- or alkaryl-terminated C2-C6 oxyalkyl or C2-C6 oligo(alkylene glycol) type (alkyl)acrylate monomer repeating units are present in 3 to 7 weight percent, and 3) The combination of (c) and (d) together constitute greater than 20.0 weight percent of the repeating units of the comb copolymer viscosity modifier, based on the weight of all repeating units in the copolymer.

27. A polymethacrylate comb copolymer viscosity improver having: 1), 2) and 3) when measured on a blend of said copolymer viscosity improver and a Group III base oil having a KV100 of about 4 cSt and a viscosity index (ASTM D2270) of about 120 having a KV100 of about 8 cSt: 1) A relative KV140 / relative KV20 ratio of 1.9 or higher; 2) a relative KV100 / relative KV70 ratio of 1.30 or higher; and 3) Viscosity index of 320 or higher (ASTM 2270D).

28. The polymethacrylate comb copolymer viscosity modifier of claim 27, wherein the polymethacrylate having a VI of about 120 and a Kv of about 4 cSt 100 The Group III base oil also has a Kv of approximately 2 cSt. 140 、Kv of about 44cSt 20 and Kv of about 19cSt 70 .

29. A method of providing improved fuel economy having a FEI (Fuel Economy Improvement) difference of greater than 10% compared to a Toyota 0W-8 GLV-1 lubricating oil, comprising introducing the lubricating oil composition of claim 1 into an internal combustion engine and operating the engine.

30. The lubricating oil composition of claim 1, further comprising: 1) a molybdenum-containing material providing 20 to 40 ppm Mo to the lubricating oil composition, 2) a zinc alkylthiophosphate, wherein the alkyl group is derived from at least one secondary alcohol, 3) about 3.3 mass % of the blocked dispersant.

Images