Lubricant composition comprising core-shell colloidal zinc-containing particles

Abstract

The present invention relates to the use of a colloid comprising a core of a zinc compound and a shell comprising a metal surfactant, such as a salicylate and / or sulfonate, a metal alkanoate and / or a metal carboxylate, as an additive in lubricant compositions having good antiwear properties, in particular for engine crankcase applications.

Description

priority

[0001] This invention claims priority to and the benefit of United Kingdom patent application number GB2402436.6 filed on February 21, 2024. Field of the Invention

[0002] The present invention relates to the use of colloids of a core containing zinc compounds and a shell containing metal containing surfactants, such as salicylates and / or sulfonates, alkanoates and / or carboxylates, as additives in lubricant compositions having good antiwear properties, in particular for engine crankcase applications. Background Art

[0003] The present invention relates to lubricating oil compositions, such as those used in internal combustion engines, such as automotive lubricating oil compositions, or marine oils, or transmission or gear oils, exhibiting improved wear characteristics. More particularly, the present invention relates to automotive crankcase lubricating oil compositions for gasoline (spark-ignited) and diesel (compression-ignited, spark-assisted compression-ignited) internal combustion engines, such compositions being referred to as crankcase lubricants; and to the use of additives in such lubricating oil compositions for reducing friction and / or wear between moving parts in use of such engines and / or improving the fuel economy performance of engines lubricated with the lubricating oil compositions.

[0004] Engine durability is an important consideration in lubricant selection, especially for heavy-duty diesel engine applications. Original equipment manufacturers (OEMs) have continuously increased their oil drain intervals, and average vehicle lifespans have steadily increased over the past few decades. Similarly, there has been a trend toward using ashless antiwear agents, which have a lower impact on aftertreatment systems, such as diesel particulate filters, in heavy-duty diesel vehicles.

[0005] Environmental and regulatory requirements are driving the need to improve the efficiency of internal combustion engines. Lower viscosity lubricants require less energy to pump around the engine, thus improving its fuel economy. However, lower viscosity lubricants result in thinner oil films between contacting engine parts (e.g., in the valve train, piston area, and bearings), which can lead to higher wear rates, reduced friction improvement, etc. Conventionally, zinc dialkyl dithiophosphates (ZDDPs) are often used as lubricant additives to prevent engine wear and / or reduce friction in boundary lubrication conditions.

[0006] In addition to driving improvements in fuel economy, it is also desirable to reduce emissions from vehicles. Exhaust emissions are typically controlled through post-processing devices, such as catalytic converters, which typically use precious metal catalysts to convert combustion products into less harmful species. However, these catalysts are particularly negatively affected by phosphorus and sulfur, which affect their catalytic activity / effectiveness. Another post-processing device is a particulate filter, which can become clogged with sulfated ash or sludge generated by the combustion of heavy-duty diesel. Therefore, it is desirable to reduce the content of sulfated ash, phosphorus, and sulfur (SAPS) derived from heavy-duty diesel. ZDDP and zinc dithiocarbamate additives provide significant amounts of SAPS to lubricating oils, and therefore it is also desirable to reduce the use of ZDDP and the like. However, it is generally necessary to add anti-wear components containing SAPS to ensure good anti-wear performance. This has led to the discovery of methods for improving the anti-wear performance of lubricating oils without further adding phosphorus. It is also desirable to improve the anti-wear performance of lubricating oils without further increasing the ash content (SASH). Similarly, it is advantageous to improve the anti-wear performance of lubricating oils by replacing components such as detergents with components that provide both anti-wear properties and detergency.

[0007] A common feature of inorganic materials is that they contribute ash. Due to ash limits set by original equipment manufacturers and the like, this generally means that other ash-forming components must be reduced to make room for new inorganic materials. The primary source of ash-producing materials in lubricants is inorganic detergents, which are often added to, among other things, increase the total base number (TBN) of the lubricant. Increasing the total base number (TBN) generally means neutralizing the acidic byproducts of combustion for a longer period of time or under more severe conditions. Although ashless components, such as amines, can also contribute to TBN, basic metal salts, often referred to as detergents, are commonly used, despite their contribution to SASH.

[0008] Therefore, it is desirable to identify antiwear agents that are preferably phosphorus-free and / or sulfur-free, exhibit excellent anti-wear and anti-scuff properties, and provide a TBN to the formulation.

[0009] US 10,000,721 (EP3240879A1) and its US continuation-in-part application US 10,781,397 disclose stoichiometric metal salts of carboxylic acids, such as zinc stearate, zinc undecylenate, zinc oleate and zinc naphthenate as antiwear components in lubricant compositions with optional detergents.

[0010] US 2008 / 0274041 A1 discloses a method for producing dispersions of nanoscale zinc oxide particles in hydrocarbons and discusses their use as catalysts in rubber vulcanization, paints, and as antioxidant additives in galvanized steel.

[0011] Similarly, US 4,193,769 relates to stable fluid zinc-containing dispersions and their preparation by pyrolysis of ZnCO3 to ZnO in a fluid containing a dispersant.

[0012] US 4,410,446 relates to stable fluid zinc-containing dispersions and their preparation by pyrolysis of zinc acetate to ZnO in a fluid containing a dispersant which is stable at the decomposition temperature.

[0013] US 8,557,751 relates to a lubricating oil composition (containing a base oil, a phosphate derivative and a zinc compound) having an element ratio (Zn / P) between zinc (Zn) and phosphorus (P) in the lubricating oil composition of 0.55 or more, and also having a certain NO resistance. x sex.

[0014] GB 1,195,041 (DE 1644915 A1) relates to an automatic transmission fluid comprising a zinc carboxylate complex of a zinc oxide complex of a zinc dialkyldithiophosphate, wherein each carboxylate group contains 1 to 20 carbon atoms, and wherein the alkyl groups of the zinc dialkyldithiophosphate are n-alkyl or isoalkyl and each contain 6 carbon atoms.

[0015] Other relevant references include: US2016 / 0186088A1 and CN102827668. Summary of the Invention SUMMARY OF THE INVENTION

[0016] The present inventors have now surprisingly found that colloids having a core of zinc containing compounds and a shell of metal bound surfactants (e.g. metal sulfonates, salicylates and / or metal carboxylates) can be used in lubricant compositions, such as automotive lubricating oil compositions, for use in marine oils, transmission fluids or gear oils, or in internal combustion engines, such as diesel engines, or for providing excellent anti-wear properties and a favourable contribution to TBN. The lubricating compositions of the invention may also reduce friction, thereby helping to provide improved fuel economy properties.

[0017] The present invention relates to a concentrate and / or lubricating oil composition comprising the following components or obtained by mixing the following components: (A) 1 to 99.99 wt. %, based on the weight of the lubricating composition, of one or more base oils; (B) at least one phosphorus-containing compound selected from detergents, friction modifiers, or antiwear additives other than the colloidal particles described in (C); (C) 0.01 to 10 wt. % of colloidal particles, based on the weight of the composition, comprising: a) a core of one or more hydrocarbon-insoluble zinc-containing compounds, and b) a shell of one or more of the following: 1) one or more metal-containing surfactants, wherein the metal M comprises a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and the surfactant comprises a hydrocarbyl-substituted sulfonate salt of formula (I) or a hydrocarbyl-substituted salicylate salt of formula (II), where R A and R B are each independently a linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon group having 1 to 70 carbon atoms, wherein when n>1, all R A The sum of the number of carbon atoms in the group and all R B The sum of the number of carbon atoms in the group is 100 or less carbon atoms, and Ar is a monocyclic or polycyclic aromatic group; n is an integer from 1 to the maximum possible number of substitutions on Ar, wherein if m=0, n=1; m is an integer from 1 to 3, x is an integer from 1 to 5; y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 8; 2) one or more metal alkanoates represented by formula (III): wherein M is a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and R C is selected from linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon groups having 6 to 70 carbon atoms, or aromatic groups or alkyl aromatic groups, wherein the aromatic group has 6 to 20 carbon atoms and the alkyl group has 1 to 20 carbon atoms; x is an integer from 1 to 5, wherein in the case of x>1, the R C The groups may be the same or different, y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 8, The lubricating oil composition has a Zn / P ratio (element mass basis as measured by ASTM D5185) of 1.1 to 5.0.

[0018] In some embodiments, the hydrocarbon insoluble zinc-containing compound is selected from at least one of zinc, zinc oxide, zinc hydroxide, zinc carbonate and zinc halide or a mixture thereof. In some embodiments, the colloidal particles have an average particle size measured by dynamic light scattering in the range of 5 nm to 1 μm, such as 20 nm to 500 nm or 20 nm to 200 nm. In some embodiments, the metal M in formula (I), (II) or (III) is selected from at least one of sodium, potassium, lithium, magnesium, calcium, barium or a mixture thereof; or wherein the metal M is selected from at least one of gold, silver, palladium, platinum, zirconium, vanadium, molybdenum, nickel, copper, zinc, aluminum or a mixture thereof. In some embodiments, Ar in formula (I) or formula (II) is benzene or naphthalene.

[0019] In certain embodiments, the surfactant of formula (I) is a metal-containing hydrocarbyl-substituted phenyl sulfonate surfactant of formula (Ia), wherein M is selected from calcium, magnesium, barium or zinc or a combination thereof, such as calcium, magnesium, or zinc, or calcium or zinc; R A are independently of one another linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon groups having 6 to 50 carbon atoms, such as 10 to 40 or 12 to 37 carbon atoms; n is an integer from 1 to 5, such as 1 to 4, such as 1, 2 or 3, such as 1, wherein if m=0, then n=1; m is 0 to 3, such as 0 or 1; all R A The sum of the number of carbon atoms in the group is 60 or less carbon atoms; x is 2; y is 2; and optionally, p is 0.

[0020] In certain embodiments, the surfactant of formula (II) is a metal-containing hydrocarbyl-substituted phenyl salicylate surfactant of formula (IIa), wherein M is selected from calcium, magnesium, barium or zinc or a combination thereof; such as calcium, magnesium or zinc or a combination thereof; or calcium or zinc or a combination thereof; R B are independently linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon groups having 6 to 50 carbon atoms, such as 10 to 48 or 12 to 37 carbon atoms; n is an integer from 1 to 4, such as 1 to 3, such as 1 or 2, such as 1; all R B The sum of the number of carbon atoms in the group is 60 or less carbon atoms; x is 2, y is 2; and optionally, p is 0.

[0021] In some embodiments, M in formula (I), (Ia), (II), (IIa) or (III) is selected from calcium, magnesium or zinc or a combination thereof; such as calcium or zinc or a combination thereof. In some embodiments, R in formula (III) is a linear, cyclic or branched alkyl or alkenyl group having 6 to 48 carbon atoms, such as 8 to 40 or 10 to 20 carbon atoms. In some embodiments, the metal alkanoate of formula (III) is one or more of zinc neodecanoate, zinc neoundecanoate, zinc neododecanoate, zinc neotridecanoate, zinc neotetradecanoate, zinc neopentadecanoate, zinc neohexadecanoate, zinc neoheptadecanoate, zinc stearate, zinc neooctadecanoate, zinc oleate, zinc neononadecanoate and zinc neoeicosanoate. In some embodiments, the metal alkanoate has a quaternary carbon atom at the 2 position, i.e., connected to a carboxylate group.

[0022] In some embodiments, the lubricating composition further comprises one or more components selected from one or more friction modifiers; one or more antioxidants; one or more pour point depressants; one or more defoaming agents; one or more viscosity modifiers; one or more dispersants; one or more inhibitors and / or rust inhibitors; and / or one or more antiwear agents different from those of component (C).

[0023] In certain embodiments, the lubricating composition comprises the following components: (A) the base oil is present in an amount of 50 to 99 weight percent based on the weight of the lubricating composition; (B) said at least one phosphorus-containing compound selected from detergents, friction modifiers, or antiwear additives other than the colloidal particles described in (C) is present in an amount of 0.001 to 5 weight percent; C) the colloidal particles are present in an amount of 0.01 to 10 wt %, such as 0.01 to 6 wt %, based on the total weight of the lubricating composition; D) optionally, one or more friction modifiers different from those of component (B) present in an amount of 0.01 to 5 weight percent based on the total weight of the lubricating composition; E) optionally, one or more antioxidants present in an amount of 0.01 to 10 wt % based on the total weight of the lubricating composition; F) optionally, one or more pour point depressants present in an amount of 0.01 to 5 weight percent based on the total weight of the lubricating composition; G) optionally, one or more defoaming agents present in an amount of 0.001 to 5 wt % based on the total weight of the lubricating composition; H) optionally, one or more viscosity modifiers are present in an amount of 0.001 to 6 wt % based on the total weight of the lubricating composition; I) optionally, one or more dispersants are present in an amount of 0.01 to 20 wt % based on the total weight of the lubricating composition; J) optionally, one or more inhibitors and / or rust inhibitors are present in an amount of 0.01 to 5 wt. %, based on the total weight of the lubricating composition; and K) optionally, one or more antiwear agents different from those of components (B) and (C) present in an amount of 0.001 to 5 wt. %, based on the total weight of the lubricating composition; L) Optionally, one or more detergents other than those of component (B) and those in the colloidal particles described in (C) are present at 0.1 to 20 wt. %, based on the total weight of the lubricating composition.

[0024] Preferably, the lubricating composition has an adhesive wear of 100 hours or more, such as 120 hours or more, 130 hours or more, or 140 hours or more, as measured by ASTM D8074-16. Preferably, the lubricating composition has a Zn / P ratio (element mass basis) in the lubricating composition of 1.1 to 4.7, such as 1.2 to 4.7, or 1.3 to 4.5, 1.4 to 4.5, 1.5 to 4.5, or 2.5 to 4.0. Preferably, the ligand L in formulas (I) to (III) is selected from water, hydroxide, halides, ammonia, amino, amido, alcoholates, and mixtures thereof. Preferably, the colloidal particles have a metal / surfactant molar ratio MR of at least 5, such as 5 to 50, or 6 to 40, or 7 to 30. In some embodiments, the lubricating composition preferably has a total base number (TBN) of 1 to 30 mgKOH / g, such as 5 to 25 mgKOH / g, 5 to 20 mgKOH / g, such as 7 to 17 mgKOH / g, such as 13 to 15 mgKOH / g, as measured by ASTM D2896. In addition, the lubricating composition has a zinc content of 500 ppm or more, such as 800 ppm or more, or 1000 ppm or more, such as 1500 ppm or more, or 2000 ppm or more, as measured by ASTM D5185.

[0025] In some embodiments, the lubricating composition has a phosphorus content of no greater than 2000 ppm, such as no greater than 1600 ppm, no greater than 1200 ppm, such as no greater than 800 ppm, such as from 1 to 1600 ppm, such as from 10 to 1200 ppm, such as from 100 to 800 parts per million (ppm), based on the total mass of the lubricating composition as measured by ASTM D5185.

[0026] In some embodiments, the lubricating composition is an internal combustion engine oil, such as a petrol or gasoline or heavy duty diesel engine oil, or a marine engine oil or a gas turbine oil. In some embodiments, the lubricating composition is a transmission fluid or a gear oil.

[0027] In some embodiments, the lubricating composition comprises greater than 500 ppm Zn and less than 500 ppm P, preferably greater than 1000 ppm Zn and less than 1000 ppm P, wherein the lubricating composition has an adhesive wear of greater than 100 hours and, optionally, a total base number of greater than 7 mgKOH / g. In some embodiments, the lubricating composition comprises zinc dialkyldithiophosphate in an amount of 2 wt.% or less, such as 1 wt.% or less. In some embodiments, the lubricating composition has a Zn content of less than 150 μm as measured by the HFRR method described herein. 3 , such as less than 140μm 3 or less than 135μm 3 wear scar volume.

[0028] In certain embodiments, the present invention provides a method for achieving an adhesive wear (ASTM D8074-16) of 100 hours or more for a lubricating composition having 500 ppm or more, preferably 1000 ppm or more, of zinc, comprising: (i) providing a lubricating composition according to any one of claims 1 to 24 to a crankcase of an internal combustion engine; (ii) providing a hydrocarbon fuel in an internal combustion engine; and (iii) combusting the fuel in an internal combustion engine.

[0029] In certain embodiments, the present invention provides a method of lubricating an automotive internal combustion engine during engine operation, comprising: (i) providing a lubricating composition according to any one of claims 1 to 24 to a crankcase of an internal combustion engine; (ii) providing a hydrocarbon fuel in an internal combustion engine; and (iii) combusting the fuel in an internal combustion engine. Preferably, the engine is a diesel engine or a gas engine, or a marine engine, or an automobile engine.

[0030] In certain embodiments, the present invention provides a concentrate composition comprising or obtained by combining the following components: (A) 1 to less than 50 weight percent, based on the weight of the concentrate composition, of one or more base oils; (B) at least one phosphorus-containing compound selected from detergents, friction modifiers, or antiwear additives other than the colloidal particles described in (C); (C) 0.1 to 50 wt. % of colloidal particles, based on the weight of the composition, comprising: a) a core of one or more hydrocarbon-insoluble zinc-containing compounds, and b) a shell of one or more of the following: 1) one or more metal-containing surfactants, wherein the metal M comprises a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and the surfactant comprises a hydrocarbyl-substituted sulfonate salt of formula (I) or a hydrocarbyl-substituted salicylate salt of formula (II), where R A and R B are each independently a linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon group having 1 to 70 carbon atoms, wherein when n>1, all R A The sum of the number of carbon atoms in the group and all R B The sum of the number of carbon atoms in the group is 100 or less carbon atoms, and Ar is a monocyclic or polycyclic aromatic group; n is an integer from 1 to the maximum possible number of substitutions on Ar, wherein if m=0, n=1; m is an integer from 0 to 3, x is an integer from 1 to 5; y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 8; 2) one or more metal alkanoates represented by formula (III): wherein M is a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and R C is selected from linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon groups having 6 to 70 carbon atoms, or aromatic groups or alkyl aromatic groups, wherein the aromatic group has 6 to 20 carbon atoms and the alkyl group has 1 to 20 carbon atoms; x is an integer from 1 to 5, wherein in the case of x>1, the R C The groups may be the same or different, y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 8; wherein the concentrate composition has a Zn / P ratio (elemental mass basis as measured by ASTM D5185) of 1.1 to 5.0.

[0031] In certain embodiments, the present invention provides a composition for use as an anti-wear additive in an internal combustion engine, transmission fluid, or gear oil, the composition comprising or being a mixture of the following components: (A) 1 to less than 50 weight percent, based on the weight of the composition, of one or more base oils; (B) at least one phosphorus-containing compound selected from detergents, friction modifiers, or antiwear additives other than the colloidal particles described in (C); (C) 0.1 to 50 wt. % of colloidal particles, based on the weight of the composition, comprising: a) a core of one or more hydrocarbon-insoluble zinc-containing compounds, and b) a shell of one or more of the following: 1) one or more metal-containing surfactants, wherein the metal M comprises a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and the surfactant comprises a hydrocarbyl-substituted aromatic sulfonate of formula (I) or a hydrocarbyl-substituted salicylate group of formula (II), where R A and R B are each independently a linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon group having 1 to 70 carbon atoms, wherein when n>1, all R A The sum of the number of carbon atoms in the group and all R B The sum of the number of carbon atoms in the group is 100 or less carbon atoms, and Ar is a monocyclic or polycyclic aromatic group; n is an integer from 1 to the maximum possible number of substitutions on Ar, wherein if m=0, n=1; m is an integer from 0 to 3, x is an integer from 1 to 5; y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 8; 2) one or more metal alkanoates represented by formula (III): wherein M is a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and R C is selected from linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon groups having 6 to 70 carbon atoms, or aromatic groups or alkyl aromatic groups, wherein the aromatic group has 6 to 20 carbon atoms and the alkyl group has 1 to 20 carbon atoms; x is an integer from 1 to 5, wherein in the case of x>1, the R C The groups may be the same or different, y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 4; wherein the composition has a Zn / P ratio (element mass basis as measured by ASTM D5185) of 1.1 to 5.0. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 (Fig. 1) is a graph illustrating HFRR data of a lubricating oil composition containing the colloidal particles of the present invention compared to a lubricating composition not containing the colloidal particles of the present invention.

[0033] Figure 2 (Fig. 2) Schematic diagram of a composition having a ZnO core and a Ca-surfactant shell (where the surfactant is R-phenylsulfonate or R-salicylate, where R is an alkyl group).

[0034] Figure 3 (Fig. 3) Schematic diagram of a composition having a ZnO core and a Zn-surfactant shell (where the surfactant is R-phenylsulfonate or R-salicylate, where R is an alkyl group).

[0035] Figure 4 (Fig. 4) Schematic diagram of a composition having a ZnO core and a Zn-surfactant shell (where the surfactant is a zinc alkanoate / carboxylate, where R is an alkyl group). definition

[0036] For purposes of this specification and throughout the claims of the present invention, where the following words and expressions are used, they shall have the meanings set out below.

[0037] For purposes herein, the new numbering scheme of the periodic table of the elements is used as described in CHEMICAL AND ENGINEERING NEWS, 63(5), 27 (1985). Alkali metals are Group 1 metals (e.g., Li, Na, K, etc.). Alkaline earth metals are Group 2 metals (e.g., Mg, Ca, Ba, etc.).

[0038] The expression "consisting of" or "consisting essentially of" or cognates may be encompassed by "comprising" or cognates, wherein "consisting essentially of" permits the inclusion of substances that do not materially affect the characteristics of the composition for which it is applied.

[0039] The term "major amount" means greater than 50 weight percent of the composition, such as greater than 60 weight percent of the composition, such as greater than 70 weight percent of the composition, such as 80 to 99.009 weight percent of the composition, such as 80 to 99.9 weight percent of the composition, such as 80 to 99.009 weight percent of the composition, based on the mass of the composition.

[0040] The term "minor amount" means 50 wt.% or less of the composition, based on the mass of the composition; such as 40 wt.% or less of the composition; such as 30 wt.% or less of the composition, such as 20 to 0.001 wt.%, such as 20 to 0.1 wt.%.

[0041] Unless otherwise indicated, the term "weight %" refers to the mass percentage of a component based on the mass of the composition measured in grams, and is alternatively referred to as weight percent ("weight %", "wt. %" or "% w / w").

[0042] The term "active ingredient" (also referred to as "ai" or "AI") refers to an additive material that is neither a diluent nor a solvent.

[0043] The terms "group" and "radical" are used interchangeably herein.

[0044] 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," particularly a "refined hydrocarbon," the hydrocarbon may also contain minor amounts (e.g., where the heteroatom does not substantially alter the hydrocarbon nature of the hydrocarbon compound) of one or more heteroatoms or heteroatom-containing groups (e.g., halogens, particularly chlorine and fluorine, amino, alkoxy, mercapto, alkylmercapto, nitro, nitroso, sulfoxy, etc.).

[0045] 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, particularly chlorine and fluorine, amino, alkoxy, mercapto, alkylmercapto, nitro, nitroso, sulfoxy, etc.) are known to those skilled in the art.

[0046] The term "alkyl" refers to a carbon and hydrogen group (e.g., C1 to C 70 , or as C1 to C 12Groups, as further described herein). The alkyl group in a compound is typically directly bonded to the compound via a carbon atom. Unless otherwise specified, an alkyl group can be linear (i.e., unbranched) or branched, cyclic, acyclic, or part 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.

[0047] The term "alkene" refers to a carbon and hydrogen compound (e.g., C2 to C 70 Groups such as C2 to C 12 groups, as described in further detail herein).

[0048] The term "alkenyl" refers to a carbon and hydrogen group (e.g., C2 to C 70 Groups such as C2 to C 12 Groups, as further described herein). An alkenyl group in a compound is typically bonded directly to the compound via a carbon atom. Unless otherwise specified, an alkenyl group may be linear (i.e., unbranched) or branched, cyclic, acyclic, or partially cyclic / acyclic.

[0049] The term "alkylene" refers to a C1 to C 20 , preferably C1 to C 10 A 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.

[0050] The term "alkynyl" refers to a C2 to C 70 (such as C2 to C 12 ) group.

[0051] The term "aryl" refers to a group containing at least one aromatic ring (i.e., monocyclic or polycyclic), such as cyclopentadiene, phenyl, naphthyl, anthracenyl, etc. Aryl is usually C5 to C 40 (such as C5 to C 18 , such as C6 to C20 ) 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.

[0052] The term "substituted" means that a hydrogen atom has been replaced by a hydrocarbon group, a heteroatom or a heteroatom-containing group. Alkyl substituted derivatives mean that a hydrogen atom has been replaced by an alkyl group. "Alkyl substituted phenyl" is a phenyl group in which a 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.

[0053] The term "halogen" or "halo" refers to a Group 17 atom or a group of Group 17 atoms, such as fluorine, chlorine, bromine, and iodine.

[0054] The term "ashless" with respect to an additive means that the additive does not include metals.

[0055] The term "ash-containing" with respect to an additive means that the additive includes a metal.

[0056] 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.

[0057] The term "effective minor amount" with respect to an additive refers to an amount of such additive that is less than 50% by weight of the lubricating oil composition such that the additive provides the desired technical effect.

[0058] Unless otherwise indicated, the term "ppm" means parts per million by mass based on the total mass of the lubricating oil composition.

[0059] The term "metal content" of a lubricating oil composition or additive component, such as zinc content, magnesium content, molybdenum content or total metal content (ie, the sum of all individual metal contents) is measured by ASTM D5185.

[0060] With respect to additive components or lubricating oil compositions (ie, unused lubricating oil compositions), the term "total base number," also referred to as "TBN," refers to the total base number as measured by ASTM D2896.

[0061] The term "total acid number," also referred to as "TAN," refers to the total acid number as measured by ASTM D664.

[0062] The term "adhesive wear" is measured by ASTM 8074-16, which is also known as the DD13 Scuffing Test.

[0063] "Phosphorus content" is measured by ASTM D5185.

[0064] "Sulfur content" is measured by ASTM D2622.

[0065] "Sulfated ash content" is measured by ASTM D874.

[0066] The "zinc content" of a lubricant composition is measured by ASTM D5185.

[0067] The term "neo acids" refers to carboxylic acids exhibiting a highly branched structure wherein the carboxylic acid functionality is attached to a quaternary carbon atom and wherein the other moiety bonded to the quaternary carbon is a saturated linear, branched or cyclic alkyl group.

[0068] Neodecanoic acid is a compound with the general structural formula C 10 H 20 O2 C 10 A mixture of neo-acids. The components of the mixture are acids having three alkyl groups at carbon 2, including but not limited to 2,2,3,5-tetramethylhexanoic acid, 2,4-dimethyl-2-isopropylpentanoic acid, 2,5-dimethyl-2-ethylhexanoic acid, 2,2-dimethyloctanoic acid, and 2,2-diethylhexanoic acid.

[0069] The term "aliphatic hydrocarbyl fatty acid" refers to an aliphatic hydrocarbon fatty acid having a C7 to C 29 , preferably C9 to C 27 , most preferably C 11 to C 23 Such compounds may be referred to herein as aliphatic (C7 to C 29 ), more preferably (C9 to C 27 ), most preferably (C 11 to C 23 ) Hydrocarbyl monocarboxylic acid or hydrocarbon fatty acid (wherein C x to C y The total number of carbon atoms in the aliphatic hydrocarbon chain of the fatty acid, including the total carbon atoms in the fatty acid itself due to the presence of the carboxyl carbon atom x+1 to C y+1carbon atoms). Preferably, the aliphatic hydrocarbyl fatty acid has an even number of carbon atoms, including the carboxyl carbon atom. The aliphatic hydrocarbyl chain of the fatty acid may be saturated or unsaturated (i.e., comprises 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., comprise 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.

[0070] The term "aliphatic hydrocarbyl fatty acid ester" refers to an ester obtainable by converting the monocarboxylic acid functional group of the corresponding aliphatic hydrocarbyl fatty acid into an ester group. Suitably, the monocarboxylic acid functional group of the aliphatic hydrocarbyl fatty acid is converted into a hydrocarbyl 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.

[0071] The term "sulfurized aliphatic hydrocarbyl fatty acid ester" refers to a compound obtained by sulfurizing an aliphatic hydrocarbyl fatty acid ester as defined herein.

[0072] The term "absent" when referring to a component included in the lubricating oil compositions 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.

[0073] As used herein, the terms "oil-soluble" and "oil-dispersible" or homologous 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, for example, soluble or stably dispersed in the oil to the extent that they will have a desired effect in the oil's environment of use. In particular, the terms "oil-soluble" and "oil-dispersible" mean that the specified compound / material is soluble or stably dispersed in the oil to the extent that it will have a desired effect in the oil's environment of use, without precipitation over at least 4 weeks, such as 6 weeks, 8 weeks, 10 weeks or 12 weeks. In addition, if desired, the additional incorporation of other additives may also allow the incorporation of higher amounts of a specific additive.

[0074] As used herein, the terms "oil-insoluble" and "oil-indispersible" or cognate terms do not necessarily mean that the compound or additive is insoluble, insoluble, immiscible, or unable to be suspended in oil in all proportions. Rather, they mean that they are insoluble or not stably dispersible in oil, for example, to an extent that impairs or reduces their intended effect in the environment in which the oil is used. In particular, the terms "oil-insoluble" and "oil-indispersible" mean that the specified compound / material exhibits precipitation in a period of less than 4 weeks, such as 3 weeks.

[0075] Unless otherwise specified, kinematic viscosity (KV 100 、KV 40 ) was determined according to ASTM D445-19a and reported in cSt.

[0076] Unless otherwise indicated, all percentages reported are weight percent on an active ingredient basis, ie, without taking into account carrier or diluent oil.

[0077] It is also understood that the various components used (essential as well as optimal and conventional) may react under conditions of formulation, storage or use, and the invention also provides products obtainable or obtained as a result of any such reaction.

[0078] Furthermore, it is to be understood that any upper and lower limits of amounts, ranges, and ratios recited herein are independently combinable.

[0079] It is also to be understood that the preferred features of each aspect of the present invention are considered as the preferred features of each other aspect of the present invention. Accordingly, the preferred and more preferred features of one aspect of the present invention may be independently combined with other preferred and / or more preferred features of the same or different aspects of the present invention. Details

[0080] The features of the invention will now be described in more detail as follows, which relate where appropriate to each and every aspect of the invention.

[0081] The lubricating oil composition of the present invention comprises 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 invention encompasses compositions comprising the components before mixing, or after mixing, or both.

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

[0083] The present invention relates to a lubricating oil composition (also referred to as a "lubricant composition", "lubricating composition" or "lubricant oil composition") comprising the following components or a mixture of the following components: (A) 1 to 99.99 wt % (or 30 to 95 wt %, or 50 to 90 wt %, or 60 to 95 wt %, or 70 to 85 wt %) of one or more base oils, based on the weight of the lubricating composition; (B) at least one phosphorus-containing compound selected from detergents, friction modifiers, or antiwear additives other than the colloidal particles described in (C); (C) 0.01 to 10 wt % (particularly 0.1 to 5 wt %, or 0.5 to 3 wt %, or 0.75 to 2 wt %, or 0.75 to 1.5 wt %) of colloidal particles, based on the weight of the composition, comprising: a) a core of one or more hydrocarbon-insoluble zinc-containing compounds, and b) a shell of one or more of the following: 1) one or more metal-containing surfactants, wherein the metal M comprises a Group 1, 2, 4, 5, 6, 10, 11, 12 or 13 metal, such as sodium, potassium, lithium, magnesium, calcium, barium, gold, silver, palladium, platinum, zirconium, vanadium, molybdenum, platinum, nickel, copper, zinc, aluminum or a mixture of 2, 3, 4, 5, 6, 7 or 8 metals, such as a mixture of 2 or 3 of sodium, magnesium, calcium, zinc, nickel, copper and aluminum, such as calcium or magnesium, and / or zinc; the surfactant comprises a hydrocarbyl-substituted aliphatic or aromatic sulfonate of formula (I) or a hydrocarbyl-substituted salicylate of formula (II), where R A and R B Each independently of the other is a linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon group having 1 to 70 carbon atoms, such as C1 to C 70 (or C1 to C 60 , or C1 to C 50 , or C1 to C 40 , or C1 to C 30 , or C1 to C 20 , or C1 to C 10 , or C1 to C6, or C2 to C4) linear, branched or cyclic alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, a monocyclic or polycyclic variant thereof or any isomer thereof, or a C2 to C6) linear, branched or cyclic alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, a monocyclic or polycyclic variant thereof or any isomer thereof, or a C2 to C4) linear, branched or cyclic alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonadecyl, eicosyl, a monocyclic or polycyclic variant thereof or any isomer thereof, or a C2 to C6) linear, branched or cyclic alkyl, such as methyl, 70 (or C2 to C 60 , or C2 to C 50 , or C2 to C 40 , or C2 to C 30 , or C2 to C 20 , or C2 to C 10 , or C2 to C6, or C2 to C4) linear, branched or cyclic alkenyl, such as ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, a monocyclic or polycyclic variant thereof or any isomer thereof, wherein when n>1, all R A The sum of the number of carbon atoms in the group and all R B The total number of carbon atoms in the group is 100 or less carbon atoms, and Ar is a monocyclic or polycyclic aromatic group, such as C5 to C 20 Aromatic groups, or C6 to C 20 , such as benzene, naphthalene, fluorene, phenalene, phenanthrene, anthracene, pyrene, tetracene, (chrysene), perylene or a mixture thereof; n is an integer from 1 to the maximum possible number of substitutions on Ar, wherein if m=0, then n=1; m is an integer from 0 to 3; x is an integer from 1 to 5; y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, such as water, hydroxide, halogen, ammonia, amino, amido, alkoxide and mixtures thereof; and p is an integer from 0 to 8; 2) one or more metal alkanoates represented by formula (III): wherein M is a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal, such as sodium, potassium, lithium, magnesium, calcium, barium, gold, silver, palladium, platinum, zirconium, vanadium, molybdenum, nickel, copper, zinc, aluminum, or a mixture of 2, 3, 4, 5, 6, 7, or 8 metals, such as a mixture of 2 or 3 of sodium, magnesium, calcium, zinc, nickel, copper, and aluminum, such as calcium or magnesium, and / or zinc; R C is a linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon group having 6 to 70 carbon atoms, such as C6 to C 70 (or C1 to C 60 , or C6 to C 50 , or C6 to C 40 , or C6 to C 30 , or C6 to C 20 , or C6 to C 10 , or C6 to C8, or C 10 to C 20 ) linear, branched or cyclic alkyl, such as hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, monocyclic or polycyclic variants thereof or any isomers thereof; or C6 to C8 containing one or more double bonds 70 (or C6 to C 60 , or C6 to C 50 , or C6 to C 40 , or C6 to C 30 , or C6 to C 20 , or C6 to C 10 , or C6 to C8) linear, branched or cyclic alkenyl, such as hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, a monocyclic or polycyclic variant thereof or any isomer thereof; or an aromatic group or an alkyl aromatic group, wherein the aromatic group has 6 to 20 carbon atoms, such as benzene, naphthalene, fluorene, phenanthene, anthracene, pyrene, tetracene, perylene, such as benzene or naphthalene or a mixture thereof, and the alkyl group has 1 to 20 carbon atoms, (or C1 to C 10 , or C1 to C6, or C2 to C4 linear, branched or cyclic alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl or any isomer thereof); x is an integer from 1 to 5, wherein when x>1, said R C The groups may be the same or different, y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, such as water, hydroxide, halogen, ammonia, amino, amido, alkoxide, and mixtures thereof; and p is an integer from 0 to 8; wherein the lubricating oil composition has a Zn / P ratio (elemental mass basis as measured by ASTM D5185) of 1.1 to 5.0.

[0084] In one embodiment, the present invention relates to a lubricating oil composition comprising or obtained by mixing the following components: (A) 1 to 99.99 wt % (or 30 to 95 wt %, or 50 to 90 wt %, or 60 to 95 wt %, or 70 to 85 wt %) of one or more base oils, based on the weight of the lubricating composition; (B) at least one phosphorus-containing compound selected from detergents, friction modifiers, or antiwear additives other than the colloidal particles described in (C); (C) 0.01 to 10 wt % (particularly 0.1 to 5 wt %, or 0.5 to 3 wt %, or 0.75 to 2 wt %, or 0.75 to 1.5 wt %) of colloidal particles, based on the weight of the composition, comprising: a) a core of one or more hydrocarbon-insoluble zinc-containing compounds, and b) a shell of one or more hydrocarbyl-substituted aliphatic or aromatic sulfonate surfactants of formula (I), wherein the metal M comprises a Group 1, 2, 4, 5, 6, 10, 11, 12 or 13 metal, such as sodium, potassium, lithium, magnesium, calcium, barium, gold, silver, palladium, platinum, zirconium, vanadium, molybdenum, nickel, copper, zinc, aluminum or a mixture of 2, 3, 4, 5, 6, 7 or 8 metals, such as a mixture of 2 or 3 of sodium, magnesium, calcium, zinc, nickel, copper and aluminum, such as calcium or magnesium, and / or zinc; Among them, each R A are independently linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon groups having 1 to 70 carbon atoms, such as C1 to C 70 (or C1 to C 60 , or C1 to C50 , or C1 to C 40 , or C1 to C 30 , or C1 to C 20 , or C1 to C 10 , or C1 to C6, or C2 to C4) linear, branched or cyclic alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, a monocyclic or polycyclic variant thereof or any isomer thereof, or a C2 to C6) linear, branched or cyclic alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, a monocyclic or polycyclic variant thereof or any isomer thereof, or a C2 to C4) linear, branched or cyclic alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonadecyl, eicosyl, a monocyclic or polycyclic variant thereof or any isomer thereof, or a C2 to C6) linear, branched or cyclic alkyl, such as methyl, 70 (or C2 to C 60 , or C2 to C 50 , or C2 to C 40 , or C2 to C 30 , or C2 to C 20 , or C2 to C 10 , or C2 to C6, or C2 to C4) linear, branched or cyclic alkenyl, such as ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, a monocyclic or polycyclic variant thereof or any isomer thereof, wherein when n>1, all R A The total number of carbon atoms in the group is 100 or less; and Ar is a monocyclic or polycyclic aromatic group, such as C5 to C 20 Aromatic groups such as benzene, naphthalene, fluorene, phenanthracene, anthracene, pyrene, tetracene, perylene, such as benzene or naphthalene, or benzene, or a mixture thereof; n is an integer from 1 to the maximum possible number of substitutions on Ar, wherein if m=0, then n=1; m is an integer from 0 to 3, x is an integer from 1 to 5; y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, such as water, hydroxide, halogen, ammonia, amino, amido, alkoxide, and mixtures thereof; and p is an integer from 0 to 8; wherein the lubricating oil composition has a Zn / P ratio (elemental mass basis as measured by ASTM D5185) of 1.1 to 5.0.

[0085] In an exemplary embodiment thereof, the surfactant of formula (I) is a metal-containing hydrocarbyl-substituted sulfonate surfactant of formula (Ia):

[0086] In embodiments of colloidal particles comprising a shell of a sulfonate surfactant having formula (I) or (Ia), the sulfonate may be an aliphatic sulfonate such that m=0 and Ar is absent, and n is 1 such that the sulfonate has the formula R A -SO 3- , where R A As defined herein.

[0087] In other embodiments of colloidal particles comprising a shell of a sulfonate surfactant having formula (I) or (Ia), the sulfonate may be an aromatic sulfonate, whereby m is at least 1, or 2 or 3, and Ar is present, and n is at least 1 up to the maximum possible number of substitutions on Ar, for example, for benzene n is 1 to 5, for naphthalene n is 1 to 7. In the case where Ar = benzene, n may be 1 to 3, such as 1 or 2, or 1, and the surfactant may also be of a different R A A mixture of sulfonates of different substitution numbers.

[0088] In a particular embodiment of the surfactant of formula (Ia), the metal M is selected from calcium, magnesium, barium, or zinc or a combination thereof, such as calcium, magnesium, or zinc, or calcium, or zinc; R A are independently linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon groups having 6 to 50 carbon atoms, such as 10 to 40 or 12 to 37 carbon atoms; n is an integer from 1 to 5, such as 1 to 4, such as 1, 2 or 3, such as 1; m is 0 to 3, such as 0 or 1, or 2; wherein if m=0, then n=1; all R A The total number of carbon atoms in the group is 60 or less carbon atoms; x is 2; and y is 2.

[0089] In an exemplary embodiment, m=1, and the surfactant of formula (Ia) is a hydrocarbyl-substituted phenyl or naphthyl sulfonate. In a further exemplary embodiment, the lubricating composition comprises colloidal particles having a core of zinc, zinc oxide, a zinc salt such as zinc carbonate, zinc hydroxide, a zinc halide such as zinc fluoride, zinc chloride, zinc bromide, zinc iodide, preferably zinc oxide, and a shell of the surfactant of formula (Ia), wherein the metal M is calcium or magnesium or a mixture thereof, preferably calcium, and R A It is C 30 to C 40 alkyl, and n is 1 or 2, such as 1, or a mixture thereof.

[0090] In a further embodiment, the present invention relates to a lubricating oil composition comprising or obtained by mixing the following components: (A) 1 to 99.99 wt % (or 30 to 95 wt %, or 50 to 90 wt %, or 60 to 95 wt %, or 70 to 85 wt %) of one or more base oils, based on the weight of the lubricating composition; (B) at least one phosphorus-containing compound selected from detergents, friction modifiers, or antiwear additives other than the colloidal particles described in (C); (C) 0.01 to 10 wt % (particularly 0.1 to 5 wt %, or 0.5 to 3 wt %, or 0.75 to 2 wt %, or 0.75 to 1.5 wt %) of colloidal particles, based on the weight of the composition, comprising: a) a core of one or more hydrocarbon-insoluble zinc-containing compounds, and b) a shell of one or more hydrocarbyl-substituted salicylate surfactants of formula (II): wherein the metal M comprises a Group 1, 2, 4, 5, 6, 10, 11, 12 or 13 metal, such as sodium, potassium, lithium, magnesium, calcium, barium, gold, silver, palladium, platinum, zirconium, vanadium, molybdenum, nickel, copper, zinc, aluminum or a mixture of 2, 3, 4, 5, 6, 7 or 8 metals, such as a mixture of 2 or 3 of sodium, magnesium, calcium, zinc, nickel, copper and aluminum, such as calcium, or magnesium, and / or zinc; Among them, each R B are independently linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon groups having 1 to 70 carbon atoms, such as C1 to C 70 (or C1 to C 60 , or C1 to C 50 , or C1 to C 40 , or C1 to C 30 , or C1 to C 20 , or C1 to C 10 , or C1 to C6, or C2 to C4) linear, branched or cyclic alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, a monocyclic or polycyclic variant thereof or any isomer thereof, or a C2 to C6) linear, branched or cyclic alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, a monocyclic or polycyclic variant thereof or any isomer thereof, or a C2 to C4) linear, branched or cyclic alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonadecyl, eicosyl, a monocyclic or polycyclic variant thereof or any isomer thereof, or a C2 to C6) linear, branched or cyclic alkyl, such as methyl, 70 (or C2 to C 60 , or C2 to C 50 , or C2 to C 40 , or C2 to C 30 , or C2 to C 20 , or C2 to C 10, or C2 to C6, or C2 to C4) linear, branched or cyclic alkenyl, such as ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, a monocyclic or polycyclic variant thereof or any isomer thereof, wherein when n>1, all R B The total number of carbon atoms in the group is 70 or less, and Ar is a monocyclic or polycyclic aromatic group, such as C5 to C 20 Aromatic groups such as benzene, naphthalene, fluorene, phenanthracene, anthracene, pyrene, tetracene, perylene or a mixture thereof; n is an integer from 1 to the maximum possible number of substitutions on Ar, m is an integer from 1 to 3, x is an integer from 1 to 5; y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, such as water, hydroxide, halogen, ammonia, amino, amido, alkoxide, and mixtures thereof; and p is an integer from 0 to 8; wherein the lubricating oil composition has a Zn / P ratio (elemental mass basis as measured by ASTM D5185) of 1.1 to 5.0.

[0091] In an exemplary embodiment thereof, the surfactant of formula (II) is a metal-containing hydrocarbyl-substituted phenyl salicylate surfactant of formula (IIa):

[0092] In a particular embodiment thereof, the metal M is selected from calcium, magnesium, barium or zinc or a combination thereof; such as calcium, magnesium or zinc or a combination thereof; or calcium or zinc or a combination thereof; R B are independently linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon groups having 6 to 50 carbon atoms, such as 10 to 48 or 12 to 37 carbon atoms; n is an integer from 1 to 4, such as 1 to 3, such as 1 or 2, such as 1; all R B The total number of carbon atoms in the group is 60 or less carbon atoms; x is 2, and y is 2.

[0093] In yet a further embodiment, the present invention relates to a lubricating oil composition comprising or obtained by mixing the following components: (A) 1 to 99.99 wt % (or 30 to 95 wt %, or 50 to 90 wt %, or 60 to 95 wt %, or 70 to 85 wt %) of one or more base oils, based on the weight of the lubricating composition; (B) at least one phosphorus-containing compound selected from detergents, friction modifiers, or antiwear additives other than the colloidal particles described in (C); (C) 0.01 to 10 wt % (particularly 0.1 to 5 wt %, or 0.5 to 3 wt %, or 0.75 to 2 wt %, or 0.75 to 1.5 wt %) of colloidal particles, based on the weight of the composition, comprising: a) a core of one or more hydrocarbon-insoluble zinc-containing compounds, and b) a shell of one or more metal alkanoates represented by formula (III): wherein M is a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal, such as sodium, potassium, lithium, magnesium, calcium, barium, gold, silver, palladium, platinum, zirconium, vanadium, molybdenum, nickel, copper, zinc, aluminum, or a mixture of 2, 3, 4, 5, 6, 7, or 8 metals, such as a mixture of 2 or 3 of sodium, magnesium, calcium, zinc, nickel, copper, and aluminum, such as calcium or magnesium, and / or zinc; R C is a linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon group having 6 to 70 carbon atoms, such as C8 to C 70 (or C6 to C 60 , or C6 to C 50 , or C6 to C 40 , or C6 to C 30 , or C6 to C 20 , or C6 to C 10 , or C6 to C8, or C 10 to C 20 ) linear, branched or cyclic alkyl, such as hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, monocyclic or polycyclic variants thereof or any isomers thereof; or C6 to C8 containing one or more double bonds 70 (or C6 to C 60 , or C6 to C 50 , or C6 to C 40 , or C6 to C 30 , or C6 to C 20 , or C6 to C 10 , or C6 to C8) linear, branched or cyclic alkenyl, such as hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosene, a monocyclic or polycyclic variant thereof or any isomer thereof; or an aromatic group or an alkyl aromatic group (aralkyl), wherein the aromatic group has 6 to 20 carbon atoms, such as benzene, naphthalene, fluorene, phenanthene, anthracene, pyrene, tetracene, Perylene, such as benzene or naphthalene, or a mixture thereof, and the alkyl group of the aralkyl group has 1 to 20 carbon atoms, (or C1 to C 10 , or C1 to C6, or C2 to C4 linear, branched or cyclic alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl or any isomer thereof); x is an integer from 1 to 5, wherein when x>1, said R C The groups may be the same or different, y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, such as water, hydroxide, halogen, ammonia, amino, amido, alkoxide, and mixtures thereof; and p is an integer from 0 to 8; wherein the lubricating oil composition has a Zn / P ratio (elemental mass basis as measured by ASTM D5185) of 1.1 to 5.0.

[0094] In an exemplary embodiment thereof, the surfactant of formula (III) is a surfactant of formula (IIIa) as further defined below.

[0095] In one embodiment thereof, the metal alkanoate of formula (III) is a zinc alkanoate, wherein R C Derived from fatty acids, such as monounsaturated or diunsaturated fatty acids, for example monounsaturated fatty acids, such as crotonic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid; or di-unsaturated fatty acids, such as linoleic acid, eicosadienoic acid, docosadienoic acid; any isomers or mixtures thereof.

[0096] In a particular embodiment, the metal alkanoate of formula (III) is zinc alkanoate, wherein R CDerived from one or more neoacids, such as neodecanoic acid, neoundecanoic acid, neododecanoic acid, neotridecanoic acid, neotetradecanoic acid, neopentadecanoic acid, neohexadecanoic acid, neoheptadecanoic acid, neooctadecanoic acid, neononadecanoic acid, neoeicosanoic acid and isomers thereof. In particular, the zinc alkanoate that can be used can be zinc neodecanoate and / or zinc ethylhexanoate. In some embodiments, the metal alkanoate has a quaternary carbon atom at the 2 position, i.e., connected to a carboxylate group.

[0097] In some embodiments, the metal alkanoate of formula (III) is zinc alkanoate, wherein R C Derived from one or more linear aliphatic acids such as capric, lauric, myristic, stearic, arachidic acid, or unsaturated carboxylic or fatty acids such as myristoleic, palmitoleic, oleic, linoleic, aracidonic, and erucic acid.

[0098] In particular, the metal alkanoate of formula (III) may be a metal alkanoate of formula (IIIa): wherein M is a Group 4, 5, 10, 11 or 12 metal, such as nickel, palladium, platinum, copper, silver, gold, zinc, tin, zirconium, hafnium, titanium, vanadium, molybdenum, niobium, tantalum or a mixture of two, three, four, five, six, seven or more Group 4, 5, 10, 11 and 12 metals, preferably M is zirconium, vanadium, molybdenum or zinc, and preferably M is zinc; R 1 、R 2 and R 3 are each independently hydrogen or C1 to C 20 (or C1 to C 10 , or C1 to C6, or C2 to C4) linear, branched or cyclic alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl or any isomer thereof, wherein R 1 、R 2 and R 3 3, 2, 1 or none of them are hydrogen, R 4 、R 5 and R 6 Each independently C1 to C 20 (or C1 to C 10, or C1 to C6, or C2 to C4) linear, branched or cyclic alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl or any isomer thereof, and where R 1 +R 2 +R 3 =7 or more carbon atoms, i.e. R 1 、R 2 and R 3 is 7 or more carbon atoms (or 7 to 40, or 8 to 22, or 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms); and R 4 +R 5 +R 6 =7 or more carbon atoms, i.e. R 4 、R 5 and R 6 is 7 or more carbon atoms (or 7 to 40, or 8 to 22, or 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms); and R 1 +R 2 +R 3 and R 4 +R 5 +R 6 The alkanoates may be the same or different (i.e., symmetrical alkanoates) and independently have more than 7 carbon atoms, such as 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30 carbon atoms, and particularly 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms.

[0099] In particular, R 1 、R 2 and R 3 is derived from one or more neoacids; and R 4 、R 5 and R 6 Derived from the same or different neo acids (e.g., neodecanoic acid, neoundecanoic acid, neododecanoic acid, neotridecanoic acid, neotetradecanoic acid, neopentadecanoic acid, neohexadecanoic acid, neoheptadecanoic acid, neooctadecanoic acid, neononadecanoic acid, neoeicosanoic acid, and isomers thereof).

[0100] In particular, the useful metal surfactants / soaps of formula (I), (Ia), (II), (IIa), (III), or (IIIa) used as shells in the colloidal particles of the present invention are liquid at 24°C, preferably liquid at 60°C. In particular, the useful metal surfactants used in the colloidal particles described herein and the colloidal particles described herein themselves remain stably dispersed at engine starting temperatures, such as above -32°C, such as above 0°C, such as above 30°C, such as above 40°C, such as above 60°C, such as from -30°C to 60°C, such as from 0 to less than 80°C, and are liquid at engine operating temperatures, such as above 80°C, such as above 150°C, such as above 200°C. In some embodiments, the metal surfactant is liquid at -15°C and liquid at 80°C.

[0101] In all embodiments of formula (I), (Ia), (II), (IIa), (III) or (IIIa), the hydrocarbon-insoluble zinc-containing compound may be selected from at least one of zinc, zinc oxide, a zinc salt such as zinc carbonate, zinc hydroxide, a zinc halide such as zinc fluoride, zinc chloride, zinc bromide, zinc iodide, preferably at least one of zinc, zinc oxide and zinc carbonate, or a mixture thereof.

[0102] The colloidal particles may have an average particle size in the range of 5 nm to 1 μm, such as 20 nm to 500 nm, or 20 nm to 200 nm, as determined by dynamic light scattering as described in the Examples section below.

[0103] In certain embodiments, the metal M in formula (I), (Ia), (II), (IIa), (III) or (IIIa) is selected from at least one of sodium, potassium, lithium, magnesium, calcium, barium or a mixture thereof, preferably calcium or magnesium; or the metal M is selected from at least one of gold, silver, palladium, platinum, zirconium, vanadium, molybdenum, nickel, copper, zinc, aluminum or a mixture thereof, preferably zinc, or calcium, or a mixture of two or three of zinc, calcium and magnesium.

[0104] Preferably, Ar in formula (I) or formula (II) is benzene or naphthalene.

[0105] In embodiments, the lubricating compositions described herein may further comprise 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 modifiers; 1) one or more dispersants; J) one or more inhibitors and / or rust preventatives; and / or K) one or more antiwear agents not falling within formula (I); L) One or more detergents other than those of component (B) and those in the colloidal particles described in (C).

[0106] In certain embodiments of the lubricating composition: A) the base oil is present in an amount of 50 to 99 weight percent based on the weight of the lubricating composition; and B) the at least one phosphorus-containing compound selected from detergents, friction modifiers, or antiwear additives other than the colloidal particles described in (C) is present in an amount of 0.001 to 5 weight percent; and C) The colloidal particles are present in an amount of 0.01 to 10 wt % or 0.01 to 6 wt % based on the total weight of the lubricating composition.

[0107] In an embodiment of the lubricating composition: D) optionally, one or more friction modifiers different from those of component (B) present in an amount of 0.01 to 5 weight percent based on the total weight of the lubricating composition; E) optionally, one or more antioxidants present in an amount of 0.01 to 5 wt % based on the total weight of the lubricating composition; F) optionally, one or more pour point depressants present in an amount of 0.01 to 5 weight percent based on the total weight of the lubricating composition; G) optionally, one or more defoaming agents present in an amount of 0.001 to 5 wt % based on the total weight of the lubricating composition; H) optionally, one or more viscosity modifiers are present in an amount of 0.001 to 6 wt % based on the total weight of the lubricating composition; I) optionally, one or more dispersants are present in an amount of 0.01 to 20 wt % based on the total weight of the lubricating composition; J) optionally, one or more inhibitors and / or rust inhibitors are present in an amount of 0.001 to 5 wt. %, based on the total weight of the lubricating composition; K) optionally, one or more antiwear agents different from those of components B) and C) present in an amount of 0.001 to 5 wt. %, based on the total weight of the lubricating composition; and L) Optionally, one or more detergents other than those of component (B) and those in the colloidal particles described in (C) are present at 0.1 to 20 wt. %, based on the total weight of the lubricating composition.

[0108] For the purposes of the present invention and the claims thereto, the colloidal particles of component C) are not added to the above-mentioned components B, D, E, F, G, H, I, J, K and / or L for determining the weight percentages, although they may exhibit similar properties. For example, the colloidal particles of component C) may positively influence wear but are not counted in component K) for determining the weight percentage of the antiwear agent.

[0109] In some embodiments, all of ingredients D, E, F, G, H, I, J, K, and L are present in addition to the base oil, the phosphorus-containing compound, and the one or more colloidal particles described herein.

[0110] In some embodiments, ingredients D, E, F, G, H, I, and J are present in addition to the base oil, the phosphorus-containing compound, and the colloidal particles described herein.

[0111] In some embodiments, ingredients I, F, and G are present in addition to the base oil, the phosphorus-containing compound, and the one or more colloidal particles described herein.

[0112] In some embodiments, ingredients D, E, F, G, H, I, and J are present in addition to the base oil, the phosphorus-containing compound, and the one or more colloidal particles described herein.

[0113] In some embodiments, ingredients I, F, and G are present in addition to the base oil, the phosphorus-containing compound, and the one or more colloidal particles described herein.

[0114] Suitably, the lubricant composition may have an adhesive wear as measured by ASTM D8074-16 of 100 hours or more, or 120 hours or more, or 130 hours or more, or 140 hours or more, such as from 100 to 200 hours.

[0115] Suitably, the lubricant composition may have a total base number (TBN) as measured by ASTM D2896 of 1 to 30 mgKOH / g, such as 5 to 25 mgKOH / g, 6 to 20 mgKOH / g, such as 7 to 17 mgKOH / g, such as 13 to 16 mgKOH / g, or 4 to 17 mgKOH / g as measured by ASTM D2896, preferably 5 to 16 mgKOH / g, such as 6 to 15 mgKOH / g, such as 8 to 14 mgKOH / g.

[0116] Suitably, the lubricant composition may have: i. 100 hours or more, or 120 hours or more of adhesive wear, a Zn / P ratio (element mass basis) of 1.1 to 5.0 (e.g., 1.1 to 4.7, or 1.2 to 4.7, or 1.3 to 4.5, 1.4 to 4.5, 1.5 to 4.5, or 2.5 to 4.0); and ii. a total base number (TBN) of 4 to 17 mgKOH / g, preferably 5 to 16 mgKOH / g, such as 6 to 15 mgKOH / g, such as 8 to 14 mgKOH / g, as measured by ASTM D2896.

[0117] Suitably, the lubricant composition may have a Total Base Number (TBN) (ASTM D2896) that is at least 5% higher (or at least 10% higher, or at least 20% higher, or at least 50% higher) than the TBN measured in the same formulation tested under the same conditions except that a conventional detergent (e.g., calcium salicylate having a TBN of 225 mgKOH / g) is used instead of the zinc-containing colloidal particles defined in the present invention at the same total detergent content.

[0118] Alternatively, the lubricant composition may have a Total Base Number (ASTM D2896) that is at least 10% higher (or at least 20% higher, or at least 50% higher) than the TBN measured for the same formulation tested under the same conditions at the same total detergent content, except that the zinc-containing colloidal particles defined in the present invention are absent.

[0119] Furthermore, the use of colloidal particles in the lubricant compositions described herein provides a way to improve antiwear properties by increasing the SASH above the existing SASH in the lubricant composition formulation, but without adding more phosphorus. Alternatively, the use of colloidal particles described herein can be used to maintain detergency (TBN) while improving antiwear performance after replacing the detergent with colloidal zinc-containing particles.

[0120] Suitably, the lubricant composition may have an adhesive wear as measured by ASTM D8074 that is at least 20% higher (or at least 30% higher, or at least 40% higher, or at least 50% higher, or at least 60% higher, or at least 70% higher, or at least 100% higher) than the adhesive wear measured in the same formulation tested under the same conditions except that calcium alkylphenyl sulfonate is used instead of the zinc-containing colloidal particles defined in the present invention.

[0121] Suitably, the lubricant composition may have an adhesive wear as measured by ASTM D8074-16 that is at least 20% higher (or at least 30% higher, or at least 40% higher, or at least 50% higher, or at least 60% higher, or at least 70% higher, or at least 100% higher) than the adhesive wear measured in the same formulation tested under the same conditions but in the absence of the zinc-containing colloidal particles defined in the present invention.

[0122] The zinc-containing colloidal particles in the lubricating composition of the present invention may have a metal / surfactant molar ratio MR of at least 5, such as from 5 to 50, or from 6 to 40, or from 7 to 30, which is measured as moles of metal per molar equivalent of metal surfactant (soap), calculated from the actual Zn content of the prepared colloidal particle dispersion and the amount of surfactant used to form the soap assuming 100% conversion.

[0123] The lubricating composition of the present invention may contain a zinc content of greater than 500 ppm, such as greater than 800 ppm, or greater than 1000 ppm, such as greater than 1500 ppm, or greater than 2000 ppm, or greater than 2500 ppm, or greater than 3000 ppm, or greater than 3500 ppm, or greater than 4000 ppm, such as from 1500 to 4500 ppm, or from 2000 to 4000 ppm, as measured by ASTM D5185.

[0124] The lubricating composition of the present invention may contain a low phosphorus content, i.e., no greater than 2000 ppm, such as no greater than 1600 ppm, no greater than 1200 ppm, such as no greater than 800 ppm, such as 1 to 1600 ppm, such as 10 to 1200 ppm, such as 100 to 800 parts per million (ppm), based on the total mass of the lubricating composition as measured by ASTM D5185.

[0125] The lubricating composition of the present invention may be a heavy duty diesel engine oil, or a marine engine oil, or a petrol or gasoline engine oil, or a lubricating oil for an engine fueled by liquefied petroleum gas (LPG) or an alternative fuel type comprising at least one of ammonia, hydrogen, methanol, ethanol or biodiesel.

[0126] In one embodiment, the lubricating composition comprises greater than 1000 ppm Zn, such as greater than 1500 ppm or greater than 2000 ppm Zn, and less than 1000 ppm P, such as less than 900 ppm or less than 800 ppm P, based on the total mass of the lubricating composition as measured by ASTM D5185, wherein the lubricating composition has an adhesive wear of greater than 100 hours (ASTM D 8074-16) and, optionally, a total base number of greater than 7 mgKOH / g as measured by ASTM D2896.

[0127] In the lubricating composition, such as those used in internal combustion engines, the zinc dialkyldithiophosphate is present at 2 wt % or less, such as 1.5 wt % or less, or 1 wt % or less, based on the total mass of the lubricating composition.

[0128] The lubricating composition may have a thickness of less than 150 μm as measured by the High Frequency Reciprocating Rig (HFRR) method described in the Experimental Section below. 3 , such as less than 140μm 3 , or less than 135μm 3 wear scar volume.

[0129] The lubricating composition of the present invention may contain a zinc atom / phosphorus atom ratio of 1.2 to 5.0, or 2.0 to 4.5, preferably 2.5 to 4.0, based on the total mass of the lubricating composition as measured by ASTM D5185.

[0130] Typically, the lubricating composition may contain a low sulphur content. Preferably, the lubricating composition contains up to 0.4, more preferably up to 0.3, most preferably up to 0.2, such as 0.1 to 0.4 wt% sulphur based on the total mass of the lubricating composition as measured by ASTM D2622.

[0131] Typically, the lubricating compositions, such as those used in internal combustion engines, e.g., heavy-duty diesel engines, can contain a low sulfated ash content, e.g., 1.0 wt. % or less, preferably 0.9 wt. % or less, preferably 0.8 wt. % or less, or 0.7 wt. % or less, preferably 0.5 wt. % or less, or from 0.001 to 0.5 wt. % sulfated ash, based on the total mass of the lubricating composition, as measured by ASTM D874.

[0132] Typically, the lubricating composition, such as those used in internal combustion engines, has a kinematic viscosity at 100° C. (“KV100”) of 2 to 30 cSt, such as 2 to 20 cSt, such as 5 to 15 cSt (determined according to ASTM D445-19a). For marine oils, the kinematic viscosity is generally higher than the above values.

[0133] Typically, the lubricating composition has a total base number of 1 to 30, such as 5 to 15 mgKOH / g (determined according to ASTM D2896).

[0134] Typically, the lubricating composition has a high temperature high shear viscosity (HTHS) of 0.5 to 20, such as 1 to 10 cP, such as 2 to 4 cP at 150° C. and a shear rate of 1.0×10 6 s −1 (determined according to ASTM D4683-20).

[0135] Preferably, the lubricating composition of the present invention is 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. The lubricating composition is preferably in the form of SAE 10W-X, SAE 5W-X, or SAE 0W-X, more preferably in the form of SAE 5W-X or SAE 0W-X, wherein X represents any one of 8, 12, 16, 20, 30, 40, and 50. X is preferably 8, 12, 16, or 20. (See standard SAE J300 published by SAE International, formerly known as the Society of Automotive Engineers.) A.Base oil

[0136] The base oils useful herein (also referred to as "base stocks," "lubricating base stocks," or "oils of lubricating viscosity") can be single oils or blends of oils, and are generally the major liquid component of lubricating compositions (also referred to as lubricants), into which additives and optional additional oils are mixed, for example, to make lubricating compositions, such as finished lubricant compositions, concentrates, or other lubricating compositions.

[0137] The base oil can be selected from vegetable oils, animal oils, mineral oils and synthetic lubricating oils and mixtures thereof. Its viscosity ranges from light distillate mineral oils to heavy lubricating oils such as gas engine oils, mineral lubricating oils, motor vehicle oils and heavy diesel engine oils. Typically, the kinematic viscosity ("KV") of the base oil at 100°C is 100 ") is 2 to 30, especially 5 to 20 cSt (determined according to ASTM D445-19a). Typically, the base oil has a viscosity of 1.0 x 106 s at 150 ° C and 1.0 x 106 s -1 The high temperature high shear (HTHS) viscosity at a shear rate is 0.5 to 20 cP, such as 1 to 10 cP, such as 2 to 5 cP (determined according to ASTM D4683-20).

[0138] Typically, when the lubricating oil base stock is used in the preparation of the concentrate, it is advantageously present in a concentrate-forming amount to provide a concentrate containing 1 to 99 weight percent, 5 weight percent to 80 weight percent, 10 weight percent to 70 weight percent, or 5 weight percent to 50 weight percent, of the active ingredient, based on the weight of the concentrate.

[0139] The conventional oil that can be used as base oil comprises animal oil and vegetable oil (for example castor oil and lard), liquid petroleum oil and hydrorefined and / or solvent treated paraffin type, naphthenic type and mixed paraffin-naphthenic type mineral lubricating oil.The oil derived from coal or shale is also available base oil.Base oil can use various different methods to make, include but not limited to distillation, solvent refining, hydrogen processing, oligomerization, esterification and re-refining.

[0140] Synthetic lubricating oils useful as base oils herein include hydrocarbon oils such as homo- and co-polymerized 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.

[0141] In another embodiment, the base oil comprises 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 greater; preferably having a viscosity index ("VI") as measured by ASTM D2270 of 100 or greater, preferably 110 or greater, more preferably 120 or greater, more preferably 130 or greater, more preferably 140 or greater; 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.

[0142] In another embodiment, the polyalphaolefin oligomers useful in the present invention comprise C 20 to C 1500 Alkanes, preferably C 40 to C 1000 Alkanes, preferably C 50 to C 750 Alkanes, preferably C 50 to C 500Paraffin. PAO oligomers are in one embodiment 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 PAO is a dimer, trimer, tetramer, pentamer, etc. of an 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, the olefin is 1-decene, and the PAO is a mixture of dimers, trimers, tetramers, and pentamers (and higher) of 1-decene. Available PAOs are more particularly described in, for example, U.S. Patents 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).

[0143] The PAOs useful in the present invention 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.

[0144] 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.

[0145] Another class of suitable synthetic lubricating oils that can be used as base oils comprises the 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 complex esters formed by reacting 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid.

[0146] 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.

[0147] Ideal ester base oils are used as Esterex TM Available from Esters (ExxonMobil Chemical Company, Houston Texas).

[0148] 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.

[0149] Other synthetic lubricating oils useful herein include liquid esters of phosphorus-containing acids (eg, tricresyl phosphate, trioctyl phosphate, diethyl decylphosphonate) and polymeric tetrahydrofuran.

[0150] Unrefined oils, refined oils, and re-refined oils can be used in the lubricating compositions of the present invention. Unrefined oils are those obtained directly from natural or synthetic sources without further purification. 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 the refined oil previously used. Such re-refined oils are also referred to as regenerated oils or reprocessed oils, and are usually processed in addition to remove spent additives and oil cracking products. Re-refined base oils are preferably substantially free of materials introduced by manufacture, contamination, or previous use.

[0151] 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. Patents 10,913,916 (col. 4, line 62 to col. 5, line 60) and 10,781,397 (col. 14, line 54 to col. 15, line 5, and col. 16, line 44 to col. 17, line 55).

[0152] Various base oils are typically classified as Class I, Class II, Class III, Class IV, or Class V according to the API EOLCS 1509 definition (American Petroleum Institute Publication 1509, see Section E.1.3, 19th Edition, January 2021, www.API.org). Generally speaking, Class I base stocks have a viscosity index between about 80 and 120 and contain more than about 0.03% sulfur and / or less than about 90% saturates. Class II base stocks have a viscosity index between about 80 and 120 and contain less than or equal to about 0.03% sulfur and greater than or equal to about 90% saturates. Class III base stocks have a viscosity index greater than about 120 and contain less than or equal to about 0.03% sulfur and greater than about 90% saturates. Class IV base stocks include polyalphaolefins (PAOs). Class V base stocks include base stocks not included in Classes I-IV. (Viscosity index is measured by ASTM D2270, saturates are measured by ASTM D2007, and sulfur is measured by ASTM D2622, ASTM D4294, ASTM D4927, and ASTM D3120).

[0153] The base oils useful in the formulated lubricating compositions of the present invention are any one, two, three or more of the various oils described herein. In a desirable embodiment, the base oils useful in the formulated lubricating compositions of the present invention are those described as API Group I, Group II, Group III (including Group III+), Group IV and Group V oils and mixtures thereof, preferably API Group II, Group III, Group IV and Group V oils and mixtures thereof, more preferably Group III, Group III+, Group IV and Group V base oils due to their excellent volatility, stability, viscosity and cleanliness characteristics. Small amounts of Group I base stocks may be tolerated, such as for diluting additives for incorporation into formulated lubricating oil products, but are generally kept to a minimum, for example, only to the extent that they are used as diluents / carrier oils for additives used on an "as-received" basis. With respect to Group II oils, it is more useful that the Group II base stocks are within the higher quality range associated with such oils, i.e., Group II oils having a viscosity index of 100 to 120.

[0154] The base oils useful herein may be selected from any synthetic, natural, or re-refined oil (such as those commonly used as crankcase lubricants for spark-ignition and compression-ignition engines). If desired, mixtures of synthetic and / or natural and / or re-refined base oils may be used. If desired, multi-modal mixtures (such as bimodal or trimodal mixtures) of Group I, II, III, IV, and / or V base stocks may be used.

[0155] The base oil or base oil blend used herein conveniently has a kinematic viscosity at 100° C. [KV] of about 2 to about 40 cSt, or 3 to 30 cSt, or 4 to 20 cSt, or 5 to 10 cSt at 100° C. 100 , measured in accordance with ASTM D445-19a and reported in centistokes (cSt) or its equivalent in mm2 / 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 2 cSt, preferably about 2.5 cSt to about 9 cSt.

[0156] The base oil or base oil blend preferably has a saturates content as determined by ASTM D2007 of at least 65 wt%, more preferably at least 75 wt%, such as at least 85 wt%, such as greater than 90 wt%.

[0157] Preferably, the base oil or base oil blend has a sulfur content of less than 1 wt%, preferably less than 0.6 wt%, most preferably less than 0.4 wt%, such as less than 0.3 wt%, based on the total mass of the lubricating composition as measured by ASTM D2622.

[0158] 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 weight percent, such as less than or equal to 25 weight percent, such as less than or equal to 20 weight percent, such as less than or equal to 16 weight percent, such as less than or equal to 12 weight percent, such as less than or equal to 10 weight percent, based on the total mass of the lubricating composition.

[0159] 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 (as determined by ASTM D2270).

[0160] The base oil can be provided in a major amount and combined with one or more additive components as described below in a minor amount to form the 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 by any method known to those skilled in the art before, simultaneously with, or after adding other additives.

[0161] The base oil can provide with minor amount, and it combines with one or more additive components as described below of minor amount, to constitute the additive concentrate.Can realize this preparation by adding the additive directly in the oil or by adding the one or more additives with the additive dispersion or being dissolved in the oil in the form of its solution, slurry or suspension.Additive can be added in the oil before, simultaneously or afterwards adding other additives by any method well known to those skilled in the art.

[0162] 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.

[0163] 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 wt %, or 50 to 97 wt %, or 60 to 95 wt %, or 70 to 95 wt %, based on the weight of the lubricating composition.

[0164] The present invention also relates to lubricating oil compositions comprising or blending the functionalized hydrogenated / saturated polymers described herein and at least 40 weight percent of a hydrocarbon base oil, such as a Group I, II and / or III oil, such as a Group II or III oil.

[0165] The present invention also relates to an additive concentrate comprising or admixed from the functionalized hydrogenated / saturated polymers described herein and at least 1 wt. % of a hydrocarbon base oil, such as a Group I, II and / or III oil, such as a Group I or II oil.

[0166] The above-described base oils and blends thereof may also be used in making concentrates, and in making lubricants therefrom.

[0167] 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 "adpack") containing one or more co-additives, as described below, in a single concentrate.

[0168] Concentrates, also known as additive packages or adpacks, are compositions that typically have less than 50% by weight (e.g., less than 40%, such as less than 30% by weight, such as less than 25%, such as less than 20%) of base oil, which are typically then further blended with additional base oils and other components, such as viscosity improvers and pour point depressants, to form a lubricant product.

[0169] The present invention relates to a concentrate composition comprising the following components or obtained by mixing the following components: (A) 1 to less than 50 wt. % (or 5 to 45 wt. %, or 7 to 40 wt. %, or 10 to 35 wt. %, or 10 to 25 wt. %) of one or more base oils, based on the weight of the composition; (B) optionally, 0.001 to 5 wt. % (particularly 0.01 to 4 wt. %, or 0.02 to 3 wt. %, or 0.1 to 2 wt. %) of at least one phosphorus-containing compound selected from detergents, friction modifiers, or antiwear additives other than the colloidal particles described in (C), based on the weight of the composition; (C) 0.1 to 50 wt. % (particularly 0.15 to 20 wt. %, or 0.20 to 10 wt. %, or 0.25 to 5 wt. %), based on the weight of the composition, of one or more colloidal particle dispersions comprising: a) a core of one or more hydrocarbon-insoluble zinc-containing compounds, and b) a shell of one or more of the following: 1) one or more metal-containing surfactants, wherein the metal M comprises a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and the surfactant comprises a hydrocarbyl-substituted sulfonate or hydrocarbyl-substituted salicylate group of formula (I) or (II), where R A and R B are each independently a linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon group having 1 to 70 carbon atoms, wherein when n>1, all R A The sum of the number of carbon atoms in the group and all R B The total number of carbon atoms in the group is 100 or less carbon atoms, and Ar is a monocyclic or polycyclic aromatic group; n is an integer from 1 to the maximum possible number of substitutions on Ar, m is an integer from 1 to 3, x is an integer from 1 to 5; y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 8; 2) one or more metal alkanoates represented by formula (III): wherein M is a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and R C is selected from linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon groups having 6 to 70 carbon atoms, or aromatic groups or alkyl aromatic groups, wherein the aromatic group has 6 to 20 carbon atoms and the alkyl group has 1 to 20 carbon atoms; x is an integer from 1 to 5, wherein in the case of x>1, the R C The groups may be the same or different, y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 8; (D) Optional additional components, antioxidants, pour point depressants, defoamers, viscosity improvers, corrosion inhibitors, antiwear agents, extreme pressure additives, demulsifiers, seal compatibilizers, additive diluent base oils, friction modifiers (such as organic FMs, such as organic esters, such as fatty acid esters), acid scavengers, etc.

[0170] In the concentrate embodiment, the surfactant of formula (I), (II) or (III) may be those of formula (Ia), (IIa) or (IIIa) described above, including all preferred embodiments thereof.

[0171] The concentrate may be present in the lubricating oil composition at 0.5 to 35 wt%, such as 5 to 30 wt%, such as 7.5 to 25 wt%, such as 10 to 22.5 wt%, such as 15 to 20 wt%, based on the mass of the lubricating oil composition. B. Colloidal particles

[0172] The colloidal particles useful in the present invention are typically prepared as a dispersion in a base oil, and the dispersion comprises core-shell colloidal particles having: a) a core of one or more hydrocarbon-insoluble zinc-containing compounds, and b) a shell of one or more of the following: 1) one or more metal-containing surfactants, wherein the metal M comprises a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and the surfactant comprises a hydrocarbyl-substituted aromatic sulfonate or hydrocarbyl-substituted salicylate group of formula (I) or (II), where R A and R B are each independently a linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon group having 1 to 70 carbon atoms, wherein when n>1, all R A The sum of the number of carbon atoms in the group and all R BThe total number of carbon atoms in the group is 100 or less carbon atoms, and Ar is a monocyclic or polycyclic aromatic group; n is an integer from 1 to the maximum possible number of substitutions on Ar, m is an integer from 1 to 3, x is an integer from 1 to 45; y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 4; 2) one or more metal alkanoates represented by formula (III): wherein M is a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and R C is selected from linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon groups having 6 to 70 carbon atoms, or aromatic groups or alkyl aromatic groups, wherein the aromatic group has 6 to 20 carbon atoms and the alkyl group has 1 to 20 carbon atoms; x is an integer from 1 to 5, wherein in the case of x>1, the R C The groups may be the same or different, y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 8.

[0173] Preferred dispersions of core-shell colloidal particles may also have a surfactant of formula (Ia), (IIa) or (IIIa) as described above, including all preferred embodiments thereof. synthesis

[0174] The dispersions of colloidal zinc-containing particles having a core-shell structure described herein can be produced in several ways, for example involving heating ZnCO3 in the presence of a high-boiling base oil containing a dispersant soluble in the base oil to cause it to decompose into ZnO and CO2 at a temperature significantly lower than the temperature required to decompose ZnCO3 in a dry state into ZnO.

[0175] For a zinc-only dispersion, i.e., a ZnO core within a Zn surfactant shell, a suitable metal-free surfactant, such as those described herein, for example, an alkylarylsulfonic acid or alkylsalicylic acid or an alkanoic acid, is combined with a high-boiling base oil and zinc carbonate. This mixture is heated with stirring in an inert gas stream to a temperature of about 200 to 400°C, such as 250 to 350°C, or about 300°C, for several hours, such as 2 to 6 hours, such as 3 to 5 hours, or about 4 hours. After cooling back to room temperature, the crude product is dissolved in about 5 times its volume of an organic solvent, such as xylene, and centrifuged, for example, at about 3000 rpm, such as 2900 rpm, for about 1 hour. The supernatant is decanted from the residue, and the solvent is stripped on a rotary evaporator. The resulting product is a stable dispersion of particles comprising ZnO cores within a Zn-detergent shell.

[0176] To produce mixed metal systems, such as Ca- or Mg-sulfonate or salicylate stabilized colloids (or other Group 1, 2, 4, 5, 6, 10, 11, 12 or 13 metal-containing surfactants disclosed elsewhere herein), this same approach can be used by using preformed metal-containing surfactant species, i.e., Ca or Mg sulfonate, salicylate, alkanoate, etc., in place of the metal-free acid.

[0177] In another embodiment of the method for preparing a dispersion of zinc-containing particles having a core-shell structure as described herein, a detergent or surfactant (in free acid form) is combined with an organic solvent such as xylene and a high-boiling base oil. Calcium hydroxide and methanol are added, and the mixture is heated to approximately 40°C for 20 minutes and then cooled back to room temperature, i.e., 25°C. Methanolic solutions of zinc chloride and sodium hydroxide are added simultaneously but separately to the reaction mixture. Following addition, the mixture is heated to approximately 70°C over approximately 45 minutes until the methanol begins to reflux. The methanol is then completely withdrawn, and the temperature is further increased to approximately 140°C and maintained for a period of time before being allowed to cool back to room temperature. Once cooled, additional xylene is loaded into the reactor, the mixture is stirred, and then allowed to settle. The mixture is centrifuged, the supernatant is decanted from the residue, and the volatile solvent is removed on a rotary evaporator. The resulting product is a stable dispersion of particles containing a ZnO core encased in a Zn-surfactant shell.

[0178] In another embodiment of the method for preparing a dispersion of zinc-containing particles having a core-shell structure as described herein, a detergent or surfactant is loaded into a reactor along with a high-boiling base oil and a metal hydroxide. This mixture is heated to approximately 150°C under a nitrogen stream and stirred for 10 minutes to remove water from the reaction. Zinc carbonate is then added to maintain the internal temperature between approximately 140 and 155°C. The reaction is then heated to a temperature of approximately 200 to 400°C, such as 250 to 350°C, or approximately 300°C, for several hours, such as 2 to 6 hours, for example, 3 to 5 hours, or approximately 4 hours, and then allowed to cool back to room temperature. The crude product is dissolved in approximately 5 times its volume of xylene and centrifuged. The supernatant is decanted from the residue and the solvent is stripped on a rotary evaporator. The resulting product is a stable dispersion of particles comprising a ZnO core enclosed in a metal-surfactant shell.

[0179] The particle size of the colloidal particles in the dispersion can be about 5 nm to 1 μm, such as 5 nm to 500 nm, or 10 nm to 300 nm, or 10 nm to 200 nm, or 20 nm to 150 nm, as determined by dynamic light scattering (volume average) as described in the Examples section.

[0180] The colloidal dispersion can have a Zn content of about 5 to 35 wt %, such as 5 to 30 wt %, or 5 to 35 wt %, such as 5 to 30 wt %, as determined by ASTM D 4891, based on the total weight of the colloidal dispersion. In certain embodiments, the Zn content is the maximum content possible while still providing a stable dispersion, i.e., exhibiting no precipitate over a period of at least 4 weeks.

[0181] The colloidal dispersion prepared by the above method is a neutral or overbased, typically overbased, detergent system, i.e., having a higher metal / ligand stoichiometry than would be expected for a neutral metal species. The colloidal dispersion may have a TBN as measured by ASTM D2896 of 100 mgKOH / g or greater, such as 200 mgKOH / g or greater, 250 mgKOH / g or greater, 300 mgKOH / g or greater, such as 200 to 800 mgKOH / g, 225 to 700 mgKOH / g, 250 to 650 mgKOH / g, or 300 to 600 mgKOH / g, such as 150 to 650 mgKOH / g.

[0182] In certain embodiments, the colloidal dispersions used in the lubricating oil compositions or concentrates of the present invention are free of sulfur and / or phosphorus.

[0183] In certain embodiments, the colloidal particles have a (non-stoichiometric) metal (zinc) / surfactant molar ratio MR greater than 1, such as equal to or greater than 2, 3, 5, 10, 15, 20, 30 or 40, and less than 40, 30, 35, 20, 15, such as a metal compound / surfactant molar ratio greater than 1 to 40, 2 to 30, 5 to 30, 10 to 30, or 10 to 20.

[0184] The prepared dispersion of colloidal particles is stable and preferably remains stable in the oil formulation at 25°C for at least 4 weeks.

[0185] In certain embodiments, the colloidal dispersion used in the lubricating oil composition or concentrate of the present invention is a mixed metal system, i.e., wherein the colloidal particles comprise a core comprising a Zn compound (e.g., Zn, ZnO, ZnCO3, or mixtures thereof, preferably ZnO) and a shell comprising a metal surfactant of a non-Zn Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal. In certain embodiments thereof, the colloidal particles comprise a core comprising a Zn compound (e.g., Zn, ZnO, ZnCO3, or mixtures thereof, preferably ZnO) and a shell comprising a metal surfactant of a Group 1 or 2 metal, such as an alkaline earth metal, such as calcium, magnesium, or barium, preferably Ca or Mg, such as Ca. In a specific embodiment, the colloidal particles comprise a core of ZnO or a mixture of ZnO and ZnCO3 and a Ca- or Mg-surfactant, such as a ZnO core and a Ca-surfactant shell.

[0186] In other embodiments, the colloidal dispersion used in the lubricating oil composition or concentrate of the present invention is a zinc-only system, i.e., wherein the colloidal particles comprise a core containing a Zn-containing compound, such as Zn, ZnO, ZnCO3, or a mixture thereof, preferably ZnO, and a shell containing a zinc detergent. In certain embodiments thereof, the colloidal particles comprise a core containing a Zn-containing compound, such as Zn, ZnO, ZnCO3, or a mixture thereof, preferably ZnO, and a shell of an alkylaromatic zinc sulfonate of formula (I) or (Ia), an alkyl zinc salicylate of formula (II) or (IIa), or a zinc alkanoate of formula (III). In specific embodiments, the colloidal particles comprise a core of ZnO or a mixture of ZnO and ZnCO3 and a shell of a zinc alkanoate of formula (III). In certain embodiments, the colloidal particles comprise a core of ZnO or a mixture of ZnO and ZnCO3 and a shell of an alkyl zinc salicylate of formula (II), such as (IIa). In other embodiments, the colloidal particles comprise a core of ZnO or a mixture of ZnO and ZnCO3 and a shell of an alkyl aromatic zinc sulfonate of formula (I), such as (Ia).

[0187] In some embodiments of the present invention, the lubricating composition may comprise a combination of colloidal particles (C), wherein the shell may comprise a surfactant of formula (I), (II) and / or (III), such as a mixture of colloidal particles based on formula (I) and (II), (I) and (III), (II) and (III), or (I), (II) and (III). Wherein, the colloidal particles of formula (I) may be aliphatic sulfonates or aromatic sulfonates, or a mixture of aliphatic and aromatic sulfonates. As described above, the surfactant of formula (I) and / or (II) may also be a mixed metal system, wherein M is different from Zn, such as calcium or magnesium. It is believed that mixed metal systems can provide differences in particle size and stability in some compositions, so the colloidal particles can be adjusted according to the properties of other additives in the lubricant composition.

[0188] The lubricating compositions herein may typically comprise 0.01 to 10 wt %, alternatively 0.1 to 10 wt %, alternatively 0.2 to 5 wt %, alternatively 0.3 to 2.5 wt %, alternatively 0.4 to 1.2 wt %, preferably 0.5 to 1 wt % of one or more zinc-containing colloidal dispersions described herein, based on the total weight of the lubricating composition.

[0189] The zinc-containing colloidal dispersion can be included in the lubricating composition of the present invention as a separate component or as part of a concentrate, such as an additive package, along with other additive components. The concentrate (e.g., additive package) compositions herein can typically contain 0.01 to 10 wt. %, or 0.1 to 10 wt. %, or 0.2 to 5 wt. %, or 0.3 to 2.5 wt. %, or 0.4 to 1.2 wt. %, and in some embodiments, 0.5 to 1 wt. % of one or more zinc-containing colloidal dispersions described herein, based on the total weight of the concentrate composition.

[0190] The lubricating composition according to the present invention may further comprise one or more additives, such as detergents, friction modifiers, antioxidants, pour point depressants, defoamers, viscosity improvers, dispersants, corrosion inhibitors, antiwear agents, extreme pressure additives, demulsifiers, seal compatibilizers, additive diluent base oils, etc. Specific examples of such additives are described, for example, in the Kirk-Othmer Encyclopedia of Chemical Technology, 3rd Edition, Vol. 14, pp. 477-526, and several are discussed in more detail below. C. Detergent

[0191] 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 a substantially stoichiometric amount 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 (greater than the stoichiometric amount) of the metal base may be incorporated. Such detergents, sometimes referred to as overbased, may have a TBN of 100 mg KOH / g or greater, such as 200 mg KOH / g or greater, and typically have a TBN of 250 mg KOH / g or greater, such as 300 mg KOH / g or greater, 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. Overbased metal detergents can be obtained, for example, by reacting an excess of a metal compound (e.g., an oxide or hydroxide) with an acidic gas (e.g., carbon dioxide), or other methods generally known to those skilled in the art.

[0192] Suitable detergents include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, naphthenates, and other oil-soluble carboxylates of metals, particularly alkali metals (Group 1 metals, e.g., Li, Na, K, Rb) or alkaline earth metals (Group 2 metals, e.g., Be, Mg, Ca, Sr, Ba), particularly sodium, potassium, lithium, calcium, and magnesium, such as 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 of sodium, potassium, lithium, calcium, or magnesium, or other oil-soluble carboxylates of Group 1 and / or 2 metals.

[0193] Preferably, the detergent additive useful in the present invention comprises a calcium and / or magnesium metal salt. The detergent may be a calcium and / or magnesium carboxylate (including 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.

[0194] 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, and sulfonate / phenate / salicylate, as described, for example, in U.S. Patent Nos. 6,429,178; 6,429,179; 6,153,565; and 6,281,179. When, for example, a hybrid sulfonate / phenate detergent is used, the hybrid detergent is considered equivalent to the amounts of separate phenate and sulfonate detergents incorporating similar amounts of phenate and sulfonate soap, respectively.

[0195] Overbased metal-containing detergents can be sodium, calcium, magnesium, or mixtures thereof of phenates, sulfur-containing phenates, sulfonates, salixarates, and salicylates. Overbased phenates and salicylates typically have a total base number of 180 to 650 mg KOH / g, such as 200 to 450 TBN mg KOH / g. Overbased sulfonates typically have a total base number of 250 to 600 mg KOH / g, or 300 to 500 mg KOH / g. In 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 Publication 2005 / 065045 (granted as U.S. Patent No. 7,407,919). The overbased detergent may be present in an amount of 0% to 15% by weight, or 0.1% to 10% by weight, or 0.2% to 8% by weight, or 0.2% to 3% by weight, based on the lubricating composition. For example, in a heavy-duty diesel engine, the detergent may be present in an amount of 2% to 3% by weight of the lubricating composition. For a passenger car engine, the detergent may be present in an amount of 0.2% to 1% by weight of the lubricating composition.

[0196] 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.

[0197] 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 less than 150 mg KOH / g, such as less than 100 mg KOH / g.

[0198] Alternatively, the detergent additive is a combination of magnesium salicylate and magnesium sulfonate.

[0199] The magnesium detergent provides 200-4000 ppm of magnesium atoms to the lubricating composition thereof, suitably 200-2000 ppm, 300 to 1500 ppm or 450-1200 ppm of magnesium atoms (ASTM D5185).

[0200] The detergent composition may comprise (or consist of) a combination of one or more magnesium sulfonate detergents and one or more calcium salicylate detergents.

[0201] The combination of one or more magnesium sulfonate detergents and one or more calcium salicylate detergents provides to the lubricating composition thereof: 1) 200-4000 ppm of atomic magnesium, suitably 200-2000 ppm, 300 to 1500 or 450-1200 ppm of atomic magnesium (ASTM D5185), and 2) at least 500 ppm, preferably at least 750, 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).

[0202] The detergent may comprise one or more calcium detergents, such as calcium carboxylate (eg, salicylate), sulfonate, or phenate detergents.

[0203] Suitably, the calcium detergent has a TBN of 30 to 700 mg KOH / g (ASTM D2896), such as 50 to 650 mg KOH / g, such as 200 to 500 mg KOH / g, such as 240 to 450 mg KOH / g, or 150 mg KOH / g or less, such as 100 mg KOH / g or less, or 200 mg KOH / g or more, or 300 mg KOH / g or more, or 350 mg KOH / g or more.

[0204] 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.

[0205] Calcium detergents are 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, 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 from 500 to 4000 ppm, preferably from 750 to 3000 ppm, more preferably from 900 to 2000 ppm, of atomic calcium to the lubricating oil composition (ASTM D5185).

[0206] Suitably, the total atomic weight of metals from detergents other than the colloidal particles described herein in the lubricating compositions according to all aspects of the present invention 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 other than the colloidal particles described herein in the lubricating oil compositions according to all aspects of the present invention 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 other than the colloidal particles described herein in the lubricating oil compositions according to all aspects of the present invention is suitably from 500 to 5000 ppm, preferably from 500 to 3000 ppm, more preferably from 500 to 2000 ppm (ASTM D5185). In some embodiments of the present invention, these detergents may be partially or completely replaced by the colloidal particles / dispersions described herein - by maintaining the total detergency (TBN) while maintaining or improving the anti-wear properties of the lubricant composition.

[0207] Sulfonate detergents can be prepared from sulfonic acids, which are typically obtained by sulfonation of alkyl-substituted aromatic hydrocarbons (such as those obtained from the 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 in the presence of a catalyst using an alkylating agent having from about 3 to more than 70 carbon atoms. Alkaryl sulfonates typically 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 metal compound is selected taking into account the desired TBN of the final product, but is typically from about 100 to 220% by weight (preferably at least 125% by weight) of the stoichiometric amount required.

[0208] 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.

[0209] Carboxylate detergents (e.g. salicylates) can be prepared by reacting aromatic carboxylic acids (e.g. C 5-100 、C 9-30 、C 14-24The aromatic carboxylic acid can be prepared by reacting an alkyl-substituted hydroxybenzoic acid with an appropriate metal compound, such as an oxide or hydroxide, and neutral or overbased products can be obtained by methods well known in the art. The aromatic moiety of the aromatic carboxylic acid may contain heteroatoms, such as nitrogen and oxygen. The moiety preferably contains only carbon atoms; more preferably, the moiety 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.

[0210] Preferred substituents in oil-soluble salicylic acids are alkyl substituents. In alkyl-substituted salicylates, the alkyl group advantageously contains 5 to 100, preferably 9 to 30, and 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.

[0211] 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.

[0212] Furthermore, since metal organic and inorganic base salts used as detergents can contribute to the sulfated ash content of the lubricating oil composition, in some embodiments of the present invention, the amount of such additives is minimized. To maintain a low sulfur content, salicylate detergents may be used and the lubricating compositions herein may contain one or more salicylate detergents (the detergents are preferably used in an amount of 0.05 to 20.0 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).

[0213] 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.

[0214] 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.

[0215] Typically, lubricating compositions formulated for heavy-duty diesel engines contain from about 0.5 to about 10 weight percent, alternatively from about 2.5 to about 7.5 weight percent, alternatively from about 4 to about 6.5 weight percent detergent, based on the lubricating composition. D. Friction modifier

[0216] A friction modifier is any material that can alter the coefficient of friction of a surface lubricated with any lubricant or fluid containing such a material. If desired, friction modifiers, also known as friction reducers or lubricity agents or oiliness agents, and other such agents that alter 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 conjunction with the base oils or lubricating compositions of the present disclosure. Friction modifiers that reduce the coefficient of friction are particularly advantageously combined with the base oils and lubricating compositions of the present disclosure.

[0217] Exemplary friction modifiers may include, for example, organometallic compounds or materials or mixtures thereof. Exemplary organometallic friction modifiers useful in the lubricating oil formulations of the present disclosure include, for example, tungsten and / or molybdenum compounds, such as molybdenum amines, molybdenum diamines, organic tungstates, molybdenum dithiocarbamates, molybdenum dithiophosphates, molybdenum amine complexes, molybdenum carboxylates, and mixtures thereof. Examples of useful 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.

[0218] Other known friction modifiers include oil-soluble organo-molybdenum compounds. Such organo-molybdenum friction modifiers can also provide antioxidant and anti-wear benefits to lubricating oil compositions. Examples of such oil-soluble organo-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.

[0219] Alternatively, the molybdenum compound may be an acidic molybdenum compound. These compounds react with basic nitrogen compounds and are generally hexavalent as determined by ASTM Test D-664 or D-2896 titration procedures. Examples include molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, such as sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide, or similar acidic molybdenum compounds.

[0220] Molybdenum compounds useful in the compositions of the present invention 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 dialkyldithiocarbamates of molybdenum.

[0221] Another class of organic molybdenum compounds useful in the lubricating compositions of the present invention are trinuclear molybdenum compounds, particularly those of the formula Mo3S k L n Q z 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 from 1 to 4, k varies from 4 to 7, Q is selected from neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers, and z is from 0 to 5 including non-stoichiometric values. There should be at least 21 carbon atoms, such as at least 25, at least 30, or at least 35 carbon atoms, among all ligand organic groups.

[0222] Lubricating oil compositions useful in all aspects of the present invention 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 invention 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 invention preferably contain from 10 to 1000, such as from 30 to 750 or from 40 to 500 ppm of molybdenum (measured as molybdenum atoms).

[0223] For more information on useful Mo-containing friction modifiers, see US 10,829,712 (column 8, line 58 to column 11, line 31).

[0224] Ashless friction modifiers may be present in the lubricating oil composition of the present invention and are well known and include esters formed by reacting carboxylic acids and anhydrides with alkanols and amine-based friction modifiers. Other available friction modifiers typically include polar end groups (e.g., carboxyl or hydroxyl groups) covalently bonded to a lipophilic hydrocarbon chain. Esters of carboxylic acids and anhydrides with alkanols are described in US Pat. No. 4,702,850. Examples of other conventional organic friction modifiers are described by 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. Typically, the total amount of organic ashless friction modifier in the lubricant according to the present invention is no more than 5% by weight, preferably no more than 2% by weight, and more preferably no more than 0.5% by weight, based on the total mass of the lubricating oil composition.

[0225] 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.

[0226] Exemplary alkoxylated fatty acid esters include, for example, polyoxyethylene stearate, fatty acid polyglycol esters, etc. These may include polyoxypropylene stearate, polyoxybutylene stearate, polyoxyethylene isostearate, polyoxypropylene isostearate, polyoxyethylene palmitate, and the like.

[0227] 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 alkyl amides, polypropoxylated alkyl amides, and the like.

[0228] 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.

[0229] Exemplary boronized glycerol fatty acid esters include, for example, boronized glycerol monooleate, boronized saturated mono-, di- and triglycerides, boronized glycerol monostearate, etc. Except for glycerol polyol, these can also include trimethylolpropane, pentaerythritol, sorbitan, etc. These esters can be polyol monocarboxylic acid esters, polyol dicarboxylic acid esters and sometimes, polyol tricarboxylic acid esters. Preferred can 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 isostearate, linoleate, etc. Ethoxylated, propoxylated, butoxylated fatty acid esters of polyol (especially using glycerol as base polyol (underlying polyol)) can be used for this.

[0230] Exemplary fatty alcohol ethers include, for example, stearyl ether, myristyl ether, etc. Alcohols (including fatty alcohols having C3 to C 50 The alcohol portion of the base may preferably be stearyl, myristyl, C 11 -C 13 hydrocarbon, oleyl, isostearyl, etc.

[0231] Useful concentrations of friction modifiers can be from 0.01 wt % to 5 wt %, or from about 0.1 wt % to about 2.5 wt %, or from about 0.1 wt % to about 1.5 wt %, or from about 0.1 wt % to about 1 wt %. The concentration of molybdenum-containing materials is typically described as Mo metal concentration. Advantageous concentrations of Mo can be from 25 ppm to 700 ppm or more, with a typical preferred range of 50-200 ppm. All types of friction modifiers can be used alone or in combination with the materials of the present disclosure. Mixtures of two or more friction modifiers or mixtures of friction modifiers with alternative surface active materials are also generally desirable. For example, combinations of Mo-containing compounds with polyol fatty acid esters (such as glycerol monooleate) can be used for this. E. Antioxidants

[0232] Antioxidants delay oxidative degradation of base oils during use. Such degradation can lead to deposits on metal surfaces, the formation of sludge, or increased viscosity in the lubricant. A wide variety of oxidation inhibitors are available for use in lubricating oil compositions. See, for example, Lubricants and Related Products, Klamann, Wiley VCH, 1984; US Pat. No. 4,798,684; and US Pat. No. 5,084,197.

[0233] 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 dihydroxyaryl compounds in which the hydroxyl groups are in the ortho or para position relative 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-butylphenol) and 4,4′-methylene-bis(2,6-di-tert-butylphenol).

[0234] 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 polymetallic organocompounds; 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 US Pat. No. 8,048,833.

[0235] Non-phenolic oxidation inhibitors that may be used include aromatic amine antioxidants, which may be used as such or in combination with phenols. Typical examples of non-phenolic antioxidants include: alkylated and non-alkylated aromatic amines, such as those of formula R 8 R 9 R 10 N-aromatic monoamine, wherein R 8 is an aliphatic, aromatic or substituted aromatic group, R 9 is an aromatic or substituted aromatic group, and R 10 is H, alkyl, aryl or R 11 S(O)XR 12 , where R 11 is an alkylene group, an alkenylene group or an aralkylene group, R 12 is an alkyl or alkenyl, aryl or alkaryl group, and x is 0, 1 or 2. The aliphatic group R 8It may contain from 1 to about 20 carbon atoms, preferably from about 6 to 12 carbon atoms. The aliphatic group is typically a saturated aliphatic group. Preferably, R 8 and R 9 are aromatic or substituted aromatic groups, and the aromatic group may be a condensed ring aromatic group, such as naphthyl. 8 and R 9 It can be linked to other groups such as S.

[0236] 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.

[0237] 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 invention 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 weight % 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 ) hydrocarbyl 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 US 10,731,101 (column 15, line 55 to column 22, line 12).

[0238] The antioxidants useful herein include hindered phenols and arylamines. These antioxidants can be used independently or in combination with each other.

[0239] Typical antioxidants include: Irganox TM L67, ETHANOX TM 4702、Lanxess Additin TM RC 7110; ETHANOX TM4782J; Irganox TM 1135. Irganox TM 5057, sulphurised lard and palm oil fatty acid methyl esters.

[0240] The antioxidant additive may be used in an amount of about 0.01 to 5 wt %, preferably about 0.01 to 3 wt %, more preferably 0.01 to 1.5 wt %, more preferably 0.01 to less than 1 wt %, based on the weight of the lubricating composition.

[0241] The compositions according to the present disclosure may contain additives that have different listed functions and also have a secondary effect as antioxidants (for example, phosphorus-containing antiwear agents such as ZDDP may also have an antioxidant effect). These additives are not counted as antioxidants for the purpose of determining the amount of antioxidant in the lubricating oil compositions or concentrates herein. F. Pour point depressant

[0242] 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 can be added to the lubricating compositions of the present disclosure to lower 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, vinyl carboxylate polymers, and terpolymers of dialkyl fumarates, vinyl fatty acids, and allyl vinyl ethers. U.S. Patent Nos. 1,815,022; 2,015,748; 2,191,498; 2,387,501; 2,655,479; 2,666,746; 2,721,877; 2,721,878; and 3,250,715 describe useful pour point depressants and / or their preparation. Such additives can be used in amounts of about 0.01 to 5% by weight, preferably about 0.01 to 1.5% by weight. G. Defoaming agent

[0243] Defoaming agents can be advantageously added to the lubricant compositions described herein. These agents prevent or delay the formation of stable foam. Silicones and organic polymers are typical defoaming agents. For example, polysiloxanes, such as silicone oil or polydimethylsiloxane, provide defoaming properties.

[0244] 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.

[0245] For example, it is possible that the lubricating oil composition comprises a defoamer comprising a polyalkylsiloxane, such as a polydialkylsiloxane, for example wherein the alkyl group is C1-C 10 Alkyl, such as polydimethylsiloxane (PDMS), also known as silicone oil. Alternatively, silicone 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 50 to 450.

[0246] 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 50 to 450, 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 polyether (such as ethylene oxide-propylene oxide copolymer), long chain hydrocarbon group (such as C 11 -C 100 Alkyl) or aryl (e.g. C6-C 14 Preferably, R 1 and R 2 One of them is CH3.

[0247] The siloxane according to Formula 1 is incorporated to provide from about 0.1 to less than about 30 ppm Si, or from about 0.1 to about 25 ppm Si, or from about 0.1 to about 20 ppm Si, or from about 0.1 to about 15 ppm Si, or from about 0.1 to about 10 ppm Si, based on the total weight of the lubricant composition. More preferably, it is in the range of about 3-10 ppm Si.

[0248] In one embodiment, silicone defoamers useful herein are available from Dow Corning Corporation and Union Carbide Corporation, such as Dow Corning FS-1265 (1000 centistokes), Dow Corning DC-200, and Union Carbide UC-L45. Silicone defoamers useful herein are polydimethylsiloxanes, phenyl-methylpolysiloxanes, linear, cyclic, or branched siloxanes, silicone polymers and copolymers, and organo-silicone copolymers. Silicone polyether copolymer defoamers available from OSI Specialties, Inc. of Farmington Hills, Mich., may also be substituted or included. One such material is sold as SILWET-L-7220.

[0249] 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.

[0250] 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 to acrylate defoamer of about 5:1 to about 1:5, see, for example, US 2021 / 0189283A1. H. Viscosity improver

[0251] Viscosity modifiers (also known as viscosity index improvers or viscosity modifiers) may be included in the lubricating compositions described herein. Viscosity modifiers provide high and low temperature operability to the lubricant. These additives provide shear stability at elevated temperatures and acceptable viscosity at low temperatures. Suitable viscosity modifiers include high molecular weight hydrocarbons, polyesters, and viscosity modifier dispersants that can act as both viscosity modifiers and dispersants. Typical molecular weights of these polymers range from about 10,000 to 1,500,000 g / mol, more typically from about 20,000 to 1,200,000 g / mol, and even more typically from about 50,000 to 1,000,000 g / mol.

[0252] Examples of suitable viscosity modifiers are linear or star polymers and copolymers of methacrylates, butadiene, olefins or alkylated styrenes. Polyisobutylene is a commonly used viscosity modifier. Another suitable viscosity modifier is polymethacrylate (e.g., copolymers of alkyl methacrylates of various chain lengths), some of which also serve as pour point depressants. Other suitable viscosity modifiers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (e.g., copolymers of acrylates of various chain lengths). Specific examples include styrene-isoprene or styrene-butadiene based polymers with molecular weights of 50,000 to 200,000 g / mol.

[0253] 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") was purchased from Chevron Oronite Company LLC; sold 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, for example, under the trade designations "SV200" and "SV600." Hydrogenated diene-styrene block copolymers useful as viscosity modifiers herein are available from Infineum International Limited, for example, under the trade designation "SV 50."

[0254] Polymers useful as viscosity modifiers herein include polymethacrylate or polyacrylate polymers, such as linear polymethacrylate or polyacrylate polymers, such as those available under the trade name "Viscoplex TM "(e.g. Viscoplex TM 6-954) available from Evonik Industries, or those available under the trade name Asteric TM (e.g. LubrizolTM 87708 and Lubrizol 87725) are star polymers available from Lubrizol Corporation.

[0255] Vinyl aromatic-containing polymers useful as viscosity modifiers herein can be derived from vinyl aromatic monomers, such as styrenic monomers, such as styrene. Exemplary vinyl aromatic-containing copolymers useful herein can be represented by the 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).

[0256] 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.

[0257] In some embodiments, the viscosity modifier can be functionalized, such as with one or more amines, imides, esters, alcohols, etc. to form a dispersant viscosity modifier ("DVM"). In some embodiments, the lubricating composition of the present invention comprises one or more dispersant viscosity modifiers. Suitable dispersant viscosity modifiers include functionalized polyolefins, such as ethylene-propylene copolymers that have been functionalized with acylating agents, such as maleic anhydride and amines; polymethacrylates functionalized with amines or esterified styrene-maleic anhydride copolymers reacted with amines. A more detailed description of dispersant viscosity modifiers is disclosed in International Publication WO2006 / 015130 or U.S. Patent Nos. 4,863,623; 6,107,257; 6,107,258; and 6,117,825. In some embodiments, dispersant viscosity modifiers may include those described in U.S. Pat. No. 4,863,623 (see column 2, line 15 to column 3, line 52) or International Publication WO 2006 / 015130 (see page 2, paragraph

[0008] and the preparation examples described in paragraphs

[0065] to

[0073] ).

[0258] Available DVMs also include functionalized polymers described in USSN 63 / 379,006 filed October 11, 2022, including but not limited to amide, imide, ester and / or alcohol functionalized partially or fully saturated C-containing 4-5A polymer of an olefin having an Mw / Mn of less than 2, a functionality distribution (Fd) value of 3.5 or less, and an Mn of the polymer prior to functionalization of 10,000 g / mol or greater, provided that if the polymer prior to functionalization is a copolymer of isoprene and butadiene, the Mn of the copolymer is greater than 25,000 g / mol. The dispersant viscosity modifier may be present in an amount of 0 to 5 wt%, or 0.01 to 4 wt%, or 0.05 to 2 wt% of the lubricating composition.

[0259] Viscosity improvers are typically added as concentrates in a large amount of diluent oil. "As delivered" viscosity improvers or dispersants Viscosity improvers in "as delivered" polymer concentrates typically contain from 20 to 75 weight percent living polymer for polymethacrylate or polyacrylate polymers, or from 8 to 20 weight percent living polymer for olefin copolymers, hydrogenated polyisoprene star polymers, or hydrogenated diene-styrene block copolymers. I. Dispersant

[0260] During engine operation, oil-insoluble oxidation byproducts are produced. Dispersants help keep these byproducts in solution, thereby reducing their deposition on metal surfaces. The dispersants used in the formulations of the lubricating compositions herein can be ashless or ash-forming in nature. Dispersants are preferably ashless. So-called ashless dispersants are organic materials that do not substantially form ash when burned. For example, metal-free dispersants or boronized metal-free dispersants are considered ashless. In contrast, metal-containing detergents tend to form ash when burned.

[0261] Dispersants useful herein typically contain a polar group attached to a relatively high molecular weight hydrocarbon chain. The polar group typically contains at least one element of nitrogen, oxygen, or phosphorus. Typical hydrocarbon chains contain 50 to 400 carbon atoms. Dispersants of (Poly)alkenylsuccinic derivatives

[0262] One particularly useful class of dispersants includes (poly)alkenyl succinic acid derivatives, typically prepared by the reaction of a long-chain hydrocarbyl-substituted succinic acid compound (typically a hydrocarbyl-substituted succinic anhydride) with a polyhydroxy or polyamino compound. The long-chain hydrocarbyl group that constitutes the lipophilic portion of the molecule (which provides oil solubility) is typically a polyisobutylene group (the long-chain hydrocarbyl group, such as a polyisobutylene group, typically has an Mn of 400 to 3000 g / mol, such as 450 to 2500 g / mol). Many examples of this type of dispersant are well known commercially and in the literature. Exemplary U.S. patents describing such dispersants include U.S. Patent Nos. 3,172,892; 3,2145,707 (3,215,707); 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 No. 0 471 071 and European Patent Application No. 0 451 380, to which reference is made for this purpose.

[0263] Hydrocarbyl-substituted succinic acid and hydrocarbyl-substituted succinic anhydride derivatives are useful dispersants. In particular, succinimide, succinate or succinate ester amides prepared by reacting 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 one equivalent of a polyhydroxy or polyamino compound (such as an alkyleneamine) are particularly useful. The hydrocarbyl-substituted succinic acid and hydrocarbyl-substituted succinic anhydride derivatives may 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.

[0264] Succinimides particularly useful herein are formed by the condensation reaction between 1) a hydrocarbyl-substituted succinic anhydride, such as polyisobutylene succinic anhydride (PIBSA); and 2) a polyamine (PAM). Examples of suitable polyamines include polyalkylene polyamines, hydroxy-substituted polyamines, polyoxyalkylene polyamines, and combinations thereof. Examples of polyalkylene 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 marketed under trade names such as HPA. TM and HPA-X TM Purchased from Dow Chemical as E-100 TM Available from Huntsman Chemical, etc. Examples of hydroxy-substituted polyamines include N-hydroxyalkyl-alkylene polyamines, such as N-(2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)piperazine and / or N-hydroxyalkylated alkylene diamines of the type described, for example, in U.S. Patent 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 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 US 3,087,936; US 3,172,892; US 3,219,666; US 3,272,746; US 3,322,670; US 3,652,616; US 3,948,800; US 6,821,307; and Canadian Patent No. 1,094,044.

[0265] Succinates 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.

[0266] The succinate 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.

[0267] 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. Pat. 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, PIBSA esters of methylene-bridged naphthoxyethanols (i.e., 2-hydroxyethyl-1-naphthol ether (or hydroxy-terminated naphthol ethylene oxide oligomer ether)) can be used herein.

[0268] The molecular weight of the hydrocarbyl-substituted succinic anhydrides used in the preceding paragraphs is typically from 350 to 4000 g / mol, such as from 400 to 3000 g / mol, such as from 450 to 2800 g / mol, such as from 800 to 2500 g / mol. The (poly)alkenyl succinic acid derivatives described above can be post-reacted with various reagents, such as sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid.

[0269] The dispersant may be present in the lubricant in an amount from 0.1 to 20 wt % of the composition, such as from 0.2 to 15 wt %, such as from 0.25 to 10 wt %, such as from 0.3 to 5 wt %, such as from 1.0 to 3.0 wt % of the lubricating oil composition.

[0270] The (poly)alkenylsuccinic acid derivatives described above may also be post-reacted with a boron compound such as boric acid, borate esters or highly boronated dispersants to form boronated dispersants typically having from about 0.1 to about 5 moles of boron per mole of dispersant reaction product.

[0271] Useful dispersants herein include boronated succinimides, including those derived from monosuccinimides, bissuccinimides, and / or mixtures of monosuccinimides and bissuccinimides, wherein the hydrocarbyl succinimides are 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 mixtures of such hydrocarbylene groups, typically having high terminal vinylic groups.

[0272] 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.

[0273] 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.

[0274] Borated dispersants may be used in combination with non-borated dispersants and may be the same or different compounds as the non-borated dispersants. In one embodiment, the lubricating composition may include one or more boron-containing dispersants and one or more non-borated dispersants, wherein the total amount of dispersants may be from 0.01% to 20% by weight, or from 0.1% to 15% by weight, or from 0.1% to 10% by weight, or from 0.5% to 8% by weight, or from 1.0% to 6.5% by weight, or from 0.5% to 2.2% by weight of the lubricating composition, and wherein the ratio of borated dispersant to non-borated dispersant may be from 1:10 to 10:1 (weight:weight), or from 1:5 to 3:1, or from 1:3 to 2:1. Dispersants of Mannich Bases

[0275] Mannich base dispersants useful herein are typically made by reacting an amine component, a hydroxyaromatic compound (substituted or unsubstituted, such as an alkyl substituted compound), such as an alkylphenol, and an aldehyde, such as formaldehyde. See US 4,767,551 and US 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 US Pat. Nos. 3,697,574; 3,703,536; 3,704,308; 3,751,365; 3,756,953; 3,798,165; 3,803,039; US 4,231,759; US 9,938,479; US 7,491,248; US 10,899,986 and WO 01 / 42399. Polymethacrylate or polyacrylate derivative dispersants

[0276] 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 esters containing 5 to 25 carbon atoms in the ester group. Representative examples are shown in U.S. Patent Nos. 2,100,993 and 6,323,164. Polymethacrylate and polyacrylate dispersants are typically relatively low molecular weight.

[0277] The lubricating compositions of the present invention typically comprise a dispersant in an amount of from 0.1% to 20% by weight of the composition, such as from 0.2% to 15% by weight, such as from 0.25% to 10% by weight, such as from 0.3% to 5% by weight, such as from 1.0% to 3.0% by weight of the lubricating oil composition. Alternatively, the dispersant may be present in an amount of from 0.1% to 5% by weight, or from 0.01% to 4% by weight, or from 0.05% to 2% by weight of the lubricating composition.

[0278] For further information on dispersants useful herein, see US 10,829,712, col. 13, line 36 to col. 16, line 67, and US 7,485,603, col. 2, line 65 to col. 6, line 22, col. 8, line 25 to col. 14, line 53, and col. 23, line 40 to col. 26, line 46. J.Corrosion Inhibitors / Antirust Agents

[0279] 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.

[0280] 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 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 20 Hydrocarbyl or substituted hydrocarbyl. It may contain a ring structure that is alkyl or aryl in nature and / or contain heteroatoms such as N, O or S. Examples of suitable compounds may include benzotriazole, alkyl-substituted benzotriazoles (e.g., tolyltriazole, ethylbenzotriazole, hexylbenzotriazole, octylbenzotriazole, etc.), aryl-substituted benzotriazoles, alkylaryl- or arylalkyl-substituted benzotriazoles, and the like, and combinations thereof. For example, the triazole may comprise or be benzotriazole and / or an alkylbenzotriazole, wherein the alkyl group contains 1 to about 20 carbon atoms, or 1 to about 8 carbon atoms. Non-limiting examples of such corrosion inhibitors may comprise or be benzotriazole, tolyltriazole and / or an optionally substituted benzotriazole, such as Irgamet available from BASF of Ludwigshafen, Germany. TM 39. Preferred corrosion inhibitors may comprise or be benzotriazole and / or tolyltriazole.

[0281] Additionally or alternatively, the corrosion inhibitor may include a substituted thiadiazole of the following structure: where R 15 and R 16 In some embodiments, the present invention provides the thiadiazoles of the present invention.Independently being hydrogen or alkyl, this group can be aliphatic or aromatic, comprises cyclic, alicyclic, aralkyl, aryl and alkaryl, and wherein each w is 1,2,3,4,5 or 6 (preferably 2,3 or 4, as 2) independently.These substituted thiadiazoles are derived from 2,5-dimercapto-1,3,4-thiadiazole (DMTD) molecule.Many derivatives of DMTD have been described in the art, and any such compound can be included in the fluid used in the present disclosure.For example, US 2,719,125, US 2,719,126 and US 3,087,937 have described the preparation of various 2,5-bis-(hydrocarbon disulfide)-1,3,4-thiadiazoles.

[0282] 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 linked to the sulfide sulfur atom. The preparation of these thioester-containing DMTD derivatives is described, for example, in US 2,760,933. DMTD derivatives prepared by condensation of DMTD with α-halogenated aliphatic carboxylic acids having at least 10 carbon atoms are described, for example, in US 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.

[0283] The preparation of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazoles is described, for example, in US Pat. No. 3,663,561.

[0284] 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 obtained under the trade name 4313 is sold and available from Afton Chemical Company.

[0285] The preparation of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazoles is described, for example, in US Pat. No. 3,663,561.

[0286] 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.

[0287] 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 in which the non-aqueous medium comprises or is a lubricating oil base stock, for example, better compatibility is generally achieved when the hydrocarbyl moieties are each at least C4. 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, monohexyldibutyl borate, and the like, and combinations thereof.

[0288] When used, the corrosion inhibitor may comprise a substituted thiadiazole, a substituted benzotriazole, a substituted triazole, a trisubstituted borate, or a combination thereof.

[0289] When desired, corrosion inhibitors may be used in any effective amount, but when used, may generally be used in amounts of about 0.001 to 5.0 wt %, e.g., 0.005 to 3.0 wt %, or 0.01 to 1.0 wt %, based on the weight of the composition. Alternatively, 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.

[0290] In some embodiments, the 3,4-oxypyridinone-containing compositions can be substantially free (e.g., 0, or less than 0.001 wt %, 0.0005 wt % or less, no intentionally added, and / or absolutely free) of triazoles, benzotriazoles, substituted thiadiazoles, imidazoles, thiazoles, tetrazoles, hydroxyquinolines, oxazolines, imidazolines, thiophenes, indoles, indazoles, quinolines, benzoxazines, dithiols, oxazoles, oxatriazoles, pyridines, piperazines, triazines, derivatives thereof, combinations thereof, or all corrosion inhibitors. K. Anti-wear agent

[0291] The antiwear agents described herein do not include compounds represented by formula (I) above. The compositions according to the present disclosure may contain additives having different listed functions and also having a secondary effect as antiwear agents (for example, organic molybdenum friction modifiers (such as molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum alkylxanthates, and molybdenum alkylthioxanthates) may also have an antiwear effect). For the purpose of determining the amount of antiwear additive in the lubricating oil composition or concentrate herein, these additives are not counted as antiwear additives.

[0292] The lubricating oil composition of the present invention may contain one or more anti-wear agents that can reduce friction and excessive wear. Any anti-wear agent known to those of ordinary skill in the art can be used in the lubricating oil composition. Non-limiting examples of suitable anti-wear agents include zinc dithiophosphates, metal (e.g., Pb, Sb, Mo, etc.) salts of dithiophosphoric acids, metal (e.g., Zn, Pb, Sb, Mo, etc.) salts of dithiocarbamic acids, metal (e.g., Zn, Pb, Sb, etc.) salts of fatty acids, boron compounds, phosphates, phosphites, amine salts of phosphates or thiophosphates, 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 can range from about 0.01 wt % to about 5 wt %, from about 0.05 wt % to about 3 wt %, or from about 0.1 wt % to about 1 wt %.

[0293] In some embodiments, the antiwear agent is or comprises a dihydrocarbyl dithiophosphate metal salt, such as a zinc dialkyl dithiophosphate compound. The metal of the dihydrocarbyl dithiophosphate metal salt can be an alkali metal or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper. In some embodiments, the metal is zinc. In other embodiments, the alkyl group of the dihydrocarbyl dithiophosphate metal salt has about 3 to about 22 carbon atoms, about 3 to about 18 carbon atoms, about 3 to about 12 carbon atoms, or about 3 to about 8 carbon atoms. In further embodiments, the alkyl group is linear or branched.

[0294] Useful antiwear agents also include substituted or unsubstituted thiophosphoric acids, salts of which include zinc-containing compounds such as zinc dithiophosphate compounds selected from the group consisting of dialkyl-, diaryl- and / or alkylaryl-zinc dithiophosphates.

[0295] Metal alkylthiophosphates, more particularly metal dialkyl dithiophosphates wherein the metal component is zinc, or zinc dialkyl dithiophosphate (ZDDP) can be useful components of the lubricating compositions of the present disclosure. ZDDP can be derived from a primary alcohol, a secondary alcohol, or a mixture thereof. ZDDP compounds generally have the formula Zn[SP(S)(OR 1 )(OR 2 )]2, where R 1 and R 2 It is C1-C18 Alkyl, preferably C2-C 12 Alkyl groups. These alkyl groups can be straight chain or branched. The alcohol used in ZDDP can be 2-propanol, butanol, sec-butanol, pentanol, hexanol, such as 4-methyl-2-pentanol, n-hexanol, n-octanol, 2-ethylhexanol, alkylated phenols, etc. A mixture of secondary alcohols or a mixture of primary and secondary alcohols can be used. Alkyl aryl groups can also be used. Available zinc dithiophosphates include secondary zinc dithiophosphates, such as those available from The Lubrizol Corporation under the trade names "LZ 677A", "LZ 1095" and "LZ1371", from Chevron Oronite under the trade name "OLOA 262" and from HiTEC TM 7169" from Afton Chemical.

[0296] The ZDDP is 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 %, and 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 ZDDP is a secondary ZDDP and is present in an amount of about 0.6 to 1.0 wt % of the total weight of the lubricating composition.

[0297] 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.

[0298] The ZDDP and / or zinc carbamate is 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 %, and 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 ZDDP is a secondary ZDDP and is present in an amount of about 0.6 to 1.0 wt % of the total weight of the lubricating composition.

[0299] 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. L. Other additives

[0300] Other optional additives include demulsifiers, see 10,829,712 (column 20, lines 34-40). Generally, small amounts of demulsifier components can be used herein. Preferred demulsifier components are described in EP 330,522. They are obtained by reacting an alkylene oxide with an adduct obtained by reacting a diepoxide with a polyol.

[0301] 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 %.

[0302] When a lubricating oil composition contains one or more of the additives discussed above, the additives are generally incorporated into the composition in amounts sufficient to enable them to perform their intended functions. Typical amounts of such additives useful in the present disclosure, particularly for crankcase lubricants, are shown in Table 1 below.

[0303] It is important to note 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 percent (wt.%) indicated below is based on the total weight of the lubricating oil composition.

[0304] Typical Amounts of Optional Lubricant Components in LOC

[0305] Typical Amounts of Optional Lubricant Components in LOC (Continued) Additive formulations D (wt.%) E (wt.%) F (wt.%) Dispersants, boronized 0.1-10 0.5-8 0.5-5 Dispersants, non-boronated 0.1 to 30 0.5 to 20 1 to 15 detergent 0.1-19.8 0.25-9 0.25 to 5 colloidal particles 0.01-9.8 0.1-8 0.5 to 5 Functionalized olefin copolymers 0.1-15 0.5-5 0.5 to 3 Amine and / or phenol (preferably amine) based antioxidants 0.01-7 0.10-5 1 to 5 Sulfurized fatty acid esters 0.01-20 0.1 to 10 0.5-5 Molybdenum-containing compounds 0.01-10 0.1 to 7 0.1 to 5 defoaming agent 0.0-5 0.001-0.2 0.001-0.1 Friction modifiers 0-5 0-1.5 0.1 to 5 Viscosity improvers 0.01-25 1-20 5-15 Linear alpha olefins 0 to 10 0.1 to 5 0.1 to 2.5 Optional additional additives 0-20 0.1-10 0.1-10 base oil margin margin margin

[0306] 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, ratios and properties are available, and the selection of an appropriate package will take into account the use of the final composition.

[0307] In another aspect, the lubricating oil compositions described herein contain 500 to 3000 ppm, or 500 to 2800 ppm, of a Group 4, 5, 10, 11, 12, or 13 metal (e.g., a Group 10, 11, 12, or 13 metal such as zinc).

[0308] The lubricating oil compositions described herein preferably contain 500 to 3000 ppm, or 500 to 2800 ppm, of a metal selected from nickel, palladium, platinum, copper, silver, gold, zinc, tin, zirconium, hafnium, titanium, vanadium, molybdenum, niobium and tantalum (e.g., zinc).

[0309] Alternatively, the lubricating oil compositions described herein contain 500 to 3000 ppm, alternatively 500 to 2800 ppm, alternatively 500 to 2000 ppm zinc.

[0310] Alternatively, the lubricating oil compositions described herein contain 600 to 4000 ppm, or 700 to 3000 ppm, or 800 to 2500 ppm of zinc derived from the zinc colloidal particles and any ZDDP (zinc dialkyldithiophosphate) and / or ZDDC (zinc dialkyldithiocarbamate) present.

[0311] Alternatively, zinc dialkyldithiophosphate is present in the lubricating compositions described herein at 1 wt % or less, such as 0.5 wt % or less, such as 0.1 wt % or less, such as 0.01 wt % or less, or no dialkyldithiophosphate is present.

[0312] Alternatively, zinc dialkyldithiocarbamate is absent or present in the lubricating compositions described herein at 1 wt % or less, such as 0.5 wt % or less, such as 0.1 wt % or less, such as 0.01 wt % or less.

[0313] Alternatively, the zinc dialkyldithiophosphates and zinc dialkyldithiocarbamates are present in the lubricating compositions described herein at 1 wt % or less, such as 0.5 wt % or less, such as 0.1 wt % or less, such as 0.01 wt % or less.

[0314] Alternatively, the lubricating compositions described herein have an adhesive wear result (ASTM D 8074-16) of 100 hours or more and a Zn / P ratio (elemental mass basis) of 1.1 to 5.0 (e.g., 1.1 to 4.9, or 1.1 to 4.8, or 1.1 to 4.7, or 1.2 to 4.7, or 1.3 to 4.5, or 2.5 to 4.0, in weight percent), wherein the lubricating composition contains a zinc-containing compound other than zinc dialkyldithiophosphate and / or zinc dialkyldithiocarbamate.

[0315] Alternatively, the lubricating compositions described herein have an adhesive wear of greater than 100 hours (ASTM D 8074-16) and at least 1000 ppm zinc, wherein the lubricating composition contains a zinc-containing compound other than zinc dialkyldithiophosphate and / or zinc dialkyldithiocarbamate.

[0316] Alternatively, the lubricating compositions described herein have an adhesive wear (ASTM D 8074-16) of greater than 100 hours. fuel

[0317] The present invention also relates to a method for lubricating an internal combustion engine of an automobile during engine operation, comprising: (i) providing a lubricating composition as described herein to a crankcase of an automotive internal combustion engine; (ii) providing hydrocarbon fuel in an automotive internal combustion engine; and (iii) combusting the fuel in an automotive internal combustion engine, such as a spark-ignited or compression-ignited two-stroke or four-stroke reciprocating engine, such as a diesel engine, or a passenger car engine (such as a spark-ignited internal combustion engine).

[0318] The present invention 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 wt% renewable fuel, or 1 to 75 wt% renewable fuel, or 1 to 50 wt% renewable fuel, or 5 to 50 wt% renewable fuel, based on the total mass of renewable fuel and petroleum-derived fuel.

[0319] 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 cooking oil, animal fat and / or fish fat) 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 help 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. Such 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 the desired properties depending on the intended use.

[0320] Furthermore, the lubricating compositions can be used in any type of internal combustion engine, for example in cars or trucks, or in marine engines, gas engines, large engines or turbines. They can be used in any engine that uses petrol, gasoline or diesel, or alternative fuels such as liquefied natural gas (LNG), ammonia, hydrogen, etc. use

[0321] The lubricating oils described herein can be used in a range of internal combustion engines, such as compression-ignition and spark-ignition engines. Examples include engines for passenger cars, light commercial vehicles, and heavy-duty on-highway trucks; engines for aviation, power generation, locomotives, and marine equipment / engines; and heavy-duty off-highway engines, such as those used in agriculture, construction, and mixing.

[0322] The lubricating composition of the present invention can be used as a marine lubricant, such as trunk piston engine oil (TPEO), MDCL (marine diesel engine cylinder lubricant), system oil, and the like.

[0323] Additionally, the lubricating composition may be used as a transmission fluid or oil, or a gear oil.

[0324] The lubricating compositions of the present invention may also be used as lubricants for natural gas engines (eg, natural gas is the fuel used to run the engine, commonly referred to as GEO or [natural] gas engine oil).

[0325] The lubricating composition of the present invention can be used to lubricate mechanical engine components, particularly in internal combustion engines, such as spark ignition or compression ignition two-stroke or four-stroke reciprocating engines, by adding the lubricant thereto. Typically, they are crankcase lubricants, such as passenger car motor oils or heavy-duty diesel engine lubricants.

[0326] In particular, the lubricating composition of the present invention is suitably used for lubricating the crankcase of a compression ignition internal combustion engine, such as a heavy-duty diesel engine. The lubricating composition of the present invention is particularly suitable for internal combustion engines that are susceptible to piston liner wear due to long-term operation, and thus the present invention can extend the life of the engine.

[0327] In particular, the lubricating composition of the present invention is suitably used for lubrication of the crankcase of a spark-ignition turbocharged internal combustion engine.

[0328] The lubricating oils of the present disclosure are particularly useful in high compression spark-ignition internal combustion engines.

[0329] The present invention further relates to the use of the composition described above as an anti-wear additive in internal combustion engine oils, transmission or gear oils, wherein the composition comprises the following components or is obtained by mixing the following components: (A) 1 to less than 50 mass % of one or more base oils, based on the weight of the composition; (B) at least one phosphorus-containing compound selected from detergents, friction modifiers, or antiwear additives other than the colloidal particles described in (C); (C) 0.1 to 50 mass % of colloidal particles, based on the weight of the composition, comprising: a) a core of one or more hydrocarbon-insoluble zinc-containing compounds, and b) a shell of one or more of the following: 1) one or more metal-containing surfactants, wherein the metal M comprises a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and the surfactant comprises a hydrocarbyl-substituted aromatic sulfonate of formula (I) or a hydrocarbyl-substituted salicylate group of formula (II), where R A and R B are each independently a linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon group having 1 to 70 carbon atoms, wherein when n>1, all R A The sum of the number of carbon atoms in the group and all R B The total number of carbon atoms in the group is 100 or less carbon atoms, and Ar is a monocyclic or polycyclic aromatic group; n is an integer from 1 to the maximum possible number of substitutions on Ar, m is an integer from 1 to 3, x is an integer from 1 to 5; y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 8; 2) one or more metal alkanoates represented by formula (III): wherein M is a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and R C is selected from linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon groups having 6 to 70 carbon atoms, or aromatic groups or alkyl aromatic groups, wherein the aromatic group has 6 to 20 carbon atoms and the alkyl group has 1 to 20 carbon atoms; x is an integer from 1 to 5, wherein in the case of x>1, the R C The groups may be the same or different, y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 8; wherein the composition has a Zn / P ratio of 1.1 to 5.0 (elemental mass basis as measured by ASTM D5185); optionally having all preferred colloidal components described herein.

[0330] The present invention further relates to: 1. A lubricating oil composition comprising the following components or a mixture of the following components: (A) 1 to 99.99 wt. %, based on the weight of the lubricating composition, of one or more base oils; (B) at least one phosphorus-containing compound selected from detergents, friction modifiers, or antiwear additives other than the colloidal particles described in (C); (C) 0.01 to 10 wt. % of colloidal particles, based on the weight of the composition, comprising: a) a core of one or more hydrocarbon-insoluble zinc-containing compounds, and b) a shell of one or more of the following: 1) one or more metal-containing surfactants, wherein the metal M comprises a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; the surfactant comprises a hydrocarbyl-substituted sulfonate group of formula (I) or a hydrocarbyl-substituted salicylate group of formula (II), where R A and R B are each independently a linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon group having 1 to 70 carbon atoms, wherein when n>1, all R A The sum of the number of carbon atoms in the group and all R B The total number of carbon atoms in the group is 100 or less carbon atoms, and Ar is a monocyclic or polycyclic aromatic group; n is an integer from 1 to the maximum possible number of substitutions on Ar, wherein if m=0, n=1; m is an integer from 1 to 3, x is an integer from 1 to 5; y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 8; 2) one or more metal alkanoates represented by formula (III): wherein M is a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and R C is selected from linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon groups having 6 to 70 carbon atoms, or aromatic groups or alkyl aromatic groups, wherein the aromatic group has 6 to 20 carbon atoms and the alkyl group has 1 to 20 carbon atoms; x is an integer from 1 to 5, wherein in the case of x>1, the R C The groups may be the same or different, y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 8, The lubricating oil composition has a Zn / P ratio (element mass basis as measured by ASTM D5185) of 1.1 to 5.0. 2. The lubricating composition of paragraph 1, wherein the hydrocarbon-insoluble zinc-containing compound is selected from at least one of zinc, zinc oxide, zinc hydroxide, zinc carbonate, and zinc halide, or mixtures thereof. 3. The lubricating composition of paragraph 1 or 2, wherein the colloidal particles have a mean particle diameter determined by dynamic light scattering in the range of 5 nm to 1 μm, such as 20 nm to 500 nm, or 20 nm to 200 nm. 4. The lubricating composition of any one of paragraphs 1 to 3, wherein the metal M in formula (I), (II) or (III) is selected from at least one of sodium, potassium, lithium, magnesium, calcium, barium or a mixture thereof; or wherein the metal M is selected from at least one of gold, silver, palladium, platinum, zirconium, vanadium, molybdenum, nickel, copper, zinc, aluminum or a mixture thereof. 5. The lubricating composition of any of paragraphs 1 to 4, wherein Ar in formula (I) or formula (II) is benzene or naphthalene. 6. The lubricating composition of paragraph 5, wherein the surfactant of formula (I) is a metal-containing hydrocarbyl-substituted phenyl sulfonate surfactant of formula (Ia), wherein M is selected from calcium, magnesium, barium or zinc or a combination thereof, such as calcium, magnesium or zinc, or calcium or zinc; R A are independently of one another linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon groups having 6 to 50 carbon atoms, such as 10 to 40 or 12 to 37 carbon atoms; n is an integer from 1 to 5, such as 1 to 4, such as 1, 2 or 3, such as 1, wherein if m=0, then n=1; m is 0 to 3, such as 0 or 1; all R A The sum of the number of carbon atoms in the group is 60 or less carbon atoms; x is 2; y is 2; and optionally, p is 0. 7. The lubricating composition of paragraph 5, wherein the surfactant of formula (II) is a metal-containing hydrocarbyl-substituted phenyl salicylate surfactant of formula (IIa), wherein M is selected from calcium, magnesium, barium or zinc or a combination thereof; such as calcium, magnesium or zinc or a combination thereof; or calcium or zinc or a combination thereof; R B are independently linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon groups having 6 to 50 carbon atoms, such as 10 to 48 or 12 to 37 carbon atoms; n is an integer from 1 to 4, such as 1 to 3, such as 1 or 2, such as 1; all R B The sum of the number of carbon atoms in the group is 60 or less carbon atoms; x is 2, y is 2; and optionally, p is 0. 8. The lubricating composition of any one of paragraphs 1 to 7, wherein M in formula (I), (Ia), (II), (IIa) or (III) is selected from calcium, magnesium or zinc or a combination thereof; such as calcium or zinc or a combination thereof. 9. The lubricating composition of any of paragraphs 1 to 8, wherein R in formula (III) is a linear, cyclic or branched alkyl or alkenyl group having 6 to 48 carbon atoms, such as 8 to 40 or 10 to 20 carbon atoms. 10. The lubricating composition of paragraph 9, wherein the metal alkanoate of formula (III) is one or more of zinc neodecanoate, zinc neoundecanoate, zinc neododecanoate, zinc neotridecanoate, zinc neotetradecanoate, zinc neopentadecanoate, zinc neohexadecanoate, zinc neoheptadecanoate, zinc stearate, zinc neooctadecanoate, zinc oleate, zinc neononadecanoate, and zinc neoeicosanoate. 11. The lubricating composition of paragraph 9 or 10, wherein the metal alkanoate has a quaternary carbon atom at the 2 position, ie, connected to a carboxylate group. 12. The lubricating composition of any of paragraphs 1 to 11, further comprising one or more components selected from one or more friction modifiers; one or more antioxidants; one or more pour point depressants; one or more defoaming agents; one or more viscosity modifiers; one or more dispersants; one or more inhibitors and / or rust inhibitors; and / or one or more antiwear agents different from those of component (C). 13. The lubricating composition of any of paragraphs 1 to 12, wherein: (A) the base oil is present in an amount of 50 to 99 weight percent based on the weight of the lubricating composition; (B) said at least one phosphorus-containing compound selected from detergents, friction modifiers, or antiwear additives other than the colloidal particles described in (C) is present in an amount of 0.001 to 5 weight percent; C) the colloidal particles are present in an amount of 0.01 to 10 wt %, such as 0.01 to 6 wt %, based on the total weight of the lubricating composition; D) optionally, one or more friction modifiers different from those of component (B) present in an amount of 0.01 to 5 weight percent based on the total weight of the lubricating composition; E) optionally, one or more antioxidants present in an amount of 0.01 to 10 wt % based on the total weight of the lubricating composition; F) optionally, one or more pour point depressants present in an amount of 0.01 to 5 weight percent based on the total weight of the lubricating composition; G) optionally, one or more defoaming agents present in an amount of 0.001 to 5 wt % based on the total weight of the lubricating composition; H) optionally, one or more viscosity modifiers are present in an amount of 0.001 to 6 wt % based on the total weight of the lubricating composition; I) optionally, one or more dispersants are present in an amount of 0.01 to 20 wt % based on the total weight of the lubricating composition; J) optionally, one or more inhibitors and / or rust inhibitors are present in an amount of 0.01 to 5 wt. %, based on the total weight of the lubricating composition; and K) optionally, one or more antiwear agents different from those of components (B) and (C) present in an amount of 0.001 to 5 wt. %, based on the total weight of the lubricating composition; L) Optionally, one or more detergents other than those of component (B) and those in the colloidal particles described in (C) are present at 0.1 to 20 wt. %, based on the total weight of the lubricating composition. 14. The lubricating composition of any of paragraphs 1 to 13, wherein the lubricating composition has an adhesive wear as measured by ASTM D8074-16 of 100 hours or greater, such as 120 hours or greater, 130 hours or greater, or 140 hours or greater. 15. The lubricating composition of any of paragraphs 1 to 14, wherein the Zn / P ratio (element mass basis) in the lubricating composition is from 1.1 to 4.9, such as from 1.1 to 4.8, such as from 1.1 to 4.7, such as from 1.2 to 4.7, or from 1.3 to 4.5, 1.4 to 4.5, 1.5 to 4.5, or 2.5 to 4.0. 16. The lubricating composition of any of paragraphs 1 to 15, wherein the ligand L is selected from the group consisting of water, hydroxide, halide, ammonia, amino, amido, alcoholate, and mixtures thereof. 17. The lubricating composition of any of paragraphs 1 to 16, wherein the colloidal particles have a metal / surfactant molar ratio MR of at least 5, such as 5 to 50, or 6 to 40, or 7 to 30. 18. The lubricating composition of any of paragraphs 1 to 17, wherein the composition has a total base number (TBN) of 1 to 30 mgKOH / g, such as 5 to 25 mgKOH / g, 5 to 20 mgKOH / g, such as 7 to 17 mgKOH / g, such as 13 to 15 mgKOH / g, as measured by ASTM D2896. 19. The lubricating composition of any of paragraphs 1 to 18, having a zinc content of 500 ppm or greater, such as 800 ppm or greater, or 1000 ppm or greater, such as 1500 ppm or greater, or 2000 ppm or greater, as determined by ASTM D5185. 20. The lubricating composition of any of paragraphs 1 to 18, having a phosphorus content of no greater than 2000 ppm, such as no greater than 1600 ppm, no greater than 1200 ppm, such as no greater than 800 ppm, such as from 1 to 1600 ppm, such as from 10 to 1200 ppm, such as from 100 to 800 parts per million (ppm), based on the total mass of the lubricating composition as measured by ASTM D5185. 21. The lubricating composition of any one of paragraphs 1 to 20, wherein the lubricating composition is an internal combustion engine oil, such as petrol or gasoline or a heavy duty diesel engine oil, or a marine engine oil or a gas turbine oil. 22. The lubricating composition of any one of paragraphs 1 to 20, wherein the lubricating composition is a transmission fluid or a gear oil. 23. The lubricating composition of any one of paragraphs 1 to 22, comprising greater than 500 ppm Zn and less than 500 ppm P, preferably greater than 1000 ppm Zn and less than 1000 ppm P, wherein the lubricating composition has an adhesive wear time of greater than 100 hours and, optionally, a total base number of greater than 7 mgKOH / g. 24. The lubricating composition of any of paragraphs 1 to 23, wherein the zinc dialkyldithiophosphate is present at 2 wt % or less, such as 1 wt % or less. 25. The lubricating composition of any of paragraphs 1 to 24, wherein the lubricating composition has a relative humidity of less than 150 μm as measured by the HFRR method described herein. 3 , such as less than 140μm 3 , or less than 135μm 3 wear scar volume. 26. A method of obtaining an adhesive wear (ASTM D 8074-16) of 100 hours or more for a lubricating composition having 500 ppm or more, preferably 1000 ppm or more, of zinc, comprising: (i) providing the lubricating composition of any one of paragraphs 1 to 24 to a crankcase of an internal combustion engine; (ii) providing a hydrocarbon fuel in an internal combustion engine; and (iii) combusting the fuel in an internal combustion engine. 27. A method for lubricating an automotive internal combustion engine during engine operation, comprising: (i) providing the lubricating composition of any one of paragraphs 1 to 24 to a crankcase of an internal combustion engine; (ii) providing a hydrocarbon fuel in an internal combustion engine; and (iii) combusting the fuel in an internal combustion engine. 28. The method of paragraph 27, wherein the engine is a diesel engine or a gas engine. 29. The method of paragraph 27, wherein the engine is a marine engine. 30. The method of paragraph 27, wherein the engine is an automotive engine. 31. A concentrate composition comprising or obtained by mixing the following components: (A) 1 to less than 50 weight percent, based on the weight of the concentrate composition, of one or more base oils; (B) at least one phosphorus-containing compound selected from detergents, friction modifiers, or antiwear additives other than the colloidal particles described in (C); (C) 0.1 to 50 wt. %, based on the weight of the composition, of colloidal particles according to any one of the preceding claims, comprising: a) a core of one or more hydrocarbon-insoluble zinc-containing compounds, and b) a shell of one or more of the following: 1) one or more metal-containing surfactants, wherein the metal M comprises a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and the surfactant comprises a hydrocarbyl-substituted sulfonate salt of formula (I) or a hydrocarbyl-substituted salicylate salt of formula (II), where R A and R B are each independently a linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon group having 1 to 70 carbon atoms, wherein when n>1, all R A The sum of the number of carbon atoms in the group and all R B The sum of the number of carbon atoms in the group is 100 or less carbon atoms, and Ar is a monocyclic or polycyclic aromatic group; n is an integer from 1 to the maximum possible number of substitutions on Ar, wherein if m=0, n=1; m is an integer from 0 to 3, x is an integer from 1 to 5; y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 8; 2) one or more metal alkanoates represented by formula (III): wherein M is a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and RC is selected from linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon groups having 6 to 70 carbon atoms, or aromatic groups or alkyl aromatic groups, wherein the aromatic group has 6 to 20 carbon atoms and the alkyl group has 1 to 20 carbon atoms; x is an integer from 1 to 5, wherein in the case of x>1, the R C The groups may be the same or different, y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 8; wherein the concentrate composition has a Zn / P ratio (elemental mass basis as measured by ASTM D5185) of 1.1 to 5.0. 29. A composition for use as an anti-wear additive in an internal combustion engine, transmission fluid or gear oil, the composition comprising or obtained by mixing the following components: (A) 1 to less than 50 weight percent, based on the weight of the composition, of one or more base oils; (B) at least one phosphorus-containing compound selected from detergents, friction modifiers, or antiwear additives other than the colloidal particles described in (C); (C) 0.1 to 50 wt. %, based on the weight of the composition, of colloidal particles according to any one of the preceding claims, comprising: a) a core of one or more hydrocarbon-insoluble zinc-containing compounds, and b) a shell of one or more of the following: 1) one or more metal-containing surfactants, wherein the metal M comprises a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and the surfactant comprises a hydrocarbyl-substituted aromatic sulfonate of formula (I) or a hydrocarbyl-substituted salicylate group of formula (II), where R A and R B are each independently a linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon group having 1 to 70 carbon atoms, wherein when n>1, all R A The sum of the number of carbon atoms in the group and all R B The sum of the number of carbon atoms in the group is 100 or less carbon atoms, and Ar is a monocyclic or polycyclic aromatic group; n is an integer from 1 to the maximum possible number of substitutions on Ar, wherein if m=0, n=1; m is an integer from 0 to 3, x is an integer from 1 to 5; y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 8; 2) one or more metal alkanoates represented by formula (III): wherein M is a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and R C is selected from linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon groups having 6 to 70 carbon atoms, or aromatic groups or alkyl aromatic groups, wherein the aromatic group has 6 to 20 carbon atoms and the alkyl group has 1 to 20 carbon atoms; x is an integer from 1 to 5, wherein in the case of x>1, the R C The groups may be the same or different, y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 8; wherein the composition has a Zn / P ratio (element mass basis as measured by ASTM D5185) of 1.1 to 5.0. 30. A method of lubricating an internal combustion engine during engine operation, comprising: (i) providing the lubricating composition of any one of paragraphs 1 to 24 to a crankcase of an internal combustion engine; (ii) providing fuel in an internal combustion engine; and (iii) combusting the fuel in an internal combustion engine, wherein the fuel comprises a hydrocarbon fuel derived from petroleum and / or a biological source; a hydrogen fuel, optionally in combination with liquefied natural gas; and / or an ammonia fuel.

[0331] The present invention also relates to: 1A. A lubricating composition comprising or obtained by mixing the following components: (A) 1 to 99.99 wt. %, based on the weight of the lubricating composition, of one or more base oils; (B) at least one phosphorus-containing compound selected from detergents, friction modifiers, or antiwear additives other than the colloidal particles described in (C); (C) 0.01 to 10 wt. % of colloidal particles, based on the weight of the composition, comprising: a) a core of one or more hydrocarbon-insoluble zinc-containing compounds, and b) a shell of one or more of the following: 1) one or more metal-containing surfactants, wherein the metal M comprises a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and the surfactant comprises a hydrocarbyl-substituted sulfonate salt of formula (I) or a hydrocarbyl-substituted salicylate salt of formula (II), where R A and R B are each independently a linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon group having 1 to 70 carbon atoms, wherein when n>1, all RA The sum of the number of carbon atoms in the group and all R B The total number of carbon atoms in the group is 100 or less carbon atoms, and Ar is a monocyclic or polycyclic aromatic group; n is an integer from 1 to the maximum possible number of substitutions on Ar, wherein if m=0, n=1; m is an integer from 1 to 3, x is an integer from 1 to 5; y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 8; 2) one or more metal alkanoates represented by formula (III): wherein M is a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and R C is selected from linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon groups having 6 to 70 carbon atoms, or aromatic groups or alkyl aromatic groups, wherein the aromatic group has 6 to 20 carbon atoms and the alkyl group has 1 to 20 carbon atoms; x is an integer from 1 to 5, wherein in the case of x>1, the R C The groups may be the same or different, y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 8, The lubricating oil composition has a Zn / P ratio (element mass basis as measured by ASTM D5185) of 1.1 to 5.0. 2A. The lubricating composition of paragraph 1, wherein the hydrocarbon-insoluble zinc-containing compound is selected from at least one of zinc, zinc oxide, zinc hydroxide, zinc carbonate, and zinc halides, or mixtures thereof. 3A. The lubricating composition of paragraph 1 or 2, wherein the colloidal particles have an average particle size determined by dynamic light scattering in the range of 5 nm to 1 μm, such as 20 nm to 500 nm, or 20 nm to 200 nm. 4A. The lubricating composition of any of paragraphs 1 to 3, wherein the metal M in formula (I), (II), or (III) is selected from at least one of sodium, potassium, lithium, magnesium, calcium, barium, or mixtures thereof; or wherein the metal M is selected from at least one of gold, silver, palladium, platinum, zirconium, vanadium, molybdenum, nickel, copper, zinc, aluminum, or mixtures thereof. 5A. The lubricating composition of any of paragraphs 1 to 4, wherein Ar in formula (I) or formula (II) is benzene or naphthalene. 6A. The lubricating composition of any of paragraphs 1 to 5, further comprising one or more components selected from one or more friction modifiers; one or more antioxidants; one or more pour point depressants; one or more defoaming agents; one or more viscosity modifiers; one or more dispersants; one or more inhibitors and / or rust inhibitors; and / or one or more antiwear agents different from those of component (C). 7A. The lubricating composition of any one of paragraphs 1 to 6, wherein: (A) the base oil is present in an amount of 50 to 99 weight percent based on the weight of the lubricating composition; (B) said at least one phosphorus-containing compound selected from detergents, friction modifiers, or antiwear additives other than the colloidal particles described in (C) is present in an amount of 0.001 to 5 weight percent; C) the colloidal particles are present in an amount of 0.01 to 10 wt %, such as 0.01 to 6 wt %, based on the total weight of the lubricating composition; D) optionally, one or more friction modifiers different from those of component (B) present in an amount of 0.01 to 5 weight percent based on the total weight of the lubricating composition; E) optionally, one or more antioxidants present in an amount of 0.01 to 10 wt % based on the total weight of the lubricating composition; F) optionally, one or more pour point depressants present in an amount of 0.01 to 5 weight percent based on the total weight of the lubricating composition; G) optionally, one or more defoaming agents present in an amount of 0.001 to 5 wt % based on the total weight of the lubricating composition; H) optionally, one or more viscosity modifiers are present in an amount of 0.001 to 6 wt % based on the total weight of the lubricating composition; I) optionally, one or more dispersants are present in an amount of 0.01 to 20 wt % based on the total weight of the lubricating composition; J) optionally, one or more inhibitors and / or rust inhibitors are present in an amount of 0.01 to 5 wt. %, based on the total weight of the lubricating composition; and K) optionally, one or more antiwear agents different from those of components (B) and (C) present in an amount of 0.001 to 5 wt. %, based on the total weight of the lubricating composition; L) Optionally, one or more detergents other than those of component (B) and those in the colloidal particles described in (C) are present at 0.1 to 20 wt. %, based on the total weight of the lubricating composition. 8A. The lubricating composition of any of paragraphs 1 to 7, wherein the lubricating composition has an adhesive wear of 100 hours or greater, such as 120 hours or greater, 130 hours or greater, or 140 hours or greater, as measured by ASTM D8074-16. 9A. The lubricating composition of any of paragraphs 1 to 8, having a zinc content of 500 ppm or greater, such as 800 ppm or greater, or 1000 ppm or greater, such as 1500 ppm or greater, or 2000 ppm or greater, as determined by ASTM D5185. 10A. The lubricating composition of any of paragraphs 1 to 9, having a phosphorus content of no greater than 2000 ppm, such as no greater than 1600 ppm, no greater than 1200 ppm, such as no greater than 800 ppm, such as from 1 to 1600 ppm, such as from 10 to 1200 ppm, such as from 100 to 800 parts per million (ppm), based on the total mass of the lubricating composition as measured by ASTM D5185. 11A. A method of obtaining an adhesive wear (ASTM D 8074-16) of 100 hours or more for a lubricating composition having 500 ppm or more, preferably 1000 ppm or more, of zinc, comprising: (i) providing the lubricating composition of any one of paragraphs 1 to 10 to a crankcase of an internal combustion engine; (ii) providing a hydrocarbon fuel in an internal combustion engine; and (iii) combusting the fuel in an internal combustion engine. 12A. A method of lubricating an automotive internal combustion engine during engine operation, comprising: (i) providing the lubricating composition of any one of paragraphs 1 to 10 to a crankcase of an internal combustion engine; (ii) providing a hydrocarbon fuel in an internal combustion engine; and (iii) combusting the fuel in an internal combustion engine. 13A. The method of paragraph 12, wherein the engine is a diesel engine, a gas engine, or a marine engine. 14A. A concentrate composition comprising or obtained by mixing the following components: (A) 1 to less than 50 weight percent, based on the weight of the concentrate composition, of one or more base oils; (B) at least one phosphorus-containing compound selected from detergents, friction modifiers, or antiwear additives other than the colloidal particles described in (C); (C) 0.1 to 50 wt. % of colloidal particles, based on the weight of the composition, comprising: a) a core of one or more hydrocarbon-insoluble zinc-containing compounds, and b) a shell of one or more of the following: 1) one or more metal-containing surfactants, wherein the metal M comprises a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and the surfactant comprises a hydrocarbyl-substituted sulfonate salt of formula (I) or a hydrocarbyl-substituted salicylate salt of formula (II), where R A and R Bare each independently a linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon group having 1 to 70 carbon atoms, wherein when n>1, all R A The sum of the number of carbon atoms in the group and all R B The sum of the number of carbon atoms in the group is 100 or less carbon atoms, and Ar is a monocyclic or polycyclic aromatic group; n is an integer from 1 to the maximum possible number of substitutions on Ar, wherein if m=0, n=1; m is an integer from 0 to 3, x is an integer from 1 to 5; y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 8; 2) one or more metal alkanoates represented by formula (III): wherein M is a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and R C is selected from linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon groups having 6 to 70 carbon atoms, or aromatic groups or alkyl aromatic groups, wherein the aromatic group has 6 to 20 carbon atoms and the alkyl group has 1 to 20 carbon atoms; x is an integer from 1 to 5, wherein in the case of x>1, the R C The groups may be the same or different, y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 8; wherein the concentrate composition has a Zn / P ratio (elemental mass basis as measured by ASTM D5185) of 1.1 to 5.0. 15A. A composition for use as an anti-wear additive in an internal combustion engine, transmission fluid or gear oil, the composition comprising or consisting of the following components: (A) 1 to less than 50 weight percent, based on the weight of the composition, of one or more base oils; (B) at least one phosphorus-containing compound selected from detergents, friction modifiers, or antiwear additives other than the colloidal particles described in (C); (C) 0.1 to 50 wt. % of colloidal particles, based on the weight of the composition, comprising: a) a core of one or more hydrocarbon-insoluble zinc-containing compounds, and b) a shell of one or more of the following: 1) one or more metal-containing surfactants, wherein the metal M comprises a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and the surfactant comprises a hydrocarbyl-substituted aromatic sulfonate of formula (I) or a hydrocarbyl-substituted salicylate group of formula (II), where R A and R B are each independently a linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon group having 1 to 70 carbon atoms, wherein when n>1, all R A The sum of the number of carbon atoms in the group and all R B The sum of the number of carbon atoms in the group is 100 or less carbon atoms, and Ar is a monocyclic or polycyclic aromatic group; n is an integer from 1 to the maximum possible number of substitutions on Ar, wherein if m=0, n=1; m is an integer from 0 to 3, x is an integer from 1 to 5; y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 8; 2) one or more metal alkanoates represented by formula (III): wherein M is a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and R C is selected from linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon groups having 6 to 70 carbon atoms, or aromatic groups or alkyl aromatic groups, wherein the aromatic group has 6 to 20 carbon atoms and the alkyl group has 1 to 20 carbon atoms; x is an integer from 1 to 5, wherein in the case of x>1, the R C The groups may be the same or different, y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 8; wherein the composition has a Zn / P ratio (element mass basis as measured by ASTM D5185) of 1.1 to 5.0. experiment

[0332] Unless otherwise indicated, all molecular weights are number average molecular weights.

[0333] Mn (number average molecular weight), Mw (weight average molecular weight), and Mz (z average molecular weight) are determined according to the GPC procedure in the experimental section of USSN 63 / 379,006, filed October 11, 2022, and are reported in g / mol.

[0334] AI or ai is the active ingredient. Test Procedure

[0335] Total Base Number is determined according to ASTM D2896 and reported in mgKOH / g.

[0336] HTHS150 (High Temperature High Shear 150) is measured according to ASTM D4683-20 ​​and is reported in centipoise (cP).

[0337] Viscosity index is measured according to ASTM D2270.

[0338] KV 100 It is the kinematic viscosity measured at 100°C according to ASTM D445-19a.

[0339] Phosphorus content was determined by ASTM D5185.

[0340] The zinc content in the colloidal particle preparation samples was determined by inductively coupled plasma atomic emission spectroscopy according to ASTM D4951. The zinc content in the oil formulations was determined by inductively coupled plasma atomic emission spectroscopy according to ASTM D5185.

[0341] Anti-wear performance was determined by bench testing (High Frequency Reciprocating Rig - HFRR) and engine testing (DD13 Scuff - ASTM D8074-16).

[0342] HFRR Test: The oils were tested using a High Frequency Reciprocating Tester (HFRR) available from PCS Instruments, London. In this test, a steel ball was loaded and reciprocated against a steel disk. The load between the ball and disk was set at 4 N to give a contact pressure of 1.046 GPa. The ball was driven at a frequency of 40 Hz over a stroke length of 1 mm for a duration of 300 minutes, increasing by 20°C every 60 minutes from 40°C to 120°C. The test was performed in duplicate to provide the wear scar volume for each sample. The wear scar was measured using optical profilometry (ZeScope Surface Mapping System, ZEMETRICS).

[0343] Adhesive wear testing was conducted according to ASTM D8074-16. The DD13 scuffing test (ASTM D8074-16) evaluates the liner scuffing and ring distress performance of engine oils in turbocharged and intercooled four-cycle diesel engines equipped with exhaust gas recirculation (EGR), uncoated top piston rings, and running on ultra-low sulfur diesel fuel. The test engine was a four-stroke Detroit Diesel DD13 12.8L six-cylinder diesel engine equipped with EGR. The engine was disassembled before each test, the components were solvent cleaned and measured, and reassembled using new pistons, uncoated rings, cylinder liners, and connecting rod bearings. The test was conducted using ASTM D8074-16 Standard Test Method for Evaluation of Diesel Engine Oils in DD13 Diesel Engines, Version 20170104, where time to scuff was determined from a test endpoint where the liner scuffing did not exceed 27%, the iron change did not exceed 25 ppm between any two-hour intervals, and the crankcase pressure did not exceed 2 kPa absolute. The acceptance limit for meeting the specifications set by Detroit Diesel was a minimum time to scuff of 31 hours.

[0344] DLS measurements for particle size determination were performed as follows: Prepare the sample for DLS analysis by being diluted to about 2 weight % in heptane, and use vortex mixer to mix, let it stand for 30 minutes, then filter through 0.45 μm filter.Then the sample is transferred in the quartz cuvette with 10mm optical path length (path length).Use Malvern Zetasizer Nano, analyze sample at 25 ℃.By sample balance 2 minutes, then measure 3 positions in sample.Then use Origin Pro to analyze raw data to measure half height full width and centroid (half height full width and centroid) of any peak by the integration of volume curve, thus obtain volume average particle size (volume average particle size). Material

[0345] PIB is polyisobutylene.

[0346] PIBSA is polyisobutylene succinic anhydride.

[0347] PIBSA-PAM is polyisobutylene succinic anhydride-polyalkyleneamine.

[0348] M n is the number average molecular weight. Example

[0349] The invention is now described in the following examples, which are not intended to limit the scope of the claims hereof. Preparation of Example Colloid System:

[0350] Example 1a - ZnO core, alkylphenylsulfonate zinc shell:

[0351] Alkylphenyl sulfonate (MW approximately 670 g / mol) (40 g) was loaded into the reactor along with a high boiling base oil (40 g) and zinc carbonate (90 g). The system was equipped with a stainless steel Rushton turbine with an overhead stirrer. A nitrogen stream was introduced via a port connector on the lid and a foam over pathway connected to a flask of equal volume to the reactor. The reaction was heated to 300°C for 4 hours and then allowed to cool back to room temperature. The crude product was dissolved in ~5 volumes of xylene and centrifuged at 2900 rpm for 1 hour. The supernatant was decanted from the residue and the solvent was stripped on a rotary evaporator. Target MR: 24.04; Found Zn 32.72 wt%; Calculated MR: 22.12; Particle size: 10-140 nm as measured by DLS.

[0352] Example 1b - ZnO core, alkylphenylsulfonate zinc shell:

[0353] Alkylphenyl sulfonate (MW approximately 670 g / mol) (300 g) was loaded into the reactor along with a high boiling base oil (300 g) and zinc carbonate (600 g). The system was equipped with a stainless steel Rushton turbine with an overhead stirrer. A nitrogen stream was introduced via a port connector on the lid and a foam over pathway connected to a flask of equal volume to the reactor. The reaction was heated to 300° C. for 4 hours and then allowed to cool back to room temperature. The crude product was dissolved in ~5 volumes of xylene and centrifuged at 2900 rpm for 1 hour. The supernatant was decanted from the residue and the solvent was stripped on a rotary evaporator. Zn: 34.10 wt %; calculated MR: 21.96.

[0354] Example 2 - ZnO core, zinc oleate shell:

[0355] Oleic acid (11 g) was loaded into a glass reactor along with a high viscosity polyalphaolefin base oil (75 g) and zinc carbonate (60 g). The remaining equipment was assembled - a stainless steel Rushton turbine with an overhead stirrer. A nitrogen stream was introduced via a port connector on the lid and a foam over pathway connected to a flask of equal volume to the reactor. The reaction was heated to 300°C for 4 hours and then allowed to cool back to room temperature. The crude product was dissolved in ~5 volumes of xylene and centrifuged at 2900 rpm for 1 hour. The supernatant was decanted from the residue and the solvent was stripped on a rotary evaporator. Zn: 11.72 wt%; Calculated MR: 10.47; Particle size: 20-140 nm as measured by DLS.

[0356] Example 3 - ZnO core, zinc neodecanoate shell:

[0357] Capric acid (26.7g) is loaded into a 3L baffled reactor together with xylene (1067g), methanol (42g) and base oil (94.3). A nitrogen inlet and condenser are installed for the reactor. The system is purged with nitrogen and stirred at 400rpm. A solution of sodium hydroxide (71.8g) in methanol (284g) is loaded into a pressure-balanced dropping funnel, and another solution of zinc chloride (122.4g) in methanol (242g) is loaded into a separate pressure-balanced dropping funnel. These two solutions are loaded into the reaction at the same rate over 10 minutes. Once the addition is complete, the dropping funnel is removed and the reaction is heated to 70°C over 45 minutes. Once 70°C is reached, methanol begins to distill from the reaction, and the temperature is ramped up to 80°C over 50 minutes. The temperature is then raised to 140°C over 45 minutes and maintained for 20 minutes, and then allowed to cool to room temperature. Xylene (600 g) was charged to the reaction vessel and the mixture was stirred for 5 minutes. The mixture was decanted from the reactor and placed in a centrifuge at 2900 rpm for 1 hour. The supernatant was decanted from the solids, and the solvent was removed on a rotary evaporator to yield the product. Zn: 22.36 wt%; Calculated MR: 7.80.

[0358] Example 4a - ZnO core, calcium alkylphenyl sulfonate shell: Calcium alkylphenyl sulfonate (MW approximately 1378 g / mol) (30 g) was loaded into a 1 L glass reactor along with a base oil (high viscosity synthetic polyalphaolefin 60 g) and zinc carbonate (60 g). The remaining equipment was assembled - a stainless steel Rushton turbine with an overhead stirrer. A nitrogen stream was introduced via a port connector on the lid and a foam over pathway connected to a flask of equal volume to the reactor. The reaction was heated to 300°C for 4 hours and then allowed to cool back to room temperature. The crude product was dissolved in ~5 volumes of xylene and centrifuged at 2900 rpm for 1 hour. The supernatant was decanted from the residue and the solvent was stripped on a rotary evaporator. Zn: 8.78 wt%; Calculated MR: 6.95; Particle size: 15-150 nm as measured by DLS.

[0359] Example 4b - ZnO core, calcium alkylphenyl sulfonate shell:

[0360] Alkylbenzene sulfonic acid (72.9 g) was loaded into a 1 L baffled reactor along with a high boiling point base oil (75 g) and calcium hydroxide (4.0 g). The system was equipped with a nitrogen inlet to ensure that there was a nitrogen stream through the system. The reaction was heated to 150° C. and held for 10 minutes before the addition of zinc carbonate (150 g). No foaming was observed, but the temperature dropped when the cold reagents were added, so the addition was limited to keep the temperature within 10° C. of the set point. Once all the zinc carbonate was added, the reaction was heated to 300° C. The reaction was soaked at 300° C. for 10 hours. The reaction was cooled to room temperature. Xylene (600 ml) was loaded into the reactor and the mixture was stirred at 400 rpm until all the materials had been absorbed into a mobile suspension. The mixture was centrifuged at 2900 rpm for 1 hour. The solvent was removed on a rotary evaporator to obtain the product. Zn: 25.70 wt%; calculated MR: 17.75; Ca: 0.61 wt%; S: 1.23 wt%;

[0361] Example 4 c-ZnO core, Ca-alkylphenyl sulfonate (made with 2 eq. Ca(OH)2) shell:

[0362] Alkylphenyl sulfonate (MW approximately 670 g / mol) (73 g) was loaded into a 1 L baffled reactor along with a high boiling point base oil (150 g) and calcium hydroxide (8.0 g). The system was equipped with FFKM seals, stainless steel clamps, an overhead stirrer, a 1 L catch pot, and a NaOH scrubber with an inlet to allow nitrogen to flow through the vessel. The reaction was heated to 150° C. and held for 10 minutes, during which time some moisture formed in the reactor lid. Zinc carbonate (150 g) was loaded into the reactor via a port in the reactor lid. Once all the zinc carbonate was added, the reaction was heated to 300° C. The reactor was insulated from 200° C. to aid heating. The reaction was soaked at 300° C. for 4 hours, after which the heat was removed and the reaction was allowed to cool to room temperature. Xylene (600 ml) was loaded into the reactor and the mixture was stirred at 400 rpm until all the material had been absorbed into a mobile suspension. The mixture was then drained from the vessel and centrifuged at 2900 rpm for 1 hour. The supernatant was decanted from the residue and the solvent removed on a rotary evaporator. Initial solvent removal was performed at 60°C (~20 mbar), with the temperature increased to 120°C (10 mbar) to remove the final solvent residue. Zn: 12.80 wt%; Ca: 0.59 wt%; calculated MR: 11.83.

[0363] Example 5 - ZnO core, alkylphenyl magnesium sulfonate shell:

[0364] Alkylphenyl sulfonate (MW approximately 670g / mol, 78.8g) is loaded into a 1.5L baffled glass reactor. High boiling point base oil (150g) is then loaded into the reactor along with magnesium hydroxide (3.21g). The remaining equipment is assembled - overhead stirrer, foam over pathway (foam over pathway) (1.5L catch pot), NaOH scrubber, stainless steel temperature probe, controller coupled heating mantle and nitrogen inlet. The reaction is heated to 150°C over 30 minutes. Once the temperature stabilizes, zinc carbonate (150g) is loaded into the reaction via an open port. The reaction is then heated to 300°C for 4 hours. The reaction is then allowed to cool back to room temperature. Xylene (0.6L) is loaded into the reactor and the mixture is stirred until all reaction mixtures have been drawn into a brown slurry. The slurry is transferred to a large beaker and another 2L of xylene is added. The mixture is centrifuged at 2900rpm for 1 hour. The supernatant was decanted from the residue and the solvent was removed on a rotary evaporator. Zn: 12.80 wt%; Mg: 0.88 wt%; Calculated MR: 10.43.

[0365] Example 6 - ZnO core, zinc nonylnaphthalenesulfonate shell:

[0366] 4,6-Dinonylnaphthalene-2-sulfonic acid (75 g) was loaded into a 1.5 L glass reactor along with a high boiling point base oil (150 g) and zinc carbonate (150 g). The remaining equipment was assembled with a stainless steel Rushton turbine with an overhead stirrer, a stainless steel temperature probe, and a WEST controller coupled to a heating mantle. A nitrogen stream was introduced via a port connector on the lid, with the exhaust directed via a foam over pathway (a flask of equal volume to the reactor) and a sodium hydroxide scrubber. The reaction was heated to 300° C. for 4 hours and then allowed to cool back to room temperature. The crude product was dissolved in ~5 volumes of xylene and centrifuged at 2900 rpm for 1 hour. The supernatant was decanted from the residue and the solvent removed on a rotary evaporator. Zn: 14.80 wt %; calculated MR: 7.92.

[0367] Example 7 - Metathesis reaction of calcium salicylate stabilization

[0368] Base oil (121 g), calcium hydroxide (8.8 g) and methanol (59 g) were added to a 3L reactor flask containing alkyl salicylic acid (362 g / mol, 65 g) and xylene (1053 g). The mixture was heated to 40 ° C for 15 minutes to generate calcium salicylate and then allowed to cool back to 25 ° C. A solution of sodium hydroxide (64 g) in methanol (253 g) was loaded into a pressure-balanced dropping funnel and assembled to the reactor. A solution of zinc chloride (109 g) in methanol (215 g) was loaded into a separate pressure-balanced dropping funnel and also assembled to the reactor. The two methanol solutions were added simultaneously over 15 minutes at approximately the same volume rate, and an exotherm of 5 ° C was observed. Once the addition was complete, the reaction was heated to 70 ° C and the solvent was distilled off from the reaction mixture. The reaction was then heated to 140 ° C over 50 minutes and soaked for 20 minutes. The reaction was then allowed to cool to room temperature. Xylene (600 g) was loaded into a container and the mixture was stirred for 10 minutes. The mobile suspension was decanted and centrifuged at 2900 rpm for 1 hour. The supernatant was decanted from the residue, and the solvent was removed on a rotary evaporator to leave the product. Zn: 14.35 wt% (18.74% by BI); Ca: 1.55 wt%; Particle size: 10 to 50 nm, as measured by DLS.

[0369] Example 8 - ZnO core, zinc salicylate shell: Prepare a solution of ZnCl2 (63g) and NaOH (37g) in MeOH (respectively 124g and 145g). Xylene (507g), base oil (24g) and alkyl salicylate (MW=362 grams / mole, 52g) are loaded into a glass reactor. The mixture is stirred at 400rpm to form a uniform solution. The methanol solution is loaded into a separate pressure-balanced dropping funnel, and the solution is loaded into the reaction simultaneously. Once the addition is complete, the reaction is heated to 65°C and methanol begins to distill from the reactor. The temperature is slowly raised to 80°C to completely remove methanol from the reaction mixture. Once methanol stops distillation, the reaction is heated to 145°C and water and xylene are removed by distillation. Once approximately 200mL of xylene has been removed, the reaction is cooled to room temperature. Additional xylene (200g) is added to the diluted mixture to further centrifuge. The mixture is decanted from the reactor and centrifuged at 3000rpm for 30 minutes. The supernatant was then decanted from the residue and the solvent was stripped on a rotary evaporator. Zn: 28.80% by weight, determined by BI (back titration) as follows: A known amount of sample was diluted in a 70:28:2 (volume-based) mixture of cyclohexane / IPA / water and digested with 0.5M ethanolic perchloric acid. The resulting solution was titrated with 0.1M KOH solution. The first inflection point on the titration curve, EP1, can be used to determine basicity using the following equation: Knowing the total alkalinity of the sample and the nature of the raw materials introduced in the synthesis, it is reasonable to assume that the total alkalinity content of the zinc colloid comes from the presence of zinc salts in the composition. The zinc content can therefore be calculated using the following equation: wt.-% Zinc = 0.5*[Alkalinity]*Aw(Zn)*0.1

[0370] A series of representative fully formulated heavy duty diesel (HDD) engine oils shown in Table 1 below were prepared for antiwear performance testing in bench testing (High Frequency Reciprocating Machine - HFRR) and engine testing (DD13 Scuff - ASTM D8074-16) by mixing the following zinc-containing colloid additives with the base oil and other additives at 60°C. Examples A and H represent comparative lubricating oil compositions to which no zinc-containing colloid was added, while Examples B to G and I represent lubricating oil compositions of the present invention. Oil formulations have ash content requirements that can be detrimental to exhaust aftertreatment systems. Therefore, any metal added to the formulation must be balanced by removing metals from the other components. In the case of these components, the traditional calcium sulfonate detergent was removed and replaced with a zinc-containing colloid, which was shown to provide improved antiwear performance at relatively similar ash contributions and TBNs. Full details of the formulations used are listed below: Table 1 1) In addition to the components noted in the table, Examples A through I contained the common additives discussed above as follows: All Examples contained the same amount of boronated PIBSA-PAM, except for Examples H and I that had none. All Examples contained the same amount of a PIBSA ester and a Mo friction modifier, prepared in a manner similar to Example 1 of US 2009 / 0203559, except for Examples H and I that had none. Examples A through G each contained the same amount of a blend of a diphenylamine antioxidant and a fatty acid methyl ester antioxidant, except for Examples H and I that had none. Examples H and I included each another but equal amounts of a blend of a diphenylamine antioxidant and a sulfurized alkyl methyl ester instead. Examples A to F each included the same amount of 7.2% amine functionalized hydrogenated polyisoprene prepared as described in USSN 63 / 379,006 filed October 11, 2022, and Examples G to I included each the same but different amount. Examples A to G included each the same amount of a PDMS anti-foamant and of polyisobutylene (Mn~1000), and Examples H and I included each another but equal amount of both instead. Examples included the same amount of pour point depressant and viscosity modifier (830 cSt KV 100Examples included the same amount of a pour point depressant and a viscosity modifier (830 cSt KV100), and Examples H and I had non-identical ones than that of Example A to G.

[0371] By adjusting the amount of zinc-containing colloidal particles added to the lubricating oil composition to achieve a zinc / phosphorus ratio between 2.86 and 3.38 (Examples B to F), significant improvements in HFRR wear performance were observed compared to Comparative Example A. The superior DD13 scuff test results of Example I over Comparative Example H demonstrate that lubricating oil compositions including zinc-containing colloidal particles can significantly improve engine scuffing performance.

[0372] All documents described herein are incorporated herein by reference to the extent that they are not inconsistent with this document, 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, there is no intention 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 a composition, element or element group, it is to be understood that we also envision the same composition or element group with the conjunction "substantially consisting of," "consisting of," "selected from," or "is" 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: (A) 1 to 99.99 wt. %, based on the weight of the lubricating composition, of one or more base oils; (B) at least one phosphorus-containing compound selected from detergents, friction modifiers, or antiwear additives other than the colloidal particles described in (C); (C) 0.01 to 10 wt. % of colloidal particles, based on the weight of the composition, comprising: a) a core of one or more hydrocarbon-insoluble zinc-containing compounds, and b) a shell of one or more of the following: 1) one or more metal-containing surfactants, wherein the metal M comprises a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and the surfactant comprises a hydrocarbyl-substituted sulfonate salt of formula (I) or a hydrocarbyl-substituted salicylate salt of formula (II), where R A and R B are each independently a linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon group having 1 to 70 carbon atoms, wherein when n>1, all R A The sum of the number of carbon atoms in the group and all R B The total number of carbon atoms in the group is 100 or less carbon atoms, and Ar is a monocyclic or polycyclic aromatic group; n is an integer from 1 to the maximum possible number of substitutions on Ar, wherein if m=0, n=1; m is an integer from 1 to 3, x is an integer from 1 to 5; y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 8; 2) one or more metal alkanoates represented by formula (III): wherein M is a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and R C is selected from linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon groups having 6 to 70 carbon atoms, or aromatic groups or alkyl aromatic groups, wherein the aromatic group has 6 to 20 carbon atoms and the alkyl group has 1 to 20 carbon atoms; x is an integer from 1 to 5, wherein in the case of x>1, the R C The groups may be the same or different, y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 8, The lubricating oil composition has a Zn / P ratio (element mass basis as measured by ASTM D5185) of 1.1 to 5.

0.

2. The lubricating composition according to claim 1, wherein the hydrocarbon-insoluble zinc-containing compound is at least one selected from the group consisting of zinc, zinc oxide, zinc hydroxide, zinc carbonate and zinc halide or mixtures thereof. 3 . The lubricating composition according to claim 1 , wherein the colloidal particles have an average particle size measured by dynamic light scattering in the range of 5 nm to 1 μm.

4. The lubricating composition according to claim 1, wherein the metal M in formula (I), (II) or (III) is selected from at least one of sodium, potassium, lithium, magnesium, calcium, barium or a mixture thereof; or wherein the metal M is selected from at least one of gold, silver, palladium, platinum, zirconium, vanadium, molybdenum, nickel, copper, zinc, aluminum or a mixture thereof.

5. The lubricating composition according to claim 1, wherein Ar in formula (I) or formula (II) is benzene or naphthalene.

6. The lubricating composition according to claim 5, wherein the surfactant of formula (I) is a metal-containing hydrocarbyl-substituted phenyl sulfonate surfactant of formula (Ia), wherein M is selected from calcium, magnesium, barium or zinc or a combination thereof; R A are independently of one another linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon groups having 6 to 50 carbon atoms; n is an integer from 1 to 5, wherein if m=0, then n=1; m is 0 to 3; all R A The sum of the number of carbon atoms in the group is 60 or less carbon atoms; x is 2; y is 2; and optionally, p is 0.

7. The lubricating composition according to claim 5, wherein the surfactant of formula (II) is a metal-containing hydrocarbyl-substituted phenyl salicylate surfactant of formula (IIa), wherein M is selected from calcium, magnesium, barium or zinc or a combination thereof; R B are independently linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon groups having 6 to 50 carbon atoms; n is an integer from 1 to 4; all R B The sum of the number of carbon atoms in the group is 60 or less carbon atoms; x is 2, y is 2; and optionally, p is 0.

8. The lubricating composition according to claim 1, wherein M in formula (I), (II), or (III) is selected from calcium, magnesium, or zinc, or a combination thereof.

9. The lubricating composition according to claim 1, wherein R in formula (III) is a linear, cyclic or branched alkyl or alkenyl group having 6 to 48 carbon atoms.

10. The lubricating composition according to claim 9, wherein the metal alkanoate of formula (III) is one or more of zinc neodecanoate, zinc neoundecanoate, zinc neododecanoate, zinc neotridecanoate, zinc neotetradecanoate, zinc neopentadecanoate, zinc neohexadecanoate, zinc neoheptadecanoate, zinc stearate, zinc neooctadecanoate, zinc oleate, zinc neononadecanoate and zinc neoeicosanoate.

11. The lubricating composition of claim 9, wherein the metal alkanoate has a quaternary carbon atom at the 2 position connected to the carboxylate group.

12. The lubricating composition of claim 10, wherein the metal alkanoate has a quaternary carbon atom at the 2 position connected to the carboxylate group.

13. The lubricating composition of claim 1 , further comprising one or more components selected from one or more friction modifiers; one or more antioxidants; one or more pour point depressants; one or more defoaming agents; one or more viscosity modifiers; one or more dispersants; one or more inhibitors and / or rust inhibitors; and / or one or more antiwear agents different from those of component (C).

14. The lubricating composition of claim 1, wherein: (A) the base oil is present in an amount of 50 to 99 weight percent based on the weight of the lubricating composition; (B) said at least one phosphorus-containing compound selected from detergents, friction modifiers, or antiwear additives other than the colloidal particles described in (C) is present in an amount of 0.001 to 5 weight percent; C) the colloidal particles are present in an amount of 0.01 to 10 wt %, such as 0.01 to 6 wt %, based on the total weight of the lubricating composition; D) optionally, one or more friction modifiers different from those of component (B) present in an amount of 0.01 to 5 weight percent based on the total weight of the lubricating composition; E) optionally, one or more antioxidants present in an amount of 0.01 to 10 wt % based on the total weight of the lubricating composition; F) optionally, one or more pour point depressants present in an amount of 0.01 to 5 weight percent based on the total weight of the lubricating composition; G) optionally, one or more defoaming agents present in an amount of 0.001 to 5 wt % based on the total weight of the lubricating composition; H) optionally, one or more viscosity modifiers are present in an amount of 0.001 to 6 wt % based on the total weight of the lubricating composition; I) optionally, one or more dispersants are present in an amount of 0.01 to 20 wt % based on the total weight of the lubricating composition; J) optionally, one or more inhibitors and / or rust inhibitors are present in an amount of 0.01 to 5 wt. %, based on the total weight of the lubricating composition; and K) optionally, one or more antiwear agents different from those of components (B) and (C) present in an amount of 0.001 to 5 wt. %, based on the total weight of the lubricating composition; L) Optionally, one or more detergents other than those of component (B) and those in the colloidal particles described in (C) are present at 0.1 to 20 wt. %, based on the total weight of the lubricating composition.

15. The lubricating composition of claim 1, wherein the lubricating composition has an adhesive wear of 100 hours or more as measured by ASTM D8074-16.

16. The lubricating composition of claim 1, wherein the Zn / P ratio (element mass basis) in the lubricating composition is from 1.1 to 4.

9.

17. The lubricating composition according to claim 1, wherein the ligand L is selected from the group consisting of water, hydroxide, halogen, ammonia, amino, amido, alkoxide, and mixtures thereof.

18. The lubricating composition of claim 1, wherein the colloidal particles have a metal / surfactant molar ratio MR of at least 5.

19. The lubricating composition of claim 1, wherein the composition has a total base number (TBN) of 1 to 30 mgKOH / g as measured by ASTM D2896.

20. The lubricating composition of claim 1, having a zinc content of 500 ppm or greater as measured by ASTM D5185.

21. The lubricating composition of claim 1, having a phosphorus content of no greater than 2000 ppm based on the total mass of the lubricating composition as measured by ASTM D5185.

22. The lubricating composition of claim 1, wherein the lubricating composition is an internal combustion engine oil or a gas turbine oil.

23. The lubricating composition of claim 1, wherein the lubricating composition is a transmission fluid or a gear oil.

24. The lubricating composition of claim 1, comprising greater than 500 ppm of Zn and less than 500 ppm of P, wherein the lubricating composition has an adhesive wear of 100 hours or more and, optionally, a total base number of 7 mgKOH / g or more.

25. The lubricating composition of claim 1, comprising greater than 1000 ppm of Zn and less than 1000 ppm of P, wherein the lubricating composition has an adhesive wear of 100 hours or more and, optionally, a total base number of 7 mgKOH / g or more.

26. The lubricating composition of claim 1, wherein the zinc dialkyldithiophosphate is present at 2 wt% or less.

27. The lubricating composition of claim 1, wherein the lubricating composition has a relative humidity of less than 150 μm as measured by the HFRR method described herein. 3 wear scar volume.

28. A method of obtaining an adhesive wear (ASTM D 8074-16) of 100 hours or more for a lubricating composition having 500 ppm or more zinc, preferably 1000 ppm or more zinc, comprising: (i) providing the lubricating composition according to claim 1 to a crankcase of an internal combustion engine; (ii) providing a hydrocarbon fuel in an internal combustion engine; and (iii) combusting the fuel in an internal combustion engine.

29. 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 fuel in an internal combustion engine; and (iii) combusting the fuel in an internal combustion engine, wherein the fuel comprises a hydrocarbon fuel derived from petroleum and / or biological sources; a hydrogen fuel, optionally in combination with liquefied natural gas; and / or an ammonia fuel.

30. The method of claim 29, wherein the engine is a diesel engine, a gas engine, or a marine engine.

31. A concentrate composition comprising or obtained by mixing the following components: (A) 1 to less than 50 weight percent, based on the weight of the concentrate composition, of one or more base oils; (B) at least one phosphorus-containing compound selected from detergents, friction modifiers, or antiwear additives other than the colloidal particles described in (C); (C) 0.1 to 50 wt. % of colloidal particles, based on the weight of the composition, comprising: a) a core of one or more hydrocarbon-insoluble zinc-containing compounds, and b) a shell of one or more of the following: 1) one or more metal-containing surfactants, wherein the metal M comprises a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and the surfactant comprises a hydrocarbyl-substituted sulfonate salt of formula (I) or a hydrocarbyl-substituted salicylate salt of formula (II), where R A and R B are each independently a linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon group having 1 to 70 carbon atoms, wherein when n>1, all R A The sum of the number of carbon atoms in the group and all R B The sum of the number of carbon atoms in the group is 100 or less carbon atoms, and Ar is a monocyclic or polycyclic aromatic group; n is an integer from 1 to the maximum possible number of substitutions on Ar, wherein if m=0, n=1; m is an integer from 0 to 3, x is an integer from 1 to 5; y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 8; 2) one or more metal alkanoates represented by formula (III): wherein M is a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and R C is selected from linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon groups having 6 to 70 carbon atoms, or aromatic groups or alkyl aromatic groups, wherein the aromatic group has 6 to 20 carbon atoms and the alkyl group has 1 to 20 carbon atoms; x is an integer from 1 to 5, wherein in the case of x>1, the R C The groups may be the same or different, y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 8; wherein the concentrate composition has a Zn / P ratio (elemental mass basis as measured by ASTM D5185) of 1.1 to 5.

0.

32. An anti-wear additive comprising the following components or a mixture of the following components: (A) 1 to less than 50 weight percent, based on the weight of the composition, of one or more base oils; (B) at least one phosphorus-containing compound selected from detergents, friction modifiers, or antiwear additives other than the colloidal particles described in (C); (C) 0.1 to 50 wt. % of colloidal particles, based on the weight of the composition, comprising: a) a core of one or more hydrocarbon-insoluble zinc-containing compounds, and b) a shell of one or more of the following: 1) one or more metal-containing surfactants, wherein the metal M comprises a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and the surfactant comprises a hydrocarbyl-substituted aromatic sulfonate of formula (I) or a hydrocarbyl-substituted salicylate group of formula (II), where R A and R B are each independently a linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon group having 1 to 70 carbon atoms, wherein when n>1, all R A The sum of the number of carbon atoms in the group and all R B The sum of the number of carbon atoms in the group is 100 or less carbon atoms, and Ar is a monocyclic or polycyclic aromatic group; n is an integer from 1 to the maximum possible number of substitutions on Ar, wherein if m=0, n=1; m is an integer from 0 to 3, x is an integer from 1 to 5; y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 8; 2) one or more metal alkanoates represented by formula (III): wherein M is a Group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and R C is selected from linear, cyclic or branched, saturated or unsaturated, aliphatic hydrocarbon groups having 6 to 70 carbon atoms, or aromatic groups or alkyl aromatic groups, wherein the aromatic group has 6 to 20 carbon atoms and the alkyl group has 1 to 20 carbon atoms; x is an integer from 1 to 5, wherein in the case of x>1, the R C The groups may be the same or different, y is an integer from 1 to 5, L is a ligand that saturates the coordination sphere of M, and p is an integer from 0 to 8; wherein the composition has a Zn / P ratio (element mass basis as measured by ASTM D5185) of 1.1 to 5.

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33. The composition of claim 1, wherein the colloidal particles have an average particle size in the range of 20 to 200 nm as determined by dynamic light scattering; wherein M in formula (I) or (II) is selected from calcium, magnesium or a combination thereof; wherein the metal alkanoate of formula (III) is one or more of zinc neodecanoate, zinc neoundecanoate, zinc neododecanoate, zinc neotridecanoate, zinc neotetradecanoate, zinc neopentadecanoate, zinc neohexadecanoate, zinc neoheptadecanoate, zinc stearate, zinc neooctadecanoate, zinc oleate, zinc neononadecanoate and zinc neoeicosanoate, wherein the metal alkanoate has a quaternary carbon atom at the 2 position connected to the carboxylate group; wherein the Zn / P ratio (element mass basis) in the lubricating composition is from 1.5 to 4.5; and The colloidal particles have a metal / surfactant molar ratio MR of 6 to 40.

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