Lubricating oil composition

Abstract

A lubricating oil for hybrid engines comprises a major amount of oil of lubricating viscosity, a boron-containing compound in an amount providing 50 to 300 ppm of boron to the lubricating oil composition, an overbased calcium salicylate or a mixture of an overbased calcium sulfonate and an overbased calcium salicylate, each having a total base number greater than 150 mg KOH / g as measured by ASTM D-2896, present in an amount providing 800 ppm to 1800 ppm of calcium to the lubricating oil composition, zinc dithiophosphate (ZnDTP) in an amount providing 100 to 800 ppm of phosphorus to the lubricating oil composition, and a non-dispersant comb polymethacrylate (PMA) viscosity index improver (VII). The boron-containing compound comprises a boronated dispersant. The lubricating oil composition has a KV of 6 cSt to 8.5 cSt at 100°C, a KV of 25 cSt to 35 cSt at 40°C, and a VI of over 200.

Description

[Technical field]

[0001] background Modern lubricants are often formulated according to strict specifications set by the original equipment manufacturer. To meet the strict specifications, carefully selected lubricant additives are blended with a base oil of lubricating viscosity. A typical lubricant composition may contain, for example, dispersants, detergents, antioxidants, antiwear agents, rust inhibitors, corrosion inhibitors, antifoam agents, and / or friction modifiers. The particular application or use (e.g., hybrid vehicles) determines the combination of additives that are formulated into the lubricant composition. [Background technology]

[0002] Hybrid vehicles rely on two very different types of power technologies: an internal combustion engine and an electric motor. The internal combustion engine primarily drives the vehicle at higher speeds. The electric motor drives the vehicle at lower speeds and can also assist the internal combustion engine when additional power is required. In a hybrid vehicle, it is important to balance the power between the engine and the electric motor as the vehicle speed increases.

[0003] Hybrid vehicles typically feature a start-stop system that shuts off the engine when the car is stopped and pauses the engine's fuel system when the car is only powered by the motor or braking action. As a result, water and fuel buildup in the oil becomes an issue because the engine cannot adequately evaporate the water and fuel. This results in the formation of an unstable emulsion that negatively impacts engine performance and leads to corrosion of engine parts.

[0004] Because the differences between hybrid and conventional automobiles are so great, conventional engine oils are not necessarily optimized for use in hybrid vehicles, and therefore there is a need for lubricant compositions specifically designed for hybrid vehicles. Summary of the Invention

[0005] Disclosure Summary In one aspect, the present disclosure provides a lubricating oil composition for use in a hybrid engine, the lubricating oil composition comprising a major amount of oil of lubricating viscosity, a boron-containing compound present in an amount to provide the lubricating oil composition with from 40 to 400 ppm of boron, and a calcium-containing compound present in an amount to provide the lubricating oil composition with from 800 ppm to 1800 ppm of calcium. and a non-dispersant comb polymethacrylate (PMA) viscosity index improver (VII). The lubricating oil composition comprises an overbased calcium salicylate or a mixture of overbased calcium sulfonate and overbased calcium salicylate, each having a total base number of greater than 150 mg KOH / g for a detergent concentrate as measured by the method of D-2896; zinc dithiophosphate (ZnDTP) in an amount providing the lubricating oil composition with 100 to 800 ppm phosphorus; and a non-dispersant comb polymethacrylate (PMA) viscosity index improver (VII). The boron-containing compound comprises a boronated dispersant, the lubricating oil composition has a kinematic viscosity (KV) at 100°C of 6 cSt to 8.5 cSt, a KV at 40°C of 25 cSt to 35 cSt, and a viscosity index (VI) of greater than 200.

[0006] In another aspect, the present invention is a method of lubricating a hybrid engine comprising administering to the hybrid engine a lubricating oil, the lubricating oil comprising a major amount of oil of lubricating viscosity, a boron-containing compound present in an amount to provide the lubricating oil composition with from 40 to 400 ppm of boron, and an ASTM D 111644-1 amount of calcium present in an amount to provide the lubricating oil composition with from 800 ppm to 1800 ppm of calcium. and a non-dispersant comb polymethacrylate (PMA) viscosity index improver (VII). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] Detailed Description While the present disclosure is susceptible to various modifications and alternative forms, specific embodiments thereof are described in detail herein. It should be understood, however, that the description of specific embodiments herein is not intended to limit the disclosure to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the present disclosure as defined by the appended claims.

[0008] To facilitate understanding of the subject matter disclosed herein, certain terms, abbreviations, or other shorthand notations used herein are defined below. Any term, abbreviation, or shorthand notation not defined will be understood to have its ordinary meaning as used by those of ordinary skill in the art at the time of filing of this application.

[0009] As used herein, the following terms have the following meanings unless otherwise specified: As used herein, the following words and expressions, if used, have the meanings indicated below.

[0010] By "major amount" it is meant greater than 50% by weight of the composition.

[0011] "Minor amount" means less than 50% by weight of the composition, expressed relative to the listed additive and relative to the total mass of all additives present in the composition, calculated as the active ingredient of the additive(s).

[0012] "Active ingredient" or "actives" or "oil-free" refers to additive materials that are not diluents or solvents.

[0013] All percentages reported are by weight on an active ingredient basis (ie, without regard to carrier or diluent oil) unless otherwise noted.

[0014] The abbreviation "ppm" means parts per million by weight based on the total weight of the lubricating oil composition.

[0015] High temperature high shear (HTHS) viscosity at 150° C. was measured according to ASTM D4683.

[0016] 100℃(KV 100 ) and kinematic viscosity at 40°C (KV 40 ) was measured according to ASTM D445.

[0017] Viscosity Index (VI) was measured according to ASTM D2270.

[0018] The term "metal" refers to an alkali metal, an alkaline earth metal, or a mixture thereof.

[0019] Throughout this specification and the claims, the terms oil-soluble or oil-dispersible are used. Oil-soluble or oil-dispersible means that the amount required to provide the desired level of activity or performance can be added by dissolving, dispersing or suspending in oil of lubricating viscosity. Typically, this means that at least about 0.001% by weight of the material can be added to the lubricating oil composition. For further discussion of oil-solubility and oil-dispersibility, particularly the term "stably dispersible", see U.S. Pat. No. 4,320,019, which is expressly incorporated herein by reference for its relevant teachings in this regard.

[0020] As used herein, the term "sulfated ash" refers to non-combustible residues resulting from detergents and metal additives in lubricating oils. Sulfated ash can be measured using ASTM test D874.

[0021] As used herein, the term "Total Base Number" or "TBN" refers to the amount of base equivalent to milligrams of KOH in one gram of sample. Thus, a higher TBN value reflects a more alkaline product and therefore higher alkalinity. TBN was measured using the ASTM D2896 test. TBN values ​​are based on detergent concentrates.

[0022] The boron, calcium, magnesium, molybdenum, phosphorus, sulfur, and zinc contents were determined according to ASTM D5185.

[0023] Nitrogen content was measured according to ASTM D4629.

[0024] All ASTM standards referred to herein are the most current editions as of the filing date of this application.

[0025] Unless otherwise specified, all percentages are by weight.

[0026] The present invention provides a lubricant optimized for hybrid engines. The lubricant includes (a) an oil of lubricating viscosity, (b) a boron-containing compound including a boronated dispersant, (c) one or more overbased calcium detergents, (d) optionally one or more magnesium-containing detergents, (e) a zinc dithiophosphate, and (f) a non-dispersant comb polymethacrylate (PMA). The KV100°C of the lubricant composition is between 6 cSt and 8.5 cSt, the KV40°C of the lubricant composition is between 25 cSt and 35 cSt, and the VI of the lubricant composition is greater than 200.

[0027] Oil of lubricating viscosity Oils of lubricating viscosity (sometimes referred to as "base stocks" or "base oils") are the primary liquid constituents of lubricants into which additives and possibly other oils are blended, for example, to provide the final lubricant (i.e., lubricant composition). Base oils are useful for making concentrates and for making lubricant compositions therefrom, and may be selected from natural and synthetic lubricating oils and combinations thereof.

[0028] Natural oils include animal and vegetable oils, liquid petroleum oils, and hydrorefined and solvent-treated mineral lubricating oils of the paraffinic, naphthenic, and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.

[0029] Synthetic lubricating oils include hydrocarbon oils such as polymerized and copolymerized olefins (e.g., polybutylene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutylene, poly(1-hexene), poly(1-octene), poly(1-decene), 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. Polymerized olefins can also be derived from biological sources, such as hydrocarbon terpenes, such as myrcene, ocimene, farnesene, etc., which can be copolymerized with other olefins and further isomerized if necessary.

[0030] Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., malonic acid, alkyl malonic acids, alkenyl malonic acids, succinic acid, alkyl and alkenyl succinic acids, maleic acid, fumaric acid, azelaic acid, suberic acid, sebacic acid, adipic acid, linoleic acid dimer, phthalic acid, and the like) with various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, and the like). 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, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid.

[0031] Esters useful as synthetic oils include C 5 ~C 12 Also included are esters made from monocarboxylic acids and polyols, and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.

[0032] Biologically derived esters are also useful as synthetic oils.

[0033] The base oil may be derived from Fischer-Tropsch synthesized hydrocarbons. Fischer-Tropsch synthesized hydrocarbons are produced using a Fischer-Tropsch catalyst. 2and CO. These hydrocarbons typically require further processing to make them useful as base oils. For example, the hydrocarbons can be hydroisomerized; hydrocracked and hydroisomerized; dewaxed, or hydroisomerized and dewaxed, using processes well known to those skilled in the art.

[0034] The base oil may be a renewable or bio-based engine oil. Examples of such engine oils are disclosed in WO2016061050 and US20190338211, which are incorporated herein by reference. According to some embodiments, the renewable or bio-based base oil includes bio-based hydrocarbons, such as isoparaffinic hydrocarbons derived from hydrocarbon terpenes, such as myrcene, ocimene, and farnesene. In some embodiments, the bio-based hydrocarbons are produced from fatty acids or fatty acid esters.

[0035] Unrefined oils, refined oils and re-refined oils can be used in the lubricating oil composition of the present invention. Unrefined oils are those obtained directly from natural or synthetic sources without further purification treatment. For example, shale oil obtained directly from retorting operation, petroleum oil obtained directly from distillation, or ester oil obtained directly from esterification process and used without further treatment are 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 known to those skilled in the art, such as distillation, solvent extraction, acid or base extraction, filtration, and percolation.

[0036] Re-refined oils are obtained by processes similar to those used to obtain refined oils, but applied to refined oils already in use. Such re-refined oils are also known as reclaimed or reprocessed oils and are often further processed by techniques for the approval of used additives and oil breakdown products.

[0037] Thus, the base oils that can be used to prepare the lubricating oil compositions of the present invention can be selected from any of the base oils in Groups I to V specified in the American Petroleum Institute (API) Base Oil Compatibility Guidelines, API Publication 1509. Such base oil groups are summarized in Table 1 below. [Table 1]

[0038] Suitable base oils for use herein include any of the various corresponding API Group II, Group III, Group IV, and Group V oils, and combinations thereof, preferably Group III through Group V oils due to their superior volatility, stability, viscometric, and cleanliness characteristics.

[0039] The oil of lubricating viscosity (also referred to as base oil) used in the lubricating oil compositions of the present disclosure is typically present in a major amount (e.g., greater than 50 wt%, preferably greater than about 70 wt%, more preferably about 80 to about 99.5 wt%, and most preferably about 85 to about 98 wt%, based on the total weight of the composition). As used herein, the expression "base oil" should be understood to mean a base stock or blend of base stocks that is a lubricating oil component produced by a single manufacturer to the same specifications (irrespective of source or location of the manufacturer), meeting the same manufacturer's specifications, and identified by a unique formulation, product identification number, or both. As used herein, a base oil may be any oil of lubricating viscosity, now known or later discovered, used in formulating lubricating oil compositions.

[0040] As one skilled in the art will readily recognize, the viscosity of a base oil is determined by its intended use. Thus, the viscosity of a base oil as used herein is typically in the range of about 2 to about 2000 centistokes (cSt) at 100°C (C). In general, individual base oils used as engine oils have a kinematic viscosity in the range of about 2 cSt to about 30 cSt at 100°C, preferably about 3 cSt to about 16 cSt, and most preferably about 4 cSt to about 12 cSt.

[0041] The lubricating oil composition may be a multigrade oil having a viscosity grade of SAE 0W-XX, where XX is any of 12, 16, and 20. According to a preferred embodiment, the lubricating oil composition has a viscosity grade of SAE 0W-20.

[0042] The lubricating oil composition has a viscosity index of at least 200 (e.g., 200-400 or 200-300). If the viscosity index of the lubricating oil composition is less than 135, it may be difficult to improve fuel economy while maintaining a desired HTHS viscosity at 150°C. If the viscosity index of the lubricating oil composition is more than 400, the volatility may decrease, and problems may occur due to insufficient solubility of additives and insufficient matching with sealing materials. According to another embodiment, the lubricating oil composition has a viscosity index of 200-290, 200-280, 200-270, 200-260, 200-250, or 200-240. In another embodiment, the lubricating oil composition has a viscosity index of 210-290, 210-280, 210-270, 210-260, 210-250, or 210-240. In other embodiments, the lubricating oil composition has a viscosity index of 220-290, 220-280, 220-270, 220-260, 220-250, or 220-240.

[0043] The lubricating oil composition has a kinematic viscosity at 100°C in the range of 6.0 cSt to 8.0 cSt (for example, 6.0 mm 2 / s~7.9mm 2 / s, 6.0mm 2 / s~7.8mm 2 / s, 6.0 cSt to 7.7 cSt, 6.0 cSt to 7.6 cSt, 6.0 cSt to 7.5 cSt, 6.0 cSt to 7.4 cSt, 6.0 cSt to 7.3 cSt, 6.0 cSt to 7.2 cSt, 6.0 cSt to 7.1 cSt, 6.0 cSt to 7.0 cSt). In other embodiments, the lubricating oil composition has a kinematic viscosity at 100° C. in the range of 6.0 cSt to 8.0 cSt (e.g., 7.0 cSt to 8.0 cSt, 7.1 cSt to 8.0 cSt, 7.2 cSt to 8.0 cSt, 7.3 cSt to 8.0 cSt, 7.4 cSt to 8.0 cSt, and 7.5 cSt to 8.0 cSt). In other embodiments, the lubricating oil composition has a kinematic viscosity at 100° C. in the range of 6.0 cSt to 8.0 cSt (e.g., 6.1 cSt to 8.0 cSt, 6.2 cSt to 8.0 cSt, 6.3 cSt to 8.0 cSt, 6.4 cSt to 8.0 cSt, 6.5 cSt to 8.0 cSt, 6.6 cSt to 8.0 cSt, 6.7 cSt to 8.0 cSt, 6.6 cSt to 8.0 cSt, and 6.9 cSt to 8.0 cSt.

[0044] The lubricating oil composition has a kinematic viscosity at 40°C in the range of 25 cSt to 35 cSt (e.g., 25 cSt to 34 cSt, 25 cSt to 33 cSt, 25 cSt to 32 cSt, 25 cSt to 31 cSt, and 25 cSt to 30 cSt. In other embodiments, the lubricating oil composition has a kinematic viscosity at 40°C in the range of 25 cSt to 35 cSt (e.g., 26 cSt to 35 cSt, 27 cSt to 35 cSt, 28 cSt to 35 cSt, 29 cSt to 35 cSt, and 30 cSt to 35 cSt.

[0045] Typically, the level of sulfur in the lubricating oil composition is about 0.7 wt% or less, based on the total weight of the lubricating oil composition. For example, the lubricating oil composition can have a sulfur level of about 0.01 wt% to 0.5 wt%, 0.01 wt% to 0.4 wt%, 0.01 wt% to 0.3 wt%, 0.01 wt% to 0.2 wt%, or 0.01 wt% to 0.10 wt%. In one embodiment, the level of sulfur in the lubricating oil composition is about 0.60 wt% or less, about 0.50 wt% or less, about 0.40 wt% or less, about 0.30 wt% or less, about 0.20 wt% or less, or about 0.10 wt% or less, based on the total weight of the lubricating oil composition.

[0046] In one embodiment, the level of phosphorus in the lubricating oil composition is about 0.08 wt.% or less, e.g., from about 0.01 wt.% to about 0.08 wt.% phosphorus, based on the total weight of the lubricating oil composition. In one embodiment, the level of phosphorus in the lubricating oil composition is about 0.07 wt.% or less, e.g., from about 0.01 wt.% to about 0.07 wt.% phosphorus, based on the total weight of the lubricating oil composition. In one embodiment, the level of phosphorus in the lubricating oil composition is about 0.05 wt.% or less, e.g., from about 0.01 wt.% to about 0.05 wt.% phosphorus, based on the total weight of the lubricating oil composition.

[0047] In one embodiment, the lubricating oil composition produces a sulfated ash level of about 1.00 wt% or less as measured by ASTM D874, e.g., about 0.10 wt% to about 1.00 wt% sulfated ash as measured by ASTM D874. In one embodiment, the lubricating oil composition produces a sulfated ash level of about 0.80 wt% or less as measured by ASTM D874, e.g., about 0.10 wt% to about 0.80 wt% sulfated ash as measured by ASTM D874. In one embodiment, the lubricating oil composition produces a sulfated ash level of about 0.60 wt% or less as measured by ASTM D874, e.g., about 0.10 wt% to about 0.60 wt% sulfated ash as measured by ASTM D874.

[0048] Suitably, the lubricating oil composition may have a total base number (TBN) of 4 to 15 mgKOH / g (e.g., 5 mgKOH / g to 12 mgKOH / g, 6 mgKOH / g to 12 mgKOH / g, or 8 mgKOH / g to 12 mgKOH / g).

[0049] The lubricating oil composition can also contain conventional lubricant additives to provide auxiliary functions, resulting in a finished lubricating oil composition in which these additives are dispersed or dissolved.For example, the lubricating oil composition can be blended with antioxidants, ashless dispersants, antiwear agents, detergents such as metal detergents, rust inhibitors, demulsifiers, friction modifiers, metal deactivators, pour point inhibitors, viscosity modifiers, antifoam agents, cosolvents, corrosion inhibitors, dyes, extreme pressure agents, and the like, and mixtures thereof.Various additives are known and commercially available.These additives, or their analogous compounds, can be used to prepare the lubricating oil composition of the present invention by conventional blending procedures.

[0050] Each of the foregoing additives, when used, is used in a functionally effective amount to impart the desired properties to the lubricant. Thus, for example, if the additive is an ashless dispersant, a functionally effective amount of the ashless dispersant is an amount sufficient to impart the desired dispersant characteristics to the lubricant. In general, the concentration of each of these additives when used may range from about 0.001 to about 20% by weight, for example, from about 0.01 to about 10% by weight, unless otherwise specified.

[0051] Boron-Containing Compounds The lubricating oil composition of the present invention contains a boronated dispersant in an amount to provide 40 to 400 ppm of boron, for example, 50 to 290 ppm, 50 to 280 ppm, 50 to 270 ppm, 50 to 260 ppm, 50 to 250 ppm, 50 to 240 ppm, 50 to 230 ppm, 50 to 200 ppm, 50 to 190 ppm, 50 to 180 ppm, 50 to 170 ppm, 50 to 160 ppm, or 50 to 150 ppm (by weight) based on the weight of the lubricating oil composition.

[0052] Examples of borated dispersants include borated ashless dispersants such as borated polyalkenyl succinic anhydrides; borated non-nitrogen containing derivatives of polyalkylene succinic anhydrides; borated basic nitrogen compounds selected from the group consisting of succinimides, carboxylic acid amides, hydrocarbyl monoamines, hydrocarbyl polyamines, Mannich bases, phosphonoamides, thiophosphonamides and phosphoramides, thiazoles (e.g., 2,5-dimercapto-1,3,4-thiadiazole, mercaptobenzothiazole and derivatives thereof), triazoles (e.g., alkyltriazoles and benzotriazoles), copolymers (e.g., products prepared by copolymerization of long chain alkyl acrylates or methacrylates with monomers of the above functionality); and the like and combinations thereof. Preferred boronated dispersants are succinimide derivatives of boron, such as boronated polyisobutenyl succinimide.

[0053] Examples of borated ashless dispersants are the borated ashless hydrocarbyl succinimide dispersants prepared by reacting a hydrocarbyl succinic acid or anhydride with an amine. Preferred hydrocarbyl succinic acids or anhydrides are those in which the hydrocarbyl group is 3 or C 4Polymers of monoolefins, particularly polyisobutylenes, in which the polyisobutenyl group has a number average molecular weight (Mn) of 700 to 5,000, more preferably 900 to 2,500. Such dispersants generally have at least one, preferably 1 to 2, more preferably 1.1 to 1.8 succinic acid groups for each polyisobutenyl group. In one embodiment, the oil-soluble or oil-dispersible boronated polyisobutylene succinimide dispersant is derived from a polyisobutylene group having a number average molecular weight of about 550 to about 5000. In one embodiment, the oil-soluble or oil-dispersible boronated polyisobutylene succinimide dispersant is derived from a polyisobutylene group having a number average molecular weight of about 550 to about 4000. In one embodiment, the oil-soluble or oil-dispersible boronated polyisobutylene succinimide dispersant is derived from a polyisobutylene group having a number average molecular weight of about 550 to about 3000. In one embodiment, the oil-soluble or oil-dispersible borated polyisobutylene succinimide dispersant is derived from a polyisobutylene group having a number average molecular weight of greater than 550 to about 2300. In one embodiment, the oil-soluble or oil-dispersible borated polyisobutylene succinimide dispersant is derived from a polyisobutylene group having a number average molecular weight of from about 950 to about 2300. In one embodiment, the oil-soluble or oil-dispersible borated polyisobutylene succinimide dispersant is derived from a polyisobutylene group having a number average molecular weight of from about 950 to about 1700. In one embodiment, the oil-soluble or oil-dispersible borated polyisobutylene succinimide dispersant is derived from a polyisobutylene group having a number average molecular weight of about 2300. In one embodiment, the oil-soluble or oil-dispersible borated polyisobutylene succinimide dispersant is derived from a polyisobutylene group having a number average molecular weight of about 1700. In one embodiment the oil-soluble or oil-dispersible boronated polyisobutylene succinimide dispersant is derived from a polyisobutylene group having a number average molecular weight of about 1000.

[0054] Preferred amines for reaction to form succinimides are polyamines having from 2 to 60 carbon atoms and from 2 to 12 nitrogen atoms per molecule. Particularly preferred amines include polyalkylene amines represented by the formula: NH 2 (CH 2 ) n -(NH(CH 2 ) n ) m -NH 2 (wherein n is 2-3 and m is 0-10.) Illustrative examples include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, and the like, as well as commercially available mixtures of such polyamines. Amines containing other groups such as hydroxy, alkoxy, amido, nitride and imidazoline groups, as well as polyoxyalkylene polyamines, can also be used. The amine is reacted with the alkenyl succinic acid or anhydride, typically by heating the reactants to 100° C.-250° C., preferably 125° C.-175° C., for 1-10 hours, preferably 2-6 hours, such that the molar ratio of alkenyl succinic acid or anhydride to polyamine is about 1:1-10:1, preferably 1:1-3:1, a conventional ratio, preferably about 1:1.

[0055] Boronation of alkenyl succinimide dispersants is also well known in the art, as disclosed in U.S. Patents 3,087,936 and 3,254,025. The succinimides can be treated with a boron compound selected from the group consisting of boron, boron oxide, boron halides, boric acid and esters thereof in an amount to provide, for example, from 0.1 atomic ratio of boron to the respective atomic ratio of nitrogen in the dispersant, to an atomic ratio of 10 of boron.

[0056] The boronated product generally contains 0.1-2.0 wt. % boron, preferably 0.2-0.8 wt. % boron, based on the total weight of the boronated dispersant. The boron is believed to exist as a dehydrated boric acid polymer bonded to the metaborate salt of the imide. The boronation reaction is readily accomplished by adding 1-3 wt. % (based on the weight of the dispersant) of said boron compound.

[0057] Detergent The lubricating oil of the present invention includes one or more detergents. The one or more detergents may be an overbased calcium salicylate or a mixture of overbased calcium sulfonate and overbased calcium salicylate. The detergents individually have a TBN of greater than 150 mg KOH / g (as measured by ASTM D-2896). The detergent(s) are present in an amount to provide the lubricating oil composition with about 800 ppm to about 1800 ppm (e.g., 800-1700, 900-1600, 1000-1500, 1100-1400, 1200-1300) of calcium. Optionally, the one or more detergents may include a magnesium-containing detergent in an amount to provide the lubricating oil composition with 100-600 ppm of magnesium. The detergents may be prepared by any suitable method. In one embodiment, the magnesium detergent is an overbased magnesium sulfonate detergent.

[0058] Sulfonates can be prepared from sulfonic acids, which are typically obtained by sulfonation of alkyl-substituted aromatic hydrocarbons, such as those obtained from petroleum fractionation, or by alkylation of aromatic hydrocarbons. Examples include those obtained by alkylation of benzene, toluene, xylene, naphthalene, diphenyl, or their halogen derivatives. The 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 80 or more carbon atoms (e.g., from about 16 to 60 carbon atoms) per alkyl-substituted aromatic moiety.

[0059] Salicylates can be prepared by reacting a basic metal compound with at least one carboxylic acid and removing water from the reaction product. Detergents prepared from salicylic acid are a class of detergents prepared from carboxylic acids. Useful salicylates include long chain alkyl salicylates. One useful family of compositions has the following structure: [ka] [Wherein, R″ is C 1 ~C 30 (For example, C 13 ~C 30 ) alkyl group, n is an integer from 1 to 4, and M is an alkaline earth metal (eg, Ca or Mg).

[0060] Hydrocarbyl-substituted salicylic acids can be prepared from phenols by the Kolbe reaction (see U.S. Pat. No. 3,595,791). Metal salts of hydrocarbyl-substituted salicylic acids can be prepared by metathesis of the metal salt in a polar solvent, such as water or an alcohol.

[0061] The term "overbased" refers to metal salts such as sulfonates, salicylates, and phenates, in which the amount of metal present exceeds the stoichiometric amount. Such salts may have a conversion level of more than 100% (i.e., contain more than 100% of the theoretical amount of metal required to convert the acid to its "normal" or "neutral" salt). The expression "metal ratio", often abbreviated as MR, is used to indicate the ratio of the total chemical equivalents of metal in an overbased salt to the chemical equivalents of metal in a neutral salt, according to known chemical reactivity and stoichiometry. In normal or neutral salts, the metal ratio is 1, whereas in overbased salts, the MR is greater than 1. These are commonly called overbased, hyperbased, or superbased salts, and may be salts of organic sulfur acids, salicylates, or phenols.

[0062] The overbased detergent has a TBN of 150 mg KOH / gram or more, about 250 mg KOH / gram or more, or about 300 mg KOH / gram or more, or about 350 mg KOH / gram or more, or about 375 mg KOH / gram or more, or about 400 mg KOH / gram or more of TBN of the detergent concentrate.

[0063] The overbased detergent may have a metal to substrate ratio of 1.1:1, or 2:1, or 4:1, or 5:1, or 7:1, or 10:1.

[0064] Overbased sulfonates and / or salicylates The lubricating oil composition comprises an overbased calcium salicylate or a mixture of an overbased calcium sulfonate and an overbased calcium salicylate, each having a total base number of greater than 150 mg KOH / g as measured by the method of ASTM D-2896, present in an amount to provide the lubricating oil composition with from 800 ppm to 1700 ppm of calcium. In other embodiments, the overbased calcium salicylate or a mixture of an overbased calcium sulfonate and an overbased calcium salicylate, each having a total base number of greater than 150 mg KOH / g as measured by the method of ASTM D-2896, present in an amount to provide the lubricating oil composition with from 800 ppm to 1800 ppm of calcium, e.g., from 800 to 1250 ppm of calcium, e.g., from 850 to 1250 ppm of calcium. In other embodiments, the overbased calcium salicylate or mixture of overbased calcium sulfonate and overbased calcium salicylate, individually having a total base number of greater than 150 mg KOH / g as measured by the method of ASTM D-2896, are present in an amount to provide the lubricating oil composition with from 800 ppm to 1800 ppm of calcium, from 900 to 1700 ppm of calcium, or from 950 to 1700 ppm of calcium.

[0065] Magnesium-containing detergents The one or more magnesium-containing detergents may be overbased magnesium-containing detergents having a total base number of greater than 150 mgKOH / g, as measured by the method of ASTM D-2896. The one or more overbased magnesium-containing detergents may be overbased magnesium sulfonate detergents, overbased magnesium phenate detergents, overbased magnesium salicylate detergents, or mixtures thereof. In certain embodiments, the magnesium detergents may have a TBN of about 250 mgKOH / gram or more, or about 300 mgKOH / gram or more, or about 350 mgKOH / gram or more, or about 375 mgKOH / gram or more, or about 400 mgKOH / gram or more, based on the detergent concentrate.

[0066] Preferred magnesium-containing detergents include magnesium sulfonates, magnesium phenates, and magnesium salicylates, especially magnesium sulfonate.

[0067] The magnesium-containing detergent can be used in an amount that provides at least 100 ppm (e.g., 100-600 ppm, 100-500 ppm, 100-400 ppm, 150-600 ppm, 150-550 ppm, 150-500 ppm, 200-600 ppm, 200-550 ppm, 200-500 ppm, 250-600 ppm, 250-550 ppm, 250-500 ppm (by weight) of magnesium to the lubricating oil composition.

[0068] Zinc dithiophosphate (ZnDTP) Antiwear agents reduce wear on metal parts. Suitable antiwear agents include metal dihydrocarbyl dithiophosphates, such as zinc dihydrocarbyl dithiophosphate (ZnDTP) of the formula: Zn[SP(=S)(OR 1 )(OR 2 )] 2 [In the formula, R 1 and R 2may be the same or different hydrocarbyl radicals having 1 to 18 (e.g., 2 to 12) carbon atoms, including radicals such as alkyl, alkenyl, aryl, arylalkyl, alkaryl, and alicyclic radicals. 1 and R 2 Particularly preferred as groups are alkyl groups having 2 to 8 carbon atoms (e.g., the alkyl radical can be ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 2-ethylhexyl). To obtain oil solubility, the total number of carbon atoms (i.e., R 1 +R 2 ) is at least 5. Thus, the zinc dihydrocarbyl dithiophosphate may comprise a zinc dialkyl dithiophosphate. The zinc dialkyl dithiophosphate may be a primary or secondary zinc dialkyl dithiophosphate, or mixtures thereof. The ZnDTP is present in an amount to provide the lubricating oil composition with 100 to 800 ppm phosphorus.

[0069] Molybdenum-Containing Compounds The lubricating oil composition of the present invention may contain an amount of a molybdenum-containing compound that provides the lubricating oil composition with about 50 to about 1000, e.g., about 50 to about 900 ppm, about 50 to about 800 ppm, about 50 to about 750 ppm, about 50 to about 500 ppm, about 50 to about 450 ppm, about 50 to about 400 ppm, about 50 to about 350, or about 50 to about 300 ppm of molybdenum.

[0070] The oil-soluble molybdenum-containing compound may have the functional performance of an antiwear agent, an antioxidant, a friction modifier, or mixtures thereof. The oil-soluble molybdenum-containing compound may include molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, molybdenum dithiophosphinate, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, trinuclear organomolybdenum compounds, molybdenum esters, molybdenum amides, and / or mixtures thereof. The molybdenum sulfides may include molybdenum disulfide. The molybdenum disulfide may be in the form of a stable dispersion. In one embodiment, the oil-soluble molybdenum compound may be selected from the group consisting of molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound may be molybdenum dithiocarbamate.

[0071] Molybdenum dithiocarbamate (MoDTC) is an organo-molybdenum compound represented by the following structure. [ka] [In the formula, R 1 , R 2 , R 3 and R 4 are, independently of each other, straight or branched alkyl groups having 4 to 18 carbon atoms (e.g., 8 to 13 carbon atoms).

[0072] Molybdenum dithiophosphate (MoDTP) is an organo-molybdenum compound represented by the following structure. [ka] [In the formula, R 5 , R 6 , R 7 and R 8are, independently of each other, straight or branched alkyl groups having 4 to 18 carbon atoms (e.g., 8 to 13 carbon atoms).

[0073] Suitable examples of molybdenum-containing compounds that may be used include commercially available materials sold under the trade names Molyvan 822®, Molyvan® A, Molyvan 2000®, and Molyvan 855® by RT Vanderbilt Co., Ltd., Sakura-Lube® S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710 by Adeka Corporation, and mixtures thereof. Suitable molybdenum components are described in U.S. Pat. Nos. 5,650,381, Re. 37,363E1, Re. 38,929E1, and Re. 40,595E1, the entireties of which are incorporated herein by reference.

[0074] Additionally, the molybdenum-containing compound may be an acidic molybdenum compound, such as molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, such as sodium hydrogen molybdate, MoOCl 4 , MoO 2 Br 2 , Mo 2 O 3 Cl 6 , molybdenum trioxide or similar acidic molybdenum compounds. Alternatively, the molybdenum may be provided in the composition by molybdenum / sulfur complexes of basic nitrogen compounds, as described, for example, in U.S. Patent Nos. 4,263,152, 4,285,822, 4,283,295, 4,272,387, 4,265,773, 4,261,843, 4,259,195 and 4,259,194, and U.S. Patent Application Publication No. 2002 / 0038525, the entire contents of which are incorporated herein by reference.

[0075] Another suitable class of molybdenum-containing compounds is represented by the formula: Mo 3 S k L n Q z and mixtures thereof, such as those of the formula: wherein S represents sulfur, L represents an independently selected ligand having an organic group having a sufficient number of carbon atoms to render the compound soluble or dispersible in oil, n is 1 to 4, k varies from 4 to 7, Q is selected from the group of neutral electron donor compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5, including non-stoichiometric values. There may be at least 21 carbon atoms in total in the organic groups of all the ligands, e.g., at least 25, at least 30, or at least 35 carbon atoms. Additional suitable molybdenum-containing compounds are described in U.S. Pat. No. 6,723,685, the entire contents of which are incorporated herein by reference.

[0076] In one embodiment, the molybdenum amine is a molybdenum-succinimide complex. Suitable molybdenum-succinimide complexes are described, for example, in U.S. Pat. No. 8,076,275. These complexes are prepared by a process comprising reacting an acidic molybdenum compound with an alkyl or alkenyl succinimide of a polyamine or mixtures thereof of the following structure: [ka] [Wherein, R is C 24 ~C 350 (For example, C 70 ~C 128 ), R' is a straight or branched alkylene group having 2 to 3 carbon atoms, x is 1 to 11, and y is 1 to 10.

[0077] The molybdenum-containing compound used to prepare the molybdenum-succinimide complex is an acidic molybdenum compound or a salt of an acidic molybdenum compound. "Acidic" means that the molybdenum compound reacts with basic nitrogen compounds as measured by ASTM D664 or D2896. Generally, acidic molybdenum compounds are hexavalent. Representative examples of suitable molybdenum compounds include molybdenum trioxide, molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, such as hydrogen salts (e.g., sodium hydrogen molybdate), MoOCl 4 , MoO 2 Br 2 , Mo 2 O 3 Cl 6 etc.

[0078] Succinimides that can be used to prepare molybdenum-succinimide complexes are disclosed in numerous references and are well known in the art. Certain basic classes of succinimides and related materials encompassed by the term "succinimide" are taught in U.S. Pat. Nos. 3,172,892, 3,219,666, and 3,272,746. The term "succinimide" is understood in the art to include many of the amide, imide, and amidine species that can be formed. However, the predominant product is succinimide, and the term has generally been accepted to mean the reaction product of an alkyl or alkenyl substituted succinic acid or anhydride with a nitrogen-containing compound. A preferred succinimide is one prepared by reacting polyisobutenyl succinic anhydride having about 70 to 128 carbon atoms with a polyalkylene polyamine prepared from triethylenetetramine, tetraethylenepentamine, and mixtures thereof.

[0079] The molybdenum-succinimide complex can be post-treated with a sulfur source at a suitable pressure and at a temperature not exceeding 120° C. to obtain a molybdenum sulfide-succinimide complex. The sulfurization step can be carried out for about 0.5 to 5 hours (e.g., 0.5 to 2 hours). Suitable sulfur sources include elemental sulfur, hydrogen sulfide, phosphorus pentasulfide, sulfur compounds of the formula R 2 S x wherein R is a hydrocarbyl (e.g., C 1 ~C 10 alkyl), where x is at least 3; 1 ~C 10 These include mercaptans, inorganic sulfides and polysulfides, thioacetamides, and thioureas.

[0080] Viscosity modifier Viscosity modifiers (VM), also called viscosity index improvers (VII), are present in lubricating oil compositions to impart high and low temperature operability. Viscosity modifiers increase the viscosity of the lubricating oil composition at high temperatures, thereby increasing film thickness, but have limited effect on viscosity at low temperatures.

[0081] Viscosity modifiers may be used to provide their sole function, or they may be multifunctional, with multifunctional viscosity modifiers also functioning as dispersants.

[0082] Examples of suitable viscosity modifiers are polymers and copolymers of methacrylates, butadienes, olefins, or alkylated styrenes. 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).

[0083] The viscosity modifier may be present in the lubricating oil composition in a total amount of 0.001 wt.% to 10 wt.%, based on the total weight of the lubricating oil composition. In other embodiments, the viscosity modifier may be present in a total amount of 0.01 wt.% to 8 wt.%, 0.1 wt.% to 5 wt.%, 0.4 wt.% to 4 wt.%, 0.6 wt.% to 3 wt.%, 0.7 wt.% to 2 wt.%, 1 wt.% to 1.5 wt.%, or 1.05 wt.% to 1.44 wt.%, based on the total weight of the lubricating oil composition. In some exemplary embodiments, the viscosity modifier may be present in a total amount of 1.0 wt.% to 1.2 wt.%, 1.3 wt.% to 1.4 wt.%, or 1.4 wt.% to 1.5 wt.%, based on the total weight of the lubricating oil composition.

[0084] A particularly useful viscosity modifier is non-dispersible comb polymethacrylate (comb PMA).

[0085] Non-dispersible comb-type polymethacrylate Non-dispersible comb polymethacrylate (comb PMA) is a comb polymer that can be used as a viscosity modifier or viscosity index improver.

[0086] In one embodiment, the non-dispersed comb PMA has a weight average molecular weight (Mw) of 300,000 g / mol to 600,000 g / mol, 350,000 g / mol to 550,000 g / mol, 375,000 g / mol to 500,000 g / mol, or 390,000 g / mol to 460,000 g / mol.

[0087] In one embodiment, the non-dispersed comb PMA has a number average molecular weight (Mn) of 35,000 g / mol to 105,000 g / mol, 45,000 g / mol to 95,000 g / mol, 55,000 g / mol to 85,000 g / mol, or 65,000 g / mol to 75,000 g / mol. In another embodiment, the non-dispersed comb PMA has a number average molecular weight (Mn) of 150,000 g / mol to 250,000 g / mol or 200,000 g / mol to 215,000 g / mol.

[0088] In one embodiment, the non-dispersed comb PMA has a Shear Stability Index (SSI) of 0.1-1.0, 0.2-0.9, or 0.3-0.8.

[0089] The non-dispersant comb PMA of the lubricating oil composition may be described as described in US2017 / 0298287A1 and JP2019014802, the disclosures of which are incorporated herein by reference. The non-dispersant comb PMA may be provided by Viscoplex® Viscosity Index Improver 3-201 and / or 3-162, sold by Evonik.

[0090] According to one embodiment, the non-dispersible comb PMA is provided by a compound called Viscoplex® 3-201, which contains comb PMA as the main resin component. This non-dispersible comb PMA has a weight average molecular weight (Mw) of 420,000 g / mol, a number average molecular weight (Mn) of 70,946 g / mol, and an Mw / Mn of 5.92. This compound has at least a unit derived from a macromonomer with an Mn of 500 or more. The non-dispersible comb PMA is present in an amount of 19% by weight relative to the total weight of the compound.

[0091] According to another embodiment, the non-dispersible comb PMA is provided by a compound called Viscoplex® 3-162, which also contains a comb PMA as the main resin component, having a weight average molecular weight (Mw) of 399,292 g / mol, a number average molecular weight (Mn) of 205,952 g / mol, a Mw / Mn of 1.94, and a shear stability index (SSI) of 0.6.

[0092] According to another embodiment, the non-dispersible comb PMA is provided by a combination of compounds, for example Viscoplex® 3-201 in combination with Viscoplex® 3-162.

[0093] The non-dispersant comb PMA is generally present in an amount of from 0.5% to 25%, from 1% to 20%, from 2% to 18%, from 4% to 16%, or from 5% to 15% by weight, based on the total weight of the lubricating oil composition.

[0094] Other viscosity modifiers Linear poly(meth)acrylates (PMAs) are generally synthesized by simple free radical copolymerization of a mixture of different alkyl methacrylates. Unlike comb PMAs, conventional linear PMAs are characterized by the presence of mainly short alkyl chain lengths (usually 1-50 carbons) and the absence of long alkyl chain macromonomers that give comb polymers their characteristic shape. With PMAs, better low temperature rheological properties can be obtained than with OCPs. On the other hand, the thickening efficiency of PMAs is generally inferior to that of OCPs, and therefore PMAs must be used in higher concentrations to achieve the same effect. See U.S. Pat. Nos. 3,607,749 and 8,778,857, and European Patent No. 0225,598.

[0095] Olefin copolymer (OCP) viscosity modifiers with high thickening efficiency are advantageous in multigrade finished lubricants, reducing formulation costs and reducing the risk of deposit formation. This advantage comes from the lower amount of polymer used in the fully formulated oil. Traditionally, and as is well known in the art, the thickening efficiency of OCPs is increased by maximizing the ethylene content, which creates the risk that the polymer will cause low temperature performance defects in the finished lubricant. Low temperature defects can be mitigated by using a blend of amorphous and semi-crystalline ethylene-based copolymers in the lubricant formulation, allowing for improved thickening efficiency, shear stability index, low temperature viscosity performance and pour point. See, for example, U.S. Pat. Nos. 7,402,235 and 5,391,617, and European Patent No. 0638,611.

[0096] Hydrogenated styrene-diene (HSD) type viscosity index improvers can be prepared by copolymerizing styrene and butadiene and hydrogenating the unsaturated copolymer. The hydrogenated styrene-diene copolymers can be linear block copolymers or star-shaped. Star-shaped HSD copolymers, due to their radial structure, exhibit superior shear stability compared to linear copolymers, do not cause polymer degradation under severe engine operating conditions, and reduce permanent viscosity loss of the lubricating oil. For examples of HSD copolymers as viscosity modifiers in lubricating oils, see, for example, U.S. Pat. Nos. 4,116,917, 3,772,196, and 4,788,316.

[0097] example The following examples are for illustrative purposes only and are not intended to limit the scope of the present disclosure in any way.

[0098] Each of the inventive and comparative examples was formulated with a borated and ethylene carbonate post-treated succinimide dispersant, an overbased calcium sulfonate detergent, an amine antioxidant, a borated ester friction modifier, a molybdenum succinimide complex, a mixture of primary and secondary ZnDTP, and trace amounts of an antifoam agent, a mixture of polymethacrylate-based pour point depressants. In addition, some examples also contained an overbased calcium salicylate detergent and / or a neutral calcium sulfonate detergent.

[0099] Table 1 summarizes the metal content and metal sources present in Examples 1-7 and Comparative Examples 1-7. Each sample also includes either a non-dispersant comb PMA viscosity modifier, an olefin copolymer viscosity modifier, a linear PMA viscosity modifier, or a styrene-isoprene copolymer viscosity modifier. The balance of the lubricating composition is made up of a Group III base oil. Table 1 ([Table 1-1] to [Table 1-3]) also includes the viscoelastic properties of each sample. [Table 1-1] [Table 1-2] [Table 1-3] The boron comes from a borated succinimide dispersant, and the calcium comes from at least three different detergent sources: an overbased calcium sulfonate with a TBN of 425 mg KOH / g and a Ca content of 16.1 wt.% based on the concentrate, an overbased salicylate detergent with a TBN of 175 mg KOH / g and a Ca content of 6.25 wt.% based on the concentrate, and a low overbased calcium sulfonate detergent with a TBN of 17 mg KOH / g and a Ca content of 2.3 wt.% based on the concentrate. Each sample also contains phosphorus from an approximately 2:1 mixture of primary and secondary zinc dialkyldithiophosphates. The molybdenum is from a molybdenum succinimide antioxidant.

[0100] Mini Rotational Viscometer Test (MRV) In this modified MRV test, the test oil is first mixed with 10% by weight of water at a speed of 10,000 rpm for 1 minute, then cooled to the test temperature (-35°C in this case) in a mini rotational viscometer cell for 24 hours. Each cell contains a calibrated rotor and stator set, where the rotor is rotated by a string wrapped around the rotor shaft and attached to a weight. Starting with a 10g weight, a series of increasing weights are applied to the string until rotation occurs to determine the yield stress. The results are recorded in Pascals as the applied force, or yield stress. A 150g weight is then added to measure the apparent viscosity of the oil. The greater the apparent viscosity, the greater the likelihood that the oil will not be continuously and adequately delivered to the oil pump inlet. The results are recorded in viscosity (centipoise).

[0101] The results of the MRV test for each lubricating oil composition are shown below in Table 2. The Examples passed the MRV test, while the Comparative Examples failed the MRV test. [Table 2]

[0102] While the present disclosure is susceptible to various modifications and alternative forms, specific embodiments thereof are described in detail herein. It should be understood, however, that the description of specific embodiments herein is not intended to limit the disclosure to the particular forms disclosed, but rather, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the present disclosure as defined by the appended claims.

[0103] It should be noted that not all of the acts described in the general description or examples are required, that some of the specific acts may not be required, and that one or more additional acts may be performed in addition to the acts described. Furthermore, the order in which the acts are listed is not necessarily the order in which they are performed.

[0104] Benefits, other advantages, and solutions to problems have been described herein with respect to particular embodiments, however, the benefits, advantages, solutions to problems, and any feature or features that may give rise to or make more pronounced any benefit, advantage, or solution should not be construed as a critical, essential, or essential feature of any claim.

[0105] The details and descriptions of the embodiments set forth herein are intended to provide a general understanding of the structure of the various embodiments.

[0106] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a list of features is not necessarily limited to only those features, but may include other features not expressly listed or that are inherent to such process, method, article, or apparatus. Furthermore, unless expressly stated otherwise, "or" refers to an inclusive or, not an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or absent), A is false (or absent) and B is true (or present), or both A and B are true (or present).

[0107] The use of "a" or "an" is used to describe elements and components described herein. This is done merely for convenience and to give a general sense and scope of the scope of the embodiments of the present disclosure. This description should be read as including one or at least one, unless otherwise clearly indicated, and the singular includes the plural and vice versa. When referring to a value, the term "averaged" shall mean the mean, geometric mean, or median. The group numbers corresponding to columns in the periodic table of the elements use the "New Notation" convention described in the CRC Handbook of Chemistry and Physics, 81st Edition (2000-2001).

[0108] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Materials, methods, and examples are illustrative only and are not intended to be limiting. To the extent not described herein, many details regarding specific materials and processing operations are conventional and can be found in textbooks and other sources within the lubricants and oil and gas industries.

[0109] The present specification and examples are not intended to serve as an exhaustive and comprehensive description of all elements and features of formulations, compositions, devices, and systems that use the structures or methods described herein. Separate embodiments may be provided in combination in a single embodiment, and conversely, various features that are described in connection with a single embodiment for brevity may be provided separately or in any subcombination. Furthermore, references to values ​​described within ranges include every value within that range. Many other embodiments will be apparent to those skilled in the art only after reading this specification. Other embodiments may be used and derived from the present disclosure, making structural substitutions, logical substitutions, or other changes without departing from the scope of the present disclosure. Thus, the present disclosure should be considered as illustrative rather than restrictive. The following is further disclosed regarding the present invention. [1] A lubricating oil composition for a hybrid engine, comprising: (a) a major amount of oil of lubricating viscosity; (b) a borated dispersant in an amount to provide 40 to 400 ppm of boron to the lubricating oil composition; (c) an overbased calcium salicylate or a mixture of overbased calcium sulfonate and overbased calcium salicylate, individually having a total base number of greater than 150 mg KOH / g as measured by the method of ASTM D-2896, present in an amount to provide said lubricating oil composition with from 800 ppm to 1800 ppm of calcium; (d) zinc dithiophosphate (ZnDTP) in an amount to provide 100 to 800 ppm of phosphorus to the lubricating oil composition; (e) a non-dispersant comb-type polymethacrylate (PMA) viscosity index improver (VII), The lubricating oil composition has a KV of 6 cSt to 8.5 cSt at 100°C, a KV of 25 cSt to 35 cSt at 40°C, and a VI of over 200. [2] The lubricating oil composition according to [1], further comprising one or more magnesium-containing detergents in an amount to provide 100 to 600 ppm of magnesium to the lubricating oil composition. [3] [1] The lubricating oil composition according to [1], wherein the boronated dispersant is a boronated succinimide dispersant. [4] The lubricating oil composition according to [1], further comprising a molybdenum-containing compound in an amount that provides the lubricating oil composition with 50 to 1000 ppm of molybdenum. [5] The lubricating oil composition of [1], further comprising a friction modifier, an ashless antiwear additive, an antioxidant, a metal deactivator, a seal swell additive, a foam inhibitor, or a viscosity modifier. [6] The lubricating oil composition according to [1], wherein the zinc dithiophosphate is a zinc dialkyldithiophosphate. [7] The lubricating oil composition according to [1], wherein the oil of lubricating viscosity is a Group III base oil. [8] The lubricating oil composition according to [1], wherein the viscosity grade of the lubricating oil is 0W-12, 0W-16, or 0W-20. [9] 1. A method of lubricating a hybrid engine, comprising: (a) a major amount of oil of lubricating viscosity; (b) a borated dispersant in an amount to provide 40 to 400 ppm of boron to the lubricating oil composition; (c) an overbased calcium salicylate or a mixture of overbased calcium sulfonate and overbased calcium salicylate, individually having a total base number of greater than 150 mg KOH / g as measured by the method of ASTM D-2896, present in an amount to provide said lubricating oil composition with from 800 ppm to 1800 ppm of calcium; (d) zinc dithiophosphate (ZnDTP) in an amount to provide 100 to 800 ppm of phosphorus to the lubricating oil composition; (e) a non-dispersant comb polymethacrylate (PMA) viscosity index improver (VII), The method, wherein the lubricating oil composition has a KV at 100°C of 6 cSt to 8.5 cSt, a KV at 40°C of 25 cSt to 35 cSt, and a VI of the lubricating oil composition of more than 200.

[10] The lubricating oil further comprises The lubricating oil composition according to [9], further comprising one or more magnesium-containing detergents in an amount to provide 100 to 600 ppm of magnesium to the lubricating oil composition.

[11] 10. The method of claim 9, wherein the boronated dispersant is a boronated succinimide dispersant.

[12] The method of [9], wherein the lubricating oil further comprises a molybdenum-containing compound in an amount to provide the lubricating oil composition with 50 to 1000 ppm of molybdenum.

[13] The method of claim 9, wherein the lubricating oil further comprises a friction modifier, an ashless antiwear additive, an antioxidant, a metal deactivator, a seal swell additive, a foam inhibitor, or a viscosity modifier.

[14] The method according to [9], wherein the zinc dithiophosphate is a zinc dialkyldithiophosphate.

[15] 10. The method of claim 9, wherein the oil of lubricating viscosity is a Group III base oil.

[16] The method of claim 9, wherein the lubricating oil has a viscosity grade of 0W-12, 0W-16, or 0W-20.

Claims

1. A lubricating oil composition for a hybrid engine, comprising: (a) a major amount of oil of lubricating viscosity; (b) a borated dispersant in an amount providing 40 to 400 ppm of boron to said lubricating oil composition; and (c) an overbased calcium salicylate or a mixture of overbased calcium sulfonate and overbased calcium salicylate, individually having a total base number of greater than 150 mg KOH / g as measured by the method of ASTM D-2896, present in an amount to provide from 950 ppm to 1800 ppm of calcium to said lubricating oil composition; (d) zinc dithiophosphate (ZnDTP) in an amount providing 100 to 800 ppm phosphorus to the lubricating oil composition; and (e) a non-dispersant comb polymethacrylate (PMA) viscosity index improver (VII); The lubricating oil composition has a KV at 100° C. of 6 cSt to 8.5 cSt, a KV at 40° C. of 25 cSt to 35 cSt, and a VI of over 200.

2. 10. The lubricating oil composition of claim 1, further comprising one or more magnesium-containing detergents in an amount providing 100 to 600 ppm of magnesium to said lubricating oil composition.

3. 2. The lubricating oil composition of claim 1, wherein the borated dispersant is a borated succinimide dispersant.

4. 10. The lubricating oil composition of claim 1, further comprising a molybdenum-containing compound in an amount providing said lubricating oil composition with 50 to 1000 ppm of molybdenum.

5. 10. The lubricating oil composition of claim 1, further comprising a friction modifier, an ashless antiwear additive, an antioxidant, a metal deactivator, a seal swell additive, a foam inhibitor, or a viscosity modifier.

6. 2. The lubricating oil composition of claim 1, wherein the zinc dithiophosphate is a zinc dialkyldithiophosphate.

7. 10. The lubricating oil composition of claim 1, wherein the oil of lubricating viscosity is a Group III base oil.

8. The lubricating oil composition of claim 1, wherein the lubricating oil has a viscosity grade of 0W-12, 0W-16, or 0W-20.

9. 1. A method of lubricating a hybrid engine, comprising: (a) a major amount of oil of lubricating viscosity; (b) a borated dispersant in an amount providing 40 to 400 ppm of boron to said lubricating oil composition; and (c) an overbased calcium salicylate or a mixture of overbased calcium sulfonate and overbased calcium salicylate, individually having a total base number of greater than 150 mg KOH / g as measured by the method of ASTM D-2896, present in an amount to provide from 950 ppm to 1800 ppm of calcium to said lubricating oil composition; (d) zinc dithiophosphate (ZnDTP) in an amount providing 100 to 800 ppm phosphorus to the lubricating oil composition; and (e) a non-dispersant comb polymethacrylate (PMA) viscosity index improver (VII), The method, wherein the lubricating oil composition has a KV at 100° C. of 6 cSt to 8.5 cSt, a KV at 40° C. of 25 cSt to 35 cSt, and a VI of the lubricating oil composition is greater than 200.

10. The lubricating oil further comprises 10. The method of claim 9 including one or more magnesium-containing detergents in an amount to provide 100 to 600 ppm of magnesium to the lubricating oil composition.

11. 10. The method of claim 9, wherein the borated dispersant is a borated succinimide dispersant.

12. The method of claim 9, wherein the lubricating oil further comprises a molybdenum-containing compound in an amount to provide the lubricating oil composition with 50 to 1000 ppm of molybdenum.

13. 10. The method of claim 9, wherein the lubricating oil further comprises a friction modifier, an ashless antiwear additive, an antioxidant, a metal deactivator, a seal swell additive, a foam inhibitor, or a viscosity modifier.

14. 10. The method of claim 9, wherein the zinc dithiophosphate is a zinc dialkyldithiophosphate.

15. 10. The method of claim 9, wherein the oil of lubricating viscosity is a Group III base oil.

16. 10. The method of claim 9, wherein the lubricating oil has a viscosity grade of 0W-12, 0W-16, or 0W-20.

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