Lubricating oil composition

Abstract

A lubricating oil for a hybrid engine comprising a major amount of an oil of lubricating viscosity; a boron-containing compound in an amount to provide 50 ppm to 300 ppm of boron to the lubricating oil composition; an overbased calcium salicylate or a mixture of an overbased calcium salicylate and an overbased calcium sulfonate, individually having a total base number greater than 150 mg KOH / g as measured by the method of ASTM D-2896, in an amount to provide 800 ppm to 1800 ppm of calcium to the lubricating oil composition; zinc dithiophosphate (ZnDTP) in an amount to bring 100 ppm to 800 ppm of phosphorus to the lubricating oil composition; and a non-dispersant pectinate polymethacrylate (PMA) viscosity index improver (VII). The boron-containing compound includes a borated dispersant. The KV of the lubricating oil composition at 100°C is 6 cSt to 8.5 cSt, the KV of the lubricating oil composition at 40°C is 25 cSt to 35 cSt, and the VI of the lubricating oil composition is greater than 200.

Description

Background Technology

[0001] Modern lubricants are formulated to the stringent specifications typically set by original equipment manufacturers (OEMs). To meet these stringent specifications, carefully selected lubricant additives are blended with base oils that have a lubricating viscosity. Typical lubricant compositions may contain, for example, dispersants, detergents, antioxidants, wear inhibitors, rust inhibitors, corrosion inhibitors, foam inhibitors, and / or friction modifiers. The specific application or use (e.g., hybrid vehicles) determines the set of additives incorporated into the lubricant composition.

[0002] Hybrid vehicles rely on two distinct types of powertrain technology—an internal combustion engine and an electric motor. The internal combustion engine primarily drives the vehicle at high speeds. The electric motor drives the vehicle at low speeds and can also assist the internal combustion engine when additional power is needed. For hybrid vehicles, it is crucial to distribute power from the engine and electric motor in a well-balanced manner as vehicle speed increases.

[0003] Hybrid vehicles typically feature a start-stop system, where the engine stops when the vehicle is stationary, and the engine fuel system is suspended when the vehicle is driven solely by the electric motor or brakes. Therefore, the accumulation of water and fuel in the fuel becomes a problem because the engine cannot adequately evaporate the water and fuel. This leads to the formation of unstable emulsions that negatively impact engine performance and cause corrosion of engine components.

[0004] The differences between hybrid vehicles and conventional motor vehicles are so significant that conventional engine oils are not necessarily optimized for use in hybrid vehicles. Therefore, lubricant compositions specifically designed for hybrid vehicles are required. Summary of the Invention

[0005] In one aspect, this disclosure provides a lubricating oil composition for a hybrid power engine, the lubricating oil composition comprising: a major amount of an oil having a lubricating viscosity; a boron-containing compound, the amount of which provides the lubricating oil composition with 40 ppm to 400 ppm of boron; and a mixture of superalkaline calcium salicylate or superalkaline calcium sulfonate and superalkaline calcium salicylate, individually having a total base value greater than 150 mg KOH / g based on a detergent concentrate as determined by ASTM D-2896, which provides the lubricating oil composition with 800 ppm to 1800 ppm of total base value. The lubricating oil composition contains ppm of calcium; zinc dithiophosphate (ZnDTP) in an amount providing 100 to 800 ppm of phosphorus; and a non-dispersed comb-shaped polymethyl methacrylate (PMA) viscosity index improver (VII), wherein the boron-containing compound includes a borate dispersant, the lubricating oil composition having a kinematic viscosity (KV) of 6 to 8.5 cSt at 100°C, a KV of 25 to 35 cSt at 40°C, and a viscosity index (VI) greater than 200.

[0006] In another aspect, the present invention provides a method for lubricating a hybrid power engine, the method comprising providing a lubricating oil to the hybrid power engine, the lubricating oil comprising: a major amount of an oil having a lubricating viscosity; a boron-containing compound, the amount of which provides 40 ppm to 400 ppm of boron to the lubricating oil composition; and a superalkaline calcium salicylate or a mixture of superalkaline calcium sulfonate and superalkaline calcium salicylate having a total base value greater than 150 mg KOH / g as determined by ASTM D-2896, which provides 800 ppm to 1800 ppm of boron to the lubricating oil composition. The composition contains ppm of calcium; zinc dithiophosphate (ZnDTP) in an amount providing 100 to 800 ppm of phosphorus to the lubricating oil composition; and a non-dispersed comb-shaped polymethyl methacrylate (PMA) viscosity index improver (VII), wherein the boron-containing compound includes a borate dispersant, the lubricating oil composition having 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 greater than 200. Detailed Implementation

[0007] While this disclosure is susceptible to various modifications and alternatives, specific embodiments thereof are described in detail herein. However, it should be understood that the description of specific embodiments herein is not intended to limit this disclosure to the particular form disclosed, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the disclosure as defined by the appended claims.

[0008] To facilitate understanding of the subject matter disclosed herein, many terms, abbreviations, or other shorthand are defined below as used herein. Any undefined term, abbreviation, or shorthand should be understood to have the common meaning as used by a person skilled in the art at the time of filing of this application.

[0009] As used herein, the following terms have the following meanings unless expressly stated to the contrary. In this specification, the following words and expressions, if used and as used, have the following meanings.

[0010] "Main amount" means more than 50% by weight of the composition.

[0011] "A small amount" means less than 50% by weight of the composition, expressed relative to the total mass of the stated additives and all additives present in the composition, and is considered to be an active ingredient of one or more additives.

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

[0013] Unless otherwise stated, all percentages reported are based on weight % of the active ingredient (i.e., without regard to carriers or diluent oils).

[0014] The abbreviation "ppm" refers to parts per million (ppm) of the total weight of the lubricating oil composition.

[0015] Determine the high temperature high shear (HTHS) viscosity at 150°C according to ASTM D4683.

[0016] According to ASTM D445, 100℃ (KV) is determined. 100 ) and 40℃ (KV) 40 The kinematic viscosity at )

[0017] The viscosity index (VI) is determined according to ASTM D2270.

[0018] The term "metal" refers to alkali metals, alkaline earth metals, or mixtures thereof.

[0019] The terms "oil-soluble" or "oil-dispersible" are used throughout the specification and claims. "Oil-soluble" or "oil-dispersible" means that the amount required to provide the desired level of activity or performance can be incorporated by being dissolved, dispersed, or suspended in an oil having a lubricating viscosity. Typically, this means that at least about 0.001% by weight of the material can be incorporated into the lubricating oil composition. For further discussion of the terms "oil-soluble" and "oil-dispersible," particularly "stable dispersibility," see U.S. Patent No. 4,320,019, whose relevant teachings in this regard are expressly incorporated herein by reference.

[0020] As used herein, the term "sulfated ash" refers to the non-flammable residue produced by cleaning agents and metal additives in lubricating oils. Sulfated ash can be determined using ASTM test D874.

[0021] As used herein, the term "Total Base Number" or "TBN" refers to the amount of alkali equivalent to milligrams of KOH per gram of sample. Therefore, a higher TBN value reflects a greater amount of alkaline product and thus a higher alkalinity. TBN is determined using the ASTM D2896 test. TBN values ​​are based on detergent concentrates.

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

[0023] Nitrogen content is determined according to ASTM D4629.

[0024] All ASTM standards mentioned herein are the latest versions as of the date of this application.

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

[0026] This invention provides a lubricating oil optimized for hybrid engines. The lubricating oil comprises (a) an oil having a lubricating viscosity; (b) a boron-containing compound containing a boronized dispersant; (c) one or more over-alkaline calcium detergents; (d) optionally one or more magnesium-containing detergents; (e) zinc dithiophosphate; and (f) non-dispersed comb-shaped polymethyl methacrylate (PMA). 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 greater than 200.

[0027] Oil with lubricating viscosity

[0028] An oil with a lubricating viscosity (sometimes referred to as a "base oil" or "base stock") is the main liquid component of a lubricant. Additives and possibly other oils are blended into this main liquid component, for example, to prepare the final lubricant (or lubricant composition). Base oils can be used to prepare concentrates and lubricant compositions thereof, and can be selected from natural and synthetic lubricants and combinations thereof.

[0029] Natural oils include animal and vegetable oils, liquid petroleum, and hydrorefined, solvent-treated alkanes, cycloalkanes, and mixed alkanes-cycloalkanes type mineral lubricating oils. Oils derived from coal or shale with lubricating viscosity are also useful base oils.

[0030] Synthetic lubricants include hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutene, polypropylene, propylene-isobutylene copolymer, chlorinated polybutene, poly(1-hexene), poly(1-octene), poly(1-decene); alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2-ethylhexyl)benzene); polyphenols (e.g., biphenyl, terphenyl, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides, as well as their derivatives, analogs, and homologues. The polymerized olefins may also be derived from biogenic sources, such as terpenes, such as myrcene, ocimene, and farnesene, which may also be copolymerized with other olefins and further isomerized if desired.

[0031] Another suitable category of synthetic lubricants comprises esters of dicarboxylic acids (e.g., malonic acid, alkylmalonic acid, alkenylmalonic acid, succinic acid, alkylsuccinic acid and alkenylsuccinic acid, maleic acid, fumaric acid, azelaic acid, octanoic acid, sebacic acid, adipic acid, linoleic acid dimer, phthalic acid) with various alcohols (e.g., butanol, hexanol, dodecyl alcohol, 2-ethylhexanol, ethylene glycol, diethylene glycol monoether, propylene glycol). Suitable 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, di(eicosyl) sebacate, 2-ethylhexyl diester of linoleic acid dimer, and complex esters formed by reacting 1 mole of sebacate with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid.

[0032] Esters that can be used as synthetic oils also include those from C5 to C6. 12 Esters made from monocarboxylic acids and polyols, as well as polyol ethers (such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol).

[0033] In addition, esters from biological sources can also be used as synthetic oils.

[0034] Base oils can be derived from Fischer-Tropsch synthetic hydrocarbons. Fischer-Tropsch synthetic hydrocarbons are produced from syngas containing H2 and CO using a Fischer-Tropsch catalyst. These hydrocarbons typically require further processing before they can be used as base oils. For example, the hydrocarbon may be hydroisomerized using methods known to those skilled in the art; hydrocracking and hydroisomerizing; dewaxing; or hydroisomerizing and dewaxing.

[0035] The base oil can 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, renewable or bio-based base oils include bio-based hydrocarbons, such as isoparaffins derived from hydrocarbon terpenes (such as myrcene, ocimene, and farnesene). In some embodiments, the bio-based hydrocarbons are derived from fatty acids or fatty esters.

[0036] Unrefined, refined, and refined oils can be used in the lubricating oil compositions of the present invention. Unrefined oils are oils obtained directly from natural or synthetic sources without further purification treatment. For example, shale oil obtained directly from a dry distillation operation, petroleum obtained directly from distillation, or esterified oil obtained directly from an esterification process and used without further treatment would be unrefined oils. Refined oils are similar to unrefined oils, except that they are further processed in one or more purification steps to improve one or more properties. Many such purification techniques, such as distillation, solvent extraction, acid or alkali extraction, filtration, and percolation, are known to those skilled in the art.

[0037] Refined oils are obtained through processes similar to those used to obtain refined oils that are already in use. These refined oils are also known as recycled oils or reprocessed oils, and are typically further processed using techniques used to approve waste additives and oil decomposition products.

[0038] Therefore, the base oils that can be used to prepare the lubricating oil compositions of the present invention may be selected from any of the base oils in Group IV specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines (API Publication 1509). Such groups of base oils are summarized in Table 1 below:

[0039] Table 1

[0040]

[0041] (a) Groups I-III are mineral oil base oils.

[0042] (b) Determined according to ASTM D2007.

[0043] (c) Determined according to ASTM D2622, ASTM D3120, ASTM D4294 or ASTM D4927.

[0044] (d)Determined according to ASTM D2270.

[0045] The base oils used in this document are any kind corresponding to API Group II, III, IV and V oils and combinations thereof, with Group III to V oils preferred due to their special volatility, stability, viscosity and cleanliness characteristics.

[0046] The oil having a lubricating viscosity used in the lubricating oil compositions of this disclosure, also referred to as a base oil, is typically present in a major amount, for example, greater than 50% by weight, preferably greater than about 70% by weight, more preferably about 80% to about 99.5% by weight, and most preferably about 85% to about 98% by weight, based on the total weight of the composition. As used herein, “base oil” should be understood to mean a base oil stock or a blend of base oil stocks, which is a lubricant component produced by a single manufacturer to the same specifications (regardless of the source of feed or the location of the manufacturer), conforming to the same manufacturer’s specifications, and identified by a unique formulation, product identification number, or both. The base oil used herein can be any oil having a lubricating viscosity that is currently known or subsequently discovered for formulating lubricating oil compositions.

[0047] As will be readily understood by those skilled in the art, the viscosity of a base oil depends on the application. Therefore, the viscosity of the base oils used herein will typically be in the range of about 2 to about 2000 centistokes (cSt) at 100°C. Generally, base oils used alone as engine oils will have a kinematic viscosity range at 100°C of about 2 cSt to about 30 cSt, preferably about 3 cSt to about 16 cSt, and most preferably about 4 cSt to about 12 cSt.

[0048] The lubricating oil composition can be a multi-grade oil with a viscosity grade of SAE 0W-XX, where XX is any one of 12, 16, and 20. According to a preferred embodiment, the lubricating oil composition has a viscosity grade of SAE 0W-20.

[0049] The lubricating oil composition has a viscosity index of at least 200 (e.g., 200 to 400 or 200 to 300). If the viscosity index of the lubricating oil composition is less than 135, it may be difficult to maintain the desired HTHS viscosity at 150°C while improving fuel efficiency. If the viscosity index of the lubricating oil composition exceeds 400, evaporation performance may decrease, and defects may occur due to insufficient solubility of additives and inadequate compatibility with sealing materials. According to other embodiments, the lubricating oil composition has a viscosity index of 200 to 290, 200 to 280, 200 to 270, 200 to 260, 200 to 250, or 200 to 240. In other embodiments, the lubricating oil composition has a viscosity index of 210 to 290, 210 to 280, 210 to 270, 210 to 260, 210 to 250, or 210 to 240. In other embodiments, the lubricating oil composition has a viscosity index of 220 to 290, 220 to 280, 220 to 270, 220 to 260, 220 to 250, or 220 to 240.

[0050] The kinematic viscosity of the lubricating oil composition at 100°C is between 6.0 cSt and 8.0 cSt (e.g., 6.0 mm). 2 / s to 7.9 mm 2 / s, 6.0 mm 2 / s to 7.8 mm 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 kinematic viscosity of the lubricating oil composition at 100°C is 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 kinematic viscosity of the lubricating oil composition at 100°C is 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).

[0051] The kinematic viscosity of the lubricating oil composition at 40°C is 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 kinematic viscosity of the lubricating oil composition at 40°C is 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).

[0052] Generally, the sulfur level in the lubricating oil composition is less than or equal to about 0.7% by weight, based on the total weight of the lubricating oil composition. For example, the lubricating oil composition may have a sulfur level of about 0.01% to 0.5% by weight, 0.01% to 0.4% by weight, 0.01% to 0.3% by weight, 0.01% to 0.2% by weight, or 0.01% to 0.10% by weight. In one embodiment, the sulfur level in the lubricating oil composition is less than or equal to about 0.60% by weight, less than or equal to about 0.50% by weight, less than or equal to about 0.40% by weight, less than or equal to about 0.30% by weight, less than or equal to about 0.20% by weight, or less than or equal to about 0.10% by weight, based on the total weight of the lubricating oil composition.

[0053] In one embodiment, the phosphorus level in the lubricating oil composition is less than or equal to about 0.08% by weight, for example, from about 0.01% by weight to about 0.08% by weight, based on the total weight of the lubricating oil composition. In another embodiment, the phosphorus level in the lubricating oil composition is less than or equal to about 0.07% by weight, for example, from about 0.01% by weight to about 0.07% by weight, based on the total weight of the lubricating oil composition. In yet another embodiment, the phosphorus level in the lubricating oil composition is less than or equal to about 0.05% by weight, for example, from about 0.01% by weight to about 0.05% by weight, based on the total weight of the lubricating oil composition.

[0054] In one embodiment, as determined by ASTM D874, the level of sulfated ash produced by the lubricating oil composition is less than or equal to about 1.00% by weight, for example, as determined by ASTM D874, the level of sulfated ash is from about 0.10% by weight to about 1.00% by weight. In one embodiment, as determined by ASTM D874, the level of sulfated ash produced by the lubricating oil composition is less than or equal to about 0.80% by weight, for example, as determined by ASTM D874, the level of sulfated ash is from about 0.10% by weight to about 0.80% by weight. In one embodiment, as determined by ASTM D874, the level of sulfated ash produced by the lubricating oil composition is less than or equal to about 0.60% by weight, for example, as determined by ASTM D874, the level of sulfated ash is from about 0.10% by weight to about 0.60% by weight.

[0055] Suitablely, the lubricating oil composition of the present invention may have a total base number (TBN) of 4 KOH / g to 15 mg KOH / g (e.g., 5 mg KOH / g to 12 mg KOH / g, 6 mg KOH / g to 12 mg KOH / g or 8 mg KOH / g to 12 mg KOH / g).

[0056] The lubricating oil compositions of the present invention may also contain conventional lubricant additives for imparting auxiliary functions, to obtain a finished lubricating oil composition in which these additives are dispersed or dissolved. For example, the lubricating oil composition may be blended with antioxidants, ashless dispersants, anti-wear agents, detergents (such as metal cleaners), rust inhibitors, demulsifiers, friction modifiers, metal passivators, pour point depressants, viscosity modifiers, defoamers, cosolvents, corrosion inhibitors, dyes, extreme pressure agents, and mixtures thereof. Many additives are known and commercially available. These additives or similar compounds can be used to prepare the lubricating oil compositions of the present invention through common blending procedures.

[0057] Each of the aforementioned additives is used in a functionally effective amount to impart the desired properties to the lubricant. Therefore, for example, if the additive is an ashless dispersant, the functionally effective amount of that ashless dispersant will be sufficient to impart the desired dispersive properties to the lubricant. Generally, unless otherwise stated, the concentration range of each of these additives in use can be from about 0.001 wt% to about 20 wt%, such as from about 0.01 wt% to about 10 wt%.

[0058] Boron-containing compounds

[0059] The lubricating oil composition of the present invention comprises a boronized dispersant, the amount of which is provided by weight from 40 ppm to 400 ppm, for example 50 ppm to 290 ppm, 50 ppm to 280 ppm, 50 ppm to 270 ppm, 50 ppm to 260 ppm, 50 ppm to 250 ppm, 50 ppm to 240 ppm, 50 ppm to 230 ppm, 50 ppm to 200 ppm, 50 ppm to 190 ppm, 50 ppm to 180 ppm, 50 ppm to 170 ppm, 50 ppm to 160 ppm, and 50 ppm to 150 ppm of boron.

[0060] Examples of boronized dispersants include boronized ashless dispersants, such as boronized polyolefin succinic anhydride; boronized nitrogen-free derivatives of polyalkylene succinic anhydride; boronized basic nitrogen compounds selected from the group consisting of succinimides, carboxylic amides, alkyl monoamines, alkyl polyamines, Mannich bases, phosphonamides, thiophosphonamides and phosphoramides, thiazoles (e.g., 2,5-dimercapto-1,3,4-thiadiazole, mercaptobenzothiazole and its derivatives), triazoles (e.g., alkyltriazoles and benzotriazoles), copolymers containing carboxylic acid esters having one or more additional polar functional groups including amines, amides, imides, imides, hydroxyl groups, carboxyl groups, etc. (e.g., products prepared by copolymerization of long-chain alkyl acrylates or methacrylates with monomers having the above-described functions); and combinations thereof. Preferred boronized dispersants are boron succinimide derivatives, such as, for example, boronized polyisobutylene succinimide.

[0061] Examples of boronized ashless dispersants include boronized ashless hydrocarbon succinimide dispersants prepared by reacting a hydrocarbon succinic acid or anhydride with an amine. Preferred hydrocarbon succinic acids or anhydrides are polymers in which the hydrocarbon groups are derived from C3 or C4 monoolefins (especially polyisobutylene), wherein the polyisobutylene groups have 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 one to two, more preferably 1.1 to 1.8 succinic acid groups for each polyisobutylene group. In one embodiment, an oil-soluble or oil-dispersible boronized polyisobutylene succinimide dispersant is derived from a polyisobutylene group having a number average molecular weight of about 550 to about 5,000. In another embodiment, an oil-soluble or oil-dispersible boronized polyisobutylene succinimide dispersant is derived from a polyisobutylene group having a number average molecular weight of about 550 to about 4,000. In one embodiment, the oil-soluble or oil-dispersible borate polyisobutylene succinimide dispersant is derived from polyisobutylene groups having a number average molecular weight of about 550 to about 3000. In one embodiment, the oil-soluble or oil-dispersible borate polyisobutylene succinimide dispersant is derived from polyisobutylene groups having a number average molecular weight of greater than 550 to about 2300. In one embodiment, the oil-soluble or oil-dispersible borate polyisobutylene succinimide dispersant is derived from polyisobutylene groups having a number average molecular weight of about 950 to about 2300. In one embodiment, the oil-soluble or oil-dispersible borate polyisobutylene succinimide dispersant is derived from polyisobutylene groups having a number average molecular weight of about 950 to about 1700. In one embodiment, the oil-soluble or oil-dispersible borate polyisobutylene succinimide dispersant is derived from polyisobutylene groups having a number average molecular weight of about 2300. In one embodiment, the oil-soluble or oil-dispersible borate polyisobutylene succinimide dispersant is derived from polyisobutylene groups having a number average molecular weight of about 1700. In another embodiment, the oil-soluble or oil-dispersible borate polyisobutylene succinimide dispersant is derived from polyisobutylene groups having a number average molecular weight of about 1000.

[0062] Preferred amines for the reaction to form succinimide are polyamines having 2 to 60 carbon atoms and 2 to 12 nitrogen atoms per molecule. Particularly preferred amines include polyalkylene amines represented by the following formula:

[0063] NH2(CH2) n —(NH(CH2) n ) m —NH2

[0064] Where n is 2 to 3 and m is 0 to 10. Illustrative examples include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, etc., and commercially available mixtures of such polyamines. Amines containing other groups such as hydroxyl, alkoxy, amide, nitride, and imidazoline groups can also be used; polyoxyethylene polyamines can also be used. The amine is reacted with an alkenyl succinic acid or anhydride in a conventional ratio of about 1:1 to 10:1, preferably 1:1 to 3:1, and preferably in a ratio of about 1:1. This is typically carried out by heating the reactants to 100° to 250°C, preferably 125° to 175°C, and holding for 1 to 10 hours, preferably 2 to 6 hours.

[0065] Boronization of alkenyl succinimide dispersants is also well known in the art, as disclosed in U.S. Patent Nos. 3,087,936 and 3,254,025. The succinimide can be treated, for example, with a boron compound selected from the group consisting of boron, boron oxide, boron halide, boric acid, and their esters, wherein the amount of boron compound provides 0.1 to 10 atomic proportions of boron for every atomic proportion of nitrogen in the dispersant.

[0066] Based on the total weight of the borate dispersant, the borate product will generally contain 0.1% to 2.0% by weight, preferably 0.2% to 0.8% by weight, of boron. Boron is thought to exist as a dehydrated borate polymer linked to a metaborate of an imide. Adding 1% to 3% by weight (based on the weight of the dispersant) of the boron compound readily facilitates the borate reaction.

[0067] Cleaning agents

[0068] The lubricating oil of the present invention comprises one or more cleaning agents. The cleaning agents may be superalkaline calcium salicylate or a mixture of superalkaline calcium sulfonate and superalkaline calcium salicylate. The cleaning agent alone has a TBN greater than 150 mg KOH / g (as measured by ASTM D-2896). The cleaning agents are present in an amount of calcium providing the lubricating oil composition from about 800 ppm to about 1800 ppm (e.g., 800 ppm to 1700 ppm, 900 ppm to 1600 ppm, 1000 ppm to 1500 ppm, 1100 ppm to 1400 ppm, 1200 ppm to 1300 ppm). Optionally, the cleaning agents may include a magnesium-containing cleaning agent providing the lubricating oil composition from 100 ppm to 600 ppm of magnesium. The cleaning agents can be prepared by any compatible method. In one embodiment, the magnesium cleaning agent is a superalkaline magnesium sulfonate cleaning agent.

[0069] Sulfonates can be prepared from sulfonic acids, which are typically obtained by sulfonating alkyl-substituted aromatic hydrocarbons (such as those obtained from petroleum fractionation or by alkylation of aromatic hydrocarbons). Examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, biphenyl, or their halogen derivatives. Alkylation can be carried out in the presence of a catalyst using an alkylating agent having about 3 to more than 70 carbon atoms. Alkyl aryl sulfonates typically contain about 9 to 80 or more carbon atoms (e.g., about 16 to 60 carbon atoms) per alkyl-substituted aromatic moiety.

[0070] Salicylates can be prepared by reacting an alkali metal compound with at least one carboxylic acid and removing water from the reaction product. Cleaning agents prepared from salicylic acid are a class of cleaning agents prepared from carboxylic acids. Useful salicylates include long-chain alkyl salicylates. A family of useful compositions has the following structures:

[0071]

[0072] Where R” represents C1 to C 30 (e.g., C) 13 To C 30 alkyl groups; n It is an integer from 1 to 4; and M is an alkaline earth metal (e.g., Ca or Mg).

[0073] Hydroxyl-substituted salicylic acids can be prepared from phenols via the Kolbe reaction (see U.S. Patent No. 3,595,791). Metal salts of alkyl-substituted salicylic acids can be prepared by metathesis of the metal salt in polar solvents such as water or alcohol.

[0074] The term "superbasic" refers to metal salts, such as those of sulfonic acids, salicylic acids, and phenols, in which the amount of metal present exceeds the stoichiometric amount. Such salts can have conversion levels exceeding 100% (i.e., they can 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 represent the ratio of the total stoichiometric amount of metal in a superbasic salt to the stoichiometric amount of metal in a neutral salt, based on known chemical reactivity and stoichiometry. In normal or neutral salts, the metal ratio is 1, while in superbasic salts, MR is greater than 1. These are often referred to as superbasic, overbasic, or hyperbasic salts and may be organosulfates, salicylates, or phenolates.

[0075] Overly alkaline detergents have a TBN of greater than 150 mg KOH / g or higher, about 250 mg KOH / g or higher, or about 300 mg KOH / g or higher, or about 350 mg KOH / g or higher, or about 375 mg KOH / g or higher, or about 400 mg KOH / g or higher, based on the detergent concentrate.

[0076] Overly alkaline cleaning agents may have metal-to-substrate ratios of 1.1:1, 2:1, 4:1, 5:1, 7:1, or 10:1.

[0077] Overly alkaline sulfonates and / or salicylates

[0078] The lubricating oil composition comprises a superalkaline calcium salicylate or a mixture of superalkaline calcium sulfonate and superalkaline calcium salicylate, having a total base value greater than 150 mg KOH / g as measured by ASTM D-2896, which provides the lubricating oil composition with an amount of calcium ranging from 800 ppm to 1700 ppm. In other embodiments, the superalkaline calcium salicylate or a mixture of superalkaline calcium sulfonate and superalkaline calcium salicylate, having a total base value greater than 150 mg KOH / g as measured by ASTM D-2896, provides the lubricating oil composition with an amount of calcium ranging from 800 ppm to 1800 ppm, for example, 800 ppm to 1250 ppm or 850 ppm to 1250 ppm. In other embodiments, a superalkaline calcium salicylate or a mixture of superalkaline calcium sulfonate and superalkaline calcium salicylate, having a total base value greater than 150 mg KOH / g as measured by ASTM D-2896, is present alone to provide the lubricating oil composition with amounts of 800 ppm to 1800 ppm calcium, 900 ppm to 1700 ppm calcium, and 950 ppm to 1700 ppm calcium.

[0079] Magnesium-containing cleaning agents

[0080] The one or more magnesium-containing cleaning agents may be over-alkaline magnesium-containing cleaning agents having a total base number greater than 150 mg KOH / g as measured by ASTM D-2896. The one or more over-alkaline magnesium-containing cleaning agents may be over-alkaline magnesium sulfonate cleaning agents, over-alkaline magnesium phenolate cleaning agents, over-alkaline magnesium salicylate cleaning agents, or mixtures thereof. In some embodiments, the magnesium cleaning agent may have a TBN of about 250 mg KOH / g or higher, or about 300 mg KOH / g or higher, or about 350 mg KOH / g or higher, or about 375 mg KOH / g or higher, or about 400 mg KOH / g or higher, based on the cleaning agent concentrate.

[0081] Preferred magnesium-containing cleaning agents include magnesium sulfonate, magnesium phenolate, and magnesium salicylate, especially magnesium sulfonate.

[0082] Magnesium-containing detergents may be used to provide a minimum amount of magnesium (e.g., 100 ppm to 600 ppm, 100 ppm to 500 ppm, 100 ppm to 400 ppm, 150 ppm to 600 ppm, 150 ppm to 550 ppm, 150 ppm to 500 ppm, 200 ppm to 600 ppm, 200 ppm to 550 ppm, 200 ppm to 500 ppm, 250 ppm to 600 ppm, 250 ppm to 550 ppm, 250 ppm to 500 ppm) for a lubricating oil composition by weight.

[0083] Zinc dithiophosphate (ZnDTP)

[0084] Anti-wear agents can reduce wear on metal parts. Suitable anti-wear agents include dialkyl dithiophosphate metal salts, such as zinc dialkyl dithiophosphate (ZnDTP) with the following formula:

[0085] Zn[S–P(=S)(OR 1 (OR) 2 )]2

[0086] Where R 1 and R 2 It can be the same or different hydrocarbon groups having 1 to 18 (e.g., 2 to 12) carbon atoms, and includes groups such as alkyl, alkenyl, aryl, aralkyl, alkylaryl, and alicyclic groups. Particularly preferred is R. 1 and R 2 The group is an alkyl group having 2 to 8 carbon atoms (for example, the alkyl group can be ethyl, etc.). just propyl, isopropyl, just Butyl, isobutyl, Zhong Butyl, just pentyl, isopentyl, just Hexyl, isohexyl, 2-ethylhexyl). To obtain oil solubility, the total number of carbon atoms (i.e., R) 1 +R 2 The content will be at least 5%. Dialkyl zinc dithiophosphate may therefore contain dialkyl zinc dithiophosphate. Dialkyl zinc dithiophosphate may be primary or secondary dialkyl zinc dithiophosphate or a mixture thereof. ZnDTP is present to provide the lubricating oil composition with an amount of phosphorus from 100 ppm to 800 ppm.

[0087] molybdenum compounds

[0088] The lubricating oil composition of the present invention may contain a molybdenum-containing compound in an amount providing the lubricating oil composition from about 50 ppm to about 1000 ppm, for example, from about 50 ppm to about 900 ppm, from about 50 ppm to about 800 ppm, from about 50 ppm to about 750 ppm, from about 50 ppm to about 500 ppm, from about 50 ppm to about 450 ppm, from about 50 ppm to about 400 ppm, from about 50 ppm to about 350 ppm, or from about 50 ppm to about 300 ppm of molybdenum.

[0089] Oil-soluble molybdenum-containing compounds may possess functional properties as anti-wear agents, antioxidants, friction modifiers, or mixtures thereof. Oil-soluble molybdenum-containing compounds may include molybdenum dithiocarbamate, molybdenum dialkyl dithiophosphate, molybdenum dithiophosphonate, amine salts of molybdenum compounds, molybdenum xanthate, molybdenum thioxanthate, molybdenum sulfide, molybdenum carboxylate, molybdenum alkoxide, trinuclear organomolybdenum compounds, molybdenum esters, molybdenum amides, and / or mixtures thereof. Molybdenum sulfide includes molybdenum dithiophosphate. Molybdenum dithiophosphate 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 dialkyl dithiophosphate, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound may be molybdenum dithiocarbamate.

[0090] Molybdenum dithiocarbamate (MoDTC) is an organomolybdenum compound represented by the following structure:

[0091]

[0092] Where R 1 R 2 R 3 and R 4 They are independent of each other and are linear or branched alkyl groups having 4 to 18 carbon atoms (e.g., 8 to 13 carbon atoms).

[0093] Molybdenum dithiophosphate (MoDTP) is an organomolybdenum compound represented by the following structure:

[0094]

[0095] Where R 5 R 6 R 7 and R 8 They are independent of each other and are linear or branched alkyl groups having 4 to 18 carbon atoms (e.g., 8 to 13 carbon atoms).

[0096] Suitable examples of molybdenum-containing compounds that may be used include commercial materials sold by RT Vanderbilt Co., Ltd. under trade names such as Molyvan 822™, Molyvan™ A, Molyvan 2000™, and Molyvan 855™, and commercial materials available from Adeka Corporation under trade names such as Sakura-Lube™ S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710, as well as mixtures thereof. Suitable molybdenum components are described in U.S. Patent Nos. 5,650,381, US RE 37,363 E1, US RE 38,929 E1, and US RE 40,595 E1, the entire contents of which are incorporated herein by reference.

[0097] Alternatively, the molybdenum-containing compound can be an acidic molybdenum compound. This includes 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. Alternatively, the composition may be provided with molybdenum from a molybdenum / sulfur complex of a basic nitrogen compound 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 Publication No. 2002 / 0038525, the entire contents of which are incorporated herein by reference.

[0098] Another suitable class of molybdenum-containing compounds are trinuclear molybdenum compounds, such as Mo3S k L n Q zThose and mixtures thereof, wherein S represents sulfur, L represents an independently selected ligand having an organic group containing a sufficient number of carbon atoms to make the compound soluble or dispersible in oil, n is 1 to 4, k varies from 4 to 7, Q is selected from the group consisting of neutral electron-donating compounds (such as water, amines, alcohols, phosphine, and ethers), and z is in the range of 0 to 5, and includes non-stoichiometric values. At least 21 total carbon atoms may be present in the organic groups of all ligands, such as at least 25, at least 30, or at least 35 carbon atoms. Other suitable molybdenum-containing compounds are described in U.S. Patent No. 6,723,685, the entire contents of which are incorporated herein by reference.

[0099] In one embodiment, the molybdenum amine is a molybdenum-succinimide complex. Suitable molybdenum-succinimide complexes are described, for example, in U.S. Patent No. 8,076,275. These complexes are prepared by a method comprising reacting an acidic molybdenum compound with an alkyl or alkenyl succinimide or a mixture thereof having the following structure:

[0100]

[0101] Where R is C 24 To C 350 (For example, C) 70 To C 128 )alkyl or alkenyl; R' is a straight-chain or branched alkylene group having 2 to 3 carbon atoms; x From 1 to 11; and y It is 1 to 10.

[0102] The molybdenum-containing compounds used to prepare molybdenum-succinimide complexes are acidic molybdenum compounds or salts of acidic molybdenum compounds. "Acidic" means that the molybdenum compound will react with a basic nitrogen compound, 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), MoOCl4, MoO2Br2, Mo2O3Cl6, etc.

[0103] Succinimides that can be used to prepare molybdenum-succinimide complexes are disclosed in numerous references and are well known in the art. Certain basic types of succinimides and related materials covered by the term "succinimid" in the art are taught in U.S. Patent Nos. 3,172,892, 3,219,666, and 3,272,746. The term "succinimid" is understood in the art to include many amides, imides, and amidines that may also be formed. However, the primary product is succinimid, and the term is generally accepted to refer to the product of the reaction of an alkyl or alkenyl-substituted succinic acid or anhydride with a nitrogen-containing compound. Preferred succinimides are those prepared by reacting a polyisobutylene succinic anhydride of about 70 to 128 carbon atoms with a polyalkylene polyamine selected from triethylenetetramine, tetraethylpentamine, and mixtures thereof.

[0104] The molybdenum-succinimide complex can be post-treated with a sulfur source under suitable pressure and at a temperature not exceeding 120°C to obtain a sulfidated molybdenum-succinimide complex. The sulfidation step can be carried out for a period of approximately 0.5 to 5 hours (e.g., 0.5 to 2 hours). Suitable sulfur sources include elemental sulfur, hydrogen sulfide, phosphorus pentasulfide, and R₂S. x Organic polysulfides (where R is a hydrocarbon group (e.g., C1 to C2)) 10 alkyl) and x It is at least 3) C1 to C 10 Thiols, inorganic sulfides and polysulfides, thioacetamides and thioureas.

[0105] Viscosity modifier

[0106] Viscosity modifiers (VMs), sometimes called viscosity index improvers (VIIs), are present in lubricating oil compositions to impart operability at both high and low temperatures. Viscosity modifiers increase the viscosity of the lubricating oil composition at elevated temperatures (which increases film thickness) while having a limited effect on viscosity at low temperatures.

[0107] Viscosity modifiers can be used to impart a single function or can be multifunctional. Multifunctional viscosity modifiers can also act as dispersants.

[0108] Examples of suitable viscosity modifiers are polymers and copolymers of methacrylates, butadiene, olefins, or alkylated styrene. 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).

[0109] 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 is 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.

[0110] A particularly useful viscosity modifier is non-dispersed comb-shaped polymethyl methacrylate (comb-shaped PMA).

[0111] Non-disperse comb-shaped polymethacrylate

[0112] Non-dispersed comb-shaped polymethyl methacrylate (comb-shaped PMA) is a comb-shaped polymer that can be used as a viscosity modifier or viscosity index improver.

[0113] In one embodiment, the weight-average molecular weight (Mw) of the nondispersive comb-shaped PMA is from 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.

[0114] In one embodiment, the number-average molecular weight (Mn) of the nondispersive comb-shaped PMA is from 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 number-average molecular weight (Mn) of the nondispersive comb-shaped PMA is from 150,000 g / mol to 250,000 g / mol, or 200,000 g / mol to 215,000 g / mol.

[0115] In one embodiment, the shear stability index (SSI) of the non-dispersed comb-shaped PMA is 0.1 to 1.0, 0.2 to 0.9, or 0.3 to 0.8.

[0116] Non-dispersible comb-shaped PMAs of lubricating oil compositions are described in US 2017 / 0298287A1 and JP2019014802, the disclosures of which are incorporated herein by reference. Non-dispersible comb-shaped PMAs can be produced by Viscoplex. ® Viscosity index improvers 3-201 and / or 3-162 are available from Evonik.

[0117] According to one implementation, the non-dispersive comb-shaped PMA is composed of a structure called Viscoplex. ® The compound of 3-201 is provided, comprising comb-shaped PMA as the major resin component. The non-dispersed comb-shaped 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 ratio of 5.92. The compound has at least one building block derived from a macromonomer with an Mn of 500 or greater. The non-dispersed comb-shaped PMA is present in an amount of 19% by weight based on the total weight of the compound.

[0118] According to another implementation, the non-dispersive comb-shaped PMA is composed of a structure called Viscoplex. ® Compound 3-162 is provided, which also contains comb-shaped PMA as the main resin component. This non-dispersed comb-shaped PMA has 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 ratio of 1.94, and a shear stability index (SSI) of 0.6.

[0119] According to another embodiment, the nondispersive comb-shaped PMA is composed of a combination of compounds, such as Viscoplex. ® 3-201 and Viscoplex ® A combination of 3-162 is available.

[0120] Non-dispersed comb-shaped PMA is typically present in amounts of 0.5% to 25% by weight, 1% to 20% by weight, 2% to 18% by weight, 4% to 16% by weight, or 5% to 15% by weight, based on the total weight of the lubricating oil composition.

[0121] Other viscosity modifiers

[0122] Linear poly(meth)acrylates (PMAs) are generally synthesized via simple free radical copolymerization of mixtures of different alkyl methacrylates. Unlike comb-shaped PMAs, conventional linear PMAs are characterized by a predominantly short alkyl chain length (typically 1-50 carbon atoms) and lack the long alkyl chain macromonomers that impart the characteristic shape of comb-shaped polymers. PMAs allow for superior low-temperature rheological properties compared to OCPs. On the other hand, PMAs are generally less efficient at thickening than OCPs, thus requiring higher concentrations to achieve the same effect. See U.S. Patents 3,607,749 and 8,778,857, and European Patent 0225,598.

[0123] Olefin copolymer (OCP) viscosity modifiers with high thickening efficiency offer advantages in multi-grade finished lubricants, reducing formulation costs and the risk of deposit formation. This benefit stems from the reduced use of polymers in the overall formulation. Traditionally and as is known in the art, the thickening efficiency of OCPs has been increased by maximizing ethylene content, but this exposes the polymers to the risk of low-temperature performance defects in the finished lubricant. Low-temperature drawbacks can be mitigated by using blends of amorphous and semi-crystalline ethylene-based copolymers in lubricant formulations, which have allowed for improvements in thickening efficiency, shear stability index, low-temperature viscosity properties, and pour point. See, for example, U.S. Patents 7,402,235 and 5,391,617, and European Patent 0638,611.

[0124] Hydrogenated styrene-diene (HSD) viscosity index improvers can be prepared by copolymerizing styrene and butadiene and hydrogenating the unsaturated copolymer. The hydrogenated styrene-diene copolymer can be a linear block copolymer or a star-shaped copolymer. Star-shaped HSD copolymers exhibit superior shear stability compared to their linear counterparts due to their radial structure, resisting polymer degradation even under harsh engine operating conditions and reducing permanent viscosity reduction in lubricating oils. See examples of HSD copolymers as viscosity modifiers in lubricating oils in U.S. Patent Nos. 4,116,917, 3,772,196, and 4,788,316.

[0125] Example

[0126] The following examples are intended for illustrative purposes only and do not limit the scope of this disclosure in any way.

[0127] Each embodiment and comparative embodiment of the invention is formulated from the following mixture: a succinimide dispersant post-treated with borate and ethylene carbonate, a superalkaline calcium sulfonate cleaner, an amine antioxidant, a borate ester friction modifier, a molybdenum succinimide complex, a mixture of primary and secondary ZnDTP, and small amounts of foam inhibitors and polymethacrylate-based pour point depressants. Furthermore, some examples also contain a superalkaline calcium salicylate cleaner and / or a neutral calcium sulfonate cleaner.

[0128] Table 1 summarizes the metal content and metal sources present in Examples 1 to 7 and Comparative Examples 1 to 7. Each sample also contains a non-dispersed comb-shaped PMA viscosity modifier, an olefin copolymer viscosity modifier, a linear PMA viscosity modifier, or a styrene-isoprene copolymer viscosity modifier. The remainder of the lubricating composition consists of Group III base oils. Table 1 also includes the viscoelastic properties of the samples.

[0129] Table 1

[0130]

[0131]

[0132]

[0133] Boron is derived from boronized succinimide dispersants. Calcium can be derived from at least three different detergent sources: a superalkaline calcium sulfonate with a TBN of 425 mg KOH / g and a Ca content of 16.1 wt% based on the concentrate; a superalkaline 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 superalkaline calcium sulfonate detergent with a TBN of 17 mg KOH / g and a Ca content of 2.3 wt% based on the concentrate.

[0134] The sample also contained phosphorus, derived from an approximately 2:1 mixture of primary and secondary dialkyl dithiophosphate zinc. Molybdenum was derived from molybdenum succinimide antioxidant.

[0135] Miniature rotational viscometer (MRV) testing

[0136] In this modified MRV test, the test oil is first mixed with 10% by weight of water at 10,000 rpm for 1 minute, and then cooled to the test temperature (-35°C in this case) in a micro rotational viscometer cell and held for 24 hours. Each cell contains a calibrated rotor-stator assembly, in which the rotor is rotated by a rope wound around a rotor shaft and attached to a weight. Starting with a weight of 10 g, a series of progressively increasing weights are applied to the rope until rotation occurs to determine the yield stress. The result is reported as the yield stress as the applied force in Pascals. Then, a weight of 150 g is applied to determine the apparent viscosity of the oil. The higher the apparent viscosity, the more likely the oil may not be able to be continuously and adequately supplied to the oil pump inlet. The result is reported as the viscosity in centipoises.

[0137] The MRV test results for each of these lubricant compositions are listed in Table 2 below. The examples passed the MRV test, while the comparative examples failed the MRV test.

[0138] Table 2

[0139]

[0140] While this disclosure is susceptible to various modifications and alternatives, specific embodiments thereof are described in detail herein. However, it should be understood that the description of specific embodiments herein is not intended to limit this disclosure to the particular form disclosed, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the disclosure as defined by the appended claims.

[0141] Please note that not all activities described in the general description or embodiments are necessary, and a particular activity may not be required. Furthermore, one or more further activities may be performed in addition to the described activities. Also, the order in which the activities are listed does not necessarily represent the order in which they are performed.

[0142] The benefits, other advantages, and solutions to the problems have been described herein with respect to specific embodiments. However, the benefits, advantages, solutions to the problems, and any features that may lead to or make more apparent any benefit, advantage, or solution should not be construed as key, essential, or fundamental features of any or all claims.

[0143] The descriptions and illustrations of the implementation schemes described herein are intended to provide a general understanding of the structure of the various implementation schemes.

[0144] As used herein, the terms “comprises / comprising,” “includes / including,” “has / having,” or any other variation thereof are intended to cover non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a list of features is not necessarily limited to those features, but may include other features not expressly listed or other features inherent to such a process, method, article, or apparatus. Furthermore, unless expressly stated to the contrary, “or” refers to inclusive or rather, not exclusive or. For example, condition A or B satisfies any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); and both A and B are true (or exist).

[0145] The term "an" or "a" is used to describe the elements and components described herein. This is done solely for convenience and to give a general meaning to the scope of embodiments of this disclosure. This description should be understood to include an or at least one, and the singular includes the plural, and vice versa, unless clearly intended otherwise. When referring to a value, the term "average" is intended to mean the mean, geometric mean, or median. Group numbers corresponding to columns within the periodic table use the "new notation" convention as seen in the CRC Handbook of Chemistry and Physics, 81st edition (2000-2001).

[0146] 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 pertains. Materials, methods, and examples are illustrative rather than limiting. For the purposes not described herein, many details regarding particular materials and processing behaviors are conventional and can be found in textbooks and other sources within the lubricants and oil and gas industries.

[0147] The description and illustrations are not intended to be an exhaustive and comprehensive description of all elements and characteristics of formulations, compositions, devices, and systems using the structures or methods described herein. Individual embodiments may also be provided in combination in a single embodiment, and conversely, various features described in the context of a single embodiment for brevity may also be provided individually or in any sub-combination. Furthermore, references to values ​​stated within the scope include every value within that scope. Many other embodiments may become apparent to a person skilled in the art only after reading this description. Other embodiments may be used and deduced from this disclosure, such that structural substitutions, logical substitutions, or other changes can be made without departing from the scope of this disclosure. Therefore, this disclosure should be considered illustrative rather than restrictive.

Claims

1. A lubricating oil composition for a hybrid engine, comprising: (a) The main amount of oil with lubricating viscosity; (b) A boron-oxidized dispersant, wherein the amount provides 40 ppm to 400 ppm of boron to the lubricating oil composition; (c) A superalkaline calcium salicylate or a mixture of superalkaline calcium sulfonate and superalkaline calcium salicylate present in the form of calcium in an amount of 800 ppm to 1800 ppm, each having a total base number greater than 150 mg KOH / g as measured by the method of ASTM D-2896. (d) Zinc dithiophosphate (ZnDTP), in an amount that provides the lubricating oil composition with 100 ppm to 800 ppm of phosphorus; and (e) Non-dispersed comb-shaped polymethyl methacrylate (PMA) viscosity index improver VII, and The KV of the lubricating oil composition at 100°C is 6 cSt to 8.5 cSt, the KV of the lubricating oil composition at 40°C is 25 cSt to 35 cSt, and the VI of the lubricating oil composition is greater than 200.

2. The lubricating oil composition of claim 1, further comprising: One or more magnesium-containing cleaning agents, wherein the amount provides 100 ppm to 600 ppm of magnesium to the lubricating oil composition.

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

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

5. The lubricating oil composition of claim 1, further comprising a friction modifier, an ashless anti-wear additive, an antioxidant, a metal passivator, a sealing swelling additive, a foam inhibitor, or a viscosity modifier.

6. The lubricating oil composition of claim 1, wherein the zinc dithiophosphate is dialkyl zinc dithiophosphate.

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

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

9. A method of lubricating a hybrid power engine, the method comprising providing a lubricating oil composition to the hybrid power engine, the lubricating oil composition comprising: (a) The main amount of oil with lubricating viscosity; (b) A boronizing dispersant, wherein the amount of boron provided by the lubricating oil composition is from 40 ppm to 400 ppm; (c) A superalkaline calcium salicylate or a mixture of superalkaline calcium sulfonate and superalkaline calcium salicylate present in the form of calcium in an amount of 800 ppm to 1800 ppm, each having a total base number greater than 150 mg KOH / g as measured by ASTM D-2896. (d) Zinc dithiophosphate (ZnDTP), in an amount providing 100 ppm to 800 ppm of phosphorus to the lubricating oil composition; (e) Non-dispersed comb-shaped polymethyl methacrylate (PMA) viscosity index improver VII, The KV of the lubricating oil composition at 100°C is 6 cSt to 8.5 cSt, the KV of the lubricating oil composition at 40°C is 25 cSt to 35 cSt, and the VI of the lubricating oil composition is greater than 200.

10. The method of claim 9, wherein the lubricating oil composition further comprises: One or more magnesium-containing cleaning agents, wherein the amount provides 100 ppm to 600 ppm of magnesium to the lubricating oil composition.

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

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

13. The method of claim 9, wherein the lubricating oil composition further comprises a friction modifier, an ashless anti-wear additive, an antioxidant, a metal passivator, a sealing swelling additive, a foam inhibitor, or a viscosity modifier.

14. The method of claim 9, wherein the zinc dithiophosphate is dialkyl zinc dithiophosphate.

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

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

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