Low-dispersion, high-VI engine oil for improving fuel efficiency

Abstract

A lubricating composition is disclosed, comprising: an oil having a lubricating viscosity in the majority of the volume; a non-boronating dispersant; a boronating dispersant in an amount sufficient to impart less than about 160 ppm of boron to the lubricating composition, wherein the combination of the non-boronating dispersant and the boronating dispersant imparts at least about 250 ppm of nitrogen to the lubricating composition; a molybdenum-containing compound in an amount sufficient to impart at least about 400 ppm of molybdenum to the lubricating composition, wherein the molybdenum-containing compound includes molybdenum dithiocarbamate; a perbasic calcium salicylate detergent; and a viscosity index improver (VII), wherein the high-temperature high-shear viscosity (HTHS100) of the lubricating composition at 100°C is 3.0 mPa·s to 4.5 mPa·s.

Description

[Technical Field]

[0001] Designing automotive lubricants that improve fuel efficiency while simultaneously maintaining the suppression of wear, deposits, and / or varnish has long been a critical challenge for lubricant manufacturers. While fuel efficiency can be improved by reducing the viscosity of the lubricant, this approach appears to be approaching the limits of current equipment capabilities. Various friction modifiers (FMs) are used to reduce surface friction in engines and thereby improve fuel efficiency, but the use of FMs is often limited by their undesirable effects, such as deposit formation and seal degradation. Therefore, there is a clear need for novel methods to improve fuel efficiency through new lubricant formulations. [Overview of the Initiative]

[0002] This disclosure provides a method for improving the fuel efficiency of an internal combustion engine by lubricating engine components with a composition containing a low-addition boronating dispersant, a molybdenum-based friction modifier such as molybdenum dithiocarbamate (MoDTC), a calcium salicylate detergent, and a comb-type viscosity index improver. The viscosity index improver maintains appropriate lubricant viscosity even at high engine operating temperatures, while the combination of the dispersant, friction modifier, and salicylate detergent works synergistically to provide protection against wear and deposits.

[0003] By using the disclosed high viscosity index lubricating compositions, it is possible to achieve a significant improvement in fuel efficiency while maintaining good wear and deposit suppression. The disclosed lubricating compositions are suitable for use in internal combustion engines equipped with roller follower valve trains.

[0004] This disclosure relates to an automotive engine lubrication composition comprising: a) an oil having a majority of the lubrication viscosity; b) a non-boronating dispersant; c) a boronating dispersant in an amount sufficient to impart less than about 160 ppm of boron to the lubrication composition, wherein the combination of the non-boronating dispersant and the boronating dispersant imparts at least about 250 ppm of nitrogen to the lubrication composition; d) a molybdenum-containing compound in an amount sufficient to impart at least about 400 ppm of molybdenum to the lubrication composition, wherein the molybdenum-containing compound includes molybdenum dithiocarbamate; e) a perbasic calcium salicylate detergent; and f) a viscosity index improver (VII), wherein the high-temperature high-shear viscosity (HTHS100) of the lubrication composition at 100°C is 3.0 mPa·s to 4.5 mPa·s.

[0005] The present disclosure further relates to a method for improving the fuel efficiency of an internal combustion engine equipped with a roller follower valve train, comprising lubricating the internal combustion engine with a lubricating composition comprising: a) an oil having a majority of the lubricating viscosity; b) a non-boronating dispersant; c) a boronating dispersant in an amount sufficient to give the lubricating composition less than about 160 ppm of boron, wherein the combination of the non-boronating dispersant and the boronating dispersant gives the lubricating composition at least about 250 ppm of nitrogen; d) a molybdenum-containing compound in an amount sufficient to give the lubricating composition at least about 400 ppm of molybdenum, wherein the molybdenum-containing compound comprises molybdenum dithiocarbamate; e) a perbasic calcium salicylate detergent; and f) a viscosity index improver (VII).

[0006] The disclosure further relates to the use of a lubricating composition for improving the fuel efficiency of an internal combustion engine, wherein the lubricating composition comprises: a) an oil having a majority of the lubricating viscosity; b) a non-boronating dispersant; c) a boronating dispersant in an amount sufficient to give the lubricating composition less than about 160 ppm of boron, wherein the combination of the non-boronating dispersant and the boronating dispersant gives the lubricating composition at least about 250 ppm of nitrogen; d) a molybdenum-containing compound in an amount sufficient to give the lubricating composition at least about 400 ppm of molybdenum, wherein the molybdenum-containing compound includes molybdenum dithiocarbamate; e) a perbasic calcium salicylate detergent; and f) a viscosity index improver (VII). [Modes for carrying out the invention]

[0007] This disclosure is subject to various modifications and alternative forms, and specific embodiments 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 any particular form, but rather to encompass all modifications, equivalents, and alternatives that fall within the spirit and scope of this disclosure as defined by the appended claims.

[0008] To facilitate understanding of the subject matter disclosed herein, several terms, abbreviations, or other abbreviations used herein are defined below. Any term, abbreviation, or abbreviation not defined herein is understood to have the ordinary meaning used by a person skilled in the art at the time of filing this application.

[0009] As used herein, the following terms have the meanings set forth below unless otherwise specified. In this specification, the following words and expressions have the meanings given below when used.

[0010] "More than half" means more than 50% by weight of the composition.

[0011] "Small amount" means less than 50% by weight of the composition when expressed as the active ingredient of one or more additives relative to the additive(s) described and relative to the total weight of all additives present in the composition.

[0012] "Active ingredient" or "active agent" or "oil-free" refers to an additive substance that is neither a diluent nor a solvent.

[0013] All percentages described are, unless otherwise specified, weight percentages based on the active ingredient (i.e., regardless of carrier or diluent oil).

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

[0015] The high temperature high shear (HTHS100) viscosity at 100 °C was measured in accordance with ASTM D6616.

[0016] The high temperature high shear (HTHS150) viscosity at 150 °C was measured in accordance with ASTM D4683.

[0017] The shear stability index (SSI) is measured in accordance with ASTM D6278.

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

[0019] The term "oil-soluble" means that for a particular additive, the amount necessary to provide the desired level of activity or performance can be added by dissolving, dispersing, or suspending it in an oil of lubricating viscosity. Usually, this means that at least 0.001% by weight of the additive can be added to the lubricating composition.

[0020] An "engine" or "combustion engine" is a heat engine in which combustion of fuel occurs in a combustion chamber. An "internal combustion engine" is a heat engine in which combustion of fuel occurs in a closed space ("combustion chamber"). A "spark-ignition engine" is a heat engine in which combustion is ignited, usually by a spark from a spark plug. This is in contrast to a "compression-ignition engine" (usually a diesel engine), in which the heat generated by fuel injection and compression is sufficient to start combustion without an external spark.

[0021] A "roller follower valve train" is a specific type of mechanism for opening and closing the intake and exhaust valves of an internal combustion engine, and includes a roller ring and finger follower mechanism positioned between the cam and the rocker arm.

[0022] As used herein, the terms "Total Base Count" or "TBN" refer to the amount of bases equivalent to milligrams of KOH in one gram of sample. Therefore, a higher TBN value indicates a greater amount of alkali product and thus higher alkalinity. TBN was measured using the ASTM D2896 test.

[0023] The boron, calcium, magnesium, molybdenum, phosphorus, sulfur, and zinc content was measured according to ASTM D5185.

[0024] Nitrogen content was measured according to ASTM D4629.

[0025] All ASTM standards referenced herein are the most current versions as of the filing date of this application.

[0026] Unless otherwise specified, all percentages are weight percentages.

[0027] This disclosure provides a lubricating composition comprising a) an oil of lubricating viscosity, b) a non-boronating dispersant, c) a boronating dispersant, d) a molybdenum-containing compound, e) a perbasic calcium salicylate detergent, and f) a viscosity index improver (VII), wherein the high-temperature high-shear viscosity (HTHS100) of the lubricating composition at 100°C is 3.0 mPa·s to 4.5 mPa·s. This lubricating composition is particularly suitable for internal combustion engines equipped with a direct-acting valve train or a roller-follower valve train, and is particularly suitable for engines equipped with a roller-follower valve train.

[0028] Furthermore, this specification also provides a method for improving the combustion efficiency of an internal combustion engine equipped with a roller follower valve train. The use of lubricating compositions for improving fuel efficiency of an internal combustion engine equipped with a roller follower valve train is also provided.

[0029] Lubricating viscosity of oil Oils with lubricating viscosity (sometimes referred to as "base stock" or "base oil") are the main liquid component of lubricants, and are combined with additives and, optionally, other oils to produce, for example, the final lubricant (or lubricant composition). Base oils are useful in producing concentrates and from which lubricating compositions are made, and can be selected from natural and synthetic lubricants, or combinations thereof.

[0030] Natural oils include animal and vegetable oils, liquid petroleum, and hydrorefined and solvent-treated mineral lubricants of the paraffinic, naphthenic, and mixed paraffinic-naphthenic types. Oils with lubricating viscosity derived from coal or shale are also useful base oils.

[0031] Examples of synthetic lubricants include polymerized and copolymerized olefins (e.g., hydrocarbon oils such as polybutylene, polypropylene, propylene-isobutylene copolymer, chlorinated polybutylene, poly(1-hexene), poly(1-octene), and 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 homologs. Polymerized olefins can also be derived from bio-derived sources such as hydrocarbon terpenes such as myrcene, ocimene, and farnesene, which can copolymerize with other olefins and, if necessary, can be further isomerized.

[0032] Another suitable class of synthetic lubricants includes 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, suberic acid, sebacic acid, adipic acid, linoleic acid dimer, phthalic acid) and various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelaate, diisodecyl azelaate, dioctyl phthalate, didecyl phthalate, dieicosyl 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.

[0033] Esters useful as synthetic oils include C5-C 12Examples include esters produced from monocarboxylic acids and polyols, as well as polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol.

[0034] Furthermore, esters derived from biological sources are also useful as synthetic oils.

[0035] Base oils can also be derived from Fischer-Tropsch synthetic hydrocarbons. Fischer-Tropsch synthetic hydrocarbons are produced from synthesis gas containing H2 and CO using a Fischer-Tropsch catalyst. Such hydrocarbons usually require further processing to be useful as base oils. For example, hydrocarbons can be subjected to hydrogen isomerization, hydrocracking and hydrogen isomerization, dewaxing, or hydrogen isomerization and dewaxing using processes well known to those skilled in the art.

[0036] The base oil may be a renewable or bio-derived 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-derived 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 hydrocarbon is produced from fatty acids or fatty acid esters.

[0037] Unrefined oils, refined oils, and re-refined oils may be used in this lubricating composition. Unrefined oils are those obtained directly from natural or synthetic sources without further refining. For example, shale oil obtained directly from a carbonization operation, petroleum obtained directly from distillation, or ester oil obtained directly from an esterification process and used without further processing are unrefined oils. Refined oils are similar to unrefined oils, except that they have been further processed in one or more refining steps to improve one or more properties. Many such refining techniques, such as distillation, solvent extraction, acid or base extraction, filtration, and osmosis, are well known to those skilled in the art.

[0038] Refined oil can also be obtained by processes similar to those used to obtain refined oil, which are applied to refined oil that has already been used. Such refined oil is also known as recovered oil or recycled oil and is often further processed by techniques to remove spent additives and oil decomposition products.

[0039] Therefore, the base oil that can be used to manufacture the lubricating composition of the present invention can be selected from any of the base oils in Groups I to IV summarized in Table 1 below. [Table 1]

[0040] Suitable base oils for use as described herein are any of the types corresponding to API Group II, Group III, Group IV, and Group V oils, or combinations thereof. In some embodiments, suitable base oils include Group III to Group V oils due to their excellent volatility, stability, viscosity, and detergency properties.

[0041] In the lubricating compositions of this disclosure, the oil (also called the base oil) of a lubricating viscosity for use may be present in a majority amount, for example, more than about 50% by weight. In some embodiments, the base oil may be present in an amount greater than about 70% by weight. In some embodiments, the base oil may be present in an amount of about 80% to about 99.5% by weight. In some embodiments, the base oil may be present in a maximum amount of about 85% to about 98% by weight. Where used herein, the expression “base oil” should be understood to mean a base stock or mixture of base stocks that is a lubricating component manufactured by a single manufacturer to the same specifications (regardless of the source or location of the manufacturer), meeting the specifications of the same manufacturer and identified by a unique chemical formula, product identification number, or both. The base oil as used herein may be any oil of currently known or future-discovered lubricating viscosity used in formulating the lubricating compositions.

[0042] The viscosity of a base oil is determined by its application. Therefore, the viscosity of base oils used herein can typically range from approximately 2 to approximately 2000 centistokes (cSt) at 100 degrees Celsius (°C). Generally, the kinematic viscosity range at 100°C for individual base oils used as engine oils is approximately 2 cSt to approximately 30 cSt, approximately 3 cSt to approximately 16 cSt, or approximately 4 cSt to approximately 12 cSt.

[0043] The lubricating composition may be a multigrade oil having viscosity grades such as SAE 0W-8, 0W-12, 0W-16, 0W-20, 0W-26, 0W-30, 0W-40, 0W-50, 0W-60, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W-20, 10W-30, 10W-40, 10W-50, 15W, 15W-20, 15W-30, and 15W-40.

[0044] The lubricating compositions disclosed herein may contain an oil having a lubricating viscosity of more than half the volume. In some embodiments, the lubricating viscosity oil may be a base oil of group II, a base oil of group III, a base oil of group IV, a base oil of group V, or a combination thereof. In some embodiments, the lubricating viscosity oil may be a base oil of group III.

[0045] In some embodiments, the high-temperature high-shear viscosity (HTHS100) of the lubricating composition at 100°C may be between 1.0 mPa·s and 6.5 mPa·s, for example, between 1.5 mPa·s and 6.0 mPa·s, 2.0 mPa·s and 5.5 mPa·s, between 2.5 mPa·s and 5.0 mPa·s, between 2.7 mPa·s and 4.7 mPa·s, or between 3.0 mPa·s and 4.5 mPa·s.

[0046] Non-boronated dispersant Exemplary lubricating compositions disclosed herein may include non-boronized dispersants. Non-boronized dispersants include succinimide dispersants, such as those described herein, that have not been post-treated with a boron source.

[0047] Suitable dispersants include hydrocarbyl succinimide, mixed esters / amides of hydrocarbyl-substituted succinic acid, hydroxy esters of hydrocarbyl-substituted succinic acid, and Mannich condensation products of hydrocarbyl-substituted phenols, formaldehyde, and polyamines. Condensation products of polyamines and hydrocarbyl-substituted phenyl acids are also suitable. A mixture of these dispersants can also be used.

[0048] In one embodiment, polyalkenylbis-succinimide is the following polyalkenyl-substituted succinic anhydride [ka] This can be obtained by reacting a polyamine with a polyalkenyl substituent (wherein R is a polyalkenyl substituent derived from a polyalkene group having a number average molecular weight of about 500 to about 3000). In one embodiment, R is a polyalkenyl substituent derived from a polyalkene group having a number average molecular weight of about 1000 to about 2500. In another embodiment, R is a polyisobutenyl substituent derived from polyisobutene having a number average molecular weight of about 500 to about 3000.

[0049] In some embodiments, the amine preferred for the reaction to form succinimide can be a polyamine having 2 to 60 carbon atoms and 2 to 12 nitrogen atoms per molecule. In some embodiments, the amine includes a polyalkyleneamine represented by the following chemical formula: NH2(CH2) n -(NH(CH2) n ) m -NH2(II) (wherein n is 2 to 3 and m is 0 to 10). Exemplary examples include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, and commercially available mixtures of such polyamines. Amines containing other groups such as hydroxy, alkoxy, amide, nitride, and imidazoline groups can also be used in the same way as polyoxyalkylene polyamines. Particularly suitable polyalkylene polyamines are those of the formula H2N-(R'NH) x -H (wherein R' is a linear or branched alkylene group having 2 or 3 carbon atoms, and x is 1 to 9). Typical examples of suitable polyalkylene polyamines include ethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, pentaethylenehexamine, and heavy polyamines (e.g., ethyleneamine E-100 available from Huntsman Company).

[0050] The amine can be reacted with an alkenyl succinic acid or anhydride in a conventional molar ratio of about 1:1 to 10:1 or 1:1 to 3:1 between alkenyl succinic acid or anhydride and the polyamine, or in a molar ratio of about 1:1 between alkenyl succinic acid or anhydride and the polyamine, typically by heating the reactants at 100°C to 250°C or 125°C to 175°C for 1 to 10 hours. In some embodiments, the amine is reacted by heating the reactants for about 2 to 6 hours.

[0051] Boronated dispersant Exemplary lubricating compositions disclosed herein may contain boronating dispersants. The boronating dispersants may be present in amounts that impart boron to the lubricating composition in amounts of about 300 ppm, about 250 ppm, about 200 ppm, about 180 ppm, or less than about 160 ppm. In some embodiments, the boronating dispersants may be included in amounts that impart boron to the lubricating composition in amounts of about 30 ppm to about 300 ppm, about 40 ppm to about 250 ppm, about 50 ppm to about 200 ppm, about 60 ppm to about 190 ppm, about 70 ppm to about 180 ppm, about 80 ppm to about 170 ppm, or about 90 ppm to about 160 ppm.

[0052] Some lubricating compositions disclosed herein include combinations of non-boronated dispersants and boronated dispersants. The combination of non-boronated dispersants and boronated dispersants may be present in an amount sufficient to impart at least about 100 ppm, about 150 ppm, about 200 ppm, about 210 ppm, about 220 ppm, about 230 ppm, about 240 ppm, or about 250 ppm of nitrogen to the lubricating composition. In some embodiments, the dispersant combination may be present in an amount sufficient to provide the lubricating composition with nitrogen at approximately 100 ppm to 1500 ppm, 150 ppm to 1000 ppm, 200 ppm to 800 ppm, 230 ppm to 700 ppm, 250 ppm to 600 ppm, 270 ppm to 580 ppm, 300 ppm to 560 ppm, or 320 ppm to 540 ppm.

[0053] The total amount of non-boronated dispersants and boronated dispersants present in the lubricating composition can be approximately 0.5% to 7.0% by weight, approximately 0.6% to 6.0% by weight, approximately 0.7% to 5.5% by weight, approximately 0.8% to 5.0% by weight, approximately 0.9% to 4.5% by weight, approximately 1.0% to 4.0% by weight, approximately 1.1% to 3.8% by weight, approximately 1.2% to 3.6% by weight, approximately 1.4% to 3.4% by weight, or approximately 1.5% to 3.2% by weight.

[0054] Examples of boronated dispersants include boronated ashless dispersants such as boronated polyalkenyl succinic anhydrides; boronated non-nitrogen-containing derivatives of polyalkylene succinic anhydrides; copolymers containing carboxylic acid esters having one or more further polar functional groups, including 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 their derivatives), triazoles (e.g., alkyltriazoles and benzotriazoles), amines, amides, imines, imides, hydroxyls, carboxyls, etc. (e.g., products prepared by copolymerization of long-chain alkyl acrylates or methacrylates with monomers having the above functions); and boronated basic nitrogen compounds selected from the group consisting of these and combinations thereof. In some cases, the boronating dispersant is a succinimide derivative of boron, such as borated polyisobutenyl succinimide.

[0055] Examples of boronated ashless dispersants include ashless hydrocarbyl succinimide borooxide dispersants prepared by reacting hydrocarbyl succinic acid or an anhydride with an amine. In some examples, the hydrocarbyl succinic acid or anhydride is derived from a C3 or C4 monoolefin polymer, particularly polyisobutylene, and the polyisobutenyl group has a number average molecular weight (M) of about 700 to about 5,000, or about 900 to about 2,500. n) are the dispersants having. Such dispersants generally have at least one, one to two, or 1.1 to 1.8 succinic acid groups for each polyisobutenyl group. In one embodiment, an oil-soluble or oil-dispersible borated polyisobutylene succinimide dispersant is derived from a polyisobutylene group having a number average molecular weight of about 550 to about 5000. In one embodiment, an oil-soluble or oil-dispersible borated polyisobutylene succinimide dispersant is derived from a polyisobutylene group having a number average molecular weight of about 550 to about 4000. In one embodiment, an oil-soluble or oil-dispersible borated polyisobutylene succinimide dispersant is derived from a polyisobutylene group having a number average molecular weight of about 550 to about 3000. In one embodiment, an oil-soluble or oil-dispersible borated polyisobutylene succinimide dispersant is derived from a polyisobutylene group having a number average molecular weight of about 550 or more to about 2300. In one embodiment, the oil-soluble or oil-dispersible borated 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 borated 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 borated 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 borated polyisobutylene succinimide dispersant is derived from polyisobutylene groups having a number average molecular weight of about 1700. In one embodiment, the oil-soluble or oil-dispersible borated polyisobutylene succinimide dispersant is derived from polyisobutylene groups having a number average molecular weight of about 1000.

[0056] Boronization of alkenyl succinimide dispersants is also described in U.S. Patents No. 3,087,936 and 3,254,025. Succinimide can be treated, for example, with a boron compound selected from the group consisting of boron, boron oxide, boron halides, boronic acids, and their esters, in an amount that gives boron at an atomic ratio of 0.1 to 10 relative to each atomic ratio of nitrogen in the dispersant.

[0057] The boration product can generally contain about 0.1 wt.% to 2.0 wt.% or about 0.2 wt.% to 0.8 wt.% of boron relative to the total weight of the boration dispersant. The boron is thought to exist as a dehydrated boric acid polymer bonded to the metaborate of the imide. The borooxidation reaction is easily carried out by adding about 1 wt% to 3 wt% (relative to the weight of the dispersant) of the above boron compound (e.g., boric acid) as a slurry in mineral oil to the dispersant, heating with stirring at 135°C to 165°C for 1 to 5 hours, and then filtration of the product by nitrogen stripping. Alternatively, boric acid can also be added to a high-temperature reaction mixture of succinic acid or anhydride and an amine, while removing water.

[0058] Molybdenum-containing compounds The lubricating compositions disclosed herein may include molybdenum-containing compounds, including molybdenum dithiocarbamate (MoDTC). The molybdenum-containing compounds may further include molybdenum-amine complexes, molybdenum dithiophosphates, or combinations thereof. Suitable molybdenum-containing compounds are described herein.

[0059] The molybdenum-containing compound can be included in an amount sufficient to provide at least about 200 ppm, about 250 ppm, about 300 ppm, about 350 ppm, about 400 ppm, about 450 ppm, or about 500 ppm of molybdenum to the lubricating composition. In some embodiments, the molybdenum-containing compound can be present in an amount sufficient to provide from about 200 ppm to about 2000 ppm, from about 300 ppm to about 1800 ppm, from about 400 ppm to about 1600 ppm, from about 500 ppm to about 1500 ppm, from about 600 ppm to about 1400 ppm, from about 700 ppm to about 1300 ppm, from about 800 ppm to about 1200 ppm, or from about 900 ppm to about 1100 ppm of molybdenum to the lubricating composition.

[0060] The molybdenum-containing compound can have the functional performance of an antiwear agent, an antioxidant, a friction modifier, or a mixture thereof. Examples of the molybdenum-containing compound include molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, molybdenum dithiophosphinate, amine salts of molybdenum compounds, molybdenum xanthate, molybdenum thioxanthate, molybdenum sulfide, molybdenum carboxylate, molybdenum alkoxide, trinuclear organic molybdenum compounds, molybdenum esters, molybdenum amides, and / or mixtures thereof. Examples of molybdenum sulfide include molybdenum disulfide. Molybdenum disulfide can be in the form of a stable dispersion. In one embodiment, the molybdenum-containing compound can be selected from the group consisting of molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the molybdenum-containing compound can be molybdenum dithiocarbamate.

[0061] Molybdenum dithiocarbamate (MoDTP) is an organomolybdenum compound represented by the following structure:

Chemical formula

[0062] Generally, MoDTC can be prepared by reacting molybdenum trioxide or a molybdate with an alkali sulfide or alkali hydrosulfide, then adding carbon disulfide and a secondary amine to the reaction mixture, and reacting the resulting mixture at a suitable temperature. To prepare molybdenum dithiocarbamate, it is sufficient to use secondary amines with different hydrocarbon groups in the above process, or to use two or more different secondary amines. Symmetrical molybdenum dithiocarbamate can be prepared in a similar manner, except that only one secondary amine is used.

[0063] Suitable molybdenum dithiocarbamate compounds include, but are not limited to, molybdenum dibutyldithiocarbamate, molybdenum dipentyldithiocarbamate, molybdenum dihexyldithiocarbamate, molybdenum dioctyldithiocarbamate, molybdenum didecyldithiocarbamate, molybdenum didodecyldithiocarbamate, molybdenum ditridecyldithiocarbamate, molybdenum di(butylphenyl)dithiocarbamate, or molybdenum di(nonylphenyl)dithiocarbamate.

[0064] In some embodiments, the molybdenum-containing compound further comprises molybdenum dithiophosphate. Molybdenum dithiophosphate (MoDTP) is an organic molybdenum compound represented by the following structure. [ka] In the formula, R 5 , R 6 , R 7 , and R 8Each of these is independently an alkyl group, alkenyl group, cycloalkyl group, or cycloalkenyl group having 4 to 18 carbon atoms (e.g., 8 to 13 carbon atoms), or an aryl group having 6 to 18 carbon atoms. The alkyl group or alkenyl group may be linear, branched, or a mixture thereof.

[0065] Suitable molybdenum dithiophosphate compounds include, but are not limited to, dibutyl molybdenum dithiophosphate, dipentyl molybdenum dithiophosphate, dihexyl molybdenum dithiophosphate, dioctyl molybdenum dithiophosphate, didecyl molybdenum dithiophosphate, didodecyl molybdenum dithiophosphate, ditridecyl molybdenum dithiophosphate, di(butylphenyl) molybdenum dithiophosphate, or di(nonylphenyl) molybdenum dithiophosphate.

[0066] In some embodiments, the molybdenum-containing compound further comprises a molybdenum-amine complex. In some embodiments, the molybdenum-amine complex may be 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 process comprising reacting an acidic molybdenum compound with an alkyl or alkenyl succinimide of a polyamine having the following structure or a mixture thereof: [ka] (In the formula, R is C 24 ~C 350 (For example, C 70 ~C 128 ) is an alkyl or alkenyl group, where R' is a linear or branched alkylene group having 2 to 3 carbon atoms, x is 1 to 11, and y is 1 to 10). The alkyl or alkenyl group may be linear, branched, or a mixture thereof.

[0067] Generally, the acidic molybdenum compounds used to prepare molybdenum succinimide complexes are hexavalent. "Acidic" means that the molybdenum compound reacts with basic nitrogen compounds when measured by ASTM D664 or D2896. Typical examples of suitable acidic molybdenum compounds include molybdenum trioxide, molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other molybdenum salts such as other alkali metal molybdates and hydrogen salts (e.g., sodium hydrogen molybdate), MoOCl4, MoO2Br2, and Mo2O3Cl6.

[0068] Succinimides that can be used to prepare molybdenum-succinimid complexes are disclosed in numerous references and are well known in the art. Specific basic types of succinimides and related substances encompassed by the term “succinimide” are taught in U.S. Patents 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 main product is succinimide, and the term has been widely accepted to mean the reaction product of alkyl-substituted or alkenyl-substituted succinic acid or anhydride with a nitrogen-containing compound. Certain succinimides are prepared by reacting polyisobutenyl succinic anhydride, having about 70 to about 128 carbon atoms, with a polyalkylene polyamine selected from triethylenetetramine, tetraethylenepentamine, and mixtures thereof.

[0069] Molybdenum succinimide complexes can be post-treated with a sulfur source at appropriate pressure and a temperature of 120°C or lower to obtain molybdenum succinimide sulfide complexes. The sulfidation process can be carried out over approximately 0.5 to 5 hours (for example, 0.5 to 2 hours). Suitable sulfur sources include elemental sulfur, hydrogen sulfide, phosphorus pentasulfide, and R2S. x Organic polysulfides (wherein R is hydrocarbyl (e.g., C1-C))10 It is alkyl, and x is at least 3), C1~C 10 It contains mercaptans, inorganic sulfides and inorganic polysulfides, thioacetamides, and thiourea.

[0070] Suitable examples of molybdenum-containing compounds that can be used include commercially available materials sold by RT Vanderbilt Co. Ltd. under trade names such as Molyvan 822®, Molyvan® A, Molyvan® 2000, and Molyvan® 855, as well as Sakura-Lube® S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710 sold by Adeka Corporation. Further suitable molybdenum compounds are described in U.S. Patent No. 5,650,381, U.S. Reissue Patent No. RE37,363E1, U.S. Reissue Patent No. 38,929E1, and U.S. Reissue Patent No. 40,595E1, which are incorporated herein by reference in their entirety.

[0071] Calcium salicylate cleaning agent The lubricating compositions of this disclosure include a perbasic calcium salicylate detergent. The perbasic calcium salicylate may be present in an amount sufficient to provide the lubricating composition with approximately 300 ppm to approximately 2500 ppm, approximately 400 ppm to approximately 2400 ppm, approximately 500 ppm to approximately 2300 ppm, approximately 600 ppm to approximately 2200 ppm, approximately 700 ppm to approximately 2100 ppm, approximately 800 ppm to approximately 2000 ppm, approximately 900 ppm to approximately 1900 ppm, approximately 1000 ppm to approximately 1800 ppm, approximately 1100 ppm to approximately 1700 ppm, or approximately 1200 ppm to approximately 1600 ppm of calcium.

[0072] Salicylate detergents 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 belong to one category of detergents prepared from carboxylic acids. Useful salicylates include long-chain alkyl salicylates. One useful category of compositions has the following structure: [ka] In the formula, R'' represents C1~C 30 (For example, C 13 ~C 30 ) is an alkyl group, n is an integer from 1 to 4, and M is an alkaline earth metal (e.g., Ca or Mg).

[0073] Hydrocarbyl-substituted salicylic acid can be prepared from phenol by the Kolbe reaction (see U.S. Patent No. 3,595,791). Metal salts of hydrocarbyl-substituted salicylic acid can be prepared by double decomposition of the metal salt in a polar solvent (such as water or alcohol).

[0074] Salts containing substantially stoichiometric amounts of metal are described as neutral salts and have a total base number (TBN) of 0 to approximately 80 mg KOH / g. Useful detergents may be neutral, slightly overbasic, or highly overbasic.

[0075] The term "overbasic" refers to metal salts such as sulfonates, salicylates, and phenates in which the amount of metal present exceeds the stoichiometric amount. Such salts can have a conversion rate greater than 100% (i.e., these salts may contain more than 100% of the metal required to convert an acid to its "normal" or "neutral" salt). The expression "metallic ratio," often abbreviated as MR, is used to specify the ratio of the total chemical equivalents of metal in an overbasic salt to the chemical equivalents of metal in a neutral salt, based on known chemical reactivity and stoichiometry. In normal or neutral salts, the metallic ratio is 1, and in overbasic salts, the MR is greater than 1. These are generally called overbasic salts, hyperbased salts, or superbased salts, and may be salts of organic sulfur acids, salicylic acids, or phenols.

[0076] The overbasic detergent has approximately 150 mg KOH / gram of TBN, approximately 250 mg KOH / gram or more of TBN, approximately 300 mg KOH / gram or more of TBN, approximately 350 mg KOH / gram or more of TBN, approximately 375 mg KOH / gram or more of TBN, or approximately 400 mg KOH / gram or more of TBN relative to the detergent concentrate.

[0077] The overbasic detergent may have a metal-to-substrate ratio of 1.1:1, 2:1, 4:1, 5:1, 7:1, or 10:1.

[0078] Magnesium cleaning agent The lubricating compositions of this disclosure may further comprise a magnesium detergent. The magnesium detergent of this disclosure may be included in an amount sufficient to provide the lubricating composition with magnesium in the following concentrations: about 100 ppm to about 2200 ppm, about 200 ppm to about 1000 ppm, about 250 ppm to about 900 ppm, about 300 ppm to about 800 ppm, about 350 ppm to about 700 ppm, about 400 ppm to about 600 ppm, or about 450 ppm to about 550 ppm.

[0079] In some embodiments, magnesium cleaning agents include magnesium sulfonate, magnesium carbohydrate, and magnesium salicylate, particularly magnesium sulfonate and magnesium salicylate. In one embodiment, the magnesium cleaning agent is magnesium sulfonate. Magnesium sulfonate may be neutral, slightly overbasic, or highly overbasic.

[0080] Sulfonates can be prepared from sulfonic acids typically obtained by sulfonation of alkyl-substituted aromatic hydrocarbons, such as those obtained from fractional distillation of petroleum, or by alkylation of aromatic hydrocarbons. Examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl, or their halogen derivatives. Alkylation can be carried out in the presence of an alkylating agent having about 3 to more than 70 carbon atoms and a catalyst. Alkyl sulfonates typically contain about 9 to 80 or more carbon atoms (e.g., about 16 to 60 carbon atoms) per alkyl-substituted aromatic moiety.

[0081] Charcoal salts can be prepared by reacting alkaline earth metal hydroxides or oxides (e.g., CaO, Ca(OH)2, MgO, or Mg(OH)2) with alkylphenols or alkyl sulfide phenols. Useful alkyl groups include linear or branched C1-C12 30 (For example, C4~C 20 Examples include alkyl groups or mixtures thereof. Suitable phenols include isobutylphenol, 2-ethylhexylphenol, nonylphenol, and dodecylphenol. It should be noted that the starting alkylphenol may contain more than one alkyl substituent, each being an independent linear or branched chain. When non-sulfurized alkylphenols are used, the sulfurization product can be obtained by methods well known in the art. These methods involve heating a mixture of alkylphenol and a sulfurizing agent (e.g., elemental sulfur, sulfur halides such as sulfur dichloride, and the like), and then reacting the sulfurized phenol with an alkaline earth metal base.

[0082] Salicylate detergents 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 belong to a category of detergents prepared from carboxylic acids. Useful salicylates include long-chain alkyl salicylates.

[0083] Viscosity index improver (VII) The lubricating compositions of this disclosure include a viscosity index improver (VII). In some embodiments, the viscosity index improver is linear (conventional) polymethacrylate (PMA) or comb-type polymethacrylate (PMA).

[0084] Viscosity index improvers in lubricating compositions have a shear stability index (SSI) of 50.0 or less, 40.0 or less, 30.0 or less, 25.0 or less, 20.0 or less, 15.0 or less, 10.0 or less, 5.0 or less, or 1.0 or less, as measured by ASTM method D6278. In some embodiments, the SSI of the viscosity index improver is 0.1 to 1.0, 0.2 to 0.9, 0.3 to 0.8, or 0.4 to 0.7. In some embodiments, the SSI of the viscosity index improver is 1.0 to 50.0, 5.0 to 40.0, 10.0 to 35.0, or 20.0 to 30.0.

[0085] The total amount of viscosity index improver present in the lubricating composition can be approximately 2.0% to 15.0% by weight, approximately 4.0% to 12.5% ​​by weight, approximately 5.0% to 11.0% by weight, approximately 5.5% to 10.5% by weight, approximately 6.0% to 10.0% by weight, approximately 6.5% to 9.5% by weight, approximately 6.8% to 9.0% by weight, or approximately 7.0% to 8.5% by weight.

[0086] Linear or conventional poly(meth)acrylates (PMAs) are generally synthesized by simple free-radical copolymerization of mixtures of different alkyl methacrylates. To impart oil solubility, linear PMA viscosity index improvers typically contain methacrylate repeating units having alkyl side chains with hydrocarbon groups, such as alkyl chains containing 6 to 24 carbon atoms.

[0087] Non-limiting examples of linear PMA include Viscoplex® viscosity index improvers 12-075, 12-115, and / or 12-199, sold by Evonik RohMax USA, Inc.

[0088] Comb-type polymers often contain relatively long side chains attached to the polymer's main chain, also known as the backbone. Comb-type PMAs typically have a number-average molecular weight (M) greater than approximately 500 g / mol. n The methacrylate polymer has at least one repeating methacrylate unit derived from a polyolefin macromonomer. The exact proportion is indicated by the degree of molar branching. The macromonomer contains olefin repeating units derived from alkenes or alkadienes, such as ethylene, propylene, n-butene, isobutene, butadiene, and isoprene.

[0089] Comb-type PMAs are described in US2017 / 0298287A1 and JP2019014802, which are incorporated herein by reference. Non-limiting examples of comb-type PMAs include Viscoplex® viscosity index improvers 3-201 and / or 3-162, sold by Evonik RohMax USA, Inc.

[0090] Viscoplex(registered trademark) 3-201 has a weight-average molecular weight (M w ) is 420,000 g / mol, and the number average molecular weight (M n ) is 70,946 g / mol, M w / M n It is 5.92. This compound has at least M nIt has constituent units derived from more than 500 macromonomers. Comb-type PMA is present in an amount of 19% by weight relative to the total weight of the compound. Viscoplex(registered trademark) 3-162 has a weight-average molecular weight (M w ) is 399,292 g / mol, and the number average molecular weight (M n ) is 205,952 g / mol, M w / M n The value is 1.94, and it is a comb-type PMA with an SSI < 1.0 when measured by ASTM method D6278.

[0091] Zinc dithiophosphate (ZnDTP) The lubricating compositions of this disclosure may further comprise zinc dithiophosphate (ZnDTP). Zinc dithiophosphate is an anti-wear agent that reduces wear on engine components and has the following formula: Zn[SP(=S)(OR 1 )(OR 2 )]2(VII) (In the formula, R 1 and R 2 R may be the same or different hydrocarbyl radicals having 1 to 18 (e.g., 2 to 12) carbon atoms, including alkyl, alkenyl, aryl, arylalkyl, alkaryl, and alicyclic radicals. In some embodiments, R 1 and R 2 The group is an alkyl group having 2 to 8 carbon atoms (for example, alkyl radicals may be ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, or 2-ethylhexyl). To obtain oil solubility, the total number of carbon atoms (i.e., R) 1 +R 2 ) is at least 5. Therefore, zinc dihydrocarbyl dithiophosphate may include zinc dialkyldithiophosphate (ZDDP). Zinc dialkyldithiophosphate (ZnDTP) may be primary ZnDTP containing a primary alkyl group, or secondary zinc dialkyldithiophosphate containing a secondary alkyl group, or a mixture thereof. In some embodiments, zinc dithiophosphate is secondary zinc dithiophosphate.

[0092] In some embodiments, zinc dithiophosphate may be present in an amount sufficient to provide the lubricating composition with approximately 200 ppm to approximately 1500 ppm, approximately 300 ppm to approximately 1400 ppm, approximately 400 ppm to approximately 1300 ppm, approximately 500 ppm to approximately 1200 ppm, approximately 600 ppm to approximately 1100 ppm, approximately 700 ppm to approximately 1000 ppm, approximately 750 ppm to approximately 950 ppm, or approximately 800 ppm to approximately 900 ppm of zinc.

[0093] Other additives The lubricating compositions of the present invention may also contain other conventional additives, which can impart or improve desirable properties of the lubricating composition in which they are dispersed or dissolved. Any additive well known to those skilled in the art can be used in the lubricating compositions disclosed herein. Several suitable additives are described in Mortier et al., “Chemistry and Technology of Lubricants”, 2nd Edition, London, Springer, (1996), and Leslie R. Rudnick, “Lubricant Additives: Chemistry and Applications”, New York, Marcel Dekker (2003). For example, lubricating compositions can be mixed with antioxidants, anti-wear agents, cleaning agents (such as metal cleaners), rust inhibitors, de-tarnishes, deemulsifiers, metal deactivators, friction modifiers, pour point depressants, antifoaming agents, cosolvents, corrosion inhibitors, dispersants, multifunctional agents, dyes, extreme pressure additives, and mixtures thereof. Various additives are known and commercially available. These additives, or similar compounds thereof, can be used in the preparation of the lubricating compositions of this disclosure by conventional mixing methods.

[0094] In the preparation of lubricating formulations, a common method is to introduce additives in the form of a concentrate of the active ingredient at a concentration of about 10 to about 100% by weight in a hydrocarbon oil, such as lubricating mineral oil, or other suitable solvent.

[0095] Typically, these concentrates can be diluted with approximately 3 to 100 (e.g., 5 to 40) parts by weight of lubricating oil per 1 part by weight of additive package when forming the finished lubricant (e.g., crankcase motor oil). The purpose of the concentrates is, of course, to reduce the difficulty and cumbersome handling of different substances and to facilitate their dissolution or dispersion in the final blend.

[0096] Each of the above additives, when used, is used in a functionally effective amount to impart the desired properties to the lubricant. Therefore, for example, if the additive is a friction modifier, a functionally effective amount of this friction modifier will be sufficient to give the lubricant the desired friction modulating properties.

[0097] Generally, the concentration of each additive in a lubricating composition, when used, can be in the range of approximately 0.001% to approximately 20% by weight, approximately 0.01% to approximately 15% by weight, approximately 0.1% to approximately 10% by weight, approximately 0.005% to approximately 5% by weight, or approximately 0.1% to approximately 2.5% by weight, relative to the total weight of the lubricating composition. Furthermore, the total amount of additives in the lubricating composition can be in the range of approximately 0.001% to approximately 20% by weight, approximately 0.01% to approximately 10% by weight, or approximately 0.1% to approximately 5% by weight, relative to the total weight of the lubricating composition. [Examples]

[0098] The following examples are for illustrative purposes only and do not limit the scope of this disclosure in any way.

[0099] Example 1 The lubricating composition was prepared by mixing the following components. a) 1.50% by weight of boronated dispersant b) 0.25% by weight of a non-boronated dispersant c) Calcium salicylate surfactant with a calcium content of approximately 1410 ppm d) Mg content: approximately 470 ppm magnesium sulfonate surfactant e) Regarding Zn content, approximately 850 ppm secondary ZnDTP f) Molybdenum compound with a Mo content of approximately 1000 ppm g) 7.90% comb-type viscosity index improver h) A mixture of base oil A (Yubase 4 Plus) and base oil B (Yubase 3)

[0100] The remainder of the lubricating composition contains small amounts of antioxidants and defoamers. The high-temperature high-shear viscosity (HTHS100) of the finished oil at 100°C was 4.25 mPa·s, and the high-temperature high-shear viscosity (HTHS150) at 150°C was 2.23 mPa·s.

[0101] Example 2 The lubricating composition was prepared by mixing the following components. a) 2.50% by weight of boronated dispersant b) 0.50% by weight of a non-boronated dispersant c) Calcium salicylate surfactant with a calcium content of approximately 1410 ppm d) Mg content: approximately 470 ppm magnesium sulfonate surfactant e) Regarding Zn content, approximately 850 ppm secondary ZnDTP f) Molybdenum compound with a Mo content of approximately 1000 ppm g) 7.50% comb-type viscosity index improver h) A mixture of base oil A (Yubase 4 Plus) and base oil B (Yubase 3)

[0102] The remainder of the lubricating composition contains small amounts of antioxidants and defoamers. The high-temperature high-shear viscosity (HTHS100) of the finished oil at 100°C was 4.42 mPa·s, and the high-temperature high-shear viscosity (HTHS150) at 150°C was 2.32 mPa·s.

[0103] Example 3 The lubricating composition was prepared by mixing the following components. a) 1.50% by weight of boronated dispersant b) 1.50% by weight of a non-boronated dispersant c) Calcium salicylate surfactant with a calcium content of approximately 1410 ppm d) Mg content: approximately 470 ppm magnesium sulfonate surfactant e) Regarding Zn content, approximately 850 ppm secondary ZnDTP f) Molybdenum compound with a Mo content of approximately 1000 ppm g) 7.50% comb-type viscosity index improver h) A mixture of base oil A (Yubase 4 Plus) and base oil B (Yubase 3)

[0104] The remainder of the lubricating composition contains small amounts of antioxidants and defoamers. The high-temperature high-shear viscosity (HTHS100) of the finished oil at 100°C was 4.42 mPa·s, and the high-temperature high-shear viscosity (HTHS150) at 150°C was 2.32 mPa·s.

[0105] Example 4 The lubricating composition was prepared by mixing the following components. a) 1.50% by weight of boronated dispersant b) 0.25% by weight of a non-boronated dispersant c) Calcium salicylate surfactant with a calcium content of approximately 1410 ppm d) Mg content: approximately 470 ppm magnesium sulfonate surfactant e) Regarding Zn content, approximately 850 ppm secondary ZnDTP f) Molybdenum compound with a Mo content of approximately 1000 ppm g) 7.30% comb-type viscosity index improver h) A mixture of base oil A (Yubase 4 Plus) and base oil B (Yubase 3)

[0106] The remainder of the lubricating composition contains small amounts of antioxidants and defoamers. The high-temperature high-shear viscosity (HTHS100) of the finished oil at 100°C was 4.49 mPa·s, and the high-temperature high-shear viscosity (HTHS150) at 150°C was 2.36 mPa·s.

[0107] Comparative Example 1 The lubricating composition was prepared by mixing the following components. a) 0.75% by weight of boronated dispersant b) 0.13% by weight of a non-boronated dispersant c) Calcium salicylate surfactant with a calcium content of approximately 1410 ppm d) Mg content: approximately 470 ppm magnesium sulfonate surfactant e) Regarding Zn content, approximately 850 ppm secondary ZnDTP f) Molybdenum compound with a Mo content of approximately 1000 ppm g) 9.40% comb-type viscosity index improver h) A mixture of base oil A (Yubase 4 Plus) and base oil B (Yubase 3)

[0108] The remainder of the lubricating composition contains small amounts of antioxidants and defoamers. The high-temperature high-shear viscosity (HTHS100) of the finished oil at 100°C was 4.32 mPa·s, and the high-temperature high-shear viscosity (HTHS150) at 150°C was 2.34 mPa·s.

[0109] The lubricating composition was prepared by mixing the following components. Comparative Example 2 a) 0.38% by weight of boronated dispersant b) 0.063% by weight of a non-boronated dispersant c) Calcium salicylate surfactant with a calcium content of approximately 1410 ppm d) Mg content: approximately 470 ppm magnesium sulfonate surfactant e) Regarding Zn content, approximately 850 ppm secondary ZnDTP f) Molybdenum compound with a Mo content of approximately 1000 ppm g) 9.65% comb-type viscosity index improver h) A mixture of base oil A (Yubase 4 Plus) and base oil B (Yubase 3)

[0110] The remainder of the lubricating composition contains small amounts of antioxidants and defoamers. The high-temperature high-shear viscosity (HTHS100) of the finished oil at 100°C was 4.28 mPa·s, and the high-temperature high-shear viscosity (HTHS150) at 150°C was 2.32 mPa·s.

[0111] Comparative Example 3 The lubricating composition was prepared by mixing the following components. a) 3.00% by weight of boronated dispersant b) 0.50% by weight of a non-boronated dispersant c) Calcium salicylate surfactant with a calcium content of approximately 1410 ppm d) Mg content: approximately 470 ppm magnesium sulfonate surfactant e) Regarding Zn content, approximately 850 ppm secondary ZnDTP f) Molybdenum compound with a Mo content of approximately 1000 ppm g) 7.80% comb-type viscosity index improver h) A mixture of base oil A (Yubase 4 Plus) and base oil B (Yubase 3)

[0112] The remainder of the lubricating composition contains small amounts of antioxidants and defoamers. The high-temperature high-shear viscosity (HTHS100) of the finished oil at 100°C was 4.50 mPa·s, and the high-temperature high-shear viscosity (HTHS150) at 150°C was 2.31 mPa·s.

[0113] Comparative Example 4 The lubricating composition was prepared by mixing the following components. a) Calcium salicylate surfactant with a calcium content of approximately 1410 ppm b) Magnesium sulfonate surfactant with a magnesium content of approximately 470 ppm. c) Zn content of approximately 850 ppm of secondary ZnDTP d) Molybdenum compound with a Mo content of approximately 1000 ppm e) 10.50% comb-type viscosity index improver f) A mixture of base oil A (Yubase 4 Plus) and base oil B (Yubase 3)

[0114] The remainder of the lubricating composition contains small amounts of antioxidants and defoamers. The high-temperature high-shear viscosity (HTHS100) of the finished oil at 100°C was 4.30 mPa·s, and the high-temperature high-shear viscosity (HTHS150) at 150°C was 2.37 mPa·s.

[0115] Comparative Example 5 The lubricating composition was prepared by mixing the following components. a) 0.25% by weight of boronated dispersant b) 1.50% by weight of a non-boronated dispersant c) Calcium salicylate surfactant with a calcium content of approximately 1410 ppm d) Mg content: approximately 470 ppm magnesium sulfonate surfactant e) Regarding Zn content, approximately 850 ppm secondary ZnDTP f) Molybdenum compound with a Mo content of approximately 1000 ppm g) 7.30% comb-type viscosity index improver h) A mixture of base oil A (Yubase 4 Plus) and base oil B (Yubase 3)

[0116] The remainder of the lubricating composition contains small amounts of antioxidants and defoamers. The high-temperature high-shear viscosity (HTHS100) of the finished oil at 100°C was 4.50 mPa·s, and the high-temperature high-shear viscosity (HTHS150) at 150°C was 2.36 mPa·s.

[0117] JASO M366 Fuel Economy Test The above lubricating compositions were tested for their fuel efficiency performance in a gasoline motor engine (Toyota 2ZR-FXE).

[0118] Detailed equipment configuration, a description of the baseline calibration (BC) oil, and the conditions for the Toyota 2ZR-FXE test can be found in the JASO M366 test method. The test oil is pre-conditioned by running the engine at an oil temperature of 88°C and 1350 rpm for 10 hours. Fuel consumption measurement consists of six steady-state operating conditions representing WLTC (low-speed phase, medium-speed phase, and high-speed phase). Fuel consumption (kg / h) is calculated as the sum of fuel consumption for each phase using weighting factors.

[0119] For the candidate oil tests, the Fuel Economy Improvement (FEI) is calculated as a relative improvement rate (percentage change) relative to the average of the two BC oils, as shown below. A higher FEI value indicates better overall fuel economy performance.

number

[0120] The results of the fuel efficiency tests are shown in Table 2 below. The fuel efficiency improvement rate (FEI) results, as seen in Comparative Example 3, show that when the amount of boron from the boronating dispersant is increased to approximately 160 ppm or more, the FEI falls outside the acceptable limit (>1.01%). As shown in Comparative Examples 1, 2, 4, and 5, the nitrogen content provided by the combination of non-boronating and boronating dispersants needs to exceed approximately 320 ppm in order to maintain the FEI within an acceptable range. [Table 2]

[0121] This disclosure is subject to various modifications and alternative forms, and specific embodiments 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 any particular form, but rather to encompass all modifications, equivalents, and alternatives that fall within the spirit and scope of this disclosure as defined by the appended claims.

[0122] Please note that not all actions described in the general description or examples are necessarily required, some of the actions may not be necessary, and one or more additional actions may be performed in addition to those described. Furthermore, the order in which the actions are listed does not necessarily indicate the order in which they are performed.

[0123] Benefits, other advantages, and solutions to problems have been described herein in relation to specific embodiments. However, any benefit, advantage, solution, solution, or any feature(s) that may result in or make more clear any benefit, advantage, solution, or solution should not be construed as material, necessary, or essential to any or all of the claims.

[0124] The details and descriptions of the embodiments described herein are intended to provide a general understanding of the structures of various embodiments.

[0125] This specification and description are not intended to serve as a comprehensive and exhaustive description of all elements and features of formulations, compositions, apparatus, and systems that use the structures or methods described herein. Different embodiments may be provided as combinations in a single embodiment, and conversely, various features described in relation to a single embodiment for the sake of brevity may be provided separately or in any partial combination. Furthermore, references to values ​​described as ranges include all values ​​within that range. Many other embodiments will be obvious to those skilled in the art only after reading this specification. Other embodiments can be used and derived from this disclosure so that structural substitutions, logical substitutions, or other modifications can be made without departing from the scope of this disclosure. Therefore, this disclosure should be considered illustrative and not restrictive.

Claims

1. A lubricating composition, a) Oil with a lubricating viscosity that is more than half the volume, b) Non-boronized dispersant, c) A boronating dispersant in an amount sufficient to provide the lubricating composition with less than approximately 160 ppm of boron, The combination of the non-boronized dispersant and the boronized dispersant provides the lubricating composition with at least about 250 ppm of nitrogen. d) A molybdenum-containing compound in an amount sufficient to provide the lubricating composition with at least about 400 ppm of molybdenum, The molybdenum-containing compound, which includes molybdenum dithiocarbamate, e) Overbasic calcium salicylate cleaning agent, f) A viscosity index improver (VII) is included, The lubricating composition wherein the high-temperature high-shear viscosity (HTHS100) of the lubricating composition at 100°C is 3.0 mPa·s to 4.5 mPa·s.

2. The lubricating composition according to claim 1, wherein the boronizing dispersant is present in an amount sufficient to provide the lubricating composition with about 90 ppm to about 160 ppm of boron.

3. The lubricating composition according to claim 1, wherein the combination of the non-boronized dispersant and the boronized dispersant provides the lubricating composition with at least about 250 ppm to about 600 ppm of nitrogen.

4. The lubricating composition according to claim 1, wherein the molybdenum-containing compound further comprises a molybdenum-amine complex, molybdenum dithiophosphate, or a combination thereof.

5. The lubricating composition according to claim 1, wherein the molybdenum-containing compound is present in an amount sufficient to provide the lubricating composition with approximately 400 ppm to approximately 1600 ppm of molybdenum.

6. The lubricating composition according to claim 1, wherein the overbasic calcium salicylate detergent is present in an amount sufficient to provide the lubricating composition with approximately 800 ppm to approximately 2000 ppm of calcium.

7. The lubricating composition according to claim 1, wherein the viscosity index improver (VII) is a linear polymethacrylate (PMA) or a comb-type polymethacrylate (PMA).

8. The lubricating composition according to claim 1, wherein the viscosity index improver has a shear stability index (SSI) of less than approximately 30 when measured by ASTM method D6278.

9. The lubricating composition according to claim 1, further comprising a magnesium detergent, wherein the magnesium detergent is present in an amount sufficient to provide the lubricating composition with approximately 300 ppm to approximately 700 ppm of magnesium.

10. The lubricating composition according to claim 1, wherein the oil having the aforementioned lubricating viscosity is a base oil of group III.

11. The lubricating composition according to claim 1, further comprising zinc dithiophosphate, wherein the zinc dithiophosphate is present in an amount sufficient to provide the lubricating composition with about 500 ppm to about 1200 ppm of zinc.

12. The lubricating composition according to claim 11, wherein the zinc dithiophosphate is a secondary zinc dithiophosphate.

13. A method for improving the fuel efficiency of an internal combustion engine equipped with a roller follower valve train, comprising lubricating the internal combustion engine with a lubricating composition, wherein the lubricating composition is a) Oil with a lubricating viscosity that is more than half the volume, b) Non-boronized dispersant, c) A boronating dispersant in an amount sufficient to provide the lubricating composition with less than approximately 160 ppm of boron, The combination of the non-boronized dispersant and the boronized dispersant provides the lubricating composition with at least about 250 ppm of nitrogen. d) A molybdenum-containing compound in an amount sufficient to provide the lubricating composition with at least about 400 ppm of molybdenum, The molybdenum-containing compound, which includes molybdenum dithiocarbamate, e) Overbasic calcium salicylate cleaning agent, f) The method comprising a viscosity index improver (VII).

14. The method according to claim 13, wherein the high-temperature high-shear viscosity (HTHS100) of the lubricating composition at 100°C is 3.0 mPa·s to 4.5 mPa·s.

15. The method according to claim 13, wherein the boronizing dispersant is present in an amount sufficient to provide the lubricating composition with boron in a concentration of about 90 ppm to about 160 ppm.

16. The method according to claim 13, wherein the combination of the non-boronized dispersant and the boronized dispersant provides the lubricating composition with at least about 250 ppm to about 600 ppm of nitrogen.

17. The method according to claim 13, wherein the molybdenum-containing compound further comprises a molybdenum-amine complex, molybdenum dithiophosphate, or a combination thereof.

18. The method according to claim 13, wherein the molybdenum-containing compound is present in an amount sufficient to provide the lubricating composition with approximately 400 ppm to approximately 1600 ppm of molybdenum.

19. The method according to claim 13, wherein the overbasic calcium salicylate cleaning agent is present in an amount sufficient to provide the lubricating composition with approximately 800 ppm to approximately 2000 ppm of calcium.

20. The method according to claim 13, wherein the viscosity index improver (VII) is a linear polymethacrylate (PMA) or a comb-type polymethacrylate (PMA).

21. The method according to claim 13, wherein the viscosity index improver has a shear stability index (SSI) of less than approximately 30 when measured by ASTM method D6278.

22. The method according to claim 13, wherein the lubricating composition further comprises a magnesium detergent, the magnesium detergent is present in an amount sufficient to provide the lubricating composition with about 300 ppm to about 700 ppm of magnesium.

23. The method according to claim 13, wherein the oil having the aforementioned lubricating viscosity is a base oil of group III.

24. The method according to claim 13, wherein the lubricating composition further comprises zinc dithiophosphate, and the zinc dithiophosphate is present in an amount sufficient to provide the lubricating composition with about 500 ppm to about 1200 ppm of zinc.

25. The method according to claim 24, wherein the zinc dithiophosphate is secondary zinc dithiophosphate.

26. The method according to claim 13, wherein the rate of improvement in fuel efficiency is measured by the JASO M366 fuel efficiency test.

27. The method according to claim 26, wherein the fuel efficiency improvement rate (FEI) measured by the JASO M366 fuel efficiency test is higher than 1.10%.

28. The use of a lubricating composition for improving the fuel efficiency of an internal combustion engine equipped with a roller follower valve train, wherein the lubricating composition is a) Oil with a lubricating viscosity that is more than half the volume, b) Non-boronized dispersant, c) A boronating dispersant in an amount sufficient to provide the lubricating composition with less than approximately 160 ppm of boron, The combination of the non-boronized dispersant and the boronized dispersant provides the lubricating composition with at least about 250 ppm of nitrogen. d) A molybdenum-containing compound in an amount sufficient to provide the lubricating composition with at least about 400 ppm of molybdenum, The molybdenum-containing compound, which includes molybdenum dithiocarbamate, e) Overbasic calcium salicylate cleaning agent, f) The use comprising a viscosity index improver (VII).

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