High performance lubricating oil composition

Abstract

A lubricating oil composition is described. The composition includes one or more base oils of lubricating viscosity, one or more nitrogen-containing dispersants present in an amount to provide 320 to 600 ppm of N to the lubricating oil composition, one or more magnesium-containing detergents present in an amount to provide 300 to 600 ppm of Mg to the lubricating oil composition, at least two calcium-containing detergents including a calcium sulfonate with a total base number of at least 600 mg / KOH on an oil-free basis, and a calcium phenate with a total base number of at least 300 mg / KOH on an oil-free basis, one or more aryl amine ashless antioxidants present in an amount to provide at least 85 ppm of N to the lubricating oil composition, at least one molybdenum-containing additive present in an amount to provide between 40 to 350 ppm of Mo to the lubricating oil composition. At least one of the one or more magnesium containing detergent additive is magnesium sulfonate. At least two calcium-containing detergents are present in an amount to provide between 800 to 1300 ppm of Ca to the lubricating oil composition.

Description

[0001] HIGH PERFORMANCE LUBRICATING OIL COMPOSITION CROSS-REFERENCE TO RELATED APPLICATION

[0002] [1] This application claims the benefit of U.S. Provisional Patent Application No.

[0003] 63 / 779,002, filed March 27, 2025, which is incorporated by reference herein in its entirety.

[0004] FIELD OF THE INVENTION

[0005] [2] This disclosure relates to a lubricating oil composition designed to meet modern engine oil specifications while providing good fuel economy performance in engines.

[0006] BACKGROUND OF THE INVENTION

[0007] [3] A big driver of lubricant evolution or improvements is the adoption of industry specifications, such as the upcoming ILSAC GF-7. This new specification targets improvements in fuel economy and emissions, thus requiring engine oils to perform at high levels while adhering to more stringent environmental standards.

[0008] SUMMARY

[0009] [4] In one aspect, the present disclosure relates to a lubricating oil composition comprising: one or more base oils of lubricating viscosity; one or more nitrogen-containing dispersants present in an amount to provide 320 to 600 ppm of N to the lubricating oil composition, one or more magnesium-containing detergents present in an amount to provide 300 to 600 ppm of Mg to the lubricating oil composition, wherein at least one of the one or more magnesium containing detergent additive is magnesium sulfonate; at least two calcium-containing detergents including a calcium sulfonate with a total base number of at least 600 mg / KOH on an oil-free basis, and a calcium phenate with a total base number of at least 300 mg / KOH on an oil-free basis, wherein the at least two calcium-containing detergents are present in an amount to provide between 800 to 1300 ppm of Ca to the lubricating oil composition;Atorney Docket No.: T-12767-WO01 one or more aryl amine ashless antioxidants present in an amount to provide at least 85 ppm of N to the lubricating oil composition; and at least one molybdenum-containing additive present in an amount to provide between 40 to 350 ppm of Mo to the lubricating oil composition.

[0010] [5] In another aspect, the present disclosure relates to a method of improving fuel economy comprising lubricating an engine with a lubricating oil composition comprising: one or more base oils of lubricating viscosity; one or more nitrogen-containing dispersants present in an amount to provide 320 to 600 ppm of N to the lubricating oil composition, one or more magnesium-containing detergents present in an amount to provide 300 to 600 ppm of Mg to the lubricating oil composition, wherein at least one of the one or more magnesium containing detergent additive is magnesium sulfonate; at least two calcium-containing detergents including a calcium sulfonate with a total base number of at least 600 mg / KOH on an oil-free basis, and a calcium phenate with a total base number of at least 300 mg / KOH on an oil-free basis, wherein the at least two calcium-containing detergents are present in an amount to provide between 800 to 1300 ppm of Ca to the lubricating oil composition; one or more aryl amine ashless antioxidants present in an amount to provide at least 85 ppm of N to the lubricating oil composition; and at least one molybdenum-containing additive present in an amount to provide between 40 to 350 ppm of Mo to the lubricating oil composition.

[0011] DETAILED DESCRIPTION OF THE INVENTION

[0012] [6] While the disclosure is susceptible to various modifications and alternative forms, specific embodiments thereof are herein described in detail. It should be understood, however, that the description herein of specific embodiments is not intended to limit the disclosure to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the disclosure as defined by the appended claims.Attorney Docket No.: T-12767-WO01

[0013] Definitions

[0014] [7] To facilitate the understanding of the subject matter disclosed herein, a number of terms, abbreviations or other shorthand as used herein are defined below. Any term, abbreviation or shorthand not defined is understood to have the ordinary meaning used by a skilled artisan contemporaneous with the submission of this application.

[0015] [8] All percentages reported are weight % on an active ingredient basis (i.e., without regard to carrier or diluent oil) unless otherwise stated.

[0016] [9] A “major amount” means in excess of about 50 wt. % of a composition.

[0017]

[0010] “Active ingredients” or “actives” refer to additive material that is not diluent or solvent.

[0018]

[0011] The term “hydrocarbyl” refers to a chemical group or moiety derived from hydrocarbons including saturated and unsaturated hydrocarbons. Examples of hydrocarbyl groups include alkenyl, alkyl, polyalkenyl, polyalkyl, phenyl, and the like.

[0019]

[0012] The term “metal” refers to alkali metals, alkaline earth metals, or mixtures thereof.

[0020]

[0013] The term “alkali metal” refers to lithium, sodium, potassium, rubidium, and cesium.

[0021]

[0014] The term “alkaline earth metal” refers to calcium, barium, magnesium, and strontium.

[0022]

[0015] The term “overbased” is intended to define additives which contain a metal content in excess of that required by the stoichiometry of the particular metal and the particular organic acid used. The excess metal exists in the form of particles of inorganic base (e.g., a hydroxide or carbonate) surrounded by a sheath of metal salt. The sheath serves to maintain the particles in dispersion in a liquid oleaginous vehicle. The amount of excess metal is commonly expressed as the ratio of total equivalence of excess metal to equivalence of organic acid and is typically in a range of 0.1 to 30.Atorney Docket No.: T-12767-WO01

[0023]

[0016] The term “Total Base Number” or “TBN” as used herein refers to the amount of base equivalent to milligrams of KOH in one gram of sample. Thus, higher TBN numbers reflect more alkaline products, and therefore a greater alkalinity. TBN was determined using ASTM D 2896 test.

[0024]

[0017] “Active ingredients” or “actives” or “oil free” refers to additive material that is not in diluent or solvent.

[0025]

[0018] Kinematic viscosity (KV) at 100°C values were measured in accordance with ASTMD445.

[0026]

[0019] The term “olefins” refers to a class of unsaturated aliphatic hydrocarbons having one or more carbon-carbon double bonds, obtained by a number of processes. Those containing one double bond are called mono-alkenes, and those with two double bonds are called dienes, alkyldienes, or diolefins. Alpha olefins are particularly reactive because the double bond is between the first and second carbons, e.g., 1 -octene and 1 -octadecene, and are used as the starting point for medium-biodegradable surfactants. Linear and branched olefins are also included in the definition of olefins.

[0027]

[0020] The term “Normal Alpha Olefins” refers to olefins which are straight chain, nonbranched hydrocarbons with carbon-carbon double bond present in the alpha or primary position of the hydrocarbon chain.

[0028]

[0021] The term “Isomerized Normal Alpha Olefin” refers to an alpha olefin that has been subjected to isomerization conditions which results in an alteration of the distribution of the olefin species present and / or the introduction of branching along the alkyl chain. The isomerized olefin product may be obtained by isomerizing a linear alpha olefin containing from about 10 to about 40 carbon atoms, such as from about 10 to 30 carbon atoms, about 20 to about 28 carbon atoms, or from about 20 to about 24 carbon atoms.Attorney Docket No.: T-12767-WO01

[0029] Description

[0030]

[0022] The present disclosure relates to lubricating oil compositions that provide superior fuel economy performance while meeting GF-7 requirements. The lubricating oil composition of this disclosure includes base oil, nitrogen-containing dispersant(s), magnesium-containing detergent(s), combination of calcium-containing detergents, ashless antioxidant(s), and molybdenum-containing additive(s). Additionally, the lubricating oil composition has a total base number between 6.0 and 9.5 mg KOH / g as measured by ASTM D-2896, boron content of 80 ppm or less, and a sulfated ash content of 0.55 to 0.95 wt%.

[0031] Nitrogen-containing Dispersants

[0032]

[0023] The lubricating oil composition includes one or more nitrogen-containing dispersants. The dispersants are present in an amount to provide 320 to 600 ppm of N to the lubricating oil composition, such as from 320 to 595 ppm of N, 320 to 590 ppm of N, 320 to 585 ppm of N, 320 to 580 ppm of N, 320 to 575 ppm of N, 325 to 600 ppm of N, 325 to 595 ppm of N, 325 to 590 ppn of N, 325 to 585 ppm of N, 325 to 580 ppm of N, or 325 to 575 ppm of N.

[0033]

[0024] Specific examples of nitrogen-containing dispersants include hydrocarbyl-substituted succinimides such as polyalkenyl succinimides (including polyalkenyl bissuccinimides). In general, the nitrogen content from the nitrogen-containing dispersant based on the lubricating oil composition is from about 0.01 wt % to about 5.0 wt % such as from about 0.01 wt.% to 4.0 wt.%, 0.01 wt.% to 3.0 wt.%, 0.01 wt.% to 2.0 wt.%, 0.1 wt.% to 5.0 wt.%, 0.1 wt.% to 4.0 wt.%, 0.1 wt.% to 3.0 wt.%, 0.1 wt.% to 2.0 wt.%, 0.5 wt.% to 5.0 wt.%, 0.5 wt.% to 4.0 wt.%, 0.5 wt.% to 3.0 wt.%, or 0.5 wt.% to 2.0 wt.%.

[0034]

[0025] By way of an example, a polyalkenyl bis-succinimide can be obtained by reacting a polyalkenyl-substituted succinic anhydride below:Attomey Docket No.: T-12767-WO01

[0035] 0

[0036] R / /

[0037] o

[0038] /

[0039]

[0040] 0

[0041] wherein R is a polyalkenyl substituent is derived from a polyalkene group having a number average molecular weight of from about 500 to about 3000, with a polyamine. In one embodiment, R is a polyalkenyl substituent derived from a polyalkene group having a number average molecular weight of from about 1000 to about 2500. In one embodiment, R is a polyisobutenyl substituent derived from a polyisobutene having a number average molecular weight of from about 500 to about 3000. In another embodiment, R is a polyisobutenyl substituent derived from a polyisobutene having a number average molecular weight of from about 1000 to about 2500.

[0042]

[0026] Suitable polyamines for use in preparing the bis-succinimides include polyalkylene polyamines. Such polyalkylene polyamines will typically contain about 2 to about 12 nitrogen atoms and about 2 to 24 carbon atoms. Particularly suitable polyalkylene polyamines are those having the formula: H2N — (R'NH)x — H wherein R' is a straight- or branched-chain alkylene group having 2 or 3 carbon atoms and x is 1 to 9. Representative examples of suitable polyalkylene polyamines include ethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, pentaethylene hexamine, and heavy polyamines (e.g., Ethyleneamine E-100, available from Huntsman Company).

[0043]

[0027] Generally, the polyalkenyl-substituted succinic anhydride is reacted with the polyamine at a temperature of about 130°C to about 220°C (e.g., 145°C to 175°C). The reaction can be carried out under an inert atmosphere, such as nitrogen or argon. Generally, a suitable molar charge of polyamine to polyalkenyl-substituted succinic anhydride is from about 0.35:1 to about 0.6: 1 (e.g., 0.4: 1 to 0.5:1). As used herein, the “molar charge of polyamine to polyalkenyl-Attorney Docket No.: T-12767-WO01 substituted succinic anhydride” means the ratio of the number of moles of polyamine to the number of succinic groups in the succinic anhydride reactant.

[0044]

[0028] Suitable polyalkenyl bis-succinimides may be represented by the following generalized structure:

[0045] o o

[0046] Rx J!h'i / R

[0047] \ _ / :

[0048] N . p R' . N . R' . N

[0049] / y \ i

[0050]

[0051] 0 0

[0052] wherein R and R' are as described herein above and y is 1 to 11.

[0053] Post-Treatment of Polyalkenyl Succinimide

[0054]

[0029] In some embodiments, the succinimide dispersant may be post-treated. Suitable post-treatment reagents include reactive boron compounds or organic carbonates (e.g., ethylene carbonate).

[0055]

[0030] Suitable boron compounds that can be used as a source of boron include, for example, boric acid, a boric acid salt, a boric acid ester, and the like. Representative examples of a boric acid include orthoboric acid, metaboric acid, paraboric acid, and the like. Representative examples of a boric acid salt include ammonium borates, such as ammonium metaborate, ammonium tetraborate, ammonium pentaborate, ammonium octaborate, and the like. Representative examples of a boric acid ester include monomethyl borate, dimethyl borate, trimethyl borate, monoethyl borate, diethyl borate, triethyl borate, monopropyl borate, dipropyl borate, tripropyl borate, monobutyl borate, dibutyl borate, tributyl borate, and the like.Attorney Docket No.: T-12767-WO01 Detergents

[0056]

[0031] The lubricating oil compositions of the present disclosure may include one or more detergents. A detergent is an additive that reduces formation of deposits such as high-temperature varnish and lacquer deposits in engines. The detergent normally has acid-neutralizing properties and is capable of keeping finely-divided solids in suspension. Most detergents are metal salts of acidic organic compounds.

[0057]

[0032] Detergents generally include a polar head with a long hydrophobic tail. The polar head includes a metal salt of an acidic organic compound. In the art, detergents are generally referred to as neutral or overbased. Detergents which contain a substantially stoichiometric amount of the metal salt are usually described as normal or neutral detergents. In embodiments where a large amount of a metal base is incorporated in the detergent by reacting excess metal compound (e.g., an oxide or hydroxide) with an acidic gas (e.g., carbon dioxide), the detergents are referred to as being overbased.

[0058]

[0033] Overbased metal detergents are generally produced by carbonating (with CO2) a mixture of hydrocarbons, detergent acid (for example sulfonic acid or carboxylate), metal oxide or hydroxides (for example calcium oxide or calcium hydroxide) and promoters such as xylene, methanol, and / or water. For example, for preparing an overbased calcium sulfonate, in carbonation, the calcium oxide or hydroxide reacts with the gaseous carbon dioxide to form calcium carbonate. The sulfonic acid is neutralized with an excess of CaO or Ca(0H)2, to form the sulfonate.

[0059]

[0034] Compounds that may be used in the detergents include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and naphthenates and other oil-soluble carboxylates of a metal, particularly the alkali or alkaline earth metals, e.g., barium, sodium, potassium, lithium, calcium, and magnesium. The most commonlyAtorney Docket No.: T-12767-WO01 used metals are calcium and magnesium, which may both be present in detergents used in a lubricant, and mixtures of calcium and / or magnesium with sodium.

[0060]

[0035] Generally, the amount of the detergent can be from about 0.001 wt. % to about 50 wt. %, or from about 0.05 wt. % to about 25 wt. %, or from about 0.1 wt. % to about 20 wt. %, or from about 0.01 to 15 wt. % based on the total weight of the lubricating oil composition.

[0061] Magnesium-containing Detergents

[0062]

[0036] The lubricating oil composition includes one or more magnesium-containing detergents, wherein at least one of the one or more magnesium containing detergent additive is magnesium sulfonate. The magnesium-containing detergent is present in an amount to provide 300 to 600 ppm of Mg to the lubricating oil composition.

[0063]

[0037] In general, a magnesium-containing detergent is any detergent that can coordinate with magnesium. Particularly useful detergents include oil-soluble sulfonates (e.g., alkaryl sulfonates), hydroxyaromatic carboxylates (e.g., salicylates, alkylhydroxybenzoates, etc.), and phenates.

[0064] Calcium-containing Detergents

[0065]

[0038] The lubricating oil composition includes at least two calcium-containing detergents. The at least two calcium-containing detergent includes a calcium sulfonate with a total base number of at least 600 mg / KOH on an oil-free basis and a calcium phenate.

[0066]

[0039] In some embodiments, the calcium phenate has a total base number of at least 300 mg / KOH on an oil-free basis. Alternatively, the calcium phenate has a total base number of no more than 250 mg / KOH on an oil-free basis.

[0067]

[0040] In general, a calcium-containing detergent is any detergent that can coordinate with calcium. Particularly useful detergents include oil-soluble sulfonates (e.g., alkaryl sulfonates),Atorney Docket No.: T-12767-WO01 hydroxyaromatic carboxylates (e.g., salicylates, alkylhydroxybenzoates, etc.), and phenates (including sulfurized calcium phenates).

[0068]

[0041] In some embodiments, the calcium-containing detergent is a calcium phenate comprising an alkyl group derived from an isomerized normal alpha olefin having from about 10 to about 40 carbon atoms per molecule having and isomerization level (I) of the normal alpha olefin of from about 0.1 to about 0.4. These isomerized phenate detergents are useful for their detergency and antioxidant properties. In addition, metal salts of isomerized phenate detergents made from isomerized normal alpha olefin, have a reduced content of unreacted tetrapropenyl phenol or tetrapropenyl phenate.

[0069]

[0042] The isomerization level (I) represents the relative amount of methyl groups (CH3) attached to the methylene backbone groups (-CH2-) and is defined by I = m / (m + n) where m is the NMR integral for methyl groups with chemical shifts between 0.30 ± 0.03 to 1.01 ± 0.03 ppm, and n is the NMR integral for methylene groups with chemical shifts between 1.01 ± 0.03 to 1.38 ± 0.10 ppm.

[0070]

[0043] In one aspect of the present disclosure, the phenate detergent is an alkylated phenate detergent wherein the alkyl group is derived from an isomerized normal alpha olefin having from about 10 to about 40 carbon atoms per molecule such as from about 10 to about 30, from about 14 to about 30, from about 16 to about 30, from about 18 to about 30, from about 20 to about 28, from about 20 to about 24, or from about 18 to about 28 carbon atoms per molecule.

[0071]

[0044] In one aspect of the present disclosure, an isomerization level (I) of the normal alpha olefin of the alkylated phenate detergent is between from about 0.10 to about 0.40, or from about 0.10 to about 0.30, or from about 0.12 to about 0.30, or from about 0.22 to about 0.30.

[0072]

[0045] In one embodiment, the isomerization level of the normal alpha olefin is about 0.22 to 0.30, and the normal alpha olefin has from about 20 to about 24 carbon atoms. In anotherAtorney Docket No.: T-12767-WO01 embodiment, the isomerization level of the normal alpha olefin is about 0.26, and the normal alpha olefin has from about 20 to about 24 carbon atoms.

[0073]

[0046] The at least two calcium-containing detergents are present in an amount to provide between 800 to 1300 ppm of Ca to the lubricating oil composition.

[0074]

[0047] In some embodiments, at least 280 ppm of Ca is provided by the calcium phenate.

[0075]

[0048] In some embodiments, the lubricating oil composition includes no more than 120 ppm of calcium from calcium phenate derived from tetrapropenyl phenol or tetrapropenyl phenate.

[0076] Ashless Antioxidants

[0077]

[0049] The lubricating oil composition includes one or more aryl amine ashless antioxidants. The antioxidant is present in an amount to provide at least 85 ppm of N to the lubricating oil composition.

[0078]

[0050] Suitable aryl amine ashless antioxidants include diarylamines such as alkylated diphenylamines phenyl-alpha-naphthalene and alkylated phenyl-alpha-naphthalenes.

[0079]

[0051] More specific examples of aryl amine ashless antioxidants include N-phenyl-2-naphthylamine, 4,4’ -dioctyldiphenylamine, butylated / octylated diphenylamine, nonylated diphenylamine, and octylated N-phenyl-2-naphthylamine.

[0080] Molybdenum-containing Additive

[0081]

[0052] The lubricating oil composition includes at least one molybdenum-containing additive. The additive is present in an amount to provide between 40 to 350 ppm of Mo to the lubricating oil composition.

[0082]

[0053] Suitable molybdenum-containing additives include oil-soluble organo-molybdenum compounds, such as molybdenum succinimide. In some embodiments, the organo-molybdenum compound may include a molybdenum-sulfur core wherein the sulfur part isAtorney Docket No.: T-12767-WO01 dithiocarbamate dithiophosphate, dithiophosphinate, xanthate, thioxanthate, sulfide, or mixtures thereof. In some embodiments, the molybdenum-containing additive is dinuclear or trinuclear.

[0083] Ashless Friction Modifiers

[0084]

[0054] The lubricating oil composition may also include one or more ashless friction modifiers, such as ashless ester-based friction modifier. A friction modifier is any material that can alter the coefficient of friction of a surface lubricated by any lubricant or fluid containing such material. Suitable friction modifiers may include fatty amines, esters such as glycerol monooleate, glycerol cocoate, borated glycerol esters, fatty phosphites, fatty acid amides, fatty epoxides, borated fatty epoxides, alkoxylated fatty amines, borated alkoxylated fatty amines, or fatty imidazolines, and condensation products of carboxylic acids and polyalkylene-polyamines. As used herein, the term “fatty” in relation to friction modifiers means a carbon chain having 10 to 22 carbon atoms, typically a straight carbon chain. In some embodiments, the ashless friction modifier includes a bio-derived ester.

[0085]

[0055] The friction modifier can be present at 0.01 to 10.0 wt. % of the lubricating oil composition.

[0086] Oil of lubricating viscosity

[0087]

[0056] The lubricating oil composition includes oil of lubricating viscosity. In some embodiments, the oil of lubricating viscosity is present from 1 wt.% to 99 wt.% based on total weight of the lubricating oil composition.

[0088]

[0057] When added to finished oil, the oil of lubricating viscosity (sometimes referred to as “base stock” or “base oil”) is the primary liquid constituent of a lubricant, into which additives and possibly other oils are blended, for example to produce a final lubricant (or lubricant composition).Atorney Docket No.: T-12767-WO01

[0089]

[0058] A base oil is also useful for making concentrates (i.e., additive package) as well as for making lubricating compositions therefrom and may be selected from natural and synthetic lubricating oils and combinations thereof.

[0090]

[0059] Natural oils include animal and vegetable oils, liquid petroleum oils and hydrorefined, solvent-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.

[0091]

[0060] Synthetic lubricating oils include hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propyl ene-isobutylene copolymers, chlorinated polybutylenes, poly(l -hexenes), poly(l -octenes), poly(l -decenes); alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzenes; polyphenols (e.g., biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogues and homologues thereof. Polymerized olefins can also be derived from bio-derived sources such as hydrocarbon terpenes such as myrcene, ocimene and farnesene which can also be co-polymerized with other olefins and further isomerized if desired.

[0092]

[0061] Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., malonic acid, alkyl malonic acids, alkenyl malonic acids, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, fumaric acid, azelaic acid, suberic acid, sebacic acid, adipic acid, linoleic acid dimer, phthalic acid) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleicAtorney Docket No.: T-12767-WO01 acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.

[0093]

[0062] Esters useful as synthetic oils also include those made from C5 to C12 monocarboxylic acids and polyols, and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol. Esters from bioderived sources may also be useful as synthetic oils.

[0094]

[0063] The base oil may be derived from Fischer-Tropsch synthesized hydrocarbons. Fischer-Tropsch synthesized hydrocarbons are made from synthesis gas containing H2 and CO using a Fischer-Tropsch catalyst. Such hydrocarbons typically require further processing in order to be useful as the base oil. For example, the hydrocarbons may be hydroisomerized; hydrocracked and hydroisomerized; dewaxed; or hydroisomerized and dewaxed; using processes known to those skilled in the art.

[0095]

[0064] The base oil may be a renewable or bio-derived base oil. Examples of such base oils are disclosed in W02016061050 and US20190338211, which is incorporated herein by reference. According to some embodiments, the renewable or bio-derived base oil includes a biobased hydrocarbon, such as an isoparaffinic hydrocarbon derived from hydrocarbon terpenes, such as myrcene, ocimene, and famesene. In some embodiments, the biobased hydrocarbon is produced from fatty acids or fatty esters.

[0096]

[0065] Unrefined, refined and re-refined oils can be used in the present lubricating composition. Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further treatment would be unrefined oil. Refined oils are similar to the unrefined oils except they have been further treated in one or more purification stepsAttorney Docket No.: T-12767-WO01 to improve one or more properties. Many such purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration and percolation are known to those skilled in the art.

[0097]

[0066] By applying similar refining processes to already-refined oils that have been used in service as those processes that are used to obtain those refined oils in the first place, re-refined oils may be obtained. Such re-refined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for approval of spent additive and oil breakdown products.

[0098]

[0067] Hence, the base oil which may be used to make the present lubricating composition may be selected from any of the base oils in Groups I-V as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines (API Publication 1509). Such base oil groups are summarized in Table 1 below:

[0099] Table 1

[0100] Base Oil Properties

[0101] Group Saturates"", wt. % Sulfur^, wt. % Viscosity Index'"' Group I <90 and / or >0.03 80 to <120 Group II >90 <0.03 80 to <120 Group III >90 <0.03 >120

[0102] Group IV Polyalphaolefins (PAOs)

[0103] Group V All other base stocks not included in Groups I, II, III, or IV

[0104]

[0105] (a)Determined in accordance with ASTM D2007.

[0106] Determined in accordance with ASTM D2622, ASTM D3120, ASTM D4294 or ASTM D4927.

[0107] (c) Determined in accordance with ASTM D2270.

[0108]

[0068] Base oils suitable for use herein are any of the variety corresponding to API Group II, Group III, Group IV, and Group V oils and combinations thereof. In one embodiment, the base oil is a Group I base oil or a blend of two or more different Group I base oils. Suitable Group IAtorney Docket No.: T-12767-WO01 base oils include any light overhead cuts from a vacuum distillation column, such as, for example, any Light Neutral, Medium Neutral, and Heavy Neutral base stocks. The base oil may also include residual base stocks or bottoms fractions such as bright stock. Bright stock is a high viscosity base oil which has been conventionally produced from residual stocks or bottoms and has been highly refined and dewaxed.

[0109]

[0069] In one embodiment, the base oil is a Group III base oil or a blend of two or more different Group III base oils. Suitable Group III base oils include, for example, paraffinic mineral oils obtained by a suitable combination of refining processes such as hydrorefining and dewaxing in respect of lubricating oil fractions obtained by atmospheric distillation of crude oil. In another embodiment, the base oil is a mixture of different base oils such as a mixture of Group II and Group III

[0110]

[0070] In some embodiments, the lubricating oil composition includes less than 1 wt.% of PAO base oil and ester base oil based on total lubricating oil composition.

[0111] Additional Lubricating Oil Additives

[0112]

[0071] The lubricating oil compositions of the present disclosure may also contain conventional additives that can impart or improve any desirable property of the lubricating oil composition in which these additives are dispersed or dissolved. Any additive known to a person of ordinary skill in the art may be used in the lubricating oil compositions disclosed herein. Some suitable additives have been 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), both of which are incorporated herein by reference. For example, the lubricating oil compositions can be blended with antioxidants (including ashless antioxidants), anti-wear agents, metal detergents, rust inhibitors, dehazing agents, demulsifying agents, metal deactivating agents, friction modifiers, viscosity modifiers (including polymeric viscosity modifiers), pour point depressants, antifoaming agents,Atorney Docket No.: T-12767-WO01 co-solvents, corrosion-inhibitors, ashless dispersants, multifunctional agents, dyes, extreme pressure agents and the like and mixtures thereof. A variety of the additives are known and commercially available. These additives, or their analogous compounds, can be employed for the preparation of the lubricating oil compositions of the disclosure by the usual blending procedures.

[0113]

[0072] Additional lubricating oil additives include one or more zinc dialkyldithiophosphate. Zinc dialkyldithiophosphates have linkages that may be derived from alcohol(s) including primary alcohol(s) and / or secondary alcohol(s). In some embodiments, the lubricating oil composition includes dialkyldithiophosphate derived from primary alcohol and the zinc dialkyldithiophosphate derived from secondary alcohol are present in a molar ratio of 0:100 to 100:0. In some embodiments, the zinc dialkyldithiophosphates have an average total carbon content of 10 to 60 carbon atoms per molecule of zinc alkyldithiophosphate, such as from 10 to 55 carbon atoms per molecule, 10 to 50 carbon atoms per molecule, 10 to 45 carbon atoms per molecule, 10 to 40 carbon atoms per molecule, 10 to 35 carbon atoms per molecule, 15 to 60 carbon atoms per molecule, 15 to 55 carbon atoms per molecule, 15 to 50 carbon atoms per molecule, 15 to 45 carbon atoms per molecule, 15 to 40 carbon atoms per molecule, or 15 to 35 carbon atoms per molecule.

[0114]

[0073] Additional lubricating oil additives may optionally include one or more viscosity index improvers, such as alkyl methacrylate polymers, polyolefins, olefin-based copolymers (e.g., ethylene-propylene or styrene-diene copolymers), and the like, and mixtures thereof.

[0115]

[0074] In the preparation of lubricating oil formulations, it is common practice to introduce the additives in the form of 10 to 80 wt. % active ingredient concentrates in hydrocarbon oil, e.g. mineral lubricating oil, or other suitable solvent. Usually, these concentrates may be diluted with 3 to 100, e.g., 5 to 40, parts by weight of lubricating oil per part by weight of the additive package in forming finished lubricants, e.g. crankcase motor oils. The purpose ofAttorney Docket No.: T-12767-WO01 concentrates is to make the handling of the various materials less difficult and awkward as well as to facilitate solution or dispersion in the final blend.

[0116]

[0075] The lubricating oil composition may have a high temperature high shear (HTHS) viscosity at 150°C of 3.7 cP or less, such as 3.6 cP or less, 3.5 cP or less, 3.4 cP or less, 3.3 cP or less, 3.2 cP or less, 3.1 cP or less, 3.0 cP or less, 2.9 cP or less, 2.8 cP or less, 2.7 cP or less, 2.6 cP or less, 2.5 cP or less, 2.4 cP or less, 2.3 cP or less, 2.2 cP or less, 2.1 cP or less, 2.0 cP or less, 1.9 cP or less, 1.8 cP or less, 1.7 cP or less, 1.0 to 3.5 cP, 1.7 to 3.5 cP, 2.0 to 3.5 cP, 2.3 to 3.5 cP, 1.0 to 2.9 cP, 1.3 to 2.9 cP, 1.7 to 2.9 cP, 2.0 to 2.9 cP, 2.3 to 2.9 cP, 1.0 to 2.6 cP, 1.3 to 2.6 cP, 1.0 cP to 2.3 cP, 1.3 cP to 2.3 cP, 1.3 cP to 2.3 cP.

[0117]

[0076] The lubricating oil composition may have a kinematic viscosity KV at 100°C (ASTM D445) in the range of 4.0 to 16.3 mm2 / s such as 4.0 to 15 mm2 / s, 4.0 to 14 mm2 / s, 4.0 to 13 mm2 / s, 5.0 to 16.3 mm2 / s, 5.0 to 15 mm2 / s, 5.0 to 14 mm2 / s, 5.0 to 13 mm2 / s, 6.1 to 16.3 mm2 / s, 6.1 to 15 mm2 / s, 6.1 to 14 mm2 / s, or 6.1 to 13 mm2 / s.

[0118]

[0077] The following examples are presented to exemplify embodiments of the invention but are not intended to limit the invention to the specific embodiments set forth. Unless indicated to the contrary, all parts and percentages are by weight. All numerical values are approximate. When numerical ranges are given, it should be understood that embodiments outside the stated ranges may still fall within the scope of the invention. Specific details described in each example should not be construed as necessary features of the invention.

[0119] EXAMPLES

[0120]

[0078] The following examples are intended for illustrative purposes only and do not limit in any way the scope of the present invention. Lubricating oil samples were tested for their ability to impact fuel economy via Sequence VIE Engine Test in accordance with ASTM D8114 specification. The test measures Fuel Economy Index (FEI) and provides a pass / fail outcomeAtorney Docket No.: T-12767-WO01 based on retention of fuel economy index (FEI2). Pass / fail criteria depends on the viscosity of the finished oil sample tested. According to GF-7, FEI2 limit for XW-20 oil is 2.1%, XW-30 oil is 1.8%, while 10W-30 oil is 1.4%. The results of the tests are summarized in Table 2 below.

[0121] Table 2

[0122] Comp. Comp. Comp.

[0123] Ex. I10Ex. 210Ex. 110Ex. 210Ex. 310

[0124] Base Oil (Group

[0125] Balance Balance Balance Balance Balance III)

[0126] N from

[0127] Dispersant (ppm 437 437 437 397 397 N)

[0128] Mg (ppm)1510 510 510 450 450

[0129] Ca Sulfonate 1

[0130] 967 966 966 750 750 (ppm Ca)2

[0131] Ca Phenate (ppm

[0132] 400 400 400 321 321 Ca)3

[0133] Total Ca (ppm) 1367 1366 1410 1071 1071

[0134] Boron (ppm)4105 38 40 38 38 N from Ashless

[0135] Aryl Amine 441

[0136] 442 441 272 272 Antioxidant

[0137] (PPm)5

[0138] Mo (ppm)6180 180 710 180 180

[0139] Ashless FM 1

[0140] - 0.3 - - (wt%)7- Ashless FM 2

[0141] - - - 0.3 0.15 (wt%)8

[0142] ZDDP (ppm Zn)9892 892 890 820 820

[0143]

[0144] Attorney Docket No.: T-12767-WO01 TBN (mg

[0145] 8.4 8.4 8.4 6.6 6.6 KOH / g)

[0146] Sulfated Ash

[0147] 1.0 1.0 0.9 0.6 0.6 (wt%)

[0148] Viscosity Grade 0W-20 0W-20 0W-20 0W-20 5W-30 KV100 (cSt) 8.65 8.61 8.70 8.61 12.05 HTHS150 (cP) 2.6 2.6 2.6 2.6 - Fuel Economy

[0149] Fail Fail Pass Pass Retention (FEI2) Fail

[0150]

[0151] 1Mg from a 635 TB ST Mg Sulfonate detergent (oil-free basis)

[0152] 2Ca from a 708 TBN Ca Sulfonate detergent (oil-free basis)

[0153] 3Ca from a 375 TBN Ca Phenate detergent (oil-free basis) wherein the alkyl group is derived from a C20 to C24 isomerized normal alpha olefin and I is about 0.26.

[0154] 4All boron is derived from a borated succinimide dispersant

[0155] 5N from a dinonyldiphenylamine antioxidant

[0156] 6Mo from a molybdenum succinimide antioxidant

[0157] 7Ashless FM l is a glycerol monooleate

[0158] 8Ashless FM 2 is a glycerol cocoate

[0159] 9Zn from a Zinc dialkyldithiophosphate having an average carbon content of 10 to 60 carbons per molecule of Zinc dialkyldithiophosphate.

[0160] 10Includes an olefin copolymer viscosity index improver

[0161]

[0079] While the disclosure is susceptible to various modifications and alternative forms, specific embodiments thereof are herein described in detail. It should be understood, however, that the description herein of specific embodiments is not intended to limit the disclosure to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the disclosure as defined by the appended claims.Atorney Docket No.: T-12767-WO01

[0162]

[0080] Note that not all of the activities described in the general description or the examples are required, that a portion of a specific activity may not be required, and that one or more further activities may be performed in addition to those described. Still further, the order in which activities are listed is not necessarily the order in which they are performed.

[0163]

[0081] Benefits, other advantages, and solutions to problems have been described herein with regard to specific embodiments. However, the benefits, advantages, solutions to problems, and any feature(s) that may cause any benefit, advantage, or solution to occur or become more pronounced are not to be construed as a critical, required, or essential feature of any or all the claims.

[0164]

[0082] The specification and illustrations of the embodiments described herein are intended to provide a general understanding of the structure of the various embodiments.

[0165]

[0083] The specification and illustrations are not intended to serve as an exhaustive and comprehensive description of all the elements and features of formulations, compositions, apparatus and systems that use the structures or methods described herein. Separate embodiments may also be provided in combination in a single embodiment, and conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination. Further, reference to values stated in ranges includes each and every value within that range. Many other embodiments may be apparent to skilled artisans only after reading this specification. Other embodiments may be used and derived from the disclosure, such that a structural substitution, logical substitution, or another change may be made without departing from the scope of the disclosure. Accordingly, the disclosure is to be regarded as illustrative rather than restrictive.

Claims

Attorney Docket No.: T-12767-WO01What is Claimed:

1. A lubricating oil composition comprising:one or more base oils of lubricating viscosity;one or more nitrogen-containing dispersants present in an amount to provide 320 to 600 ppm of N to the lubricating oil composition,one or more magnesium-containing detergents present in an amount to provide 300 to 600 ppm of Mg to the lubricating oil composition, wherein at least one of the one or more magnesium containing detergent additive is magnesium sulfonate;at least two calcium-containing detergents including a calcium sulfonate with a total base number of at least 600 mg / KOH on an oil-free basis, and a calcium phenate with a total base number of at least 300 mg / KOH on an oil-free basis, wherein the at least two calcium-containing detergents are present in an amount to provide between 800 to 1300 ppm of Ca to the lubricating oil composition;one or more aryl amine ashless antioxidants present in an amount to provide at least 85 ppm of N to the lubricating oil composition; andat least one molybdenum-containing additive present in an amount to provide between 40 to 350 ppm of Mo to the lubricating oil composition.

2. The lubricating oil composition of claim 1, further comprising an ashless friction modifier.

3. The lubricating oil composition of claim 2, wherein the ashless friction modifier is an ashless ester-based friction modifier.

4. The lubricating oil composition of claim 3, wherein the ashless ester-based friction modifier is derived from coconut oil.Attorney Docket No.: T-12767-WO015. The lubricating oil composition of claim 1, further comprising zinc dialkyldithiophosphate derived from primary alcohol or secondary alcohol, or both.

6. The lubricating oil composition of claim 5, wherein the primary alcohol and the secondary alcohol are present in a molar ratio of 0: 100 to 100:0 and have an average total carbon content of 10 to 60 carbon atoms per molecule of zinc alkyldithiophosphate.

7. The lubricating oil composition of claim 1, wherein lubricating oil composition includes less than 1 wt.% of PAO base oil and ester base oil, based on total lubricating oil composition.

8. The lubricating oil composition of claim 1, wherein the lubricating oil composition includes less than 120 ppm of calcium from calcium phenate derived from tetrapropenyl phenol or tetrapropenyl phenate.

9. The lubricating oil composition of claim 1, wherein the lubricating oil composition includes sulfurized calcium phenate detergent.

10. The lubricating oil composition of claim 1, wherein the sulfurized calcium phenate includes an alkyl group derived from an isomerized normal alpha olefin having from about 10 to 40 carbons.

11. The lubricating oil composition of claim 1, wherein the alkyl group of the calcium phenate is derived from an isomerized normal alpha olefin with an isomerization level (I) of from about 0.1 to about 0.4.Attorney Docket No.: T-12767-WO0110. The lubricating oil composition of claim 1, wherein the lubricating oil composition includes less than 80 ppm of boron.

11. The lubricating oil composition of claim 1, wherein the lubricating oil composition has a total base number of 6.0 to 9.5 mg KOH / g as measured by ASTM D-2896 and a sulfated ash content of 0.6 to 1.0 wt.%.

12. The lubricating oil composition of claim 1, wherein the one or more base oils of lubricating viscosity is present in at least 50 wt.% based on total weight of the lubricating oil composition.

13. The lubricating oil composition of claim 1, wherein the lubricating oil composition includes calcium phenate present in an amount to provide at least 280 ppm of Ca to the lubricating oil composition.

14. A method of improving fuel economy comprising lubricating an engine with a lubricating oil composition comprising:one or more base oils of lubricating viscosity;one or more nitrogen-containing dispersants present in an amount to provide 320 to 600 ppm of N to the lubricating oil composition,one or more magnesium-containing detergents present in an amount to provide 300 to 600 ppm of Mg to the lubricating oil composition, wherein at least one of the one or more magnesium containing detergent additive is magnesium sulfonate;at least two calcium-containing detergents including a calcium sulfonate with a total base number of at least 600 mg / KOH on an oil-free basis, and a calcium phenate with a total baseAttorney Docket No.: T-12767-WO01number of at least 300 mg / KOH on an oil-free basis, wherein the at least two calcium-containing detergents are present in an amount to provide between 800 to 1300 ppm of Ca to the lubricating oil composition;one or more aryl amine ashless antioxidants present in an amount to provide at least 85 ppm of N to the lubricating oil composition; andat least one molybdenum-containing additive present in an amount to provide between 40 to 350 ppm of Mo to the lubricating oil composition.

15. The method of claim 14, wherein the lubricating oil composition includes less than 80 ppm of boron and has a total base number of 6.0 to 9.5 mg KOH / g as measured by ASTM D-2896 and a sulfated ash content of 0.6 to 1.0 wt.%.

16. The method of claim 14, wherein the lubricating oil composition further comprises an ashless friction modifier.

17. The method of claim 16, wherein the ashless friction modifier is an ashless ester-based friction modifier.

18. The method of claim 14, wherein the lubricating oil composition further comprises zinc dialkyldithiophosphate derived from primary alcohol or secondary alcohol, or both.

19. The method of claim 14, wherein the lubricating oil composition includes less than 1 wt.% of PAO base oil and ester base oil, based on total lubricating oil composition.Attorney Docket No.: T-12767-WO0120. The method of claim 14, wherein the lubricating oil composition includes less than 120 ppm of calcium from calcium phenate derived from tetrapropenyl phenol or tetrapropenyl phenate.

21. The method of claim 14, wherein the lubricating oil composition includes sulfurized calcium phenate detergent.

22. The method of claim 21, wherein the sulfurized calcium phenate includes an alkyl group derived from an isomerized normal alpha olefin having from about 10 to 40 carbons.

23. The method of claim 22, wherein the alkyl group of the calcium phenate is derived from an isomerized normal alpha olefin with an isomerization level (I) of from about 0.1 to about 0.4.

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