Crankcase lubricant for engines

Abstract

A method for preventing or reducing copper corrosion in a hybrid vehicle, hydrogen, natural gas, or ammonia fueled internal combustion engine is described. The method involves the step of lubricating the internal combustion engine with a lubricating oil composition that includes a fatty acid sorbitan ester present in an amount of 0.1 wt.% to 5 wt.% based on the total lubricating oil composition.

Description

Attorney Docket No. : T-12572-WO01CRANKCASE LUBRICANT FOR ENGINESCROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 714,200, filed October 31, 2024, which is incorporated by reference herein in its entirety.FIELD OF THE INVENTION

[0002] This disclosure relates to a lubricating oil composition designed specifically for use in hybrid vehicles or natural gas, hydrogen fueled, or ammonia fueled engines. More particularly, this disclosure relates to a crankcase lubricating oil composition containing fatty acid sorbitan esters.BACKGROUND OF THE INVENTION

[0003] Hydrogen and ammonia are being evaluated by various engine manufacturers as low / zero carbon fuels to meet the stringent tailpipe CO2 and greenhouse gas emissions regulations. Hydrogen and ammonia have unique properties when compared to more conventional fuels such as diesel, gasoline, and natural gas. One of the major combustion by-products in hydrogen and ammonia engines is water vapor, which can find its way into the crankcase via blow-by gases. Once in the crankcase, the water vapor can condense and lead to water build-up in the engine oil, which can lead to corrosion of copper and iron / steel which are key materials for critical hardware like - bearings, cylinder liner, pistons, gears etc. Similar challenges are present in hybrid vehicles, natural gas and ammonia fueled engines.SUMMARYAttorney Docket No. : T-12572-WO01

[0004] In one aspect, the present disclosure relates to a method for preventing or reducing copper corrosion in a hybrid vehicle, hydrogen, natural gas, or ammonia fueled internal combustion engine, the method including the step of lubricating the internal combustion engine with a lubricating oil composition comprising a fatty acid sorbitan ester present in an amount of 0.1 wt.% to 5 wt.% based on the total lubricating oil composition.

[0005] In another aspect, the present disclosure relates to the use of a fatty acid sorbitan ester in a crankcase lubricant to reduce or prevent corrosion in a hybrid vehicle, natural gas, hydrogen, or ammonia fueled internal combustion engine, wherein the fatty acid sorbitan ester is present in 0.1 wt.% to 5.0 wt.% based on the total weight of the lubricating oil composition.DETAILED DESCRIPTION OF THE INVENTION

[0006] 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.Definitions

[0007] 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.Attorney Docket No. : T-12572-WO01

[0008] All percentages reported are weight % on an active ingredient basis (i.e., without regard to carrier or diluent oil) unless otherwise stated.

[0009] A “major amount” means in excess of about 50 wt.% of a composition.

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

[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.

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

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

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

[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.

[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.DescriptionAttorney Docket No. : T-12572-WO01

[0017] The present disclosure relates to lubricating oil compositions for reducing or preventing corrosion in hybrid vehicles or natural gas, hydrogen, or ammonia fueled engines and methods of using the compositions thereof. It is contemplated that as technology matures, hydrogen fueled combustion engines will be increasingly adopted in various types of gaseous- fueled applications including on-road, off-road automobiles, marine vessels, railroad trains, stationary gas engines, gas cogeneration systems and the like.

[0018] In one embodiment, the lubricating oil composition is designed to be used to lubricate crankcase (“crankcase lubricant”). The lubricating oil composition includes an oil of lubricating viscosity and a fatty acid sorbitan ester. In one embodiment, the lubricating oil composition of this disclosure may be a monograde engine oil, e.g., a SAE 20, SAE 30, SAE 40, SAE 50 or SAE 60 viscosity grade engine oil.

[0019] In one embodiment, the lubricating oil composition of this disclosure may be a multigrade engine oil, e g., an engine oil with a SAE viscosity grade of 0W-X, 5W-X, 10W-X, 15W-X, 20W-X or 25W-X, where X may be selected from 8, 12, 16, 20, 30, 40, 50, or 60.Fatty Acid Sorbitan Esters

[0020] The lubricating oil composition of this disclosure includes a fatty acid sorbitan ester. The fatty acid sorbitan ester may be represented by the following generalized structure:wherein R is a C8-C30 hydrocarbyl group. In some embodiments, R is saturated or unsaturated.In some embodiments, R is linear or branched. In some embodiments, R is aryl or aliphatic.Attorney Docket No. : T-12572-WO01Specific examples of R include phenyl, lauryl group, stearyl group, oleyl group, myristyl group, and the like.

[0021] The fatty acid sorbitan ester is present at 0.1 wt.% to about 5.0 wt.% based on the total weight of the lubricating oil composition, such as 0.1 wt.% to 4.8 wt.%, 0.1 wt.% to 4.6 wt.%, 0.1 wt.% to 4.4 wt.%, 0.1 wt.% to 4.2 wt.%, 0.1 wt.% to 4.0 wt.%, 0.1 wt.% to 3.8 wt.%, 0.1 wt.% to 3.6 wt.%, 0.1 wt.% to 3.4 wt.%, 0.1 wt.% to 3.2 wt.%, 0.1 wt.% to 3.0 wt.%, 0.1 wt.% to 2.8 wt.%, 0.1 wt.% to 2.6 wt.%, 0.1 wt.% to 2.4 wt.%, 0.1 wt.% to 2.2 wt.%, 0.1 wt.% to 2.0 wt.%, 0.5 wt.% to 5.0 wt.%, 0.5 wt.% to 4.8 wt.%, 0.5 wt.% to 4.6 wt.%, 0.5 wt.% to 4.4 wt.%, 0.5 wt.% to 4.2 wt.%, 0.5 wt.% to 4.0 wt.%, 0.5 wt.% to 3.0 wt.%, 0.5 wt.% to 2.8 wt.%, 0.5 wt.% to 2.6 wt.%, 0.5 wt.% to 2.4 wt.%, 0.5 wt.% to 2.2 wt.%, 0.5 wt.% to 2.0 wt.%, 1.0 wt.% to 5.0 wt.%, 1.0 wt.% to 4.8 wt.%, 1.0 wt.% to 4.6 wt.%, 1.0 wt.% to 4.4 wt.%, 1.0 wt.% to 4.2 wt.%, 1.0 wt.% to 4.0 wt.%, 1.0 wt.% to 3.8 wt.%, 1.0 wt.% to 3.6 wt.%, 1.0 wt.% to 3.4 wt.%, 1.0 wt.% to 3.2 wt.%, 1.0 wt.% to 3.0 wt.%, 1.0 wt.% to 2.8 wt.%, 1.0 wt.% to 2.6 wt.%, 1.0 wt.% to 2.4 wt.%, 1.0 wt.% to 2.2 wt.%, or 1.0 wt.% to 2.0 wt.%.Detergents

[0022] The lubricating oil may further include a metal detergent such as, but not limited to, sulfonate or phenate detergent. In some embodiments, the sulfonate is a Ca or Mg sulfonate. In some embodiments, the phenate is a Ca or Mg sulfonate.

[0023] A typical detergent is an anionic material that contains a long chain hydrophobic portion of the molecule and a smaller anionic or oleophobic hydrophilic portion of the molecule. The counterion is typically calcium or magnesium.

[0024] Salts that contain stoichiometric amount of the metal are described as neutral salts and have a total base number (TBN) of from 0 to 80 mg KOH / g as measured by ASTM D-2896.Attorney Docket No. : T-12572-WO01

[0025] Many detergents are overbased, containing large amounts of a metal base that is achieved by reacting an excess of a metal compound (e.g., a metal hydroxide or oxide) rich an acidic gas (e.g., carbon dioxide).

[0026] Useful detergents can be neutral, mildly overbased, or highly overbased.

[0027] In some embodiments, at least some detergent used in the detergent system may be overbased. Overbased detergents help neutralize acidic impurities produced by the combustion process and entrapped in the oil. The degree of overbasing generally depends on the ratio of metallic ion to anionic portion of the detergent on an equivalent basis.

[0028] An overbased detergent will typically have a TBN of 10 mg KOH / g or higher as measured by ASTM D-2896, such as from 15 mg KOH / g or higher, 25 mg KOH / g or higher, 50 mg KOH / g or higher, 75 mg KOH / g or higher, 100 mg KOH / g or higher, 125 mg KOH / g or higher, 150 mg KOH / g or higher, 175 mg KOH / g or higher, 200 mg KOH / g or higher, 225 mg KOH / g or higher, 250 mg KOH / g or higher, 275 mg KOH / g or higher, 300 mg KOH / g or higher, 325 mg KOH / g or higher, 350 mg KOH / g or higher, 375 mg KOH / g or higher, 400 mg KOH / g or higher, 425 mg KOH / g or higher, 450 mg KOH / g or higher, 475 mg KOH / g or higher, 500 mg KOH / g or higher, 525 mg KOH / g or higher, 550 mg KOH / g or higher, 575 mg KOH / g or higher, 600 mg KOH / g or higher and 650 mg KOH / g or higher.

[0029] In some embodiments, the overbased detergent has a TBN of 10 to 650 mg KOH / g as measured by ASTM D-2896, such as 10 to 600 mg KOH / g, 10 to 550 mg KOH / g, 10 to 500 mg KOH / g, 10 to 450 mg KOH / g, 10 to 400 mg KOH / g, 10 to 350 mg KOH / g, 10 to 300 mg KOH / g, 10 to 250 mg KOH / g, 10 to 200 mg KOH / g, 10 to 150 mg KOH / g, 10 to 100 mg KOH / g, 10 to 50 mg KOH / g, 50 to 650 mg KOH / g, 50 to 600 mg KOH / g, 50 to 550 mg KOH / g, 50 to 500 mg KOH / g, 50 to 450 mg KOH / g, 50 to 400 mg KOH / g, 50 to 350 mg KOH / g, 50 to 300 mg KOH / g,Attorney Docket No. : T-12572-WO0150 to 250 mg KOH / g, 50 to 200 mg KOH / g, 50 to 150 mg KOH / g, 50 to 100 mg KOH / g, 100 to650 mg KOH / g, 100 to 600 mg KOH / g, 100 to 550 mg KOH / g, 100 to 500 mg KOH / g, 100 to 450 mg KOH / g, 100 to 400 mg KOH / g, 100 to 350 mg KOH / g, 100 to 300 mg KOH / g, 100 to 250 mgKOH / g, 100 to 200 mg KOH / g, 100 to 150 mg KOH / g, 150 to 650 mg KOH / g, 150 to 600 mgKOH / g, 150 to 550 mg KOH / g, 150 to 500 mg KOH / g, 150 to 450 mg KOH / g, 150 to 400 mgKOH / g, 150 to 350 mg KOH / g, 150 to 300 mg KOH / g, 150 to 250 mg KOH / g, 150 to 200 mgKOH / g, 200 to 650 mg KOH / g, 200 to 600 mg KOH / g, 200 to 550 mg KOH / g, 200 to 500 mgKOH / g, 200 to 450 mg KOH / g, 200 to 400 mg KOH / g, 200 to 350 mg KOH / g, 200 to 300 mgKOH / g, 200 to 250 mg KOH / g, 250 to 650 mg KOH / g, 250 to 600 mg KOH / g, 250 to 550 mgKOH / g, 250 to 500 mg KOH / g, 250 to 450 mg KOH / g, 250 to 400 mg KOH / g, 250 to 350 mgKOH / g, 250 to 300 mg KOH / g, 300 to 650 mg KOH / g, 300 to 600 mg KOH / g, 300 to 550 mgKOH / g, 300 to 500 mg KOH / g, 300 to 450 mg KOH / g, 300 to 400 mg KOH / g, 300 to 350 mgKOH / g, 350 to 650 mg KOH / g, 350 to 600 mg KOH / g, 350 to 550 mg KOH / g, 350 to 500 mgKOH / g, 350 to 450 mg KOH / g, 350 to 400 mg KOH / g, 400 to 650 mg KOH / g, 400 to 600 mgKOH / g, 400 to 550 mg KOH / g, 400 to 500 mg KOH / g, 400 to 450 mg KOH / g, 450 to 650 mgKOH / g, 450 to 600 mg KOH / g, 450 to 550 mg KOH / g, 450 to 500 mg KOH / g, 500 to 650 mgKOH / g, 500 to 600 mg KOH / g, 500 to 550 mg KOH / g, 550 to 650 mg KOH / g, 550 to 600 mgKOH / g, or 600 to 650 mg KOH / g.

[0030] In some embodiments, the overbased detergent has a TBN of 10 to 150 mg KOH / g, such as from 10 to 140 mg KOH / g, 10 to 130 mg KOH / g, 10 to 120 mg KOH / g, 10 to 110 mg KOH / g, 10 to 100 mg KOH / g, 10 to 90 mg KOH / g, 10 to 80 mg KOH / g, 10 to 70 mg KOH / g, 10 to 60 mg KOH / g, 10 to 50 mg KOH / g, 10 to 40 mg KOH / g, 10 to 30 mg KOH / g, 10 to 20 mg KOH / g, 20 to 150 mg KOH / g, 20 to 140 mg KOH / g, 20 to 130 mg KOH / g, 20 to 120 mg KOH / g,Attorney Docket No. : T-12572-WO0120 to 110 mg KOH / g, 20 to 100 mg KOH / g, 20 to 90 mg KOH / g, 20 to 80 mg KOH / g, 20 to 70 mg KOH / g, 20 to 60 mg KOH / g, 20 to 50 mg KOH / g, 20 to 40 mg KOH / g, 20 to 30 mg KOH / g,30 to 150 mg KOH / g, 30 to 140 mg KOH / g, 30 to 130 mg KOH / g, 30 to 120 mg KOH / g, 30 to 110 mg KOH / g, 30 to 100 mg KOH / g, 30 to 90 mg KOH / g, 30 to 80 mg KOH / g, 30 to 70 mg KOH / g, 30 to 60 mg KOH / g, 30 to 50 mg KOH / g, 30 to 40 mg KOH / g, 40 to 150 mg KOH / g, 40 to 140 mg KOH / g, 40 to 130 mg KOH / g, 40 to 120 mg KOH / g, 40 to 110 mg KOH / g, 40 to 100 mg KOH / g, 40 to 90 mg KOH / g, 40 to 80 mg KOH / g, 40 to 70 mg KOH / g, 40 to 60 mg KOH / g, 40 to 50 mg KOH / g, 50 to 150 mg KOH / g, 50 to 140 mg KOH / g, 50 to 130 mg KOH / g, 50 to 120 mg KOH / g, 50 to 110 mg KOH / g, 50 to 100 mg KOH / g, 50 to 90 mg KOH / g, 50 to 80 mg KOH / g,50 to 70 mg KOH / g, 50 to 60 mg KOH / g, 60 to 150 mg KOH / g, 60 to 140 mg KOH / g, 60 to 130 mg KOH / g, 60 to 120 mg KOH / g, 60 to 110 mg KOH / g, 60 to 100 mg KOH / g, 60 to 90 mgKOH / g, 60 to 80 mg KOH / g, 60 to 70 mg KOH / g, 80 to 150 mg KOH / g, 80 to 140 mg KOH / g, 80 to 130 mg KOH / g, 80 to 120 mg KOH / g, 80 to 110 mg KOH / g, 80 to 100 mg KOH / g, 80 to 90 mg KOH / g, 90 to 150 mg KOH / g, 90 to 140 mg KOH / g, 90 to 130 mg KOH / g, 90 to 120 mg KOH / g, 90 to 110 mg KOH / g, 90 to 100 mg KOH / g, 100 to 150 mg KOH / g, 100 to 140 mgKOH / g, 100 to 130 mg KOH / g, 100 to 120 mg KOH / g, 100 to 110 mg KOH / g, 110 to 150 mgKOH / g, 110 to 140 mg KOH / g, 110 to 130 mg KOH / g, 110 to 120 mg KOH / g, 120 to 150 mgKOH / g, 120 to 140 mg KOH / g, 120 to 130 mg KOH / g, 130 to 150 mg KOH / g, 130 to 140 mgKOH / g, or 140 to 150 mg KOH / g.Oil of Lubricating Viscosity

[0031] 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.Attorney Docket No. : T-12572-WO01

[0032] 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).

[0033] 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.

[0034] 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.

[0035] Synthetic lubricating oils include hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(l -hexenes), poly (1 -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.

[0036] 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.,Attorney Docket No. : T-12572-WO01 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 linoleic 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.

[0037] 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 bio-derived sources may also be useful as synthetic oils.

[0038] 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.

[0039] 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 farnesene. In some embodiments, the biobased hydrocarbon is produced from fatty acids or fatty esters.Attorney Docket No. : T-12572-WO01

[0040] 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 steps 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.

[0041] 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.

[0042] 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:Table 1(a) Determined in accordance with ASTM D2007.Attorney Docket No. : T-12572-WO01(b) Determined in accordance with ASTM D2622, ASTM D3120, ASTM D4294 or ASTM D4927.(c) Determined in accordance with ASTM D2270.

[0043] 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 I 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.

[0044] In one embodiment, the base oil is a Group II base oil or a blend of two or more different Group II base oils. Suitable Group II 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.Additional Lubricating Oil Additives

[0045] 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 incorporatedAttorney Docket No. : T-12572-WO01 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, 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.

[0046] The lubricating oil composition of the present invention can contain one or more detergents. Metal -containing or ash-forming detergents function as both detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life. Detergents generally comprise a polar head with a long hydrophobic tail. The polar head comprises a metal salt of an acidic organic compound. The salts may contain a substantially stoichiometric amount of the metal in which case they are usually described as normal or neutral salts. A large amount of a metal base may be incorporated by reacting excess metal compound (e.g., an oxide or hydroxide) with an acidic gas (e.g., carbon dioxide).

[0047] Detergents that may be used include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and naphthenates and other oilsoluble carboxylates of a metal, particularly the alkali or alkaline earth metals, e.g., barium, sodium, potassium, lithium, calcium, and magnesium. The most commonly 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.Attorney Docket No. : T-12572-WO01

[0048] The lubricating oil composition of the present invention can contain one or more antiwear agents that can reduce friction and excessive wear. Any anti-wear agent known by a person of ordinary skill in the art may be used in the lubricating oil composition. Non-limiting examples of suitable anti-wear agents include zinc dithiophosphate, metal (e.g., Pb, Sb, Mo and the like) salts of dithiophosphates, metal (e.g., Zn, Pb, Sb, Mo and the like) salts of dithiocarbamates, metal (e g., Zn, Pb, Sb and the like) salts of fatty acids, boron compounds, phosphate esters, phosphite esters, amine salts of phosphoric acid esters or thiophosphoric acid esters, reaction products of dicyclopentadiene and thiophosphoric acids and combinations thereof. The amount of the antiwear agent may vary from about 0.01 wt.% to about 5 wt.%, from about 0.05 wt.% to about 3 wt.%, or from about 0.1 wt.% to about 1 wt.%, based on the total weight of the lubricating oil composition.

[0049] In certain embodiments, the anti-wear agent is or comprises a dihydrocarbyl di thiophosphate metal salt, such as zinc dialkyl dithiophosphate compounds. The metal of the dihydrocarbyl dithiophosphate metal salt may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper. In some embodiments, the metal is zinc. In other embodiments, the alkyl group of the dihydrocarbyl dithiophosphate metal salt has from about 3 to about 22 carbon atoms, from about 3 to about 18 carbon atoms, from about 3 to about 12 carbon atoms, or from about 3 to about 8 carbon atoms. In further embodiments, the alkyl group is linear or branched.

[0050] The amount of the dihydrocarbyl dithiophosphate metal salt including the zinc dialkyl dithiophosphate salts in the lubricating oil composition disclosed herein is measured by its phosphorus content. In some embodiments, the phosphorus content of the lubricating oilAttorney Docket No. : T-12572-WO01 composition disclosed herein is from about 0.01 wt.% to about 0.14 wt.%, based on the total weight of the lubricating oil composition.

[0051] The lubricating oil composition of the present invention can contain one or more friction modifiers that can lower the friction between moving parts. Any friction modifier known by a person of ordinary skill in the art may be used in the lubricating oil composition. Non-limiting examples of suitable friction modifiers include fatty carboxylic acids; derivatives (e.g., alcohol, esters, borated esters, amides, metal salts and the like) of fatty carboxylic acid; mono-, di- or trialkyl substituted phosphoric acids or phosphonic acids; derivatives (e.g., esters, amides, metal salts and the like) of mono-, di- or tri-alkyl substituted phosphoric acids or phosphonic acids; mono-, di- or tri-alkyl substituted amines; mono- or di-alkyl substituted amides and combinations thereof. In some embodiments examples of friction modifiers include, but are not limited to, alkoxylated fatty amines; borated fatty epoxides; fatty phosphites, fatty epoxides, fatty amines, borated alkoxylated fatty amines, metal salts of fatty acids, fatty acid amides, glycerol esters, borated glycerol esters; and fatty imidazolines as disclosed in U.S. Patent No. 6,372,696, the contents of which are incorporated by reference herein; friction modifiers obtained from a reaction product of a C4 to C75, or a C6 to C24, or a C6 to C20, fatty acid ester and a nitrogen-containing compound selected from the group consisting of ammonia, and an alkanolamine and the like and mixtures thereof. The amount of the friction modifier may vary from about 0.01 wt.% to about 10 wt.%, from about 0.05 wt.% to about 5 wt.%, or from about 0.1 wt.% to about 3 wt.%, based on the total weight of the lubricating oil composition.

[0052] The lubricating oil composition of the disclosure can contain a molybdenum- containing friction modifier. The molybdenum-containing friction modifier can be any one of theAttorney Docket No. : T-12572-WO01 known molybdenum-containing friction modifiers or the known molybdenum-containing friction modifier compositions.

[0053] Preferred molybdenum-containing friction modifier is, for example, sulfurized oxymolybdenum dithiocarbamate, sulfurized oxymolybdenum dithiophosphate, aminemolybdenum complex compound, oxymolybdenum diethylate amide, and oxymolybdenum monoglyceride. Most preferred is a molybdenum dithiocarbamate friction modifier.

[0054] The lubricating oil composition of the invention generally contains the molybdenum- containing friction modifier in an amount of 0.01 to 0.15 wt.% in terms of the molybdenum content.

[0055] The lubricating oil composition of the invention preferably contains an organic oxidation inhibitor in an amount of 0.01-5 wt.%, preferably 0.1-3 wt.%. The oxidation inhibitor can be a hindered phenol oxidation inhibitor or a diarylamine oxidation inhibitor. The diarylamine oxidation inhibitor is advantageous in giving a base number originating from the nitrogen atoms. The hindered phenol oxidation inhibitor is advantageous in producing no NOx gas.

[0056] Examples of the hindered phenol oxidation inhibitors include 2,6-di-t-butyl-p-cresol, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-methylenebis(6-t-butyl-o-cresol), 4,4'- isopropylidenebis(2,6-di-t-butylphenol), 4,4'-bis(2,6-di-t-butylphenol), 2,2'-methylenebis(4- methyl-6-t-butylphenol), 4,4'-thiobis(2-methyl-6-t-butylphenol), 2,2-thio-diethylenebis[3-(3,5-di- t-butyl-4-hydroxyphenyl)propionate], octyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, and octyl 3-(3,54-butyl-4-hydroxy-3- methylphenyl)propionate, and commercial products such as, but not limited to, Irganox LI 35® (BASF), Naugalube 531® (Chemtura), and Ethanox 376® (SI Group).Attorney Docket No. : T-12572-WO01

[0057] Examples of the diarylamine oxidation inhibitors include alkyldiphenylamine having a mixture of alkyl groups of 4 to 9 carbon atoms, p,p'-dioctyldiphenylamine, phenylnaphthylamine, phenyl-naphthylamine, alkylated-naphthylamine, and alkylated phenylnaphthylamine.

[0058] Each of the hindered phenol oxidation inhibitor and diarylamine oxidation inhibitor can be employed alone or in combination. If desired, other oil soluble oxidation inhibitors can be employed in combination with the above-mentioned oxidation inhibitor(s).

[0059] The lubricating oil composition of the invention may further contain an oxymolybdenum complex of succinimide, particularly a sulfur-containing oxymolybdenum complex of succinimide. The sulfur-containing oxymolybdenum complex of succinimide can provide increased oxidation inhibition when it is employed in combination with the above- mentioned phenolic or amine oxidation inhibitors.

[0060] 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 of 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.Preparing Lubricating Oil Compositions

[0061] The lubricating oil compositions disclosed herein can be prepared by any method known to a person of ordinary skill in the art for making lubricating oils. In some embodiments, the base oil can be blended or mixed with the sulfurized calcium phenate detergent describedAttorney Docket No. : T-12572-WO01 herein. Optionally, one or more other additives in addition to the phenolic-based calcium detergent can be added. The phenolic-based calcium detergent compounds and the optional additives may be added to the base oil individually or simultaneously. In some embodiments, the phenolic-based calcium detergent compounds and the optional additives are added to the base oil individually in one or more additions and the additions may be in any order. In other embodiments, the phenolic- based calcium detergent compounds and the additives are added to the base oil simultaneously, optionally in the form of an additive concentrate. In some embodiments, the solubilizing of the phenolic-based calcium detergent or any solid additives in the base oil may be assisted by heating the mixture to a temperature from about 25° C to about 200° C, from about 50° C to about 150° C or from about 75° C to about 125° C.

[0062] Any mixing or dispersing equipment known to a person of ordinary skill in the art may be used for blending, mixing or solubilizing the ingredients. The blending, mixing or solubilizing may be carried out with a blender, an agitator, a disperser, a mixer (e.g., planetary mixers and double planetary mixers), a homogenizer (e.g., Gaulin homogenizers and Rannie homogenizers), a mill (e.g., colloid mill, ball mill and sand mill) or any other mixing or dispersing equipment known in the art.Application of the Lubricating Oil Compositions

[0063] The lubricating oil composition disclosed herein may be suitable for use as motor oils (that is, engine oils or crankcase oils) or in stationary applications (that is, stationary gas engines or gas cogeneration systems), in a hydrogen fueled combustion engine, one that is susceptible to knock (pre-ignition).

[0064] 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 indicatedAttorney Docket No. : T-12572-WO01 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.EXAMPLES

[0065] 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 reduce or prevent corrosion via modified HTCBT test.Baseline 1

[0066] Baseline 1 is an SAE 15W-40 viscosity grade lubricating oil with the following components: a) Group II base oils: b) Mixture borated and non-borated succinimide dispersants c) Mixture of overbased phenate and sulfonate detergents d) ZnDTP e) Molybdenum succinimide f) Phenolic antioxidantModified HTCBT (Modified D-6594)

[0067] The ASTM D6594 HTCBT modified was used to test engine lubricants to determine their tendency to corrode various metals, specifically alloys of lead and copper commonly used in cam followers and bearings. Four metal specimens of copper, lead, tin and phosphor bronze were immersed in a measured amount of engine oil. The oil, at an elevated temperature (170° C), isAttorney Docket No. : T-12572-WO01 blown with air (5 1 / h) for a period of time (168 h) with 2 volume% of water addition to the oil. When the test was completed, the copper specimen and the stressed oil are examined to detect corrosion and corrosion products, respectively. The concentrations of copper, lead, and tin in the new oil and stressed oil and the respective changes in metal concentrations were reported.

[0068] The results of the modified HTCBT are shown in Table 2.Table 2Compound A = sorbitan mono-oleate (CAS 1338-43-8)

[0069] 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.

[0070] 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.

[0071] 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 moreAttorney Docket No. : T-12572-WO01 pronounced are not to be construed as a critical, required, or essential feature of any or all the claims.

[0072] The specification and illustrations of the embodiments described herein are intended to provide a general understanding of the structure of the various embodiments.

[0073] 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-12572-WO01What is Claimed:

1. A method for preventing or reducing copper corrosion in a hybrid vehicle, hydrogen, natural gas, or ammonia fueled internal combustion engine, the method including the step of lubricating the internal combustion engine with a lubricating oil composition comprising a fatty acid sorbitan ester present in an amount of 0.1 wt.% to 5 wt.% based on the total lubricating oil composition.

2. The method of claim 1, wherein the fatty acid sorbitan ester can be represented by the following generalized structure:wherein R is a C8-C30 hydrocarbyl group.

3. The method of claim 2, wherein R is linear or branched.

4. The method of claim 2, wherein R is saturated or unsaturated.

5. The method of claim 2, wherein R is aryl or aliphatic group.

6. The method of claim 1, wherein R is lauryl group, stearyl group, oleyl group, or myristyl group.

7. The method of claim 1, wherein the lubricating oil composition further comprises a detergent or dispersant.Attorney Docket No. : T-12572-WO018. Use of a fatty acid sorbitan ester in a crankcase lubricant to reduce or prevent corrosion in a hybrid vehicle, natural gas, hydrogen, or ammonia fueled internal combustion engine, wherein the fatty acid sorbitan ester is present in 0.1 wt.% to 5.0 wt.% based on the total weight of the lubricating oil composition.

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