EP3087165A1 - Verfahren zur verbesserung der brennstoffeffizienz eines motors - Google Patents

Verfahren zur verbesserung der brennstoffeffizienz eines motors

Info

Publication number
EP3087165A1
EP3087165A1 EP14727103.5A EP14727103A EP3087165A1 EP 3087165 A1 EP3087165 A1 EP 3087165A1 EP 14727103 A EP14727103 A EP 14727103A EP 3087165 A1 EP3087165 A1 EP 3087165A1
Authority
EP
European Patent Office
Prior art keywords
oil
group
friction modifier
fatty acid
lubricating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP14727103.5A
Other languages
English (en)
French (fr)
Other versions
EP3087165B1 (de
Inventor
Smruti A. DANCE
Dennis A. Gaal
Mrugesh Nilesh PATEL
Douglas E. Deckman
Erik Herz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Technology and Engineering Co
Original Assignee
ExxonMobil Research and Engineering Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US14/219,300 external-priority patent/US9506008B2/en
Application filed by ExxonMobil Research and Engineering Co filed Critical ExxonMobil Research and Engineering Co
Publication of EP3087165A1 publication Critical patent/EP3087165A1/de
Application granted granted Critical
Publication of EP3087165B1 publication Critical patent/EP3087165B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/06—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic nitrogen-containing compound
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
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    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C—CHEMISTRY; METALLURGY
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
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    • C10M2207/02—Hydroxy compounds
    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
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    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
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    • C10M2207/10—Carboxylix acids; Neutral salts thereof
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    • C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
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    • C10M2207/26—Overbased carboxylic acid salts
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    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of saturated carboxylic or carbonic acid
    • C10M2209/062—Vinyl esters of saturated carboxylic or carbonic acids, e.g. vinyl acetate
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    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
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    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
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    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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    • C10M2219/046—Overbasedsulfonic acid salts
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
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    • C10M2219/066—Thiocarbamic type compounds
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    • C10M2223/045—Metal containing thio derivatives
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    • C10M2229/02—Unspecified siloxanes; Silicones
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    • C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

Definitions

  • This disclosure relates to improving fuel efficiency and friction reduction properties, while maintaining or improving deposit control, in an engine lubricated with a lubricating oil by including a combination of (i) a friction modifier mixture and (ii) a detergent in the lubricating oil.
  • Contemporary lubricants such as engine oils use mixtures of additives such as dispersants, detergents, inhibitors, viscosity index improvers and the like to provide engine cleanliness and durability under a wide range of performance conditions of temperature, pressure, and lubricant service life.
  • Lubricant-related performance characteristics such as high temperature deposit control and fuel economy are extremely advantageous attributes as measured by a variety of bench and engine tests.
  • adding organic friction modifiers to a lubricant formulation imparts frictional benefits at low temperatures, consequently improving the lubricant fuel economy performance.
  • adding increased levels of organic friction modifier can invite high temperature performance issues.
  • engine deposits are undesirable consequences of high levels of friction modifier in an engine oil formulation at high temperature engine operation.
  • a major challenge in engine oil formulation is simultaneously achieving high temperature deposit control while also achieving improved fuel economy.
  • This disclosure relates in part to a method for improving fuel efficiency and reducing frictional properties, while maintaining or improving deposit control, in an engine lubricated with a lubricating oil by including a unique combination of (i) a friction modifier mixture and (ii) a detergent in the lubricating oil.
  • the lubricating oils of this disclosure are useful in internal combustion engines including direct injection, gasoline and diesel engines.
  • This disclosure also relates in part to a method for improving fuel efficiency and reducing frictional properties, while maintaining or improving deposit control, in an engine lubricated with a lubricating oil by using as the lubricating oil a formulated oil.
  • the formulated oil has a composition comprising a lubricating oil base stock as a major component; and a combination of (i) a friction modifier mixture comprising a first friction modifier, and at least one other friction modifier different from said first friction modifier, and (ii) a detergent, as a minor component.
  • the first friction modifier and the at least one other friction modifier are selected from the group consisting of an alkoxylated fatty acid ester, alkanolamide, polyol fatty acid ester, borated glycerol fatty acid ester, and fatty alcohol ether.
  • the detergent comprises a petroleum derived calcium sulfonate. Fuel efficiency and friction reduction properties are improved and deposit control is maintained or improved as compared to friction reduction properties and deposit control achieved using a lubricating engine oil containing a minor component other than the combination of the friction modifier mixture and detergent.
  • This disclosure further relates in part to a lubricating engine oil having a composition comprising a lubricating oil base stock as a major component; and a combination of (i) a friction modifier mixture comprising a first friction modifier, and at least one other friction modifier different from said first friction modifier, and (ii) a detergent, as a minor component.
  • the first friction modifier and the at least one other friction modifier are selected from the group consisting of an alkoxylated fatty acid ester, alkanolamide, polyol fatty acid ester, borated glycerol fatty acid ester, and fatty alcohol ether.
  • the detergent comprises a petroleum derived calcium sulfonate. Fuel efficiency and friction reduction properties are improved and deposit control is maintained or improved as compared to friction reduction properties and deposit control achieved using a lubricating engine oil containing a minor component other than the combination of the friction modifier mixture and detergent.
  • Fig. 1 shows formulation embodiments of this disclosure, in particular, individual contributions of components to a baseline formulation used in the Examples.
  • Fig. 2 shows formulation embodiments of this disclosure. Formulation details are shown in weight percent based on the total weight percent of the formulation, of various formulations. Fig. 2 also shows the results of testing of the formulations.
  • Fig. 3 shows a comparison of formulation embodiments of this disclosure and decreased treat rate formulations set forth in the Examples.
  • Fig. 4 shows a comparison of formulation embodiments of this disclosure and other detergents (i.e., a synthetic calcium sulfonate detergent) used in the Examples.
  • Fig. 5 shows a comparison of formulation embodiments of this disclosure including various friction modifiers and detergents used in the Examples.
  • Fig. 6 shows a comparison of formulation embodiments of this disclosure including various antioxidants used in the Examples.
  • Fig. 7 graphically shows average integrated Stribeck friction coefficients from mini-traction machine (MTM) measurements performed at 140°C for lubricating oils containing Organic Metallic FM l(i.e., a molybdenum diamine) and Organic Metallic FM 4 (i.e., a molybdenum dithiocarbamate).
  • MTM mini-traction machine
  • Fig. 8 shows a comparison of formulation embodiments of this disclosure and other base stock oils used in the Examples.
  • Fig. 9 shows formulation embodiments of this disclosure. Fig. 9 also shows the results of testing of the formulations.
  • Fig. 10 depicts other exemplary lubricant formulations of the present disclosure with individual contributions of components used in such formulations.
  • Fig. 1 1 depicts still other exemplary formulations of the present disclosure with individual contributions of components used in such formulations.
  • Fig. 12 depicts still yet other exemplary formulations of the present disclosure with individual contributions of components used in such formulations.
  • a formulated oil that has a unique combination of (i) a friction modifier mixture and (ii) a detergent.
  • the formulated oil preferably comprises a lubricating oil base stock as a major component, and a combination of (i) a friction modifier mixture and (ii) a detergent, as a minor component, and optionally other additives such as a metal dialkyl dithiio phosphate, and a viscosity index improver.
  • the lubricating oils of this disclosure are particularly advantageous as passenger vehicle engine oil (PVEO) products.
  • the lubricating oils of this disclosure provide excellent engine protection including engine cleanliness and anti-wear performance. This benefit has been demonstrated for the lubricating oils of this disclosure in the Sequence IIIG (ASTM D7320) engine test.
  • the lubricating oils of this disclosure provide improved fuel efficiency.
  • a lower HTHS viscosity engine oil generally provides superior fuel economy to a higher HTHS viscosity product. This benefit has been demonstrated for the lubricating oils of this disclosure in the Sequence VID Fuel Economy (ASTM D7589) engine test.
  • the lubricating engine oils of this disclosure have a composition sufficient to pass wear protection requirements of one or more engine tests selected from Sequence IIIG and others.
  • Lubricating base oils that are useful in the present disclosure are both natural oils, and synthetic oils, and unconventional oils (or mixtures thereof) can be used unrefined, refined, or rerefined (the latter is also known as reclaimed or reprocessed oil).
  • Unrefined oils are those obtained directly from a natural or synthetic source and used without added purification. These include shale oil obtained directly from retorting operations, petroleum oil obtained directly from primary distillation, and ester oil obtained directly from an esterification process. Refined oils are similar to the oils discussed for unrefined oils except refined oils are subjected to one or more purification steps to improve at least one lubricating oil property.
  • Groups I, II, III, IV and V are broad base oil stock categories developed and defined by the American Petroleum Institute (API Publication 1509; www.API.org) to create guidelines for lubricant base oils.
  • Group I base stocks have a viscosity index of between 80 to 120 and contain greater than 0.03% sulfur and/or less than 90% saturates.
  • Group II base stocks have a viscosity index of between 80 to 120, and contain less than or equal to 0.03% sulfur and greater than or equal to 90% saturates.
  • Group III stocks have a viscosity index greater than 120 and contain less than or equal to 0.03 % sulfur and greater than 90% saturates.
  • Group IV includes polyalphaolefms (PAO).
  • Group V base stock includes base stocks not included in Groups I-IV. The table below summarizes properties of each of these five groups.
  • Natural oils include animal oils, vegetable oils (castor oil and lard oil, for example), and mineral oils. Animal and vegetable oils possessing favorable thermal oxidative stability can be used. Of the natural oils, mineral oils are preferred. Mineral oils vary widely as to their crude source, for example, as to whether they are paraffinic, naphthenic, or mixed paraffinic-naphthenic. Oils derived from coal or shale are also useful. Natural oils vary also as to the method used for their production and purification, for example, their distillation range and whether they are straight run or cracked, hydrorefmed, or solvent extracted.
  • Group II and/or Group III hydroprocessed or hydrocracked basestocks including synthetic oils such as polyalphaolefins, alkyl aromatics and synthetic esters are also well known basestock oils.
  • Synthetic oils include hydrocarbon oil.
  • Hydrocarbon oils include oils such as polymerized and interpolymerized olefins (polybutylenes, polypro- pylenes, propylene isobutylene copolymers, ethylene-olefin copolymers, and ethylene-alphaolefm copolymers, for example).
  • Polyalphaolefin (PAO) oil base stocks are commonly used synthetic hydrocarbon oil.
  • PAOs derived from C 6; C 8 , Ci 0 , C 12 , C 14 olefins or mixtures thereof may be utilized. See U.S. Patent Nos. 4,956,122; 4,827,064; and 4,827,073.
  • the number average molecular weights of the PAOs which are known materials and generally available on a major commercial scale from suppliers such as ExxonMobil Chemical Company, Chevron Phillips Chemical Company, BP, and others, typically vary from 250 to 3,000, although PAO's may be made in viscosities up to 100 cSt (100°C).
  • the PAOs are typically comprised of relatively low molecular weight hydrogenated polymers or oligomers of alphaolefms which include, but are not limited to, C 2 to C 32 alphaolefms with the C 6 to C 16 alphaolefins, such as 1-hexene, 1-octene, 1-decene, 1-dodecene and the like, being preferred.
  • the preferred polyalphaolefins are poly- 1-hexene, poly-l-octene, poly-l -decene and poly- l-dodecene and mixtures thereof and mixed olefm-derived polyolefins.
  • the dimers of higher olefins in the range of C 14 to C J8 may be used to provide low viscosity base stocks of acceptably low volatility.
  • the PAOs may be predominantly trimers and tetramers of the starting olefins, with minor amounts of the higher oligomers, having a viscosity range of 1.5 to 12 cSt.
  • PAO fluids of particular use may include 3.0 cSt, 3.4 cSt, and/or 3.6 cSt and combinations thereof. Bi-modal mixtures of PAO fluids having a viscosity range of 1.5 to 100 cSt may be used if desired.
  • the PAO fluids may be conveniently made by the polymerization of an alphaolefm in the presence of a polymerization catalyst such as the Friedel- Crafts catalysts including, for example, aluminum trichloride, boron trifluoride or complexes of boron trifluoride with water, alcohols such as ethanol, propanol or butanol, carboxylic acids or esters such as ethyl acetate or ethyl propionate.
  • a polymerization catalyst such as the Friedel- Crafts catalysts including, for example, aluminum trichloride, boron trifluoride or complexes of boron trifluoride with water, alcohols such as ethanol, propanol or butanol, carboxylic acids or esters such as ethyl acetate or ethyl propionate.
  • a polymerization catalyst such as the Friedel- Crafts catalysts including, for example, aluminum trichloride, boron triflu
  • Other useful lubricant oil base stocks include wax isomerate base stocks and base oils, comprising hydroisomerized waxy stocks (e.g. waxy stocks such as gas oils, slack waxes, fuels hydrocracker bottoms, etc.), hydroisomerized Fischer-Tropsch waxes, Gas-to-Liquids (GTL) base stocks and base oils, and other wax isomerate hydroisomerized base stocks and base oils, or mixtures thereof Fischer-Tropsch waxes, the high boiling point residues of Fischer- Tropsch synthesis, are highly paraffmic hydrocarbons with very low sulfur content.
  • hydroisomerized waxy stocks e.g. waxy stocks such as gas oils, slack waxes, fuels hydrocracker bottoms, etc.
  • hydroisomerized Fischer-Tropsch waxes e.g. waxy stocks such as gas oils, slack waxes, fuels hydrocracker bottoms, etc.
  • GTL Gas-to-Liquids
  • the hydroprocessing used for the production of such base stocks may use an amorphous hydrocracking/hydroisomerization catalyst, such as one of the specialized lube hydrocracking (LHDC) catalysts or a crystalline hydrocracking/hydroisomerization catalyst, preferably a zeolitic catalyst.
  • an amorphous hydrocracking/hydroisomerization catalyst such as one of the specialized lube hydrocracking (LHDC) catalysts or a crystalline hydrocracking/hydroisomerization catalyst, preferably a zeolitic catalyst.
  • LHDC specialized lube hydrocracking
  • a zeolitic catalyst preferably ZSM-48 as described in U.S. Patent No. 5,075,269, the disclosure of which is incorporated herein by reference in its entirety.
  • Processes for making hydrocracked/hydroisomerized distillates and hydrocracked/hydroisomerized waxes are described, for example, in U.S. Patent Nos.
  • Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base oils, and other wax-derived hydroisomerized (wax isomerate) base oils be advantageously used in the instant disclosure, and may have useful kinematic viscosities at 100°C of 3 cSt to 50 cSt, preferably 3 cSt to 30 cSt, more preferably 3.5 cSt to 25 cSt, as exemplified by GTL 4 with kinematic viscosity of 4.0 cSt at 100°C and a viscosity index of 141.
  • Gas-to-Liquids (GTL) base oils may have useful pour points of -20°C or lower, and under some conditions may have advantageous pour points of -25 °C or lower, with useful pour points of -30°C to -40°C or lower.
  • Useful compositions of Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base oils, and wax-derived hydroisomerized base oils are recited in U.S. Patent Nos. 6,080,301 ; 6,090,989, and 6,165,949 for example, and are incorporated herein in their entirety by reference.
  • the hydrocarbyl aromatics can be used as base oil or base oil component and can be any hydrocarbyl molecule that contains at least 5% of its weight derived from an aromatic moiety such as a benzenoid moiety or naphthenoid moiety, or their derivatives.
  • These hydrocarbyl aromatics include alkyl benzenes, alkyl naphthalenes, alkyl diphenyl oxides, alkyl naphthols, alkyl diphenyl sulfides, alkylated bis-phenol A, alkylated thiodiphenol, and the like.
  • the aromatic can be mono-alkylated, dialkylated, polyalkylated, and the like.
  • the aromatic can be mono- or poly-functionalized.
  • the hydrocarbyl groups can also be comprised of mixtures of alkyl groups, alkenyl groups, alkynyl, cycloalkyl groups, cycloalkenyl groups and other related hydrocarbyl groups.
  • the hydrocarbyl groups can range from C 6 up to C 60 with a range of C 8 to C 2 o often being preferred.
  • a mixture of hydrocarbyl groups is often preferred, and up to three such substituents may be present.
  • the hydrocarbyl group can optionally contain sulfur, oxygen, and/or nitrogen containing substituents.
  • the aromatic group can also be derived from natural (petroleum) sources, provided at least 5% of the molecule is comprised of an above-type aromatic moiety.
  • Viscosities at 100°C of approximately 3 cSt to 50 cSt are preferred, with viscosities of approximately 3.4 cSt to 20 cSt often being more preferred for the hydrocarbyl aromatic component.
  • an alkyl naphthalene where the alkyl group is primarily comprised of 1-hexadecene is used.
  • Other alkylates of aromatics can be advantageously used.
  • Naphthalene or methyl naphthalene, for example, can be alkylated with olefins such as octene, decene, dodecene, tetradecene or higher, mixtures of similar olefins, and the like.
  • Useful concentrations of hydrocarbyl aromatic in a lubricant oil composition can be 2% to 25%, preferably 4% to 20%, and more preferably 4% to 15%, depending on the application.
  • Alkylated aromatics such as the hydrocarbyl aromatics of the present disclosure may be produced by well-known Friedel-Crafts alkylation of aromatic compounds. See Friedel-Crafts and Related Reactions, Olah, G. A. (ed.), Inter- science Publishers, New York, 1963.
  • an aromatic compound such as benzene or naphthalene
  • an olefin, alkyl halide or alcohol in the presence of a Friedel-Crafts catalyst. See Friedel-Crafts and Related Reactions, Vol. 2, part 1 , chapters 14, 17, and 18, See Olah, G. A. (ed.), Inter- science Publishers, New York, 1964.
  • catalysts are known to one skilled in the art.
  • the choice of catalyst depends on the reactivity of the starting materials and product quality requirements.
  • strong acids such as A1C1 3 , BF 3 , or HF may be used.
  • milder catalysts such as FeCl 3 or SnCl 4 are preferred.
  • Newer alkylation technology uses zeolites or solid super acids.
  • Esters comprise a useful base stock. Additive solvency and seal compatibility characteristics may be secured by the use of esters such as the esters of dibasic acids with monoalkanols and the polyol esters of mono- carboxylic acids.
  • Esters of the former type include, for example, the esters of dicarboxylic acids such as phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, etc., with a variety of alcohols such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, etc.
  • dicarboxylic acids such as phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, etc
  • esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, etc.
  • Particularly useful synthetic esters are those which are obtained by reacting one or more polyhydric alcohols, preferably the hindered polyols (such as the neopentyl polyols, e.g., neopentyl glycol, trimethylol ethane, 2-methyl-2- propyl- 1 ,3 -propanediol, trimethylol propane, pentaerythritol and dipentaerythritol) with alkanoic acids containing at least 4 carbon atoms, preferably C 5 to C 30 acids such as saturated straight chain fatty acids including caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, and behenic acid, or the corresponding branched chain fatty acids or unsaturated fatty acids such as oleic acid, or mixtures of any of these materials.
  • the hindered polyols such as the neopentyl polyo
  • Suitable synthetic ester components include the esters of trimethylol propane, trimethylol butane, trimethylol ethane, pentaerythritol and/or dipentaerythritol with one or more monocarboxylic acids containing from 5 to 10 carbon atoms. These esters are widely available commercially, for example, the Mobil P-41 and P-51 esters of ExxonMobil Chemical Company.
  • esters derived from renewable material such as coconut, palm, rapeseed, soy, sunflower and the like. These esters may be monoesters, di-esters, polyol esters, complex esters, or mixtures thereof. These esters are widely available commercially, for example, the Mobil P-51 ester of ExxonMobil Chemical Company.
  • Engine oil formulations containing renewable esters are included in this disclosure.
  • the renewable content of the ester is typically greater than 70 weight percent, preferably more than 80 weight percent and most preferably more than 90 weight percent.
  • Renewable esters can be preferred in combination with the friction modifier mixture and detergent of this disclosure.
  • Other useful fluids of lubricating viscosity include non-conventional or unconventional base stocks that have been processed, preferably catalytically, or synthesized to provide high performance lubrication characteristics.
  • Non-conventional or unconventional base stocks/base oils include one or more of a mixture of base stock(s) derived from one or more Gas-to-Liquids (GTL) materials, as well as isomerate/isodewaxate base stock(s) derived from natural wax or waxy feeds, mineral and or non-mineral oil waxy feed stocks such as slack waxes, natural waxes, and waxy stocks such as gas oils, waxy fuels hydrocracker bottoms, waxy raffinate, hydrocrackate, thermal crackates, or other mineral, mineral oil, or even non-petroleum oil derived waxy materials such as waxy materials received from coal liquefaction or shale oil, and mixtures of such base stocks.
  • GTL Gas-to-Liquids
  • GTL materials are materials that are derived via one or more synthesis, combination, transformation, rearrangement, and/or degradation/deconstructive processes from gaseous carbon-containing compounds, hydrogen-containing compounds and/or elements as feed stocks such as hydrogen, carbon dioxide, carbon monoxide, water, methane, ethane, ethylene, acetylene, propane, propylene, propyne, butane, butylenes, and butynes.
  • GTL base stocks and/or base oils are GTL materials of lubricating viscosity that are generally derived from hydrocarbons; for example, waxy synthesized hydrocarbons, that are themselves derived from simpler gaseous carbon-containing compounds, hydrogen-containing compounds and/or elements as feed stocks.
  • GTL base stock(s) and/or base oil(s) include oils boiling in the lube oil boiling range (1) separated/fractionated from synthesized GTL materials such as, for example, by distillation and subsequently subjected to a final wax processing step which involves either or both of a catalytic dewaxing process, or a solvent dewaxing process, to produce lube oils of reduced/low pour point; (2) synthesized wax isomerates, comprising, for example, hydrodewaxed or hydroisomerized cat and/or solvent dewaxed synthesized wax or waxy hydrocarbons; (3) hydrodewaxed or hydroisomerized cat and/or solvent dewaxed Fischer- Tropsch (F-T) material (i.e., hydrocarbons, waxy hydrocarbons, waxes and possible analogous oxygenates); preferably hydrodewaxed or hydroisomerized/followed by cat and/or solvent dewaxing dewaxed F-T waxy hydrocarbons, or hydrodewaxed or
  • GTL base stock(s) and/or base oil(s) derived from GTL materials are characterized typically as having kinematic viscosities at 100°C
  • the GTL base stock(s) and/or base oil(s) are typically highly paraffmic (>90% saturates), and may contain mixtures of monocycloparaffins and multicycloparaffms in combination with non-cyclic isoparaffins.
  • the ratio of the naphthenic (i.e., cycloparaffm) content in such combinations varies with the catalyst and temperature used.
  • GTL base stock(s) and/or base oil(s) typically have very low sulfur and nitrogen content, generally containing less than 10 ppm, and more typically less than 5 ppm of each of these elements.
  • the sulfur and nitrogen content of GTL base stock(s) and/or base oil(s) obtained from F-T material, especially F-T wax, is essentially nil.
  • the absence of phosphorous and aromatics make this materially especially suitable for the formulation of low SAP products.
  • GTL base stock and/or base oil and/or wax isomerate base stock and/or base oil is to be understood as embracing individual fractions of such materials of wide viscosity range as recovered in the production process, mixtures of two or more of such fractions, as well as mixtures of one or two or more low viscosity fractions with one, two or more higher viscosity fractions to produce a blend wherein the blend exhibits a target kinematic viscosity.
  • the GTL material, from which the GTL base stock(s) and/or base oil(s) is/are derived is preferably an F-T material (i.e., hydrocarbons, waxy hydrocarbons, wax).
  • the GTL base stock(s) and/or base oil(s) are typically highly paraffmic (>90% saturates), and may contain mixtures of monocycloparaffins and multicycloparaffms in combination with non-cyclic isoparaffins.
  • the ratio of the naphthenic (i.e., cycloparaffm) content in such combinations varies with the catalyst and temperature used.
  • GTL base stock(s) and/or base oil(s) and hydrodewaxed, or hydroisomerized/cat (and/or solvent) dewaxed base stock(s) and/or base oil(s) typically have very low sulfur and nitrogen content, generally containing less than 10 ppm, and more typically less than 5 ppm of each of these elements.
  • the sulfur and nitrogen content of GTL base stock(s) and/or base oil(s) obtained from F-T material, especially F-T wax, is essentially nil.
  • the absence of phosphorous and aromatics make this material especially suitable for the formulation of low sulfur, sulfated ash, and phosphorus (low SAP) products.
  • Base oils for use in the formulated lubricating oils useful in the present disclosure are any of the variety of oils corresponding to API Group I, Group II, Group III, Group IV, and Group V oils and mixtures thereof, preferably API Group II, Group III, Group IV, and Group V oils and mixtures thereof, more preferably the Group III to Group V base oils due to their exceptional volatility, stability, viscometric and cleanliness features.
  • Minor quantities of Group I stock, such as the amount used to dilute additives for blending into formulated lube oil products, can be tolerated but should be kept to a minimum, i.e. amounts only associated with their use as diluent/carrier oil for additives used on an "as-received" basis.
  • the base oil constitutes the major component of the engine oil lubricant composition of the present disclosure and typically is present in an amount ranging from 50 to 99 weight percent, preferably from 70 to 95 weight percent, and more preferably from 85 to 95 weight percent, based on the total weight of the composition.
  • the base oil may be selected from any of the synthetic or natural oils typically used as crankcase lubricating oils for spark- ignited and compression-ignited engines.
  • the base oil conveniently has a kinematic viscosity, according to ASTM standards, of 2.5 cSt to 12 cSt (or mm 2 Is) at 100°C and preferably of 2.5 cSt to 9 cSt (or mm 2 Is) at 100° C.
  • Mixtures of synthetic and natural base oils may be used if desired.
  • Mixtures of Group III, IV, V may be preferable.
  • Friction modifier mixtures useful in this disclosure are any materials that can alter the coefficient of friction of a surface lubricated by any lubricant or fluid containing such material(s).
  • Mixtures of friction modifiers also known as friction reducers, or lubricity agents or oiliness agents, and other such agents that change the ability of base oils, formulated lubricant compositions, or functional fluids, to modify the coefficient of friction of a lubricated surface can be effectively used in combination with the base oils or lubricant compositions of the present disclosure. Friction modifier mixtures that lower the coefficient of friction are particularly advantageous in combination with the base oils and lube compositions of this disclosure.
  • Illustrative friction modifier mixtures useful in the lubricating engine oil formulations of this disclosure include, for example, a first friction modifier, and at least one other friction modifier different from said first friction modifier.
  • the first friction modifier and the at least one other friction modifier are selected from the group consisting of an alkoxylated fatty acid ester, alkanolamide, polyol fatty acid ester, borated glycerol fatty acid ester, and fatty alcohol ether.
  • Illustrative alkoxylated fatty acid esters include, for example, polyoxyethylene stearate, fatty acid polyglycol ester, and the like. These can include polyoxypropylene stearate, polyoxybutylene stearate, polyoxyethylene isostearate, polyoxypropylene isostearate, polyoxyethylene palmitate.
  • Illustrative alkanolamides include, for example, lauric acid diethylalkanolamide, palmic acid diethylalkanolamide, and the like. These can include oleic acid diethyalkanolamide, stearic acid diethylalkanolamide, oleic acid diethylalkanolamide, polyethoxylated hydrocarbylamides, polypropoxylated hydrocarbylamides.
  • Illustrative polyol fatty acid esters include, for example, glycerol mono-oleate, saturated mono-, di, and tri- glyceride esters, glycerol mono- stearate, and the like. These can include polyol esters and hydroxyl-containing polyol esters. In addition to glycerol polyols, these can include trimethylolpropane, pentaerythritol, sorbitan, and the like. These esters can be polyol monocarboxylate esters, polyol dicarboxylate esters, and on occasion polyoltricarboxylate esters.
  • Preferred can be the glycerol mono-oleates, glycerol dioleates, glycerol trioleates, glycerol monostearates, glycerol distearates, and glycerol tristearates and the corresponding glycerol monopalmitates, glycerol dipalmitates, and glycerol tripalmitates, and the respective isostearates, linoleates, and the like.
  • the glycerol esters can be preferred as well as mixtures containing any of these. Ethoxylated, propoxylated, butoxylated fatty acid esters of polyols, especially using glycerol as underlying polyol can be preferred.
  • Illustrative borated glycerol fatty acid esters include, for example, borated glycerol mono-oleate, borated saturated mono-, di, and tri- glyceride esters, borated glycerol mono-stearate, and the like.
  • Illustrative fatty alcohol ethers include, for example, stearyl ether, myristyl ether, and the like. Alcohols, including those that have carbon numbers from C 3 to C 50 , can be ethoxylated, propoxylate, or butoxylated to form the corresponding fatty alkyl ethers.
  • the underlying alcohol portion can preferably be stearyl, myristyl, C u - C 13 hydrocarbon, oleyl, isosteryl, and the like.
  • a preferred friction modifier mixture of this disclosure comprises an ethoxylated fatty acid ester and a glycerol fatty acid ester.
  • a preferred formulation of this disclosure comprises a lubricating oil base stock that includes a Group I, Group II, Group III, Group IV and/or Group V base oil and a friction modifier mixture that includes an ethoxylated fatty acid ester and a glycerol fatty acid ester.
  • Useful concentrations of friction modifier mixtures may range from 0.01 weight percent to 10-15 weight percent or more, often with a preferred range of 0.1 weight percent to 5 weight percent, or 0.1 weight percent to 2.5 weight percent, or 0.1 weight percent to 1.5 weight percent, or 0.1 weight percent to 1 weight percent.
  • the weight ratio of the first friction modifier to the other friction modifier can range from 0.1 : 1 to 1 :0.1.
  • Illustrative detergents useful in combination with the friction modifier mixture of this disclosure include, for example, alkali metal detergents, alkaline earth metal detergents, or mixtures of one or more alkali metal detergents and one or more alkaline earth metal detergents.
  • 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 anionic portion of the detergent is typically derived from an organic acid such as a sulfur acid, carboxylic acid, phosphorous acid, phenol, or mixtures thereof.
  • the counterion is typically an alkaline earth or alkali metal.
  • Salts that contain a substantially stochiometric amount of the metal are described as neutral salts and have a total base number (TBN, as measured by ASTM D2896) of from 0 to 80.
  • TBN total base number
  • Many compositions are overbased, containing large amounts of a metal base that is achieved by reacting an excess of a metal compound (a metal hydroxide or oxide, for example) with an acidic gas (such as carbon dioxide).
  • a metal compound a metal hydroxide or oxide, for example
  • an acidic gas such as carbon dioxide
  • Useful detergents can be neutral, mildly overbased, or highly overbased.
  • Illustrative detergents include calcium sulfonates, magnesium sulfonates, calcium salicylates, magnesium salicylates, calcium phenates, magnesium phenates and other related components (including borated detergents), and mixtures thereof.
  • Preferred detergents include calcium sulfonate, magnesium sulfonate and calcium salicylate.
  • a petroleum derived calcium sulfonate is the preferred detergent for use in combination with the friction modifier mixture.
  • the detergent concentration in the lubricating oils of this disclosure can range from 0.01 to 6.0 weight percent, preferably 0.01 to 5.0 weight percent, and more preferably from 2.0 weight percent to 4.0 weight percent, based on the total weight of the lubricating oil.
  • the detergent concentrations are given on an "as delivered” basis.
  • the active detergent is delivered with a process oil.
  • the "as delivered” detergent typically contains from 20 weight percent to 80 weight percent, or from 40 weight percent to 60 weight percent, of active detergent in the "as delivered” detergent product.
  • the formulated lubricating oil useful in the present disclosure may additionally contain one or more of the other commonly used lubricating oil performance additives including but not limited to antiwear agents, dispersants, other detergents, corrosion inhibitors, rust inhibitors, metal deactivators, extreme pressure additives, anti-seizure agents, wax modifiers, viscosity index improvers, viscosity modifiers, fluid-loss additives, seal compatibility agents, metal- containing organic complex friction modifiers, lubricity agents, anti-staining agents, chromophoric agents, defoamants, demulsifiers, emulsifiers, densifiers, wetting agents, gelling agents, tackiness agents, colorants, and others.
  • the other commonly used lubricating oil performance additives including but not limited to antiwear agents, dispersants, other detergents, corrosion inhibitors, rust inhibitors, metal deactivators, extreme pressure additives, anti-seizure agents, wax modifiers, viscosity index improver
  • a metal alkylthiophosphate and more particularly a metal dialkyl dithio phosphate in which the metal constituent is zinc, or zinc dialkyl dithio phosphate is a useful component of the lubricating oils of this disclosure.
  • ZDDP can be derived from primary alcohols, secondary alcohols or mixtures thereof.
  • ZDDP compounds generally are of the formula Zn[SP(S)(O 1 )(O 2 )] 2 where R 1 and R 2 are Ci -Cjg alkyl groups, preferably C 2 -Ci 2 alkyl groups. These alkyl groups may be straight chain or branched. Alkyl aryl groups may also be used.
  • Preferable zinc dithiophosphates which are commercially available include secondary zinc dithiophosphates such as those available from for example, The Lubrizol Corporation under the trade designations "LZ 677A”, “LZ 1095” and “LZ 1371", from for example Chevron Oronite under the trade designation "OLOA 262" and from for example Afton Chemical under the trade designation "HITEC 7169".
  • the ZDDP is typically used in amounts of from 0.4 weight percent to 1.2 weight percent, preferably from 0.5 weight percent to 1.0 weight percent, and more preferably from 0.6 weight percent to 0.8 weight percent, based on the total weight of the lubricating oil, although more or less can often be used advantageously.
  • the ZDDP is a secondary ZDDP and present in an amount of from 0.6 to 1.0 weight percent of the total weight of the lubricating oil.
  • Low phosphorus engine oil formulations are included in this disclosure.
  • the phosphorus content is typically less than 0.12 weight percent preferably less than 0.10 weight percent and most preferably less than 0.085 weight percent. Low phosphorus can be preferred in combination with the friction modifier mixture and detergent.
  • Viscosity index improvers also known as VI improvers, viscosity modifiers, and viscosity improvers
  • VI improvers also known as VI improvers, viscosity modifiers, and viscosity improvers
  • Viscosity index improvers can be included in the lubricant compositions of this disclosure.
  • Viscosity index improvers provide lubricants with high and low temperature operability. These additives impart shear stability at elevated temperatures and acceptable viscosity at low temperatures.
  • Suitable viscosity index improvers include high molecular weight hydrocarbons, polyesters and viscosity index improver dispersants that function as both a viscosity index improver and a dispersant.
  • Typical molecular weights of these polymers are between 10,000 to 1 ,500,000, more typically 20,000 to 1 ,200,000, and even more typically between 50,000 and 1 ,000,000.
  • suitable viscosity index improvers are linear or star- shaped polymers and copolymers of methacrylate, butadiene, olefins, or alkylated styrenes.
  • Polyisobutylene is a commonly used viscosity index improver.
  • Another suitable viscosity index improver is polymethacrylate (copolymers of various chain length alkyl methacrylate s, for example), some formulations of which also serve as pour point depressants.
  • suitable viscosity index improvers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (copolymers of various chain length acrylates, for example). Specific examples include styrene-isoprene or styrene -butadiene based polymers of 50,000 to 200,000 molecular weight.
  • Olefin copolymers are commercially available from Chevron Oronite Company LLC under the trade designation "PA ATONE®” (such as “PARATONE® 8921 “ and “PARATONE® 8941”); from Afton Chemical Corporation under the trade designation “HiTEC®” (such as “HiTEC® 5850B”; and from The Lubrizol Corporation under the trade designation "Lubrizol® 7067C”.
  • PA ATONE® such as "PARATONE® 8921 “ and “PARATONE® 8941”
  • HiTEC® such as "HiTEC® 5850B”
  • Lubrizol® 7067C trade designation
  • Polyisoprene polymers are commercially available from Infmeum International Limited, e.g. under the trade designation "SV200”
  • diene-styrene copolymers are commercially available from Infineum International Limited, e.g. under the trade designation "SV 260”.
  • the viscosity index improvers may be used in an amount of less than 2.0 weight percent, preferably less than 1.0 weight percent, and more preferably less than 0.5 weight percent, based on the total weight of the formulated oil or lubricating engine oil. Viscosity improvers are typically added as concentrates, in large amounts of diluent oil.
  • the viscosity index improvers may be used in an amount of from 0.25 to 2.0 weight percent, preferably 0.15 to 1.0 weight percent, and more preferably 0.05 to 0.5 weight percent, based on the total weight of the formulated oil or lubricating engine oil.
  • Illustrative other detergents useful in this disclosure include, for example, alkali metal detergents, alkaline earth metal detergents, or mixtures of one or more alkali metal detergents and one or more alkaline earth metal detergents.
  • 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 anionic portion of the detergent is typically derived from an organic acid such as a sulfur acid, carboxylic acid, phosphorous acid, phenol, or mixtures thereof.
  • the counterion is typically an alkaline earth or alkali metal.
  • Salts that contain a substantially stochiometric amount of the metal are described as neutral salts and have a total base number (TBN, as measured by ASTM D2896) of from 0 to 80.
  • TBN total base number
  • Many compositions are overbased, containing large amounts of a metal base that is achieved by reacting an excess of a metal compound (a metal hydroxide or oxide, for example) with an acidic gas (such as carbon dioxide).
  • Useful detergents can be neutral, mildly overbased, or highly overbased. These detergents can be used in mixtures of neutral, overbased, highly overbased calcium salicylate, sulfonates, phenates and/or magnesium salicylate, sulfonates, phenates.
  • the TBN ranges can vary from low, medium to high TBN products, including as low as 0 to as high as 600.
  • Mixtures of low, medium, high TBN can be used, along with mixtures of calcium and magnesium metal based detergents, and including sulfonates, phenates, salicylates, and carboxylates.
  • a detergent mixture with a metal ratio of 1 in conjunction of a detergent with a metal ratio of 2, and as high as a detergent with a metal ratio of 5, can be used. Borated detergents can also be used.
  • Alkaline earth phenates are another useful class of other detergent. These detergents can be made by reacting alkaline earth metal hydroxide or oxide (CaO, Ca(OH) 2 , BaO, Ba(OH) 2 , MgO, Mg(OH) 2 , for example) with an alkyl phenol or sulfurized alkylphenol.
  • alkaline earth metal hydroxide or oxide Ca(OH) 2 , BaO, Ba(OH) 2 , MgO, Mg(OH) 2 , for example
  • Useful alkyl groups include straight chain or branched Ci -C 30 alkyl groups, preferably, C 4 -C 20 or mixtures thereof. Examples of suitable phenols include isobutylphenol, 2-ethylhexylphenol, nonylphenol, dodecyl phenol, and the like.
  • starting alkylphenols may contain more than one alkyl substituent that are each independently straight chain or branched and can be used from 0.5 to 6 weight percent.
  • the sulfurized product may be obtained by methods well known in the art. These methods include heating a mixture of alkylphenol and sulfurizing agent (including elemental sulfur, sulfur halides such as sulfur dichloride, and the like) and then reacting the sulfurized phenol with an alkaline earth metal base.
  • Metal salts of carboxylic acids are also useful as other detergents. These carboxylic acid detergents may be prepared by reacting a basic metal compound with at least one carboxylic acid and removing free water from the reaction product. These compounds may be overbased to produce the desired TBN level.
  • Detergents made from salicylic acid are one preferred class of detergents derived from carboxylic acids.
  • Useful salicylates include long chain alkyl salicylates.
  • One useful family of compositions is of the formula
  • Hydrocarbyl-substituted salicylic acids may be prepared from phenols by the Kolbe reaction (see U.S. Patent No. 3,595,791).
  • the metal salts of the hydrocarbyl-substituted salicylic acids may be prepared by double decomposition of a metal salt in a polar solvent such as water or alcohol.
  • Alkaline earth metal phosphates are also used as other detergents and are known in the art.
  • the other detergents may be simple detergents or what is known as hybrid or complex detergents.
  • the latter detergents can provide the properties of two detergents without the need to blend separate materials. See U.S. Patent No. 6,034,039.
  • Preferred other detergents include calcium phenates, calcium sulfonates, calcium salicylates, magnesium phenates, magnesium sulfonates, magnesium salicylates and other related components (including borated detergents), and mixtures thereof.
  • Preferred mixtures of detergents include magnesium sulfonate and calcium salicylate, magnesium sulfonate and calcium sulfonate, magnesium sulfonate and calcium phenate, calcium phenate and calcium salicylate, calcium phenate and calcium sulfonate, calcium phenate and magnesium salicylate, calcium phenate and magnesium phenate.
  • the other detergent concentration in the lubricating oils of this disclosure can range from 0.01 to 6.0 weight percent, preferably 0.01 to 5.0 weight percent, and more preferably from 2.0 weight percent to 4.0 weight percent, based on the total weight of the lubricating oil.
  • the other detergent concentrations are given on an “as delivered” basis.
  • the active detergent is delivered with a process oil.
  • the "as delivered” detergent typically contains from 20 weight percent to 80 weight percent, or from 40 weight percent to 60 weight percent, of active detergent in the "as delivered” detergent product.
  • Dispersants help keep these byproducts in solution, thus diminishing their deposition on metal surfaces.
  • Dispersants used in the formulation of the lubricating oil may be ashless or ash- forming in nature.
  • the dispersant is ashless.
  • So called ashless dispersants are organic materials that form substantially no ash upon combustion.
  • non-metal-containing or borated metal-free dispersants are considered ashless.
  • metal- containing detergents discussed above form ash upon combustion.
  • Suitable dispersants typically contain a polar group attached to a relatively high molecular weight hydrocarbon chain.
  • the polar group typically contains at least one element of nitrogen, oxygen, or phosphorus.
  • Typical hydrocarbon chains contain 50 to 400 carbon atoms.
  • a particularly useful class of dispersants are the alkenylsuccinic derivatives, typically produced by the reaction of a long chain hydrocarbyl substituted succinic compound, usually a hydrocarbyl substituted succinic anhydride, with a polyhydroxy or polyamino compound.
  • the long chain hydrocarbyl group constituting the oleophilic portion of the molecule which confers solubility in the oil, is normally a polyisobutylene group.
  • Many examples of this type of dispersant are well known commercially and in the literature. Exemplary U.S. patents describing such dispersants are U.S. Patent Nos.
  • Hydrocarbyl-substituted succinic acid and hydrocarbyl-substituted succinic anhydride derivatives are useful dispersants.
  • succinimide, succinate esters, or succinate ester amides prepared by the reaction of a hydrocarbon-substituted succinic acid compound preferably having at least 50 carbon atoms in the hydrocarbon substituent, with at least one equivalent of an alkylene amine are particularly useful, although on occasion, having a hydrocarbon substituent between 20-50 carbon atoms can be useful.
  • Succinimides are formed by the condensation reaction between hydrocarbyl substituted succinic anhydrides and amines. Molar ratios can vary depending on the polyamine. For example, the molar ratio of hydrocarbyl substituted succinic anhydride to TEPA can vary from 1 : 1 to 5: 1. Representative examples are shown in U.S. Patent Nos. 3,087,936; 3, 172,892; 3,219,666; 3,272,746; 3,322,670; and 3,652,616, 3,948,800; and Canada Patent No. 1 ,094,044.
  • Succinate esters are formed by the condensation reaction between hydrocarbyl substituted succinic anhydrides and alcohols or polyols. Molar ratios can vary depending on the alcohol or polyol used. For example, the condensation product of a hydrocarbyl substituted succinic anhydride and pentaerythritol is a useful dispersant.
  • Succinate ester amides are formed by condensation reaction between hydrocarbyl substituted succinic anhydrides and alkanol amines.
  • suitable alkanol amines include ethoxylated polyalkylpolyamines, propoxylated polyalkylpolyamines and polyalkenylpolyamines such as polyethylene polyamines.
  • propoxylated hexamethylenediamine Representative examples are shown in U.S. Patent No. 4,426,305.
  • the molecular weight of the hydrocarbyl substituted succinic anhydrides used in the preceding paragraphs will typically range between 800 and 2,500 or more.
  • the above products can be post-reacted with various reagents such as sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid.
  • the above products can also be post reacted with boron compounds such as boric acid, borate esters or highly borated dispersants, to form borated dispersants generally having from 0.1 to 5 moles of boron per mole of dispersant reaction product.
  • Mannich base dispersants are made from the reaction of alkylphenols, formaldehyde, and amines. See U.S. Patent No. 4,767,551 , which is incorporated herein by reference. Process aids and catalysts, such as oleic acid and sulfonic acids, can also be part of the reaction mixture. Molecular weights of the alkylphenols range from 800 to 2,500. Representative examples are shown in U.S. Patent Nos. 3,697,574; 3,703,536; 3,704,308; 3,751 ,365; 3,756,953; 3,798, 165; and 3,803,039.
  • Typical high molecular weight aliphatic acid modified Mannich condensation products useful in this disclosure can be prepared from high molecular weight alkyl-substituted hydroxyaromatics or HN® 2 group- containing reactants.
  • Hydrocarbyl substituted amine ashless dispersant additives are well known to one skilled in the art; see, for example, U.S. Patent Nos. 3,275,554; 3,438,757; 3,565,804; 3,755,433, 3,822,209, and 5,084,197.
  • Preferred dispersants include borated and non-borated succinimides, including those derivatives from mono-succinimides, bis-succinimides, and/or mixtures of mono- and bis-succinimides, wherein the hydrocarbyl succinimide is derived from a hydrocarbylene group such as polyisobutylene having a Mn of from 500 to 5000, or from 1000 to 3000, or 1000 to 2000, or a mixture of such hydrocarbylene groups, often with high terminal vinylic groups.
  • Other preferred dispersants include succinic acid-esters and amides, alkylphenol- polyamine-coupled Mannich adducts, their capped derivatives, and other related components.
  • Such additives may be used in an amount of 0.1 to 20 weight percent, preferably 0.5 to 8 weight percent, or more preferably 0.5 to 4 weight percent. On an active ingredient basis, such additives may be used in an amount of 0.06 to 14 weight percent, preferably 0.3 to 6 weight percent.
  • the hydrocarbon portion of the dispersant atoms can range from C60 to C400, or from C70 to C300, or from C70 to C200. These dispersants may contain both neutral and basic nitrogen, and mixtures of both. Dispersants can be end-capped by borates and/or cyclic carbonates.
  • the dispersant concentrations are given on an “as delivered” basis.
  • the active dispersant is delivered with a process oil.
  • the "as delivered” dispersant typically contains from 20 weight percent to 80 weight percent, or from 40 weight percent to 60 weight percent, of active dispersant in the "as delivered” dispersant product.
  • Antioxidants retard the oxidative degradation of base oils during service. Such degradation may result in deposits on metal surfaces, the presence of sludge, or a viscosity increase in the lubricant.
  • One skilled in the art knows a wide variety of oxidation inhibitors that are useful in lubricating oil compositions. See, Klamann in Lubricants and Related Products, op cite, and U.S. Patent Nos. 4,798,684 and 5,084,197, for example.
  • Useful antioxidants include hindered phenols. These phenolic antioxidants may be ashless (metal-free) phenolic compounds or neutral or basic metal salts of certain phenolic compounds. Typical phenolic antioxidant compounds are the hindered phenolics which are the ones which contain a sterically hindered hydroxyl group, and these include those derivatives of dihydroxy aryl compounds in which the hydroxyl groups are in the o- or p-position to each other. Typical phenolic antioxidants include the hindered phenols substituted with C 6 + alkyl groups and the alkylene coupled derivatives of these hindered phenols.
  • phenolic materials of this type 2-t-butyl- 4-heptyl phenol; 2-t-butyl-4-octyl phenol; 2-t-butyl-4-dodecyl phenol; 2,6-di-t- butyl-4-heptyl phenol; 2,6-di-t-butyl-4-dodecyl phenol; 2-methyl-6-t-butyl-4- heptyl phenol; and 2-methyl-6-t-butyl-4-dodecyl phenol.
  • Other useful hindered mono-phenolic antioxidants may include for example hindered 2,6-di-alkyl- phenolic proprionic ester derivatives.
  • Bis-phenolic antioxidants may also be advantageously used in combination with the instant disclosure.
  • ortho-coupled phenols include: 2,2'-bis(4-heptyl-6-t-butyl-phenol); 2,2'-bis(4- octyl-6-t-butyl-phenol); and 2,2'-bis(4-dodecyl-6-t-butyl-phenol).
  • Para-coupled bisphenols include for example 4,4'-bis(2,6-di-t-butyl phenol) and 4,4'- methylene-bis(2,6-di-t-butyl phenol).
  • Effective amounts of one or more catalytic antioxidants may also be used.
  • the catalytic antioxidants comprise an effective amount of a) one or more oil soluble polymetal organic compounds; and, effective amounts of b) one or more substituted N,N'-diaryl-o-phenylenediamine compounds or c) one or more hindered phenol compounds; or a combination of both b) and c).
  • Catalytic antioxidants are more fully described in U.S. Patent No. 8, 048,833, herein incorporated by reference in its entirety.
  • Non-phenolic oxidation inhibitors which may be used include aromatic amine antioxidants and these may be used either as such or in combination with phenolics.
  • Typical examples of non-phenolic antioxidants include: alkylated and non-alkylated aromatic amines such as aromatic monoamines of the formula is an aliphatic, aromatic or substituted aromatic group, R 9 is an aromatic or a substituted aromatic group, and R 10 is H, alkyl, aryl or R n S(O) x R 12 where R 1 1 is an alkylene, alkenylene, or aralkylene group, R 12 is a higher alkyl group, or an alkenyl, aryl, or alkaryl group, and x is 0, 1 or 2.
  • the aliphatic group R 8 may contain from 1 to 20 carbon atoms, and preferably contains from 6 to 12 carbon atoms.
  • the aliphatic group is a saturated aliphatic group.
  • both R 8 and R 9 are aromatic or substituted aromatic groups, and the aromatic group may be a fused ring aromatic group such as naphthyl.
  • Aromatic groups R 8 and R 9 may be joined together with other groups such as S.
  • Typical aromatic amines antioxidants have alkyl substituent groups of at least 6 carbon atoms.
  • Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl, and decyl. Generally, the aliphatic groups will not contain more than 14 carbon atoms.
  • the general types of amine antioxidants useful in the present compositions include diphenylamines, phenyl naphthylamines, phenothiazines, imidodibenzyls and diphenyl phenylene diamines. Mixtures of two or more aromatic amines are also useful. Polymeric amine antioxidants can also be used.
  • aromatic amine antioxidants useful in the present disclosure include: ⁇ , ⁇ '-dioctyldiphenylamine; t-octylphenyl-alpha- naphthylamine; phenyl-alphanaphthylamine; and p-octylphenyl-alpha- naphthylamine.
  • Sulfurized alkyl phenols and alkali or alkaline earth metal salts thereof also are useful antioxidants.
  • Preferred antioxidants include hindered phenols, arylamines. These antioxidants may be used individually by type or in combination with one another. Such additives may be used in an amount of 0.01 to 5 weight percent, preferably 0.01 to 1.5 weight percent, more preferably zero to less than 1.5 weight percent, more preferably zero to less than 1 weight percent.
  • pour point depressants also known as lube oil flow improvers
  • pour point depressants may be added to lubricating compositions of the present disclosure to lower the minimum temperature at which the fluid will flow or can be poured.
  • suitable pour point depressants include polymethacrylates, polyacrylates, polyarylamides, condensation products of haloparaffin waxes and aromatic compounds, vinyl carboxylate polymers, and terpolymers of dialkylfumarates, vinyl esters of fatty acids and allyl vinyl ethers.
  • Seal compatibility agents help to swell elastomeric seals by causing a chemical reaction in the fluid or physical change in the elastomer.
  • Suitable seal compatibility agents for lubricating oils include organic phosphates, alkoxysulfolanes (C 10 alcohol, for example), aromatic esters, aromatic hydrocarbons, esters (butylbenzyl phthalate, for example), and polybutenyl succinic anhydride. Such additives may be used in an amount of 0.01 to 3 weight percent, preferably 0.01 to 2 weight percent.
  • Anti-foam agents may advantageously be added to lubricant compositions. These agents retard the formation of stable foams. Silicones and organic polymers are typical anti-foam agents. For example, polysiloxanes, such as silicon oil or polydimethyl siloxane, provide antifoam properties. Anti-foam agents are commercially available and may be used in conventional minor amounts along with other additives such as demulsifiers; usually the amount of these additives combined is less than 1 weight percent and often less than 0.1 weight percent.
  • Antirust additives are additives that protect lubricated metal surfaces against chemical attack by water or other contaminants. A wide variety of these are commercially available.
  • One type of antirust additive is a polar compound that wets the metal surface preferentially, protecting it with a film of oil.
  • Another type of antirust additive absorbs water by incorporating it in a water-in-oil emulsion so that only the oil touches the metal surface.
  • Yet another type of antirust additive chemically adheres to the metal to produce a non-reactive surface.
  • suitable additives include zinc dithiophosphates, metal phenolates, basic metal sulfonates, fatty acids and amines. Such additives may be used in an amount of 0.01 to 5 weight percent, preferably 0.01 to 1.5 weight percent.
  • metal-containing organic complex friction modifiers may also be used.
  • Metal-containing organic complex friction modifiers useful in this disclosure are any materials that can alter the coefficient of friction of a surface lubricated by any lubricant or fluid containing such material(s).
  • Metal-containing organic complex friction modifiers also known as friction reducers, or lubricity agents or oiliness agents, and other such agents that change the ability of base oils, formulated lubricant compositions, or functional fluids, to modify the coefficient of friction of a lubricated surface can be effectively used in combination with the base oils or lubricant compositions of the present disclosure.
  • Metal-containing organic complex friction modifiers that lower the coefficient of friction are particularly advantageous in combination with the base oils and lube compositions of this disclosure.
  • Illustrative metal-containing organic complex friction modifiers useful in the lubricating engine oil formulations of this disclosure include, for example, molybdenum amine, molybdenum diamine, an organotungstenate, a molybdenum dithiocarbamate, molybdenum dithiophosphates, molybdenum amine complexes, molybdenum carboxylates, and the like. Similar tungsten based compounds may be preferable.
  • Useful concentrations of the metal- containing organic complex friction modifiers may range from 0.01 weight percent to 5 weight percent, or 0.1 weight percent to 2.5 weight percent.
  • Useful concentration of molybdenum can range from 25 to 700 ppm, or more preferably from 50 to 200 ppm.
  • Typical amounts of such additives useful in the present disclosure are shown in Table 1 below.
  • the weight amounts in the table below, as well as other amounts mentioned herein, are directed to the amount of active ingredient (that is the non-diluent portion of the ingredient).
  • the weight percent (wt%) indicated below is based on the total weight of the lubricating oil composition.
  • Anti-foam Agent 0.001-3 0.001-0.15
  • additives are all commercially available materials. These additives may be added independently but are usually precombined in packages which can be obtained from suppliers of lubricant oil additives. Additive packages with a variety of ingredients, proportions and characteristics are available and selection of the appropriate package will take the requisite use of the ultimate composition into account.
  • the detergents used in the formulations were a petroleum derived calcium sulfonate (Detergent 1), a synthetic calcium sulfonate (Detergent 2), a low base calcium salicylate (Detergent 3), a mixed calcium salicylate (Detergent 4), and a magnesium sulfonate.
  • the friction modifiers used in the formulations included organic friction modifiers and organic metallic friction modifiers.
  • the organic friction modifiers were an ethoxylated fatty ester (Organic FM 1), an alkanolamide (Organic FM 2), a borated glycerol mono-oleate (Organic FM 3), a stearyl ether (Organic FM 4), and a mixture of saturated mono-, di-, and tri-glyceride esters (Organic FM 5).
  • the organic metallic friction modifiers were a molybdenum complex containing diamine and ester species (Organic Metallic FM 1), an organotungstenate (Organic Metallic FM 2), a different organotungstenate (Organic Metallic FM 3), and a molybdenum dithiocarbamate (Organic Metallic FM 4).
  • the antioxidants used in the formulations were a phenolic alkylene oxide (Antioxidant 1), a different phenolic alkylene oxide (Antioxidant 2), and a diphenyl amine (Antioxidant 3).
  • Bench testing was conducted for formulations of this disclosure.
  • the bench testing included the following: kinematic viscosity (KV) at 100°C measured by ASTM D445; integrated mini traction machine (MTM) friction at 140°C as described below; and thermo-oxidation engine oil simulation testing (TEOST 33C - SAE 932837 and SAE 962039).
  • KV kinematic viscosity
  • MTM integrated mini traction machine
  • TEOST 33C - SAE 932837 and SAE 962039 thermo-oxidation engine oil simulation testing
  • HTHS thermo-oxidation engine oil simulation testing
  • the Mini Traction Machine is a fully automated instrument manufactured by PCS Instruments and identified as Model MTM. The test specimens and apparatus configuration are such that realistic pressure, temperature and speed can be attained without requiring very large loads, motors or structures.
  • a small sample of fluid (50 milliliters) is placed in a test cell and the machine automatically runs either through a range of speeds, slide-to-roll ratios, temperatures and loads, or at specifically set temperature, slide-to-roll ratio and speed range to generate information regarding the friction performance of a test fluid without further operator intervention.
  • the working of the MTM is known and familiar to those of skill in the art.
  • PCMO passenger car motor oil
  • Fig. 1 outlines the benefits and detriments for individual components, and provides the baseline data for the unique chemistries in accordance with this disclosure.
  • Fig. 1 shows individual contributions of components in Comparative Examples 1-12 to a baseline formulation, Baseline 1.
  • Baseline 1 has only a mixed calcium salicylate detergent (Detergent 4) in its formulation. There are no other detergents or friction modifiers present in this formulation. Going from left to right, 1% of each of the detergents and friction modifiers are added to the baseline formulation to gauge their impact on the overall friction and deposits compared to the baseline formulation.
  • Comparative Example 1 shows a petroleum derived calcium sulfonate detergent (Detergent 1) provides equivalent friction to that of Baseline 1 , but with improved deposit performance.
  • the ethoxylated fatty ester friction modifier (Organic FM 1) results in Comparative Example 4 showing equivalent deposit control to that of Baseline 1 and slightly reduced friction.
  • another organic friction modifier, a borated glycerol mono-oleate (Organic FM 3) in Comparative Example 6 shows lower deposits and equivalent friction compared to that of Baseline 1.
  • Fig. 2 shows the TEOST 33C and MTM data for these formulations compared to Baselines 1 and 2, where Baseline 2 is a comparable formulation to the Inventive Examples and contains other organic and organic metallic friction modifiers.
  • Inventive Example 1 is one example of a preferred formulation, showing the low MTM friction and good deposit control in the TEOST 33C.
  • Inventive Example 2 shows similar excellent friction reduction and better deposit control at a lower concentration level of Organic Metallic FM 4.
  • Inventive Example 3 shows a formulation with the preferred additive combination and a different molybdenum FM (Organic Metallic FM 1).
  • Inventive Example 4 shows that additional salicylate detergent (Detergent 3) in combination with the preferred additive combination still provides favorable frictional and deposit performance.
  • Comparative Example 13 shows that the removal of Organic FM 3 from the formulation negatively impacts the frictional performance and causes increased deposits.
  • Comparative Example 14 shows that there is a balance for the deposit control in the unique composition, as an increase in Detergent 1 (at a constant ash) led to a significant increase in deposits.
  • Comparative Examples 15 and 16 show the importance of Detergent 1 in the Inventive Examples as the deposits are significantly increased when Detergent 1 is replaced by Detergent 3.
  • FIG. 3 shows a comparison of Inventive Example 3 and the decreased treat rate formulation, Inventive Example 5.
  • Inventive Example 5 had similarly favorable deposit performance as Inventive Example 3, but the integrated friction was approximately twice that of Inventive Example 3. Although the increased frictional performance in Inventive Example 5 is less favorable, the overall frictional performance is still significantly lower than that of Baselines 1 and 2 or many other Comparative Examples.
  • Inventive Example 5 was run in the TEOST 33C deposits test, the results were once again surprising, as excellent deposit protection was observed.
  • the industry standard Sequence IIIG engine test was conducted on Inventive Example 5.
  • WPD weighted piston deposits
  • Fig. 4 shows, using Detergent 2 in place of Detergent 1 can have similar deposit improvement results. However, unlike in the Inventive Examples, a reduction in frictional performance is not seen with Detergent 2.
  • the difference in viscosity grade between the two formulations is a result of the viscosity modifier (VM) treat rate.
  • VM viscosity modifier
  • Increasing VM concentration in going from a SAE OW-16 for Baseline 3 to a SAE OW-20 for Comparative Example 17 is expected to have a negative impact on deposits.
  • a 0.75% treat of Detergent 2 is added for Comparative Example 17, the results show a reduction in deposits. While Baseline 3 provided a IIIG WPD rating of 4.3, the addition of Detergent 2 provided additional cleaning benefit and yielded a IIIG WPD rating of 5.8.
  • Antioxidant 2 and with no antioxidant.
  • Alternate chemistries such as Organic Metallic FM 1 , containing no phosphorous or sulfur in its chemical composition, may provide similar excellent friction performance but yield lower or equivalent deposits than the baseline formulation.
  • Organic Metallic FM 1 was blended into the baseline formulation and compared to Organic Metallic FM 4 at equivalent metal elemental content, all other components being held constant. The resulting oils were compared using MTM Stribeck friction measurements, as shown in Fig. 7. Deposit testing yielded very good and equivalent results of 18 mg for FM 4 and FM 1 , respectively. Therefore, Organic Metallic FM 1 and Organic Metallic FM 4 are considered equivalent and desirable for this disclosure.
  • High quality Group III basestocks including GTL, are considered interchangeable and desirable for the purposes of this disclosure.
  • exchanging Group IIIA and Group IIIB is expected to have minimal viscometric impact on the formulations and no impact in terms of cleanliness performance, fuel economy, or efficacy of the additives.
  • Inventive Example 1 having one example of the preferred formulation, is provided for reference, showing the low MTM friction and good deposit control in the TEOST 33C.
  • the relevant changes in weight percent for the organic friction modifiers and the detergents have been bolded to highlight the data supporting desired low friction (low MTM results) and low deposits (low TEOST 33C results).
  • amounts of Detergent 1 at 1.0 weight percent and 3.0 weight percent show desired low friction and low deposits.
  • amounts of Detergent 1 at 0.5 weight percent show less desired higher friction and higher deposits.
  • Detergent 2 at 1.0 weight percent and 3.0 weight percent show undesired high friction compared to the blends with Detergent 1.
  • amounts of Organic FM 1 at 0.25 weight percent and 0.75 weight percent show desired low friction and low deposits.
  • amounts of Organic FM 1 at 0.1 weight percent show higher friction.
  • amounts of Organic FM 3 at 0.1 weight percent show desired low friction and low deposits.
  • amounts of Organic FM 3 at 0.5 weight percent and 0.75 weight percent show undesired higher friction.
  • Fig. 9 show desired amounts of the combination of Organic FM 1 , Organic FM 3, and Detergent 1 in the lubricating oils of this disclosure.
  • This combination provides the desired deposit control and frictional performance.
  • desired deposit control (as determined by TEOST 33C) is below 20 mg, preferably below 17.5 mg, and more preferably below 15 mg.
  • desired frictional performance (as determined by MTM) is below 0.15, preferably below 0.125, and more preferably below 0.10.
  • the lubricating engine oil formulations in Figure 10 are combinations of additives and base stocks and are expected to have a kinematic viscosity at 100 °C about 6 mm 2 /s and an HTHS viscosity at 150 °C about 2.0 cP.
  • the lubricating engine oil formulations in Examples 32-35 are expected to have a phosphorous level about 0 ppm.
  • the lubricating engine oil formulations in Examples 36-39 are expected to have a phosphorous level about 300 ppm.
  • the lubricating engine oil formulations in Examples 40-43 are expected to have a phosphorous level of about 700 ppm.
  • the lubricating engine oils in Examples 32-34 are expected to have a sulfated ash level (measured by ASTM D874) around 0.3 weight percent and a total base number (measured by ASTM D2896) about 4.
  • the lubricating engine oils in Examples 35-43 are expected to have a sulfated ash level (measured by ASTM D874) greater than or equal to 1.0 weight percent and a total base number (measured by ASTM D2896) greater than or equal to 9.
  • the lubricating engine oil formulations in Examples 32, 36, and 40 do not contain molybdenum.
  • the lubricating engine oil formulations in Examples 33, 37, and 41 are expected to have molybdenum levels about 90 ppm.
  • the lubricating engine oil formulations in Examples 34, 38, and 42 are expected to have molybdenum levels about 250 ppm.
  • the lubricating engine oil formulations in Examples 35, 39, and 43 are expected to have molybdenum levels about 500 ppm.
  • the lubricating engine oil formulations in Figure 1 1 are combinations of additives and base stocks and are expected to have a kinematic viscosity at 100 °C about 5 mm 2 /s and an HTHS viscosity at 150 °C about 1.7 cP.
  • the lubricating engine oil formulations in Examples 44-47 are expected to have a phosphorous level about 0 ppm.
  • the lubricating engine oil formulations in Examples 48-51 are expected to have a phosphorous level about 300 ppm.
  • the lubricating engine oil formulations in Examples 52-55 are expected to have a phosphorous level about 700 ppm.
  • the lubricating engine oils in Examples 44- 46 are expected to have a sulfated ash level (measured by ASTM D874) about 0.3 weight percent and a total base number (measured by ASTM D2896) about 4.
  • the lubricating engine oils in Examples 47-55 are expected to have a sulfated ash level (measured by ASTM D874) greater than or equal to 1.0 weight percent and a total base number (measured by ASTM D2896) greater than or equal to 9.
  • the lubricating engine oil formulations in Examples 44, 48, and 52 do not contain molybdenum.
  • the lubricating engine oil formulations in Examples 45, 49, and 53 are expected to have molybdenum levels about 90 ppm.
  • the lubricating engine oil formulations in Examples 46, 50, and 54 are expected to have molybdenum levels about 250 ppm.
  • the lubricating engine oil formulations in Examples 47, 51, and 55 are expected to have molybdenum levels about 500 ppm.
  • the lubricating engine oil formulations in Figure 12 are combinations of additives and base stocks and are expected to have a kinematic viscosity at 100 °C about 4 mm 2 /s and an HTHS viscosity at 150 °C about 1.4 cP.
  • the lubricating engine oil formulations in Examples 56-59 are expected to have a phosphorous level about 0 ppm.
  • the lubricating engine oil formulations in Examples 60-63 are expected to have a phosphorous level about 300 ppm.
  • the lubricating engine oil formulations in Examples 64-67 are expected to have a phosphorous level about 700 ppm.
  • the lubricating engine oils in Examples 56- 58 are expected to have a sulfated ash level (measured by ASTM D874) about 0.3 weight percent and a total base number (measured by ASTM D2896) about 4.
  • the lubricating engine oils in Examples 59-67 are expected to have a sulfated ash level (measured by ASTM D874) greater than or equal to 1.0 weight percent and a total base number (measured by ASTM D2896) greater than or equal to 9.
  • the lubricating engine oil formulations in Examples 56, 60, and 64 do not contain molybdenum.
  • the lubricating engine oil formulations in Examples 57, 61 , and 65 are expected to have molybdenum levels about 90 ppm.
  • the lubricating engine oil formulations in Examples 58, 62, and 66 are expected to have molybdenum levels about 250 ppm.
  • the lubricating engine oil formulations in Examples 59, 63, and 67 are expected to have molybdenum levels about 500 ppm.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
EP14727103.5A 2013-12-23 2014-04-01 Verwendung zur verbesserung der brennstoffeffizienz eines motors Not-in-force EP3087165B1 (de)

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US201361920130P 2013-12-23 2013-12-23
US14/219,300 US9506008B2 (en) 2013-12-23 2014-03-19 Method for improving engine fuel efficiency
PCT/US2014/032474 WO2015099820A1 (en) 2013-12-23 2014-04-01 Method for improving engine fuel efficiency

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WO2022099291A1 (en) * 2020-11-06 2022-05-12 Exxonmobil Research And Engineering Company Engine oil lubricant compositions and methods for making same with steel corrosion protection

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