EP2633012B1 - Verwendung und methode zur reduzierung von ventilablagerungen in einem motor - Google Patents

Verwendung und methode zur reduzierung von ventilablagerungen in einem motor Download PDF

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Publication number
EP2633012B1
EP2633012B1 EP11836848.9A EP11836848A EP2633012B1 EP 2633012 B1 EP2633012 B1 EP 2633012B1 EP 11836848 A EP11836848 A EP 11836848A EP 2633012 B1 EP2633012 B1 EP 2633012B1
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EP
European Patent Office
Prior art keywords
lubricating oil
foam inhibitor
siloxane
engine
group
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EP11836848.9A
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English (en)
French (fr)
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EP2633012A4 (de
EP2633012A2 (de
Inventor
Michelle Morcos
Jeffrey J. Toman
Farzan Parsinejad
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Chevron Oronite Co LLC
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Chevron Oronite Co LLC
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Classifications

    • 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
    • C10M155/00—Lubricating compositions characterised by the additive being a macromolecular compound containing atoms of elements not provided for in groups C10M143/00 - C10M153/00
    • C10M155/02—Monomer containing silicon
    • 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
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—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
    • C10M145/12—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 monocarboxylic
    • C10M145/14—Acrylate; Methacrylate
    • 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
    • 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
    • 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
    • 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
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • 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
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • 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
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/02—Unspecified siloxanes; Silicones
    • 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
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • 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
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
    • 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
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/042—Siloxanes with specific structure containing aromatic substituents
    • 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
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
    • C10M2229/052—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines

Definitions

  • the present invention generally relates to a method for reducing intake valve deposits in Direct Injection Spark Ignition (DISI) engines. Also provided is a method for reducing intake valve deposits in a DISI engine by top treating an oil of lubricating viscosity with a lubricating oil additive concentrate.
  • DISI Direct Injection Spark Ignition
  • DISI direct injection spark ignition
  • Such engines inject gasoline, directly into the combustion chamber of the engine, rather than introducing the gasoline indirectly through the intake manifold by means of, for example, carburetors or port fuel injectors. Because the gasoline. is injected directly into the combustion chambers, it enables precise control over the amount of fuel burned and the timing of the injection.
  • intake valves of DISI engines are likely to form large amounts of intake valve deposits (“IVD” hereinafter), since there is no gasoline at the site of the intake valves to provide deposit control additives to combat deposits or deposit precursors. These valve deposits interfere with valve operation, reduce the efficiency of the engine, and have a negative impact on driveability.
  • Konishi, Japanese Patent Publication No. 2003-155492 discloses lubricants containing polybutenyl succinimide, dithio zinc phosphate, phenol and/or amine group ash-free antioxidant and alkaline-earth metal group cleaner, and which do not contain viscosity index improvers.
  • Calder U.S. Patent Application Publication No.2004/0198614 discloses a method of reducing intake valve deposits in a direct injection engine, the method comprising lubricating the engine with a lubricating oil composition comprising a base oil mixture, the base oil mixture comprising (i) a Group III, a Group IV oil, or a mixture thereof, in combination with (ii) a synthetic ester oil, the weight ratio of (i) to (ii) being from about 0.2:1 to about 6:1.
  • U.S. Patent Application Publication No. 2006/0052252 discloses a lubricant composition containing a mixture of at least two Fischer-Tropsch derived base oils and one or more additives wherein one Fischer-Tropsch derived base oil (low viscosity component) has a kinematic viscosity at 100.degree. C. of less than 7 cSt and the second Fischer-Tropsch derived base oil (high viscosity component) has a kinematic viscosity at 100.degree. C. of more than 18 cSt.
  • one Fischer-Tropsch derived base oil low viscosity component
  • high viscosity component has a kinematic viscosity at 100.degree. C. of more than 18 cSt.
  • a number of patent documents disclose the use of foam inhibitors in a generic manner in gasoline direct injection engines. These include: U.S. Patent Application Publication Nos. 2008/0234153 , 2008/0248981 and 2008/0110799 ; and Japanese Patent Publication Nos. 2008-120908 , 2001-262172 , 2008-231192 , and 2008-231191 .
  • intake valve deposits are recognized as a problem in DISI engines.
  • a number of attempts have been made to alleviate the problem of reducing intake valve deposits in DISI engines.
  • One embodiment of the present invention is directed to the use of a foam inhibitor selected from the group consisting of polysiloxanes and polymethacrylates in a lubricating oil composition comprising a major amount of an oil of lubricating viscosity for reducing intake valve deposits in a Direct Injection Spark Ignition engine by at least 10% compared to operating the engine with said lubricating oil composition without any foam inhibitor;wherein the concentration of said foam inhibitor in said lubricating oil composition is from 30 to 500 ppmw; and wherein the foam inhibitor is not poly (phenyl-methyl) siloxane.
  • Direct Injection Spark Ignition engine is equipped with positive crankcase ventilation.
  • Another embodiment of the present invention is directed to a method for reducing intake valve deposits in a Direct Injection Spark Ignition engine that is equipped with positive crankcase ventilation, the method comprising operating the engine with a lubricating oil composition comprising:
  • Another embodiment of the present invention is directed to a method for reducing intake valve deposits in a Direct Injection Spark Ignition engine that is equipped with positive crankcase ventilation, the method comprising:
  • the lubricating oil composition may further comprise at least one additive selected from the group consisting of antioxidants, antiwear agents, detergents, rust inhibitors, demulsifiers, friction modifiers, extreme pressure agents, viscosity index improvers, pour point depressants, dispersants, corrosion inhibitors, and combinations thereof.
  • top treating means adding the lubricating oil concentrate described herein to the crankcase oil already present in the DISI engine.
  • the present invention is based on the surprising discovery that the addition of larger than typical amounts of foam inhibiting additives to lubricants used to lubricate direct injection gasoline engines can substantially decrease the amount of intake valve deposits in said engines.
  • the typical amount of foam inhibiting additives used in many lubricants varies from 5 to 30 ppmw.
  • the increased amount of added foam inhibitor is quite small, and enables a large reduction in IVD deposits without the use of expensive specialty lubricants or base oils such as polyalphaolefins (Group IV) or ester (Group V) lubricants.
  • This finding also enables the aftermarket addition of small amounts of foam inhibitor boosters in gasoline direct injection engines lubricated with conventional lubricants.
  • the invention relates to the use of a foam inhibitor as defined in claim 1 and methods for reducing intake valve deposits as defined in claims 9 and 10.
  • Positive crankcase ventilation is a method for reducing emissions in an engine in which combustion gases that escape from the combustion chamber past the piston and piston rings into the crankcase (often called “blow-by") are returned through the intake manifold to the combustion chamber, where the re-circulated hydrocarbons are burned.
  • the oil of lubricating viscosity for use in the lubricating oil compositions of the present invention is typically present therein in a major amount, e.g., an amount of greater than 50 wt. %, preferably greater than about 70 wt. %, more preferably from about 80 to about 99.5 wt. % and most preferably from about 85 to about 98 wt. %, based on the total weight of the composition.
  • base oil as used herein shall be understood to mean a base stock or blend of base stocks which is a lubricant component that is produced by a single manufacturer to the same specifications (independent of feed source or manufacturer's location); that meets the same manufacturer's specification; and that is identified by a unique formula, product identification number, or both.
  • the base oil for use herein can be any presently known or later-discovered oil of lubricating viscosity used in formulating lubricating oil compositions for any and all such applications, e.g., engine oils, marine cylinder oils, functional fluids such as hydraulic oils, gear oils, transmission fluids, etc.
  • the selection of the particular base oil depends on the contemplated application of the lubricant and the presence of other additives.
  • the oil of lubricating viscosity useful in the practice of the invention may range in viscosity from light distillate mineral oils to heavy lubricating oils such as gasoline engine oils, mineral lubricating oils and heavy duty diesel oils.
  • the base oils for use herein can optionally contain viscosity index improvers, e.g., polymeric alkylmethacrylates; olefinic copolymers, e.g., an ethylene-propylene copolymer or a styrene-butadiene copolymer; and the like and mixtures thereof.
  • the lubricating oil compositions of this invention can be prepared by admixing, by conventional techniques, an appropriate amount of the foam inhibitor compounds disclosed herein in an additive concentrate with an oil of lubricating viscosity and conventional lubricating oil additives
  • the viscosity of the base oil is dependent upon the application. Accordingly, the viscosity of a base oil for use herein will ordinarily range from about 2 to about 2000 centistokes (cSt) (2 to 2000 mm 2 /s) at 100° Centigrade (C).
  • the base oils used as engine oils will have a kinematic viscosity range at 100°C of about 2 cSt to about 30 cSt (2 to 30 mm 2 /s), preferably about 3 cSt to about 16 cSt (3 to 16 mm 2 /s), and most preferably about 4 cSt to about 12 cSt (4 to 12 mm 2 /s) and will be selected or blended depending on the desired end use and the additives in the finished oil to give the desired grade of engine oil, e.g., a lubricating oil composition having an SAE Viscosity Grade of 0W, 0W-20, 0W-30, 0W-40, 0W-50, 0W-60, 5W, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W, 10W-20, 10W-30, 10W-40, 10W-50, 15W, 15W-20, 15W-30 or 15W-40.
  • Oils used as gear oils can have viscosities
  • Base stocks may be manufactured using a variety of different processes including, but not limited to, distillation, solvent refining, hydrogen processing, oligomerization, esterification, and rerefining. Rerefined stock shall be substantially free from materials introduced through manufacturing, contamination, or previous use.
  • the base oil of the lubricating oil compositions of this invention may be any natural or synthetic lubricating base oil.
  • Suitable hydrocarbon synthetic oils include, but are not limited to, oils prepared from the polymerization of ethylene or from the polymerization of 1-olefins to provide polymers such as polyalphaolefin or PAO oils, or from hydrocarbon synthesis procedures using carbon monoxide and hydrogen gases such as in a Fischer-Tropsch process.
  • a suitable base oil is one that comprises little, if any, heavy fraction; e.g., little, if any, lube oil fraction of viscosity 20 cSt (20 mm 2 /s)or higher at 100°C.
  • the base oil may be derived from natural lubricating oils, synthetic lubricating oils or mixtures thereof.
  • Suitable base oil includes base stocks obtained by isomerization of synthetic wax and slack wax, as well as hydrocracked base stocks produced by hydrocracking (rather than solvent extracting) the aromatic and polar components of the crude.
  • Suitable base oils include those in all API categories I, II, III, IV and V as defined in API Publication 1509, 14th Edition, Addendum I, Dec. 1998.
  • Group IV base oils are polyalphaolefins (PAO).
  • Group V base oils include all other base oils not included in Group I, II, III, or IV.
  • the oil of lubricating viscosity comprises at least 50 wt-% of a Group III basestock. In another embodiment of the present invention, the oil of lubricating viscosity comprises at least 50 wt-% of an API Group II basestock. In a further embodiment of the present invention, the oil of lubricating viscosity comprises at least 50 wt-% of a mixture of Group II and Group III basestocks.
  • the oil of lubricating viscosity does not contain either a Group IV or a Group V basestocks.
  • the base oil is a mixture of Group II, Group III, and Group IV basestocks.
  • Natural oils may also be employed and include mineral lubricating oils such as, for example, liquid petroleum oils, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types, oils derived from coal or shale, animal oils, vegetable oils (e.g., rapeseed oils, castor oils and lard oil), and the like.
  • mineral lubricating oils such as, for example, liquid petroleum oils, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types, oils derived from coal or shale, animal oils, vegetable oils (e.g., rapeseed oils, castor oils and lard oil), and the like.
  • Synthetic lubricating oils may also be employed and include, but are not limited to, hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins, e.g., polybutylenes, polypropylene, propylene-isobutylene copolymers, chlorinates polybutylenes, poly(1-hexenes), poly(1-octenes), poly(1-decenes), and the like and mixtures thereof; alkylbenzenes such as dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)-benzenes, and the like; polyphenyls such as biphenyls, terphenyls, alkylated polyphenyls, and the like; alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivative, analog
  • oils employed include, but are not limited to, oils made by polymerizing olefins of less than 5 carbon atoms such as ethylene, propylene, butylenes, isobutene, pentene, and mixtures thereof. Methods of preparing such polymer oils are well known to those skilled in the art.
  • Additional synthetic hydrocarbon oils employed include liquid polymers of alpha olefins having the proper viscosity.
  • Especially useful synthetic hydrocarbon oils are the hydrogenated liquid oligomers of C 6 to C 12 alpha olefins such as, for example, 1-decent trimer.
  • Another class of synthetic lubricating oils include, but are not limited to, alkylene oxide polymers, i.e., homopolymers, interpolymers, and derivatives thereof where the terminal hydroxyl groups have been modified by, for example, esterification or etherification.
  • oils are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxide, the alkyl and phenyl ethers of these polyoxyalkylene polymers (e.g., methyl poly propylene glycol ether having an average molecular weight of 1,000, diphenyl ether of polyethylene glycol having a molecular weight of 500 to 1000, dimethyl ether of polypropylene glycol having a molecular weight of 1,000 to 1,500, etc.) or mono- and polycarboxylic esters thereof such as, for examples, the acetic esters, mixed C 3 -C 8 fatty acid esters, or the C 13 oxo acid diester of tetraethylene glycol.
  • the alkyl and phenyl ethers of these polyoxyalkylene polymers e.g., methyl poly propylene glycol ether having an average molecular weight of 1,000, diphenyl ether of polyethylene glycol having a molecular weight of 500 to 1000, dimethyl
  • Yet another class of synthetic lubricating oils include, but are not limited to, the esters of dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acids, alkyl malonic acids, alkenyl malonic acids, etc., with a variety of alcohols, e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.
  • dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric
  • 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, the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid and the like.
  • Esters may also be employed as synthetic oils and include, but are not limited to, those made from carboxylic acids having from about 5 to about 12 carbon atoms with alcohols, e.g., methanol, ethanol, etc., polyols and polyol ethers such as neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, and the like.
  • alcohols e.g., methanol, ethanol, etc.
  • polyols and polyol ethers such as neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, and the like.
  • Silicon-based oils such as, for example, polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxy-siloxane oils and silicate oils, comprise another class of synthetic lubricating oils which may be employed in the present invention. Specific examples of these include, but are not limited to, tetraethyl silicate, tetra-isopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-hexyl) silicate, tetra-(p-tert-butylphenyl) silicate, hexyl-(4-methyl-2-pentoxy) disiloxane, poly (methyl) siloxanes, poly (methylphenyl) siloxanes, and the like.
  • the lubricating oil may be derived from undefined, refined and rerefined oils, either natural, synthetic or mixtures of two or more of any of these of the type disclosed hereinabove.
  • Unrefined oils are those obtained directly from a natural or synthetic source (e.g., coal, shale, or tar sands bitumen) without further purification or treatment.
  • undefined oils include, but are not limited to, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from distillation or an ester oil obtained directly from an esterification process, each of which is then used without further treatment.
  • 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.
  • Rerefined oils are obtained by treating used oils in processes similar to those used to obtain refined oils. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products.
  • Lubricating oil base stocks derived from the hydroisomerization of wax may also be used, either alone or in combination with the aforesaid natural and/or synthetic base stocks.
  • Such wax isomerate oil is produced by the hydroisomerization of natural or synthetic waxes or mixtures thereof over a hydroisomerization catalyst.
  • Natural waxes are typically the slack waxes recovered by the solvent dewaxing of mineral oils; synthetic waxes are typically the wax produced by the Fischer-Tropsch process.
  • a foam inhibitor is a lubricant additive that, when added in small amounts to a lubricant, either inhibits the formation of foam, accelerates the breaking of foam, or both. At least one foam inhibitor or mixtures thereof is employed in the lubricating oil composition of the presently claimed invention.
  • the foam inhibitor employed is selected from the group consisting of polysiloxanes, polymethacrylates, and combinations thereof, provided that the foam inhibitor may not be poly (phenyl-methyl) siloxane. In one embodiment, the foam inhibitor is a poly dimethyl siloxane.
  • the foam inhibitor is a poly (dimethyl, phenyl-methyl) siloxane. In one embodiment, the foam inhibitor is a mixture of poly dimethyl siloxane and poly (dimethyl, phenyl-methyl) siloxane.
  • the foam inhibitor is a polymethacrylate.
  • the foam inhibitor is a poly (trifluoropropylmethyl) siloxane.
  • the amount of the foam inhibitor in the lubricating oil composition may vary from 50 to 500 ppmw, or from 75 to 500 ppmw, or from 100 to 500 ppmw, or from 150 to 500 ppmw, or from 200 ppmw to 400 ppmw, based on the total weight of the lubricating oil composition.
  • the reduction in intake valve deposits is at least 20%, or at least 30%, or at least 40%, or at least 50% compared to operating the engine with the lubricating oil composition without any foam inhibitor.
  • the amount of the foam inhibitor in the lubricating oil concentrate may vary from 0.01 wt.% to 1 wt.% , from 0.02 wt.% to 0.8 wt.%, from 0.03 wt.% to 0.7 wt.%, or from 0.04 wt.% to 0.6 wt.%, based on the total weight of the lubricating oil concentrate.
  • the foam inhibitor can be conveniently added to the lubricating oil concentrate in the form of a foam inhibitor concentrate, which contains the foam inhibitor and at least one solvent.
  • the lubricating oil compositions of the present invention may also contain other conventional additives for imparting auxiliary functions to give a finished lubricating oil composition in which these additives are dispersed or dissolved.
  • the lubricating oil compositions can be blended with antioxidants, anti-wear agents, ashless dispersants, detergents, rust inhibitors, dehazing agents, demulsifying agents, metal deactivating agents, friction modifiers, pour point depressants, co-solvents, package compatibilisers, corrosion-inhibitors, dyes, extreme pressure agents and the like and mixtures thereof.
  • antioxidants antioxidants, anti-wear agents, ashless dispersants, detergents, rust inhibitors, dehazing agents, demulsifying agents, metal deactivating agents, friction modifiers, pour point depressants, co-solvents, package compatibilisers, corrosion-inhibitors, dyes, extreme pressure agents and the like and mixtures thereof.
  • additives are known and commercially available. These additives, or their analogous compounds, may be employed for
  • antioxidants include, but are not limited to, aminic types, e.g., diphenylamine, phenyl-alpha-napthyl-amine, N,N-di(alkylphenyl) amines; and alkylated phenylene-diamines; phenolics such as, for examples, BHT, sterically hindered alkyl phenols such as 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butyl-4-(2-octyl-3-propanoic) phenol; and mixtures thereof.
  • aminic types e.g., diphenylamine, phenyl-alpha-napthyl-amine, N,N-di(alkylphenyl) amines
  • alkylated phenylene-diamines alkylated phenylene-diamines
  • antiwear agents include, but are not limited to, zinc dialkyldithiophosphates and zinc diaryldithiophosphates, e.g., those described in an article by Born et al, entitled “Relationship between Chemical Structure and Effectiveness of some Metallic Dialkyl- and Diaryl-dithiophosphates in Different Lubricated Mechanism", appearing in Lubrication Science 4-2 January 1992, see for examples pages 97-100 ; aryl phosphates and phosphites, sulfur-containing esters, phosphosulfur compounds, metal or ash-free dithiocarbamates, xanthates, alkyl sulfides and the like and mixtures thereof.
  • ashless dispersants include, but are not limited to, amines, alcohols, amides, or ester polar moieties attached to the polymer backbones via bridging groups.
  • An ashless dispersant of the present invention may be, for examples, selected from oil soluble salts, esters, amino-esters, amides, imides, and oxazolines of long chain hydrocarbon substituted mono and dicarboxylic acids or their anhydrides; thiocarboxylate derivatives of long chain hydrocarbons, long chain aliphatic hydrocarbons having a polyamine attached directly thereto; and Mannich condensation products formed by condensing a long chain substituted phenol with formaldehyde and polyalkylene polyamine.
  • Carboxylic dispersants are reaction products of carboxylic acylating agents (acids, anhydrides, esters, etc.) comprising at least about 34 and preferably at least about 54 carbon atoms with nitrogen containing compounds (such as amines), organic hydroxy compounds (such as aliphatic compounds including monohydric and polyhydric alcohols, or aromatic compounds including phenols and naphthols), and/or basic inorganic materials.
  • carboxylic acylating agents as acids, anhydrides, esters, etc.
  • nitrogen containing compounds such as amines
  • organic hydroxy compounds such as aliphatic compounds including monohydric and polyhydric alcohols, or aromatic compounds including phenols and naphthols
  • basic inorganic materials include imides, amides, and esters.
  • Succinimide dispersants are a type of carboxylic dispersant. They are produced by reacting hydrocarbyl-substituted succinic acylating agent with organic hydroxy compounds, or with amines comprising at least one hydrogen atom attached to a nitrogen atom, or with a mixture of the hydroxy compounds and amines.
  • succinic acylating agent refers to a hydrocarbon-substituted succinic acid or a succinic acid-producing compound, the latter encompasses the acid itself.
  • Such materials typically include hydrocarbyl-substituted succinic acids, anhydrides, esters (including half esters) and halides.
  • Succinic-based dispersants have a wide variety of chemical structures.
  • One class of succinic-based dispersants may be represented by the formula: wherein each R 1 is independently a hydrocarbyl group, such as a polyolefin-derived group. Topically the hydrocarbyl group is an alkyl group, such as a polyisobutyl group. Alternatively expressed, the R 1 groups can contain about 40 to about 500 carbon atoms, and these atoms may be present in aliphatic forms.
  • R 2 is an alkylene group, commonly an ethylene (C 2 H 4 ) group.
  • succinimide dispersants include those described in, for example, U.S. Patent Nos. 3,172,892 , 4,234,435 and 6,165,235 .
  • the polyalkenes from which the substituent groups are derived are typically homopolymers and interpolymers of polymerizable olefin monomers of 2 to about 16 carbon atoms, and usually 2 to 6 carbon atoms.
  • the amines which are reacted with the succinic acylating agents to form the carboxylic dispersant composition can be monoamines or polyamines.
  • Succinimide dispersants are referred to as such since they normally contain nitrogen largely in the form of imide functionality, although the amide functionality may be in the form of amine salts, amides, imidazolines as well as mixtures thereof.
  • a succinimide dispersant one or more succinic acid-producing compounds and one or more amines are heated and typically water is removed, optionally in the presence of a substantially inert organic liquid solvent/diluent.
  • the reaction temperature can range from about 80°C up to the decomposition temperature of the mixture or the product, which typically falls between about 100°C to about 300°C. Additional details and examples of procedures for preparing the succinimide dispersants of the present invention include those described in, for example, U.S. Patent Nos. 3,172,892 , 3,219,666 , 3,272,746 , 4,234,435 , 6,165,235 and 6,440,905 .
  • Suitable ashless dispersants may also include amine dispersants, which are reaction products of relatively high molecular weight aliphatic halides and amines, preferably polyalkylene polyamines.
  • amine dispersants include those described in, for examples, U.S. Patent Nos. 3,275,554 , 3,438,757 , 3,454,555 and 3,565,804 .
  • Suitable ashless dispersants may further include "Mannich dispersants," which are reaction products of alkyl phenols in which the alkyl group contains at least about 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines). Examples of such dispersants include those described in, for example, U.S. Patent Nos. 3,036,003 , 3,586,629 , 3,591,598 and 3,980,569 .
  • Suitable ashless dispersants may also be post-treated ashless dispersants such as post-treated succinimides, e.g., post-treatment processes involving borate or ethylene carbonate as disclosed in, for example, U.S. Patent Nos. 4,612,132 and 4,746,446 ; and the like as well as other post-treatment processes.
  • the carbonate-treated alkenyl succinimide is a polybutene succinimide derived from polybutenes having a molecular weight of about 450 to about 3000, preferably from about 900 to about 2500, more preferably from about 1300 to about 2400, and most preferably from about 2000 to about 2400, as well as mixtures of these molecular weights.
  • it is prepared by reacting, under reactive conditions, a mixture of a polybutene succinic acid derivative, an unsaturated acidic reagent copolymer of an unsaturated acidic reagent and an olefin, and a polyamine, such as disclosed in U.S. Patent No. 5,716,912 .
  • Suitable ashless dispersants may also be polymeric, which are interpolymers of oil-solubilizing monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins with monomers containing polar substitutes.
  • polymeric dispersants include, those described in, for example, U.S. Patent Nos. 3,329,658 ; 3,449,250 and 3,666,730 .
  • an ashless dispersant for use in the lubricating oil composition is a bis-succinimide derived from a polyisobutenyl group having a number average molecular weight of about 700 to about 2300.
  • the dispersant(s) for use in the lubricating oil compositions of the present invention are preferably non-polymeric (e g., are mono- or bis-succinimides).
  • the one or more ashless dispersants are present in the lubricating oil composition in an amount ranging from about 0.01 wt. % to about 10 wt. %, based on the total weight of the lubricating oil composition.
  • metal detergents include sulphonates, alkylphenates, sulfurized alkyl phenates, carboxylates, salicylates, phosphonates, and phosphinates.
  • Commercial products are generally referred to as neutral or overbased.
  • Overbased metal detergents are generally produced by carbonating a mixture of hydrocarbons, detergent acid, for example: sulfonic acid, alkylphenol, carboxylate etc., metal oxide or hydroxides (for example calcium oxide or calcium hydroxide) and promoters such as xylene, methanol and water.
  • detergent acid for example: sulfonic acid, alkylphenol, carboxylate etc.
  • metal oxide or hydroxides for example calcium oxide or calcium hydroxide
  • promoters such as xylene, methanol and water.
  • the calcium oxide or hydroxide reacts with the gaseous carbon dioxide to form calcium carbonate.
  • the sulfonic acid is neutralized with an excess of CaO or Ca(OH) 2 , to form the
  • 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, and would typically have a total base number or TBN (as can be measured by ASTM D2896) of from 0 to about 80.
  • TBN total base number
  • 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).
  • the resulting overbased detergent comprises neutralized detergent as the outer layer of a metal base (e.g., carbonate) micelle.
  • a metal base e.g., carbonate
  • Such overbased detergents may have a TBN of about 150 or greater, and typically will have a TBN of from about 250 to about 450 or more.
  • Detergents that may be used include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and naphthenates and other oil-soluble carboxylates of a metal, particularly the alkali or alkaline earth metals, e.g., barium, sodium, potassium, lithium, calcium, and magnesium.
  • 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.
  • Particularly convenient metal detergents are neutral and overbased calcium sulfonates having TBN of from about 20 to about 450, neutral and overbased calcium phenates and sulfurized phenates having TBN of from about 50 to about 450 and neutral and overbased magnesium or calcium salicylates having a TBN of from about 20 to 450. Combinations of detergents, whether overbased or neutral or both, may be used.
  • the detergent can be one or more alkali or alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid.
  • Suitable hydroxyaromatic compounds include mononuclear monohydroxy and polyhydroxy aromatic hydrocarbons having 1 to 4, and preferably 1 to 3, hydroxyl groups.
  • Suitable hydroxyaromatic compounds include phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol, and the like.
  • the preferred hydroxyaromatic compound is phenol.
  • the alkyl substituted moiety of the alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid is derived from an alpha olefin having from 10 to 80 carbon atoms.
  • the olefins employed may be linear, isomerized linear, branched or partially branched linear.
  • the olefin may be a mixture of linear olefins, a mixture of isomerized linear olefins, a mixture of branched olefins, a mixture of partially branched linear or a mixture of any of the foregoing.
  • the mixture of linear olefins that may be used is a mixture of normal alpha olefins selected from olefins having from 12 to 30 carbon atoms per molecule.
  • the normal alpha olefins are isomerized using at least one of a solid or liquid catalyst.
  • the olefins are a branched olefinic propylene oligomer or mixture thereof having from 20 to 80 carbon atoms, i.e., branched chain olefins derived from the polymerization of propylene.
  • the olefins may also be substituted with other functional groups, such as hydroxy groups, carboxylic acid groups, heteroatoms, and the like.
  • the branched olefinic propylene oligomer or mixtures thereof have from 20 to 60 carbon atoms.
  • the branched olefinic propylene oligomer or mixtures thereof have from 20 to 40 carbon atoms.
  • the alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid is an alkali or alkaline earth metal salt of an alkyl-substituted hydroxybenzoic acid that is derived from an alkyl-substituted hydroxybenzoic acid in which the alkyl groups are the residue of normal alpha-olefins containing at least 75 mole% C 20 or higher normal alpha-olefins.
  • At least 50 mole % (e.g., at least 60 mole %, at least 70 mole %, at least 80 mole %, at least 85 mole %, at least 90 mole %, at least 95 mole %, or at least 99 mole %) of the alkyl groups contained within the alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid such as the alkyl groups of an alkali or alkaline earth metal salt of an alkyl-substituted hydroxybenzoic acid are C 14 to C 18 .
  • the resulting alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid will be a mixture of ortho and para isomers.
  • the product will contain 1 to 99% ortho isomer and 99 to 1% para isomer.
  • the product will contain 5 to 70% ortho and 95 to 30% para isomer.
  • the alkali or alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid can be neutral or overbased.
  • an overbased alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid is one in which the BN of the alkali or alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid has been increased by a process such as the addition of a base source (e.g., lime) and an acidic overbasing compound (e.g., carbon dioxide).
  • a base source e.g., lime
  • an acidic overbasing compound e.g., carbon dioxide
  • Overbased salts may be low overbased, e.g., an overbased salt having a BN below 100.
  • the BN of a low overbased salt may be from 5 to 50.
  • the BN of a low overbased salt may be from 10 to 30.
  • the BN of a low overbased salt may be from 15 to 20.
  • Overbased detergents may be medium overbased, e.g., an overbased salt having a BN from 100 to 250.
  • the BN of a medium overbased salt may be from 100 to 200.
  • the BN of a medium overbased salt may be from 125 to 175.
  • Overbased detergents may be high overbased, e.g., an overbased salt having a BN above 250.
  • the BN of a high overbased salt may be from 250 to 450.
  • Sulfonates may be prepared from sulfonic acids which are typically obtained by the sulfonation of alkyl substituted aromatic hydrocarbons such as those obtained from the fractionation of petroleum or by the alkylation of aromatic hydrocarbons. Examples included those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl or their halogen derivatives.
  • the alkylation may be carried out in the presence of a catalyst with alkylating agents having from 3 to more than 70 carbon atoms.
  • the alkaryl sulfonates usually contain from 9 to 80 or more carbon atoms, preferably from about 16 to about 60 carbon atoms per alkyl substituted aromatic moiety.
  • the oil soluble sulfonates or alkaryl sulfonic acids may be neutralized with oxides, hydroxides, alkoxides, carbonates, carboxylate, sulfides, hydrosulfides, nitrates, borates and ethers of the metal.
  • the amount of metal compound is chosen having regard to the desired TBN of the final product but typically ranges from 100 to 220 wt. % (preferably at least 125 wt. %) of that stoichiometrically required.
  • Metal salts of phenols and sulfurized phenols are prepared by reaction with an appropriate metal compound such as an oxide or hydroxide and neutral or overbased products may be obtained by methods well known in the art.
  • Sulfurized phenols may be prepared by reacting a phenol with sulfur or a sulfur containing compound such as hydrogen sulfide, sulfur monohalide or sulfur dihalide, to form products which are generally mixtures of compounds in which 2 or more phenols are bridged by sulfur containing bridges.
  • the one or more detergents are present in the lubricating oil composition in an amount ranging from 0.01 wt. % to 10 wt. %, based on the total weight of the lubricating oil composition.
  • rust inhibitors include, but are not limited to, nonionic polyoxyalkylene agents, e.g., polyoxyethylene lauryl ether, polyoxyethylene higher alcohol, ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene octyl stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol monooleate, and polyethylene glycol monooleate; stearic acid and other fatty acids; dicarboxylic acids; metal soaps; fatty acid amine salts; metal salts of heavy sulfonic acid; partial carboxylic acid ester of polyhydric alcohol; phosphoric esters; (short-chain) alkenyl succinic acids; partial esters thereof and nitrogen-containing derivatives thereof; synthetic alkarylsulfonates, e.g., metal dinonylnaphthalene sulf
  • 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, berated glycerol esters; and fatty imidazolines as disclosed in U.S. Patent No.
  • friction modifiers obtained from a reaction product of a C 4 to C 75 , preferably a C 6 to C 24 , and most preferably a C 6 to C 20 , fatty acid ester and a nitrogen-containing compound selected from the group consisting of ammonia, and an alkanolamine and the like and mixtures thereof.
  • a pour point depressant examples include, but are not limited to, polymethacrylates, alkyl acrylate polymers, alkyl methacrylate polymers, di(tetra-paraffin phenol)phthalate, condensates of tetra-paraffin phenol, condensates of a chlorinated paraffin with naphtalene and combinations thereof.
  • a pour point depressant comprises an ethylene-vinyl acetate copolymer, a condensate of chlorinated paraffin and phenol, polyalkyl styrene and the like and combinations thereof.
  • the amount of the pour point depressant may vary from 0.01 wt. % to 10 wt. %.
  • demulsifier examples include, but are not limited to, anionic surfactants (e.g., alkyl-naphtalene sulfonates, alkyl benzene sulfonates and the like), nonionic alkoxylated alkylphenol resins, polymers of alkylene oxides (e.g., polyethylene oxide, polypropylene oxide, block copolymers of ethylene oxide, propylene oxide and the like), esters of oil soluble acids, polyoxyethylene sorbitan ester and the like and combinations thereof.
  • the amount of the demulsifier may vary from 0.01 wt. % to 10 wt. %.
  • Examples of a corrosion inhibitor include, but are not limited to, half esters or amides of dodecylsuccinic acid, phosphate esters, thiophosphates, alkyl imidazolines, sarcosines and the like and combinations thereof.
  • the amount of the corrosion inhibitor may vary from 0.01 wt. % to 5 wt. %.
  • an extreme pressure agent examples include, but are not limited to, sulfurized animal or vegetable fats or oils, sulfurized animal or vegetable fatty acid esters, fully or partially esterified esters of trivalent or pentavalent acids of phosphorus, sulfurized olefins, dihydrocarbyl polysulfides, sulfurized Diels-Alder adducts, sulfurized dicyclopentadiene, sulfurized or co-sulfurized mixtures of fatty acid esters and monounsaturated olefins, co-sulfurized blends of fatty acid, fatty acid ester and alpha-olefin, functionally-substituted dihydrocarbyl polysulfides, thia-aldehydes, thia-ketones, epithio compounds, sulfur-containing acetal derivatives, co-sulfurized blends of terpene and acyclic olefins, and polysulfide olefin products, amine salts of
  • each of the foregoing additives when used, is used at a functionally effective amount to impart the desired properties to the lubricant.
  • a functionally effective amount of this friction modifier would be an amount sufficient to impart the desired friction modifying characteristics to the lubricant.
  • the concentration of each of these additives, when used may range, unless otherwise specified, from 0.001% to 20% by weight, and in one embodiment 0.01% to 10% by weight based on the total weight of the lubricating oil composition.
  • the lubricating oil additives of the present invention may be provided as an additive package or concentrate in which the additives are incorporated into a substantially inert, normally liquid organic diluent such as, for example, mineral oil, naphtha, benzene, toluene or xylene to form an additive concentrate.
  • a substantially inert, normally liquid organic diluent such as, for example, mineral oil, naphtha, benzene, toluene or xylene to form an additive concentrate.
  • Lubricating oil concentrates are also contemplated herein. These concentrates usually include at least from 90 wt. % to 10 wt. %, or from 80 wt. % to 20 wt. %, or from 70 wt. % to 30 wt. %, or from 60 wt. % to 40 wt. % of a diluent oil, and from 10 wt. % to 90 wt. %, or from 20 wt. % to 80 wt. %, or from 30 wt. % to 70 wt. %, or from 40 wt. % to 60 wt.
  • the concentrates contain sufficient diluent to make them easy to handle during shipping and storage.
  • Suitable diluents for the concentrates include any inert diluent, preferably an oil of lubricating viscosity, so that the concentrate may be readily mixed with lubricating oils to prepare lubricating oil compositions.
  • Suitable lubricating oils that may be used as diluents typically have viscosity in the range from 35 to 500 Saybolt Universal Seconds (SUS) at 100° F (38 °C), although any oil of lubricating viscosity may be used.
  • additives can be admixed with the foregoing lubricating oil concentrate to enhance performance.
  • additives include, but are not limited to antioxidants, antiwear agents, detergents, rust inhibitors, demulsifiers, friction modifiers, extreme pressure agents, viscosity index improvers, pour point depressants, dispersants, corrosion inhibitors, and the like, at the usual levels in accordance with well known practice.
  • the foam inhibitors of the present invention may be employed as a top treatment for crankcase lubricants employed in DISI engines.
  • the top treatment lubricating oil concentrate may be added at from 0.01 to 5% by weight to the oil, or from 0.5 to 2% by weight to the oil, based on the total weight of the lubricant composition.
  • the top treatment lubricating oil concentrate is added to the original DISI engine lubricating oil composition in an amount such that the final concentration of the foam inhibitor of the present invention is between 150 and 500 ppmw, and preferably between 200 and 400 ppmw, based on the total weight of the lubricant oil composition in the engine.
  • the addition of the top treatment lubricating oil concentrate results in at least a 10% reduction in IVD compared to operating the engine with a lubricating oil without any top treatment lubricating oil concentrate.
  • the addition of the top treatment lubricating oil concentrate results in at least a 20% reduction in IVD compared to operating the engine with a lubricating oil without any top treatment lubricating oil concentrate.
  • the addition of the top treatment lubricating oil concentrate results in at least a 30% reduction in IVD compared to operating the engine with a lubricating oil without any top treatment lubricating oil concentrate. In one embodiment, the addition of the top treatment lubricating oil concentrate results in at least a 40% reduction in IVD compared to operating the engine with a lubricating oil without any top treatment lubricating oil concentrate. In one embodiment, the addition of the top treatment lubricating oil concentrate results in at least a 50% reduction in IVD compared to operating the engine with a lubricating oil without any top treatment lubricating oil concentrate.
  • the lubricating oil compositions of Examples 1 and 2 below were evaluated using the 2001 Mitsubishi 1.8L DISI 212 hour Intake Valve Deposit Test ("Mitsubishi IVD, Test"), described hereinafter.
  • the 2001 Mitsubishi 1.8L DISI engine used in this procedure is mounted on an engine stand and connected to a dynamometer with load and speed control.
  • the Mitsubishi DISI engine is a wall guided engine with capability to run both homogenous and lean-stratified combustion. For carrying out the tests described herein, the engine was run on a lean-stratified combustion mode.
  • the engine is first flushed with the oil to be tested, refilled with test oil, and then operated for 30 minutes running at the test cycle.
  • the engine is then stopped, the oil drained, and a fresh sample of test oil is added to the engine.
  • the 212 hr test is then started, which consists of approximately 636 repeats of the test cycle.
  • the engine is operated for 1 minute at idle speed (750 +- 150 rpm) and no load, followed by 19 minutes of operation at low load (20.0 N/m) and low speed (1400 +- 10 rpm).
  • the engine is stopped, and the oil level checked, and if necessary additional test oil is added to the full mark.
  • the engine head is removed and the intake valves as well as the combustion chamber are rated for the deposit weights.
  • the eight intake valves (two per cylinder) in the engine are rinsed using hexane and weighed. Intake valves are weighed before and after the test and the difference in weight represent the weight of the deposit accumulates during the test.
  • Foam Inhibitor A was a poly (phenyl-methyl) siloxane; B a mixture of poly dimethyl siloxane and poly (dimethyl,phenyl-methyl) siloxane; C a polymethacrylate: D a poly (trifluoropropylmethyl) siloxane; and E a poly (dimethyl, phenyl-methyl) siloxane.
  • the results are shown in Table 1 below.

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Claims (15)

  1. Verwendung eines Schaumverhütungsmittels, ausgewählt aus der Gruppe Polysiloxane und Polymethacrylate, in einer Schmierölzusammensetzung, umfassend eine größere Menge eines Öls mit Schmierviskosität, zum Verringern der Aufnahme von Ventilablagerungen in einem direkteinspritzenden Ottomotor um mindestens 10%, im Vergleich dazu, wenn der Motor mit der Schmierölzusammensetzung ohne Schaumverhütungsmittel betrieben wird;
    wobei die Konzentration des Schaumverhütungsmittels in der Schmierölzusammensetzung von 30 bis 500 Gew.-ppm ist; und
    wobei das Schaumverhütungsmittel nicht Poly(phenylmethyl)siloxan ist.
  2. Verwendung gemäß Anspruch 1, wobei das Schaumverhütungsmittel ausgewählt ist aus der Gruppe Polydimethylsiloxan, Poly(dimethyl,phenyl-methyl)siloxan, Poly(trifluoropropylmethyl)siloxan, und Gemisch aus Polydiemthylsiloxan und Poly(dimethyl,phenylmethyl)siloxan.
  3. Verwendung gemäß Ansprüchen 1 bis 2, wobei die Konzentration des Schaumverhütungsmittels in der Schmierölzusammensetzung von 100 bis 500 Gew.-ppm ist, oder 150 bis 500 Gew.-ppm, oder 200 bis 400 Gew.-ppm.
  4. Verwendung gemäß Ansprüchen 1 bis 3, wobei die Verringerung der Aufnahme von Ventilablagerungen mindestens 20% ist, oder mindestens 30%, oder mindestens 40%, oder mindestens 50%.
  5. Verwendung gemäß Ansprüchen 1 bis 4, wobei die Schmierölzusammensetzung mindestens ein Zusatzmittel umfasst, ausgewählt aus der Gruppe Detergenzien, Dispersionsmittel, Antioxidationsmittel, Antiabriebmittel, Rosthemmer, Enttrüber, Demulgatoren, Metalldeaktivierer, Reibungsmodifizierer, Fließpunktverringerer, Ko-Lösungsmittel, Paketkompatibilisierer, Korrosionshemmer, Farbmittel, Extremdruckmittel und deren Gemische.
  6. Verwendung gemäß Ansprüchen 1 bis 5, wobei das Öl mit Schmierviskosität mindestens 50 Gew.-% eines Basisöls der API Gruppe II oder der Gruppe III umfasst, oder deren Gemische.
  7. Verwendung gemäß irgendeinem vorhergehenden Anspruch, wobei die Schmierölzusammensetzung mit einem Schmierölkonzentrat, umfassend das Schaumverhütungsmittel, nachbehandelt ist, wahlweise wobei die Konzentration des Schaumverhütungsmittels im Schmierölkonzentrat von 0,1 bis 1,0 Gew.-% ist, oder von 0,02 bis 0,8 Gew.-%, oder von 0,03 bis 0,7 Gew.-%, oder von 0,04 bis 0,6 Gew.-%.
  8. Verwendung gemäß irgendeinem vorhergehenden Anspruch, wobei der direkteinspritzende Ottomotor mit einer geschlossenen Kurbelgehäuseentlüftung ausgestattet ist.
  9. Verfahren zum Verringern der Aufnahme von Ventilablagerungen in einem direkteinspritzenden Ottomotor, ausgestattet mit einer geschlossenen Kurbelgehäuseentlüftung, das Verfahren umfassend Betreiben des Motors mit einer Schmierölzusammensetzung, umfassend
    (a) eine größere Menge eines Öls mit Schmierviskosität; und
    (b) mindestens ein Schaumverhütungsmittel, ausgewählt aus der Gruppe Polysiloxane und Polymethacrylate;
    wobei das Schaumverhütungsmittel nicht Poly(phenylmethyl)siloxan ist; und zudem, wobei die Konzentration des Schaumverhütungsmittels in der Schmierölzusammensetzung von 30 bis 500 Gew.-ppm ist, zum Erreichen von mindestens 10% Verringerung der Aufnahme von Ventilablagerungen im direkteinspritzenden Ottomotor, im Vergleich dazu, wenn der Motor mit der Schmierölzusammensetzung ohne Schaumverhütungsmittel betrieben wird.
  10. Verfahren zum Verringern der Aufnahme von Ventilablagerungen in einem direkteinspritzenden Ottomotor, ausgestattet mit einer geschlossenen Kurbelgehäuseentlüftung, das Verfahren umfassend
    (a) Betreiben des Motors mit einer Schmierölzusammensetzung;
    (b) Nachbehandeln des Schmieröls mit einem Schmierölkonzentrat, umfassend mindestens ein Schaumverhütungsmittel, ausgewählt aus der Gruppe Polysiloxane und Polymethacrylate, um so eine nachbehandelte Schmierölzusammensetzugn bereitzustellen;
    wobei das Schaumverhütungsmittel nicht Poly(phenylmethyl)siloxan ist; und zudem, wobei die Endkonzentration des Schaumverhütungsmittels in der nachbehandelten Schmierölzusammensetzung von 30 bis 500 Gew.-ppm ist, zum Erreichen von mindestens 10% Verringerung der Aufnahme von Ventilablagerungen im direkteinspritzenden Ottomotor, im Vergleich dazu, wenn der Motor mit der Schmierölzusammensetzung aus Schritt (a) ohne Nachbehandlung betrieben wird, wahlweise, wobei die Konzentration des Schaumverhütungsmittels im Schmierölkonzentrat von 0,1 bis 1,0 Gew.-% ist, oder von 0,02 bis 0,8 Gew.-%, oder von 0,03 bis 0,7 Gew.-%, oder von 0,04 bis 0,6 Gew.-%.
  11. Verfahren gemäß Ansprüchen 9 bis 10, wobei das Schaumverhütungsmittel ausgewählt ist aus der Gruppe Polydimethylsiloxan, Poly(dimethyl,phenyl-methyl)siloxan, Poly(trifluoropropylmethyl)siloxan, und Gemisch aus Polydiemthylsiloxan und Poly(dimethyl,phenylmethyl)siloxan.
  12. Verfahren gemäß Ansprüchen 9 bis 11, wobei die Endkonzentration des Schaumverhütungsmittels in der nachbehandelten Schmierölzusammensetzung von 100 bis 500 Gew.-ppm ist, oder von 150 bis 500 Gew.-ppm, oder von 200 bis 400 Gew.-ppm.
  13. Verfahren gemäß Ansprüchen 9 bis 12, wobei die Verringerung der Aufnahme von Ventilablagerungen mindestens 20% ist, oder mindestens 30%, oder mindestens 40%, oder mindestens 50%.
  14. Verfahren gemäß Ansprüchen 9 bis 13, wobei die nachbehandelte Schmierölzusammensetzung mindestens ein Zusatzmittel umfasst, ausgewählt aus der Gruppe Detergenzien, Dispersionsmittel, Antioxidationsmittel, Antiabriebmittel, Rosthemmer, Enttrüber, Demulgatoren, Metalldeaktivierer, Reibungsmodifizierer, Fließpunktverringerer, Ko-Lösungsmittel, Paketkompatibilisierer, Korrosionshemmer, Farbmittel, Extremdruckmittel und deren Gemische.
  15. Verfahren gemäß Ansprüchen 9 bis 14, wobei das Schmieröl mindestens 50 Gew.-% eines Basisöls der API Gruppe II oder der Gruppe III umfasst, oder deren Gemische.
EP11836848.9A 2010-10-29 2011-10-13 Verwendung und methode zur reduzierung von ventilablagerungen in einem motor Active EP2633012B1 (de)

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EP2911761A1 (de) * 2012-10-24 2015-09-02 The Procter & Gamble Company Antischaumzusammensetzungen mit teilweise phenylbeladenem polyorganosilicium
CN104232246B (zh) * 2013-06-07 2017-02-01 中国石油化工股份有限公司 一种润滑油复合型抗泡剂及其应用
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CA2816055C (en) 2018-08-28
CN103201364B (zh) 2016-09-14
US20120108476A1 (en) 2012-05-03
JP2013540878A (ja) 2013-11-07
WO2012058012A2 (en) 2012-05-03
EP2633012A2 (de) 2013-09-04
WO2012058012A3 (en) 2012-07-19
CA2816055A1 (en) 2012-05-03
JP5828597B2 (ja) 2015-12-09
CN103201364A (zh) 2013-07-10
SG189464A1 (en) 2013-05-31

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