EP4159832A1 - Schmierölzusammensetzungen - Google Patents

Schmierölzusammensetzungen Download PDF

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Publication number
EP4159832A1
EP4159832A1 EP21200776.9A EP21200776A EP4159832A1 EP 4159832 A1 EP4159832 A1 EP 4159832A1 EP 21200776 A EP21200776 A EP 21200776A EP 4159832 A1 EP4159832 A1 EP 4159832A1
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Prior art keywords
mass
oil
composition
lubricating oil
compound
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EP21200776.9A
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English (en)
French (fr)
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EP4159832B1 (de
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Joshua Smith
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Infineum International Ltd
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Infineum International Ltd
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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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/24—Aldehydes; Ketones
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/08—Aldehydes; Ketones
    • C10M2207/085—Aldehydes; Ketones used as base material
    • 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
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure

Definitions

  • This invention relates to lubricating oil compositions containing certain vanadium compounds.
  • the compounds provide the compositions with friction reducing and anti-wear properties.
  • the lubricating oil compositions are useful in the lubrication of internal combustion engines, such as those found in vehicles.
  • Metal-containing additives have long been used in lubricating oil compositions of various types.
  • ZDDP zinc dialkyldithiophosphate
  • Molybdenum-containing compounds of different kinds are also used to improve the oxidation resistance of oils as well as providing friction modification properties.
  • Detergent compounds based on alkali and alkaline-earth metals are also widely used. However, compounds of vanadium have historically been less commonly used.
  • US 2,795,549 describes certain metal complexes containing inter alia, acids, oxides or salts of vanadium, tungsten or zirconium together with a chelating compound having two functional groups vicinal to one another.
  • chelating compounds include acetylacetone and vanadium is a preferred metal.
  • the compounds, for example, vanadyl bisacetylacetonate, are indicated to limit the oxidation of lubricating oils and to provide some protection to copper and lead-containing materials from corrosion.
  • the present invention provides a lubricating oil composition
  • a lubricating oil composition comprising at least 50 percent by mass, based on the mass of the composition of an oil of lubricating viscosity and 0.01 to 15 percent by mass, based on the mass of the composition, of a compound having structure (I): wherein R 1 and R 2 are the same or different and are linear or branched alkyl groups having from 2 to 10, preferably from 2 to 8 carbon atoms.
  • the lubricating oil composition may comprise a single compound of structure (I) or two or more different compounds of structures (I) and (II).
  • the present invention provides a method of reducing friction and/or wear between contacting surfaces of a machine, the method comprising supplying a lubricating oil composition according to the first aspect to the contacting surfaces.
  • the present invention provides the use of a compound having structure (I):
  • the compound having structure (I) is present in the lubricating oil composition in an amount of 0.01 to 10 percent by mass, based on the mass of the composition, more preferably 0.05 to 5 percent by mass, even more preferably 0.1 to 1 percent by mass.
  • the amount of compound of structure (I) present may alternatively be expressed in terms of the mass of vanadium present in the lubricating oil composition so preferably, in all aspects, the compound of structure (I) is present in an amount such as to provide the lubricating oil composition with 10 to 10,000 parts per million by mass (ppm) of vanadium, more preferably 50 to 5,000 ppm, even more preferably 50 to 1,500 ppm.
  • the machine having contacting surfaces lubricated by the composition is an internal combustion engine.
  • Suitable engines will be known to those skilled in the art and include both spark-ignited (gasoline) and compression-ignited (diesel) engines such as may be found in automotive engines used in cars, trucks, buses and other land vehicles, as well as engines used in marine applications.
  • the contacting surfaces of the engine lubricated by the composition may be those found for example, in the crank-case of the engine.
  • the lubricating oil compositions of the present invention may also find use in the lubrication of gears and manual or automatic transmission systems.
  • Compounds of structure (I) have a vanadyl core (VO 2+ ) co-ordinated to a ligand system comprised of two bidentate ligands.
  • the ligands are acetylacetonate ligands where the central carbon atom carries a linear or branched alkyl group.
  • structure (I) is a simplified representation of the compounds indicating that there will exist resonance forms where formal single and double bonds are interchangeable.
  • structure (I) is shown without any stereochemical indications for reasons of clarity. Those skilled in the art will understand that the compounds are not planar. The ligands around the vanadyl centre will normally be arranged in a square pyramid form.
  • Preferred linear alkyl groups suitable as R 1 and R 2 include ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl.
  • Preferred branched chain alkyl groups suitable as R 1 and R 2 include isopropyl, methylpropyl, secondary-butyl, tertiary-butyl, methylbutyl, dimethylpropyl, methylpentyl, dimethylbutyl, ethylbutyl, methylhexyl, dimethylpentyl, ethylpentyl, and 2-ethylhexyl.
  • R 1 and R 2 are the same or different and are linear alkyl groups.
  • At least one of R 1 and R 2 is n-propyl, n-butyl, n-hexyl or n-octyl.
  • R 1 and R 2 are the same.
  • Vanadyl (IV) sulfate hydrate (1 eq.) and sodium acetate (2.05 eq.) were combined in a suitably sized round bottom flask prior to flushing with dry N 2 .
  • the pale blue suspension obtained was degassed via N 2 sparging and an alkylpentane-2,4-dione ligand (2.05 eq.) was added slowly via syringe, resulting in a green/blue solution. Water was added until a dark green solution was afforded, with all solids dissolved. On partition of a dark green oil, more water was added to promote further precipitation. Stirring in an ice/water bath ensured full precipitation and solidification of the green oil. The solid was isolated via vacuum filtration on a glass frit, thoroughly washed with water and ethanol to remove residual starting materials and impurities. After final washing with heptane the resultant green solid was dried under vacuum.
  • Lubricating oil compositions of the invention may be lubricants suitable for use as motor vehicle motor oils comprising a major amount of oil of lubricating viscosity and minor amounts of performance-enhancing additives, including the compounds of the present invention.
  • the lubricating oil composition may also be in the form of an additive concentrate for blending with oil of lubricating viscosity to make a final lubricant.
  • the oil of lubricating viscosity (sometimes referred to as “base stock” or “base oil”) is the primary liquid constituent of a lubricant, into which additives and possibly other oils are blended, for example to produce a final lubricant (or lubricant composition).
  • a base oil which is useful for making additive concentrates as well as for making lubricating oil compositions therefrom, may be selected from natural oils (vegetable, animal or mineral) and synthetic lubricating oils and mixtures thereof.
  • base stocks and base oils in this invention are the same as those found in the American Petroleum Institute (API) publication " Engine Oil Licensing and Certification System", Industry Services Department, Fourteenth Edition, December 1996, Addendum 1, December 1998 , which categorizes base stocks as follows:
  • the base stock has a viscosity preferably of 3-12, more preferably 4-10, most preferably 4.5-8, mm 2 /s at 100°C.
  • Table E-1 Analytical Methods for Base Stock Property Test Method Saturates ASTM D 2007 Viscosity Index ASTM D 2270 Sulphur ASTM D 2622 ASTM D 4294 ASTM D 4927 ASTM D 3120
  • the oil of lubricating viscosity comprises greater than or equal to 10, more preferably greater than or equal to 20, even more preferably greater than or equal to 25, even more preferably greater than or equal to 30, even more preferably greater than or equal to 40, even more preferably greater than or equal to 45, mass % of a Group II or Group III base stock, based on the total mass of the oil of lubricating viscosity.
  • the oil of lubricating viscosity comprises greater than 50, preferably greater than or equal to 60, more preferably greater than or equal to 70, even more preferably greater than or equal to 80, even more preferably greater than or equal to 90, mass % of a Group II or Group III base stock, based on the total mass of the oil of lubricating viscosity.
  • the oil of lubricating viscosity consists essentially of a Group II and/or Group III base stock.
  • the oil of lubricating viscosity consists solely of Group II and/or Group III base stock. In the latter case it is acknowledged that additives included in the lubricating oil composition may comprise a carrier oil which is not a Group II or Group III base stock.
  • oils of lubricating viscosity that may be included in the lubricating oil composition are detailed as follows: Natural oils include animal and vegetable oils (e.g. castor and lard oil), liquid petroleum oils and hydro refined, solvent-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.
  • Synthetic lubricating oils include hydrocarbon oils such as polymerized and interpolymerized olefins (e.g. polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1-hexenes), poly(1-octenes), poly(1-decenes)); alkylbenzenes (e.g. dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzenes); polyphenols (e.g. biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogues and homologues thereof.
  • hydrocarbon oils such as polymerized and interpolymerized olefins (e.g. polybut
  • Another suitable class of synthetic lubricating oil comprises the esters of dicarboxylic acids (e.g. phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety of alcohols (e.g. butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol).
  • dicarboxylic acids e.g. phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dim
  • esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.
  • Esters useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols, and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
  • Unrefined, refined and re-refined oils can be used in the compositions of the present invention.
  • Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment.
  • a shale oil obtained directly from retorting operations a petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further treatment would be unrefined oil.
  • Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration and percolation, are known to those skilled in the art.
  • Re-refined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils that have been already used in service. Such re-refined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for treating spent additive and oil breakdown products.
  • base oil examples include gas-to-liquid (“GTL”) base oils, i.e. the base oil may be an oil derived from Fischer-Tropsch synthesised hydrocarbons made from synthesis gas containing H 2 and CO using a Fischer-Tropsch catalyst. These hydrocarbons typically require further processing in order to be useful as a base oil. For example, they may, by methods known in the art, be hydroisomerized; hydrocracked and hydroisomerized; dewaxed; or hydroisomerized and dewaxed.
  • GTL gas-to-liquid
  • the oil of lubricating viscosity may also comprise a Group I, Group IV or Group V base stocks or base oil blends of the aforementioned base stocks.
  • the lubricating compositions of the present invention preferably comprise at least 60% by weight, for example 70% by weight or more of an oil of lubricating viscosity, based on the weight of the composition.
  • the lubricating oil compositions of the present invention may further comprise additives other than a compound of formula (I). These are discussed in more detail below.
  • a dispersant is an additive whose primary function is to hold solid and liquid contaminants in suspension, thereby passivating them and reducing engine deposits at the same time as reducing sludge depositions.
  • a dispersant maintains in suspension oil-insoluble substances that result from oxidation during use of the lubricant, thus preventing sludge flocculation and precipitation or deposition on metal parts of the engine.
  • Dispersants have been used in lubricating oil compositions widely and for many years. Their structures and chemistries are well known to those skilled in the art.
  • Dispersants are preferably "ashless", being non-metallic organic materials that form substantially no ash on combustion, in contrast to metal-containing and hence ash-forming materials. They comprise a long hydrocarbon chain with a polar head, the polarity being derived from inclusion of e.g. an O, P, or N atom.
  • the hydrocarbon is an oleophilic group that confers oil-solubility, having, for example 40 to 500 carbon atoms.
  • ashless dispersants may comprise an oil-soluble polymeric backbone.
  • a preferred class of olefin polymers is constituted by polybutenes, specifically polyisobutenes (PIB) or poly-n-butenes, such as may be prepared by polymerization of a C 4 refinery stream.
  • PIB polyisobutenes
  • poly-n-butenes such as may be prepared by polymerization of a C 4 refinery stream.
  • Dispersants include, for example, derivatives of long chain hydrocarbon-substituted carboxylic acids, examples being derivatives of high molecular weight hydrocarbyl-substituted succinic acid.
  • a noteworthy group of dispersants is constituted by hydrocarbon-substituted succinimides, made, for example, by reacting the above acids (or derivatives) with a nitrogen-containing compound, advantageously a polyalkylene polyamine, such as a polyethylene polyamine.
  • reaction products of polyalkylene polyamines with alkenyl succinic anhydrides such as described in US-A-3,202,678 ; - 3,154,560 ; - 3,172,892 ; - 3,024,195 ; - 3,024,237 , -3,219,666; and -3,216,936, that may be post-treated to improve their properties, such as borated (as described in US-A-3,087,936 and - 3,254,025 ), fluorinated or oxylated.
  • boration may be accomplished by treating an acyl nitrogen-containing dispersant with a boron compound selected from boron oxide, boron halides, boron acids and esters of boron acids.
  • Preferred dispersants are succinimide-dispersants derived from a polyisobutene of number average molecular weight in the range of 1000 to 3000, preferably 1500 to 2500, and of moderate functionality.
  • the succinimide is preferably derived from highly reactive polyisobutene.
  • the dispersant comprises from 0.1 to 20 mass% of the lubricating oil composition, based on the mass of the composition, more preferably, from 0.1 to 10 mass%.
  • Oxidation inhibitors or antioxidants reduce the tendency of oils to deteriorate in service. Oxidative deterioration can be evidenced by sludge in the lubricant, varnish-like deposits on the metal surfaces, and by viscosity growth.
  • Oxidative deterioration can be evidenced by sludge in the lubricant, varnish-like deposits on the metal surfaces, and by viscosity growth.
  • Such oxidation inhibitors include hindered phenols, alkaline earth metal salts of alkylphenolthioesters having preferably C 5 to C 12 alkyl side chains, calcium nonylphenol sulfide, oil soluble phenates and sulfurized phenates, phosphosulfurized or sulfurized hydrocarbons or esters, phosphorous esters, metal thiocarbamates, oil soluble copper compounds as described in U.S. Patent No. 4,867,890 , and molybdenum-containing compounds.
  • Aromatic amines having at least two aromatic groups attached directly to the nitrogen constitute another class of compounds that is frequently used for antioxidancy.
  • Typical oil-soluble aromatic amines having at least two aromatic groups attached directly to one amine nitrogen contain from 6 to 16 carbon atoms.
  • the amines may contain more than two aromatic groups.
  • Compounds having a total of at least three aromatic groups in which two aromatic groups are linked by a covalent bond or by an atom or group (e.g., an oxygen or sulfur atom, or a -CO-, -SO 2 - or alkylene group) and two are directly attached to one amine nitrogen are also considered aromatic amines having at least two aromatic groups attached directly to the nitrogen.
  • the aromatic rings are typically substituted by one or more substituents selected from alkyl, cycloalkyl, alkoxy, aryloxy, acyl, acylamino, hydroxy, and nitro groups.
  • the amount of any such oil soluble aromatic amines having at least two aromatic groups attached directly to one amine nitrogen should preferably not exceed 0.4 mass %.
  • a detergent is an additive that reduces formation of piston deposits, for example high-temperature varnish and lacquer deposits in engines; it normally has acid-neutralising properties and is capable of keeping finely-divided solids in suspension.
  • Most detergents are based on metal "soaps", that is metal salts of acidic organic compounds.
  • Detergents generally comprise a polar head with a long hydrophobic tail, the polar head comprising the metal salt of the acidic organic compound.
  • the salts may contain a substantially stoichiometric amount of the metal when they are usually described as normal or neutral salts and would typically have a total base number or TBN at 100 % active mass (as may be measured by ASTM D2896) of from 0 to 80.
  • TBN total base number
  • Large amounts of a metal base can be included by reaction of an excess of a metal compound, such as an oxide or hydroxide, with an acidic gas such as carbon dioxide.
  • the resulting overbased detergent comprises neutralised detergent as an outer layer of a metal base (e.g. carbonate) micelle.
  • a metal base e.g. carbonate
  • Such overbased detergents may have a TBN at 100 % active mass of 150 or greater, and typically of from 200 to 500 or more.
  • detergents that may be used include oil-soluble neutral and overbased sulfonates, phenates, sulfurised phenates, thiophosphonates, salicylates and naphthenates and other oil-soluble carboxylates of a metal, particularly alkali metal or alkaline earth metals, e.g. Na, K, Li, Ca and Mg.
  • a metal particularly alkali metal or alkaline earth metals, e.g. Na, K, Li, Ca and Mg.
  • the most commonly-used metals are Ca and Mg, which may both be present in detergents used in lubricating compositions, and mixtures of Ca and/or Mg with Na.
  • Detergents may be used in various combinations.
  • Friction modifiers and fuel economy agents may also be included.
  • examples of such materials include glyceryl monoesters of higher fatty acids, for example, glyceryl mono-oleate; esters of long chain polycarboxylic acids with diols, for example, the butane diol ester of a dimerized unsaturated fatty acid; and alkoxylated alkyl-substituted mono-amines, diamines and alkyl ether amines, for example, ethoxylated tallow amine and ethoxylated tallow ether amine.
  • Other known friction modifiers comprise oil-soluble organo-molybdenum compounds.
  • organo-molybdenum friction modifiers also provide antioxidant and antiwear credits to a lubricating oil composition.
  • oil-soluble organo-molybdenum compounds include dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, sulfides, and the like, and mixtures thereof.
  • Particularly preferred are molybdenum dithiocarbamates, dialkyldithiophosphates, alkyl xanthates and alkylthioxanthates.
  • the molybdenum compound may be an acidic molybdenum compound. These compounds will react with a basic nitrogen compound as measured by ASTM test D-664 or D-2896 titration procedure and are typically hexavalent. Included are molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, e.g., hydrogen sodium molybdate, MoOCl 4 , MoO 2 Br 2 , Mo 2 O 3 Cl 6 , molybdenum trioxide or similar acidic molybdenum compounds.
  • molybdenum compounds useful in the compositions of this invention are organo-molybdenum compounds of the formula Mo(R"OCS 2 ) 4 and Mo(R"SCS 2 ) 4 wherein R" is an organo group selected from the group consisting of alkyl, aryl, aralkyl and alkoxyalkyl, generally of from 1 to 30 carbon atoms, and preferably 2 to 12 carbon atoms and most preferably alkyl of 2 to 12 carbon atoms.
  • R" is an organo group selected from the group consisting of alkyl, aryl, aralkyl and alkoxyalkyl, generally of from 1 to 30 carbon atoms, and preferably 2 to 12 carbon atoms and most preferably alkyl of 2 to 12 carbon atoms.
  • dialkyldithiocarbamates of molybdenum are especially preferred.
  • organo-molybdenum compounds useful in the lubricating compositions of this invention are trinuclear molybdenum compounds, especially those of the formula Mo 3 S k L n Q z and mixtures thereof wherein the L are independently selected ligands having organo groups with a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil, n is from 1 to 4, k varies from 4 to 7, Q is selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. At least 21 carbon atoms should be present among all the ligand organo groups, such as at least 25, at least 30, or at least 35, carbon atoms.
  • Lubricating oil compositions useful in all aspects of the present invention preferably contain at least 10 ppm, at least 30 ppm, at least 40 ppm and more preferably at least 50 ppm molybdenum.
  • lubricating oil compositions useful in all aspects of the present invention contain no more than 1000 ppm, no more than 750 ppm or no more than 500 ppm of molybdenum.
  • Lubricating oil compositions useful in all aspects of the present invention preferably contain from 10 to 1000, such as 30 to 750 or 40 to 500, ppm of molybdenum (measured as atoms of molybdenum).
  • the viscosity index of the oil of lubricating viscosity may be increased, or improved, by incorporating therein certain polymeric materials that function as viscosity modifiers (VM) or viscosity index improvers (VII).
  • VM viscosity modifiers
  • VII viscosity index improvers
  • polymeric materials useful as viscosity modifiers are those having number average molecular weights (Mn) of from 5,000 to 250,000, preferably from 15,000 to 200,000, more preferably from 20,000 to 150,000.
  • viscosity modifiers can be grafted with grafting materials such as, for example, maleic anhydride, and the grafted material can be reacted with, for example, amines, amides, nitrogen-containing heterocyclic compounds or alcohol, to form multifunctional viscosity modifiers (dispersant-viscosity modifiers).
  • grafting materials such as, for example, maleic anhydride
  • the grafted material can be reacted with, for example, amines, amides, nitrogen-containing heterocyclic compounds or alcohol, to form multifunctional viscosity modifiers (dispersant-viscosity modifiers).
  • Polymers prepared with diolefins will contain ethylenic unsaturation, and such polymers are preferably hydrogenated.
  • the hydrogenation may be accomplished using any of the techniques known in the prior art.
  • the hydrogenation may be accomplished such that both ethylenic and aromatic unsaturation is converted (saturated) using methods such as those taught, for example, in U.S. Pat. Nos. 3,113,986 and 3,700,633 or the hydrogenation may be accomplished selectively such that a significant portion of the ethylenic unsaturation is converted while little or no aromatic unsaturation is converted as taught, for example, in U.S. Pat. Nos. 3,634,595 ; 3,670,054 ; 3,700,633 and Re 27,145 . Any of these methods can also be used to hydrogenate polymers containing only ethylenic unsaturation and which are free of aromatic unsaturation.
  • LOFIs Pour point depressants
  • PPD lube oil flow improvers
  • LOFIs lube oil flow improvers
  • VM Pour point depressants
  • LOFIs lube oil flow improvers
  • grafting materials such as, for example, maleic anhydride, and the grafted material can be reacted with, for example, amines, amides, nitrogen-containing heterocyclic compounds or alcohol, to form multifunctional additives.
  • each additive is typically blended into the base oil in an amount that enables the additive to provide its desired function.
  • Representative effective amounts of such additives, when used in crankcase lubricants, are listed below. All the values listed (with the exception of detergent values since the detergents are used in the form of colloidal dispersants in an oil) are stated as mass percent active ingredient (A.I.).
  • the Noack volatility of the fully formulated lubricating oil composition is no greater than 18, such as no greater than 14, preferably no greater than 10, mass %.
  • Lubricating oil compositions useful in the practice of the present invention may have an overall sulfated ash content of from 0.5 to 2.0, such as from 0.7 to 1.4, preferably from 0.6 to 1.2, mass %.
  • additive concentrates comprising additives (concentrates sometimes being referred to as additive packages) whereby several additives can be added simultaneously to the oil to form the lubricating oil composition.
  • Vanadyl (IV) sulfate hydrate (6.33 g, 25 mmol) and sodium acetate (4.10 g, 50 mmol) were combined in a 250 mL round bottom flask which was subsequently flushed with dry N 2 .
  • ethanol 40 mL
  • the pale blue suspension obtained was degassed via N 2 sparging, and 3-propylpentane-2,4-dione (7.11 g, 50 mmol) was added slowly via syringe resulting in a green/blue solution. 20 mL of water was added until a dark green solution was afforded, with all solids dissolved.
  • Vanadyl (IV) sulfate hydrate (5 g, 21.3 mmol) and sodium acetate (3.58 g, 43.6 mmol) were combined in a 100 mL round bottom flask which was subsequently flushed with dry N 2 .
  • 2-propanol 25 mL
  • 3-propylpentane-2,4-dione 6.81 g, 43.6 mmol was added slowly via syringe. 50 mL of water was added until a dark green solution was afforded, with all solids dissolved.
  • Vanadyl (IV) sulfate hydrate (2.00 g, 8.51 mmol) and sodium acetate (1.43 g, 17.44 mmol) were combined in a 100 mL round bottom flask which was subsequently flushed with dry N 2 .
  • ethanol 40 mL
  • 3-octylpentane-2,4-dione 3.70 g, 17.44 mmol
  • 20 mL of water was added until a dark green solution was afforded, with all solids dissolved.
  • Oil compositions were then formed by adding each of the compounds to a Group III mineral oil (Yubase 4) in an amount such as to provide the oil compositions with 250 parts per million by mass of vanadium.
  • Oil A contained Compound A
  • Oil 1 contained Compound 1
  • Oil 2 contained Compound 2
  • Oil 3 contained Compound 3.
  • Compound A is vanadyl bisacetylacetonate so is the compound described in US 2,795,549 .
  • Oil A is thus used here as a comparative example.
  • Oils 1, 2 and 3 are examples of the present invention as they contain Compounds 1, 2 and 3 which all conform to Structure (I).
  • the oils were tested using a High Frequency Reciprocating Rig (HFRR) available from PCS Instruments, London.
  • HFRR High Frequency Reciprocating Rig
  • a steel ball is loaded and reciprocated against the face of a steel disc.
  • the load between the ball and the disc was set at 4N giving a contact pressure of 1.046 Gpa.
  • the ball was driven with a frequency of 40Hz over a stroke length of 1mm for a duration of 1 hour and at oil temperatures increasing from 40°C to 140°C.
  • compositions according to the present invention provided significantly better wear protection, as evidenced by the lower wear scar volumes measured.

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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)
EP21200776.9A 2021-10-04 2021-10-04 Schmierölzusammensetzungen Active EP4159832B1 (de)

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Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2795549A (en) 1954-06-29 1957-06-11 California Research Corp Lubricating oil compositions
US3024195A (en) 1959-08-24 1962-03-06 California Research Corp Lubricating oil compositions of alkylpiperazine alkenyl succinimides
US3087936A (en) 1961-08-18 1963-04-30 Lubrizol Corp Reaction product of an aliphatic olefinpolymer-succinic acid producing compound with an amine and reacting the resulting product with a boron compound
US3113986A (en) 1962-01-08 1963-12-10 Hercules Powder Co Ltd Hydrogenation of unsaturated hydrocarbons
US3154560A (en) 1961-12-04 1964-10-27 Monsanto Co Nu, nu'-azaalkylene-bis
US3172892A (en) 1959-03-30 1965-03-09 Reaction product of high molecular weight succinic acids and succinic anhydrides with an ethylene poly- amine
US3202678A (en) 1959-08-24 1965-08-24 California Research Corp Alkenyl succinimides of tetraethylene pentamine
USRE27145E (en) 1969-05-20 1971-06-22 Side-chain
US3634595A (en) 1969-03-31 1972-01-11 Giorgio Pasquali A generator of harmonic signals with a helical spring
US3670054A (en) 1969-10-29 1972-06-13 Shell Oil Co Block copolymers having reduced solvent sensitivity
US3700633A (en) 1971-05-05 1972-10-24 Shell Oil Co Selectively hydrogenated block copolymers
US4867890A (en) 1979-08-13 1989-09-19 Terence Colclough Lubricating oil compositions containing ashless dispersant, zinc dihydrocarbyldithiophosphate, metal detergent and a copper compound
US5736491A (en) * 1997-01-30 1998-04-07 Texaco Inc. Method of improving the fuel economy characteristics of a lubricant by friction reduction and compositions useful therein

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2795549A (en) 1954-06-29 1957-06-11 California Research Corp Lubricating oil compositions
US3172892A (en) 1959-03-30 1965-03-09 Reaction product of high molecular weight succinic acids and succinic anhydrides with an ethylene poly- amine
US3024195A (en) 1959-08-24 1962-03-06 California Research Corp Lubricating oil compositions of alkylpiperazine alkenyl succinimides
US3202678A (en) 1959-08-24 1965-08-24 California Research Corp Alkenyl succinimides of tetraethylene pentamine
US3254025A (en) 1961-08-18 1966-05-31 Lubrizol Corp Boron-containing acylated amine and lubricating compositions containing the same
US3087936A (en) 1961-08-18 1963-04-30 Lubrizol Corp Reaction product of an aliphatic olefinpolymer-succinic acid producing compound with an amine and reacting the resulting product with a boron compound
US3154560A (en) 1961-12-04 1964-10-27 Monsanto Co Nu, nu'-azaalkylene-bis
US3113986A (en) 1962-01-08 1963-12-10 Hercules Powder Co Ltd Hydrogenation of unsaturated hydrocarbons
US3634595A (en) 1969-03-31 1972-01-11 Giorgio Pasquali A generator of harmonic signals with a helical spring
USRE27145E (en) 1969-05-20 1971-06-22 Side-chain
US3670054A (en) 1969-10-29 1972-06-13 Shell Oil Co Block copolymers having reduced solvent sensitivity
US3700633A (en) 1971-05-05 1972-10-24 Shell Oil Co Selectively hydrogenated block copolymers
US4867890A (en) 1979-08-13 1989-09-19 Terence Colclough Lubricating oil compositions containing ashless dispersant, zinc dihydrocarbyldithiophosphate, metal detergent and a copper compound
US5736491A (en) * 1997-01-30 1998-04-07 Texaco Inc. Method of improving the fuel economy characteristics of a lubricant by friction reduction and compositions useful therein

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"American Petroleum Institute (API) publication", December 1996, INDUSTRY SERVICES DEPARTMENT, article "Engine Oil Licensing and Certification System"
GRUHN NADINE E. ET AL: "Photoelectron Spectroscopy of Bis(2,4-Pentanedione)-Oxovanadium(IV) [VO(acac) 2 ] and Derivatives:? Substituent Effects on the 2,4-Pentanedione Donor", INORGANIC CHEMISTRY, vol. 41, no. 22, 1 November 2002 (2002-11-01), Easton , US, pages 5907 - 5911, XP055896119, ISSN: 0020-1669, Retrieved from the Internet <URL:https://pubs.acs.org/doi/pdf/10.1021/ic0256056> DOI: 10.1021/ic0256056 *
PREININGER ONDREJ ET AL: "Oxovanadium(IV) complexes bearing substituted pentane-2,4-dionate ligands: Synthesis, structure and drying activity in solvent-borne alkyd paints", INORGANICA CHIMICA ACTA, vol. 462, 1 June 2017 (2017-06-01), NL, pages 16 - 22, XP055896108, ISSN: 0020-1693, DOI: 10.1016/j.ica.2017.03.008 *

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