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
  • 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
• • 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
  • C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M145/22—Polyesters
• • 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
  • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
  • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • 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
  • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
  • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M149/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
• • 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
  • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
  • C10M169/04—Mixtures of base-materials and additives
• • 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
  • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
  • C10M2201/04—Elements
  • C10M2201/041—Carbon; Graphite; Carbon black
• • 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
  • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
  • C10M2201/06—Metal compounds
  • C10M2201/065—Sulfides; Selenides; Tellurides
  • C10M2201/066—Molybdenum sulfide
• • 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
  • 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
  • C10M2209/086—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 polycarboxylic, e.g. maleic acid
• • 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
  • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
• • 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
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
  • C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
• • 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
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
  • C10M2219/024—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of esters, e.g. fats
• • 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
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
  • C10M2219/046—Overbasedsulfonic acid salts
• • 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
  • C10N2030/24—Emulsion properties
• • 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
• • 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
  • C10N2040/251—Alcohol fueled engines
• • 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
• • 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
  • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
  • C10N2060/09—Treatment with nitrogen containing compounds

Definitions

• the present application relates to a motor having improved properties. Furthermore the present invention describes a use of polymers to improve the emulsion stability of lubricants.
• Alternate fuels for transportation such as methanol, ethanol, etc. have been studied by the automotive industry for a number of years. While such fuels offer some advantages of reduced engine emissions, their use is accompanied by a number of deficiencies and limitations which must be addressed if they are to become viable alternatives to gasoline.
• the alcohol and water may accumulate in the lubricating oil resulting from the use of such alternate fuels increase corrosion and wear problems in engines using such alternate fuels, especially alcohol.
• ester group containing polymers is known in prior art, e.g. U.S. Pat. No. 4,290,925 described grafted polymethacrylates containing N-vinyl-2-pyrrolidone which are useful for preparing stable emulsions of olefin copolymers.
• U.S. Pat. No. 4,057,623 described copolymers of alkyl methacrylates and N-vinyl-2-pyrrolidone which are useful for producing water-in-oil emulsions for cosmetic applications.
• U.S. Pat. No. 3,519,565 described copolymers of alkyl methacrylates and N-vinylthiopyrrolidone which are useful for reducing engine sludge and varnish.
• GB2307916A discloses that multifunctional olefinic copolymer viscosity index improver with dispersant properties in combination with further additives can improve the emulsion stability of lubricants.
• ester group containing polymer having a high polarity discloses that ester group containing polymer having a high polarity.
• no specific motor type has been disclosed.
• the additive should improve the life time and the fuel consumption of flex-fuel motors.
• the additives should be producible in a simple and inexpensive manner, and especially commercially available components should be used. In this context, they should be producible on the industrial scale without new plants or plants of complicated construction being required for this purpose.
• the additive should not exhibit any adverse effects on the fuel consumption or the environmental compatibility of the lubricant.
• the additive should improve the emulsion stability of lubricating oils comprising a high amount of water.
• the present invention accordingly provides a motor designed for Flex Fuel compatibility comprising a lubricant composition, characterized in that the lubricant composition comprises at least one ester group containing polymer having a high polarity.
• the motor of the present invention shows an enhanced life time and lowered fuel consumption.
• the motor of the present invention enables extended oil change intervals.
• the motor provides significant improvements in economic aspects based on lower amounts of motor oil based on a specific mileage.
• the solution presented by the present invention is not limited to new motor designs and can be applied to existing flex-fuel motors.
• the motor of the present invention can have a very high compression without being detrimental effected regarding the cold start and cold run characteristics and life time and the fuel consumption of flex-fuel motors.
• the additives used in order to obtain a lubricant being able to solve the problems mentioned above can be prepared in a simple and inexpensive manner, and it is possible to use commercially available components in particular. At the same time, production is possible on the industrial scale, without new plants or plants of complex construction being required for that purpose.
• the polymers for use in accordance with the invention exhibit a particularly favorable profile of properties.
• the polymers can be configured so as to be surprisingly shear-stable, such that the lubricants have a very long service life.
• the additive for use in accordance with the invention may bring about a multitude of desirable properties in the lubricant.
• the present polymers comprising ester groups are compatible with many additives. This allows the lubricants to be adjusted to a wide variety of different requirements.
• the additives for use do not exhibit any adverse effects on fuel consumption or the environmental compatibility of the lubricant.
• present polymers comprising ester groups improve the emulsion stability of lubricating oils comprising a high amount of water.
• the present invention provides a new motor designed for Flex Fuel compatibility. These motors are usually part of flex-fuel vehicles.
• a flexible-fuel vehicle (FFV) or dual-fuel vehicle (colloquially called a flex-fuel vehicle) is an alternative fuel vehicle with an internal combustion engine designed to run on more than one fuel, usually gasoline blended with either ethanol or methanol fuel, and both fuels are stored in the same common tank.
• Flex-fuel engines are capable of burning any proportion of the resulting blend in the combustion chamber as fuel injection and spark timing are adjusted automatically according to the actual blend detected by electronic sensors.
• Flex-fuel vehicles are distinguished from bi-fuel vehicles, where two fuels are stored in separate tanks and the engine runs on one fuel at a time, for example, compressed natural gas (CNG), liquefied petroleum gas (LPG), or hydrogen.
• CNG compressed natural gas
• LPG liquefied petroleum gas
• the motor of the present invention is designed to fuels comprising at least 5%, especially at least 10%, particularly 20%, more especially at least 50% and more preferably at least 80% by volume of alcohol, e.g. methanol and/or ethanol. Furthermore, the motor of the present invention is preferably designed to fuels comprising at least 5%, especially at least 10%, particularly 20%, more especially at least 50% and more preferably at least 80% by volume of gasoline.
• the motor comprises a compression of at least 10:1, more preferably at least 12:1.
• the motor may comprise a fuel injection pump.
• the motor of the present invention may comprise an exhaust gas recirculation and/or a secondary-air system.
• the motor comprises an engine management for optimization of the fuel injection and the spark timing.
• Preferred motor of the present invention meet the requirements of exhaust emission standard Euro 5, more preferably EURO 6 as defined in Directive No. 715/2007/EC.
• the motor of the present invention comprises a lubricant composition including at least one ester group containing polymer having a high polarity.
• Polymers comprising ester groups are understood in the context of the present invention to mean polymers obtainable by polymerizing monomer compositions which comprise ethylenically unsaturated compounds having at least one ester group, which are referred to hereinafter as ester monomers. Accordingly, these polymers contain ester groups as part of the side chain.
• These polymers include especially polyalkyl (meth)acrylates (PAMA), polyalkyl fumarates and/or polyalkyl maleates.
• Ester monomers are known per se. They include especially (meth)acrylates, maleates and fumarates, which may have different alcohol radicals.
• (meth)acrylates encompasses methacrylates and acrylates, and mixtures of the two. These monomers are widely known.
• the polymer comprising ester groups comprises preferably at least 40% by weight, more preferably at least 60% by weight, especially preferably at least 80% by weight and most preferably at least 90% by weight of repeat units derived from ester monomers.
• the polymer may be a statistical copolymer comprising a high amount of dispersing repeat units being derived from a dispersing monomer.
• the statistical copolymer comprises at least 7%, more preferably at least 9% by weight of dispersing repeat units being derived from a dispersing monomer.
• the polymer may be a graft copolymer having an nonpolar polymer as graft base and an dispersing monomer as graft layer.
• graft copolymers preferably comprising 0.5 to 10% by weight, especially 0.8 to 7% by weight, more preferably 1 to 5% by weight of dispersing repeat units being derived from at least one dispersing monomer, preferably a heterocyclic vinyl compound.
• the term “repeat unit” is widely known in the technical field.
• the present polymers can preferably be obtained by means of free-radical polymerization of monomers. This opens up double bonds to form covalent bonds. Accordingly, the repeat unit arises from the monomers used.
• Dispersing monomers are understood to mean especially monomers with functional groups, for which it can be assumed that polymers with these functional groups can keep particles, especially soot particles, in solution (cf. R. M. Mortier, S. T. Orszulik (eds.): “Chemistry and Technology of Lubricants”, Blackie Academic & Professional, London, 2 nd ed. 1997).
• These include especially monomers which have boron-, phosphorus-, silicon-, sulfur-, oxygen- and nitrogen-containing groups, preference being given to oxygen- and nitrogen-functionalized monomers.
• the nonpolar graft base may comprise a small proportion of dispersing repeat units, which is preferably less than 20% by weight, more preferably less than 10% by weight and most preferably less than 5% by weight, based on the weight of the nonpolar graft base.
• the nonpolar graft base comprises essentially no dispersing repeat units.
• the nonpolar graft base of the polymer comprising ester groups may have 5 to 100% by weight, especially 20 to 98% by weight, preferably 30 to 95 and most preferably 70 to 92% by weight of repeat units derived from ester monomers having 7 to 15 carbon atoms in the alcohol radical.
• the nonpolar graft base of the polymer comprising ester groups may have 0 to 80% by weight, preferably 0.5 to 60% by weight, more preferably 2 to 50% by weight and most preferably 5 to 20% by weight of repeat units derived from ester monomers having 16 to 40 carbon atoms in the alcohol radical.
• nonpolar graft base of the polymer comprising ester groups may have 0 to 40% by weight, preferably 0.1 to 30% by weight and more preferably 0.5 to 20% by weight of repeat units derived from ester monomers having 1 to 6 carbon atoms in the alcohol radical.
• the nonpolar graft base of the polymer comprising ester groups comprises preferably at least 40% by weight, more preferably at least 60% by weight, especially preferably at least 80% by weight and most preferably at least 90% by weight of repeat units derived from ester monomers.
• Mixtures from which the graft base of the useful polymers comprising ester groups or the statistical polymers are obtainable may contain 0 to 40% by weight, especially 0.1 to 30% by weight and more preferably 0.5 to 20% by weight of one or more ethylenically unsaturated ester compounds of the formula (I)
• R is hydrogen or methyl
• R 1 is a linear or branched alkyl radical having 1 to 6 carbon atoms
• R 2 and R 3 are each independently hydrogen or a group of the formula —COOR′ in which R′ is hydrogen or an alkyl group having 1 to 6 carbon atoms.
• component (I) examples include
• (meth)acrylates fumarates and maleates which derive from saturated alcohols, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate and pentyl (meth)acrylate, hexyl (meth)acrylate; cycloalkyl (meth)acrylates such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate; (meth)acrylates which derive from unsaturated alcohols, such as 2-propynyl (meth)acrylate, allyl (meth)acrylate and vinyl (meth)acrylate.
• saturated alcohols such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-
• compositions to be polymerized to prepare the graft base or the statistical polymers preferably contain 5 to 100% by weight, preferably 10 to 98% by weight and especially preferably 20 to 95% by weight of one or more ethylenically unsaturated ester compounds of the formula (II)
• R is hydrogen or methyl
• R 4 is a linear or branched alkyl radical having 7 to 15 carbon atoms
• R 5 and R 6 are each independently hydrogen or a group of the formula —COOR′′ in which R′′ is hydrogen or an alkyl group having 7 to 15 carbon atoms.
• component (II) examples include:
• (meth)acrylates fumarates and maleates which derive from saturated alcohols, such as 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, 2-tert-butylheptyl (meth)acrylate, octyl (meth)acrylate, 3-isopropylheptyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, 5-methylundecyl (meth)acrylate, dodecyl (meth)acrylate, 2-methyldodecyl (meth)acrylate, tridecyl (meth)acrylate, 5-methyltridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate; (meth)acrylates which derive from unsaturated alcohols, for example oleyl (meth)acrylate
• preferred monomer compositions for preparing the graft base or the statistical polymers comprise 0 to 80% by weight, preferably 0.5 to 60% by weight, more preferably 2 to 50% by weight and most preferably 5 to 20% by weight of one or more ethylenically unsaturated ester compounds of the formula (III)
• R is hydrogen or methyl
• R 7 is a linear or branched alkyl radical having 16 to 40, preferably 16 to 30, carbon atoms
• R 8 and R 9 are each independently hydrogen or a group of the formula —COOR′′′ in which R′′′ is hydrogen or an alkyl group having 16 to 40, preferably 16 to 30, carbon atoms.
• component (III) examples include (meth)acrylates which derive from saturated alcohols, such as hexadecyl (meth)acrylate, 2-methylhexadecyl (meth)acrylate, heptadecyl (meth)acrylate, 5-isopropylheptadecyl (meth)acrylate, 4-tert-butyloctadecyl (meth)acrylate, 5-ethyloctadecyl (meth)acrylate, 3-isopropyloctadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, cetyleicosyl (meth)acrylate, stearyleicosyl (meth)acrylate, docosyl (meth)acrylate and/or eicosyltetratriacontyl (meth)acrylate;
• saturated alcohols such as hex
• cycloalkyl (meth)acrylates such as 2,4,5-tri-t-butyl-3-vinylcyclohexyl (meth)acrylate, 2,3,4,5-tetra-t-butylcyclohexyl (meth)acrylate; and the corresponding fumarates and maleates.
• ester compounds with a long-chain alcohol radical can be obtained, for example, by reacting (meth)acrylates, fumarates, maleates and/or the corresponding acids with long-chain fatty alcohols, which generally gives a mixture of esters, for example (meth)acrylates with different long-chain alcohol radicals.
• These fatty alcohols include Oxo Alcohol® 7911, Oxo Alcohol® 7900, Oxo Alcohol® 1100; Alfol® 610, Alfol® 810, Lial® 125 and Nafol® types (Sasol); Alphanol® 79 (ICI); Epal® 610 and Epal® 810 (Afton); Linevol® 79, Linevol® 911 and Neodol® 25E (Shell); Dehydad®, Hydrenol® and Lorol® types (Cognis); Acropol® 35 and Exxal® 10 (Exxon Chemicals); Kalcol® 2465 (Kao Chemicals).
• the (meth)acrylates are particularly preferred over the maleates and fumarates, i.e. R 2 , R 3 , R 5 , R 6 , R 8 and R 9 of the formulae (I), (II) and (III) are each hydrogen in particularly preferred embodiments.
• the weight ratio of ester monomers of the formula (II) to the ester monomers of the formula (III) may be within a wide range.
• the ratio of ester compounds of the formula (II) which have 7 to 15 carbon atoms in the alcohol radical to the ester compounds of the formula (III) which have 16 to 40 carbon atoms in the alcohol radical is preferably in the range from 50:1 to 1:30, more preferably in the range from 10:1 to 1:3, especially preferably 5:1 to 1:1.
• the monomer mixture for preparing the graft base or the statistical polymers may comprise ethylenically unsaturated monomers which can be copolymerized with the ethylenically unsaturated ester compounds of the formulae (I), (II) and/or (III).
• the preferred comonomers include
• vinyl halides for example vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride; styrene, substituted styrenes having an alkyl substituent in the side chain, for example ⁇ -methylstyrene and ⁇ -ethylstyrene, substituted styrenes having an alkyl substituent on the ring, such as vinyltoluene and p-methylstyrene, halogenated styrenes, for example monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes; vinyl and isoprenyl ethers; maleic acid and maleic acid derivatives different from those mentioned under (I), (II) and (III), for example maleic anhydride, methylmaleic anhydride, maleimide, methylmaleimide; fumaric acid and fumaric acid derivatives different from those mentioned under (I), (II) and (
• monomer mixtures for preparing the graft base may comprise dispersing monomers.
• the proportion of comonomers is preferably 0 to 50% by weight, more preferably 0.1 to 40% by weight and most preferably 0.5 to 20% by weight, based on the weight of the monomer composition for preparing the graft base or the statistical polymers.
• a preferred polymer usable in accordance with the invention comprises at least one graft layer which comprises repeat units derived from dispersing monomers.
• Dispersing monomers have been used for some time for functionalizing polymeric additives in lubricant oils, and are therefore known to those skilled in the art (cf. R. M. Mortier, S. T. Orszulik (eds.): “Chemistry and Technology of Lubricants”, Blackie Academic & Professional, London, 2 nd ed. 1997).
• R is hydrogen or methyl
• X is oxygen, sulfur or an amino group of the formula —NH— or —NR a — in which R a is an alkyl radical having 1 to 40 and preferably 1 to 4 carbon atoms
• R 10 is a radical which comprises 2 to 1000, especially 2 to 100 and preferably 2 to 20 carbon atoms and has at least one heteroatom, preferably at least two heteroatoms
• R 11 and R 12 are each independently hydrogen or a group of the formula —COX′R 10′ in which X′ is oxygen or an amino group of the formula —NH— or —NR a′ — in which R a′ is an alkyl radical having 1 to 40 and preferably 1 to 4 carbon atoms
• R 10′ is a radical comprising 1 to 100, preferably 1 to 30 and more preferably 1 to 15 carbon atoms, as dispersing monomers.
• radical comprising 2 to 1000 carbon denotes radicals of organic compounds having 2 to 1000 carbon atoms. Similar definitions apply for corresponding terms. It encompasses aromatic and heteroaromatic groups, and alkyl, cycloalkyl, alkoxy, cycloalkoxy, alkenyl, alkanoyl, alkoxycarbonyl groups, and also heteroaliphatic groups. The groups mentioned may be branched or unbranched. In addition, these groups may have customary substituents.
• Substituents are, for example, linear and branched alkyl groups having 1 to 6 carbon atoms, for example methyl, ethyl, propyl, butyl, pentyl, 2-methylbutyl or hexyl; cycloalkyl groups, for example cyclopentyl and cyclohexyl; aromatic groups such as phenyl or naphthyl; amino groups, hydroxyl groups, ether groups, ester groups and halides.
• aromatic groups denote radicals of mono- or polycyclic aromatic compounds having preferably 6 to 20 and especially 6 to 12 carbon atoms.
• Heteroaromatic groups denote aryl radicals in which at least one CH group has been replaced by N and/or at least two adjacent CH groups have been replaced by S, NH or O, heteroaromatic groups having 3 to 19 carbon atoms.
• Aromatic or heteroaromatic groups preferred in accordance with the invention derive from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane, diphenyldimethylmethane, bisphenone, diphenyl sulfone, thiophene, furan, pyrrole, triazole, oxazole, imidazole, isothiazole, isoxazole, pyrazole, 1,3,4-oxadiazole, 2,5-diphenyl-1,3,4-oxadiazole, 1,3,4-thiadiazole, 1,3,4-triazole, 2,5-diphenyl-1,3,4-triazole, 1,2,5-triphenyl-1,3,4-triazole, 1,2,4-oxadiazole, 1,2,4-thiadiazole, 1,2,4-triazole, 1,2,3-triazole, 1,2,3,4-tetrazole, benzo[b]thiophene
• the preferred alkyl groups include the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl, tert-butyl radical, pentyl, 2-methylbutyl, 1,1-dimethylpropyl, hexyl, heptyl, octyl, 1,1,3,3-tetramethylbutyl, nonyl, 1-decyl, 2-decyl, undecyl, dodecyl, pentadecyl and the eicosyl group.
• the preferred cycloalkyl groups include the cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and the cyclooctyl group, each of which is optionally substituted with branched or unbranched alkyl groups.
• the preferred alkanoyl groups include the formyl, acetyl, propionyl, 2-methylpropionyl, butyryl, valeroyl, pivaloyl, hexanoyl, decanoyl and the dodecanoyl group.
• the preferred alkoxycarbonyl groups include the methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxy-carbonyl, tert-butoxycarbonyl, hexyloxycarbonyl, 2-methylhexyloxycarbonyl, decyloxycarbonyl or dodecyl-oxycarbonyl group.
• the preferred alkoxy groups include alkoxy groups whose hydrocarbon radical is one of the aforementioned preferred alkyl groups.
• the preferred cycloalkoxy groups include cycloalkoxy groups whose hydrocarbon radical is one of the aforementioned preferred cycloalkyl groups.
• the preferred heteroatoms which are present in the R 10 radical include oxygen, nitrogen, sulfur, boron, silicon and phosphorus, preference being given to oxygen and nitrogen.
• the R 10 radical comprises at least one, preferably at least two, preferentially at least three, heteroatoms.
• the R 10 radical in ester compounds of the formula (IV) preferably has at least 2 different heteroatoms.
• the R 10 radical in at least one of the ester compounds of the formula (IV) may comprise at least one nitrogen atom and at least one oxygen atom.
• Examples of ethylenically unsaturated, polar ester compounds of the formula (IV) include aminoalkyl (meth)acrylates, aminoalkyl (meth)acrylamides, hydroxyalkyl (meth)acrylates, heterocyclic (meth)acrylates and/or carbonyl-containing (meth)acrylates.
• the hydroxyalkyl (meth)acrylates include
• carbonyl-containing (meth)acrylates include, for example,
• the heterocyclic (meth)acrylates include
• aminoalkyl (meth)acrylates and aminoalkyl (meth)acrylatamides, for example
• heterocyclic vinyl compounds are used as dispersing monomers.
• the heterocyclic vinyl compounds show improved properties in view of other dispersing monomers.
• the preferred heterocyclic vinyl compounds include 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3 dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, N-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxolane, vinylfuran, vinylthiophene, vinylthiolane, vinylthiazoles and hydrogenated vinylthiazoles, vinyloxazoles and hydrogenated vinyloxazoles, particular preference being given to using N-vinylimidazole and N-vinylpyr
• the monomers detailed above can be used individually or as a mixture.
• ester groups comprise polymers being obtained using N-vinyl-2-pyrrolidine and/or N-vinyl-2-pyrrolidone.
• composition for preparing the graft layer may also comprise non-dispersing monomers which have been detailed above. These include especially ethylenically unsaturated ester compounds of the formulae (I), (II) and/or (III).
• the proportion of dispersing repeat units, based on the weight of the polymers comprising ester groups, is preferably in the range from 0.5% by weight to 20% by weight, more preferably in the range from 1.5% by weight to 15% by weight and most preferably in the range from 2.5% by weight to 10% by weight.
• these repeat units preferably form a segment-like structure within the polymer comprising ester groups, such that preferably at least 70% by weight, more preferably at least 80% by weight, based on the total weight of the dispersing repeat units, are part of a graft layer.
• the present invention describes polymers which preferably have a high oil solubility.
• oil-soluble means that a mixture of a base oil and a polymer comprising ester groups is preparable without macroscopic phase formation, which has at least 0.1% by weight, preferably at least 0.5% by weight, of the polymers.
• the polymer may be present in dispersed and/or dissolved form in this mixture.
• the oil solubility depends especially on the proportion of the lipophilic side chains and on the base oil. This property is known to those skilled in the art and can be adjusted readily for the particular base oil via the proportion of lipophilic monomers.
• polymers which comprise ester groups and preferably have a weight-average molecular weight M w in the range from 7500 to 1 000 000 g/mol, more preferably 10 000 to 600 000 g/mol and most preferably 15 000 to 80 000 g/mol.
• the number-average molecular weight M n may preferably be in the range from 5000 to 800 000 g/mol, more preferably 7500 to 500 000 g/mol and most preferably 10 000 to 80 000 g/mol.
• the ester group containing polymer, preferably a polyalkyl(meth)acrylat may have a weight-average molecular weight M w in the range from 2000 to 1 000 000 g/mol, especially from 20 000 to 800 000 g/mol, more preferably 40 000 to 500 000 g/mol and most preferably 60 000 to 250 000 g/mol.
• the ester group containing polymer, preferably a polyalkyl(meth)acrylat may have a number average molecular weight M n in the range from 2 000 to 100 000 g/mol, especially from 4 000 to 60 000 g/mol and most preferably 5 000 to 30 000 g/mol.
• Polymers having a high molecular weight are especially useful as viscosity index improvers.
• Polymers having a low molecular weight are especially useful as pour point depressants and flow improvers.
• polymers which comprise ester groups and whose polydispersity index M w /M n is in the range from 1 to 5, more preferably in the range from 1.05 to 4.
• the number-average and weight-average molecular weights can be determined by known processes, for example gel permeation chromatography (GPC).
• the ester group containing polymer has a —CO—NR 2 -peak in the range of 1689 to 1697 cm ⁇ 1 , more preferably in the range of 1689 to 1692 cm 1 as measured by FTIR spectroscopy (25° C.)
• the polymer comprising ester groups may have a variety of structures.
• the polymer may especially be present as a graft copolymer.
• the polymers comprising ester groups for use in accordance with the invention can be obtained in various ways.
• a preferred process consists in free-radical graft copolymerization which is known per se, wherein, for example, a nonpolar graft base is obtained in a first step, onto which dispersing monomers are grafted in a second step.
• the ester group containing polymer preferably is a graft copolymer having an nonpolar alkyl (meth)acrylate polymer as graft base and an dispersing monomer as graft layer.
• Customary free-radical polymerization which is especially suitable for preparing graft copolymers, is detailed in K. Matyjaszewski, T. P. Davis, Handbook of Radical Polymerization, Wiley Interscience, Hoboken 2002. In general, a polymerization initiator and a chain transferer are used for that purpose.
• the usable initiators include the azo initiators widely known in the technical field, such as AIBN and 1,1-azobiscyclohexanecarbonitrile, and also peroxy compounds such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert-butyl per-2-ethylhexanoate, ketone peroxide, tert-butyl peroctoate, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl-carbonate, 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3,5,5-trimethylhexano
• Suitable chain transferers are in particular oil-soluble mercaptans, for example n-dodecyl mercaptan or 2-mercaptoethanol, or else chain transferers from the class of the terpenes, for example terpinolene.
• the polymerization may be carried out at standard pressure, reduced pressure or elevated pressure.
• the polymerization temperature too is uncritical. However, it is generally in the range of ⁇ 20°-200° C., preferably 50°-150° C. and more preferably 80°-130° C.
• the polymerization may be carried out with or without solvent.
• solvent is to be understood here in a broad sense.
• the solvent is selected according to the polarity of the monomers used, preference being given to using 100N oil, relatively light gas oil and/or aromatic hydrocarbons, for example toluene or xylene.
• the lubricant used in the motor of the present invention includes base oil.
• Preferred base oils include especially mineral oils, synthetic oils and natural oils.
• Mineral oils are known per se and commercially available. They are generally obtained from mineral oil or crude oil by distillation and/or refining and optionally further purification and finishing processes, the term mineral oil including in particular the higher-boiling fractions of crude or mineral oil. In general, the boiling point of mineral oil is higher than 200° C., preferably higher than 300° C., at 5000 Pa. The production by low-temperature carbonization of shale oil, coking of bituminous coal, distillation of brown coal with exclusion of air, and also hydrogenation of bituminous or brown coal is likewise possible. Accordingly, mineral oils have, depending on their origin, different proportions of aromatic, cyclic, branched and linear hydrocarbons.
• paraffin-base, naphthenic and aromatic fractions in crude oils or mineral oils, in which the term paraffin-base fraction represents longer-chain or highly branched isoalkanes, and naphthenic fraction represents cycloalkanes.
• mineral oils depending on their origin and finishing, have different fractions of n-alkanes, isoalkanes having a low degree of branching, known as mono-methyl-branched paraffins, and compounds having heteroatoms, in particular O, N and/or S, to which a degree of polar properties are attributed.
• the assignment is difficult, since individual alkane molecules may have both long-chain branched groups and cycloalkane radicals, and aromatic parts.
• the assignment can be effected to DIN 51 378, for example.
• Polar fractions can also be determined to ASTM D 2007.
• the proportion of n-alkanes in preferred mineral oils is less than 3% by weight, the fraction of O-, N- and/or S-containing compounds less than 6% by weight.
• the fraction of the aromatics and of the mono-methyl-branched paraffins is generally in each case in the range from 0 to 40% by weight.
• mineral oil comprises mainly naphthenic and paraffin-base alkanes which have generally more than 13, preferably more than 18 and most preferably more than 20 carbon atoms.
• the fraction of these compounds is generally 60% by weight, preferably 80% by weight, without any intention that this should impose a restriction.
• a preferred mineral oil contains 0.5 to 30% by weight of aromatic fractions, 15 to 40% by weight of naphthenic fractions, 35 to 80% by weight of paraffin-base fractions, up to 3% by weight of n-alkanes and 0.05 to 5% by weight of polar compounds, based in each case on the total weight of the mineral oil.
• n-alkanes having approx. 18 to 31 carbon atoms: 0.7-1.0%, slightly branched alkanes having 18 to 31 carbon atoms: 1.0-8.0%, aromatics having 14 to 32 carbon atoms: 0.4-10.7%, iso- and cycloalkanes having 20 to 32 carbon atoms: 60.7-82.4%, polar compounds: 0.1-0.8%, loss: 6.9-19.4%.
• An improved class of mineral oils results from hydrogen treatment of the mineral oils (hydroisomerization, hydrocracking, hydrotreatment, hydrofinishing). In the presence of hydrogen, this essentially reduces aromatic components and builds up naphthenic components.
• Synthetic oils include organic esters, for example diesters and polyesters, polyalkylene glycols, polyethers, synthetic hydrocarbons, especially polyolefins, among which preference is given to polyalphaolefins (PAOs), silicone oils and perfluoroalkyl ethers.
• synthetic base oils originating from gas to liquid (GTL), coal to liquid (CTL) or biomass to liquid (BTL) processes. They are usually somewhat more expensive than the mineral oils, but have advantages with regard to their performance.
• Natural oils are animal or vegetable oils, for example neatsfoot oils or jojoba oils.
• Base oils for lubricant oil formulations are divided into groups according to API (American Petroleum Institute). Mineral oils are divided into group I (non-hydrogen-treated) and, depending on the degree of saturation, sulfur content and viscosity index, into groups II and III (both hydrogen-treated). PAOs correspond to group IV. All other base oils are encompassed in group V.
• lubricant oils may also be used as mixtures and are in many cases commercially available.
• the concentration of the polymers comprising ester groups in the lubricant oil composition is preferably in the range of 0.01 to 30% by weight, more preferably in the range of 0.1-20% by weight and most preferably in the range of 0.5-10% by weight, based on the total weight of the composition.
• the lubricant oil compositions detailed here may also comprise further additives.
• additives include VI improvers, pour point improvers and DI additives (dispersants, detergents, defoamers, corrosion inhibitors, antioxidants, antiwear and extreme pressure additives, friction modifiers).
• the additionally usable VI improvers include especially polyalkyl (meth)acrylates having 1 to 30 carbon atoms in the alcohol group (PAMA; partly N/O-functional with advantageous additional properties as dispersants, antiwear additives and/or friction modifiers), which differ from the copolymers detailed in claim 1 , and poly(iso)butenes (PIB), fumarate-olefin copolymers, styrene-maleate copolymers, hydrogenated styrene-diene copolymers (HSD) and olefin copolymers (OCP).
• PAMA polyalkyl (meth)acrylates having 1 to 30 carbon atoms in the alcohol group
• PIB poly(iso)butenes
• HSD hydrogenated styrene-diene copolymers
• OCP olefin copolymers
• the pour point improvers include especially polyalkyl (meth)acrylates (PAMA) having 1 to 30 carbon atoms in the alcohol group.
• PAMA polyalkyl (meth)acrylates
• Appropriate dispersants include poly(isobutylene) derivatives, e.g. poly(isobutylene)succinimides (PIBSIs); ethylene-propylene oligomers with N/O functionalities.
• PIBSIs poly(isobutylene)succinimides
• the preferred detergents include metal-containing compounds, for example phenoxides; salicylates; thio-phosphonates, especially thiopyrophosphonates, thio-phosphonates and phosphonates; sulfonates and carbonates.
• metals these compounds may comprise especially calcium, magnesium and barium. These compounds may be used preferably in neutral or overbased form.
• defoamers which are in many cases divided into silicone-containing and silicone-free defoamers.
• the silicone-containing defoamers include linear poly(dimethylsiloxane) and cyclic poly(dimethylsiloxane).
• the silicone-free defoamers which may be used are in many cases polyethers, for example poly(ethylene glycol) or tributyl phosphate.
• inventive lubricant oil compositions may comprise corrosion inhibitors. These are in many cases divided into antirust additives and metal passivators/deactivators.
• the antirust additives used may, inter alia, be sulfonates, for example petroleumsulfonates or (in many cases overbased) synthetic alkylbenzenesulfonates, e.g.
• dinonylnaphthenesulfonates include carboxylic acid derivatives, for example lanolin (wool fat), oxidized paraffins, zinc naphthenates, alkylated succinic acids, 4-nonylphenoxy-acetic acid, amides and imides (N-acylsarcosine, imidazoline derivatives); amine-neutralized mono- and dialkyl phosphates; morpholine, dicyclohexylamine or diethanolamine.
• carboxylic acid derivatives for example lanolin (wool fat), oxidized paraffins, zinc naphthenates, alkylated succinic acids, 4-nonylphenoxy-acetic acid, amides and imides (N-acylsarcosine, imidazoline derivatives); amine-neutralized mono- and dialkyl phosphates; morpholine, dicyclohexylamine or diethanolamine.
• the metal passivators/deactivators include benzotriazole, tolyltriazole, 2-mercaptobenzothiazole, dialkyl-2,5-dimercapto-1,3,4-thiadiazole; N,N′-disalicylideneethylenediamine, N,N′-disalicylidenepropylenediamine; zinc dialkyldithiophosphates and dialkyl dithiocarbamates.
• a further preferred group of additives is that of antioxidants.
• the antioxidants include, for example, phenols, for example 2,6-di-tert-butylphenol (2,6-DTB), butylated hydroxytoluene (BHT), 2,6-di-tert-butyl-4-methylphenol, 4,4′-methylenebis(2,6-di-tert-butylphenol); aromatic amines, especially alkylated diphenylamines, N-phenyl-1-naphthylamine (PNA), polymeric 2,2,4-trimethyldihydroquinone (TMQ); compounds containing sulfur and phosphorus, for example metal dithiophosphates, e.g.
• organosulfur compounds for example dialkyl sulfides, diaryl sulfides, polysulfides, modified thiols, thiophene derivatives, xanthates, thioglycols, thioaldehydes, sulfur-containing carboxylic acids; heterocyclic sulfur/nitrogen compounds, especially dialkyldimercaptothiadiazoles, 2-mercaptobenzimidazoles; zinc and methylene bis(dialkyldithiocarbamate); organophosphorus compounds, for example triaryl and trialkyl phosphites; organocopper compounds and overbased calcium- and magnesium-based phenolates and sal
• the preferred antiwear (AW) and extreme pressure (EP) additives include phosphorus compounds, for example trialkyl phosphates, triaryl phosphates, e.g. tricresyl phosphate, amine-neutralized mono- and dialkyl phosphates, ethoxylated mono- and dialkyl phosphates, phosphites, phosphonates, phosphines; compounds containing sulfur and phosphorus, for example metal dithiophosphates, e.g.
• ZnDTPs zinc C 3-12 dialkyldithiophosphates
• ammonium dialkyldithiophosphates ammonium dialkyldithiophosphates, antimony dialkyldithiophosphates, molybdenum dialkyldithiophosphates, lead dialkyldithiophosphates
• OOS triesters reaction products of dithiophosphoric acid with activated double bonds from olefins, cyclopentadiene, norbornadiene, ⁇ -pinene, polybutene, acrylic esters, maleic esters, triphenylphosphorothionate (TPPT); compounds containing sulfur and nitrogen, for example zinc bis(amyl dithiocarbamate) or methylenebis(di-n-butyl dithiocarbamate); sulfur compounds containing elemental sulfur and H 2 S-sulfurized hydrocarbons (diisobutylene, terpene); sulfurized glycerides and fatty acid esters
• a further preferred group of additives is that of friction modifiers.
• the friction modifiers used may include mechanically active compounds, for example molybdenum disulfide, graphite (including fluorinated graphite), poly(trifluoroethylene), polyamide, polyimide; compounds which form adsorption layers, for example long-chain carboxylic acids, fatty acid esters, ethers, alcohols, amines, amides, imides; compounds which form layers through tribochemical reactions, for example saturated fatty acids, phosphoric acid and thiophosphoric esters, xanthogenates, sulfurized fatty acids; compounds which form polymer-like layers, for example ethoxylated dicarboxylic acid partial esters, dialkyl phthalates, methacrylates, unsaturated fatty acids, sulfurized olefins or organometallic compounds, for example molybdenum compounds (molybdenum dithiophosphates and molybdenum dithiocarbamates MoDTC) and
• ZnDTP is primarily an antiwear additive and extreme pressure additive, but also has the character of an antioxidant and corrosion inhibitor (here: metal passivator/deactivator).
• Preferred lubricant oil compositions have a viscosity, measured at 40° C. to ASTM D 445, in the range of 10 to 120 mm 2 /s, more preferably in the range of 20 to 100 mm 2 /s.
• the kinematic viscosity KV 100 measured at 100° C. is preferably at least 5.0 mm 2 /s, more preferably at least 5.2 mm 2 /s and most preferably at least 5.4 mm 2 /s.
• preferred lubricant oil compositions have a viscosity index determined to ASTM D 2270 in the range of 100 to 400, more preferably in the range of 125 to 325 and most preferably in the range of 150 to 250.
• lubricant compositions for the use in the motor of the present invention may preferably comprise a High Temperature High Shear (HTHS) viscosity of at least 2.4 mPas, more preferably at least 2.6 mPas as measured at 150° C. according to ASTM D4683.
• HTHS High Temperature High Shear
• the lubricant may preferably comprise a high temperature high shear of at most 10 mPas, especially at most 7 mPas more preferably at most 5 mPas as measured at 100° C. according to ASTM D4683.
• HTHS 100 -HTHS 150 preferably comprises at most 4 mPas, especially at most 3.3 mPas and more preferably at most 2.5 mPas.
• the ratio of the High Temperature High Shear (HTHS) viscosity measured at 100° C. (HTHS 100 ) to the High Temperature High Shear (HTHS) viscosity measured at 150° C. (HTHS 150 -HTHS 100 /HTHS 150 preferably comprises at most at most 2.0 mPas, especially at most 1.9 mPas.
• High Temperature High Shear (HTHS) viscosity can be determined according to D4683.
• the lubricant useful as component of the present motor may comprises a high shear stability index (SSI).
• SSI shear stability index
• the shear stability index (SSI) as measured according to ASTM D2603 Ref. B (12.5 minutes sonic treatment) could preferably amount to 35 or less, more preferably to 20 or less.
• lubricants comprising a shear stability index (SSI) as measured according to DIN 51381 (30 cycles Bosch-pump) of at most 5, especially at most 2 and more preferably at most 1 could be used.
• the lubricant useful for the present invention can preferably be designed to meet the requirements of the SAE classifications as specified in SAE J300. E.g. the requirements of the viscosity grades 0W, 5W, 10W, 15W, 20W, 25W, 20, 30, 40, 50, and 60 (single-grade) and 0W-40, 10W-30, 10W-60, 15W-40, 20W-20 and 20W-50 (multi-grade) could be adjusted.
• the lubricant composition meets the gasoline engine oil quality specifications ILSAC's GF-5, especially the emulsion retention bench test stating that a mixture of formulated oil (80%), E85 fuel (10%), and water (10%) must form a stable emulsion for at least 24 hours after mixing at 0 and 25° C.
• the lubricant of the present invention may contain at least about 1%, especially at least 5%, particularly at least 10% by volume of water. Astonishingly, such high amounts of water do not impart unduly high lowering of the motor characteristics such as life time, cold run performance and fuel consumption.
• the present invention provides a lubricant forming highly stable emulsions with water. Therefore, a specific aspect of the present invention is the use of polymers having a high polarity as emulsion stabilizer in lubricants.
• MMA methyl methacrylate
• N1214MA methacrylic acid ester of NAFOL1214
• L125MA methacrylic acid ester of LIAL125
• A1618MA methacrylic acid ester of ALFOL 1620
• DMAEMA dimethylaminoethyl methacrylate
• NVP N-vinyl-2-pyrrolidone
• nDDM n-dodecylmercapton
• tBPO t-butylperoctoate
• tBPB t-butylperbenzoate
• the additives were placed between silver chloride plates and sandwiched into a Teflon cell holder. Using a Thermo Nicolet Avatar 370 FT-IR, the additives were scanned 32 times at a resolution of 4 cm ⁇ 1 . A background scan was taken followed by the sample scan. The peak location of the disubstituted amine, —CO—NR 2 —, is observed as a shoulder peak to the strong carbonyl, C ⁇ O, stretching peak.

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• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Lubricants (AREA)
• Valve-Gear Or Valve Arrangements (AREA)
• Exhaust-Gas Circulating Devices (AREA)
• Fuel-Injection Apparatus (AREA)
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