EP0881277B1 - Verwendung von Metallsulfonaten als Reibungsmodifiziermittel - Google Patents

Verwendung von Metallsulfonaten als Reibungsmodifiziermittel Download PDF

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Publication number
EP0881277B1
EP0881277B1 EP98304251A EP98304251A EP0881277B1 EP 0881277 B1 EP0881277 B1 EP 0881277B1 EP 98304251 A EP98304251 A EP 98304251A EP 98304251 A EP98304251 A EP 98304251A EP 0881277 B1 EP0881277 B1 EP 0881277B1
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Prior art keywords
metal
hydrocarbon group
lubricating oil
group
oil composition
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French (fr)
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EP0881277B8 (de
EP0881277A2 (de
EP0881277A3 (de
Inventor
Shigeko Taguchi
Megumi Ono
Hirotaka Tomizawa
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Tonen General Sekiyu KK
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Tonen Corp
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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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
    • 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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
    • C10M135/10—Sulfonic acids or derivatives thereof
    • 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
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • 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
    • C10N2040/02—Bearings
    • 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
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
    • 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
    • C10N2040/20—Metal working
    • 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
    • C10N2040/20—Metal working
    • C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/28—Rotary 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
    • C10N2040/30—Refrigerators lubricants or compressors lubricants
    • 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
    • C10N2040/32—Wires, ropes or cables lubricants
    • 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
    • C10N2040/34—Lubricating-sealants
    • 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
    • C10N2040/36—Release agents or mold release agents
    • 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
    • C10N2040/38—Conveyors or chain belts
    • 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
    • C10N2040/40—Generators or electric motors in oil or gas winning field
    • 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
    • C10N2040/42—Flashing oils or marking oils
    • 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
    • C10N2040/44—Super vacuum or supercritical use
    • 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
    • C10N2040/50—Medical uses

Definitions

  • This invention relates to a friction modifier comprising a metal sulfonate and to a lubricating oil composition with the metal sulfonate added therein, and more specifically to a friction modifier comprising a metal sulfonate containing a specific chain hydrocarbon group and to a lubricating oil composition with the metal sulfonate added therein.
  • an automatic transmission oil which had been obtained by adding magnesium sulfonate, which is used as a metallic detergent, for example, for the dispersion of sludge occurring in lubricating oils, the solubilization of a precursor and the neutralization of an acid, especially over-based magnesium sulfonate having a base number of 300 mg-KOH/g or greater in a base stock, in order to improve friction characteristics (see JP Kokai 62-84190).
  • a lubricating oil making combined use of a metallic detergent, such as calcium sulfonate, barium sulfonate or magnesium sulfonate, with a molybdenum dialkyldithiocarbamate was also proposed (see JP Kokai 62-215697).
  • a metallic detergent such as calcium sulfonate, barium sulfonate or magnesium sulfonate
  • metal sulfonates when employed singly, are however still insufficient in friction reducing effects, so that they are merely friction modifier adjuvants for use in combination with friction modifiers such as phosphate esters and molybdenum dithiocarbamate. If a metal sulfonate having still higher friction reducing ability is identified, it is therefore believed it will find utility in a much wider range of fields and hence to have a significantly-increased industrial value. There is accordingly an outstanding intense desire for the development of such a metal sulfonate.
  • the present invention has as objects thereof the provision of a novel metal sulfonate having friction reducing ability and also the provision of a lubricating oil composition with the metal sulfonate added.
  • US-A-4,225,446 claims and describes a process for preparing a fluid, highly basic magnesium sulfonate comprising: (a) forming, in the presence of a volatile solvent, an admixture of an oil-soluble sulfonic acid and a magnesium sulfonate having a total base number in excess of about 200; (b) neutralizing the sulfonic acid; (c) forming a second admixture of (i) the sulfonate prepared from the first admixture, (ii) magnesium oxide, (iii) a naphthenic acid, and (iv) a lower alkanol; (d) treating the second admixture with carbon dioxide; (e) treating the second admixture with (i) water and (ii) ammonia or an ammonium compound during the initial phase of the carbon dioxide treatment; (f) heating the carbonated solution to remove water and the lower alkanol; (g) cooling and thereafter treating the water and lower alkanol deplete
  • EP-A-0 312 313 claims and describes an overbased metal sulfonate compound comprising a liquid vehicle and (A) at least one metal alkyl aryl sulfonate containing 1 to 3 alkyl groups, one of which alkyl groups contains an average number of carbon atoms of at least 40 while any remaining alkyl groups contain less than 10 carbon atoms, and (B) at least one metal alkyl aryl sulfonate containing 1 to 3 alkyl groups, one of which alkyl groups contains an average number of carbon atoms of 10 to 33 while any remaining alkyl groups contain less than 10 carbon atoms.
  • GB-A-2182948 (which is a counterpart of JP Kokai 62-215697 mentioned supra ) claims and discloses an automatic transmission fluid composition comprising a major amount of a mineral oil and/or synthetic oil as a base oil, and 0.1 - 5% by weight of magnesium sulfonate on the basis of the total amount of the composition as an essential component.
  • the present invention provides the use for friction reduction of a lubricating oil composition of a metal sulfonate as defined in claim 1 of the set of claims following the description below.
  • the present invention also provides the use as aforesaid in a lubricating composition as defined in claim 5 of the said set of claims.
  • Optional and/or preferred features of the invention are defined in the other claims of the said set of claims.
  • the metal sulfonatewhich is used as the friction modifier according to the present invention is composed of an organic sulfonic group, which contains a hydrocarbon group, and a metal, and is a compound which can be represented, for example, by the following formula (I): (RSO 3 ) x M It may consist of one type of the compound or may be a mixture of two or more compounds having different hydrocarbon groups.
  • R in the organic sulfonic group RSO 3 is a hydrocarbon group, which is a chain hydrocarbon group or an aromatic group with at least one chain hydrocarbon group bonded thereto.
  • Illustrative of the chain hydrocarbon group can be alkyl groups, each of which has 12-40 carbon atoms on average per organic sulfonic group as measured by 13 C-NMR and calculated supposing that there is one carbon atom bonded to a sulfonic group. It is particularly preferred to contain at least one or more alkyl groups having 12-30 carbon atoms.
  • alkyl group can include dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, pentatriacontyl, and octatriacontyl.
  • metal sulfonate according to the present invention one having an alkyl chain linearity of 20% or higher, especially of from 30% to 80% as determined by a 13 C-NMR measurement is preferred.
  • alkyl chain linearity is based on a unique concept established by the present inventors as a result of repetition of numerous experiments, and means the ratio of the number of carbon atoms in a linear portion located 5 or more atoms apart from an end of the alkyl group or 4 or more atoms apart from a branched site of the alkyl group to the total number of carbon atoms in the alkyl group. Its value is dependent on the bonding site of an aromatic group and the site of branching of the alkyl group.
  • alkyl chain linearity has been determined specifically by the following formula from a 13 C-NMR measurement.
  • Alkyl chain linearity (%) Integral intensity over a chemical shift range of from 29 ppm to 31 ppm Sum of all integral intensity over a chemical shift range of from 5 ppm to 60 ppm x 100
  • the 13 C-NMR measurement was conducted by converting the metal sulfonate into its corresponding sulfonic acid.
  • the present inventors recognized the existence of a correlation between the alkyl chain linearity and the friction reducing effects of its metal sulfonate, and have ascertained that the metal sulfonate exhibits better friction reducing effects as the linearity becomes higher and also that a linearity lower than 20% cannot exhibit the effects fully although a linearity of 20% or higher, especially of from 30% to 80% shows particularly marked effects.
  • the metal sulfonate contains two or more chain hydrocarbon groups per organic sulfonic group or is a mixture of two or more different compounds (metal sulfonates), the metal sulfonate exhibits friction reducing effects and is effective as a metal sulfonate according to the present invention provided that the alkyl chain linearity as determined by a 13 C-NMR measurement is 20% or higher.
  • a metal sulfonate, the chain hydrocarbon groups of which are each an alkyl group having 12 or more carbon atoms and a linearity of 20% or higher is preferred from the viewpoint of making it possible to substantially increase friction reducing ability.
  • the aromatic group bonded to the chain hydrocarbon groups can be either monocyclic or fused polycyclic. Those represented by the following structural formulas (a) to (g), respectively, are effective, with a phenyl group being particularly preferred.
  • the metal component represented by M in the above-described metal sulfonate (formula (I)) (RSO 3 ) x M can be an alkali metal or an alkaline earth metal. Further, a metal of an atomic number in a range of from 12 to 56 is also suited. Specific examples can include sodium, potassium, lithium, calcium, magnesium and barium. In addition, aluminum, zinc, tin, chromium, copper, cobalt are also effective. Of these, calcium, magnesium and barium are particularly preferred.
  • x is a value corresponding to the valence of the metal component M.
  • Typical illustrative compounds of the metal sulfonate according to the present invention can be represented by the following formula (II):
  • a and B may be the same or different and are each (i) an alkyl group or (ii) an aromatic group with at least one alkyl group bonded thereto, and the alkyl groups are those capable of providing 20% or higher as an average linearity of the whole alkyl groups as determined by a 13 C-NMR measurement.
  • the aromatic group can be at least one aromatic group selected from the group consisting of the above-described structural formulas (a) to (g).
  • M in the formula represents the above-described divalent metal, with an alkaline earth metal being preferred.
  • R 1 to R 10 are alkyl groups and as already described, the average total carbon numbers of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 , said average total carbon numbers being equivalent to the numbers of carbon atoms per the corresponding organic sulfonic acids, may preferably be from 12 to 40, and R 1 to R 10 have alkyl chain linearities of 20% or higher as determined by 13 C-NMR measurement.
  • each n represents the number of alkyl groups bonded to the associated aromatic group and may stand for an integer of 1 to 5, preferably of 1 to 3. In each formula, two n values can be the same or different.
  • Ms in the formulas (III) to (VII) are preferably alkaline earth metals, although they can be other divalent metals described above.
  • a process for the preparation of a metal sulfonate according to the present invention which contains one or more alkyl groups which are large in chain length and high in linearity. It is possible to adopt, for example, a process in which a sulfonic acid available by sulfonation of an alkyl-substituted aromatic hydrocarbon obtained from a petroleum fraction or of an alkyl-substituted aromatic hydrocarbon, which is an alkylation product of an aromatic hydrocarbon by an olefinic hydrocarbon, is neutralized with an alkali metal oxide, hydroxide, alkoxide or the like, followed by the adjustment of a quantity of a metal.
  • a metal sulfonate according to the present invention which has a specific alkyl chain linearity, can be prepared by mixing various metal sulfonates of different alkyl chain linearities so that the overall alkyl chain linearity is controlled to fall within the above-descried particular range.
  • the metal sulfonate can be a basic salt or over-based salt in addition to a neutral salt.
  • Its salt type can be chosen as desired depending on its application.
  • a basic salt can be one prepared by a conventional process, and can be prepared, for example, by dispersing M(OH) 2 or MCO 3 (wherein M represents an alkaline earth metal or the like) in a colloidal form in a sulfonate.
  • M(OH) 2 or MCO 3 wherein M represents an alkaline earth metal or the like
  • the present invention provides a friction modifier, especially a friction modifier for lubricating oils, which is composed of a particular metal sulfonate.
  • This friction modifier is oil-soluble. It can be used by dissolving it in a hydrocarbon or another solvent and diluting the resultant concentrate as needed or as a component of an additive package in combination with other additives.
  • the base stock can be any one of mineral base stocks, synthetic base stocks and vegetable base stocks, or can be a blended base stock of two or more of these base stocks.
  • a mineral base stock it is possible to use, for example, a mineral oil obtained by the treatment of a lubricating oil fraction, which is in turn available by vacuum distillation of an atmosphere distillation residue of paraffin-base, neutral or naphthene-base crude oil, through a refining step such as solvent refining, hydrocracking, hydro-refining, catalytic dewaxing, solvent dewaxing or clay treatment; a mineral oil obtained by subjecting a vacuum distillation residue to solvent deasphalting and then treating the resulting deasphalted oil through the above-described refining step; a mineral oil obtained by isomerizing wax components; or a blended oil thereof.
  • a refining step such as solvent refining, hydrocracking, hydro-refining, catalytic dewaxing, solvent dewaxing or clay treatment
  • an aromatic extraction solvent such as phenol, furfural or N-methylpyrrolidone
  • a solvent for the solvent dewaxing liquefied propane, MEK/toluene, MEK/MIBK, or the like
  • hydro-refined oil is preferred from the standpoint of oxidation stability and the like, and one containing, for example, 2 wt% or less of aromatic hydrocarbons and 90 wt% or more of saturated hydrocarbons can be used.
  • Examples of synthetic base stocks can include poly( ⁇ -olefin) oligomers of lubricating viscosity; polybutene; alkylbenzenes; polyol esters such as trimethylolpropane esters and pentaerythritol esters; polyoxyalkylene glycols; polyoxyalkylene glycol esters; polyoxyalkylene glycol ethers; dibasic acid esters; phosphate esters; and silicone oils.
  • These base stocks can be used either singly or in combination.
  • usable examples of vegetable base stocks can include rape seed oil, soybean oil, coconut oil, olive oil and sunflower oil.
  • the lubricating base stock employed in the lubricating oil composition according to the present invention can be produced by suitably preparing a blended base stock so that the blended base stock has properties desired for the intended application of the lubricating oil composition.
  • Concerning viscosity for example, it is preferred to control the kinematic viscosity at 100°C in a range of from 2 mm 2 /s to 30 mm 2 /s, especially from 3 mm 2 /s to 10 mm 2 /s for a lubricating oil for internal combustion engines, the kinematic viscosity at 100°C in a range of from 2 mm 2 /s to 30 mm 2 /s, especially from 3 mm 2 /s to 15 mm 2 /s for an automatic transmission fluid, and the kinematic viscosity at 40°C in a range of from 10 mm 2 /s to 1,000 mm 2 /s, especially from 20 mm 2 /s to 500 mm 2 /s.
  • the metal sulfonate according to the present invention can exhibit sufficient friction reducing effects when added to the lubricating base stock in a proportion of from 0.01 to 10 wt%, preferably from 0.05 to 5 wt% based on the whole weight of the lubricating oil composition or in a proportion of from 1 ppm to 10,000 ppm, preferably from 50 ppm to 5,000 ppm in terms of the metal, although the proportion varies depending on the application field of the lubricating oil.
  • viscosity index improvers ashless dispersants, oxidation inhibitors, extreme pressure agents, wear inhibitors, metal deactivators, pour-point depressants, rust inhibitors, other friction modifiers and other additives as needed.
  • Illustrative usable examples of the viscosity index improvers can include polymethacrylates, polyisobutylenes, ethylene-propylene copolymers, and hydrogenated styrene-butadiene copolymers. These viscosity index improvers are used generally in a proportion of from 3 wt% to 35 wt%.
  • Illustrative of the ashless dispersants can be polybutenyl-succinimides, polybutenylsuccinamides, benzylamines, and succinate esters. They can be used generally in a proportion of from 0.05 wt% to 7 wt%.
  • Illustrative examples of the oxidation inhibitors can include amine-type oxidation inhibitors such as alkylated diphenylamines, phenyl- ⁇ -naphthylamine and alkylated phenyl- ⁇ -naphthylamines; phenolic oxidation inhibitors such as 2,6-di-t-butylphenol and 4,4'-methylene-bis(2,6-di-t-butyl-phenol); and zinc dithiophosphate. They can be used generally in a proportion of from 0.05 wt% to 5 wt%.
  • extreme pressure agents can be dibenzyl sulfide and dibutyl disulfide. They can be used generally in a proportion of from 0.05 wt% to 3 wt%.
  • metal deactivators can include benzotriazole, benzotriazole derivatives, and thiadiazole. They can be used generally in a proportion of from 0.01 wt% to 3 wt%.
  • pour-point depressants can be ethylene-vinyl acetate copolymers, chlorinated paraffin-naphthalene condensation products, polymethacrylates, and polyalkylstyrenes. They can be used generally in a proportion of from 0.1 wt% to 10 wt%.
  • wear inhibitors can be phosphate esters, zinc thiophosphate, and sulfur compounds. They can be used generally in a proportion of from 0.01 wt% to 5 wt%.
  • a lubricating oil composition comprising as a base stock a hydro-refined oil, which contains 2 wt% or less of aromatic hydrocarbons and 90 wt% or more of saturated hydrocarbons, and a calcium sulfonate containing 1 to 2 C 14 - 24 alkyl groups per organic sulfonic group and having an alkyl chain linearity of 40% or higher as determined by a 13 C-NMR measurement, said calcium sulfonate having been added in a proportion of from 50 ppm to 5,000 ppm in terms of calcium based on the whole weight of the lubricating oil composition.
  • the metal sulfonate according to the present invention can be used as a friction modifier in hydraulic working oils, wet brake oils, sliding surface oils, plastic working oils, cutting oils and the like in addition to lubricating oils for internal combustion engines, automatic transmission fluids and gear oils.
  • the metal sulfonate can be used without limitations in any other oils insofar as it can exhibit its friction reducing effects.
  • alkyl chain linearities of the metal sulfonates employed in the following Examples and the performance evaluation of the lubricating oil compositions were measured or conducted by the following methods.
  • a lubricating oil composition was formulated by adding the sulfonate to a solvent-refined mineral oil "100N" (kinematic viscosity at 100°C: 4.2 mm 2 /s) in a proportion of 140 ppm in terms of calcium based on the whole weight of the lubricating oil composition.
  • the friction coefficient of the resultant lubricating oil composition was measured by the above-described method. It was found to be 0.09.
  • a lubricating oil composition was formulated in exactly the same manner as in Example 1 except that the proportion of Calcium Sulfonate 1 was increased from 140 ppm to 560 ppm in terms of calcium.
  • the resultant lubricating oil composition was subjected to a performance evaluation. Its friction coefficient was found to be 0.08, thereby indicating an improvement in friction characteristics.
  • Calcium Sulfonate 2 of the following characteristics:
  • a lubricating oil composition was formulated by adding the sulfonate to the same lubricating base stock as that employed in Example 1 in a proportion of 1,200 ppm in terms of calcium based on the whole weight of the lubricating oil composition.
  • the resultant lubricating oil composition was subjected to the above-described performance evaluation. Its friction coefficient was found to be 0.10.
  • a lubricating oil composition was formulated in exactly the same manner as in Example 3 except that the proportion of Calcium Sulfonate 2 was increased from 1,200 ppm to 2,400 ppm in terms of calcium.
  • the resultant lubricating oil composition was subjected to a performance evaluation. Its friction coefficient was found to be 0.08.
  • Calcium Sulfonate 3 of the following characteristics:
  • a lubricating oil composition was formulated by adding the sulfonate to the same lubricating base stock as that employed in Example 1 in a proportion of 2,400 ppm in terms of calcium based on the whole weight of the lubricating oil composition.
  • the resultant lubricating oil composition was subjected to the above-described performance evaluation. Its friction coefficient was found to be 0.09.
  • a lubricating oil composition was formulated in exactly the same manner as in Example 5 except that the proportion of Calcium Sulfonate 3 was increased from 2,400 ppm to 4,800 ppm in terms of calcium.
  • the resultant lubricating oil composition was subjected to a performance evaluation. Its friction coefficient was found to be 0.08.
  • Calcium Sulfonate 4 of the following characteristics:
  • a lubricating oil composition was formulated by adding the sulfonate to the same lubricating base stock as that employed in Example 1 in a proportion of 2,400 ppm in terms of calcium based on the whole weight of the lubricating oil composition. As a result of a performance evaluation, its friction coefficient was found to be 0.13.
  • Calcium Sulfonate 5 of the following characteristics:
  • a lubricating oil composition was formulated by adding the sulfonate to the same lubricating base stock as that employed in Example 1 in a proportion of 2,400 ppm in terms of calcium based on the whole weight of the lubricating oil composition.
  • the friction coefficient of the resultant lubricating oil composition was found to be 0.14.
  • a lubricating oil composition was formulated in exactly the same manner as in Comparative Example 2 except that the proportion of Calcium Sulfonate 5 was increased from 2,400 ppm to 4,800 ppm in terms of calcium. Its friction coefficient was found to be 0.13. The calcium sulfonate, the alkyl chain linearity of which is low, was also found to be unable to bring about any substantial advantageous effects on friction characteristics despite the increase in its proportion.
  • the solvent-refined mineral oil "100N” (kinematic viscosity at 100°C: 4.2 mm 2 /s), which was employed as a lubricating base stock in Example 1, was subjected by itself to a performance evaluation. Its friction coefficient was found to be 0.14.
  • a metal sulfonate having an alkyl chain linearity of 20% or higher is useful as a friction modifier for lubricating oils, and can improve the friction characteristics of lubricating oil compositions.

Claims (6)

  1. Verwendung einer Schmierölzusammensetzung von Metallsulfonat, das aus Metall und organischer Sulfongruppe zusammengesetzt ist, die eine Kohlenwasserstoffgruppe enthält, wobei die Kohlenwasserstoffgruppe eine Ketten-Kohlenwasserstoffgruppe oder ein aromatische Gruppe mit mindestens einer daran gebundenen Ketten-Kohlenwasserstoffgruppe ist, wobei die Ketten-Kohlenwasserstoffgruppe eine Alkylkettenlinearität von 20 % oder höher hat, bestimmt mittels Kohlenstoff-Kernresonanzmessung (13C-NMR-Messung), zur Reibungsverminderung.
  2. Verwendung nach Anspruch 1, bei der die Ketten-Kohlenwasserstoffgruppe eine Alkylgruppe ist.
  3. Verwendung nach Anspruch 1 oder Anspruch 2, bei der die Ketten-Kohlenwasserstoffgruppe eine oder mehrere Alkylgruppen ist, die jeweils durchschnittlich 12 bis 40 Kohlenstoffatome pro organischer Sulfongruppe haben, bestimmt mittels 13C-NMR-Messung.
  4. Verwendung nach einem der Ansprüche 1 bis 3, bei der die Ketten-Kohlenwasserstoffgruppe eine Alkyllinearität von 30 % bis 80 % hat, bestimmt mittels 13C-NMR-Messung.
  5. Verwendung nach einem der Ansprüche 1 bis 4 in einer Schmierölzusammensetzung, die Basismaterial umfasst, wobei das Metallsulfonat der Zusammensetzung in einer Menge zugefügt wird, um 1 ppm bis 10.000 ppm in Form seines Metalls zu liefern, bezogen auf das Gesamtgewicht der Schmierölzusammensetzung.
  6. Verwendung nach einem der Ansprüche 1 bis 5, bei der die Schmierölzusammensetzung mindestens ein Additiv ausgewählt aus Viskositätsindexverbesserern, aschefreien Dispergiermitteln, Oxidationsschutzmitteln, Extremdruckmitteln, Metalldesaktivatoren, Stockpunktsenkungsmitteln und Verschleißschutzmitteln umfasst.
EP98304251A 1997-05-31 1998-05-29 Verwendung von Metallsulfonaten als Reibungsmodifiziermittel Expired - Lifetime EP0881277B8 (de)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP15792197 1997-05-31
JP157921/97 1997-05-31
JP15792197 1997-05-31
JP10104021A JPH1143687A (ja) 1997-05-31 1998-03-31 金属スルホネートからなる摩擦低減剤およびそれを含有する潤滑油組成物
JP104021/98 1998-03-31
JP10402198 1998-03-31

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EP0881277A2 EP0881277A2 (de) 1998-12-02
EP0881277A3 EP0881277A3 (de) 1999-09-08
EP0881277B1 true EP0881277B1 (de) 2005-08-17
EP0881277B8 EP0881277B8 (de) 2005-10-19

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CA2330325C (en) * 1998-04-27 2003-11-25 Infineum Holdings B.V. Lubricating oil compositions
JP4673465B2 (ja) * 2000-05-17 2011-04-20 東燃ゼネラル石油株式会社 潤滑油組成物
WO2003040273A2 (en) 2001-11-05 2003-05-15 The Lubrizol Corporation Lubricating composition with improved fuel economy
US20040018946A1 (en) * 2002-07-26 2004-01-29 Aoyagi Edward I. Method of improving the frictional properties of functional fluids
JP5027426B2 (ja) * 2006-02-17 2012-09-19 昭和シェル石油株式会社 潤滑剤組成物
US20080119378A1 (en) * 2006-11-21 2008-05-22 Chevron Oronite Company Llc Functional fluids comprising alkyl toluene sulfonates
JP5211126B2 (ja) * 2010-09-30 2013-06-12 東燃ゼネラル石油株式会社 潤滑油組成物

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US3910994A (en) * 1972-07-26 1975-10-07 Universal Oil Prod Co Alkylaromatic sulfonate detergent process
US4225446A (en) * 1978-04-03 1980-09-30 Calumet Industries, Inc. Process for preparing highly basic magnesium sulfonates
JPS6284190A (ja) * 1985-10-07 1987-04-17 Nippon Oil Co Ltd 自動変速機油組成物
GB8723907D0 (en) * 1987-10-12 1987-11-18 Exxon Chemical Patents Inc Overbased metal sulphonate composition

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CA2235701C (en) 2007-05-22
EP0881277A2 (de) 1998-12-02
DE69831189D1 (de) 2005-09-22
EP0881277A3 (de) 1999-09-08
JPH1143687A (ja) 1999-02-16
DE69831189T2 (de) 2006-06-08
SG77644A1 (en) 2001-01-16
CA2235701A1 (en) 1998-11-30

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