WO1996037581A1 - Composition d'huile lubrifiante - Google Patents

Composition d'huile lubrifiante Download PDF

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Publication number
WO1996037581A1
WO1996037581A1 PCT/US1995/005144 US9505144W WO9637581A1 WO 1996037581 A1 WO1996037581 A1 WO 1996037581A1 US 9505144 W US9505144 W US 9505144W WO 9637581 A1 WO9637581 A1 WO 9637581A1
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Prior art keywords
group
represent
atom
alkyl
general formula
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PCT/US1995/005144
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English (en)
Inventor
Michihide Tokashiki
Hirotaka Tomizawa
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Exxon Research & Engineering Company
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Priority to JP6027477A priority Critical patent/JPH07216378A/ja
Application filed by Exxon Research & Engineering Company filed Critical Exxon Research & Engineering Company
Priority to EP95922076A priority patent/EP0830444A4/fr
Priority to PCT/US1995/005144 priority patent/WO1996037581A1/fr
Publication of WO1996037581A1 publication Critical patent/WO1996037581A1/fr

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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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
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    • 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
    • C10M129/68—Esters
    • C10M129/76—Esters containing free hydroxy or carboxyl groups
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/16—Amides; Imides
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
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    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/288—Partial esters containing free carboxyl groups
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
    • C10M2215/082—Amides containing hydroxyl groups; Alkoxylated derivatives
    • C—CHEMISTRY; METALLURGY
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/086—Imides
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/12—Partial amides of polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/12—Partial amides of polycarboxylic acids
    • C10M2215/122—Phtalamic 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • 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
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • 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
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
    • 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

Definitions

  • the present invention relates to a lubricating oil composition, in particular, to a lubricating composition having excellent wear resistance and extreme-pressure lubricity and a low coefficient of friction.
  • the lubricating oil composition of the present invention can be minimized in phosphorus content or made phosphorus-free, and usable in a wide variety of fields such as, for example, a lubricating oil for an internal combustion engineer or an engine oil.
  • the engine oil is usually effective in lubricating various sliding parts such as a piston ring and a cylinder liner; bearings of a crankshaft and connecting rod; valve mechanisms including a cam and valve lifter; drivers such as an oil pump and distributor, and also in cooling the inside of an engine, deterging and dispersing combustion products and preventing the rusting and corrosion thereof.
  • various properties are required of the engine oil and, in addition, the required properties are continuously changing according to improvements in performance and output of the engine and driving conditions which grow more and more severe. Therefore, various additives such as an antiwear agent, metallic detergent, ashless dispersant and oxidation inhibitor are incorporated into the engine oil for the purpose of satisfying the various properties required thereof.
  • antiwear properties of the engine oil in the boundary lubrication state are usually realized by the addition of a zinc dialkyldithiophosphate (ZnDTP).
  • ZnDTP zinc dialkyldithiophosphate
  • ZnDTP has a problem that, since phosphorus (P) contained therein poisons catalyst and oxygen sensors, exhaust gas-control systems are deteriorated. Further, the wear resistance is inclined to be lost by an interaction between ZnDTP and other additives such as succinimide and alkylamine. Under these circumstances, a lubricating oil composition having a minimum phosphorus content or free from phosphorus is required.
  • a friction modifier is added to a lubricating oil to be used for a gasoline engine in order to reduce the friction loss and fuel consumption, since the energy loss is high in friction parts in which the lubricatng oil is concerned in the gasoline engine.
  • the friction modifier and extreme-pressure agent such as a molybdenum sulf ⁇ de dialkyldithiocarbamate or an oiliness agent such as octadecylamine is used, the molybdenum sulfide dialkyldithiocarbamate which is a dithiocarbamate-type organomolybdenum compound has a particularly excellent effect of reducing the friction.
  • the object of the present invention is to provide a lubricating oil composition excellent in both wear resistance and friction characteristics.
  • the object of the present invention is to provide a lubricating oil composition containing an extreme-pressure agent which is a dithiocarbamate- type organometallic compound having friction characteristics and wear resistance superior to those of an conventional extreme-pressure agent.
  • Another object of the present invention is to provide a lubricating oil composition which contains also a dithiophosphate-type organometallic compound to further improve the wear resistance and friction characteristics.
  • a dithiocarbamate-type organometal compound such as a molybdenum sulfide dialkyldithiocarbamate has such a structure that the alkyl group is bonded to the nitrogen atom through its primary carbon atoms (namely, -CH2-N ⁇ ).
  • the friction characteristics and wear resistance of the lubricating oil composition of the present invention are further improved by adding ZnDTP and/or zinc dithiocarbamate (ZnDTC), in addition to the above-described metal dithiocarbamate, to the lube base oil.
  • ZnDTC zinc dithiocarbamate
  • ZnDTC zinc dithiocarbamate
  • the metal dithiocarbamate of the present invention is used in combination with ZnDTP, ZnDTP content can be reduced to enable reduction of the phosphorus content, since the metal dithio ⁇ carbamate is excellent in the wear resistance and friction characteristics.
  • the metal dithiocarbamate of the present invention is used solely or in combination with ZnDTC without using ZnDTP, the phosphorus-free lubricating oil composition can be obtained.
  • the coefficient of friction of the lubricating oil composition of the present invention can be further reduced by adding a fatty acid ester and/or an organic amide compound.
  • various other additives for lubricating oils can be added, if desired, to the lubricating oil composition of the present invention.
  • the lubricating oil composition of the present invention is usable in wide fields in which excellent wear resistance and friction characteristics are necessitated, such as in the field of engine oils.
  • a lubricating oil composition comprising a lube base oil and 0.01 to 10% by weight, based on the total weight of the composition, of a metal dithiocarbamate (A) represented by the general formula (1):
  • Rj, R , R3 and R4 may be the same or different from one another and each represent a hydrogen atom, saturated or unsaturated C1-C20 al yl group, C6-C26 cycloalkyl or alkyl-substituted cycloalkyl group, C6-C26 aryl, alkylaryl or arylalkyl group, or such a hydrocarbon group as above which further contains an ester bond, ether bond, hydroxyl group or carboxyl group, with the proviso that at least one of the four symbols Rj, R2, R3 and R4 must be a C5-C20 alkyl group having a secondary carbon atom, through which the group is bonded to a nitrogen atom (N) in the formula, X ⁇ and X2 each represent an oxygen or sulfur atom, and Yj and Y2 each represent an oxygen or sulfur atom.
  • N nitrogen atom
  • the present invention provides the following lubricating oil compositions 2 to 6 as preferred embodiments:
  • a lubricating oil composition which contains a lube base oil and, in addition to the above-mentioned metal dithiocarbamate (A), 0.01 to 7% by weight, based on the total weight of the composition, at least one organozinc compound selected from the group consisting of zinc dithiophosphates (B) of the general formula (2):
  • R5, R , R7 and R$ may be the same or different from one another and each represent a hydrogen atom, saturated or unsaturated C1-C20 alkyl group, C6-C26 cycloalkyl or alkyl substituted cycloalkyl group, C6-C26 aryl, alkylaryl or arylalkyl group, or such a hydrocarbon group as above which further contains an ester bond, ether bond, hydroxyl group or carboxyl group, and zinc dithiocarbamates (C) of the general formula (3):
  • R ⁇ , R 1 ⁇ R11 and W - may be the same or different from one another and each represent a hydrogen atom, saturated or unsaturated C1-C20 alkyl group, C6-C25 cycloalkyl or alkyl-substituted cycloalkyl group, C6-C26 aryl, alkylaryl or arylalkyl group, or such a hydrocarbon group as above which further contains as ester bond, ether bond, hydroxyl group or carboxyl group,
  • a lubricating oil composition according to above item 1 or 2 wherein at least two of R 1 , R2, R3 and R"4 in the general formula (1) for the metal dithiocarbamate (A) each represent an alkyl group having a secondary carbon atom, through which the group is bonded to the nitrogen atom (N) in the formula,
  • a lubricating oil composition according to any of above items 1 to 5, which comprises a lube base oil containing a fatty acid ester, a organic amide or a mixture of fatty acid ester and organic anide in addition to the metal dithiocarbamate (A) or in addition to the combination of the metal dithiocarbamate (A) with zinc dithiophosphate (B) and or zinc dithiocarbamate (C).
  • the base oils usable in the present invention are not particularly limited, and include known mineral oils and synthetic oils.
  • the mineral oils include raffinates obtained by solvent refining of a starting material for the lubricating oil with an aromatic solvent such as phenol or furfural; hydrotreated oils obtained by the hydrotreatment of the starting material with a hydrogena- tion catalyst such as cobalt or molybdenum supported on a silica/alumina carrier; and mineral oils such as a lubricating oil fraction obtained by isomerization of a wax. They include, for example, 60 neutral oil, 100 neutral oil, 150 neutral oil, 300 neutral oil, 500 neutral oil and bright stock.
  • the synthetic oils include poly-a-olefins, polybutenes, alkylbenzenes, poly- alkylene glycol esters, polyol esters and dibasic acid esters. These base oils can be used singly or in the form of a mixture of two or more of them. A mixture of such a mineral oil and synthetic oil is also usable.
  • the kinematic viscosity of the lube base oil is usually preferably in the range of 3 to 20 cSt at 100°C when the oil is used as the engine oil.
  • the metal dithiocarbamates used in the present invention are organometallic compounds represented by the above-described general formula
  • M represents a molybdenum atom (Mo) or tungsten atom (W).
  • Mo molybdenum atom
  • W tungsten atom
  • the molybdenum atom is particularly preferred to the tungsten atom.
  • X 1 , X ⁇ , ⁇ l and Y ⁇ represent an oxygen atom or sulfur atom independently from one another. These four atoms contain 0 to 3 oxygen atoms and 1 to 4 sulfur atoms in total.
  • R 1 , R2, R3 and R"4 may be the same of different from one another and each represent a hydrogen atom, saturated or unsaturated C1-C20 alkyl group, C6-C26 cycloalkyl or alkyl-substituted cycloalkyl group, C6-C26 aryl, alkylaryl or arylalkyl group, or such a hydrocarbon group as above which further contains an ester bond, ether bond, hydroxyl group or carboxyl group.
  • Each of R to R ⁇ is preferably a C5-C20 alkyl group, more preferably C_-C ⁇ % alkyl group.
  • At least one of R*, R ⁇ , R3 and R ⁇ must be a C5-C20 alkyl group having a secondary carbon atom, through which the group is bonded to a nitrogen atom (N) in the above general formula.
  • the alkyl groups having the secondary carbon atom include, for example, 1-methylpentyl, 1-ethylbutyl, 1-methylheptyl, 1-ethylhexyl, 1- methyloctyl, 1-ethylheptyl, 1-methylnonyl, 1-ethyloctyl, 1-methylundecyl, 1- ethyldecyl, 1-methylheptadecyl and 1-ethylhexadecyl groups.
  • alkyl groups having the secondary carbon atom must be bonded to the nitrogen atom (N) in the general formula (1) through the secondary carbon atom.
  • N nitrogen atom
  • 1-methylnonyl group is bonded to the nitrogen atom through the secondary carbon atom thereof as shown by the following formula:
  • [(CH 3 (CH2)3CH(C 2 H5)CH2-] contains a secondary carbon atom, it is not included in the above-defined alkyl group having the specified secondary carbon atom, since it is bonded to the nitrogen atom through the primary carbon atom.
  • the groups other than the alkyl groups having the specified secondary carbon atoms are preferably C5-C20 hydrocarbon groups such as saturated or unsaturated alkyl groups and alkylaryl groups.
  • hydrocarbon groups include saturated alkyl groups and unsaturated alkyl groups (alkenyl groups) such as n-hexyl, 2-ethylhexyl, n-octyl, nonyl, decyl, lauryl, tridecyl, oleyl and linoleyl groups, and alkylaryl groups such as nonylphenyl groups.
  • alkylaryl groups such as nonylphenyl groups.
  • particularly preferred are C -Ci 8 alkyl groups.
  • metal dithiocarbamates (A) can be used either singularly or in combination of two or more of them.
  • the relative amount of the metal dithiocarbamate (A) is about 0.01 to 10% by weight, preferably 0.05 to 7a% by weight and more preferably 0.1 to 5% by weight, based on the total weight of the whole lubricating oil composition.
  • the relative amount of the metal dithiocarbamate (A) is insufficient, it is difficult to obtain sufficient friction characteristics and wear resistance and, on the contrary, an excess amount thereof is economically disadvantageous and causes reduction in the wear resistance.
  • Zinc dithiophosphate (B and zinc dithiocarbamate (C) Zinc dithiophosphate (B and zinc dithiocarbamate (C).
  • various lubricating oil additives can be incorporated into the lubricating oil composition of the present invention.
  • a zinc dithiophosphate (B) of the above general formula (2) and/or zinc dithiocarbamate (C) of the above general formula (3) is particularly effective in further improving the wear resistance and reducing the coefficient of friction as intended in the present invention.
  • each of R ⁇ to R ⁇ represents preferably a C2-C13 hydrocarbon group, more preferably C2-C13 alkyl group.
  • each of R9 to R12 represents preferably a C2-C1 hydrocarbon group, more preferably C2-C13 alkyl group.
  • the relative amount of the zinc dithiophosphate (B) or zinc dithiocarbamate (C) or mixture thereof is about 0.01 to 7% by weight, preferably 0.03 to 5% by weight and more preferably 0.05 to 2% by weight, based on the total weight of the whole lubricating oil composition.
  • the relative amount of (B) or (C) or mixture thereof is insufficient, the effect obtained by the combination thereof with the metal dithiocarbamate (A) is insufficient for obtaining the sufficient effect of improving the wear resistance and reducing the coefficient of friction and, on the contrary, an excess amount thereof is economically disadvantageous and might impair the friction characteristics.
  • the lubricating oil composition of the present invention may contain various additives, if desired, depending on the field in which it is used, such as engine oils.
  • the additives include, for example, a friction modifier, metallic detergent, ashless detergent-dispersant, oxidation inhibitor, viscosity- index improver, rust inhibitor, antifoamer, corrosion inhibitor, pour-point depressant and wear resistant additive other than those described above.
  • the friction modifiers include fatty acid esters such as fatty acid glycerol monoesters and diesters, and fatty acid/ sorbitan monoesters and diesters; and fatty acid amides such as oleamide and lauramide.
  • fatty acid ester is used in an amount of usually 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total weight of the whole composition, the wear resistance and friction characteristics are further improved.
  • the organic amide compound is used in an amount of usually 0.01 to 5% by weight, preferably 0.05 to 2% by weight, based on the total weight of the whole composition, the copper-corroding properties are controlled and the coefficient of friction can be reduced from the initial stage.
  • the fatty acid glycerides are monoesters and diesters of the following general formulae (4) and (5):
  • R ⁇ 3, R*4 and R 1 ⁇ each represent a saturated or unsaturated C8-C22 alkyl group.
  • the fatty acid esters are usable either singularly or in combina ⁇ tion of two or more of them.
  • the metal dithiocarbamate (A) is used in combination with the fatty acid ester, wear resistance and friction characteristics more improved than those obtained when they are used separately can be obtained.
  • the fatty acid ester is added to the combination of the metal dithiocarbamate (A) and zinc dithiophosphate (B) and/or zinc dithiocarbamate (C), a lubricating oil composition having improved wear resistance and friction properties and a remarkably reduced coefficient of friction can be obtained.
  • organic amide compounds are those represented by the following general formula (6):
  • R*6 and R 1 ⁇ may be the same or different from each other an each represent a hydrogen atom, C1-C20 alkyl group, C6-C26 cycloalkyl group, C6-C26 aryl, alkylaryl or arylalkyl group, or C2-C20 alkylene oxide group, and R 18 represents a hydrogen atom, C1-C20 alkyl group, C6-C26 cycloalkyl group, C6-C26 aryl, alkylaryl or arylalkyl group, or such a hydrocarbon group as above further containing an ester bond, ether bond, hydroxyl group or carboxyl group.
  • alkylene oxide group in the general formula (6) are those represented by the following general formula (7) or (8):
  • R 1 ⁇ and R ⁇ O each represent a hydrogen atom or methyl group, and n represents an integer of 1 to 10 inclusive.
  • R 1 ⁇ and R*? each preferably represent a hydrogen atom, C2-C6 alkyl group, Cg-C ⁇ cycloalkyl group, C8-C14 alkylaryl group or alkylene oxide group wherein n represents 1 to 5, and R l8 preferably represents a saturated or unsaturated C ⁇ -Cis alkyl group, C12-C24 cycloalkyl group or C12-C24 alkylaryl group.
  • the metallic detergents include, for example, phenates, sulfonates and phosphonates of barium (Ba), calcium (Ca) and magnesium (Mg). Among them, overbased Ca sulfonate, Mg sulfonate and Ca phenate and neutral Ca sulfonate are preferred.
  • the metallic detergent is used usually in an amount of 0.1 to 10% by weight (based on the whole composition).
  • the ashless detergent-dispersants include, for example, benzyl- amine, boron derivatives of benzylamine, alkenylsuccinimides and boron derivatives of alkenylsuccinimides.
  • the ashless detergent dispersant is used usually in an amount of 0.5 to 15% by weight (based on the whole composi ⁇ tion).
  • the oxidation inhibitors include, for example, amine oxidation inhibitors such as alkylated diphenylamines, pheyl- ⁇ -naphthylamines and alkylated ⁇ -naphthylamines; and phenolic oxidation inhibitors such as 2,6-di-t- butylphenol).
  • the oxidation inhibitor is used usually in an amount of 0.05 to 2.0% by weight (based on the whole composition).
  • the viscosity-index improvers include, for example, polymethyl methacrylates, polyisobutylenes, ethylene/propylene copolymers and hydro- genated styrene-butadiene copolymers.
  • the viscosity-index improver is used usually in an amount of 0.5 to 35% by weight (based on the whole composi ⁇ tion).
  • the rust inhibitors include, for example, alkenylsuccinic acids and partial esters of them, which can be suitably added to the composition.
  • the antifoamers include, for example, dimethyl polysiloxanes and polyacrylates, which can be suitably added to the composition.
  • the wear track diameter (mm) and coefficient of friction were determined by the Shell four-ball test 30 min. after the initiation of the test.
  • the test conditions were as follows: load: 40 kg oil temperature: 90°C rotation rate: 1800 rpm, and test time: 30 minutes
  • test oil was prepared by mixing a lube base oil and components given in Table 1. The components used were as follows:
  • mineral oil 150 neutral oil having a kinematic viscosity at 100°C of 5.1 cSt (mm ⁇ /s), and synthetic oil: a mixed oil comprising 80% by weight of a poly- ⁇ -olefin and 20% by weight of diisodecyl adipate.
  • Molybdenum dithiocarbamate molybdenum sulfide dithiocarbamates of the general formula (1) where X* and X ⁇ each represent an oxygen atom (O) and ⁇ l and Y ⁇ each represent a sulfur atom (S) was used, having the following different hydrocarbon groups as indicated in Table 1 :
  • hydrocarbon group p-C8-C 13 alkyl: commercially available primary alkyl groups (mixed C8-C 3 alkyl groups) - containing molybdenum sulfide dithiocarbamate,
  • hydrocarbon group p-C 13 alkyl: commercially available primary alkyl groups (C13 alkyl groups) - containing molybdenum sulfide dithiocarbamate,
  • hydrocarbon group 1-methylheptyl: molybdenum sulfide dithio ⁇ carbamate wherein R 1 to R4 each represent a 1-methylheptyl group,
  • Zinc dithiophosphate commercially available i-C3/s-C6 alkyl type
  • Zinc dithiocarbamate commercially available n-C5/i-C5 alkyl type.
  • test oil was prepared by mixing a lube base oil with components given in Table 2.
  • the components used were as follows:
  • R represents an oleyl group
  • the lubricating oil composi ⁇ tion having wear resistance and friction characteristics far superior to those of a conventional metal sulfide dithiocarbamate containing composition can be provided.
  • the lubricating oil composition of the present invention can be minimized in the phosphorus content or made phosphorus-free.
  • the lubricating oil composition of the present invention can be used in various fields such as a field of lubricating oils for internal combustion engines, etc.

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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)

Abstract

Cette invention traite d'une composition d'huile lubrifiante contenant un agent pour pression extrême qui est un composé organométallique du type dithiocarbamate présentant des caractéristiques de résistance à l'usure et d'ordre tribologique, supérieures à celles que l'on rencontre dans les composés organométalliques habituels. Cette composition d'huile lubrifiante comporte une huile de base de graissage et 0,01 à 10 % en poids, par rapport à l'intégralité de la composition, d'un dithiocarbamate de métal représenté par la formule générale (1) dans laquelle M représente un atome Mo ou W, et dans laquelle R?1, R2, R3 et R4¿, représentent chacun un groupe hydrocarbure, à la condition que l'un au moins de R?1, R2, R3 et R4¿, représente impérativement un groupe alkyle C¿5? - C20 porteur d'un atome de carbone secondaire par le truchement duquel le groupe est lié à un atome d'azote (N) dans la formule (1), et où X?1, X2, Y1 et Y2¿ représentent, chacun, un atome d'oxygène ou de soufre.
PCT/US1995/005144 1994-01-31 1995-05-24 Composition d'huile lubrifiante WO1996037581A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP6027477A JPH07216378A (ja) 1994-01-31 1994-01-31 潤滑油組成物
EP95922076A EP0830444A4 (fr) 1995-05-24 1995-05-24 Composition d'huile lubrifiante
PCT/US1995/005144 WO1996037581A1 (fr) 1994-01-31 1995-05-24 Composition d'huile lubrifiante

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP6027477A JPH07216378A (ja) 1994-01-31 1994-01-31 潤滑油組成物
PCT/US1995/005144 WO1996037581A1 (fr) 1994-01-31 1995-05-24 Composition d'huile lubrifiante

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WO1996037581A1 true WO1996037581A1 (fr) 1996-11-28

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000071649A1 (fr) * 1999-05-19 2000-11-30 Infineum International Limited Composition d'huile lubrifiante contenant moins de 350 ppm de molybdene
US6172013B1 (en) 1997-09-17 2001-01-09 Exxon Chemical Patents Inc Lubricating oil composition comprising trinuclear molybdenum compound and diester
US6536492B2 (en) 1998-07-22 2003-03-25 Michelin Recherche Et Technique S.A. Silica-containing rubber composition vulcanizable with sulfur
EP1652908A1 (fr) * 2004-11-01 2006-05-03 Infineum International Limited Compositions d'huiles lubrifiantes
WO2006137928A2 (fr) * 2004-11-04 2006-12-28 United Technologies Corporation Lubrifiants contenant des preformulations d'additifs multifonctionnelles pour ameliorer la capacite de support de charge, augmenter la longevite a la fatigue en surface et reduire la friction
EP2248878A1 (fr) * 2009-05-01 2010-11-10 Shell Internationale Research Maatschappij B.V. Composition de lubrification
RU2451720C2 (ru) * 2006-10-27 2012-05-27 Идемицу Козан Ко., Лтд. Композиция смазочного масла

Families Citing this family (3)

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JP2006265493A (ja) * 2005-03-25 2006-10-05 Nippon Oil Corp 潤滑油組成物
US10443008B2 (en) * 2017-06-22 2019-10-15 Exxonmobil Research And Engineering Company Marine lubricating oils and method of making and use thereof
JP7168342B2 (ja) * 2018-04-27 2022-11-09 株式会社Adeka モリブデンジチオカルバメート組成物及びモリブデンジチオカルバメートの製造方法

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US4280916A (en) * 1980-03-31 1981-07-28 Shell Oil Company Lubricant composition
US4529526A (en) * 1982-11-30 1985-07-16 Honda Motor Co., Ltd. Lubricating oil composition
US4867890A (en) * 1979-08-13 1989-09-19 Terence Colclough Lubricating oil compositions containing ashless dispersant, zinc dihydrocarbyldithiophosphate, metal detergent and a copper compound

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US4867890A (en) * 1979-08-13 1989-09-19 Terence Colclough Lubricating oil compositions containing ashless dispersant, zinc dihydrocarbyldithiophosphate, metal detergent and a copper compound
US4280916A (en) * 1980-03-31 1981-07-28 Shell Oil Company Lubricant composition
US4529526A (en) * 1982-11-30 1985-07-16 Honda Motor Co., Ltd. Lubricating oil composition

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Title
See also references of EP0830444A4 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6172013B1 (en) 1997-09-17 2001-01-09 Exxon Chemical Patents Inc Lubricating oil composition comprising trinuclear molybdenum compound and diester
US6536492B2 (en) 1998-07-22 2003-03-25 Michelin Recherche Et Technique S.A. Silica-containing rubber composition vulcanizable with sulfur
WO2000071649A1 (fr) * 1999-05-19 2000-11-30 Infineum International Limited Composition d'huile lubrifiante contenant moins de 350 ppm de molybdene
US6300291B1 (en) 1999-05-19 2001-10-09 Infineum Usa L.P. Lubricating oil composition
EP1652908A1 (fr) * 2004-11-01 2006-05-03 Infineum International Limited Compositions d'huiles lubrifiantes
WO2006137928A2 (fr) * 2004-11-04 2006-12-28 United Technologies Corporation Lubrifiants contenant des preformulations d'additifs multifonctionnelles pour ameliorer la capacite de support de charge, augmenter la longevite a la fatigue en surface et reduire la friction
WO2007001445A2 (fr) * 2004-11-04 2007-01-04 United Technologies Corporation Composition d'additifs lubrifiants polyvalents
WO2007001445A3 (fr) * 2004-11-04 2007-03-22 Pratt & Whitney Composition d'additifs lubrifiants polyvalents
WO2006137928A3 (fr) * 2004-11-04 2007-03-22 Pratt & Whitney Lubrifiants contenant des preformulations d'additifs multifonctionnelles pour ameliorer la capacite de support de charge, augmenter la longevite a la fatigue en surface et reduire la friction
RU2451720C2 (ru) * 2006-10-27 2012-05-27 Идемицу Козан Ко., Лтд. Композиция смазочного масла
US8367591B2 (en) 2006-10-27 2013-02-05 Idemitsu Kosan Co., Ltd. Lubricating oil composition
EP2248878A1 (fr) * 2009-05-01 2010-11-10 Shell Internationale Research Maatschappij B.V. Composition de lubrification

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