EP0377358B1 - Stickstoffhaltige Additive mit Antioxidwirkung und diese enthaltende Schmiermittelgemische - Google Patents

Stickstoffhaltige Additive mit Antioxidwirkung und diese enthaltende Schmiermittelgemische Download PDF

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Publication number
EP0377358B1
EP0377358B1 EP89403355A EP89403355A EP0377358B1 EP 0377358 B1 EP0377358 B1 EP 0377358B1 EP 89403355 A EP89403355 A EP 89403355A EP 89403355 A EP89403355 A EP 89403355A EP 0377358 B1 EP0377358 B1 EP 0377358B1
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Prior art keywords
additives
group
radical
phenol
hydrogen atom
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French (fr)
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EP0377358A2 (de
EP0377358A3 (en
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Laurent Germanaud
Patrick Azorin
Patrick Turello
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Elf Antar France
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Elf Antar France
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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
    • 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
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/12—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
    • C10M133/14—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups
    • 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
    • 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
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/12—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
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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
    • 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
    • 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
    • C10M133/22—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms containing a carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones
    • C—CHEMISTRY; METALLURGY
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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
    • C10M133/38—Heterocyclic nitrogen compounds
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10M135/20—Thiols; Sulfides; Polysulfides
    • C10M135/28—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring
    • C10M135/30—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
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    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
    • C10M135/36—Heterocyclic sulfur, selenium or tellurium compounds the ring containing sulfur and carbon with nitrogen or oxygen
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10M159/16—Reaction products obtained by Mannich reactions
    • 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
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/062—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups bound to the aromatic 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/08—Amides [having hydrocarbon substituents containing less than thirty carbon atoms]
    • 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
    • C10M2215/08—Amides [having hydrocarbon substituents containing less than thirty carbon atoms]
    • C10M2215/082—Amides [having hydrocarbon substituents containing less than thirty carbon atoms] containing hydroxyl groups; Alkoxylated derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/086—Imides [having hydrocarbon substituents containing less than thirty carbon atoms]
    • 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
    • C10M2215/14—Containing carbon-to-nitrogen double bounds, e.g. guanidines, hydrazones, semicarbazones
    • 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
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • 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
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • 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
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/088—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
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089—Overbased 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
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/108—Phenothiazine
    • 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
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/251—Alcohol-fuelled engines
    • C—CHEMISTRY; METALLURGY
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    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B1/00—Engines characterised by fuel-air mixture compression
    • F02B1/02—Engines characterised by fuel-air mixture compression with positive ignition
    • F02B1/04—Engines characterised by fuel-air mixture compression with positive ignition with fuel-air mixture admission into cylinder

Definitions

  • the present invention relates to the preparation of new oxidation inhibitor additives and their use in lubricating compositions. It is known that lubricating oils and in particular crankcase oils intended for internal combustion engines contain various additives which serve to improve their performance. Some of these additives are used to protect the oil from oxidation caused by high temperatures or by certain metal ions dispersed in the oil.
  • This degradation of the lubricant is linked to the thermal and oxidative decomposition of the oil and the additives. It gives rise to the formation and deposition of carbonaceous substances on the walls of the piston. If these deposits become too large, they can initiate a gumming or seizing of the piston and increase the wear of the moving metal parts. It is therefore important to limit the degradation of lubricants as best as possible by using effective antioxidant additives at economically reasonable concentrations.
  • Metallic deactivators are also known which prevent the metal ions present in the oil or on the surfaces from initiating self-oxidation of lubricant. These products act by complexing of metals.
  • aromatic amines and more particularly phenothiazine derivatives are the most effective because they act according to several mechanisms, decomposition of hydroperoxides, electronic transfer agents, metal chelation and oxygen acceptors.
  • US-A-2 781 318 describes the use in synthetic lubricants of alkylphenothiazines, the alkyl groups of which are carried by the aromatic carbons of phenothazine.
  • Patent application WO-A-88 02007 describes the preparation and use of N-alkylthioalkylphenothiazines obtained by condensation of a phenothiazine and an alkylthioalkanol. The presence of a sulfur atom strengthens the antioxidant power of the phenothiazine thus substituted.
  • antioxidant additives containing aromatic nitrogen can be improved by the presence of an aminoalkylated chain.
  • phenothiazine derivatives are used.
  • Ar and Ar ′ may be substituted by alkyl or aryl radicals, preferably C1 to C12 or by hydroxyl, alkoxy, alkylthio or even halogen groups.
  • R1 is a hydrogen atom and R2 represents an arylalkyl radical, of general formula -CH2 - Ar1 where Ar1 with the abovementioned meaning.
  • the introduction of the phenolic group Ar1 strengthens the antioxidant power of the additive.
  • 2,6-diterbutyl-phenol or sulfurized dodecylphenol is used.
  • Acrylamide, chloroacetamide, iodoacetamide, acrylonitrile or chloro-3-propionitrile are good alkylation reagents.
  • the alkylation reaction is followed by the hydrogenation of the nitrile or amide groups.
  • Another method consists in reacting an epoxide, such as ethylene oxide or propylene oxide with the aromatic nitrogen, followed by an aminolysis of the alcohol intermediate by treatment with ammonia or with an amine of general formula R1-NH-R2 where R1 and R2 have the above meaning.
  • an epoxide such as ethylene oxide or propylene oxide
  • an aminolysis of the alcohol intermediate by treatment with ammonia or with an amine of general formula R1-NH-R2 where R1 and R2 have the above meaning.
  • R2 is an arylalkyl radical containing at least one phenolic OH
  • the Mannich reaction is advantageously used for its synthesis.
  • Linear or cyclic alkylaldehydes or an aromatic aldehyde are used, but preferably formaldehyde or its derivatives such as paraformaldehyde, acetaldehyde or propionaldehyde.
  • diterbutyl-2,6-phenol or sulfurized dodecylphenol will advantageously be used.
  • the reaction is carried out with stirring under an atmosphere of an inert gas such as nitrogen, at a temperature between 60 and 130 ° C and preferably around 100 ° C, for a time between 2 to 10 hours.
  • an inert gas such as nitrogen
  • the compound Ar1-CHO is salicylaldehyde, terbutylsalicylaldehyde, diterbutyl-3-5-hydroxy-4-benzaldehyde or diterbutyl-3,5-hydroxy-4-phenyl-3-propionaldehyde.
  • the compound Ar1- CO2H is salicylic acid, terbutylsalicylic acid, diterbutyl-3,5-hydroxy-4-phenyl-3-propionic acid.
  • SCHIFF bases or amides generally takes place by heating the reagents under the same operating conditions as those described for obtaining the MANNICH bases.
  • the succinic anhydride used is generally substituted by an alkyl group, preferably an oligomer.
  • the oligomer comes from the oligomerization of a C2 to C5 olefin. It has a molecular weight between 500 and 3000, and preferably between 800 and 1500. The oligomer has residual unsaturation and reacts with maleic anhydride to give the substituted succinic anhydride.
  • the operation is generally carried out by condensing 0.5 to 1.5 moles, preferably 1 mole of compound of formula (I) per mole of anhydride in an organic solvent such as toluene or xylenes, capable of removing the water formed in the azeotropic entrainment reaction.
  • an organic solvent such as toluene or xylenes
  • the additive can be incorporated in natural or synthetic lubricating oils or in mixtures of such oils.
  • natural or synthetic lubricating oils such as ordinary or refined mineral oils of paraffinic or naphthenic composition and hydrorefined oils.
  • Synthetic oils such as polybutenes, alkylbenzenes such as dinonylbenzenes and tetradecylbenzene, ethers or esters of polypropylene glycols, esters of polycarboxylic acids such as methyl adipate and pentaerythritol heptanoate, silicone oils such as polysiloxanes, total or partial esters of phosphoric acid, in particular the tricresylphosphate and alkylphosphoric acids are also suitable.
  • the concentration of additives according to the invention in the ready-to-use lubricating compositions is generally of the order of 0.01 to 10% by weight and preferably from 0.1 to 2.5% by weight.
  • antioxidant compounds according to the invention with other usual additives of lubricants such as corrosion inhibitors, detergents and antiwear, dispersant and defoamer additives.
  • the lubricant compositions containing the antioxidant compound according to the invention can be used in particular as oils for crankcases intended for internal combustion engines, as oils for crankcase, as oils for gear and to facilitate the machining of metals.
  • the stability to oxidation of lubricating compositions containing an additive of the invention is evaluated.
  • the tests are carried out at 160 ° C., using a pressurized oxygen bomb in the presence of a metal catalyst, a fuel catalyst and water so as to partially simulate the conditions under which the oil can be submitted in a gasoline engine.
  • the metal catalyst is a mixture of soluble naphthenates of Pb, Cu, Fe, Mn and Sn.
  • the oxidation stability of lubricants is assessed by measuring the induction time, that is to say the time interval between the start of the test and the rapid drop in pressure in the bomb. The longer this induction time, the more effective the antioxidant additives used in the composition of the lubricants.

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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)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)

Claims (9)

  1. Aromatischen Stickstoff enthaltende Additive mit Antioxidanswirkung für Schmieröle,
    dadurch gekennzeichnet, daß
    sie die allgemeine Formel besitzen:
    Figure imgb0007
     worin Ar und Ar′ miteinander verbunden sind, wobei sich mit dem Stickstoffatom, an das sie gebunden sind, eine heterocyclische aromatische Struktur ergibt, die ausgewählt ist unter Phenothiazin, Imidazol, Benzimidazol, Triazol oder Benzotriazol,
    - R und R′, die gleich oder verschieden sein können, einen linearen oder verzweigten Alkylenrest mit 2 bis 18 Kohlenstoffatomen bedeuten, der eventuell mit einem Halogen oder einer OH- oder NH₂-Gruppe substituiert ist,
    - X ein Sauerstoffatom, ein Schwefelatom oder eine -NH-Gruppe darstellt und
    - a eine ganze Zahl zwischen 0 und 5 ist und Y ausgewählt wird unter:

            NR₁R₂   (II)

    worin R₁ und R₂ die gleich oder verschieden sein können, ein Wasserstoffatom oder einen Alkyl-, Alkenyl-, Cycloalkyl- oder Arylalkylrest mit 1 bis 12 Kohlenstoffatomen darstellen,

            - N = CH - Ar₁   (III)

    worin Ar₁ ein Arylrest ist, der mindestens eine phenolische Gruppe enthält und ausgewählt wird unter Phenol, p-t.-butylphenol,
    2,4-Di-t.-butylphenol, 2,4-Di-t.-amylphenol, Di-t.-butylparacresol, Dodecylphenol, sulfurisiertem Dodecylphenol, Catechol, β-Naphthol oder Resorcinol,

            - NR₁ - CO - Ar₁   (IV) und

    Figure imgb0008
     worin - R₃ ein Wasserstoffatom oder ein Oligomer eines Olefins mit zwei bis fünf Kohlenstoffatomen, dessen Molekülmasse zwischen 500 und 3000 und vorzugsweise zwischen 800 und 1500 liegt.
  2. Additive nach Anspruch 1,
    dadurch gekennzeichnet, daß
    R und R′, die gleich oder verschieden sein können, einen linearen oder verzweigten Alkylenrest mit 2 bis 6 Kohlenstoffatomen, vorteilhaft mit drei Kohlenstoffatomen, darstellen.
  3. Additive nach Anspruch 1 oder 2,
    dadurch gekennzeichnet, daß
    a eine ganze Zahl zwischen 0 und 2 ist.
  4. Additive nach Anspruch 1,
    dadurch gekennzeichnet, daß
    R₁ und R₂, die gleich oder verschieden sein können, ein Wasserstoffatom oder einen Alkylrest mit 1 bis 4 Kohlenstoffatomen darstellen.
  5. Additive nach Anspruch 1,
    dadurch gekennzeichnet, daß
    daß R₁ ein Wasserstoffatom und R₂ einen Arylalkylrest der allgemeinen Formel - CH₂ - Ar₁ darstellen.
  6. Additive nach Anspruch 5,
    dadurch gekennzeichnet, daß
    das Arylradikal Ar₁ 2,4-Di-t.-butylphenol oder sulfurisiertes Dodecylphenol ist.
  7. Additive nach Anspruch 1,
    dadurch gekennzeichnet, daß
    die heterocyclische aromatische Struktur Phenothiazin ist.
  8. Schmiermittelzusammensetzung,
    dadurch gekennzeichnet, daß
    sie ein natürliches oder synthetisches Schmieröl und 0,01 bis 10 Masse-% und vorzugsweise 0,1 bis 2,5 Masse-% eines Additivs nach einem der Ansprüche 1 bis 7 enthält.
  9. Zusammensetzung nach Anspruch 8,
    dadurch gekennzeichnet, daß
    sie andere übliche Schmiermitteladditive, wie Korrosionsinhibitoren, Detergenzien, Antiverschleißmittel, Dispergiermittel und Antischaummittel enthält.
EP89403355A 1988-12-05 1989-12-05 Stickstoffhaltige Additive mit Antioxidwirkung und diese enthaltende Schmiermittelgemische Expired - Lifetime EP0377358B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8815913 1988-12-05
FR8815913A FR2639956B1 (fr) 1988-12-05 1988-12-05 Additifs azotes a effet antioxydant et compositions lubrifiantes renfermant lesdits additifs

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EP0377358A2 EP0377358A2 (de) 1990-07-11
EP0377358A3 EP0377358A3 (en) 1990-09-19
EP0377358B1 true EP0377358B1 (de) 1993-03-24

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JP (1) JP2797007B2 (de)
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8268761B2 (en) * 2009-12-08 2012-09-18 Chevron Oronite Company Llc Aminomethyl-substituted imidazole compounds for use as friction modifiers in lubricating oil compositions
JP2016117788A (ja) * 2014-12-18 2016-06-30 Ｊｘエネルギー株式会社 潤滑油添加剤、および潤滑油組成物

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB672875A (en) * 1942-07-01 1952-05-28 Anglamol Ltd Improvements in lubricating compositions containing extreme pressure addition agents
GB601419A (en) * 1944-12-13 1948-05-05 Carbide & Carbon Chem Corp Improvements in or relating to synthetic lubricant compositions
GB684640A (en) * 1949-11-14 1952-12-24 Socony Vacuum Oil Co Inc Reaction products of n-acylated polyalkylenepolyamines with alkenyl succinic acids or anhydrides or derivatives thereof
US3402200A (en) * 1966-05-19 1968-09-17 Universal Oil Prod Co N-polyaminopolyalkylenephenylenediamines
US3647694A (en) * 1969-05-29 1972-03-07 Cities Service Oil Co Lubricating oil composition
FR2140646A1 (en) * 1971-06-11 1973-01-19 Grace W R Ltd Oxidation stabilised ester lubricants - contg sec or tert aromatic amines and substd phenothiazines
US4116875A (en) * 1975-05-09 1978-09-26 Mobil Oil Corporation Multifunctional substituted triazine functional fluid additives and compositions containing same
US4247300A (en) * 1978-04-27 1981-01-27 Phillips Petroleum Company Imidazoline fuel detergents
GB8332797D0 (en) * 1983-12-08 1984-01-18 Ciba Geigy Ag Antioxidant production
US4785095A (en) * 1986-09-16 1988-11-15 The Lubrizol Corporation N-substituted thio alkyl phenothiazines

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Publication number Publication date
DE68905587T2 (de) 1993-09-23
DE68905587D1 (de) 1993-04-29
JPH02194094A (ja) 1990-07-31
JP2797007B2 (ja) 1998-09-17
EP0377358A2 (de) 1990-07-11
EP0377358A3 (en) 1990-09-19
FR2639956A1 (fr) 1990-06-08
FR2639956B1 (fr) 1993-04-23

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