EP0404650B1 - Überbasischen Molybdänkomplex enthaltende Schmieröladditive, Verfahren zu ihrer Herstellung und Zusammensetzung, die sie enthalten - Google Patents

Überbasischen Molybdänkomplex enthaltende Schmieröladditive, Verfahren zu ihrer Herstellung und Zusammensetzung, die sie enthalten Download PDF

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Publication number
EP0404650B1
EP0404650B1 EP90401695A EP90401695A EP0404650B1 EP 0404650 B1 EP0404650 B1 EP 0404650B1 EP 90401695 A EP90401695 A EP 90401695A EP 90401695 A EP90401695 A EP 90401695A EP 0404650 B1 EP0404650 B1 EP 0404650B1
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EP
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Prior art keywords
amine
molybdenum
additives according
complex
additives
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French (fr)
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EP0404650A1 (de
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Roger Gallo
Pierre Hoornaert
Jean-Philippe Roman
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Societe National Elf Aquitaine
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Societe National Elf Aquitaine
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • 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
    • C10M159/18—Complexes with metals
    • 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
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/09—Complexes with metals
    • 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
    • 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

  • This invention relates to overbased additives for lubricating oils containing an organic complex of molybdenum practically insoluble in hydrocarbons.
  • Overbased additives are alkali or alkaline earth metal salts of organic acids, overbased by carbonation with carbon dioxide.
  • the term overbased is used to designate the excess of alkali or alkaline earth metal over the stoichiometric amount necessary to neutralize the organic acid used.
  • the structure of the overbased additives is that of a colloidal dispersion, the micelles of which contain the alkali or alkaline earth metal carbonate formed during carbonation.
  • the micelles are stabilized by the alkali or alkaline earth metal salts of organic acids which have a detergent effect.
  • the salts of organic acids used in overbased additives are generally sulfonates, salicylates or sulfurized phenates, described respectively in US Patents 4,604,219, EP-A 279,493 and FR 2,305,494.
  • overbased additives are particularly useful in lubricants used in internal combustion engines of the "gasoline” type or of the "diesel” type.
  • molybdenum additives in lubricants as friction reducers.
  • the most ancient product used is molybdenum disulphide in the form of a stable dispersion.
  • oil-soluble compounds of molybdenum there may be mentioned the dithiocarbamates (EP-A 205 165), and the complexes of molybdenum with oxazoline (US 4,176,073).
  • Molybdenum complexes with compounds containing basic nitrogen from succinimides, amides, phosphonamides or Mannich bases are used in the sulfurized form (US 4,263,152, US 4,369,119, US 4,395,343).
  • molybdenum is incorporated in the form of an inorganic compound, during (US 4,601,837) or after (US 3,496,105) overbasing.
  • molybdenum derivative is incorporated into the micelles of the colloidal dispersion with the alkali or alkaline earth metal carbonate.
  • the incorporation of the molybdenum derivative into the micelle results in the formation of a single multifunctional additive, having the properties of overbased additives and those of molybdenum derivatives.
  • the advantage of this multifunctional additive compared to mixtures of overbased detergents and oil-soluble derivatives of molybdenum, lies in their greater stability and the fact that there is no competition between the two additives for access to the metal surface to be lubricated.
  • the additives according to the invention have antiwear, friction reducing and antioxidant properties in lubricant formulations.
  • This invention therefore relates to overbased additives for lubricating oils, composed of at least one detergent and of an alkali or alkaline earth metal carbonate in a diluting oil which is in the form of a colloidal dispersion, the micelles of which contain said carbonate. characterized in that at least one organic complex of molybdenum practically insoluble in hydrocarbons is incorporated in the micelles of the colloidal dispersion.
  • the amine-molybdenum complexes are particularly suitable.
  • the amine-molybdenum complexes are prepared by the reaction of an inorganic molybdenum compound with an acid reaction, with an amine.
  • molybdenum compounds can be listed molybdic acid, alkaline molybdates, sodium hydrogen molybdate, ammonium molybdate, MoOCl4, MoO2 Br2, Mo2O3Cl6 and molybdenum trioxide.
  • Sodium molybdate and ammonium molybdate are preferably used.
  • the amines used have an aliphatic or aromatic structure.
  • primary, secondary or tertiary amines are suitable provided that they form complexes with molybdenum complexes which are practically insoluble in hydrocarbons.
  • the use of primary amines, whose complexes with molybdenum are not very soluble in hydrocarbons is particularly recommended.
  • the amine group can be attached to a primary carbon, as in the amines already mentioned, but also to a secondary or tertiary carbon, as in 1-amino-1,1-dimethyl-decane and 1-amino-1,1 -dimethyl-dodecane.
  • secondary amines in which the total number of carbon does not exceed 12, generally give, with molybdenum, complexes insoluble in hydrocarbons.
  • diamines having a primary amine group are also recommended.
  • diamines of general formula (I) are sold by the company CECA S.A. under the name of DINORAM.
  • R1 represents hydrogen and R2 represents saturated or unsaturated aliphatic radicals derived from fatty acids. They are generally mixtures containing C12 to C18 alkyl radicals.
  • the amine-molybdenum complex is generally prepared in an aqueous medium.
  • the amine is added to an aqueous solution of mineral molybdenum compound.
  • the reaction medium is maintained at a temperature between 20 and 100 ° C, preferably between 50 and 90 ° C, for 0.5 to 3 hours after the addition of the amine.
  • the amount of acid necessary for neutralizing the reaction medium is added before or after the introduction of the amine.
  • a strong mineral acid is used, preferably sulfuric acid.
  • the amine-molybdenum complex precipitates. It is recovered by filtration, washed with water and optionally dried.
  • the complex has a solid or pasty appearance, depending on the type of amine used. Its color varies from white to blue. It is practically insoluble or very sparingly soluble in hydrocarbons.
  • the atomic ratio of nitrogen to molybdenum in the complex is generally between 0.25 and 4 and preferably between 0.5 and 2.
  • the molybdenum content of the complex varies depending on the nature of the amine used: it is between approximately 10 and 45%.
  • organic molydene complexes mention may also be made of complexes with oxygenated compounds.
  • glycols 1-2, 1-3 and 1-4 Particularly suitable are glycols 1-2, 1-3 and 1-4.
  • ethylene glycol and propylene glycol are used.
  • alkoxylated amines or polyamines, preferably with ethylene oxide or propylene oxide are also suitable.
  • ethylene oxide or propylene oxide are also suitable.
  • diethanolamine or tri-ethanolamine we can mention the derivatives of diethanolamine or tri-ethanolamine.
  • the preparation of these complexes can be carried out by heating the oxygenated compound to 90-100 ° C., in the presence of a molybdenum compound, such as ammonium molybdate.
  • a molybdenum compound such as ammonium molybdate.
  • the water produced by the reaction is removed under a stream of nitrogen.
  • the molybdenum content of the complexes obtained varies between 7 and 50% by weight, depending on the degree of elimination of the unreacted oxygenated compound.
  • the organic molybdenum complex can be sulfurized for example by the action of sulfuric anhydride (H2S) on a suspension of the complex in an aromatic solvent such as xylene or toluene, at a temperature between 40 ° C and 100 ° C. As soon as sulfuric anhydride is introduced, the color of the suspension changes from blue-green to orange and then to red.
  • the quantity of sulfuric anhydride introduced is such that the atomic ratio of sulfur to molybdenum is between approximately 1 and 3.
  • the process for the preparation of overbased additives according to the invention consists in carbonating a mixture containing a detergent or a detergent precursor, a derivative of an alkali or alkaline earth metal, a nitrogenous and / or oxygenated promoter, optionally a hydrocarbon solvent, a diluent oil and / or water, characterized in that said mixture contains at least one organic complex of molybdenum practically insoluble in hydrocarbons.
  • detergents which can be used in the context of the invention, there may be mentioned sulfonates, phenates, naphtenates, salicylates, phosphonates and thiophosphonates alkali or alkaline earth soluble in the hydrocarbon medium.
  • the sulfonic acids used for the preparation of the sulfonates can be of petroleum or synthetic origin. Petroleum sulfonic acids are prepared by sulfonation of oils from the distillation of petroleum. Their structure does not correspond to a well defined formula but their average molecular weight must be at least equal to 300.
  • Synthetic sulfonic acids are prepared by alkylation of aromatic compounds such as benzene, toluene, xylene or naphthalene with olefinic cuts and then by sulfonation of the alkylate obtained.
  • aromatic compounds such as benzene, toluene, xylene or naphthalene with olefinic cuts and then by sulfonation of the alkylate obtained.
  • the structure of the alkyl chains attached to the nucleus is linear or branched depending on the olefins used for the alkylation.
  • the number of carbon atoms per alkyl chain is greater than or equal to 8.
  • the preparation of the alkali or alkaline earth metal sulfonate is carried out by bringing the sulfonic acid into contact with an alkali or alkaline earth metal derivative (preferably oxide or hydroxide) in a hydrocarbon solvent, optionally in the presence of an alcohol.
  • an alkali or alkaline earth metal derivative preferably oxide or hydroxide
  • the alkali or alkaline earth metal phenates are prepared under analogous or substantially different temperature conditions, from sulfurized alkylphenol or alkylphenol.
  • the phenol ring can carry one or two linear or branched alkyl chains, having at least eight carbon atoms.
  • the most common compound is dodecylphenol.
  • the optional sulfurization of phenol is carried out by the action of sulfur monochloride S2 Cl2 or by the action of elemental sulfur at temperatures ranging from 150 to 200 ° C.
  • the sulfurized product contains approximately 1 to 1.5 sulfur atoms per phenolic nucleus.
  • the alkylsalicylic acids are prepared by alkylation of salicylic acid or by carboxylation under pressure of alkylphenols.
  • the alkyl chain contains a minimum of 12 carbon atoms.
  • the phosphonates and thiophosphonates are prepared by the action of P2O5 or P2S5 on a polyisobutene then neutralization with an alkali or alkaline earth oxide or hydroxide.
  • the molecular weight of polyisobutene is between 300 and 2000.
  • All of these detergents can be used in admixture with dispersants soluble in a hydrocarbon medium, for example of the alkylsuccinimide type or esters of alkylsuccinic acids with a molecular weight of 300 to 2500.
  • reaction medium can contain the precursors. In this case, neutralization is carried out in the reaction medium just before carbonation.
  • the alkali or alkaline earth metal derivatives can be oxides, hydroxides or alcoholates.
  • the preferred derivatives are oxides and hydroxides.
  • the reaction medium is added to stoichiometric excess relative to the detergent or its precursor.
  • the stoichiometric excess can vary between 5: 1 and 30: 1.
  • an oxygenated promoter is introduced into the reaction medium before carbonation, which is generally an aliphatic or aromatic alcohol, an alkoxyalkanol, a glycol or even an alkanolamine.
  • reaction medium which is generally an aliphatic or aromatic alcohol, an alkoxyalkanol, a glycol or even an alkanolamine.
  • aliphatic alcohols C1 to C20 or mixtures thereof.
  • the aliphatic alcohols can be used in admixture with glycols, alkoxyalkanols or alkanolamines.
  • the molar ratio of the oxygenated promoter to the detergent is generally between 1 and 30.
  • nitrogenous promoter is optional.
  • This nitrogenous promoter is generally chosen from ammonia, ammonium salts, primary, secondary or tertiary amines in C2 to C10 and their salts with carboxylic acids or boric acid, polyamines or even alkanolamines.
  • ammonia, carbonate and ammonium chloride, ethylenediamine, ethanolamine or diethanolamine are preferred.
  • the promoter to detergent molar ratio is generally between 1 and 30.
  • the hydrocarbon solvent allows perfect homogenization of the various reagents as well as a lowering of the viscosity which will subsequently facilitate the recovery of solid carbonation residues.
  • the solvent represents from 10 to 70% by weight of the reaction mixture.
  • the solvents used are the aliphatic or aromatic compounds in C6 and C12.
  • Preferred solvents are aromatic solvents such as benzene, toluene, xylene, ethylbenzene and chlorinated aromatics. Their choice is dictated by the characteristics of the additive collected, by their boiling point and by the boiling point of the azeotropes which they can form with oxygenated promoters and water.
  • the handling of the molybdenum overbased additive obtained according to the invention is facilitated by the addition of oil.
  • the oil represents approximately 20 to 50% by weight of the additive obtained. This can be added to the reaction medium before carbonation or even after this, that is to say just before the removal of the solvent.
  • the diluent oils used are paraffinic in nature, of the 100 or 150 Neutral solvent type or predominantly naphthenic in nature such as 100 - 150 pale solvent.
  • the carbonation reaction can be carried out after optional addition of water to the reaction medium.
  • the addition of water is particularly beneficial when the alkali or alkaline earth metal derivative is an oxide.
  • the amount of water added is such that the water / metal oxide molar ratio is of the order of 0.5.
  • Neutralization of the detergent precursor is then carried out, followed by carbonation of the stoichiometric excess of the alkali or alkaline earth metal derivative at a temperature between room temperature and the reflux temperature of the mixture.
  • the molar ratio of CO2 introduced to the stoichiometric excess of alkali or alkaline earth metal is between 0.6 and 1.2.
  • the mixture is optionally stabilized by heating under vacuum or under a stream of nitrogen so as to eliminate the oxygenated promoters of low boiling point and the water added as well as the water produced by carbonation. Solid residues are removed by centrifugation and / or filtration using diatomaceous earth. If the diluent oil has not been added before carbonation, it is then added before possible elimination of the hydrocarbon solvent and heavy alcohols, by heating under vacuum at temperatures of the order of 100 to 200 ° C.
  • the filtration operation can be carried out after recovery of the solvent.
  • the overbased products containing molybdenum, obtained according to the invention are clear and stable, brown in color for the sulfonates, dark green for the phenates and black for the salicylates.
  • the color is generally red for overbased detergents in the presence of a sulfurized complex.
  • the rate of incorporation of molybdenum into the additive is close to 100%, significantly higher than the rates obtained during the incorporation of inorganic derivatives of molybdenum.
  • the additive contains between 0.1 to 10% by weight and preferably 1 to 4% of molybdenum.
  • overbased additives according to the invention are entirely soluble in hydrocarbons. They are incorporated into lubricating oils of natural or synthetic origin at a concentration of between 0.5 and 40% by weight and preferably between 1 and 30% by weight.
  • the lubricant compositions thus obtained can contain other additives, with antiwear, dispersing, antioxidant effect, and polymers improving the viscosity index.
  • the basicity of these overbased additives is characterized by their alkaline value (VA) expressed in mg of KOH per gram of product. It is determined by titration using a strong acid according to standard ASTM D-2896.
  • a solution of 41.17 g of sodium molybdate Na2MoO4, 2H2O in 100 ml of water is produced.
  • the medium is acidified by the addition of 55.6 g of 30% H2SO4 and then heated to 60 ° C.
  • 21g Dinoram C from CECA SA is added.
  • Dinoram C corresponds to the formula R-NH- (CH2) 3-NH2 where R is a mixture of linear and saturated alkyl radicals, 60% C de, 20% C14, 10% C16 and 5% C18.
  • the aforementioned blue is recovered by filtration and then washed with water and methanol before drying. Finally recovered 47.1 g of blue solid containing 32.6% molybdenum and 4.4% nitrogen.
  • Example A The procedure is as in Example A but the addition of Diroram C is carried out at 60 ° C before heating and before acidification.
  • the pale blue solid recovered contains 34.1% molybdenum, 0.3% sodium and 4.46% nitrogen.
  • a dispersion of 20 g of the complex prepared in Example A is produced in 200 ml of xylene.
  • 6.7 g of H2S are injected; the dark red solid collected after removal of the solvent contains 28.4% molybdenum, 3.8% nitrogen and 23.7% sulfur.
  • the procedure is as in the example, but 9.68 g of sodium molybdate in 35 ml of water are used. 4.8 g of Dinoram O (PM 270) from CECA SA are added at 65 ° C. before heating the medium for 1 hour at 60 ° C. Dinoram O is an N-alkyl-propylene-diamine. The alkyl radical corresponds to a mixture containing 80% of oleyl radical. We then observe the gradual formation of a white solid which turns blue during acidification. After washing and drying, 8.85 g of a blue solid are recovered containing 23% molybdenum.
  • Noram C is a monoamine, R-NH2 where R is a mixture of linear and saturated alkyl radicals, 60% C de, 20% C14, 10% C16 and 5% C18. 11 g of a light blue solid containing 26.7% molybdenum are finally recovered.
  • Example D The procedure is as in Example D but 6.74 g of stearylamine from CECA SA are used. 7.68 g of a pale blue solid containing 20.5% of molybdenum and 3.4% of nitrogen are recovered.
  • Primene 81-R is a mixture of two monoamines, 1-amino-1,1-dimethyl-decane and 1-amino-1,1-dimethyl-dodecane. 15.75 g of a blue pasty product containing 12.5% molybdenum are collected.
  • Example B The procedure is as in Example B, but 9.9 g of 98% ethyl-2-hexylamine are introduced over 20 minutes in an aqueous solution containing 15.44 g of sodium molybdate and maintained at 60 ° C. After heating for 45 minutes at 60 ° C., acidification is carried out with 23.1 g of 30% sulfuric acid, before washing and drying the product. This is in the form of a white solid containing 36.8% molybdenum and 4.38% nitrogen.
  • Example A The procedure is as in Example A, but an aqueous solution containing 48.4 g of sodium molybdate is acidified with 65.4 g of 30% sulfuric acid. The solution being maintained at 60 ° C. 52.2 g of p-dodecyl aniline are added. The blue green pasty solid is dissolved in xylene in order to remove the water therefrom by azeotropic distillation. After removal of the solvent, 80 g of pasty solid containing 11.5% molybdenum and 3.41% nitrogen are recovered. It can be noted that the complexes prepared in Examples A to I are practically insoluble in hydrocarbon compounds as well as in water or in alcohols.
  • the methanol and the water produced by the reaction are removed by heating the mixture under partial vacuum.
  • the product is clear brown and stable when diluted in mineral or synthetic oils. No clouding or settling is observed after several weeks at 60 ° C.
  • Example 2 The procedure is as in Example 1, but 219.2 g of alkyl aryl sulfonic acid with branched alkyl chain (didodecylbenzenesulfonic acid) are introduced, the molecular weight of which is 520 and at 70% of active material. The amount of diluent oil is 108g. The product is in the form of a brown liquid of VA 304. It is stable when diluted in lubricating oils.
  • Example 2 The procedure is as in Example 1, but 32 g of the complex prepared in Example I are introduced before the other reagents in 520 ml of xylene. The procedure is identical to that of Example 1 except that the residues are removed by centrifugation.
  • Example 2 The procedure is as in Example 1, but successively introduced into the reactor - 600 ml of xylene, 132 g of didodecylbenzene sulfonic acid of molecular weight 520g and at 70% of active material - 30g of the complex prepared in Example A - 104g of slaked lime - 52ml of methanol - 4.4ml of ammonia and 90g of diluent oil.
  • the product collected is brown, clear and stable in oils.
  • the calcium and molybdenum contents are 10 and 2.35 respectively.
  • 77.8 g of dodecylphenol and 20 g of sulfur chloride are introduced at a temperature of 20 to 30 ° C. into a 250 ml reactor equipped with a temperature-regulating cooler and a gas bubbling device.
  • the mixture is heated under nitrogen sweep and with stirring for one hour at 150 ° C then 1 hour at 180 ° C and finally 1 hour at 200 ° C.
  • the sulfurized dodecylphenol is collected, the respective chlorine and sulfur contents of which are 2200 ppm and 11.4%.
  • Example 14 The procedure is as in Example 14, but 27 g of the complex prepared in Example B are introduced before the lime.
  • the product collected at the end of the operations and dark brown, stable in oils.
  • VA 197, its molybdenum content of 1.77%.
  • the performance of new overbased detergents containing molybdenum is examined in laboratory tests of wear, friction and oxidation.
  • the test matrices correspond to lubricants for land engines on the one hand and for marine engines on the other.
  • the products are tested in a lubricant formulation used in petrol engines (ELF Presti 15 W 40) by simply replacing the overbased detergent.
  • the samples contain 1.25% overbased detergent.
  • the test is carried out under the following conditions: Lapping 5 minutes under 200 lbs (normal load) 3 hours under 540 lbs (normal load) At the end of the test, the value of the friction torque, the wear in number of teeth of the ratchet wheel and the temperature of the oil bath tested are noted. (The wear is as much lower as the number of teeth, the friction torque and the temperature are lower). Table 1 shows that the overbased sulfonates containing an amine-molybdenum complex allow a reduction of 50 to 70% on average in the friction torque.
  • the TFOUT test (thin film oxygen uptake test) is performed on the same essence formulations. It is carried out at 160 ° C. in a pressurized oxygen bomb (90 psi) in the presence of metal catalyst (Naphtenate of Pb, Cu, Fe, Mn and Sn), water and nitro petrol oxidized so as to partially simulate the conditions to which oil can be subjected in a petrol engine.
  • Table 3 gives values of the induction time, that is to say the time between the start of the test and the start of the rapid pressure drop in the bomb.
  • the increase in the induction time is significant in the presence of the additive containing the molybdenum-amine complex.
  • overbased detergents containing molybdenum are then tested in a lubricant formulation for a marine engine (cylinder oil).
  • the basicity of the oil is 70 mg KOH / g of which only 20 mg KOH / g provided by the overbased detergent.
  • the oil also contains 0.5% DTPZ.

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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)

Claims (29)

  1. Für Schmieröle bestimmte überalkalisierte Zusätze, zusammengesetzt aus wenigstens einem Detergens und einem Alkali- oder Erdalkalimetallcarbonat in einem Verdünnungsöl, die in Form einer Kolloiddispersion mit das Carbonat enthaltenden Mizellen vorliegen, dadurch gekennzeichnet, daß wenigstens ein in den Kohlenwasserstoffen praktisch unlöslicher organischer Molybdänkomplex in die Mizellen der Kolloiddispersion aufgenommen ist.
  2. Zusätze nach Anspruch 1, dadurch gekenn zeichnet, daß sie 0,1 bis 10, vorzugsweise 1 bis 4 Gew.-% Molybdän enthalten.
  3. Zusätze nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der organische Molybdänkomplex mit einem Amin gebildet ist.
  4. Zusätze nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß der Amin-Molybdän-Komplex hergestellt ist durch Umsetzung einer anorganischen, sauer reagierenden Molybdänverbindung mit einem Amin.
  5. Zusätze nach Anspruch 4, dadurch gekennzeichnet, daß die anorganische Molybdänverbindung Molybdänsäure, ein Alkalimolybdat, Natriumhydrogenmolybdat, Ammoniummolybdat, MoOCl₄, MoO₂Br₂, MO₂O₃Cl₆ oder Molybdäntrioxid, vorzugsweise jedoch Natrium- oder Ammoniummolybdat, ist.
  6. Zusätze nach Anspruch 4, dadurch gekennzeichnet, daß das Amin ein aliphatisches primäres, sekundäres oder tertiäres Amin ist.
  7. Zusätze nach Anspruch 6, dadurch gekennzeichnet, daß das Amin ein primäres Amin wie Oleylamin, Stearylamin, Dodecylamin, tert.-Dodecylamin, Ethyl-2-Hexylamin, Cyclohexylamin, 1-Amino-1,1-dimethyldecan und 1-Amino-1,1-dimethyl-dodecan ist.
  8. Zusätze nach Anspruch 6, dadurch gekennzeichnet, daß das Amin ein sekundäres Amin mit einer Gesamtzahl an C-Atomen von höchstens 12 ist.
  9. Zusätze nach Anspruch 4, dadurch gekennzeichnet, daß das Amin ein aromatisches Amin wie p-Dodecylanilin ist.
  10. Zusätze nach Anspruch 4, dadurch gekennzeichnet, daß das Amin ein Diamin mit einer primären Amingruppe ist.
  11. Zusätze nach Anspruch 10, dadurch gekennzeichnet, daß das Diamin der allgemeinen Formel R₁R₂N-(CH₂)n-NH₂ (I) entspricht, worin R₁ und R₂ gleiche oder verschiedene Bedeutungen haben und für Wasserstoff oder einen gesättigten oder ungesättigten, unverzweigten oder verzweigten aliphatischen C₁-C₃₀- oder vorzugsweise C₈-C₂₀-Rest stehen, wobei einer der Reste R₁ oder R₂ unbedingt einen aliphatischen Rest darstellt und n einen Wert zwischen 1 und 8, vorzugsweise zwischen 2 und 4, bedeutet.
  12. Zusätze nach Anspruch 11, dadurch gekennzeichnet, daß in der allgemeinen Formel I R₁ Wasserstoff und R₂ einen von Fettsäuren oder Fettsäuregemischen abgeleiteten, gesättigten oder ungesättigten Rest bedeuten.
  13. Zusätze nach Anspruch 12, dadurch gekennzeichnet, daß R₂ wenigstens einem gesättigten oder ungesättigten C₁₂-C₁₈-Alkylrest entspricht.
  14. Zusätze nach einem der Ansprüche 3 bis 13, dadurch gekennzeichnet, daß das Atomverhältnis zwischen Stickstoff und Molybdän im Komplex zwischen 0,25 und 4 und vorzugsweise zwischen 0,5 und 2 liegt und der Molybdängehalt zwischen 10 und 45 Gew.-%.
  15. Zusätze nach einem der Ansprüche 3 bis 14, dadurch gekennzeichnet, daß der Amin-Molybdän-Komplex hergestellt wird durch Zugabe des Amins zu einer wässerigen Lösung der anorganischen Molybdänverbindung, wobei die Temperatur zwischen 20 und 100°C, vorzugsweise zwischen 50 und 90°C während 0,5 bis 3 Stunden nach Zugabe des Amins gehalten wird.
  16. Zusätze nach Anspruch 15, dadurch gekennzeichnet, daß das Reaktionsmedium durch Zugabe einer starken Mineralsäure, vorzugsweise Schwefelsäure, vor oder nach der Zugabe des Amins neutral gestellt wird.
  17. Zusätze nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der organische Molybdänkomplex mit Hilfe einer Sauerstoff enthaltenden Verbindung gebildet wird.
  18. Zusätze nach Anspruch 17, dadurch gekennzeichnet, daß die Sauerstoff enthaltende Verbindung ein alkoxyliertes Amin oder Polyamin ist.
  19. Zusätze nach Anspruch 18, dadurch gekennzeichnet, daß das Amin oder Polymain mit Ethylen- oder Propylenoxid alkoxyliert wird.
  20. Zusätze nach Anspruch 18 oder 19, dadurch gekennzeichnet, daß das alkoxylierte Amin oder Polyamin ein Diethanolamin- oder Triethanolaminderivat ist.
  21. Zusätze nach Anspruch 17, dadurch gekennzeichnet, daß die Sauerstoff enthaltende Verbindung ein 1-2-, 1-3- oder 1-4-Glykol, vorzugsweise Ethylen- oder Propylenglykol ist.
  22. Zusätze nach Anspruch 17, dadurch gekennzeichnet, daß die Sauerstoff enthaltende Verbindung ein Polyol wie Glycerin oder Trimethylolpropan ist.
  23. Zusätze nach einem der Ansprüche 17 bis 22, dadurch gekennzeichnet, daß der organische Molybdänkomplex 7 bis 50 Gew.-% Molybdän enthält.
  24. Zusätze nach einem der Ansprüche 1 bis 23, dadurch gekennzeichnet, daß der organische Molybdänkomplex in geschwefelter Form verwendet wird.
  25. Zusätze nach Anspruch 24, dadurch gekennzeichnet, daß der Komplex mit Schwefelwasserstoff geschwefelt ist.
  26. Verfahren zur Herstellung überalkalisierter Zusätze gemäß den Ansprüchen 1 bis 25 durch Überführung eines ein Detergens bzw. einen Detergensprecursor, ein Alkali- oder Erdalkalimetallderivat, einen Stickstoff enthaltenden Promotor und/oder einen Sauerstoff enthaltenden Promotor und gegebenenfalls ein Kohlenwasserstofflösungsmittel sowie ein Verdünnungsöl und/oder Wasser enthaltenden Gemisches in die Carbonatform, dadurch gekennzeichnet, daß das in die Carbonatform überzuführende Gemisch wenigstens einen in Kohlenwasserstoffen praktisch unlöslichen organischen Molybdänkomplex enthält.
  27. Verfahren nach Anspruch 26, dadurch gekennzeichnet, daß das Detergens ausgewählt wird unter Sulfonaten, Phenolaten, Naphthenaten, Salicylaten, Phosphonaten und Alkali- oder Erdalkalithiophosphonaten.
  28. Schmiermittelgemisch, dadurch gekennzeichnet, daß es ein Schmieröl natürlichen oder synthetischen Ursprungs und 0,5 bis 40, vorzugsweise 1 bis 30 Gew.-% eines Zusatzes nach einem der Ansprüche 1 bis 25 enthält.
  29. Gemisch nach Anspruch 28, dadurch gekennzeichnet, daß es Verschleißfestigkeit verleihende Zusätze, einen Dispergator, ein Antioxydans und die Viskositätszahl erhöhende Polymere enthält.
EP90401695A 1989-06-19 1990-06-15 Überbasischen Molybdänkomplex enthaltende Schmieröladditive, Verfahren zu ihrer Herstellung und Zusammensetzung, die sie enthalten Expired - Lifetime EP0404650B1 (de)

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FR8908095A FR2648473B1 (fr) 1989-06-19 1989-06-19 Additifs surbases pour huiles lubrifiantes renfermant un complexe du molybdene, leur procede de preparation et compositions renfermant lesdits additifs
FR8908095 1989-06-19

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US6528463B1 (en) 2000-03-23 2003-03-04 Ethyl Corporation Oil soluble molybdenum compositions
US6509303B1 (en) * 2000-03-23 2003-01-21 Ethyl Corporation Oil soluble molybdenum additives from the reaction product of fatty oils and monosubstituted alkylene diamines
KR100446813B1 (ko) * 2001-01-06 2004-09-01 이근희 호안 블록과 이것을 이용한 수변 식생대의 시공방법
JP4066132B2 (ja) * 2001-10-15 2008-03-26 株式会社Ａｄｅｋａ 潤滑剤及び潤滑性組成物
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AU2016307780B2 (en) 2015-08-14 2019-02-21 Vanderbilt Chemicals, Llc Additive for lubricant compositions comprising an organomolybdenum compound, and a derivatized triazole
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ES2060977T3 (es) 1994-12-01
FR2648473B1 (fr) 1994-04-01
JPH0335094A (ja) 1991-02-15
DE69004163T2 (de) 1994-05-11
US5143633A (en) 1992-09-01
FR2648473A1 (fr) 1990-12-21
DE69004163D1 (de) 1993-12-02
JP2883167B2 (ja) 1999-04-19
EP0404650A1 (de) 1990-12-27

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