EP0184043A2 - Lubricant additive - Google Patents

Lubricant additive Download PDF

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Publication number
EP0184043A2
EP0184043A2 EP85114438A EP85114438A EP0184043A2 EP 0184043 A2 EP0184043 A2 EP 0184043A2 EP 85114438 A EP85114438 A EP 85114438A EP 85114438 A EP85114438 A EP 85114438A EP 0184043 A2 EP0184043 A2 EP 0184043A2
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EP
European Patent Office
Prior art keywords
lubricant additive
additive according
lubricant
tertiary amine
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP85114438A
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German (de)
French (fr)
Other versions
EP0184043B1 (en
EP0184043A3 (en
Inventor
Hans Dipl.-Chem. Schreiber
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Optimol-Olwerke GmbH
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Optimol-Olwerke GmbH
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Priority to AT85114438T priority Critical patent/ATE37558T1/en
Publication of EP0184043A2 publication Critical patent/EP0184043A2/en
Publication of EP0184043A3 publication Critical patent/EP0184043A3/en
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Publication of EP0184043B1 publication Critical patent/EP0184043B1/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/18—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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • 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
    • C10N2010/02—Groups 1 or 11
    • 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

Definitions

  • the invention relates to a new lubricant additive.
  • the known additives improve the basic lubricants with regard to the desired properties, such as. B. Reduction of abrasion, improvement of the lubricating film adhesion, increase of the oxidation resistance, lowering of the temperatures occurring during the friction, the continuous operating temperature etc., however, no longer meet the ever increasing requirements to a satisfactory extent.
  • the object of the present invention is therefore to provide a lubricant additive which further improves the properties of lubricants to such an extent that they meet the highest requirements fully satisfactorily. This object is achieved with the present invention.
  • the invention relates to a lubricant additive which can be obtained by reacting a salt of a tertiary amine which, as N-substituents, has two polyethylene oxide radicals with two or more ethylene oxide groups, the free OH group of which may be etherified or acylated, and a saturated or unsaturated long-chain alkyl group Ammonium molybdate and / or Mo03 (molybdic acid).
  • the tertiary amine salt is preferably used in a molar ratio of 1: 1 or greater; in particular, the weight ratio of tertiary amine salt to ammonium molybdate ((NH 4 ) 2 MoO 4 ) or MoO 3 is 50 to 70 to 20 to 40, and more preferably 60 to 25.
  • ammonium molybdate is also understood to mean ammonium heteropolymolybdates or ammonium isomolybdates.
  • it may be appropriate to choose the length of the polyethylene oxide residues according to the type of base oil or fat to which the lubricant additive according to the invention is to be added; Long chain polyethylene oxide residues, preferably with n 10 to 15, z. B. used especially for glycol-based base greases.
  • An alkyl radical with 1 to 7 carbon atoms can be branched or preferably straight-chain and is, for. B. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, 2,3- or 4-methyl-pentyl; an acyl radical with 2 to 7 carbon atoms is e.g. B. one that is derived from the alkyl radicals mentioned above, such as. B. acetyl, propionyl etc.
  • the long chain saturated or unsaturated alkyl group can also be branched, but is preferably straight chain. It is preferably an alkyl radical derived from a saturated or unsaturated fatty acid, such as, for. B. the oleic acid derived oleyl radical (ectadecenyl).
  • the alkyl radical preferably has 12 to 24 and in particular 16 to 20 carbon atoms and is primarily oleyl.
  • any organic or inorganic acids such as, for. B. fatty acids, mineral acids and the like. Acids are preferred which themselves have an active activity in lubricant compositions, such as, for. B. phosphoric acids and partially esterified phosphoric acids, boric acid, sarcosides, mercaptobenzothiazoles, thioglycolic acid and other acids with acidic mercapto groups.
  • the reaction of the tertiary amine salt with the ammonium molybdate or MoO 3 takes place, in particular with a view to its later use as a package in the form of a solution or suspension in a mineral or synthetic oil, by heating in mineral or synthetic oil; the reaction is preferably carried out at a temperature of 100 to 220 ° C., in particular at 130 to 190 ° C. It is preferably reacted in the presence of a small amount of water. Good results give water additions of about 5 to about 20 wt .-%, based on the reaction product. This accelerates the reaction and lowers the required reaction temperature in the lower range.
  • the starting materials for the reaction are known or can be prepared in a manner known per se.
  • the preparation of the tertiary amine salt can e.g. B. by reacting a primary amine that already carries the long chain alkyl group as a substituent, for. B. of oleylamine, with ethylene oxide in the molar ratio required for the desired polyethylene oxide chain; the free OH group can subsequently in a known manner, for. B. etherified or esterified by reaction with an alkyl or acyl halide.
  • the conversion into the amine salt is expediently carried out by a simple salt formation reaction of the tertiary amine with the selected acid.
  • the lubricant additive preferably further contains one or more sulfur compounds from the group consisting of sulfurized esters, heavy metal dithiophosphates and heavy metal dithiocarbamates.
  • sulfur-containing esters of vegetable, animal or synthetic origin come into consideration as sulfurized esters; typical suitable commercial products are e.g. B. Lubrizol 5003® (sold by Lubrizol GmbH, Hamburg), Maisperm 2011® (sold by Lehmann, Voss & Co., Hamburg) and sulfurized jojoba oil.
  • Suitable heavy metal dithiophosphates are generally all dithiophosphates of the transition metals and rare earth metals, in particular the thiophosphates of antimony, lead, tin, iron, copper, manganese, molybdenum, nickel, vanadium, titanium and bismuth, and primarily zinc and tellurium.
  • the corresponding dithiocarbamates can also be used. In these compounds, all or some of the sulfur can also be replaced by selenium or tellurium.
  • the ratio of reaction product of tertiary amine and molybdenum compound to sulfur compound is preferably 1: 0.5 to 1:10.
  • the lubricant additive according to the invention is expediently present as a package in the form of a solution or suspension in a base oil (mineral or synthetic oil) and is sold and used in this form.
  • the lubricant additive content (tertiary amine salt / molybdenum compound reaction product and optionally sulfur compound and / or other conventional additives) is generally 30 to 90% by weight, and in particular 50 to 70% by weight.
  • Naphthenic or paraffin-based base oils and greases can be used as mineral base oils and greases, and all the usual classes for synthetic base oils and greases.
  • suitable synthetic oils are poly-alpha-olefins, glycols, esters, alkylbenzenes and silicone oils and fats soluble in organic solvents.
  • the lubricant additives according to the invention may contain further oil-soluble or non-oil-soluble additives which are customary for lubricating oils, such as, for. B. antioxidants, rust inhibitors, density swellers, antifoams, dispersants, dyes, viscosity index improvers, extreme pressure additives, but also other lubricant additives, such as. B. the additive combinations known from DE-AS 19 54 452.
  • oil-soluble or non-oil-soluble additives which are customary for lubricating oils, such as, for. B. antioxidants, rust inhibitors, density swellers, antifoams, dispersants, dyes, viscosity index improvers, extreme pressure additives, but also other lubricant additives, such as. B. the additive combinations known from DE-AS 19 54 452.
  • lubricating oils and greases with significantly improved properties can be obtained.
  • wear is reduced by the lubricant additive according to the invention, the adhesive strength of the boundary lubrication film is improved, the oxidation stability and thus the life of the lubricant is markedly increased and the coefficient of friction and thus also the operating temperature are reduced.
  • the coefficients of friction achieved with the lubricant additive according to the invention are extremely low.
  • the amount of lubricant additive according to the invention should generally be at least 3%, based on the finished lubricant composition, where the quantities most suitable for the respective lubricant and the respective intended use can easily be determined.
  • the lubricant additive according to the invention can also be used to produce lubricating oil or grease concentrates which are then added to the lubricant to the desired concentration.
  • the additives according to the invention can be used in an acidic, neutral or basic medium.
  • the invention therefore also relates to the use of the lubricant additive according to the invention for lubricants and greases, in particular for gear and engine oils.
  • the lubricant additive according to the invention it is, for. B. possible to use oils of low viscosity in applications where previously high viscosities were absolutely necessary, such as. B. in gears and differential gears.
  • solutions of the lubricant additive according to the invention obtained according to a), b) or c) can be used as such, optionally together with a sulfurized ester, a heavy metal dithiophosphate and / or a heavy metal dithiocarbamate as a package for producing improved lubricating greases and lubricating oils.
  • a lubricant additive package is produced which is used in the examples below as an additive for lubricants becomes.
  • a lubricating oil composition which contains 3% by weight of the package obtained according to Example 2 is produced by mixing the components.
  • a lubricant composition containing 8% by weight of the lubricant additive obtained according to Example 1 c) is obtained by mixing the Components manufactured.
  • the lubricant compositions a) or b) show properties which are similar to those obtained with the comparable lubricant compositions which contain 8% by weight of the package obtained according to Example 2, and which in addition to the reaction product of tertiary amine salt and molybdenum compound contain a sulfur compound.
  • FIGS. 1 to 20 The results of the tests are illustrated in FIGS. 1 to 20 in the form of SRV test sheets.
  • Figures 1 to 12 show the properties of lubricant compositions using the lubricant additive according to the invention
  • Figures 13 to 20 show the results without lubricant additive according to the invention or with other additives.
  • FIG. 1 illustrates a test in which the lubricant composition according to Example 3a) is subjected to a load increasing from 50 to 1000 Newtons under the specified operating conditions, without the lubricating effectiveness collapsing in the process. This means that the yield point of the metal is reached in the surface roughness without the lubricating effect of the grease composition according to the invention being lost.
  • FIGS. 2 to 7 In the tests illustrated by FIGS. 2 to 7 with a lubricant composition according to the invention according to Example 3 a) and the corresponding tests drawn for comparison (FIGS. 13 to 18) with Longtime PD 2, test specimens with a lapped surface (smooth) with a ground surface were used (rough) and also those with polished surface (mirror finish) used.
  • a comparison of FIGS. 4 to 6 with 15 to 17 shows the superiority of the grease according to the invention particularly clearly in the ground surface.
  • the results of the tests with lapped and with polished surface clearly show the superiority of the lubricant according to the invention.
  • With the polished surface it is particularly noteworthy that pitting occurred with the comparative product.
  • the differences in the lapped surface become increasingly serious as the load increases, in particular in the coefficients of friction and in the profilograms, but are already clearly evident at 200 N.
  • FIG. 8 shows the results with a lubricant composition according to Example 3 b) which, in comparison to Example 3 a), contains only half the amount of lubricant additive according to the invention; in comparison to FIG. 4 (lubricant composition according to Example 3a), a longer running-in time is required, but excellent friction coefficients are then also obtained.
  • FIG. 12 shows that excellent friction coefficients and surface smoothing according to the invention are achieved even with a grease.

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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

The present invention provides a lubricant additive obtainable by the reaction of a salt of a tertiary amine, which, as N-substituents, contains two polyethylene oxide residues with two or more ethylene oxide groups, the free hydroxyl groups of which can be etherified or acylated, and one saturated or unsaturated long-chain alkyl radical, with ammonium molybdate and/or MoO3.

Description

Die Erfindung betrifft einen neuen Schmiermittelzusatz.The invention relates to a new lubricant additive.

Mit der Entwicklung der Technik nehmen auch die Anforderungen zu, welche an Schmierstoffe gestellt werden. Seit langem werden daher die Grundschmierstoffe, wie Mineral- oder Syntheseöle sowie halbfeste und feste Schmierstoffe durch Zusatz von Verbesserungsmitteln den erhöhten Beanspruchungen angepaßt.With the development of technology, the requirements placed on lubricants also increase. The basic lubricants such as mineral or synthetic oils as well as semi-solid and solid lubricants have therefore been adapted to the increased demands for a long time by the addition of improvers.

Aus der DE-AS 19 54 452 ist es z. B. bekannt, einem Schmiermittel auf der Basis von Mineralöl oder Syntheseöl einen epoxydierten Fettsäureester und gegebenenfalls eine organische Schwermetallverbindung und/oder eine Schwefelphosphorverbindung zuzusetzen. Aus der DE-OS 33 03 442 sind Schmierfette auf der Basis von Mineral-oder Syntheseölen bekannt, die als Verdickungsmittel und zur Steigerung der Dauereinsatztemperatur eine Polyharnstoffverbindung enthalten. In der US-PS 41 64 473 wird eine in Kohlenwasserstoffen lösliche Molybdänverbindung der allgemeinen Formel

Figure imgb0001

in der X = O oder S und

  • R = Kohlenwasserstoff mit 1 bis 50 C-Atomen bedeuten, als Schmiermittelzusatz beschrieben.
From DE-AS 19 54 452 it is, for. B. known to add a lubricant based on mineral oil or synthetic oil an epoxidized fatty acid ester and optionally an organic heavy metal compound and / or a sulfur phosphorus compound. From DE-OS 33 03 442 lubricating greases based on mineral or synthetic oils are known which contain a polyurea compound as a thickener and to increase the long-term use temperature. In US-PS 41 64 473 is a hydrocarbon-soluble molybdenum compound of the general formula
Figure imgb0001
in the X = O or S and
  • R = hydrocarbon with 1 to 50 carbon atoms, described as a lubricant additive.

Die bekannten Zusatzmittel verbessern zwar die Grundschmiermittel hinsichtlich der gewünschten Eigenschaften, wie z. B. Verminderung des Abriebs, Verbesserung der Schmierfilmhaftung, Erhöhung der Oxidationsbeständigkeit, Herabsetzung der bei der Reibung auftretenden Temperaturen, der Dauereinsatztemperatur usw., genügen aber den immer höher werdenden Anforderungen nicht mehr in befriedigendem Maße. Aufgabe der vorliegenden Erfindung ist deshalb die Bereitstellung eines Schmiermittelzusatzes, welcher die Eigenschaften von Schmierstoffen weiter in einem Maße verbessert, daß sie auch höchsten Anforderungen voll befriedigend entsprechen. Diese Aufgabe wird mit der vorliegenden Erfindung gelöst.The known additives improve the basic lubricants with regard to the desired properties, such as. B. Reduction of abrasion, improvement of the lubricating film adhesion, increase of the oxidation resistance, lowering of the temperatures occurring during the friction, the continuous operating temperature etc., however, no longer meet the ever increasing requirements to a satisfactory extent. The object of the present invention is therefore to provide a lubricant additive which further improves the properties of lubricants to such an extent that they meet the highest requirements fully satisfactorily. This object is achieved with the present invention.

Gegenstand der Erfindung ist ein Schmiermittelzusatz, erhältlich durch Umsetzung eines Salzes eines tertiären Amins, das als N-Substituenten zwei Polyethylenoxidreste mit zwei oder mehr Ethylenoxidgruppen, deren freie OH-Gruppe verethert oder acyliert sein kann, und eine gesättigte oder ungesättigte langkettige Alkylgruppe besitzt, mit Ammoniummolybdat und/oder Mo03 (Molybdänsäure).The invention relates to a lubricant additive which can be obtained by reacting a salt of a tertiary amine which, as N-substituents, has two polyethylene oxide radicals with two or more ethylene oxide groups, the free OH group of which may be etherified or acylated, and a saturated or unsaturated long-chain alkyl group Ammonium molybdate and / or Mo03 (molybdic acid).

Das tertiäre Aminsalz wird vorzugsweise im Molverhältnis 1:1 oder größer eingesetzt; insbesondere beträgt das Gewichtsverhältnis tertiäres Aminsalz zu Ammoniummolybdat ((NH4)2MoO4) oder Mo03 50 bis 70 zu 20 bis 40, und mehr bevorzugt 60 zu 25. Unter "Ammoniummolybdat" werden im Rahmen der Erfindung auch Ammoniumheteropolymolybdate oder Ammoniumisomolybdate verstanden.The tertiary amine salt is preferably used in a molar ratio of 1: 1 or greater; in particular, the weight ratio of tertiary amine salt to ammonium molybdate ((NH 4 ) 2 MoO 4 ) or MoO 3 is 50 to 70 to 20 to 40, and more preferably 60 to 25. In the context of the invention, “ammonium molybdate” is also understood to mean ammonium heteropolymolybdates or ammonium isomolybdates.

Die Polyethylenoxidreste können verschieden und insbesondere gleich sein und besitzen vorzugsweise die Formel RO-CH2CH2(̵O-CH2CH2)̵n, worin n = 1 bis 15 und R einen Alkylrest mit 1 bis 7 Kohlenstoffatomen oder einen Acylrest mit 2 bis 7 Kohlenstoffatomen bedeutet, und insbesondere Wasserstoff ist. In einigen Fällen kann es zweckmäßig sein, die Länge der Polyethylenoxidreste nach der Art des Grundöles oder -fettes, dem der erfindungsgemäße Schmiermittelzusatz zugesetzt werden soll, zu wählen; langkettige Polyethylenoxidreste, vorzugsweise mit n = 10 bis 15, werden z. B. insbesondere für Grundfette auf Glycolbasis eingesetzt.The polyethylene oxide radicals can be different and in particular the same and preferably have the formula RO-CH 2 CH 2 (̵O-CH 2 CH 2 ) ̵ n , where n = 1 to 15 and R is an alkyl radical having 1 to 7 carbon atoms or represents an acyl radical having 2 to 7 carbon atoms, and in particular is hydrogen. In some cases it may be appropriate to choose the length of the polyethylene oxide residues according to the type of base oil or fat to which the lubricant additive according to the invention is to be added; Long chain polyethylene oxide residues, preferably with n = 10 to 15, z. B. used especially for glycol-based base greases.

Ein Alkylrest mit 1 bis 7 Kohlenstoffatomen kann verzweigt oder vorzugsweise geradkettig sein und ist z. B. Methyl, Ethyl, Propyl, Isopropyl, Butyl, Isobutyl, Pentyl, Hexyl, 2,3- oder 4-Methyl-pentyl; ein Acylrest mit 2 bis 7 Kohlenstoffatomen ist z. B. ein solcher, der sich von den vorstehend genannten Alkylresten ableitet, wie z. B. Acetyl, Propionyl usw.An alkyl radical with 1 to 7 carbon atoms can be branched or preferably straight-chain and is, for. B. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, 2,3- or 4-methyl-pentyl; an acyl radical with 2 to 7 carbon atoms is e.g. B. one that is derived from the alkyl radicals mentioned above, such as. B. acetyl, propionyl etc.

Die langkettige gesättigte oder ungesättigte Alkylgruppe kann auch verzweigt sein, ist aber vorzugsweise geradkettig. Sie ist vorzugsweise ein von einer gesättigten oder ungesättigten Fettsäure abgeleiteter Alkylrest, wie z. B. der von der ölsäure abgeleitete Oleylrest (Ectadecenyl). Vorzugsweise besitzt der Alkylrest 12 bis 24, und insbesondere 16 bis 20 Kohlenstoffatome, und ist in erster Linie Oleyl.The long chain saturated or unsaturated alkyl group can also be branched, but is preferably straight chain. It is preferably an alkyl radical derived from a saturated or unsaturated fatty acid, such as, for. B. the oleic acid derived oleyl radical (ectadecenyl). The alkyl radical preferably has 12 to 24 and in particular 16 to 20 carbon atoms and is primarily oleyl.

Als Salzkomponente können prinzipiell beliebige organische oder anorganische Säuren verwendet werden wie z. B. Fettsäuren, Mineralsäuren und dergleichen. Bevorzugt werden Säuren, welche in Schmiermittelzusammensetzungen selbst eine aktive Wirksamkeit haben wie z. B. Phosphorsäuren und teilveresterte Phosphorsäuren, Borsäure, Sarkoside, Merkaptobenzothiazole, Thioglykolsäure und andere Säuren mit sauren Merkaptogruppen.In principle, any organic or inorganic acids such as, for. B. fatty acids, mineral acids and the like. Acids are preferred which themselves have an active activity in lubricant compositions, such as, for. B. phosphoric acids and partially esterified phosphoric acids, boric acid, sarcosides, mercaptobenzothiazoles, thioglycolic acid and other acids with acidic mercapto groups.

Die Umsetzung des tertiären Aminsalzes mit dem Ammoniummolybdatoder MoO3 erfolgt, insbesondere im Hinblick auf ihre spätere Verwendung als Package in Form einer Lösung oder Suspension in einem Mineral- oder Syntheseöl, durch Erhitzen in Mineral- oder Syntheseöl; vorzugsweise wird die Umsetzung bei einer Temperatur von 100 bis 220°C, insbesondere bei 130 bis 190°C durchgeführt. Vorzugsweise wird in Gegenwart einer kleinen Menge Wasser umgesetzt. Gute Ergebnisse ergeben Wasserzusätze von etwa 5 bis etwa 20 Gew.-%, bezogen auf das Reaktionsprodukt. Hierdurch wird die Reaktion beschleunigt und die erforderliche Umsetzungstemperatur in den unteren Bereich gesenkt.The reaction of the tertiary amine salt with the ammonium molybdate or MoO 3 takes place, in particular with a view to its later use as a package in the form of a solution or suspension in a mineral or synthetic oil, by heating in mineral or synthetic oil; the reaction is preferably carried out at a temperature of 100 to 220 ° C., in particular at 130 to 190 ° C. It is preferably reacted in the presence of a small amount of water. Good results give water additions of about 5 to about 20 wt .-%, based on the reaction product. This accelerates the reaction and lowers the required reaction temperature in the lower range.

Die Ausgangsmaterialien für die Umsetzung sind bekannt oder lassen sich auf an sich bekannte Weise herstellen.The starting materials for the reaction are known or can be prepared in a manner known per se.

Die Herstellung des tertiären Aminsalzes kann z. B. durch Umsetzung eines primären Amins, das bereits den langkettigen Alkylrest als Substituent trägt, z. B. von Oleylamin, mit Ethylenoxid in dem für die gewünschte Polyethylenoxidkette erforderlichen Molverhältnis erfolgen; die freie OH-Gruppe kann nachträglich auf an sich bekannte Weise, z. B. durch Umsetzung mit einem Alkyl- oder Acylhalogenid, verethert oder verestert werden. Die Überführung in das Aminsalz erfolgt zweckmäßig durch einfache Salzbildungsreaktion des tertiären Amins mit der gewählten Säure.The preparation of the tertiary amine salt can e.g. B. by reacting a primary amine that already carries the long chain alkyl group as a substituent, for. B. of oleylamine, with ethylene oxide in the molar ratio required for the desired polyethylene oxide chain; the free OH group can subsequently in a known manner, for. B. etherified or esterified by reaction with an alkyl or acyl halide. The conversion into the amine salt is expediently carried out by a simple salt formation reaction of the tertiary amine with the selected acid.

Vorzugsweise enthält der Schmiermittelzusatz weiters ein oder mehrere Schwefelverbindungen aus der Gruppe geschwefelte Ester, Schwermetalldithiophosphate und Schwermetalldithiocarbamate.The lubricant additive preferably further contains one or more sulfur compounds from the group consisting of sulfurized esters, heavy metal dithiophosphates and heavy metal dithiocarbamates.

Als geschwefelte Ester kommen dabei alle Schwefel enthaltenden Ester pflanzlichen, tierischen oder synthetischen Ursprungs in Betracht; typische geeignete Handelsprodukte sind z. B. Lubrizol 5003® (vertrieben von Lubrizol GmbH, Hamburg), Maisperm 2011® (vertrieben von Lehmann, Voss & Co., Hamburg) und geschwefeltes Jojoba-öl.All sulfur-containing esters of vegetable, animal or synthetic origin come into consideration as sulfurized esters; typical suitable commercial products are e.g. B. Lubrizol 5003® (sold by Lubrizol GmbH, Hamburg), Maisperm 2011® (sold by Lehmann, Voss & Co., Hamburg) and sulfurized jojoba oil.

Als Schwermetalldithiophosphate eignen sich generell alle Dithiophosphate der Ubergangsmetalle und der Seltenen Erdmetalle, insbesondere die Thiophosphate von Antimon, Blei, Zinn, Eisen, Kupfer, Mangan, Molybdän, Nickel, Vanadin, Titan und Wismut, und in erster Linie von Zink und Tellur. Anstelle der Dithiophosphate können auch die entsprechenden Dithiocarbamate verwendet werden. In diesen Verbindungen kann der Schwefel ganz oder teilweise auch durch Selen oder Tellur ersetzt sein.Suitable heavy metal dithiophosphates are generally all dithiophosphates of the transition metals and rare earth metals, in particular the thiophosphates of antimony, lead, tin, iron, copper, manganese, molybdenum, nickel, vanadium, titanium and bismuth, and primarily zinc and tellurium. Instead of the dithiophosphates, the corresponding dithiocarbamates can also be used. In these compounds, all or some of the sulfur can also be replaced by selenium or tellurium.

Im erfindungsgemäßen Schmiermittelzusatz beträgt das Verhältnis von Umsetzungsprodukt aus tertiärem Amin und Molybdänverbindung zu Schwefelverbindung vorzugsweise 1:0,5 bis 1:10.In the lubricant additive according to the invention, the ratio of reaction product of tertiary amine and molybdenum compound to sulfur compound is preferably 1: 0.5 to 1:10.

Zweckmäßigerweise liegt der erfindungsgemäße Schmiermittelzusatz als Package in Form einer Lösung oder Suspension in einem Grundöl (Mineral- oder Syntheseöl) vor und wird in dieser Form vertrieben und angewendet. In einer solchen Package liegt der Gehalt an Schmiermittelzusatz (tertiäres Aminsalz/Molybdänverbindung-Umsetzungsprodukt und gegebenenfalls Schwefelverbindung und/oder weiterer üblicher Additive) in der Regel bei 30 bis 90 Gew.-%, und insbesondere bei 50 bis 70 Gew.-%. Als mineralische Grundöle und -fette können naphthenbasische oder paraffinbasische Grundöle und -fette verwendet werden, bei den synthetischen Grundölen und -fetten alle üblichen Klassen. Typische Beispiele für geeignete Syntheseöle sind Poly-alpha-olefine, Glykole, Ester, Alkylbenzole und in organischen Lösungsmitteln lösliche Silikonöle und -fette.The lubricant additive according to the invention is expediently present as a package in the form of a solution or suspension in a base oil (mineral or synthetic oil) and is sold and used in this form. In such a package, the lubricant additive content (tertiary amine salt / molybdenum compound reaction product and optionally sulfur compound and / or other conventional additives) is generally 30 to 90% by weight, and in particular 50 to 70% by weight. Naphthenic or paraffin-based base oils and greases can be used as mineral base oils and greases, and all the usual classes for synthetic base oils and greases. Typical examples of suitable synthetic oils are poly-alpha-olefins, glycols, esters, alkylbenzenes and silicone oils and fats soluble in organic solvents.

Die erfindungsgemäßen Schmiermittelzusätze können weitere für Schmieröle übliche öllösliche oder nicht- öllösliche Additive enthalten, wie z. B. Antioxidantien, Rostinhibitoren, Dichtaufquellmittel, Antischaummittel, Dispergiermittel, Farbstoffe, Viskositätsindexverbesserer, Extreme Pressure-Additive, aber auch weitere Schmiermittelzusätze, wie z. B. die aus der DE-AS 19 54 452 bekannten Additivkombinationen.The lubricant additives according to the invention may contain further oil-soluble or non-oil-soluble additives which are customary for lubricating oils, such as, for. B. antioxidants, rust inhibitors, density swellers, antifoams, dispersants, dyes, viscosity index improvers, extreme pressure additives, but also other lubricant additives, such as. B. the additive combinations known from DE-AS 19 54 452.

Mit dem erfindungsgemäßen Schmiermittelzusatz lassen sich Schmieröle und -fette mit wesentlich verbesserten Eigenschaften erhalten. Insbesondere wird durch den erfindungsgemäßen Schmiermittelzusatz der Verschleiß herabgesetzt, die Haftfestigkeit des Grenzschmierfilmes verbessert, die Oxidationsstabilität und damit die Lebensdauer des Schmierstoffes ausgeprägt erhöht und der Reibungskoeffizient und damit auch die Betriebstemperatur erniedrigt. Die mit dem erfindungsgemäßen Schmiermittelzusatz erzielten Reibwerte sind extrem niedrig. Die Menge an erfindungsgemäßem Schmiermittelzusatz (Umsetzungsprodukt von tertiärem Aminsalz mit Molybdänverbindung und gegebenenfalls Schwefelverbindungen) und gegebenenfalls weiteren üblichen Additiven sollte in der Regel mindestens 3 % betragen, bezogen auf die fertige Schmiermittelzusammensetzung, wobei sich die für das jeweilige Schmiermittel und den jeweiligen Verwendungszweck geeignetsten Mengen leicht feststellen lassen. Mit dem erfindungsgemäßen Schmiermittelzusatz können auch Schmieröl- oder Schmierfett-Konzentrate hergestellt werden, die dann dem Schmiermittel bis zur gewünschten Konzentration zugegeben werden. Desgleichen können die erfindungsgemäßen Zusatzmittel in saurem, neutralem oder basischem Milieu eingesetzt werden. Gegenstand der Erfindung ist deshalb auch die Verwendung des erfindungsgemäßen Schmiermittelzusatzes für Schmierstoffe und Schmierfette, insbesondere für Getriebe- und Motorenöle. Durch die Verwendung des erfindungsgemäßen Schmiermittelzusatzes ist es z. B. möglich, auch öle niedriger Viskosität in Einsatzgebieten zu verwenden, wo bisher hohe Viskositäten unbedingt erforderlich waren, wie z. B. in Getrieben und Differentialgetrieben.With the lubricant additive according to the invention, lubricating oils and greases with significantly improved properties can be obtained. In particular, wear is reduced by the lubricant additive according to the invention, the adhesive strength of the boundary lubrication film is improved, the oxidation stability and thus the life of the lubricant is markedly increased and the coefficient of friction and thus also the operating temperature are reduced. The coefficients of friction achieved with the lubricant additive according to the invention are extremely low. The amount of lubricant additive according to the invention (reaction product of tertiary amine salt with molybdenum compound and optionally sulfur compounds) and optionally further conventional additives should generally be at least 3%, based on the finished lubricant composition, where the quantities most suitable for the respective lubricant and the respective intended use can easily be determined. The lubricant additive according to the invention can also be used to produce lubricating oil or grease concentrates which are then added to the lubricant to the desired concentration. Likewise, the additives according to the invention can be used in an acidic, neutral or basic medium. The invention therefore also relates to the use of the lubricant additive according to the invention for lubricants and greases, in particular for gear and engine oils. By using the lubricant additive according to the invention it is, for. B. possible to use oils of low viscosity in applications where previously high viscosities were absolutely necessary, such as. B. in gears and differential gears.

Die nachfolgenden Beispiele veranschaulichen die Erfindung näher, ohne sie darauf zu beschränken.The following examples illustrate the invention in more detail without restricting it.

B e i s p i e 1 1Example: 1 1

  • a) 15 Gew.-Teile Ammoniummolybdat oder 12 Gew.-Teile Mo03, 60 Gew.-Teile tertiäres Aminsalz (n = 1; langkettiger Alkylrest = Oleyl; Borsäuresalz), 25 Gew.-Teile Mineralöl und 10 Gew.-Teile Wasser werden vermischt und 1 bis 2 Stunden bei 150°C so gerührt, daß eine homogene Mischung aufrechterhalten wird.a) 15 parts by weight of ammonium molybdate or 12 parts by weight of Mo03, 60 parts by weight of tertiary amine salt (n = 1; long-chain alkyl radical = oleyl; boric acid salt), 25 parts by weight of mineral oil and 10 parts by weight of water mixed and stirred for 1 to 2 hours at 150 ° C so that a homogeneous mixture is maintained.
  • b) Es wird wie unter a) verfahren, aber ein anderes tertiäres Amin (n = 15, Oleylrest) eingesetzt.b) The procedure is as under a), but a different tertiary amine (n = 15, oleyl radical) is used.
  • c) Es wird wie unter a) beschrieben gearbeitet, aber mit dem N-Oleylsarkosidsalz anstelle Borsäuresalz.c) The procedure is as described under a), but with the N-oleyl sarcoside salt instead of boric acid salt.

Die nach a), b) oder c) erhaltenen Lösungen des erfindungsgemäßen Schmiermittelzusatzes können als solche, gegebenenfalls zusammen mit einem geschwefelten Ester, einem Schwermetalldithiophosphat und/oder einem Schwermetalldithiocarbamat als Package zur Herstellung verbesserter Schmierfette und Schmieröle verwendet werden.The solutions of the lubricant additive according to the invention obtained according to a), b) or c) can be used as such, optionally together with a sulfurized ester, a heavy metal dithiophosphate and / or a heavy metal dithiocarbamate as a package for producing improved lubricating greases and lubricating oils.

B e i s p i e 1 2Example: 1 2

Durch Vermischen von 2 Gew.-Teilen des nach Beispiel 1 a) erhaltenen Umsetzungsproduktes in Mineralöl, 4 Gew.-Teilen geschwefeltem Ester und 2 Gew.-Teilen Zinkdithiophosphat wird ein Schmiermittelzusatz-Package hergestellt, die in den nachfolgenden Beispielen als Zusatz für Schmiermittel verwendet wird.By mixing 2 parts by weight of the reaction product obtained according to Example 1 a) in mineral oil, 4 parts by weight of sulfurized ester and 2 parts by weight of zinc dithiophosphate, a lubricant additive package is produced which is used in the examples below as an additive for lubricants becomes.

B e i s p i e 1 3Example: 1 3

  • a) Unter Verwendung von Mineralöl plus Lithiumseife als Grundfett wird eine Schmiermittelzusammensetzung, die 8 Gew.-% des nach Beispiel 2 erhaltenen Package enthält, durch Mischen der Komponenten hergestellt.a) Using mineral oil plus lithium soap as base grease, a lubricant composition containing 8% by weight of the package obtained according to Example 2 is produced by mixing the components.
  • b) wie unter a) beschrieben, wird eine Schmiermittelzusammensetzung hergestellt, die 5 Gew.-% des nach Beispiel 2 erhaltenen Package enthält.b) as described under a), a lubricant composition is prepared which contains 5% by weight of the package obtained according to Example 2.
B e i s p i e 1 4Example: 1 4

Es wird, wie im Beispiel 3 a) beschrieben, gearbeitet, aber unter Verwendung eines Grundfettes auf der Basis

  • a) Polyglykol/Lithiumseife;
  • b) Poly-alpha-olefin (niederviskos)/Lithiumseife
  • c) Ester/Lithiumseife.
The procedure is as described in Example 3 a), but using a base grease based
  • a) polyglycol / lithium soap;
  • b) Poly-alpha-olefin (low viscosity) / lithium soap
  • c) Ester / lithium soap.

B e i s p i e 1 5Example: 1 5

Unter Verwendung eines handelsüblichen Supermotoröles SAE 30 als Grundöl wird eine Schmierölzusammensetzung, die 3 Gew.-% der nach Beispiel 2 erhaltenen Package enthält, durch Mischen der Komponenten hergestellt.Using a commercially available SAE 30 super motor oil as base oil, a lubricating oil composition which contains 3% by weight of the package obtained according to Example 2 is produced by mixing the components.

B e i s p i e l 6Example 6

Unter Verwendung eines Fettes aus Li-12-hydroxistearat als Verdicker und einem Syntheseöl auf der Basis a) von Polyglykol oder b) von Estern wird eine Schmiermittelzusammensetzung, die 8 Gew.-% des nach Beispiel 1 c) erhaltenen Schmiermittelzusatzes enthält, durch Mischen der Komponenten hergestellt.Using a fat of Li-12-hydroxystearate as a thickener and a synthetic oil based on a) polyglycol or b) esters, a lubricant composition containing 8% by weight of the lubricant additive obtained according to Example 1 c) is obtained by mixing the Components manufactured.

Die Schmiermittelzusammensetzungen a) oder b) zeigen im SRV-Test ähnlich gute Eigenschaften, wie sie mit den vergleichbaren Schmiermittelzusammensetzungen erhalten werden, die 8 Gew.-% des nach Beispiel 2 erhaltenen Package enthalten, die also zusätzlich zum Umsetzungsprodukt von tertiärem Aminsalz und Molybdänverbindung noch eine Schwefelverbindung enthalten.In the SRV test, the lubricant compositions a) or b) show properties which are similar to those obtained with the comparable lubricant compositions which contain 8% by weight of the package obtained according to Example 2, and which in addition to the reaction product of tertiary amine salt and molybdenum compound contain a sulfur compound.

B e i s p i e 1 7 (Vergleichsbeispiel)B e i s p i e 1 7 (comparative example)

Wie im Beispiel 3 a) beschrieben, wird unter Verwendung von Mineralöl plus Lithiumseife als Grundfett eine Schmiermittelzusammensetzung hergestellt, die aber anstelle von 8 Gew.-% der Package gemäß Beispiel 2 8 Gew.-% der folgenden Mischung, in der das Umsetzungsprodukt von tertiärem Aminsalz und Molybdänverbindung durch die gleiche Menge einer handelsüblichen Molybdänverbindung für Schmierstoffe ersetzt ist, enthält:

  • 2 Gew.-Teile Molyvan L® (sulfuriertes Oxymolybdändialkyldithiophosphat)
  • 4 Gew.-Teile geschwefelten Ester
  • 2 Gew.-Teile Zinkdithiophosphat.
As described in Example 3 a), a lubricant composition is prepared using mineral oil plus lithium soap as the base grease, but instead of 8% by weight of the package according to Example 2, 8% by weight of the following mixture, in which the reaction product of tertiary Amine salt and molybdenum compound is replaced by the same amount of a commercially available molybdenum compound for lubricants, contains:
  • 2 parts by weight of Molyvan L® (sulfurized oxymolybdenum dialkyldithiophosphate)
  • 4 parts by weight of sulfurized ester
  • 2 parts by weight of zinc dithiophosphate.

Die Tests zur Beurteilung der Schmiereigenschaften wurden mit einem von der Anmelderin vertriebenen SRV-Gerät (vgl. R. Schumann, ant. "antriebstechnik" 19 (1980) Nr. 1-2) durchgeführt.The tests for assessing the lubricating properties were carried out using an SRV device sold by the applicant (cf. R. Schumann, ant. "Antriebstechnik" 19 (1980) No. 1-2).

Die Ergebnisse der Tests sind in den Fig. 1 bis 20 in Form von SRV-Prüfblättern veranschaulicht.The results of the tests are illustrated in FIGS. 1 to 20 in the form of SRV test sheets.

Die Figuren 1 bis 12 zeigen die Eigenschaften von Schmiermittelzusammensetzungen unter Verwendung des erfindungsgemäßen Schmiermittelzusatzes, die Figuren 13 bis 20 die Ergebnisse ohne erfindungsgemäßen Schmiermittelzusatz oder mit anderen Zusätzen.Figures 1 to 12 show the properties of lubricant compositions using the lubricant additive according to the invention, Figures 13 to 20 show the results without lubricant additive according to the invention or with other additives.

Im einzelnen betreffen die Figuren folgende Schmiermittelzusammensetzungen:

  • Fig. 1 bis 7: Schmiermittelzusammensetzung nach Beispiel 3 a),
  • Fig. 8: Schmiermittelzusammensetzung nach Beispiel 3 b),
  • Fig. 9: Schmiermittelzusammensetzung nach Beispiel 4 a),
  • Fig. 10: Schmiermittelzusammensetzung nach Beispiel 4 b),
  • Fig. 11: Schmiermittelzusammensetzung nach Beispiel 5,
  • Fig. 12: Schmiermittelzusammensetzung nach Beispiel 6,
  • Fig. 13 bis 18 (Vergleich): handelsübliches Schmierfett Longtime PD 2 (Handelsprodukt der Firma Optimol ölwerke GmbH, München)
  • Fig. 19 (Vergleich): Zusammensetzung wie Beispiel 4 a), aber ohne erfindungsgemäßen Schmiermittelzusatz,
  • Fig. 20 (Vergleich): Zusammensetzung nach Beispiel 7.
The figures relate specifically to the following lubricant compositions:
  • 1 to 7: lubricant composition according to Example 3 a),
  • 8: Lubricant composition according to Example 3 b),
  • 9: Lubricant composition according to Example 4 a),
  • 10: Lubricant composition according to Example 4 b ),
  • 11: Lubricant composition according to Example 5,
  • 12: Lubricant composition according to Example 6,
  • Fig. 13 to 18 (comparison): Commercial grease Longtime PD 2 (commercial product from Optimol Oil Works GmbH, Munich)
  • 19 (comparison): composition as in Example 4 a), but without the lubricant additive according to the invention,
  • 20 (comparison): composition according to example 7.

Die Fig. 1 veranschaulicht einen Test, bei dem die Schmiermittelzusammensetzung nach Beispiel 3 a) unter den angegebenen Betriebsbedingungen einer von 50 auf 1000 Newton steigenden Belastung unterworfen wird, ohne daß dabei die Schmierwirksamkeit zusammenbricht. Dies bedeutet, daß die Fließgrenze des Metalls in den Oberflächenrauhigkeiten erreicht wird, ohne daß die Schmierwirkung der erfindungsgemäßen Schmierfettzusammensetzung verlorengeht.FIG. 1 illustrates a test in which the lubricant composition according to Example 3a) is subjected to a load increasing from 50 to 1000 Newtons under the specified operating conditions, without the lubricating effectiveness collapsing in the process. This means that the yield point of the metal is reached in the surface roughness without the lubricating effect of the grease composition according to the invention being lost.

In den durch die Fig. 2 bis 7 veranschaulichten Tests mit einer erfindungsgemäßen Schmiermittelzusammensetzung nach Beispiel 3 a) und den zum Vergleich angezogenen entsprechenden Tests (Fig. 13 bis 18) mit Longtime PD 2 wurden Prüfkörper mit geläppter Oberfläche (glatt), mit geschliffener Oberfläche (rauh) und auch solche mit polierter Oberfläche (spiegelblank) verwendet. Bei gleicher Belastung (bei 300 N) zeigt ein Vergleich der Fig. 4 bis 6 mit 15 bis 17 die Überlegenheit des erfindungsgemäßen Fettes besonders deutlich bei der geschliffenen Fläche. Aber auch die Ergebnisse der Versuche mit geläppter und mit polierter Oberfläche zeigen deutlich die Überlegenheit des erfindungsgemäßen Schmiermittels. Bei der polierten Oberfläche ist besonders bemerkenswert, daß mit dem Vergleichsprodukt Pitting auftrat. Bei der geläppten Oberfläche werden die Unterschiede, insbesondere bei den Reibwerten und in den Profilogrammen, mit zunehmender Belastung immer gravierender, kommen aber bereits bei 200 N deutlich zum Ausdruck.In the tests illustrated by FIGS. 2 to 7 with a lubricant composition according to the invention according to Example 3 a) and the corresponding tests drawn for comparison (FIGS. 13 to 18) with Longtime PD 2, test specimens with a lapped surface (smooth) with a ground surface were used (rough) and also those with polished surface (mirror finish) used. At the same load (at 300 N), a comparison of FIGS. 4 to 6 with 15 to 17 shows the superiority of the grease according to the invention particularly clearly in the ground surface. But also the results of the tests with lapped and with polished surface clearly show the superiority of the lubricant according to the invention. With the polished surface, it is particularly noteworthy that pitting occurred with the comparative product. The differences in the lapped surface become increasingly serious as the load increases, in particular in the coefficients of friction and in the profilograms, but are already clearly evident at 200 N.

Die Fig. 9 und 19 (Vergleich) zeigen die Ergebnisse mit einer Schmiermittelzusammensetzung auf der Basis Polyglykol plus Lithiumseife mit und ohne erfindungsgemäßen Schmiermittelzusatz.9 and 19 (comparison) show the results with a lubricant composition based on polyglycol plus lithium soap with and without a lubricant additive according to the invention.

Die Fig. 7 und 20 (Vergleich) zeigen die Ergebnisse mit einer Schmiermittelzusammensetzung unter Verwendung eines erfindungsgemäßen Schmiermittelzusatzes (Beispiel 3 a)) und einer solchen mit einem bekannten Schmiermittelzusatz (Beispiel 7) auf der Basis des gleichen Grundöles (Mineralöl plus Lithiumseife); insbesondere das Profilogramm zeigt deutlich die Überlegenheit der Schmiermittelzusammensetzung mit dem erfindungsgemäßen Schmiermittelzusatz.7 and 20 (comparison) show the results with a lubricant composition using a lubricant additive according to the invention (example 3a)) and with a known lubricant additive (example 7) based on the same base oil (mineral oil plus lithium soap); in particular the profilogram clearly shows the superiority of the lubricant composition with the lubricant additive according to the invention.

Bei den Tests der Fig. 7 und 20 (Vergleich) wurden auch Elektronenrasteraufnahmen der geläppten Oberflächen der beaufschlagten Laufflächen bei 400-facher und 1500- facher Vergrößerung vor und nach dem Reibversuch aufgenommen. Der Vergleich der Verschleißflächen zeigt deutlich, daß mit dem Molyvan L® enthaltenden Produkt schuppenförmige Ausrisse auftreten, während beim erfindungsgemäßen Produkt eine sehr glatte Lauffläche erzielt wird, die an der beaufschlagten Stelle besser aussieht, als an der nicht beaufschlagten Stelle.In the tests of FIGS. 7 and 20 (comparison), electron grid images of the lapped surfaces of the loaded treads were also taken at 400x and 1500x magnification before and after the rubbing test. The comparison of the wear surfaces clearly shows that with the product containing Molyvan L® scale-like tears occur, while in the product according to the invention a very smooth running surface is obtained which looks better at the point where it is applied than when it is not.

Die Fig. 8 zeigt die Ergebnisse mit einer Schmiermittelzusammensetzung nach Beispiel 3 b), die im Vergleich zum Beispiel 3 a) nur die halbe Menge an erfindungsgemäßem Schmiermittelzusatz enthält; im Vergleich zu Fig. 4 (Schmiermittelzusammensetzung gemäß Beispiel 3 a)) wird zwar eine längere Einlaufzeit benötigt, dann aber auch hervorragende Reibwerte erhalten.FIG. 8 shows the results with a lubricant composition according to Example 3 b) which, in comparison to Example 3 a), contains only half the amount of lubricant additive according to the invention; in comparison to FIG. 4 (lubricant composition according to Example 3a), a longer running-in time is required, but excellent friction coefficients are then also obtained.

Die Fig. 10 zeigt, daß auch mit einem extrem niedrigviskosen Poly-alpha-olefin als Bestandteil des Grundfettes, das als solches besonders schlechte Schmiereigenschaften aufweist, nach Zusatz des erfindungsgemäßen Produktes gute Schmiereigenschaften zu erhalten sind.10 shows that even with an extremely low-viscosity poly-alpha-olefin as a constituent of the base grease, which as such has particularly poor lubricating properties, good lubricating properties can be obtained after adding the product according to the invention.

Die Fig. 11 zeigt die Ergebnisse mit einem handelsüblichen Supermotoröl SAE 30, das nur eine geringe Menge (3 Gew.-%) an erfindungsgemäßem Schmiermittelzusatz enthält. Die Ergebnisse zeigen, daß nach kurzer Einlaufzeit eine starke Verringerung des Reibwertes, der vorher bei etwa 0,13 lag, bis auf 0,044 auftritt. Dieses Ergebnis ist insbesondere deshalb bemerkenswert, weil bei einem solchen fertig additivierten handelsüblichen Schmieröl Detergenzien vorhanden sind, die die Wirkung des erfindungsgemäßen Schmiermittelzusatzes herabsetzen, trotzdem aber eine deutliche Verbesserung der Schmiereigenschaften erreicht wird.11 shows the results with a commercially available super motor oil SAE 30 which contains only a small amount (3% by weight) of lubricant additive according to the invention. The results show that after a short running-in period there is a sharp reduction in the coefficient of friction, which was previously around 0.13, down to 0.044. This result is particularly noteworthy because detergents of this type, which are fully additized and commercially available, detergents which reduce the effect of the lubricant additive according to the invention, but nevertheless achieve a significant improvement in the lubricating properties.

Die Fig. 12 zeigt, daß auch bei einem Schmierfett hervorragende Reibwerte und Oberflächenglätten gemäß der Erfindung erzielt werden.FIG. 12 shows that excellent friction coefficients and surface smoothing according to the invention are achieved even with a grease.

Claims (14)

1. Schmiermittelzusatz, erhältlich durch Umsetzung eines Salzes eines tertiären Amins, das als N-Substituenten zwei Polyethylenoxidreste mit zwei oder mehr Ethylenoxidgruppen, deren freie OH-Gruppe verethert oder acyliert sein kann, und eine gesättigte oder ungesättigte langkettige Alkylgruppe besitzt, mit Ammoniummolybdat und/oder MoO3.1. Lubricant additive obtainable by reacting a salt of a tertiary amine which, as N-substituents, has two polyethylene oxide radicals with two or more ethylene oxide groups, the free OH group of which may be etherified or acylated, and a saturated or unsaturated long-chain alkyl group, with ammonium molybdate and / or MoO 3 . 2. Schmiermittelzusatz nach Anspruch 1, dadurch gekennzeichnet , daß die Polyethylenoxidreste gleiche oder verschiedene Reste der Formel RO-CH2CH2 (OH-CH2CH2)n sind, worin n = 1 bis 15 und R Wasserstoff, einen Alkylrest mit 1 bis 7 Kohlenstoffatomen oder einen Acylrest mit 2 bis 7 Kohlenstoffatomen bedeutet.2. Lubricant additive according to claim 1, characterized in that the polyethylene oxide residues are identical or different residues of the formula RO-CH 2 CH 2 (OH-CH 2 CH 2 ) n , where n = 1 to 15 and R is hydrogen, an alkyl residue with 1 means up to 7 carbon atoms or an acyl radical with 2 to 7 carbon atoms. 3. Schmiermittelzusatz nach Anspruch 1 oder 2, dadurch gekennzeichnet , daß die langkettige Alkylgruppe ein von einer gesättigten oder ungesättigten Fettsäure abgeleiteter Alkylrest ist.3. Lubricant additive according to claim 1 or 2, characterized in that the long-chain alkyl group is an alkyl radical derived from a saturated or unsaturated fatty acid. 4. Schmiermittelzusatz nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die langkettige Alkylgruppe 12 bis 24 Kohlenstoffatome, insbesondere 16 bis 20 Kohlenstoffatome besitzt.4. Lubricant additive according to one of claims 1 to 3, characterized in that the long-chain alkyl group has 12 to 24 carbon atoms, in particular 16 to 20 carbon atoms. 5. Schmiermittelzusatz nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die langkettige Alkylgruppe der Oleylrest ist.5. Lubricant additive according to one of claims 1 to 4, characterized in that the long-chain alkyl group is the oleyl radical. 6. Schmiermittelzusatz nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet , daß die Umsetzung in Mineralöl oder Syntheseöl unter Erhitzen erfolgt.6. Lubricant additive according to one of the preceding claims, characterized in that the reaction in mineral oil or synthetic oil takes place with heating. 7. Schmiermittelzusatz nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet , daß das tertiäre Aminsalz im Molverhältnis 1:1 oder darüber eingesetzt wird.7. Lubricant additive according to one of the preceding claims, characterized in that the tertiary amine salt is used in a molar ratio of 1: 1 or above. 8. Schmiermittelzusatz nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet , daß das Gewichtsverhältnis tertiäres Aminsalz zu Molybdänverbindung 50 bis 70 zu 20 bis 40 beträgt.8. Lubricant additive according to one of the preceding claims, characterized in that the weight ratio of tertiary amine salt to molybdenum compound is 50 to 70 to 20 to 40. 9. Schmiermittelzusatz nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet daß man die Umsetzung bei einer Temperatur von 100 bis 220°C durchführt.9. Lubricant additive according to one of the preceding claims, characterized in that one carries out the reaction at a temperature of 100 to 220 ° C. 10. Schmiermittelzusatz nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet , daß er zusätzlich eine oder mehrere Schwefelverbindungen aus der Gruppe geschwefelte Ester, Schwermetalldithiophosphate und Schwermetalldithiocarbamate enthält.10. Lubricant additive according to one of the preceding claims, characterized in that it additionally contains one or more sulfur compounds from the group sulfurized esters, heavy metal dithiophosphates and heavy metal dithiocarbamates. 11. Verfahren nach Anspruch 10, dadurch gekennzeichnet , daß das Gewichtsverhältnis von Umsetzungsprodukt aus tertiärem Aminsalz und Molybdänverbindung zu Schwefelverbindungen 1:0,5 bis 1:10 beträgt.11. The method according to claim 10, characterized in that the weight ratio of reaction product of the tertiary amine salt and molybdenum compound to sulfur compounds is 1: 0.5 to 1:10. 12. Schmiermittelzusatz nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet , daß er in Form einer Lösung oder Suspension in einem Mineral-oder Syntheseöl vorliegt.12. Lubricant additive according to one of the preceding claims, characterized in that it is present in the form of a solution or suspension in a mineral or synthetic oil. 13. Schmiermittelzusatz nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet , daß er weitere übliche Additive enthält.13. Lubricant additive according to one of the preceding claims, characterized in that it contains further conventional additives. 14. Verwendung eines Schmiermittelzusatzes nach einem der Ansprüche 1 bis 13 für mineralische, natürliche oder synthetische Schmierstoffe und Schmierfette, insbesondere für Getriebe- und Motorenöle.14. Use of a lubricant additive according to one of claims 1 to 13 for mineral, natural or synthetic lubricants and lubricating greases, in particular for gear and motor oils.
EP85114438A 1984-12-06 1985-11-13 Lubricant additive Expired EP0184043B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85114438T ATE37558T1 (en) 1984-12-06 1985-11-13 LUBRICANT SUPPLEMENT.

Applications Claiming Priority (2)

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DE19843444553 DE3444553A1 (en) 1984-12-06 1984-12-06 LUBRICANT ADDITION
DE3444553 1984-12-06

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EP0184043A2 true EP0184043A2 (en) 1986-06-11
EP0184043A3 EP0184043A3 (en) 1987-02-04
EP0184043B1 EP0184043B1 (en) 1988-09-28

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EP (1) EP0184043B1 (en)
JP (1) JPH06104838B2 (en)
AT (1) ATE37558T1 (en)
AU (1) AU572009B2 (en)
DE (2) DE3444553A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2185492A (en) * 1986-01-16 1987-07-22 Ntn Toyo Bearing Co Ltd Greases for homokinetic joints incorporating an organic molybdenum compound
FR2648473A1 (en) * 1989-06-19 1990-12-21 Elf Aquitaine LOWERING ADDITIVES FOR LUBRICATING OILS COMPRISING A MOLYBDENUM COMPLEX, PROCESS FOR THEIR PREPARATION AND COMPOSITIONS COMPRISING SAID ADDITIVES
US10080380B2 (en) 2011-06-09 2018-09-25 ADM WILD Europe GmbH & Co. KG Process of preparing a concentrated liquid foodstuff

Families Citing this family (8)

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US4816303A (en) * 1985-04-04 1989-03-28 The B. F. Goodrich Company Process for inhibiting corrosion of metal and corrosion-inhibiting layer use therein
JPH0931483A (en) * 1995-07-20 1997-02-04 Tonen Corp Lubricant composition
JP4559550B2 (en) * 1998-08-07 2010-10-06 出光興産株式会社 Lubricating oil composition for internal combustion engines
JP2002249795A (en) * 2001-02-23 2002-09-06 Asahi Denka Kogyo Kk Lubricant and lubricative composition
JP4066132B2 (en) * 2001-10-15 2008-03-26 株式会社Ａｄｅｋａ Lubricant and lubricating composition
US7884058B2 (en) * 2003-09-30 2011-02-08 Chevron Oronite Company Llc Stable colloidal suspensions and lubricating oil compositions containing same
CN103553907B (en) * 2013-10-18 2015-09-23 湖南省华京粉体材料有限公司 A kind of preparation method of oil-soluble organic molybdenum additive
US9534186B1 (en) 2015-06-17 2017-01-03 Chevron Oronite Company Llc Multifunctional molybdenum containing compounds, method of making and using, and lubricating oil compositions containing same

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US4164473A (en) * 1977-10-20 1979-08-14 Exxon Research & Engineering Co. Organo molybdenum friction reducing antiwear additives

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US3282838A (en) * 1960-05-10 1966-11-01 Texaco Inc Petroleum liquids containing amine salts of molybdic acid
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US4382006A (en) * 1979-11-06 1983-05-03 Mobil Oil Corporation Friction reduction additives and compositions thereof

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US4164473A (en) * 1977-10-20 1979-08-14 Exxon Research & Engineering Co. Organo molybdenum friction reducing antiwear additives

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2185492A (en) * 1986-01-16 1987-07-22 Ntn Toyo Bearing Co Ltd Greases for homokinetic joints incorporating an organic molybdenum compound
GB2185492B (en) * 1986-01-16 1990-07-18 Ntn Toyo Bearing Co Ltd Grease for homokinetic joint
FR2648473A1 (en) * 1989-06-19 1990-12-21 Elf Aquitaine LOWERING ADDITIVES FOR LUBRICATING OILS COMPRISING A MOLYBDENUM COMPLEX, PROCESS FOR THEIR PREPARATION AND COMPOSITIONS COMPRISING SAID ADDITIVES
EP0404650A1 (en) * 1989-06-19 1990-12-27 Societe Nationale Elf Aquitaine Overbased lubricating oil additives containing a molybdenun complex, process of preparation and compositions containing the same
US10080380B2 (en) 2011-06-09 2018-09-25 ADM WILD Europe GmbH & Co. KG Process of preparing a concentrated liquid foodstuff

Also Published As

Publication number Publication date
EP0184043B1 (en) 1988-09-28
EP0184043A3 (en) 1987-02-04
ATE37558T1 (en) 1988-10-15
AU5047185A (en) 1986-06-12
JPH06104838B2 (en) 1994-12-21
DE3565285D1 (en) 1988-11-03
JPS61197691A (en) 1986-09-01
US4647388A (en) 1987-03-03
DE3444553A1 (en) 1986-06-12
AU572009B2 (en) 1988-04-28

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