EP0011224B1 - Lubricating and cooling agent - Google Patents

Lubricating and cooling agent Download PDF

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Publication number
EP0011224B1
EP0011224B1 EP79104352A EP79104352A EP0011224B1 EP 0011224 B1 EP0011224 B1 EP 0011224B1 EP 79104352 A EP79104352 A EP 79104352A EP 79104352 A EP79104352 A EP 79104352A EP 0011224 B1 EP0011224 B1 EP 0011224B1
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EP
European Patent Office
Prior art keywords
lubricating
weight
ammonium polyphosphate
cooling agent
parts
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.)
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EP79104352A
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German (de)
French (fr)
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EP0011224A1 (en
Inventor
Michael Ahlgrim
Gerhard Dr. Mietens
Franz-Josef Dr. Dany
Joachim Dr. Kandler
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Hoechst AG
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Hoechst AG
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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
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/24—Compounds containing phosphorus, arsenic or antimony
    • 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
    • C10M2201/02—Water
    • 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
    • C10M2201/085—Phosphorus oxides, acids or salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
    • 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
    • C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/22—Acids obtained from polymerised unsaturated 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
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • 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
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/068—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings having amino groups bound to polycyclic aromatic ring systems, i.e. systems with three or more condensed rings
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/221—Six-membered rings containing nitrogen and carbon only
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • C10M2215/226—Morpholines
    • 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
    • C10M2215/30—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2223/041—Triaryl phosphates
    • 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
    • C10M2223/043—Ammonium or amine salts 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
    • 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
    • C10M2223/047—Thioderivatives not containing metallic elements
    • 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
    • C10M2225/00—Organic macromolecular compounds containing phosphorus 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
    • C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2225/02—Macromolecular compounds from phosphorus-containg monomers, obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/241—Manufacturing joint-less pipes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/242—Hot working
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/243—Cold working
    • C—CHEMISTRY; METALLURGY
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C10N2040/245—Soft metals, e.g. aluminum
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C10N2040/246—Iron or steel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C10N2040/247—Stainless steel

Definitions

  • the invention relates to a lubricant and coolant for metalworking with an additive based on long-chain polyphosphates.
  • lubricants and coolants are used to reduce wear and increase production, by means of which the frictional resistance between the workpiece and the tool is reduced.
  • These lubricants and coolants generally consist of lubricating oils to which wear and corrosion-inhibiting additives have been added.
  • DE-A-2 048 537 describes a high-temperature lubricant based on a binder and a solvent, to which salts of ortho- and / or polyphosphoric acid with sodium and / or potassium and / or zinc and / or aluminum and / or boron are admixed are.
  • US Pat. No. 2,423,144 discloses an emulsifiable liquid oil concentrate which consists of a major amount of a liquid hydrocarbon oil with an oil-in-water emulsifier dissolved therein, which is an alkali metal polyphosphate of the general formula Na " P I - 2 0 31 - 5 is added, where n is greater than 5.
  • Inorganic and organic phosphorus compounds as additives in lubricating oils or water are therefore part of the prior art.
  • orthophosphoric or polyphosphoric acid as an additive in lubricating oils, but also in particular in water, severe corrosion occurs, which can be reduced by neutralization with alkali metal hydroxide or amines.
  • neutralizing the free acids a reduction in the lubrication must be accepted and the bases added can lead to undesired thickening, which considerably reduces the cooling effect.
  • the previously known lubricants and coolants are in need of improvement because, on the one hand, they only insufficiently cool the tool and, on the other hand, the metal oxide-phosphate glasses sintered onto the workpiece have to be removed in a subsequent etching stage by an acid treatment.
  • the invention is therefore based on the object of providing a lubricant and coolant for metalworking which has improved high-pressure properties and wear-resistant properties.
  • the lubricant and coolant is an additive based on a long-chain ammonium polyphosphate of the general formula is used, in which n corresponds to an integer from 50 to 1,000, in particular from 300 to 800, and R denotes an ammonium group.
  • ammonium polyphosphate up to 20%, in particular up to 5%.
  • ammonium groups can be replaced by hydrogen.
  • ammonium polyphosphate can be added to the lubricant and coolant in the form of a liquid, suspension or paste.
  • ammonium polyphosphate is added to the lubricant and coolant in an amount of 0.1 to 30, preferably 2 to 10,% by weight.
  • ammonium polyphosphate can be used as an additive in combination with interfaces active substances and / or anti-foaming agents and / or dyes and / or rust inhibitors and / or phosphate esters.
  • Mineral lubricating oils such as paraffin-based or naphthen-based distillate oils with a viscosity between z. B. 6 and 60 cSt at 60 ° C and / or synthetic lubricating oils, such as polyolefins and / or ester oils and / or polyoxyalkylenes, can be used.
  • Nonionic detergents such as polyoxyethylene stearate or polyoxyethylene monobutyl ether in amounts between 1 and 20% by weight of the lubricant and coolant have proven particularly useful as surface-active substances.
  • Siloxanes can be added to the lubricant and coolant as anti-foaming agents, e.g. B. polymethylsiloxane in an amount of 5-25 ppm.
  • phosphate esters e.g. B. ammonium salts of the mixture of mono- and dioleylphosphoric acid or di-n-propyldithiophosphoric acid or tricresyl phosphate in amounts of 0.01 to 10 wt.% Of the lubricant and coolant, the effect of the long-chain ammonium polyphosphate can be improved synergistically.
  • the additive according to the invention is particularly suitable for metalworking processes in which extremely high pressures and temperatures occur, for example milling, extruding or drawing and rolling processes in the cold and hot state.
  • the noise meters are a measure of the end of the frictional wear. A small number of noise meters therefore indicates a strong activation of the test substance.
  • Whitening power Sc h is the applied load at which welding of the four-ball system enters the test instrument.
  • Good force is the test force measured before the welding force was reached, at which the four-ball system is not yet welded in the test device.
  • the attached drawing shows the results of the Erichsen thermoforming test (cf. DIN 50102; January 1963).
  • the addition of long-chain ammonium polyphosphate according to the formula in claim 1 results in a significant increase in the pulling path.
  • an ammonium polyphosphate of this type Exolit 263 @ , Hoechst AG
  • naphthenic oil Coray 90®
  • a cup is drawn without With only Coray 90 8 with a draw ratio of 2.27 there is already a tear with a draw of 18.4 mm.

Description

Die Erfindung betrifft ein Schmier- und Kühlmittel für die Metallbearbeitung mit einem Additiv auf der Basis von langkettigen Polyphosphaten.The invention relates to a lubricant and coolant for metalworking with an additive based on long-chain polyphosphates.

Bekanntlich werden zur Verschleißminderung und Produktionserhöhung Schmier- und Kühlmittel verwendet, durch welche der Reibungswiderstand zwischen dem Werkstück und dem Werkzeug herabgesetzt wird. Diese Schmier- und Kühlmittel bestehen im allgemeinen aus Schmierölen, denen verschleiß und korrosionshemmende Additive zugesetzt sind.As is known, lubricants and coolants are used to reduce wear and increase production, by means of which the frictional resistance between the workpiece and the tool is reduced. These lubricants and coolants generally consist of lubricating oils to which wear and corrosion-inhibiting additives have been added.

Nach einem Vorschlag in der DE-A-1 644 875 werden einem wäßrigen Kühlmittel 0,1 bis 20 Gewichts-% eines Polyoxialkylenglykolpolyesters einer dimeren Fettsäure zugesetzt. Nachteilig ist dabei, daß die organische Verbindung durch die punktuell auftretende große Hitzeentwicklung an dem Werkzeug oxidiert und verdampft, wodurch der Aufbau einer Gleitschicht verhindert wird.According to a proposal in DE-A-1 644 875, 0.1 to 20% by weight of a polyoxyalkylene glycol polyester of a dimeric fatty acid is added to an aqueous coolant. The disadvantage here is that the organic compound is oxidized and evaporated due to the high heat generation on the tool, which prevents the formation of a sliding layer.

Aus der DE-A-1 644908 sind Schmierstoffe mit einem Gehalt an Eisen- oder Zinkpyrophosphat bekannt.From DE-A-1 644908 lubricants containing iron or zinc pyrophosphate are known.

In der DE-A-2 048 537 wird ein Hochtemperaturschmierstoff auf der Grundlage eines Binders und eines Lösungsmittels beschrieben, dem Salze der Ortho- und/oder Polyphosphorsäure mit Natrium und/oder Kalium und/oder Zink und/oder Aluminium und/oder Bor zugemischt sind.DE-A-2 048 537 describes a high-temperature lubricant based on a binder and a solvent, to which salts of ortho- and / or polyphosphoric acid with sodium and / or potassium and / or zinc and / or aluminum and / or boron are admixed are.

Nach der AT-B-278 223 wird ein Schmier- und Kühlmittel unter Zusatz von Orthophosphaten oder kondensierten Phosphaten von Alkalimetallen und Metalloxiden hergestellt.According to AT-B-278 223, a lubricant and coolant with the addition of orthophosphates or condensed phosphates of alkali metals and metal oxides is produced.

Schließlich ist aus der US-A-2 423 144 ein emulgierfähiges flüssiges Ölkonzentrat bekannt, welches aus einer Hauptmenge eines flüssigen Kohlenwasserstofföls mit darin gelöstem ÖI-in-Wasser-Emulgiermittel besteht, dem ein Alkalimetallpolyphosphat der allgemeinen Formel Na"PI-2031-5 zugesetzt ist, wobei n größer als 5 ist.Finally, US Pat. No. 2,423,144 discloses an emulsifiable liquid oil concentrate which consists of a major amount of a liquid hydrocarbon oil with an oil-in-water emulsifier dissolved therein, which is an alkali metal polyphosphate of the general formula Na " P I - 2 0 31 - 5 is added, where n is greater than 5.

Anorganische und organische Phosphorverbindungen als Additive in Schmierölen oder Wasser gehören somit zum Stand der Technik. Bei der Verwendung von Ortho- bzw. Polyphosphorsäure als Additiv in Schmierölen, aber auch insbesondere in Wasser, treten starke Korrosionen ein, die durch eine Neutralisation mit Alkalihydroxid oder Aminen reduziert werden können. Bei der Neutralisation der freien Säuren muß eine Reduzierung der Schmierung in Kauf genommen werden und es kann durch die zugesetzten Basen zu einer unerwünschten Eindickung kommen, wodurch die Kühlwirkung erheblich reduziert wird.Inorganic and organic phosphorus compounds as additives in lubricating oils or water are therefore part of the prior art. When using orthophosphoric or polyphosphoric acid as an additive in lubricating oils, but also in particular in water, severe corrosion occurs, which can be reduced by neutralization with alkali metal hydroxide or amines. When neutralizing the free acids, a reduction in the lubrication must be accepted and the bases added can lead to undesired thickening, which considerably reduces the cooling effect.

Durch die Zugabe von Phosphorsäureestern ist die Herstellung von neutralen, homogenen Schmier-und Kühlmitteln möglich. Aus Erfahrung weiß man, daß zwischen der Schmierwirkung und dem Phosphorgehalt des Schmier- und Kühlmittels ein Zusammenhang besteht. Je höher der Phosphorgehalt ist, desto bessere Ergebnisse werden mit dem Schmier- und Kühlmittel erzielt. Beim Zusatz von Phosphorsäureestern ist der Phosphorgehalt im Schmier- und Kühlmittel begrenzt, da die verwendbaren Phosphonrsäureester einen Phosphor-Gehalt von höchstens 13,4 Gew.% aufweisen können (vergl. DE-A-2 145 296).The addition of phosphoric acid esters makes it possible to produce neutral, homogeneous lubricants and coolants. Experience has shown that there is a connection between the lubricating effect and the phosphorus content of the lubricant and coolant. The higher the phosphorus content, the better results are achieved with the lubricant and coolant. When phosphoric acid esters are added, the phosphorus content in the lubricant and coolant is limited, since the usable phosphoric acid esters can have a phosphorus content of at most 13.4% by weight (cf. DE-A-2 145 296).

Die bisher bekannten Schmier- und Kühlmittel sind verbesserungsbedürftig, weil sie einerseits das Werkzeug nur unzureichend kühlen und weil andererseits die auf dem Werkstück aufgesinterten Metalloxid-Phosphat-Gläser in einer nachfolgenden Ätzstufe durch eine Säurebehandlung entfernt werden müssen.The previously known lubricants and coolants are in need of improvement because, on the one hand, they only insufficiently cool the tool and, on the other hand, the metal oxide-phosphate glasses sintered onto the workpiece have to be removed in a subsequent etching stage by an acid treatment.

Daher liegt der Erfindung die Aufgabe zugrunde, ein Schmier- und Kühlmittel für die Metallbearbeitung zu schaffen, welches verbesserte Hochdruckeigenschaften und verschleißhemmende Eigenschaften aufweist.The invention is therefore based on the object of providing a lubricant and coolant for metalworking which has improved high-pressure properties and wear-resistant properties.

Dies wird erfindungsgemäß dadurch erreicht, daß das Schmier- und Kühlmittel ein Additiv auf der Basis eines langkettigen Ammoniumpolyphosphats der allgemeinen Formel

Figure imgb0001
verwendet wird, in der n einer ganzen Zahl von 50 bis 1 000, insbesondere von 300 bis 800, entspricht und R eine Ammoniumgruppe bedeutet, enthält.This is achieved according to the invention in that the lubricant and coolant is an additive based on a long-chain ammonium polyphosphate of the general formula
Figure imgb0001
 is used, in which n corresponds to an integer from 50 to 1,000, in particular from 300 to 800, and R denotes an ammonium group.

Bei dem langkettigen Ammoniumpolyphosphat können bis zu 20 %, insbesondere bis zu 5 %. der Ammoniumgruppen durch Wasserstoff ersetzt sein.With the long-chain ammonium polyphosphate up to 20%, in particular up to 5%. of the ammonium groups can be replaced by hydrogen.

Als Additiv kann das Ammoniumpolyphosphat dem Schmier- und Kühlmittel In Form einer Flüssigkeit, Suspension oder Paste zugesetzt werden.As an additive, the ammonium polyphosphate can be added to the lubricant and coolant in the form of a liquid, suspension or paste.

Das Ammoniumpolyphosphat wird dem Schmier- und Kühlmittel in einer Menge von 0,1 bis 30, vorzugsweise von 2 bis 10, Gew.% zugesetzt.The ammonium polyphosphate is added to the lubricant and coolant in an amount of 0.1 to 30, preferably 2 to 10,% by weight.

Das Ammoniumpolyphosphat kann als Additiv verwendet werden in Kombination mit grenzflächenaktiven Stoffen und/oder Antischaummitteln und/oder Farbstoffen und/oder Rostinhibitoren und/oder Phosphatestern.The ammonium polyphosphate can be used as an additive in combination with interfaces active substances and / or anti-foaming agents and / or dyes and / or rust inhibitors and / or phosphate esters.

Als Schmierölgrundlage können mineralische Schmieröle, wie paraffinbasische oder naphtenbasische Destillatöle mit einer Viskosität zwischen z. B. 6 und 60 cSt bei 60 °C und/oder synthetische Schmieröle, wie Polyolefine und/oder Esteröle und/oder Polyoxialkylene, verwendet werden.Mineral lubricating oils, such as paraffin-based or naphthen-based distillate oils with a viscosity between z. B. 6 and 60 cSt at 60 ° C and / or synthetic lubricating oils, such as polyolefins and / or ester oils and / or polyoxyalkylenes, can be used.

Als grenzflächenaktive Stoffe haben sich insbesondere nichtionische Detergentien, wie Polyoxiäthylenstearat oder Polyoxiäthylenmonobutyläther in Mengen zwischen 1 bis 20 Gew.% des Schmier- und Kühlmittels bewährt.Nonionic detergents such as polyoxyethylene stearate or polyoxyethylene monobutyl ether in amounts between 1 and 20% by weight of the lubricant and coolant have proven particularly useful as surface-active substances.

Als Antischaummittel können dem Schmier- und Kühlmittel Siloxane zugesetzt werden, z. B. Polymethylsiloxan in einer Menge von 5-25 ppm.Siloxanes can be added to the lubricant and coolant as anti-foaming agents, e.g. B. polymethylsiloxane in an amount of 5-25 ppm.

Als Rostinhibitor können z. B. Benzotriazol oder Äthylbernsteinsäure in Mengen von etwa 200 ppm zugemischt werden.As a rust inhibitor z. B. benzotriazole or ethyl succinic acid in amounts of about 200 ppm.

Durch den Zusatz von Phosphatestern, z. B. Ammoniumsalze des Gemisches der Mono- und Dioleylphosphorsäure oder der Di-n-propyldithiophosphorsäure oder Trikresylphosphat in Mengen von 0,01 bis 10 Gew.% des Schmier- und Kühlmittels, kann die Wirkung des langkettigen Ammoniumpolyphosphats synergistisch verbessert werden.By adding phosphate esters, e.g. B. ammonium salts of the mixture of mono- and dioleylphosphoric acid or di-n-propyldithiophosphoric acid or tricresyl phosphate in amounts of 0.01 to 10 wt.% Of the lubricant and coolant, the effect of the long-chain ammonium polyphosphate can be improved synergistically.

Das erfindungsgemäße Additiv eignet sich besonders für Metallbearbeitungsverfahren, bei welchen extrem hohe Drukke und Temperaturen auftreten, beispielsweise Fräsen, Extrudieren oder Zieh- und Walzvorgänge im kalten und heißen Zustand.The additive according to the invention is particularly suitable for metalworking processes in which extremely high pressures and temperatures occur, for example milling, extruding or drawing and rolling processes in the cold and hot state.

Es hat sich gezeigt, daß bei der Heißbearbeitung von Metallen ein nach der DE-C-2 330 174 hergestelltes Ammoniumpolyphosphat mit einer mittleren Kettenlänge von n = 500 bis 1 000, insbesondere von n = 600 bis 800, eingesetzt werden kann.It has been shown that an ammonium polyphosphate produced according to DE-C-2 330 174 with an average chain length of n = 500 to 1,000, in particular n = 600 to 800, can be used in the hot working of metals.

Für die Kaltbearbeitung von Metallen, wo speziell großer Wert auf eine gute Kühlung des Werkzeuges und Werkstückes gelegt wird, eignet sich als Additiv besonders ein nach der DE-C-1 767 205 hergestelltes Ammoniumpolyphosphat mit einer mittleren Kettenlänge von n = 50 bis 400, insbesondere von n = 300 bis 400.An ammonium polyphosphate with an average chain length of n = 50 to 400, especially produced according to DE-C-1 767 205, is particularly suitable as an additive for the cold machining of metals, where great importance is attached to good cooling of the tool and workpiece from n = 300 to 400.

Die folgenden Beispiele dienen der Erläuterung der Eigenschaften des langkettigen Ammoniumpolyphosphats als Additiv in Schmier- und Kühlmitteln. Die Erfindung ist nicht auf diese Beispiele beschränkt, das gilt insbesondere der Zumischung weiterer, das Schmier- und Kühlmittel verbessernder Zusätze.The following examples illustrate the properties of long-chain ammonium polyphosphate as an additive in lubricants and coolants. The invention is not restricted to these examples; this applies in particular to the admixture of further additives which improve the lubricant and coolant.

Die Prüfung der Schmier- und Kühlmittel erfolgte mit der,Reibverschleißwaage nach Reichert (vergl. DE-U-1 749 247) sowie gemäß DIN 51 350 (Juli 1971) im Shell-Vierkugel-Apparat.The lubricants and coolants were tested using the friction wear balance according to Reichert (see DE-U-1 749 247) and in accordance with DIN 51 350 (July 1971) in the Shell four-ball apparatus.

Beispiel 1example 1

2,5 Gewichtsteile langkettiges Ammoniumpolyphosphat der Formel nach Anspruch 1 mit einer mittleren Kettenlänge von n = 300 bis 400 und einer Körnung von < 63 µ wurden in 97,5 Gewichtsteilen Wasser aufgeschlämmt. Das Testergebnis auf der Reibverschleißwaage ist in Tabelle 1 aufgeführt.2.5 parts by weight of long-chain ammonium polyphosphate of the formula according to Claim 1 with an average chain length of n = 300 to 400 and a grain size of <63 µ were slurried in 97.5 parts by weight of water. The test result on the friction wear balance is listed in Table 1.

Vergleichsbeispiel 1 aComparative Example 1 a

3,0 Gewichtsteile Phosphatester eines Handelsproduktes auf Basis von Phenol mit 6 Äthylenoxid-Einheiten wurden mit 97,0 Gewichtsteilen Wasser gemischt.3.0 parts by weight of phosphate ester of a commercial product based on phenol with 6 ethylene oxide units were mixed with 97.0 parts by weight of water.

Das Testergebnis auf der Reibverschleißwaage ist in Tabelle 1 aufgeführt.The test result on the friction wear balance is listed in Table 1.

Vergleichsbeispiel 1 bComparative Example 1 b

Die Schmierwirkung von reinem Wasser wurde bestimmt. Das Testergebnis auf der Reibverschleißwaage ist in der Tabelle 1 aufgeführt.

Figure imgb0002
AnmerkungThe lubricating effect of pure water was determined. The test result on the friction wear balance is listed in Table 1.
Figure imgb0002
 annotation

Solange die Prüfflüssigkeit zwischen Ring und Rolle der Reichert-Maschine noch keine Reaktionsschicht gebildet hat, ist ein mahlendes Geräusch hörbar. Das plötzliche Aufhören des Geräusches wird am Zählwerk der Maschine als Geräuschmeter abgelesen ; d. h. die Geräuschmeter sind eine Maßzahl für die Beendigung des Reibverschleißes. Eine kleine Geräuschmeterzahl zeigt daher eine starke Aktivierung des Prüfstoffes an.As long as the test liquid between the ring and roller of the Reichert machine has not yet formed a reaction layer, a grinding noise can be heard. The sudden cessation of the noise is read on the counter of the machine as a noise meter; d. H. the noise meters are a measure of the end of the frictional wear. A small number of noise meters therefore indicates a strong activation of the test substance.

Der Flächendruck ist ein Maß für das Lasttragevermögen des Prüfstoffes und ist aus der Belastung der Reichert-Maschine und dem Abrieb ihrer Prüfrolle errechenbar:

Figure imgb0003
mit

  • G = Belastungsgewicht [kg]
  • A = AbrIebfläche [mm2]
The surface pressure is a measure of the load-bearing capacity of the test substance and can be calculated from the load on the Reichert machine and the abrasion of its test roller:
Figure imgb0003
 With
  • G = load weight [kg]
  • A = abrasion surface [mm 2 ]

Beispiel 2Example 2

5 Gewichtsteile langkettiges Ammoniumpolyphosphat der Formel nach Anspruch 1 mit einer mittleren Kettenlänge von n = 300 bis 400 und einer Körnung von < 63 µ wurden in 95 Gewichtsteilen naphtenbaslschem Öl (Coray 90°, Fa. Esso AG) suspendiert.5 parts by weight of long-chain ammonium polyphosphate of the formula according to claim 1 with an average chain length of n = 300 to 400 and a grain size of <63 µ were suspended in 95 parts by weight of naphthenic base oil (Coray 90 °, Esso AG).

Das Testergebnis mit dem Shell-Vierkugel-Apparat ist in Tabelle 2 aufgeführt.The test result with the Shell four-ball apparatus is shown in Table 2.

Vergleichsbeispiel 2aComparative Example 2a

Die Schmierwirkung von reinem naphtenbasischen Öl (Coray 90®) wurde bestimmt.The lubricating effect of pure naphthenic oil (Coray 90®) was determined.

Das Testergebnis mit dem Shell-Vierkugel-Apparat ist in Tabelle 2 aufgeführt.The test result with the Shell four-ball apparatus is shown in Table 2.

Beispiel 3Example 3

2,5 Gewichtsteile langkettiges Ammoniumpolyphosphat (gemäß Beispiel 2) und 2,5 Gewichtsteile Phosphatester auf Basis von Oleylalkohol mit 5 Äthylenoxid-Einheiten wurden in 95 Gewichtsteilen naphtenbasischem Öl (Coray 90®) gelöst.2.5 parts by weight long-chain ammonium polyphosphate (referred to in Example 2) and 2.5 parts by weight based on Phosphatester of oleyl alcohol with 5 ethylene oxide units were dissolved in 95 parts by weight naphtenbasischem oil (Coray 90 ®).

Vergleichsbeispiel 3aComparative Example 3a

5 Gewichtsteile Phosphatester auf Basis von Oleylalkohol mit 5 Äthylenoxid-Einheiten wurden in 95 Gewichtsteilen naphtenbasischem Öl (Coray 90®) gelöst.5 parts by weight of phosphate ester based on oleyl alcohol with 5 ethylene oxide units were dissolved in 95 parts by weight of naphthenic oil (Coray 90®).

Das Testergebnis mit dem Shell-Vierkugel-Apparat ist in Tabelle 2 aufgeführt.

Figure imgb0004
The test result with the Shell four-ball apparatus is shown in Table 2.
Figure imgb0004

Anmerkungannotation

Schweißkraft ist die Prüfkraft, bei der ein Verschweißen des Vierkugelsystems im Prüfgerät eintritt.Whitening power Sc h is the applied load at which welding of the four-ball system enters the test instrument.

Gutkraft ist die vor Erreichen der Schweißkraft gemessene Prüfkraft, bei welcher noch kein Verschweißen des Vierkugelsystems im Prüfgerät eintritt.Good force is the test force measured before the welding force was reached, at which the four-ball system is not yet welded in the test device.

Beispiel 4Example 4

In der beigefügten Zeichnung sind die Tiefziehversuchsergebnisse nach Erichsen (vgl. DIN 50102 ; Januar 1963) dargestellt. Durch den Zusatz von langkettigem Ammoniumpolyphosphat gemäß Formel im Anspruch 1 tritt eine deutliche Zunahme des Ziehweges ein. Mit einer Suspension von 30 Gewichtsteilen eines derartigen Ammoniumpolyphosphats (Exolit 263@, Fa. Hoechst AG) in 70 Gewichtsteilen naphtenbasischem Öl (Coray 90® erhält man bei einem Ziehverhältnis von 2,27 (Rondendurchmesser 75 mm ; Ziehstempel 33 mm 0) einen Näpfchenzug ohne Abriß. Mit ausschließlich Coray 908 kommt es bei einem Ziehverhältnis von 2,27 bereits zum Abriß bei einer Ziehung von 18,4 mm.The attached drawing shows the results of the Erichsen thermoforming test (cf. DIN 50102; January 1963). The addition of long-chain ammonium polyphosphate according to the formula in claim 1 results in a significant increase in the pulling path. With a suspension of 30 parts by weight of an ammonium polyphosphate of this type (Exolit 263 @ , Hoechst AG) in 70 parts by weight of naphthenic oil (Coray 90®), with a draw ratio of 2.27 (disc diameter 75 mm; punch 33 mm 0), a cup is drawn without With only Coray 90 8 with a draw ratio of 2.27 there is already a tear with a draw of 18.4 mm.

Beispiel 5Example 5

10 Gewichtsteile langkettiges Ammoniumpolyphosphat gemäß Beispiel 4 (Exolit 263@, Fa. Hoechst AG) werden unter starkem Rühren in 80 Gewichtsteilen naphtenbasischem Öl (Coray 90®) suspendiert und auf 100°C erwärmt. In diese erwärmte Suspension werden 5 Gewichtsteile eines Oxialkohols (Genapol-X-050@. Fa. Hoechst AG) und 5 Gewichtsteile eines Montan-Wachses (beispielsweise Wachs OP, Handelsprodukt der Fa. Hoechst AG) eingerührt. Nach Abkühlung erhält man ein Schmierfett. Das Testergebnis mit der Reibverschleißwaage nach Reichert (vgl. Beispiel 1) ergab einen Flächendruck von 3,266 bar bei 0 Geräuschmeter. Die Messung wurde im flüssigen Zustand der Paste bei 65°C durchgeführt.10 parts by weight of long-chain ammonium polyphosphate according to Example 4 (Exolit 263 @ , Hoechst AG) are suspended in 80 parts by weight of naphthenic oil (Coray 90®) with vigorous stirring and heated to 100 ° C. 5 parts by weight of an oxy alcohol (Genapol-X-050 @ . Hoechst AG) and 5 parts by weight of a montan wax (for example wax OP, commercial product from Hoechst AG) are stirred into this heated suspension. After cooling, a grease is obtained. The test result with the friction wear balance according to Reichert (see Example 1) showed a surface pressure of 3.266 bar at 0 noise meter. The measurement was carried out in the liquid state of the paste at 65 ° C.

Claims (4)

1. Lubricating and cooling agent for use in metal working, characterized in that it contains, as an addend, a long chain ammonium polyphosphate of the general formula
Figure imgb0006
in which n is a whole number of 50 to 1,000, more especially of 300 to 800, and R stands for an ammonium group.
2. Lubricating and cooling agent as claimed in claim 1, characterized in that up to 20 %, more especially up to 5 % of the ammonium groups of the long chain ammonium polyphosphate are replaced by hydrogen.
3. Lubricating and cooling agent as claimed in claim 1 or 2, characterized in that it contains the long chain ammonium polyphosphate in a proportion of 0.1 to 30 weight %.
4. Lubricating and cooling agent as claimed in claims 1 to 3, characterized in that the long chain ammonium polyphosphate is used in combination with surfactants and/or foam inhibitors and/or coloring agents and/or rust inhibitors and/or phosphate esters.
EP79104352A 1978-11-20 1979-11-07 Lubricating and cooling agent Expired EP0011224B1 (en)

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DE19782850244 DE2850244A1 (en) 1978-11-20 1978-11-20 ADDITIVE FOR METAL WORKING

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JPH0813980B2 (en) * 1988-06-14 1996-02-14 協同油脂株式会社 Hot rolling lubricant composition for steel
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WO2014000166A1 (en) * 2012-06-27 2014-01-03 Huntsman Petrochemical Llc Emulsifier for lubricatiing oil concentrate
KR20230156905A (en) * 2021-03-17 2023-11-15 셰브런 오로나이트 컴퍼니 엘엘씨 Lubricants containing polyphosphate additives

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