EP0642571B1 - Anti-nebel-additiv für wassermischbare und wassergemischte kühlschmierstoffe - Google Patents

Anti-nebel-additiv für wassermischbare und wassergemischte kühlschmierstoffe Download PDF

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Publication number
EP0642571B1
EP0642571B1 EP93912743A EP93912743A EP0642571B1 EP 0642571 B1 EP0642571 B1 EP 0642571B1 EP 93912743 A EP93912743 A EP 93912743A EP 93912743 A EP93912743 A EP 93912743A EP 0642571 B1 EP0642571 B1 EP 0642571B1
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Prior art keywords
acid
water
weight
cooling lubricants
polymer compounds
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EP93912743A
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English (en)
French (fr)
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EP0642571A1 (de
Inventor
Ulrich Eicken
Herbert Lingmann
Raimund Browarzik
Susanne NÖLKE
Wolfgang RÖHRICHT
Manfred Gorzinski
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C10M2207/28—Esters
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    • C10M2209/109—Polyethers, i.e. containing di- or higher polyoxyalkylene groups esterified
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    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
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    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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    • C10M2215/12—Partial amides of polycarboxylic acids
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    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/024—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
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    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10M2223/042—Metal salts thereof
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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
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01—Emulsions, colloids, or micelles

Definitions

  • the invention relates to the use of clear water-soluble polymer compounds with a high molecular weight in water-miscible or water-mixed cooling lubricants to avoid the formation of mist.
  • cooling lubricants is, for example, defined in detail in an information brochure by the mechanical engineering and small iron industry professional association in Düsseldorf. With cooling lubricants, a distinction is made between non-water-miscible, water-miscible and water-mixed cooling lubricants.
  • the group of water-miscible cooling lubricants can further be divided into emulsifiable cooling lubricants and water-soluble cooling lubricants.
  • the group of water-mixed cooling lubricants can be divided into cooling lubricant emulsions and cooling lubricant solutions.
  • Water-miscible cooling lubricants ie concentrates, are mixed with water before use. Emulsifiable cooling lubricants form a discontinuous phase of an oil-in-water emulsion. Cooling lubricants that give solutions mixed with water include not only real solutions but also solutions of the association colloids, for example "solutions of soaps”. The term water-mixed cooling lubricants encompasses water-miscible cooling lubricants in the application state.
  • cooling lubricants are used in particular to reduce the wear on the tool. Due to the strong turbulence during machining, cooling lubricant mists can form, which lead to deposits in the environment, irritation of the respiratory organs when inhaled and therefore lead to undesirable working conditions.
  • An analogous problem arises with the lubrication of impact and drilling tools operated with compressed air, in particular rock drilling machines, breakers and similar devices. These usually receive the compressed air necessary for their operation from a compressor via a hose connection. The compressed air not only serves to drive the tools, but also feeds fine droplets of lubricating oil as lubricant to their moving parts. An excessively strong spray oil causes considerable difficulties, however, because the relaxed compressed air escapes freely at the device and carries the excess lubricating oil as a mist.
  • DE-A-27 14 252 discloses processing oils for metalworking with a reduced tendency to form fog, which contain an atactic polypropylene in a quantity not exceeding 0.5% by weight.
  • 098 abrasives which consist essentially of mineral oil which contain a small amount of an anti-fog additive selected from polyisobutene, Poly-n-butene and mixtures thereof which have an average molecular weight determined by viscosity in the range from 300,000 to 10,000,000.
  • US-A-3 833 502 discloses the use of clear water-soluble polymer compounds in water-miscible or water-mixed cooling lubricants to improve the adhesion to metal surfaces.
  • DE-A-26 57 268 discloses the use of an amorphous ethylene / propylene copolymer in mineral lubricating oils of compressed air tools.
  • Lubrication Engineering, Vol. 33, pp. 128-132 (1977) describes oil mists in the present field as well as the relationships between molecular weights of polymers and their effects on the oil mist. It is stated that the molecular weights of the anti-fog additives to be used should be as high as possible. In particular, it is recommended to use a polymethacrylate with an average molecular weight between 300,000 and 400,000.
  • DE-A-40 00 304 discloses spin finishes in the form of aqueous emulsions or aqueous solutions which contain water-soluble polymer compounds with weight average molecular weights> 10 6 . These are selected from polyalkylene oxides, polyacrylamides, polymethacrylamides and copolymers of acrylamide and / or methacrylamide and unsaturated carboxylic acids with 3 to 5 carbon atoms.
  • the task of the water-soluble polymer compounds is to reduce the spin-off of textile lubricants, in particular of spin finishes from fiber surfaces. This spraying brings with it an impairment of safety, for example slippery floors in the immediate vicinity of the machines, as well as breathing difficulties and skin irritation, caused by droplets being thrown off and distributed in the form of fine mist.
  • the object of the present invention is to develop new water-soluble anti-fog additives for water-miscible, i.e. Concentrates, or water-mixed, i.e. To provide application solutions, cooling lubricants, in which the formation of fog is suppressed or completely avoided.
  • the above object is achieved by the use of known, clear water-soluble polymer compounds with weight average molecular weights> 10 6 , which are selected from polyalkylene oxides, polyacrylamides, polymethacrylamides and copolymers of acrylamide and / or methacrylamide and unsaturated organic carboxylic acids with 3 to 5 carbon atoms. Atoms, in water-miscible or water-mixed cooling lubricants to avoid the formation of fog.
  • cooling lubricants modified according to the invention thus comprise water-miscible and water-mixed cooling lubricants.
  • polyethylene oxides are particularly preferred as the polymer compound.
  • Polyethylene oxides with weight average molecular weights> 10 6 are, for example, from Union Carbide as powder under the name Polyox R WSR 301 (molecular weight above 10 6 ) and Polyox R Coagulant (molecular weight 5,000,000) and polyacrylamides with weight average molecular weights> 10 6 , for example from Henkel KGaA under the name Ferrocryl R or from Stockhausen under the name Praestol R.
  • Copolymers of acrylamide and unsaturated carboxylic acids with 3 to 5 carbon atoms for example copolymers of acrylamide and acrylic acid with weight average molecular weights> 10 6 available, for example, under the name Superfloc R (manufacturer: cyanamid).
  • the clear water-soluble polymer compounds in an amount of 0.00001 wt .-% to 0.1 wt .-%, in particular 0.001 wt .-% to 0.01 wt .-%, based on the aqueous Emulsion or aqueous solution of cooling lubricants used.
  • composition of the water-miscible or water-mixed cooling lubricants can be very different.
  • emulsions frequently contain natural, paraffinic, naphthenic, paraffinic-naphthenic mineral oils in addition to other additives.
  • cooling lubricant emulsions can be built up, for example, from ester oils, fatty oil derivatives, synthetic hydrocarbons, poly- ⁇ -olefins, such as polyisobutylene or polybutenes, polypropylene glycol, trimethylolpropane ester, neopentyl-pentaerythritol ester, di- (2-ethylhexyl) sebacate, di- ( 2-ethylhexyl) adipate, dibutyl phthalate and / or esters of phosphorus-containing acids.
  • ester oils such as polyisobutylene or polybutenes
  • polypropylene glycol trimethylolpropane ester
  • neopentyl-pentaerythritol ester di- (2-ethylhexyl) sebacate
  • di- ( 2-ethylhexyl) adipate dibutyl phthalate
  • cooling lubricants are aqueous solutions of inorganic salts, such as phosphates, borates, carbonates, and organic rust inhibitors, such as amines, alkanolamines and substituted alkanolamines, and their reaction products with inorganic and organic acids.
  • inorganic salts such as phosphates, borates, carbonates, and organic rust inhibitors, such as amines, alkanolamines and substituted alkanolamines, and their reaction products with inorganic and organic acids.
  • Such acids include, for example, natural or synthetic carboxylic acids such as caprylic acid, ethylhexanoic acid, capric acid, 2,2,4-trimethylhexanoic acid, benzoic acid, substituted benzoic acids, dicarboxylic acids with 6-22 C atoms, phosphoric acid esters, dicarboxylic acid half-esters or dicarboxylic acid half-amides, citric acid, gluconic acid , Carbonic acid, phosphoric acid, polyphosphoric acid and Boric acid.
  • cooling lubricant solutions often contain water-soluble lubricants such as glycols and polyglycols as well as ethers or esters of polyglycols and other additives for setting the desired technical properties.
  • lubricants such as lubricants, antiwear agents, corrosion inhibitors, antioxidants, anionic or nonionic emulsifiers, solubilizers, antifoams, biocides and / or surfactants can be added to the base material, which comprises a predominant proportion of one or more of the cooling lubricants mentioned above. These are known per se in the prior art.
  • the cooling lubricant concentrates are diluted with water.
  • the aqueous emulsions or aqueous solutions preferably contain the cooling lubricants mentioned above in an amount of 1 to 10% by weight, in particular in an amount of 2 to 5% by weight.
  • the polymer compounds to be used as anti-fog additive are packaged in tablet form, since this form permits easier and more precise metering of the anti-fog additives according to the invention.
  • the clear water-soluble polymer compounds are preferably mixed in a 1: 1 weight ratio with 1,2-propanediol and compressed either in the temperature range from room temperature to 150 ° C. using pressure, for example in the range from 10 to 100 bar, or without pressure at temperatures in the range of 50 to 150 ° C, especially 80 to 100 ° C, sintered together.
  • pressure for example in the range from 10 to 100 bar, or without pressure at temperatures in the range of 50 to 150 ° C, especially 80 to 100 ° C, sintered together.
  • Such anti-fog additive tablets are added to the aqueous cooling lubricant emulsions or solutions in the desired dosage.
  • Aqueous emulsions or solutions of cooling lubricants in the sense of the present invention are preferably used for grinding metal surfaces.
  • a 1% by weight aqueous solution of Polyox R Coagulant (polyethylene oxide with a molecular weight of 5,000,000) was produced as an anti-fog additive for aqueous cooling lubricants.
  • the effectiveness was tested on a commercially available grinding water which consisted of 10% by weight of isononanoic acid, 30% by weight of triethanolamine, 1% by weight of corrosion inhibitor and 5% by weight of sodium metaborate in water.
  • a different amount of the anti-fog additive is added.
  • the values relate to the percentage addition of the 1% by weight solution of Polyox R Coagulant to the grinding water mentioned.
  • Table 1 below shows the visual assessment of the fog formation in the examples and the comparative example.

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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)
  • Inorganic Chemistry (AREA)
  • Lubricants (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)

Description

  • Die Erfindung betrifft die Verwendung von klarwasserlöslichen Polymerverbindungen mit hohem Molekulargewicht in wassermischbaren oder wassergemischten Kühlschmierstoffen zur Vermeidung der Nebelbildung.
  • Der Begriff der Kühlschmierstoffe ist beispielsweise in einer Informationsbroschüre der Maschinenbau- und Kleineisenindustrie-Berufsgenossenschaft Düsseldorf in ausführlicher Weise definiert. Bei Kühlschmierstoffen unterscheidet man zwischen nicht wassermischbaren, wassermischbaren und wassergemischten Kühlschmierstoffen.
  • Die Gruppe der wassermischbaren Kühlschmierstoffe läßt sich weiterhin unterteilen in emulgierbare Kühlschmierstoffe, und wasserlösliche Kühlschmierstoffe. Die Gruppe der wassergemischten Kühlschmierstoffe läßt sich unterteilen in Kühlschmieremulsionen und Kühlschmierlösungen.
  • Wassermischbare Kühlschmierstoffe, d.h. Konzentrate, werden vor der Anwendung mit Wasser gemischt. Emulgierbare Kühlschmierstoffe bilden eine diskontinuierliche Phase einer Emulsion Öl-in-Wasser. Kühlschmierstoffe, die mit Wasser gemischt Lösungen ergeben, umfassen neben echten Lösungen auch Lösungen der Assoziationskolloide, z.B. "Lösungen von Seifen". Der Begriff wassergemischte Kühlschmierstoffe umfaßt wassermischbare Kühlschmierstoffe im Anwendungszustand.
  • Begriffe wie Bohremulsion, Bohrmilch, Kühlmittel, Schleifwasser, Schleiföl oder Räumöl werden auch heute noch in der betrieblichen Umgangssprache verwendet.
  • Bei der Metallbearbeitung, insbesondere solchen Vorgängen wie Schneiden mit hoher Geschwindigkeit, Schleifen oder Verformen, werden insbesondere wassermischbare Kühlschmiermittel verwendet, um die Abnutzung des Werkzeuges zu vermindern. Durch die starke Verwirbelung bei der Bearbeitung können Kühlschmierstoff-Nebel entstehen, die in der Umgebung zu Ablagerungen führen, beim Einatmen zu Reizungen der Atemorgane und daher zu wenig erwünschten Arbeitsbedingungen führen. Ein analoges Problem tritt bei der Schmierung von mit Preßluft betriebenen Schlag- und Bohrwerkzeugen auf, insbesondere Gesteinsbohrmaschinen, Abbauhämmern und ähnlichen Geräten. Diese erhalten gewöhnlich die zu ihrem Betrieb notwendige Druckluft über eine Schlauchverbindung von einem Verdichter. Die Druckluft dient nicht nur zum Antrieb der Werkzeuge, sondern führt ihren bewegten Teilen zugleich feine Schmieröltröpfchen als Schmiermittel zu. Eine übermäßig starke Sprühölung verursacht jedoch erhebliche Schwierigkeiten, da die entspannte Druckluft am Gerät frei austritt und das überflüssige Schmieröl als Nebel mitführt.
  • Aus der DE-A-27 14 252 sind Bearbeitungsöle für die Metallbearbeitung mit verringerter Neigung zur Nebelbildung bekannt, die ein ataktisches Polypropylen in einer 0,5 Gew.-% nicht übersteigenden Menge enthalten.
  • Aus der US-A-3 919 098 sind Schleifmittel bekannt, die im wesentlichen aus Mineralöl bestehen, die eine geringe Menge eines Anti-Nebel-Additivs enthalten, das ausgewählt ist aus Polyisobuten, Poly-n-buten und deren Mischungen, die ein durch Viskosität bestimmtes mittleres Molekulargewicht im Bereich von 300 000 bis 10 000 000 aufweisen.
  • Aus der US-A-3 833 502 ist die Verwendung von klarwasserlöslichen Polymerverbindungen in wassermischbaren oder wassergemischten Kühlschmierstoffen zur Verbesserung der Adhäsion an Metalloberflächen bekannt.
  • Aus der DE-A-26 57 268 ist die Verwendung eines amorphen Ethylen/Propylen-Mischpolymerisats in Mineralschmierölen von Preßluftwerkzeugen bekannt.
  • In Lubrication Engineering, Vol. 33, S. 128-132 (1977) werden Ölnebel auf dem hier vorliegenden Gebiet sowie die Zusammenhänge von Molekulargewichten von Polymeren und deren Auswirkungen auf den Ölnebel eingehend beschrieben. Es wird angegeben, daß die Molekulargewichte der einzusetzenden Anti-Nebel-Additive so hoch wie möglich sein sollten. Insbesondere wird empfohlen, ein Polymethacrylat mit einem mittleren Molekulargewicht zwischen 300 000 und 400 000 einzusetzen.
  • Aus der DE-A-40 00 304 sind Spinnpräparationen in Form wäßriger Emulsionen oder wäßriger Lösungen bekannt, die wasserlösliche Polymerverbindungen mit Gewichtsmitteln der Molekulargewichte >106 enthalten. Diese sind ausgewählt aus Polyalkylenoxiden, Polyacrylamiden, Polymethacrylamiden und Copolymeren aus Acrylamid und/oder Methacrylamid und ungesättigten Carbonsäuren mit 3 bis 5 C-Atomen. Die Aufgabe der wasserlöslichen Polymerverbindungen besteht in einer Verminderung des Abschleuderns von textilen Gleitmitteln, insbesondere von Spinnpräparationen von Faseroberflächen. Dieses Abspritzen bringt eine Beeinträchtigung der Sicherheit mit sich, beispielsweise schlüpfrige Fußböden in der unmittelbaren Umgebung der Maschinen sowie Atmungsbehinderungen und Hautreizungen, hervorgerufen durch abgeschleuderte Tröpfchen, die sich in Form feiner Nebel verteilen.
  • Die Aufgabe der vorliegenden Erfindung besteht demgegenüber darin, neue wasserlösliche Anti-Nebel-Additive für wassermischbare, d.h. Konzentrate, oder wassergemischte, d.h. Anwendungslösungen, Kühlschmierstoffe zur Verfügung zu stellen, bei denen die Nebelbildung unterdrückt bzw. gänzlich vermieden wird.
  • Die vorstehende Aufgabe wird gelöst durch die Verwendung an von an sich bekannten klarwasserlöslichen Polymerverbindungen mit Gewichtsmitteln der Molekulargewichte >106, die ausgewählt sind aus Polyalkylenoxiden, Polyacrylamiden, Polymethacrylamiden und Copolymeren von Acrylamid und/oder Methacrylamid und ungesättigten organischen Carbonsäuren mit 3 bis 5 C-Atomen, in wassermischbaren oder wassergemischten Kühlschmierstoffen zur Vermeidung der Nebelbildung.
  • Überraschenderweise wurde gefunden, daß der Zusatz der genannten hochmolekulargewichtigen Polymerverbindungen in den genannten Kühlschmierstoffen geeignet ist, die Nebelbildung zu unterdrücken. Die erfindungsgemäß modifizierten Kühlschmierstoffe umfassen somit wassermischbare und wassergemischte Kühlschmierstoffe.
  • Besonders bevorzugt im Sinne der vorliegenden Erfindung sind Polyethylenoxide als Polymerverbindung. Polyethylenoxide mit Gewichtsmitteln der Molekulargewichte >106 werden beispielsweise von Union Carbide als Pulver unter dem Namen PolyoxR WSR 301 (Molekulargewicht oberhalb 106) und PolyoxR Coagulant (Molekulargewicht 5 000 000) und Polyacrylamide mit Gewichtsmitteln der Molekulargewichte >106, beispielsweise von Henkel KGaA unter der Bezeichnung FerrocrylR oder von Stockhausen unter der Bezeichnung PraestolR angeboten. Copolymere aus Acrylamid und ungesättigten Carbonsäuren mit 3 bis 5 C-Atomen, beispielsweise Copolymere aus Acrylamid und Acrylsäure mit Gewichtsmitteln der Molekulargewichte >106 sind beispielsweise unter dem Namen SuperflocR (Hersteller: Cyanamid) erhältlich.
  • In einer bevorzugten Ausführungsform der vorliegenden Erfindung werden die klarwasserlöslichen Polymerverbindungen in einer Menge von 0,00001 Gew.-% bis 0,1 Gew.-%, insbesondere 0,001 Gew.-% bis 0,01 Gew.-%, bezogen auf die wäßrige Emulsion oder wäßrige Lösung von Kühlschmierstoffen verwendet.
  • Die Zusammensetzung der wassermischbaren oder wassergemischten Kühlschmierstoffe kann sehr unterschiedlich sein. So enthalten Emulsionen im Sinne der vorliegenden Erfindung häufig natürliche, paraffinische, naphthenische, paraffinisch-naphthenische Mineralöle neben weiteren Zusätzen. Ferner können solche Kühlschmierstoff-Emulsionen beispielsweise aufgebaut sein aus Esterölen, Fettöl-Derivaten, synthetischen Kohlenwasserstoffen, Poly-α-olefinen, wie Polyisobutylen oder Polybutenen, Polypropylenglykol, Trimethylolpropanester, Neopentyl-pentaerythritester, Di-(2-ethylhexyl)sebacat, Di-(2-ethylhexyl)adipat, Dibutylphthalat und/oder Estern von Phosphor enthaltenden Säuren.
  • Eine weitere Ausführungsform der Kühlschmierstoffe sind wäßrige Lösungen von anorganischen Salzen, wie Phosphaten, Boraten, Carbonaten, und organischen Rostschutzmitteln, wie Aminen, Alkanolaminen und substituierten Alkanolaminen, sowie ihren Umsetzungsprodukten mit anorganischen und organischen Säuren. Solche Säuren umfassen beispielsweise natürliche oder synthetische Carbonsäuren wie Caprylsäure, Ethylhexansäure, Caprinsäure, 2,2,4-Trimethylhexansäure, Benzoesäure, substitutierte Benzoesäuren, Dicarbonsäuren mit 6 - 22 C-Atomen, Phosphorsäureester, Dicarbonsäure-Halbester oder Dicarbonsäure-Halbamide, Zitronensäure, Gluconsäure, Kohlensäure, Phosphorsäure, Polyphosphorsäure und Borsäure. Weiterhin enthalten Kühlschmierstoff-Lösungen häufig wasserlösliche Schmierstoffe wie Glykole und Polyglykole sowie Ether oder Ester von Polyglykolen und weitere Zusätze zur Einstellung der erwünschten technischen Eigenschaften.
  • Zu dem Grundmaterial, das einen überwiegenden Anteil eines oder mehrerer der oben genannten Kühlschmierstoffe umfaßt, können weitere funktionelle Zusatzstoffe, wie Schmierfähigkeitsmittel, Antiverschleißmittel, Korrosionsinhibitoren, Antioxidantien, anionische oder nichtionische Emulgatoren, Lösungsvermittler, Antischaummittel, Biozide und/oder Tenside zugesetzt werden. Diese sind an sich im Stand der Technik bekannt.
  • Zur Anwendung werden die Kühlschmierstoff-Konzentrate mit Wasser verdünnt. Die wäßrigen Emulsionen oder wäBrigen Lösungen enthalten die oben genannten Kühlschmierstoffe vorzugsweise in einer Menge von 1 bis 10 Gew.-%, insbesondere in einer Menge von 2 bis 5 Gew.-%.
  • Gemäß einer weiteren bevorzugten Ausführungsform der vorliegenden Erfindung werden die als Anti-Nebel-Additiv zu verwendenden Polymerverbindungen in Tablettenform konfektioniert, da diese Form eine leichtere und genauere Dosierung der erfindungsgemäßen Anti-Nebel-Additive erlaubt.
  • Zur Herstellung derartiger Tabletten werden die klarwasserlöslichen Polymerverbindungen vorzugsweise im Gewichtsverhältnis 1 : 1 mit 1,2-Propandiol vermischt und entweder im Temperaturbereich von Raumtemperatur bis 150 °C unter Anwendung von Druck, beispielsweise im Bereich von 10 bis 100 bar, verpreßt oder drucklos bei Temperaturen im Bereich von 50 bis 150 °C, insbesondere 80 bis 100 °C, zusammengesintert. Hierbei resultiert zunächst eine kautschukartige Masse, die im Verlauf von beispielsweise 24 Stunden kristallisiert und so eine feste Tablette ausbildet.
  • Derartige Anti-Nebel-Additiv-Tabletten werden zur Anwendung den wäßrigen Kühlschmierstoff-Emulsionen oder -Lösungen in der gewünschten Dosierung zugesetzt.
  • Wäßrige Emulsionen oder Lösungen von Kühlschmierstoffen im Sinne der vorliegenden Erfindung werden bevorzugt zum Schleifen von Metalloberflächen eingesetzt.
    • Beispiele
  • Als Anti-Nebel-Additiv für wäßrige Kühlschmierstoffe wurde eine 1 Gew.-%ige wäßrige Lösung von PolyoxR Coagulant (Polyethylenoxid mit einem Molekulargewicht von 5 000 000) hergestellt.
  • Die Wirksamkeit wurde an einem handelsüblichen Schleifwasser geprüft, das aus 10 Gew.-% Isononansäure, 30 Gew.-% Triethanolamin, 1 Gew.-% Korrosionsinhibitor sowie 5 Gew.-% Natriummetaborat in Wasser bestand.
  • Zur Beurteilung der Nebelbildung wurden 50 ml der oben genannten Schleifwässer in einen 250 ml Meßzylinder mit Stopfen gegeben und geschüttelt. Dabei bildete sich ein Schaum, der nach Beendigung des Schüttelns rasch zerfiel. Durch das Zerplatzen der Schaumblasen bildete sich ein feiner Nebel. Die sich dabei bildende Nebelmenge wurde visuell beurteilt.
  • In den Beispielen und dem Vergleichsbeispiel wird jeweils eine unterschiedliche Menge des Anti-Nebel-Additivs zugegeben. Die Werte beziehen sich jeweils auf den prozentualen Zusatz der 1 Gew.-%igen Lösung von PolyoxR Coagulant zu dem genannten Schleifwasser.
  • Die nachfolgende Tabelle 1 gibt die visuelle Beurteilung der Nebelbildung der Beispiele und des Vergleichsbeispiels wieder. Tabelle 1
    Beispiel Zusatz Nebelbildung
    1 0,001 Gew.-% verringerte Nebelbildung
    2 0,001 Gew.-% keine Nebelbildung
    3 0,01 Gew.-% keine Nebelbildung
    Vgl.1 0,0 Gew.-% starke Nebelbildung
    • Herstellung von Anti-Nebel-Additiv-Tabletten
  • Es wurden Gemische aus jeweils 1 Gew.-Teil PolyoxR Coagulant und 1 Gew.-Teil 1,2-Propandiol bei
    • a) 50 °C, Normaldruck, 24 Stunden und
    • b) 80 °C, Normaldruck, 2 Stunden
    getempert.
  • In beiden Fällen resultierten feste, belastbare Produkte. Derartige Tabletten lösen sich im Wasser allmählich auf.

Claims (9)

  1. Verwendung von klarwasserlöslichen Polymerverbindungen mit Gewichtsmitteln der Molekulargewichte >106, ausgewählt aus Polyalkylenoxiden, Polyacrylamiden, Polymethacrylamiden und Copolymeren von Acrylamid und/oder Methacrylamid und ungesättigten organischen Carbonsäuren mit 3 bis 5 C-Atomen, in wassermischbaren oder wassergemischten Kühlschmierstoffen zur Verminderung der Nebelbildung.
  2. Verwendung von Polyethylenoxiden als Polymerverbindungen nach Anspruch 1.
  3. Verwendung von klarwasserlöslichen Polymerverbindungen nach Anspruch 1 oder 2 in einer Menge von 0,00001 Gew.-% bis 0,1 Gew.-%, insbesondere 0,001 Gew.-% bis 0,01 Gew.-%, bezogen auf die wäßrige Emulsion oder wäßrige Lösung von Kühlschmierstoffen.
  4. Verwendung nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Kühlschmierstoff-Emulsionen aufgebaut sind auf natürlichen, paraffinischen, naphthenischen, paraffinisch-naphthenischen Mineralölen Esterölen, Fettöl-Derivaten, synthetischen Kohlenwasserstoffen, Poly-α-olefinen, wie Polyisobutylenen oder Polybutenen, Polypropylenglykol, Trimethylolpropanestern, Neopentyl-pentaerythritestern, Di-(2-ethylhexyl)sebacat, Di-(2-ethylhexyl)adipat, Dibutylphthalat, Estern von Phosphor enthaltenden Säuren und weiteren Zusätzen.
  5. Verwendung nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Kühlschmierstoff-Lösungen aufgebaut sind auf wäßrigen Lösungen von anorganischen Salzen, insbesondere Phosphaten, Boraten und/oder Carbonaten, und organischen Rostschutzmitteln, insbesondere Aminen, Alkanolaminen, substituierten Alkanolaminen und deren Umsetzungsprodukten mit anorganischen und/oder organischen Säuren, insbesondere natürlichen oder synthetischen Carbonsäuren, insbesondere Caprylsäure, Ethylhexansäure, Caprinsäure, 2,2,4-Trimethylhexansäure, Benzoesäure, substituierte Benzoesäuren, Dicarbonsäuren mit 6 - 22 C-Atomen, Phosphorsäureestern, Dicarbonsäure-Halbestern oder Dicarbonsäure-Halbamiden, Zitronensäure, Gluconsäure, Kohlensäure, Phosphorsäure, Polyphosphorsäure, Borsäure und weiteren Zusätzen.
  6. Verwendung nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die wäßrigen Emulsionen oder wäßrigen Lösungen funktionelle Zusatzstoffe, insbesondere Schmierfähigkeitsmittel, Antiverschleißmittel, Korrosionsinhibitoren, Antioxidantien, anionische oder nichtionische Emulgatoren, Lösungsvermittler, Antischaummittel, Biozide und/oder Tenside enthalten.
  7. Verwendung nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die wäßrigen Emulsionen oder wäßrigen Lösungen die Kühlschmierstoffe in einer Menge von 1 bis 10 Gew.-%, insbesondere von 2 bis 5 Gew.-%, enthalten.
  8. Verwendung nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die klarwasserlöslichen Polymerverbindungen zusammen mit 1,2-Propandiol im Gewichtsverhältnis 1 : 1 in Tablettenform konfektioniert sind.
  9. Verwendung nach einem oder mehreren der Ansprüche 1 bis 8 zum Schleifen von Metalloberflächen.
EP93912743A 1992-05-29 1993-05-21 Anti-nebel-additiv für wassermischbare und wassergemischte kühlschmierstoffe Expired - Lifetime EP0642571B1 (de)

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DE4217859A DE4217859A1 (de) 1992-05-29 1992-05-29 Anti-Nebel-Additiv für wassermischbare und wassergemischte Kühlschmierstoffe
DE4217859 1992-05-29
PCT/EP1993/001269 WO1993024601A1 (de) 1992-05-29 1993-05-21 Anti-nebel-additiv für wassermischbare und wassergemischte kühlschmierstoffe

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CN1036527C (zh) * 1994-08-26 1997-11-26 巢剑崙 一种煤矿液压支架用浓缩传动液
SG50827A1 (en) * 1996-05-13 1998-07-20 Lubrizol Corp Sulfonate containing copolymers as mist suppressants in soluble oil (water-based) metal working fluids
US5783529A (en) * 1997-10-24 1998-07-21 The Lubrizol Corporation Rhamsan gum as mist suppressant in metal working fluids
US6020291A (en) * 1997-11-21 2000-02-01 The Lubrizol Corporation Branched sulfonate containing copolymers as mist suppressants in soluble oil (water-based) metal working fluids
DE19931220B4 (de) 1999-07-06 2005-03-10 Clariant Gmbh Verwendung von Polymeren als Anti-Nebel-Additiv in wasserbasierenden Kühlschmierstoffen
DE19931218B4 (de) 1999-07-06 2005-06-02 Clariant Gmbh Verwendung von Polymeren als Anti-Nebel-Additiv in wasserbasierenden Kühlschmierstoffen
DE19931219C2 (de) 1999-07-06 2001-06-07 Clariant Gmbh Verwendung von Polymeren als Anti-Nebel-Additiv in wasserbasierenden Kühlschmierstoffen
US6475408B1 (en) 2000-09-28 2002-11-05 The Lubrizol Corporation Shear-stable mist-suppressing compositions
WO2014155870A1 (ja) 2013-03-26 2014-10-02 住友精化株式会社 水溶性金属加工油剤
CN106675754A (zh) * 2016-12-26 2017-05-17 广东山之风环保科技有限公司 水基切削液抑雾剂及水基切削液

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US3833502A (en) * 1973-04-30 1974-09-03 Nalco Chemical Co Method for improving the adherence of metalworking coolants to metal surfaces
US4432881A (en) * 1981-02-06 1984-02-21 The Dow Chemical Company Water-dispersible hydrophobic thickening agent
US4493777A (en) * 1982-12-20 1985-01-15 The Dow Chemical Company Water-based hydraulic fluids
US4853140A (en) * 1987-08-21 1989-08-01 Nalco Chemical Company Lubricating fluids for slicing silicon ingots
US4853447A (en) * 1987-12-21 1989-08-01 Exxon Research And Engineering Company Polymerization of cationic N,N-dimethylalkylamine type monomers
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DE59303150D1 (de) 1996-08-08

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