EP0204196A1 - Brominated alkyl benzenes as a basis of fire-resistant, biodegradable functional fluids - Google Patents

Brominated alkyl benzenes as a basis of fire-resistant, biodegradable functional fluids Download PDF

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Publication number
EP0204196A1
EP0204196A1 EP86106678A EP86106678A EP0204196A1 EP 0204196 A1 EP0204196 A1 EP 0204196A1 EP 86106678 A EP86106678 A EP 86106678A EP 86106678 A EP86106678 A EP 86106678A EP 0204196 A1 EP0204196 A1 EP 0204196A1
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Prior art keywords
derivative
functional liquid
bromotoluene
liquid according
flame
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German (de)
French (fr)
Inventor
Helmut Theunissen
Raymund Dr. Weber
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HYDROCOR FORSCHUNGS- und ANALYTIK GmbH
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HYDROCOR FORSCHUNGS- und ANALYTIK GmbH
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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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/50—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing halogen
    • C10M105/52—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing halogen containing carbon, hydrogen and halogen 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • 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
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/02—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only
    • C10M2211/024—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only aromatic
    • 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
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/06—Perfluorinated 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
    • C10M2215/02—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
    • C10M2215/064—Di- and triaryl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
    • C10M2215/082—Amides containing hydroxyl groups; Alkoxylated derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2223/045—Metal containing thio derivatives
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids

Definitions

  • the invention is a flame-retardant biodegradable functional fluid, especially a hydraulic fluid, the e-stand part contains as an essential B a bromobenzene derivative.
  • Chlorinated aromatics especially chlorinated biphenyls
  • the polychlorinated biphenyls in particular have been widely used as hydraulic fluids, as insulation fluids for electrical systems and as flame-retardant additives for plastics and the like.
  • these connections have been badly discredited.
  • Serious health and environmental effects of these products have been identified, and catastrophic hazards are possible if there is a fire, since this can form highly toxic dioxins and dibenzofurans. This has resulted in the fact that the production or at least the use of such compounds has already been completely banned by the state supervisory bodies and that severe regulations have been enacted to restrict the use of these substances.
  • GB-PS 1 504 655 describes electrical devices which contain readily biodegradable dielectric liquids, namely halogenated diphenylmethanes, which are characterized in that the halogen substituents and any alkyl substituents are only present in one of the two phenyl rings, while the other phenyl ring must be unsubstituted, where it is stated that only those halogenated diphenylmethanes which have an unsubstituted phenyl group can readily be biodegraded, while the diphenylmethanes substituted on both phenyl radicals are intended to resist microbiological degradation.
  • the older German patent application 34 02 863 describes bromine-containing benzyltoluene derivatives which can be used as functional fluids, for example hydraulic fluids or insulating fluids for electrical devices, and which are distinguished by the fact that they have a favorable environmental compatibility in that the benzyltoluene skeleton in comparison with the biphenyl skeleton Halogenated biphenyls commonly used for these purposes are more readily biodegradable.
  • DE-OS 15 94 505 describes functional liquid preparations which contain a larger amount of a dihalogenated diphenyl ether and a smaller amount of further mixture constituents which are selected from halogenated nie-drigalkyl-substituted benzenes, monohalogenated diphenyl ethers and chlorinated biphenyls and mixtures thereof.
  • halogenated Niedrigalkylbenzole such are indicated by 1 to 5 halogen atoms and 1 to 4 carbon atoms in the alkyl group, and of these smaller than M ischungs concerned spateil compounds to be employed dibromoethylbenzene preferably appears. About the sole use of such compounds or nothing is said in this document about their biodegradability.
  • U.S. Patent No. 2,257,903 discloses non-flammable liquid preparations which can be used as heat transfer liquids, dielectrics, fire extinguishing agents and flame retardants. These liquid preparations consist essentially of mixtures of brominated monoethylbenzenes with a bromine content of between about 2.0 and about 3.0 atoms of bromine per mole of ethylbenzene. No information is available on the biodegradability of these materials.
  • the functional fluids known from the prior art cannot fully satisfy because they cannot meet all the criteria of a flame-resistant functional fluid, namely hydraulic fluid, namely economical production, biodegradability, low toxicity of the fluid or its decomposition products and the like.
  • the object of the present invention is now to provide functional fluids that meet only the technological for the intended application criteria, the toxicological and economic A nforderun- gen.
  • the invention thus relates to a flame-retardant, biodegradable functional liquid, consisting of or containing at least one bromobenzene derivative of the general formula (I) where n is a number from 1 to 4 and x is a number from 1 to 5.
  • the functional liquid preferably contains, as bromobenzene derivative, a bromobenzene derivative of the general formula (II) where x is a number from 1 to 5.
  • the bromotoluene derivatives used as or in functional liquids according to the invention can be used in the form of pure compounds, in the form of isomer mixtures or also in the form of mixtures with compounds of different degrees of bromination, the selection advantageously being made so that the bromotoluenes used have a bromine content of about 60 % By weight have, in order to give particularly flame-resistant functional liquids, and on the other hand are liquid within a relatively wide temperature range of preferably -25 ° C to 220 ° C. The latter condition can easily be met by using mixtures of isomers.
  • a bromobenzene derivative used in the bromination of benzene is a mixture of bromobenzene derivatives. Mixtures of one or more bromobenzene derivatives which have 1 to 3 bromine atoms as core substituents are particularly preferably used.
  • dibromotoluene derivatives as bromobenzene derivative, which can be used in the form of the pure isomers or in the form of isomer mixtures.
  • the dibromotoluenes have proven to be particularly well suited for functional liquids, since on the one hand they have excellent technological properties which are necessary for use in or as functional liquids and on the other they show unexpectedly good environmental behavior, ie as such they have very low toxicity, no toxic decomposition products when heated, such as highly toxic dioxin derivatives, and moreover can be easily biodegraded.
  • the bromobenzene derivatives and in particular the dibromotoluenes can advantageously be used in the form of the mixture obtained in the bromination of toluene, it being possible for these compounds or also these mixtures to be advantageously combined with other brominated compounds, such as, in particular, dibromethylbenzene and / or dibromocumol.
  • other brominated compounds such as, in particular, dibromethylbenzene and / or dibromocumol.
  • the flame-retardant, biodegradable functional liquid according to the invention may also contain additives and additives customary for such functional liquids, the bromobenzene derivatives preferably being present in an amount of at least 35% by weight.
  • Additives and additives of this type include, for example, corrosion inhibitors, such as alkaline earth metal sulfonates, stabilizers, such as amine derivatives or phenolic products, wear-reducing additives, for example zinc dialkyldithiophosphates, acid acceptors, for example epoxy compounds, tetraphenyltin, etc., defoamers, such as soaps, silicones, glycols, phosphates and phosphate esters.
  • Use viscosity index improvers such as polymethacrylates or polyisobutylene and the like.
  • the functional liquids according to the invention can be used with many suitable products, such as for example, mineral oils, glycols, etc., are modified.
  • the bromobenzene derivatives used according to the invention are obtained by brominating benzene or alkylbenzene with elemental bromine, known per se, in the presence of a known halogenation catalyst, such as iron, iron trichloride, iron tribromide or the like.
  • a known halogenation catalyst such as iron, iron trichloride, iron tribromide or the like.
  • the reaction can be carried out at room temperature, but depending on the catalyst in question, temperatures between -5 and + 40 ° C are also suitable.
  • the following preparation example serves to explain the preparation of the dibromotoluene which is preferably used according to the invention.
  • Boiling point mixture 236 to 245 ° C / 1013 mbar (105 ° C / 2.5 mbar) 3,5-dibromotoluene: mp: 38 to 40 ° C, bp 246 ° C / 1013 mbar 2,6-dibromotoluene: bp 243 ° C / 1013 mbar 2,5-dibromotoluene: mp 5.6 ° C, bp 236 ° C / 1013 mbar

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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)
  • Fireproofing Substances (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Hardly inflammable biodegradable functional liquids are comprised in whole or in part of at least one brominated benzol derivative having general formula (I), wherein n has a value comprised between 1 and 4 and x has a value comprised between 1 and 5.

Description

Gegenstand der Erfindung ist eine schwerentflammbare, biologisch abbaubare funktionellen Flüssigkeit, namentlich eine Hydraulikflüssigkeit, die als wesentlichen Be-standteil ein Brombenzolderivat enthält.The invention is a flame-retardant biodegradable functional fluid, especially a hydraulic fluid, the e-stand part contains as an essential B a bromobenzene derivative.

Chlorierte Aromaten, insbesondere chlorierte Biphenyle, haben in den letzten Jahrzehnten einen bedeutenden Platz in weiten Bereichen der Technik eingenommen. Besonders die polychlorierten Biphenyle wurden in großem Umfang als Hydraulikflüssigkeiten, als Isolationsflüssigkeiten für elektrische Anlagen und als flammhemmende Zusätze für Kunststoffe und dergleichen eingesetzt. Indessen sind in den letzten Jahren diese Verbindungen in erheblichen Verruf geraten. Es wurde schwere gesundheits- und umweltschädigende Wirkungen dieser Produkte festgestellt, wobei katastrophenartige Gefahren möglich sind, wenn es zu Bränden kommt, da hierbei hochgiftige Dioxine und Dibenzofurane gebildet werden können. Dies hat dazu geführt, daß die Herstellung oder zumindest die Verwendung solcher Verbindungen von den staatlichen Aufsichtsorganen zum Teil schon völlig verboten wurde und zum Teil gravierende Vorschriften erlassen wurden, die die Verwendung dieser Stoffe einschränken sollen.Chlorinated aromatics, especially chlorinated biphenyls, have played an important role in a wide range of technology in recent decades. The polychlorinated biphenyls in particular have been widely used as hydraulic fluids, as insulation fluids for electrical systems and as flame-retardant additives for plastics and the like. In the meantime, however, these connections have been badly discredited. Serious health and environmental effects of these products have been identified, and catastrophic hazards are possible if there is a fire, since this can form highly toxic dioxins and dibenzofurans. This has resulted in the fact that the production or at least the use of such compounds has already been completely banned by the state supervisory bodies and that severe regulations have been enacted to restrict the use of these substances.

Zur Überwindung dieser Nachteile wird in der europäischen Patentanmeldung Nr. 88 650 vorgeschlagen, als Schmiermittel, die auch als Hydraulikflüssigkeiten eingesetzt werden können, chlorierte Benzyltoluole und chlorierte Benzylxylole einzusetzen, da diese Verbindungen schwer entflammbar und oxidationsbeständig und daneben biologisch abbaubar sein und im Hinblick auf ihr toxisches Verhalten Vorteile aufweisen sollen.To overcome these disadvantages, it is proposed in European Patent Application No. 88 650 to use chlorinated benzyltoluenes and chlorinated benzylxylenes as lubricants, which can also be used as hydraulic fluids, since these compounds are flame-retardant and resistant to oxidation and, besides, are biodegradable and with regard to them toxic behavior should have advantages.

Die GB-PS 1 504 655 beschreibt elektrische Vorrichtungen, die biologisch leicht abbaubare dielektrische Flüssigkeiten enthalten, nämlich halogenierte Diphenylmethane, die dadurch gekennzeichnet sind, daß die Halogensubstituenten und etwaige Alkylsubstituenten nur in einem der beiden Phenylringe vorliegen, während der andere Phenylring unsubstituiert sein muß, wobei angegeben ist, daß nur solche halogenierten Diphenylmethane, die eine unsbustituierte Phenylgruppe aufweisen, leicht biologisch abgebaut werden können, während die an beiden Phenylresten substituierten Diphenylmethane dem mikrobiologischen Abbau widerstehen sollen.GB-PS 1 504 655 describes electrical devices which contain readily biodegradable dielectric liquids, namely halogenated diphenylmethanes, which are characterized in that the halogen substituents and any alkyl substituents are only present in one of the two phenyl rings, while the other phenyl ring must be unsubstituted, where it is stated that only those halogenated diphenylmethanes which have an unsubstituted phenyl group can readily be biodegraded, while the diphenylmethanes substituted on both phenyl radicals are intended to resist microbiological degradation.

Die ältere deutsche Patentanmeldung 34 02 863 beschreibt bromhaltige Benzyltoluol-Derivate, die als funktionelle Flüssigkeiten, beispielsweise Hydraulikflüssigkeiten oder Isolationsflüssigkeiten für elektrische Vorrichtungen eingesetzt werden können und die sich dadurch auszeichnen, daß sie eine günstige Umweltverträglichkeit besitzen, indem das Benzyltoluolgerüst im Vergleich zu dem Biphenylgerüst der üblicherweise für diese Zwecke eingesetzten halogenierten Biphenyle biologisch leichter abbaubar ist.The older German patent application 34 02 863 describes bromine-containing benzyltoluene derivatives which can be used as functional fluids, for example hydraulic fluids or insulating fluids for electrical devices, and which are distinguished by the fact that they have a favorable environmental compatibility in that the benzyltoluene skeleton in comparison with the biphenyl skeleton Halogenated biphenyls commonly used for these purposes are more readily biodegradable.

Die DE-OS 15 94 505 beschreibt funktionelle Flüssigkeitszubereitungen, die eine größere Menge eines dihalogenierten Diphenylethers und eine kleinere Menge weiterer Mischungsbestandteile enthält, die aus halogenierten nie-drigalkyl-substituierten Benzolen, monohalogenierten Diphenylethern und chlorierten Biphenylen und Mischungen davon ausgewählt sind. Als halogenierte Niedrigalkylbenzole sind solche mit 1 bis 5 Halogenatomen und 1 bis 4 Kohlenstoffatomen in der Alkylgruppe angegeben, wobei von diesen als kleinerer Mischungsbestandteil einzusetzenden Verbindungen Dibromethylbenzol bevorzugt scheint. Über die alleinige Verwendung solcher Verbindungen oder über ihre biologische Abbaubarkeit ist in dieser Druckschrift nichts gesagt.DE-OS 15 94 505 describes functional liquid preparations which contain a larger amount of a dihalogenated diphenyl ether and a smaller amount of further mixture constituents which are selected from halogenated nie-drigalkyl-substituted benzenes, monohalogenated diphenyl ethers and chlorinated biphenyls and mixtures thereof. As the halogenated Niedrigalkylbenzole such are indicated by 1 to 5 halogen atoms and 1 to 4 carbon atoms in the alkyl group, and of these smaller than M ischungsbestandteil compounds to be employed dibromoethylbenzene preferably appears. About the sole use of such compounds or nothing is said in this document about their biodegradability.

Schließlich offenbart die US-PS 2 257 903 nichtbrennbare flüssige Zubereitungen, die als Wärmeübertragungsflüssigkeiten, Dielektrika, feuerlöschende Mittel und flammfest machende Mittel eingesetzt werden können. Diese flüssigen Zubereitungen bestehen im wesentlichen aus Mischungen von am Kern bromierten Monoethylbenzolen mit einem Bromgehalt zwischen etwa 2,0 und etwa 3,0 Atomen Brom pro Mol Ethylbenzol. Über die biologische Abbaubarkeit dieser Materialien finden sich keine Angaben.Finally, U.S. Patent No. 2,257,903 discloses non-flammable liquid preparations which can be used as heat transfer liquids, dielectrics, fire extinguishing agents and flame retardants. These liquid preparations consist essentially of mixtures of brominated monoethylbenzenes with a bromine content of between about 2.0 and about 3.0 atoms of bromine per mole of ethylbenzene. No information is available on the biodegradability of these materials.

Die aus dem Stand der Technik bekannten funktionellen Flüssigkeiten können nicht in vollem Umfang befriedigen, weil sie nicht alle kriterien einer schwerentflammbaren funktionellen Flüssigkeit, namentlich Hydraulikflüssigkeit, erfüllen können, nämlich wirtschaftliche Herstellung, biologische Abbaubarkeit, geringe Toxizität der Flüssigkeit oder ihrer Zersetzungsprodukte und dergleichen.The functional fluids known from the prior art cannot fully satisfy because they cannot meet all the criteria of a flame-resistant functional fluid, namely hydraulic fluid, namely economical production, biodegradability, low toxicity of the fluid or its decomposition products and the like.

Die Aufgabe der vorliegenden Erfindung besteht nun darin, funktionelle Flüssigkeiten anzugeben, die neben den für das angestrebte Einsatzgebiet technologischen Kriterien auch die toxikologischen und wirtschaftlichen Anforderun- gen erfüllen.The object of the present invention is now to provide functional fluids that meet only the technological for the intended application criteria, the toxicological and economic A nforderun- gen.

Es hat sich nun überraschenderweise gezeigt, daß eine bestimmte kleine Gruppe von Brombenzolderivaten nicht nur auf der einen Seite wertvolle technische Eigenschaften besitzt, sondern andererseits auch nicht die Gefahren und umweltschädigenden Wirkungen mit sich bringt, die den für funtkionelle Flüssigkeiten eingesetzten vorbekannten Verbindungen eigen sind, so daß sie sich besonders gut als oder für funktionelle Flüssigkeiten eignet. Gegenstand der Erfindung ist daher die schwerentflammbare, biologisch abbaubare funktionelle Flüssigkeit gemäß Hauptanspruch. Die Unteransprüche betreffen besonders bevorzugte Ausführungsformen dieses Erfindungsgegenstandes.Surprisingly, it has now been shown that a certain small group of bromobenzene derivatives not only has valuable technical properties on the one hand, but on the other hand does not have the dangers and environmentally damaging effects inherent in the known compounds used for functional liquids, so that it is particularly suitable as or for functional liquids. The invention therefore relates to the flame-retardant, biodegradable functional liquid according to the main claim. The subclaims relate to particularly preferred embodiments of this subject matter of the invention.

Die Erfindung betrifft somit eine schwerentflammbare, biologisch abbaubare funktionelle Flüssigkeit, bestehend aus oder enthaltend mindestens ein Brombenzolderivat der allgemeinen Formel (I)

Figure imgb0001
in der n für eine Zahl mit einem Wert von 1 bis 4 und x für eine Zahl mit einem Wert von 1 bis 5 stehen.The invention thus relates to a flame-retardant, biodegradable functional liquid, consisting of or containing at least one bromobenzene derivative of the general formula (I)
Figure imgb0001
 where n is a number from 1 to 4 and x is a number from 1 to 5.

Vorzugsweise enthält die funktionelle Flüssigkeit als Brombenzolderivat ein Brombenzolderivat der allgemeinen Formel (II)

Figure imgb0002
worin x für eine Zahl mit einem Wert von 1 bis 5 steht.The functional liquid preferably contains, as bromobenzene derivative, a bromobenzene derivative of the general formula (II)
Figure imgb0002
 where x is a number from 1 to 5.

Die erfindungsgemäß als oder in funktionellen Flüssigkeiten eingesetzten Bromtoluolderivate können in Form von reinen Verbindungen, in Form von Isomerengemischen oder auch in Form von Gemischen mit Verbindungen unterschiedlichen Bromierungsgrads eingesetzt werden, wobei mit Vorteil die Auswahl so erfolgt, daß die eingesetzten Bromtoluolderivate einen Bromgehalt von etwa 60 Gew.-% aufweisen, um besonders schwer entflammbare funktionelle Flüssigkeiten zu ergeben, und andererseits innerhalb eines relativ großen Temperaturbereichs von vorzugsweise -25°C bis 220°C flüssig sind. Die letztere Bedingung läßt sich ohne weiteres durch die Anwendung von Isomerengemischen erfüllen.The bromotoluene derivatives used as or in functional liquids according to the invention can be used in the form of pure compounds, in the form of isomer mixtures or also in the form of mixtures with compounds of different degrees of bromination, the selection advantageously being made so that the bromotoluenes used have a bromine content of about 60 % By weight have, in order to give particularly flame-resistant functional liquids, and on the other hand are liquid within a relatively wide temperature range of preferably -25 ° C to 220 ° C. The latter condition can easily be met by using mixtures of isomers.

Mit Vorteil verwendet man erfindungsgemäß als Brombenzolderivat ein bei der Bromierung von Benzol anfallendes Gemisch von Brombenzolderivaten. Besonders bevorzugt setzt man solche Gemische von einem oder mehreren Brombenzolderivaten ein, die 1 bis 3 Bromatome als Kernsubstituenten aufweisen.Advantageously, according to the invention, a bromobenzene derivative used in the bromination of benzene is a mixture of bromobenzene derivatives. Mixtures of one or more bromobenzene derivatives which have 1 to 3 bromine atoms as core substituents are particularly preferably used.

Als überraschend und besonders vorteilhaft hat es sich erwiesen, als Brombenzolderivat Dibromtoluolderivate einzusetzen, die in Form der reinen Isomeren oder auch in Form von Isomerengemischen eingesetzt werden können. Die Dibromtoluole haben sich als besonders gut für funktionelle Flüssigkeiten geeignet erwiesen, da sie einerseits hervorragende technologische Eigenschaften aufweisen, die für die Anwendung in oder als funktionelle Flüssigkeiten erforderlich sind, und andererseits ein unerwartet gutes Umweltverhalten zeigen, d. h. als solche ein sehr geringe Toxizität besitzen, beim Erhitzen keine giftigen Zersetzungsprodukte, wie hochgiftige Dioxinderivate ergeben und darüber hinaus leicht biologisch abgebaut werden können. Weiterhin zeigen sie im Hinblick auf ihr Brandverhalten, ihr Viskositäts-Temperatur-Verhalten, ihre Verträglichkeit mit üblicherweise eingesetzten Dichtelementmaterialien und im Hinblick auf ihr korrosives Verhalten vorteilhafte Eigenschaften, die sie für die angestrebte Verwendung besonders gut geeignet erscheinen lassen. Da gerade bezüglich des überraschenden Umweltverhaltens der erfindungsgemäß ausgewählten Brombenzolderivate und namentlich der Dibromtoluolderivate dem Stand der Technik, der eine große Vielzahl von möglichen halogenierten und bromierten Verbindungen zum Einsatz in oder als funktionelle Flüssigkeiten offenbart, keinerlei Angaben entnommen werden können, stellt die hier vorgenommene Auswahl eine erhebliche Bereicherung der Technik dar.It has proven to be surprising and particularly advantageous to use dibromotoluene derivatives as bromobenzene derivative, which can be used in the form of the pure isomers or in the form of isomer mixtures. The dibromotoluenes have proven to be particularly well suited for functional liquids, since on the one hand they have excellent technological properties which are necessary for use in or as functional liquids and on the other they show unexpectedly good environmental behavior, ie as such they have very low toxicity, no toxic decomposition products when heated, such as highly toxic dioxin derivatives, and moreover can be easily biodegraded. With regard to their fire behavior, their viscosity-temperature behavior, their compatibility with commonly used sealing element materials and their corrosive behavior, they also show advantageous properties which make them particularly suitable for the intended use. Because of the surprising environmental behavior of the bromobenzene derivatives selected in accordance with the invention and in particular of the dibromotoluene derivatives, this is the state of the art, which a large variety of possible halogenated and brominated compounds for use in or as functional liquids, no information can be obtained, the selection made here represents a significant enrichment of the technology.

Mit Vorteil kann man erfindungsgemäß die Brombenzolderivate und insbesondere die Dibromtoluole in Form des bei der Bromierung von Toluol anfallenden Gemisches einsetzen, wobei man diese Verbindungen oder auch diese Gemische mit Vorteil auch mit anderen bromierten Verbindungen kombinieren kann, wie insbesondere Dibromethylbenzol und/oder Dibromcumol. In dieser Weise wird es namentlich durch die Anwendung von Gemischen der erfindungsgemäß ausgewählten Verbindungen und den genannten anderen Verbindungen möglich, die Viskositäts-Temperatur-Eigenschaften der funktionellen Flüssigkeit auf das Einsatzgebiet anzupassen.According to the invention, the bromobenzene derivatives and in particular the dibromotoluenes can advantageously be used in the form of the mixture obtained in the bromination of toluene, it being possible for these compounds or also these mixtures to be advantageously combined with other brominated compounds, such as, in particular, dibromethylbenzene and / or dibromocumol. In this way, the use of mixtures of the compounds selected according to the invention and the other compounds mentioned makes it possible to adapt the viscosity-temperature properties of the functional liquid to the area of use.

Neben den Brombenzolderivaten kann die erfindungsgemäße schwerentflammbare, biologisch abbaubare funktionelle Flüssigkeit noch für solche funktionelle Flüssigkeiten übliche Additive und Zusätze enthalten, wobei die Brombenzolderivate vorzugsweise in einer Menge von mindestens 35 Gew.-% vorhanden sind.In addition to the bromobenzene derivatives, the flame-retardant, biodegradable functional liquid according to the invention may also contain additives and additives customary for such functional liquids, the bromobenzene derivatives preferably being present in an amount of at least 35% by weight.

Als Additive und Zusätze dieser Art kann man beispielsweise Korrosionsschutzmittel, wie Erdalkalisulfonate, Stabilisatoren, wie Aminderivate oder phenolische Produkte, verschleißmindernde Zusätze, beispielsweise Zinkdialkyldithiophosphate, Säureakzeptoren, beispielsweise Epoxidverbindungen, Tetraphenylzinn usw., Entschäumer, wie Seifen, Silicone, Glykole, Phosphatester und dergleichen, Viskositätsindexverbesserer, wie Polymethacrylate oder Polyisobutylen und dergleichen, einsetzen. Weiterhin können die erfindungsgemäßen funktionellen Flüssigkeiten mit vielen geeigneten Produkten, wie beispielsweise Mineralölen, Glykolen etc., modifiziert werden.Additives and additives of this type include, for example, corrosion inhibitors, such as alkaline earth metal sulfonates, stabilizers, such as amine derivatives or phenolic products, wear-reducing additives, for example zinc dialkyldithiophosphates, acid acceptors, for example epoxy compounds, tetraphenyltin, etc., defoamers, such as soaps, silicones, glycols, phosphates and phosphate esters. Use viscosity index improvers such as polymethacrylates or polyisobutylene and the like. Furthermore, the functional liquids according to the invention can be used with many suitable products, such as for example, mineral oils, glycols, etc., are modified.

Die erfindungsgemäß eingesetzten Brombenzolderivate, die zum Teil bekannt sind, erhält man durch an sich bekanntes Bromieren von Benzol bzw. Alkylbenzol mit elementarem Brom in Gegenwart eines bekannten Halogenierungskatalysators, wie beispielsweise Eisen, Eisentrichlorid, Eisentribromid oder dergleichen. Dabei kann die Umsetzung bei Zimmertemperatur durchgeführt werden, wobei jedoch in Abhängigkeit vom jeweiligen Katalysator beispielsweise auch Temperaturen zwischen -5 und +40°C geeignet sind.The bromobenzene derivatives used according to the invention, some of which are known, are obtained by brominating benzene or alkylbenzene with elemental bromine, known per se, in the presence of a known halogenation catalyst, such as iron, iron trichloride, iron tribromide or the like. The reaction can be carried out at room temperature, but depending on the catalyst in question, temperatures between -5 and + 40 ° C are also suitable.

Das folgende Herstellungsbeispiel dient der Erläuterung der Herstellung des erfindungsgemäß bevorzugt eingesetzten Dibromtoluols.The following preparation example serves to explain the preparation of the dibromotoluene which is preferably used according to the invention.

HerstellunasbeispielManufacturing example

Man erwärmt ein Gemisch aus 174 g Toluol und 4 g Eisenpulver auf 45°C. Dann tropft man unter Rühren langsam 544,6 g (3,4 Mol) elementares Brom zu und arbeitet nach dem Anspringen der Reaktion bei 22°C weiter. Nach Beendigung der Zugabe rührt man während weiterer 30 Minuten bei 45°C, wäscht dann das Reaktionsgemisch mit je 300 ml einer 2,5 %-igen Natriumdisulfitlösung, einer 10 %-igen Natriumhydroxidlösung und Wasser und trocknet anschließend.A mixture of 174 g of toluene and 4 g of iron powder is heated to 45 ° C. Then 544.6 g (3.4 mol) of elemental bromine are slowly added dropwise with stirring and the reaction is continued at 22 ° C. after the reaction has started. After the addition is complete, the mixture is stirred at 45 ° C. for a further 30 minutes, then the reaction mixture is washed with 300 ml portions of a 2.5% sodium disulfite solution, a 10% sodium hydroxide solution and water and then dried.

Man erhält als Rohprodukt ein Gemisch aus

Figure imgb0003
Man destilliert das Gemisch und fängt die bei 103 bis 105°C/2,5 mbar übergehende Fraktion (265 g) auf, die als Dibromtoluol identifiziert werden kann. Molekulargewicht: 250 Dichte: 1,813 n20 D: 1,6025 (2,5-Dibromtoluol)A mixture is obtained as the crude product
Figure imgb0003
 The mixture is distilled and the fraction (265 g) which transitions at 103 to 105 ° C./2.5 mbar is collected and can be identified as dibromotoluene. Molecular weight: 250 Density: 1.813 n 20 D : 1.6025 (2,5-dibromotoluene)

Es lassen sich gaschromatographisch fünf Isomere unterscheiden, die in Anteilen von 48,6 %, 37,4 %, 3,2 %, 8 % und 2,8 % vorliegen.Five isomers can be distinguished by gas chromatography, which are present in proportions of 48.6%, 37.4%, 3.2%, 8% and 2.8%.

Siedepunkt: Gemisch 236 bis 245°C/1013 mbar (105°C/2,5 mbar) 3,5-Dibromtoluol: F.p.: 38 bis 40°C, Sdp. 246°C/1013 mbar 2,6-Dibromtoluol: Sdp. 243°C/1013 mbar 2,5-Dibromtoluol: F.p. 5,6°C, Sdp. 236°C/1013 mbarBoiling point: mixture 236 to 245 ° C / 1013 mbar (105 ° C / 2.5 mbar) 3,5-dibromotoluene: mp: 38 to 40 ° C, bp 246 ° C / 1013 mbar 2,6-dibromotoluene: bp 243 ° C / 1013 mbar 2,5-dibromotoluene: mp 5.6 ° C, bp 236 ° C / 1013 mbar

Die folgenden Beispiele dienen der weiteren Erläuterung der Erfindung und betreffen Rezepturen von schwerentflammbaren Hydraulikflüssigkeiten.The following examples serve to explain the invention further and relate to formulations of flame-retardant hydraulic fluids.

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

Zusammensetzung einer schwerentflammbaren Hydraulikflüssigkeit:

Figure imgb0004
Composition of a flame-retardant hydraulic fluid:
Figure imgb0004

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

Zusammensetzung einer schwerentflammbaren Hydraulikflüssigkeit:

Figure imgb0005
Figure imgb0006
 Composition of a flame-retardant hydraulic fluid:
Figure imgb0005
Figure imgb0006

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

Zusammensetzung einer schwerentflammbaren Hydraulikflüssigkeit:

Figure imgb0007
Composition of a flame-retardant hydraulic fluid:
Figure imgb0007

B e i s p i e 1 4Example: 1 4

Zusammensetzung einer schwerentflammbaren Hydraulikflüssigkeit:

Figure imgb0008
Figure imgb0009
 Composition of a flame-retardant hydraulic fluid:
Figure imgb0008
Figure imgb0009

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

Zusammensetzung einer schwerentflammbaren Hydraulikflüssigkeit:

Figure imgb0010
Composition of a flame-retardant hydraulic fluid:
Figure imgb0010

Claims (8)

1. Schwerentflammbare, biologisch abbaubare funktionelle Flüssigkeit bestehend aus oder enthaltend mindestens ein Brombenzolderivat der allgemeinen Formel (I)
Figure imgb0011
worin n für eine Zahl mit einem Wert von 1 bis 4 und x für eine Zahl mit einem Wert von 1 bis 5 stehen.1. Flame-retardant, biodegradable functional liquid consisting of or containing at least one bromobenzene derivative of the general formula (I)
Figure imgb0011
 where n is a number from 1 to 4 and x is a number from 1 to 5. 2. Funktionelle Flüssigkeit nach Anspruch 1, dadurch gekennzeichnet , daß sie als Brombenzolderivat mindestens ein Bromtoluolderivat der allgemeinen Formel (II)
Figure imgb0012
worin x für eine Zahl mit einem Wert von 1 bis 5 steht, enthält.2. Functional liquid according to claim 1, characterized in that it contains as bromobenzene derivative at least one bromotoluene derivative of the general formula (II)
Figure imgb0012
 where x is a number from 1 to 5. 3. Funktionelle Flüssigkeit nach Anspruch 2, dadurch gekennzeichnet , daß sie als Bromtoluolderivat ein bei der Bromierung von Toluol anfallendes Gemisch von Bromtoluolderivaten enthält.3. Functional liquid according to claim 2, characterized in that it contains, as bromotoluene derivative, a mixture of bromotoluene derivatives obtained in the bromination of toluene. 4. Funktionelle Flüssigkeit nach Anspruch 3, dadurch gekennzeichnet , daß sie als Bromtoluolderivat ein oder mehrere Bromtoluolderivate mit 1 bis 3 Bromatomen am Kern enthält.4. Functional liquid according to claim 3, there characterized in that it contains one or more bromotoluene derivatives with 1 to 3 bromine atoms on the nucleus as the bromotoluene derivative. 5. Funktionelle Flüssigkeit nach Anspruch 2, dadurch gekennzeichnet , daß sie als Bromtoluolderivat mindestens ein Dibromtoluol enthält.5. Functional liquid according to claim 2, characterized in that it contains at least one dibromotoluene as bromotoluene derivative. 6. Funktionelle Flüssigkeit nach Anspruch 5, dadurch gekennzeichnet , daß sie als Dibromtoluol ein Gemisch aus mindestens zwei isomeren Dibromtoluolen enthält.6. Functional liquid according to claim 5, characterized in that it contains a mixture of at least two isomeric dibromotoluenes as dibromotoluene. 7. Funktionelle Flüssigkeit nach mindestens einem der Ansprüche 2 bis 6, dadurch gekennzeichnet, daß sie das Bromtoluolderivat im Gemisch mit Dibromethylbenzol und/oder Dibromcumol enthält.7. Functional liquid according to at least one of claims 2 to 6, characterized in that it contains the bromotoluene derivative in a mixture with dibromethylbenzene and / or dibromocumol. 8. Funktionelle Flüssigkeit nach mindestens einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß sie in Form einer Hydraulikflüssigkeit vorliegt, die mindestens 35 % des Bromtoluolderivats und gegebenenfalls übliche Zusätze für Hydraulikflüssigkeiten enthält.8. Functional liquid according to at least one of claims 1 to 7, characterized in that it is in the form of a hydraulic fluid which contains at least 35% of the bromotoluene derivative and optionally conventional additives for hydraulic fluids.
EP86106678A 1985-05-29 1986-05-15 Brominated alkyl benzenes as a basis of fire-resistant, biodegradable functional fluids Withdrawn EP0204196A1 (en)

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DE19853519221 DE3519221A1 (en) 1985-05-29 1985-05-29 BROWNED ALKYLBENZENE AS A BASE OF FLAME-RESISTANT, BIODEGRADABLE FUNCTIONAL LIQUIDS
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Citations (6)

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US2257903A (en) * 1940-02-21 1941-10-07 Dow Chemical Co Mixture of isomeric ethyl dibromobenzenes
US3192272A (en) * 1960-12-27 1965-06-29 Dow Chemical Co Tribrominated dialkyl benzenes
GB1027054A (en) * 1963-09-18 1966-04-20 Castrol Ltd Improvements in or relating to functional fluids
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US2257903A (en) * 1940-02-21 1941-10-07 Dow Chemical Co Mixture of isomeric ethyl dibromobenzenes
US3192272A (en) * 1960-12-27 1965-06-29 Dow Chemical Co Tribrominated dialkyl benzenes
GB1027054A (en) * 1963-09-18 1966-04-20 Castrol Ltd Improvements in or relating to functional fluids
US3644209A (en) * 1964-09-21 1972-02-22 Monsanto Co Functional fluid compositions
US4260506A (en) * 1979-01-26 1981-04-07 Monsanto Company Hydraulic pressure device utilizing biodegradable halogenated diphenyl methanes
EP0072008A1 (en) * 1981-08-11 1983-02-16 Hoechst Aktiengesellschaft Process for the preparation of p-chlorotoluene and/or of m-chlorotoluene

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CHEMICAL ABSTRACTS, Band 88, Nr. 5, 30. Januar 1978, Seite 463, Zusammenfassung Nr. 37344h, Columbus, Ohio, US; M.S. SALAKHOV et al.: "Liquid-phase oxidative bromination of toluene", & AZERB. KHIM. ZH. 1977, (3), 46-9 *

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