EP0150826B1 - Difficult flammable biodegradable functional fluid - Google Patents

Difficult flammable biodegradable functional fluid Download PDF

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Publication number
EP0150826B1
EP0150826B1 EP85100772A EP85100772A EP0150826B1 EP 0150826 B1 EP0150826 B1 EP 0150826B1 EP 85100772 A EP85100772 A EP 85100772A EP 85100772 A EP85100772 A EP 85100772A EP 0150826 B1 EP0150826 B1 EP 0150826B1
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EP
European Patent Office
Prior art keywords
bromine
dibromobenzyltoluene
derivatives
flame
liquids
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.)
Expired
Application number
EP85100772A
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German (de)
French (fr)
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EP0150826A2 (en
EP0150826A3 (en
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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Priority to AT85100772T priority Critical patent/ATE43628T1/en
Publication of EP0150826A2 publication Critical patent/EP0150826A2/en
Publication of EP0150826A3 publication Critical patent/EP0150826A3/en
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Publication of EP0150826B1 publication Critical patent/EP0150826B1/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/20—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances liquids, e.g. oils
    • H01B3/24—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances liquids, e.g. oils containing halogen in the molecules, e.g. halogenated oils
    • 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
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/026—Butene
    • 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
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic 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
    • 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
    • C10M2215/26—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
    • C10M2215/28—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
    • 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
    • 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
    • C10N2040/14—Electric or magnetic purposes
    • C10N2040/16—Dielectric; Insulating oil or insulators
    • 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
    • C10N2040/14—Electric or magnetic purposes
    • C10N2040/17—Electric or magnetic purposes for electric contacts

Definitions

  • the invention relates to a flame-retardant, biodegradable functional fluid, in particular a hydraulic fluid or an insulation fluid for electrical devices, which contains a bromine-containing benzyltoluene derivative and conventional additives as an essential component.
  • Chlorinated aromatics especially chlorinated biphenyls
  • the polychlorinated biphenyls 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 highly toxic dioxins and dibenzofurans can be formed. 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 restrictions have been imposed on the use of these substances.
  • EP-A-88 650 proposes to use chlorinated benzyltoluenes and chlorinated benzyloxylols as lubricants, which can also be used as hydraulic fluids, since these compounds are flame-retardant and resistant to oxidation and are also biodegradable and with regard to them toxic behavior should have advantages.
  • GB-A-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 , since 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.
  • EP-A-8 251 discloses liquid dielectrics which can be used, for example, as insulating liquids for transformers or as impregnating agents for capacitor insulator layers. These are essentially chlorinated alkylaromatic compounds which have been obtained starting from chlorotoluene and / or chloroxylene, such as, for example, tetrachlorobenzyltoluene, which are said to have advantages over the polychlorinated biphenyls hitherto used for the same purpose. The absence of the biphenyl nuclei and the presence of the alkyl groups on the aromatic nuclei are assigned a favorable effect on the biodegradation behavior.
  • EP-A-71 338 or the corresponding GB-A-2 100 740 describes electroviscous liquids which are present in the form of suspensions of finely divided hydrophilic solids in hydrophobic liquids. These electroviscous fluids are used in electronically controlled hydraulic devices. When an electric field is applied to such a suspension, the viscosity of this mixture increases drastically. The change is reversible and fast, so that such suspensions can be used, for example, in electronically controllable clutches. It is stated that the hydrophobic liquid present in the mixture has a high boiling point, a low viscosity, sufficient electrical properties, is chemically stable and, moreover, has low toxicity and should preferably be biodegradable.
  • halogenated diaryl derivatives are used as hydrophobic liquids, the aromatic nuclei of which are connected to one another by a wide variety of bridges and may have fluorine, chlorine or bromine atoms as halogen substituents.
  • the very general formula given for these diaryl derivatives includes a wide variety of compounds.
  • asymmetrically substituted diaryl derivatives are preferred because the asymmetry in the molecule is said to promote biodegradability.
  • the object of the present invention is to provide functional liquids which have all the physical properties necessary for the intended application and which can be biodegraded at the same time with high chemical stability, are largely non-toxic and do not become highly toxic products, such as dioxins, even if handled improperly , to lead.
  • the invention therefore relates to the flame-retardant, biodegradable, functional liquid according to the patent claim.
  • the invention therefore relates to a flame-retardant, biodegradable functional liquid. containing at least one bromine-containing benzyltoluene derivative and conventional additives, which is characterized in that it contains dibromobenzyltoluene of the formula (I) as the bromine-containing benzyltoluene derivative and or
  • Monobromxylylxylene of formula (11) contains in an amount of at least 35 wt .-%.
  • the bromine-containing benzyltoluene derivatives used as or in functional liquids according to the invention are therefore compounds which are substituted on both nuclei, at least one bromine substituent and one methyl group having to be present as a substituent.
  • the positions of these substituents are not essential, so that, according to the invention, all positional isomers of these bromine-containing benzyltoluene derivatives of the above general formulas I and 11 can also be used in or as functional liquids.
  • bromine-containing benzyltoluene derivatives used according to the invention have a considerably more favorable environmental compatibility than the halogenated diaryl derivatives known from the prior art, and at the same time have excellent physical properties which are particularly suitable for functional liquids, such as hydraulic liquids or insulation liquids for electrical devices make well suited.
  • bromine-containing benzyltoluene derivatives of the general formulas I and II given above which are substituted on both phenyl rings and which are used according to the invention can readily be biodegraded, which in view of the EP-A-71 338 referred to above GB-A-2 100 740 and GB-A-1 504 655 can be regarded as surprising.
  • these bromine-containing benzyltoluene derivatives of the above general formulas used according to the invention have the further surprising advantage that they are liquid under normal conditions of use and have a particularly favorable viscosity-temperature behavior.
  • the functional liquids according to the invention can of course contain the bromine-containing benzyltoluene derivatives defined above individually, but preferably in the form of mixtures, especially in the form of mixtures of the individual positional isomers of these compounds.
  • the compounds of the above general formulas selected and used according to the invention differ from the biodegradable bromine-containing benzyltoluene derivatives described in GB-A-1 504 655 in that they are not asymmetrical but are substituted on both phenyl rings and nevertheless have surprisingly advantageous properties .
  • the bromine-containing benzyltoluene derivatives used according to the invention are prepared in a manner known per se either by halogenating the corresponding non-halogen-substituted benzyltoluenes with elemental bromine in the presence of a known halogenation catalyst such as iron, FeCl 3 , FeBr 3 , AICI 3 , TiC1 4 and the like.
  • a known halogenation catalyst such as iron, FeCl 3 , FeBr 3 , AICI 3 , TiC1 4 and the like.
  • the reaction can be carried out at room temperature, but depending on the particular catalyst, temperatures between -5 and + 40 ° C. are also suitable.
  • Hal is bromine or chlorine and x is 1 and z is 0 or 1.
  • the condensation is carried out, if appropriate, in the presence of a Friedel-Crafts catalyst, such as FeCl 3 , FeBr 3 , AICI 3 and / or TiCl 4 , with an excess of compounds of the general formula III.
  • a Friedel-Crafts catalyst such as FeCl 3 , FeBr 3 , AICI 3 and / or TiCl 4
  • the bromine-containing benzyltoluene derivatives used according to the invention show a substantially improved flame retardancy with a simultaneously improved viscosity-temperature behavior.
  • the asymmetrically substituted dibromobenzyltoluene known from GB-A-1 504 655 solidifies at room temperature, while the isomer brominated on both phenyl rings only solidifies at -25 ° C., which is particularly advantageous for the use of this compound as a hydraulic fluid or insulating fluid.
  • the bromine-containing benzyltoluene derivatives used according to the invention have proven themselves not only in the case of hydraulic liquids but also in the case of insulation liquids for electrical devices, such as, for example, capacitors, transformers and the like, not only because of their favorable viscosity-temperature behavior but also because of their very favorable flame-retardant effect.
  • the functional fluids according to the invention can therefore in particular also be used as flame-retardant hydraulic fluids or flame-retardant insulation fluids which, because of their low toxicity, their low tendency to form toxic decomposition products and their biodegradability, represent a considerable enrichment of technology.
  • the bromine-containing benzyltoluene derivatives mentioned may be present individually or in the form of mixtures, especially in the form of the isomer mixtures.
  • bromination of toluene with elemental bromine is first carried out in the presence of anhydrous FeC1 3 bromotoluene, which is then brominated on the side chain.
  • anhydrous FeC1 3 bromotoluene which is then brominated on the side chain.
  • 8.3 mol of bromotoluene are heated in the presence of 0.5 g of a radical chain initiator (a, a'-azobisisobutyronitrile) to a temperature of 80 ° C. 1.66 is dripped in under irradiation with an ultraviolet lamp with an output of 300 W. Moles of bromine with cooling.
  • the resulting hydrogen bromide is absorbed in a wash bottle with chilled water.
  • the cooled mixture is then added dropwise to a condensation reaction in a suspension of 6 g FeCl 3 in 1.66 mol bromotoluene at a temperature of 30 ° C.
  • the resulting gaseous hydrogen bromide is absorbed in the same way as described above with chilled water in a wash bottle.
  • this condensation reaction the formation of by-products (brominated dibenzyltoluene) is suppressed by the large excess of bromotoluene used.
  • the mixture is heated to 50 ° C. for 30 minutes, whereupon the cooled reaction mixture is mixed with 1 liter of water and then with 1 liter of 10% strength Sodium hydroxide solution and then washed again with 1 liter of water.
  • the organic phase is dried and the excess bromotoluene is distilled off.
  • the remaining liquid is rectified at 0.4 mbar, giving 395 g of a main fraction boiling between 155 and 166 ° C. at 0.4 mbar, which is identified by mass spectrometry as dibromobenzyltoluene. An isomer investigation was not carried out.
  • the following table shows the electron current mass spectrum of the dibromobenzyltoluene obtained.
  • bromine-containing benzyltoluene derivatives used according to the invention are obtained in an analogous manner to the procedure described above using methods known per se or also by direct bromination or bromination and chlorination of benzyltoluene, in which case, however Reaction mixtures are obtained which have to be separated in a suitable manner, for example by gas chromatography, into the bromine-containing benzyltoluene derivatives of the general formulas given above used according to the invention.
  • the flame-retardant, biodegradable functional liquids according to the invention can also contain additional constituents and additives customary for the functional liquids, for example corrosion inhibitors, such as alkaline earth metal sulfonates, stabilizers, such as amine derivatives or phenolic products, wear-reducing additives, for example zinc dialkylditheakophosphates, for example epoxy compounds, tetraphenyltin, etc., and also defoamers, such as soap, silicones, glycols, phosphate esters, and viscosity index improvers, such as polymethacrylates, polyisobutylene.
  • the bromine-containing benzyltoluene derivatives used according to the invention can be modified with many suitable products, such as mineral oil, glycols, etc.
  • the biodegradability is examined with the aid of a recognized measuring method for determining the biodegradability of anionic and nonionic synthetic surfactants, namely the OECD screening test (Federal Law Gazette 1 (1977), page 245) (modified) for nonionic surfactants.
  • Aerobic, polyvalent microorganisms from the drain of a biological sewage treatment plant are used as the vaccine suspension.
  • the first sample is taken after 7 days, the second sample after 14 days and the third sample after 19 days.
  • the samples taken were processed in accordance with the instructions of the test described above and the rate of degradation was determined by gas chromatography.
  • the fire test is carried out according to the "6th Switzerland report on requirements and tests of flame-retardant liquids for hydraulic power transmission and control".
  • dibromobenzyltoluene exhibits better fire behavior than, for example, tetrachlorobenzyltoluene or polychlorinated biphenyl.
  • dibromobenzyltoluene The corrosion effect of dibromobenzyltoluene was investigated using the method of the 6th Luxembourg report mentioned above. For this purpose, two-thirds of the metals steel, copper, brass, aluminum, cadmium and zinc and the metal pairings copper-zinc, steel-aluminum, steel-cadmium and aluminum-zinc were immersed in the liquid to be tested (dibromobenzyltoluene) and in it for 28 days leave at a temperature of 35 ° C.
  • a sealing element made of the sealing material 83 FKM 575 (Viton) is immersed in the liquid to be examined, for 21 days at 60 ° C, 80 ° C, 100 ° C, 120 ° C and 150 ° C . The change in volume of the sealing element and the change in its Shore hardness are then determined.
  • the bromine-containing benzyltoluene derivative namely dibromobenzyltoluene, which is preferably used according to the invention, exhibits particularly good behavior as such and also in fully formulated hydraulic fluids, in that the volume change of the sealing material moves between ⁇ 1 and 2% and the change in the Shore hardness contributes -3 degrees.
  • a change in volume of up to 20% and a change in Shore hardness of -10 degrees are permitted.
  • the investigated comparative products based on polychlorinated biphenyl and tetrachlorobenzyltoluene show volume change values of 40% at an investigation temperature of 150 ° C.
  • dibromobenzyltoluene was pyrolyzed at temperatures between 150 and 700 ° C.
  • the sample is processed according to EPA method no. 613.
  • no highly toxic dioxin or dibenzofuran was found within the detection limit (0.5 ppb).

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Abstract

Hardly inflammable and biologically degradable functional liquid comprising at least one bromine-containing benzyl toluol derivative having the general formula (I) wherein x is 1 or 2, x' is 0 or 1, y is 0, 1 or 2, y' is 0, 1 or 2, z is 0 or 1 and z' is 1 or 2, providing that the equations y + y' = 0, 1 or 2 and x + x' + y + y' = 1, 2 or 3 are verified.

Description

Gegenstand der Erfindung ist eine schwerentflammbare, biologisch abbaubare funktionelle Flüssigkeit, namentlich ein Hydraulikflüssigkeit oder eine lsolationsflüssigkeit für elektrische Vorrichtungen, die als wesentlichen Bestandteil ein bromhaltiges Benzyltoluol-Derivat und übliche Additive enthält.The invention relates to a flame-retardant, biodegradable functional fluid, in particular a hydraulic fluid or an insulation fluid for electrical devices, which contains a bromine-containing benzyltoluene derivative and conventional additives as an essential component.

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 lsolationsflüssigkeiten für elektrische Anlagen und als flammhemmende Zusätze für Kunststoffe und dergleichen benutzt. Indessen sind in den letzten Jahren diese Verbindungen in erheblichen Verruf geraten. Es wurden 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 Beschränkungs-Vorschriften bei der Verwendung dieser Stoffe erlassen wurden.Chlorinated aromatics, especially chlorinated biphenyls, have played an important role in a wide range of technology in recent decades. In particular, the polychlorinated biphenyls 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 highly toxic dioxins and dibenzofurans can be formed. 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 restrictions have been imposed on the use of these substances.

Zur Überwindung dieser Nachteile wird in der EP-A-88 650 vorgeschlagen, als Schmiermittel, die auch als Hydraulikflüssigkeiten eingesetzt werden können, chlorierte Benzyltoluole und chlorierte Benzyloxylole enzusetzen, 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, EP-A-88 650 proposes to use chlorinated benzyltoluenes and chlorinated benzyloxylols as lubricants, which can also be used as hydraulic fluids, since these compounds are flame-retardant and resistant to oxidation and are also biodegradable and with regard to them toxic behavior should have advantages.

Die GB-A-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, da angegeben ist, daß nur solche halogenierten Diphenylmethane, die eine unsubstituierte Phenylgruppe aufweisen, leicht biologisch abgebaut werden können, während die an beiden Phenylresten substituierten Diphenylmethane dem mikrobiologischen Abbau widerstehen sollen.GB-A-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 , since 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.

Aus der EP-A-8 251 sind flüssige Dielektrika bekannt, die beispielweise als Isolierflüssigkeiten für Transformatoren oder als Imprägniermittel für Kondensatorisolatorschichten eingesetzt werden können. Es handelt sich um am Kern chlorierte alkylaromatische Verbindungen, die ausgehend von Chlortoluol und/oder Chlorxylol erhalten worden sind, wie beispielsweise Tetrachlorbenzyltoluol, von denen angegeben ist, daß sie Vorteile gegenüber den bislang für den gleichen Anwendungszweck eingesetzten polychlorierten Biphenylen aufweisen. Dabei wird der Abwesenheit der Biphenylkerne und der Anwesenheit der Alkylgruppen an den aromatischen Kernen ein günstige Wirkung auf das biologische Abbauverhalten zugeordnet.EP-A-8 251 discloses liquid dielectrics which can be used, for example, as insulating liquids for transformers or as impregnating agents for capacitor insulator layers. These are essentially chlorinated alkylaromatic compounds which have been obtained starting from chlorotoluene and / or chloroxylene, such as, for example, tetrachlorobenzyltoluene, which are said to have advantages over the polychlorinated biphenyls hitherto used for the same purpose. The absence of the biphenyl nuclei and the presence of the alkyl groups on the aromatic nuclei are assigned a favorable effect on the biodegradation behavior.

Schließlich beschreibt die EP-A-71 338 bzw. die ihr entsprechende GB-A-2 100 740 elektroviskose Flüssigkeiten, die in Form von Suspensionen feinverteilter hydrophiler Feststoffe in hydrophoben Flüssigkeiten vorliegen. Diese elektroviskosen Flüssigkeiten werden in elektronisch gesteuerten Hydraulikvorrichtungen verwendet. Beim Anlegen eines elektrischen Feldes an eine solche Suspension steigt die Viskosität dieses Gemisches drastisch an. Die Änderung ist reversibel und schnell, so daß solche Suspensionen beispielsweise in elektronisch steuerbaren Kupplungen eingesetzt werden körnnen. Es ist angegeben, daß die im Gemisch vorhandene hydrophobe Flüssigkeit einen hohen Siedepunkt, eine niedrige Viskosität, ausreichende elektrische Eigenschaften aufweisen, chemisch stabil sein und darüber hinaus eine geringe Toxizität haben und vorzugsweise biologisch abbaubar sein sollte. Zu diesem Zwecke werden nach der Lehre dieses Standes der Technik als hydrophobe Flüssigkeiten halogenierte Diarylderivate eingesetzt, deren aromatische Kerne durch die verschiedenartigsten Brücken miteinander verbunden sein und als Halogensubstituenten Fluor-, Chlor- oder Bromatome aufweisen können. Die für diese Diarylderivate angegebene sehr allgemeine Formel umfaßt eine große Vielzahl von Verbindungen.Finally, EP-A-71 338 or the corresponding GB-A-2 100 740 describes electroviscous liquids which are present in the form of suspensions of finely divided hydrophilic solids in hydrophobic liquids. These electroviscous fluids are used in electronically controlled hydraulic devices. When an electric field is applied to such a suspension, the viscosity of this mixture increases drastically. The change is reversible and fast, so that such suspensions can be used, for example, in electronically controllable clutches. It is stated that the hydrophobic liquid present in the mixture has a high boiling point, a low viscosity, sufficient electrical properties, is chemically stable and, moreover, has low toxicity and should preferably be biodegradable. For this purpose, according to the teaching of this prior art, halogenated diaryl derivatives are used as hydrophobic liquids, the aromatic nuclei of which are connected to one another by a wide variety of bridges and may have fluorine, chlorine or bromine atoms as halogen substituents. The very general formula given for these diaryl derivatives includes a wide variety of compounds.

Es ist weiterhin angegeben, daß die asymmetrisch substituierten Diarylderivate bevorzugt sind, da die Asymmetrie im Molekül die biologische Abbaubarkeit fördern soll.It is also stated that the asymmetrically substituted diaryl derivatives are preferred because the asymmetry in the molecule is said to promote biodegradability.

Die nach dem genannten Stand der Technik bekannten funktionellen Flüssigkeiten können nicht in vollem Umfang befriedigen, weil sie entweder das Kriterium der Schwerentflammbarkeit von Hydraulik- und Isolationsflüssigkeiten nicht erfüllen oder bei gegebener Schwerentflammbarkeit nachteilige Eigenschaften, wie schlechte biologische Abbaubarkeit, Toxizität der Flüssigkeit oder ihrer Zersetzungsprodukte, ungünstiges Viskositäts-Temperaturverhatten oder Unverträglichkeit mit Dichtelementen besitzen.The functional liquids known according to the state of the art mentioned cannot fully satisfy because they either do not meet the criteria of the low flammability of hydraulic and insulation liquids or, given the low flammability, have disadvantageous properties, such as poor biodegradability, toxicity of the liquid or its decomposition products, have unfavorable viscosity temperature or incompatibility with sealing elements.

Die Aufgabe der vorliegenden Erfindung besteht darin, funktionelle Flüssigkeiten anzugeben, die sämtliche für den angestrebten Anwendungzweck notwendigen physikalischen Eigenschaften aufweisen und dabei gleichzeitig bei hoher chemischer Stabilität biologisch abgebaut werden können, weitgehend untoxisch sind und auch bei unsachgemäßer Behandlung nicht zu hochtoxischen Produkten, wie beispielsweise Dioxinen, führen.The object of the present invention is to provide functional liquids which have all the physical properties necessary for the intended application and which can be biodegraded at the same time with high chemical stability, are largely non-toxic and do not become highly toxic products, such as dioxins, even if handled improperly , to lead.

Es hat sich überraschendenweise gezeigt, daß eine bestimmte Gruppe von halogenierten Diarylderivaten nicht nur auf der einen Seite wertvolle technische Eigenschaften aufweist, sondern andererseits auch nicht die Gefährlichkeit und die umweltschädigenden Wirkungen der vorbekannten Verbindungen besitzt, so daß sie sich besonders gut als oder für funktionelle Flüssigkeiten eignet.It has surprisingly been found that a certain group of halogenated diaryl derivatives not only has valuable technical properties on the one hand, but on the other hand does not have the dangerous and environmentally harmful effects of the known compounds, so that they are particularly good as or for functional liquids is suitable.

Gegenstand der Erfindung ist daher die schwerentflammbare biologisch abbaubare funktionelle Flüssigkeit gemäß Patentanspruch.The invention therefore relates to the flame-retardant, biodegradable, functional liquid according to the patent claim.

Die Erfindung betrifft daher eine schwerentflammbare, biologisch abbaubare funktionelle Flüssigkeit. enthaltend mindestens ein bromhaltiges Benzyltoluol-Derivat und übliche Additive, die dadurch gekennzeichnet ist, daß daß sie als bromhaltiges Benzyltoluol-Derivat Dibrombenzyltoluol der Formel (I)

Figure imgb0001
und/oderThe invention therefore relates to a flame-retardant, biodegradable functional liquid. containing at least one bromine-containing benzyltoluene derivative and conventional additives, which is characterized in that it contains dibromobenzyltoluene of the formula (I) as the bromine-containing benzyltoluene derivative
Figure imgb0001
 and or

Monobromxylylxylol der Formel (11)

Figure imgb0002
in einer Menge von mindestens 35 Gew.-% enthält.Monobromxylylxylene of formula (11)
Figure imgb0002
 contains in an amount of at least 35 wt .-%.

Bei den erfindungsgemäß als oder in funktionellen Flüssigkeiten verwendeten bromhaltigen Benzyltoluol-Derivaten handelt es sich also um Verbindungen, die an beiden Kernen substituiert sind, wobei mindestens ein Bromsubstituent und eine Methylgruppe als Substituent vorhanden sein müssen. Die Positionen dieser Substituenten sind nicht wesentlich, so daß erfindungsgemäß auch sämtliche Stellungsisomere dieser bromhaltigen Benzyltoluol-Derivate der obigen allgemeinen Formeln I und 11 in oder als funktionelle Flüssigkeiten verwendet werden können.The bromine-containing benzyltoluene derivatives used as or in functional liquids according to the invention are therefore compounds which are substituted on both nuclei, at least one bromine substituent and one methyl group having to be present as a substituent. The positions of these substituents are not essential, so that, according to the invention, all positional isomers of these bromine-containing benzyltoluene derivatives of the above general formulas I and 11 can also be used in or as functional liquids.

Überraschenderweise hat sich gezeigt, daß diese erfindungsgemäß verwendeten bromhaltigen Benzyltoluol-Derivate eine wesentlich günstigere Umweltverträglichkeit besitzen als die aus dem Stand der Technik bekannten halogenierten Diarylderivate, und gleichzeitig ausgezeichnete physikalische Eigenschaften aufweisen, die sich für funktionelle Flüssigkeiten, wie Hydraulikflüssigkeiten oder Isolationsflüssigkeiten für elektrische Vorrichtungen besonders gut geeignet machen.Surprisingly, it has been found that these bromine-containing benzyltoluene derivatives used according to the invention have a considerably more favorable environmental compatibility than the halogenated diaryl derivatives known from the prior art, and at the same time have excellent physical properties which are particularly suitable for functional liquids, such as hydraulic liquids or insulation liquids for electrical devices make well suited.

Überraschenderweise hat sich weiterhin gezeigt, daß die erfindungsgemäß eingesetzten bromhaltigen Benzyltoluol-Derivate der oben angegebenen allgemeinen Formeln I und II, die an beiden Phenylringen substituiert sind, ohne weiteres biologisch abgebaut werden können, was angesichts der oben angesprochenen EP-A-71 338, der GB-A-2 100 740 und der GB-A-1 504 655 als überraschend anzusehen ist. Darüber hinaus besitzen diese erfindungsgemäß verwendeten bromhaltigen Benzyltoluol-Derivate der obigen allgemeinen Formeln den weiteren überraschenden Vorteil, daß sie bei den normalen Anwendungsbedingungen flüssig sind und ein besonders günstiges Viskositäts-Temperatur-Verhalten aufweisen. Darüber hinaus besitzen sie einen hohen Flammpunkt, sind wenig toxisch und wenig korrosiv und führen auch bei unsachgemäßer Überhitzung nicht zu den hochgiftigen Dioxinprodukten, die bei Unfällen mit polychlorierten Biphenylen gelegentlich aufgetreten sind. Darüber hinaus hat sich gezeigt, daß die erfindungsgemäß verwendeten bromhaltigen Benzyltoluol-Derivate auch eine ausgezeichnete Dichtelementverträglichkeit aufweisen, so daß die erfindungsgemäß ausgewählte Gruppe von Verbindungen sich als überraschend vorteilhaft für das angestrebte Verwendungsgebiet herausgestellt hat.Surprisingly, it has further been found that the bromine-containing benzyltoluene derivatives of the general formulas I and II given above which are substituted on both phenyl rings and which are used according to the invention can readily be biodegraded, which in view of the EP-A-71 338 referred to above GB-A-2 100 740 and GB-A-1 504 655 can be regarded as surprising. In addition, these bromine-containing benzyltoluene derivatives of the above general formulas used according to the invention have the further surprising advantage that they are liquid under normal conditions of use and have a particularly favorable viscosity-temperature behavior. In addition, they have a high flash point, are not very toxic or corrosive and, even if improperly overheated, do not lead to the highly toxic dioxin products that have occasionally occurred in accidents with polychlorinated biphenyls. In addition, it has been shown that the bromine-containing benzyltoluene derivatives used according to the invention also have excellent sealing element compatibility, so that the group of compounds selected according to the invention has proven to be surprisingly advantageous for the intended field of use.

Natürlich können die erfindungsgemäßen funktionellen Flüssigkeiten die oben definierten bromhaltigen Benzyltoluol-Derivate einzeln, bevorzugt jedoch in Form von Mischungen, enthalten, zumal in Form von Mischungen der einzelnen Stellungsisomeren dieser Verbindungen.The functional liquids according to the invention can of course contain the bromine-containing benzyltoluene derivatives defined above individually, but preferably in the form of mixtures, especially in the form of mixtures of the individual positional isomers of these compounds.

Die erfindungsgemäß ausgewählten und in oder als funktionelle Flüssigkeiten verwendeten bromhaltigen Benzyltoluol-Derivate der oben angegebenen Formehr sind teilweise bekannt, beispielsweise durch die allgemeine Formel der oben bereits angesprochenen EP-A-71 338 oder aber auch durch die generische Definition der DE-A-2 336 289. Dabei vermittelt die erstgenannte Literaturstelle eine immens große Gruppe von Verbindungen, und spricht die erfindungsgemäß verwendeten weder expressis verbis noch in den Beispielen an. Die DE-A-2 336 289 beschreibt im wesentlichen chlorierte o-Benzyltoluole, die als wertvolle Ausgangsstoffe zur Herstellung von Anthracen und Antrachinon und deren Derivaten beschrieben werden. Von den in der GB-A-1 504 655 beschriebenen biologisch abbaubaren bromhaltigen Benzyltoluol-Derivaten unterscheiden sich die erfindungsgemäß ausgewählten und verwendeten Verbindungen der obigen allgemeinen Formeln dadurch, daß sie eben nicht asymmetrisch, sondern an beiden Phenylringen substituiert sind und dennoch überraschend vorteilhafte Eigenschaften aufweisen.Some of the bromine-containing benzyltoluene derivatives of the form given above, selected according to the invention and used in or as functional liquids, are known, for example from the general formula of EP-A-71 338 already mentioned above, or else from the generic definition of DE-A-2 336 289. The first cited literature provides an immensely large group of compounds and does not address the expressis verbis used according to the invention or in the examples. DE-A-2 336 289 describes essentially chlorinated o-benzyltoluenes, which are described as valuable starting materials for the preparation of anthracene and antrachinone and their derivatives. The compounds of the above general formulas selected and used according to the invention differ from the biodegradable bromine-containing benzyltoluene derivatives described in GB-A-1 504 655 in that they are not asymmetrical but are substituted on both phenyl rings and nevertheless have surprisingly advantageous properties .

Die Herstellung der erfindungsgemäß verwendeten bromhaltigen Benzyltoluol-Derivate erfolgt in an sich bekannter Weise entweder durch Halogenieren der nichthalogensubstituierten entsprechenden Benzyltoluole mit elementarem Brom in Gegenwart eines bekannten Halogenierungskatalysators wie Eisen, FeCl3, FeBr3, AICI3, TiC14 und dergleichen. Dabei kann die Umsetzung bei Zimmertemperatur durchgeführt werden, wobei jedoch, in Abhängigkeit von dem jeweiligen Katalysator, beispielsweise auch Temperaturen zwischen -5 und +40°C geeignet sind.The bromine-containing benzyltoluene derivatives used according to the invention are prepared in a manner known per se either by halogenating the corresponding non-halogen-substituted benzyltoluenes with elemental bromine in the presence of a known halogenation catalyst such as iron, FeCl 3 , FeBr 3 , AICI 3 , TiC1 4 and the like. The reaction can be carried out at room temperature, but depending on the particular catalyst, temperatures between -5 and + 40 ° C. are also suitable.

Eine weitere bevorzugte Verfahrensweise zur Herstellung der erfindungsgemäß verwendeten bromhaltigen Benzyltoluol-Derivate der obigen allgemeinen Formel I besteht in der Kondensation einer Verbindung der allgemeinen Formel III

Figure imgb0003
worin x' 0 oder 1 und z' 1 oder 2 bedeuten, mit einer Verbindung der allgemeinen Formel IV
Figure imgb0004
 Another preferred procedure for the preparation of the bromine-containing benzyltoluene derivatives of the above general formula I used according to the invention consists in the condensation of a compound of the general formula III
Figure imgb0003
 wherein x 'is 0 or 1 and z' is 1 or 2, with a compound of general formula IV
Figure imgb0004

worin Hal Brom oder Chlor bedeutet und x 1 und z 0 oder 1 bedeuten. Bei der Kondensation arbeitet man gegebenenfalls in Gegenwart eines Friedel-Crafts-Katalysators, wie beispielsweise FeCl3, FeBr3, AICI3 und/oder TiCl4, mit einem Überschuß von Verbindungen der allgemeinen Formel III.where Hal is bromine or chlorine and x is 1 and z is 0 or 1. The condensation is carried out, if appropriate, in the presence of a Friedel-Crafts catalyst, such as FeCl 3 , FeBr 3 , AICI 3 and / or TiCl 4 , with an excess of compounds of the general formula III.

Gegenüber den aus der EP-A-88 650 bekannten chlorsubstituierten Verbindungen zeigen die erfindungsgemäß verwendeten bromhaltigen Benzyltoluol-Derivate eine wesentlich verbesserte Schwerentflammbarkeit bei gleichzeitig verbessertem Viskositäts-Temperaturverhalten.Compared to the chlorine-substituted compounds known from EP-A-88 650, the bromine-containing benzyltoluene derivatives used according to the invention show a substantially improved flame retardancy with a simultaneously improved viscosity-temperature behavior.

Das aus der GB-A-1 504 655 bekannte asymmetrisch substituierte Dibrombenzyltoluol wird bei Zimmertemperatur fest, während das an beiden Phenylringen bromierte Isomere sich erst bei -25° C verfestigt, was für die Anwendung dieser Verbindung als Hydraulikflüssigkeit bzw. Isolationsflüssigkeit besonders vorteilhaft ist.The asymmetrically substituted dibromobenzyltoluene known from GB-A-1 504 655 solidifies at room temperature, while the isomer brominated on both phenyl rings only solidifies at -25 ° C., which is particularly advantageous for the use of this compound as a hydraulic fluid or insulating fluid.

Somit haben sich die erfindungsgemäß eingesetzten bromhaltigen Benzyltoluol-Derivate sowohl bei Hydraulikflüssigkeiten als auch bei Isolationsflüssigkeiten für elektrische Vorrichtungen, wie beispielsweise Kondensatoren, Transformatoren und dergleichen, nicht nur aufgrund ihres günstigen Viskositäts-Temperaturverhaltens, sondern auch wegen ihrer sehr günstigen flammhemmenden Wirkung bewährt. Die erfindungsgemäßen funktionellen Flüssigkeiten können demzufolge insbesondere auch als schwerentflammbare Hydraulik- bzw. schwerentflammbare Isolationsflüssigkeiten eingesetzt werden, die aufgrund ihrer geringen Toxizität, ihrer geringen Neigung zur Bildung giftiger Zersetzungsprodukte und ihrer biologischen Abbaubarkeit eine erhebliche Bereicherung der Technik darstellen.Thus, the bromine-containing benzyltoluene derivatives used according to the invention have proven themselves not only in the case of hydraulic liquids but also in the case of insulation liquids for electrical devices, such as, for example, capacitors, transformers and the like, not only because of their favorable viscosity-temperature behavior but also because of their very favorable flame-retardant effect. The functional fluids according to the invention can therefore in particular also be used as flame-retardant hydraulic fluids or flame-retardant insulation fluids which, because of their low toxicity, their low tendency to form toxic decomposition products and their biodegradability, represent a considerable enrichment of technology.

Wie bereits erwähnt, können anstelle der einzelnen Verbindungen in den erfindungsgemäßen funktionellen Flüssigkeiten die genannten bromhaltigen Benzyltoluol-Derivate einzeln oder auch in Form von Gemischen, namentlich in Form der lsomerengemische, enthalten sein.As already mentioned, instead of the individual compounds in the functional liquids according to the invention, the bromine-containing benzyltoluene derivatives mentioned may be present individually or in the form of mixtures, especially in the form of the isomer mixtures.

Die Erfindung sei im folgenden näher anhand von Beispielen beschrieben.The invention is described in more detail below with the aid of examples.

HerstellungsbeispielManufacturing example

Herstellung von Dibrombenzyltoluol durch Kondensation von Bromtoluol mit Brombenzylbromid.Production of dibromobenzyltoluene by condensation of bromotoluene with bromobenzylbromide.

Zur Herstellung von Dibrombenzyltoluol wird zunächst durch Bromieren von Toluol mit elementarem Brom in Gegenwart von wasserfreiem FeC13 Bromtoluol hergestellt, welches dann an der Seitenkette bromiert wird. Man erhitzt hierzu 8,3 Mol Bromtoluol in Gegenwart von 0,5 g eines Radikalketteninitiators (a,a'-Azobisisobutyronitril), auf eine Temperatur von 80° C. Unter Bestrahlung mit einer Ultraviolettlampe mit einer Leistung von 300 W tropft man 1,66 Mol Brom unter Kühlen zu. Der entstehende Bromwasserstoff wird in einer Waschflasche mit gekühltem Wasser absorbiert.To prepare dibromobenzyltoluene, bromination of toluene with elemental bromine is first carried out in the presence of anhydrous FeC1 3 bromotoluene, which is then brominated on the side chain. For this purpose, 8.3 mol of bromotoluene are heated in the presence of 0.5 g of a radical chain initiator (a, a'-azobisisobutyronitrile) to a temperature of 80 ° C. 1.66 is dripped in under irradiation with an ultraviolet lamp with an output of 300 W. Moles of bromine with cooling. The resulting hydrogen bromide is absorbed in a wash bottle with chilled water.

Das abgekühlte Gemisch wird dann zur Kondensationsreaktion in eine Suspension von 6 g FeCI3 in 1,66 Mol Bromtoluol bei einer Temperatur von 30°C eingetropft. Der entstehende gasförmige Bromwasserstoff wird in gleicher Weise, wie oben beschrieben, mit gekühltem Wasser in einer Waschflasche absorbiert. Bei dieser Kondensationsreaktion wird durch den angewandten großen Bromtoluolüberschuß die Bildung von Nebenprodukten (bromiertes Dibenzyltoluol) unterdrückt. Nach Beendigung der Zugabe wird 30 Minuten auf 50°C erwärmt, worauf das abgekühlte Reaktionsgemisch mit 1 Liter Wasser, dann mit 1 Liter 10 %-iger Natriumhydroxidlösung und anschließend erneut mit 1 Liter Wasser gewaschen wird. Man trocknet die organische Phase und destilliert den Bromtoluolüberschuß ab.The cooled mixture is then added dropwise to a condensation reaction in a suspension of 6 g FeCl 3 in 1.66 mol bromotoluene at a temperature of 30 ° C. The resulting gaseous hydrogen bromide is absorbed in the same way as described above with chilled water in a wash bottle. In this condensation reaction, the formation of by-products (brominated dibenzyltoluene) is suppressed by the large excess of bromotoluene used. After the addition has ended, the mixture is heated to 50 ° C. for 30 minutes, whereupon the cooled reaction mixture is mixed with 1 liter of water and then with 1 liter of 10% strength Sodium hydroxide solution and then washed again with 1 liter of water. The organic phase is dried and the excess bromotoluene is distilled off.

Die verbleibende Flüssigkeit wird bei 0,4 mbar rektifiziert, wobei man 395 g einer zwischen 155 und 166° C bei 0,4 mbar siedenden Hauptfraktion erhält, die massenspektrometrisch als Dibrombenzyltoluol identifiziert wird. Dabei wurde auf eine Isomerenuntersuchung verzichtet.The remaining liquid is rectified at 0.4 mbar, giving 395 g of a main fraction boiling between 155 and 166 ° C. at 0.4 mbar, which is identified by mass spectrometry as dibromobenzyltoluene. An isomer investigation was not carried out.

In der nachfolgenden Tabelle ist das Elektronenstrommassenspektrum des erhaltenen Dibrombenzyltoluols wiedergegeben.

Figure imgb0005
The following table shows the electron current mass spectrum of the dibromobenzyltoluene obtained.
Figure imgb0005

Die übrigen erfindungsgemäß eingesetzten bromhaltigen Benzyltoluol-Derivate erhält man in analoger Weise zu der oben beschriebenen Verfahrensweise unter Anwendung an sich bekannter Methoden oder auch durch direktes Bromieren oder Bromieren und Chlorieren von Benzyltoluol, wobei in diesem Fall allerdings Reaktionsgemische anfallen, die in geeigneter Weise, beispielsweise gaschromatographisch, in die erfindungsgemäß eingesetzten bromhaltigen Benzyltoluol-Derivate der oben angegebenen allgemeinen Formeln aufgetrennt werden müssen.The other bromine-containing benzyltoluene derivatives used according to the invention are obtained in an analogous manner to the procedure described above using methods known per se or also by direct bromination or bromination and chlorination of benzyltoluene, in which case, however Reaction mixtures are obtained which have to be separated in a suitable manner, for example by gas chromatography, into the bromine-containing benzyltoluene derivatives of the general formulas given above used according to the invention.

Die erfindungsgemäßen schwerentflammbaren, biologisch abbaubaren funktionellen Flüssigkeiten können neben dem bromhaltigen Benzyltoluol-Derivat auch zusätzliche, für die funktionellen Flüssigkeiten übliche Bestandteile und Zusätze enthalten, beispielsweise Korrosionsschutzmittel, wie Erdalkalisulfonate, Stabilisatoren, wie Aminderivate oder phenolische Produkte, verschleißmindernde Zusätze, beispielsweise Zinkdialkyldithiophosphate, Säureakzeptoren, beispielsweise Epoxidverbindungen, Tetraphenylzinn usw., sowie Entschäumer, wie Seife, Silicone, Glykole, Phosphatester, und Viskositätsindexverbesserer, wie Polymethacrylate, Polyisobutylen. Weiterhin können die erfindungsgemäß verwendeten bromhaltigen Benzyltoluol-Derivate mit vielen geeigneten Produkten, wie beispielsweise Mineralöl, Glykolen, etc. modifiziert werden.In addition to the bromine-containing benzyltoluene derivative, the flame-retardant, biodegradable functional liquids according to the invention can also contain additional constituents and additives customary for the functional liquids, for example corrosion inhibitors, such as alkaline earth metal sulfonates, stabilizers, such as amine derivatives or phenolic products, wear-reducing additives, for example zinc dialkylditheakophosphates, for example epoxy compounds, tetraphenyltin, etc., and also defoamers, such as soap, silicones, glycols, phosphate esters, and viscosity index improvers, such as polymethacrylates, polyisobutylene. Furthermore, the bromine-containing benzyltoluene derivatives used according to the invention can be modified with many suitable products, such as mineral oil, glycols, etc.

Die folgenden Beispiele dienen der weiteren Verdeutlichung der erfindungsgemäßen schwerentflammbaren, biologisch abbaubaren funktionellen Flüssigkeiten.The following examples serve to further illustrate the flame-retardant, biodegradable functional liquids according to the invention.

Beispiel 2Example 2

Untersuchung der Eigenschaften des erfindungsgemäß bevorzug als bromhaltiges Benzyltoluol-Derivat eingesetzten DibrombenzyltoluolsInvestigation of the properties of the dibromobenzyltoluene preferably used according to the invention as a bromine-containing benzyltoluene derivative

a) Biologische Abbaubarkeita) Biodegradability

Die Untersuchung der biologischen Abbaubarkeit erfolgt mit Hilfe eines anerkannten Meßverfahrens zur Bestimmung der biologischen Abbaubarkeit von anionischen und nichtionischen synthetischen Tensiden, nämlich dem OECD-Screening-Test (Bundesgesetzblatt 1 (1977), Seite 245) (modifiziert) für nichtionische Tenside.The biodegradability is examined with the aid of a recognized measuring method for determining the biodegradability of anionic and nonionic synthetic surfactants, namely the OECD screening test (Federal Law Gazette 1 (1977), page 245) (modified) for nonionic surfactants.

Als Impfsuspension verwendet man aerobe, polyvalente Mikroorganismen aus dem Ablauf einer biologischen Kläranlage.Aerobic, polyvalent microorganisms from the drain of a biological sewage treatment plant are used as the vaccine suspension.

Bei dieser Methode erfolgt die erste Probennahme nach 7 Tagen, die zweite Probennahme nach 14 Tagen und die dritte Probennahme nach 19 Tagen. Die gezogenen Proben wurden entsprechend der Vorschrift des oben bezeichneten Tests aufgearbeitet und die Abbaurate gaschromatographisch bestimmt.With this method, the first sample is taken after 7 days, the second sample after 14 days and the third sample after 19 days. The samples taken were processed in accordance with the instructions of the test described above and the rate of degradation was determined by gas chromatography.

Hierbei hat sich folgendes Ergebnis gezeigt:

  • Probe nach 7 Tagen: 49,3 % abgebaut
  • Probe nach 14 Tagen: 69,1 % abgebaut
  • Probe nach 19 Tagen: 82,9 % abgebaut
The following result was shown:
  • Sample after 7 days: 49.3% degraded
  • Sample after 14 days: 69.1% degraded
  • Sample after 19 days: 82.9% degraded

Überraschenderweise läßt sich das erfindungsgemäß bevorzugt eingesetzte Dibrombenzyltoluol biologisch zu mehr als 80 % abbauen.Surprisingly, more than 80% of the dibromobenzyltoluene used according to the invention can be biodegraded.

b) Brandtechnische Untersuchungb) Fire investigation

Die brandtechnische Untersuchung erfolgt nach dem "6. Luxemburger Bericht über Anforderungen und Prüfungen schwerentflammbarer Flüssigkeiten für hydraulische Kraftübertragung und Steuerung".The fire test is carried out according to the "6th Luxembourg report on requirements and tests of flame-retardant liquids for hydraulic power transmission and control".

Hierbei hat sich gezeigt, daß Dibrombenzyltoluol ein besseres brandtechnisches Verhalten zeigt als beispielsweise Tetrachlorbenzyltoluol bzw. polychloriertes Biphenyl.It has been shown here that dibromobenzyltoluene exhibits better fire behavior than, for example, tetrachlorobenzyltoluene or polychlorinated biphenyl.

c) Untersuchung der Korrosionswirkungc) Investigation of the corrosion effect

Die Korrosionswirkung von Dibrombenzyltoluol wurde nach der Methode des oben angesprochenen 6. Luxemburger Berichts untersucht. Hierzu wurden die Metalle Stahl, Kupfer, Messing, Aluminium, Cadmium und Zink sowie die Metallpaarungen Kupfer-Zink, Stahl-Aluminium, Stahl-Cadmium und Aluminium-Zink zu zwei Drittel in die zu prüfende Flüssigkeit (Dibrombenzyltoluol) eingetaucht und darin während 28 Tagen bei einer Temperatur von 35° C belassen.The corrosion effect of dibromobenzyltoluene was investigated using the method of the 6th Luxembourg report mentioned above. For this purpose, two-thirds of the metals steel, copper, brass, aluminum, cadmium and zinc and the metal pairings copper-zinc, steel-aluminum, steel-cadmium and aluminum-zinc were immersed in the liquid to be tested (dibromobenzyltoluene) and in it for 28 days leave at a temperature of 35 ° C.

Bei dieser Untersuchung hat sich gezeigt, daß bei sämtlichen Prüfblechen die durch Korrosion verursachte Gewichtsdifferenz kleiner als 1 mg ist (zulässige Gewichtsdifferenz 20 mg).This investigation has shown that the weight difference caused by corrosion is less than 1 mg for all test sheets (permissible weight difference 20 mg).

d) Verträglichkeit gegenüber Dichtelementend) Compatibility with sealing elements

Zur Untersuchung der Verträglichkeit gegenüber Dichtelementen wird ein Dichtelement aus dem Dichtungswerkstoff 83 FKM 575 (Viton) in die zu untersuchende Flüssigkeit eingetaucht, und zwar während 21 Tagen bei 60°C , 80°C, 100°C, 120°C und 150°C. Anschließend wird die Volumenänderung des Dichtelements und die Änderung seiner Shore-Härte bestimmt.To investigate the compatibility with sealing elements, a sealing element made of the sealing material 83 FKM 575 (Viton) is immersed in the liquid to be examined, for 21 days at 60 ° C, 80 ° C, 100 ° C, 120 ° C and 150 ° C . The change in volume of the sealing element and the change in its Shore hardness are then determined.

Bei dieser Untersuchung zeigt das erfindungsgemäß bevorzugt verwendete bromhaltige Benzyltoluol-Derivat, nämlich Dibrombenzyltoluol, als solches und auch in fertig formulierten Hydraulikflüssigkeiten ein besonders gutes Verhalten, indem sich die Volumenänderung des Dichtungsmaterials zwischen < 1 und 2 % bewegt und die Änderung der Shore-Härte bei -3 Grad liegt. Zulässig ist bei dieser Untersuchungsmethode eine Volumenänderung bis 20 % und eine Änderung der Shore-Härte von -10 Grad.In this investigation, the bromine-containing benzyltoluene derivative, namely dibromobenzyltoluene, which is preferably used according to the invention, exhibits particularly good behavior as such and also in fully formulated hydraulic fluids, in that the volume change of the sealing material moves between <1 and 2% and the change in the Shore hardness contributes -3 degrees. With this test method, a change in volume of up to 20% and a change in Shore hardness of -10 degrees are permitted.

Die untersuchten Vergleichsprodukte auf der Grundlage von polychloriertem Biphenyl und Tetrachlorbenzyltoluol zeigen Werte der Volumenänderung von 40 % bei einer Untersuchungstemperatur von 150°C. Bei diesen herkömmlichen Produkten muß bei Anwendung als Hydraulikflüssigkeit darauf geachtet werden, daß Temperaturen von 100°C nicht überschritten werden, da sonst die Dichtwerkstoffe in zu starkem Maße angegriffen werden und es zu Störungen kommen kann.The investigated comparative products based on polychlorinated biphenyl and tetrachlorobenzyltoluene show volume change values of 40% at an investigation temperature of 150 ° C. In the case of these conventional products, when used as hydraulic fluid, care must be taken that temperatures of 100 ° C. are not exceeded, since otherwise the sealing materials are attacked to an excessive extent and malfunctions can occur.

e) Untersuchung der Pyrolysee) Examination of pyrolysis

Zur Prüfung auf hochtoxische Zersetzungsprodukte wurde Dibrombenzyltoluol bei Temperaturen zwischen 150 und 700°C pyrolysiert. Die Aufarbeitung der Probe erfolgt nach der EPA-Methode No. 613. Bei der Analyse mit GCMS konnte kein hochtoxisches Dioxin bzw. Dibenzofuran (tri- und tetrabromiert) innerhalb der Nachweisgrenze (0,5 ppb) festgestellt werden.To test for highly toxic decomposition products, dibromobenzyltoluene was pyrolyzed at temperatures between 150 and 700 ° C. The sample is processed according to EPA method no. 613. When analyzing with GCMS, no highly toxic dioxin or dibenzofuran (tri- and tetrabrominated) was found within the detection limit (0.5 ppb).

f) Untersuchung des Viskositäts-Temperatur-Verhaltensf) Investigation of the viscosity-temperature behavior

Die erfindungsgemäße Hydraulikflüssigkeit nach dem nachfolgenden Beispiel 2 zeigt das folgende Viskositäts-Temperatur-Verhalten (1 cSt = 1 mm2/s)

  • -20° C 8320 cSt.
  • 0° C 430 cSt.
  • +20°C 83 cSt.
  • +50°C 21 cSt.
  • + 100° C 6,6 cSt.
The hydraulic fluid according to the invention according to Example 2 below shows the following viscosity-temperature behavior (1 cSt = 1 mm 2 / s)
  • -20 ° C 8320 cSt.
  • 0 ° C 430 cSt.
  • + 20 ° C 83 cSt.
  • + 50 ° C 21 cSt.
  • + 100 ° C 6.6 cSt.

Eine auf Tetrachlorbenzyltoluol aufgebaute Hydraulikflüssigkeit besitzt folgendes Verhalten:

  • -20° C fest, nicht meßbar.
  • 0°C 9730cSt.
  • +20°C 320cSt.
  • +50°C 25cSt.
  • + 100° C 4cSt.
A hydraulic fluid based on tetrachlorobenzyltoluene has the following behavior:
  • -20 ° C solid, not measurable.
  • 0 ° C 9730cSt.
  • + 20 ° C 320cSt.
  • + 50 ° C 25cSt.
  • + 100 ° C 4cSt.

Die folgenden Beispiele 2 bis 8 dienen der weiteren Erläuterung der Erfindung und betreffen die Rezepturen von schwerentflammbaren Hydraulikflüssigkeiten (Beispiele 2 bis 6) und Isolationsflüssigkeiten (Beispiele 7 und 8).The following examples 2 to 8 serve to explain the invention further and relate to the formulations of flame-retardant hydraulic fluids (examples 2 to 6) and insulation fluids (examples 7 and 8).

Beispiel 2Example 2

Zusammensetzung einer schwerentflammbaren Hydraulikflüssigkeit:

  • 93 % Dibrombenzyltoluol
  • 6 % Viskositätsindexverbesserer (Polymethacrylat)
  • 0,5 % Korrosionsschutzmittel (Bariumsulfonat)
  • 0,5 % Verschleißschutzadditiv (Zinkdialkyldithiophosphat)
Composition of a flame-retardant hydraulic fluid:
  • 93% dibromobenzyltoluene
  • 6% viscosity index improver (polymethacrylate)
  • 0.5% anti-corrosion agent (barium sulfonate)
  • 0.5% wear protection additive (zinc dialkyldithiophosphate)

Beispiel 3Example 3

Zusammensetzung einer schwerentflammbaren Hydraulikflüssigkeit:

  • 75 % Dibrombenzyltoluol
  • 23 % isopropyliertes Triphenylphosphat
  • 1 % Korrosionsschutzmittel (Alkylsulfamidocarbonsäure)
  • 1 % Säureakzeptor (Epoxidharz)
Composition of a flame-retardant hydraulic fluid:
  • 75% dibromobenzyltoluene
  • 23% isopropylated triphenyl phosphate
  • 1% anti-corrosion agent (alkylsulfamidocarboxylic acid)
  • 1% acid acceptor (epoxy resin)

Beispiel 4Example 4

Zusammensetzung einer schwerentflammbaren Hydraulikflüssigkeit:

  • 88 % Dibrombenzyltoluol
  • 10 % Butylstearat
  • 1 % Korrosionsschutzmittel (Fettsäurealkanolamid)
  • 0,5 % Oxidationsstabilisator (Aminderivat)
  • 0,5 % Verschleißschutzadditiv (Zinkdialkyldithiophosphat)
Composition of a flame-retardant hydraulic fluid:
  • 88% dibromobenzyltoluene
  • 10% butyl stearate
  • 1% anti-corrosion agent (fatty acid alkanolamide)
  • 0.5% oxidation stabilizer (amine derivative)
  • 0.5% wear protection additive (zinc dialkyldithiophosphate)

Beispiel 5Example 5

Zusammenestzung einer schwerentflammbaren Hydraulikflüssigkeit:

  • 65 % Dibrombenzyltoluol
  • 25 % monobromiertes Benzyltoluol
  • 9 % Viskositätsindexverbesserer (Polyisobutylen)
  • 1 % Korrosionsschutzmittel (Talgfettaminderivat)
Composition of a flame retardant hydraulic fluid:
  • 65% dibromobenzyltoluene
  • 25% monobrominated benzyltoluene
  • 9% viscosity index improver (polyisobutylene)
  • 1% anti-corrosion agent (tallow fat amine derivative)

Beispiel 6Example 6

Zusammensetzung einer schwerentflammbaren Hydraulikflüssigkeit.:

  • 50 % Dibrombenzyltoluol
  • 45 % monobromiertes Xylylxylol
  • 4,5 % Viskositätsindexverbesserer (Polyisobutylen)
  • 0,5 % Korrosionsschutzmittel (Talgfettaminderivat)
Composition of a flame-retardant hydraulic fluid .:
  • 50% dibromobenzyltoluene
  • 45% monobrominated xylylxylene
  • 4.5% viscosity index improver (polyisobutylene)
  • 0.5% anti-corrosion agent (tallow fat amine derivative)

Beispiel 7Example 7

Zusammensetzung einer Isolationsflüssigkeit für elektrische Vorrichtungen:

  • 99,5 % Dibrombenzyltoluol
  • 0,3 % Korrosionsschutzmittel (Talgfettaminderivat)
  • 0,2 % Epoxidharz
Composition of an insulation liquid for electrical devices:
  • 99.5% dibromobenzyltoluene
  • 0.3% anti-corrosion agent (tallow fat amine derivative)
  • 0.2% epoxy resin

Beispiel 8Example 8

Zusammensetzung einer Isolationsflüssigkeit für elektrische Vorrichtungen:

  • 50 % Dibrombenzyltoluol
  • 49,5 % monobromiertes Benzyltoluol
  • 0,3 % Korrosionsschutzmittel (Talgfettaminderivat)
  • 0,2 % Epoxidharz
Composition of an insulation liquid for electrical devices:
  • 50% dibromobenzyltoluene
  • 49.5% monobrominated benzyltoluene
  • 0.3% anti-corrosion agent (tallow fat amine derivative)
  • 0.2% epoxy resin

Claims (2)

  1. Fire resistant, biologically degradable functional fluid containing at least one bromine-containing benzyltoluene derivative and customary additives, characterized in that (sic) it contains as the bromine-containing benzyltoluene derivative a dibromobenzyltoluene of the formula(l)
    Figure imgb0008
    and/or
    a monobromoxylylxylene of the formula (II)
    Figure imgb0009
    in an amount of at least 35 % by weight.
EP85100772A 1984-01-27 1985-01-25 Difficult flammable biodegradable functional fluid Expired EP0150826B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85100772T ATE43628T1 (en) 1984-01-27 1985-01-25 FLAMMABLE, BIODEGRADABLE FUNCTIONAL FLUID.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19843402863 DE3402863A1 (en) 1984-01-27 1984-01-27 BROMYLED BENZYLTOLUOL DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THE USE THEREOF
DE3402863 1984-01-27

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DE3526873A1 (en) * 1985-07-26 1987-01-29 Hydrocor Forsch Analytik BROWNED ALKYLBENEOL DERIVATIVES AS THE BASIS OF FLAME-RETARDANT, BIODEGRADABLE FUNCTIONAL LIQUIDS
CN109022034B (en) * 2018-05-31 2021-02-23 石家庄东翔化工有限公司 Preparation method of flame-retardant paraffin for polyurethane foam gap filler
CN114507555B (en) * 2020-10-28 2023-08-08 中国石油化工股份有限公司 Biodegradable flame-retardant hydraulic oil composition

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GB669048A (en) * 1948-11-19 1952-03-26 Alfred John Rudge Improvements in or relating to lubricants
US3290253A (en) * 1963-10-21 1966-12-06 Monsanto Res Corp Chlorine-substituted diarylalkanes as hydraulic fluids
US3371120A (en) * 1964-09-21 1968-02-27 Monsanto Co 3, 4'-halogen-containing diphenyl ethers and thio ethers
DE2336289A1 (en) * 1973-07-17 1975-02-06 Basf Ag PROCESS FOR THE PREPARATION OF O-BENZYL TOLUENE
FR2273351A1 (en) * 1974-05-31 1975-12-26 Rhone Poulenc Ind
NL7605659A (en) * 1975-05-30 1976-12-02 Monsanto Co ELECTRICAL DEVICE.
US4260506A (en) * 1979-01-26 1981-04-07 Monsanto Company Hydraulic pressure device utilizing biodegradable halogenated diphenyl methanes
GB2100740B (en) * 1981-06-19 1985-03-06 James Edward Stangroom Electric field responsive (electroviscous) fluids
WO1982004442A1 (en) * 1981-06-19 1982-12-23 Stangroom James Edward Electroviscous fluids
FR2522334B1 (en) * 1982-02-26 1986-01-10 Ugine Kuhlmann APPLICATION TO THE LUBRICATION OF POLYCHLOROBENZYL POLYCHLOROTOLUENES

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