EP0210612A2 - Dérivés d'alkylbenzène bromé comme base pour des fluides fonctionnels difficilement inflammables et biodégradables - Google Patents

Dérivés d'alkylbenzène bromé comme base pour des fluides fonctionnels difficilement inflammables et biodégradables Download PDF

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Publication number
EP0210612A2
EP0210612A2 EP86110311A EP86110311A EP0210612A2 EP 0210612 A2 EP0210612 A2 EP 0210612A2 EP 86110311 A EP86110311 A EP 86110311A EP 86110311 A EP86110311 A EP 86110311A EP 0210612 A2 EP0210612 A2 EP 0210612A2
Authority
EP
European Patent Office
Prior art keywords
value
integer
brominated
general formula
hydrogen atom
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.)
Withdrawn
Application number
EP86110311A
Other languages
German (de)
English (en)
Other versions
EP0210612A3 (fr
Inventor
Helmut Theunissen
Raymund Dr. Weber
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
HYDROCOR FORSCHUNGS- und ANALYTIK GmbH
Original Assignee
HYDROCOR FORSCHUNGS- und ANALYTIK GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by HYDROCOR FORSCHUNGS- und ANALYTIK GmbH filed Critical HYDROCOR FORSCHUNGS- und ANALYTIK GmbH
Publication of EP0210612A2 publication Critical patent/EP0210612A2/fr
Publication of EP0210612A3 publication Critical patent/EP0210612A3/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • 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
    • 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 relates to a flame-retardant, biodegradable functional fluid, namely a hydraulic fluid which contains a brominated alkylbenzene derivative as an essential component.
  • 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 dangers are possible if there is a fire, since highly toxic dioxins and dibenzofurans can be formed. This has led to 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 components which are selected from halogenated lower alkyl-substituted benzenes, monohalogenated diphenyl ethers and chlorinated biphenyls and mixtures thereof.
  • Halogenated lower alkylbenzenes are those with 1 to 5 halogen atoms and 1 to 4 carbon atoms in the alkyl group, of which dibromoethylbenzene appears to be preferred among these compounds to be used as a smaller mixture component. 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-combustible 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 liquids which, in addition to the technological criteria for the intended field of use, also meet the toxicological and economic requirements.
  • 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.
  • the invention thus relates to a flame-retardant, biodegradable functional liquid consisting of or containing at least one brominated alkylbenzene derivative of the general formula I.
  • R1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R3 is a hydrogen atom or a group of the general formula in which n is an integer with a value from 1 to 4, m is an integer with a value of 1 or 2 and y represents an integer with a value of 0, 1 or 2 and x means an integer with a value from 1 to 3 with the proviso that the sum x + y has a value from 1 to 3.
  • the functional liquid contains as a brominated alkylbenzene derivative a dibromo diethylbenzene of the following general formula II a 1-bromophenyl-1-bromomethylphenylethane of the following general formula III - And / or a bis (bromotolyl) methane of the following general formula IV
  • the compounds of general formulas II to IV given above can be used in the form of pure compounds, isomer mixtures or else in the form of mixtures of these compounds with one another.
  • the brominated alkylbenzene derivatives selected according to the invention namely those of the general formulas II to IV above, in the form of the individual substances or else the isomer mixtures obtained in the brominating preparation are liquids which, as such or in combination with conventional diluents, are additives and additives can be used as functional liquids.
  • These compounds have proven to be particularly suitable for functional liquids, since on the one hand they have excellent technological properties which are required 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, do not produce any toxic decomposition products, such as highly toxic dioxin derivatives, when heated and, moreover, can be easily biodegraded.
  • the brominated alkylbenzene derivatives selected according to the invention are particularly well suited for flame-retardant hydraulic fluids, but they can also be used as a carrier for insecticides, as an effective diluent in the crop protection sector, as a flame retardant in plastics, textiles and paper, as a lubricant in metalworking fluids, as a base liquid for flame-retardant compressor fluids.
  • environmentally friendly saw chain oil as a solvent for the treatment of flame-retardant greases and waxes, as an insulation liquid for electrical devices as well as for or in flame-retardant corrosion protection agents be used.
  • the functional liquids according to the invention advantageously contain the brominated alkylbenzene derivatives in the form of the bromination mixtures used in the bromination of the starting materials, it being possible to advantageously combine these compounds or also these mixtures with other brominated compounds, such as, in particular, dibromoethylbenzene and / or dibromocumol.
  • other brominated compounds such as, in particular, dibromoethylbenzene and / or dibromocumol.
  • the flame-retardant, biodegradable functional liquid according to the invention can also contain additives and additives customary for such functional liquids, the brominated alkylbenzene 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, tetraphenylzine, etc., defoamers, such as soaps, silicones, glycols, phosphate esters and the like.
  • Use viscosity index improvers such as polymethacrylates or polyisobutylene and the like.
  • the functional liquids according to the invention can be modified with many suitable products, such as mineral oils, glycols etc.
  • the brominated alkylbenzene derivatives contained in the functional liquids according to the invention are obtained by brominating alkylbenzene derivatives 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 multinuclear brominated alkylbenzene derivatives are preferably formed by condensation of brominated alkylbenzene derivatives.
  • a mixture of 300 g of diethylbenzene and 5 g of iron powder is heated to 35 ° C. Then 6.45 g of elemental bromine are slowly added dropwise with stirring and the reaction is allowed to proceed at 23 ° C. after starting.
  • the mixture is stirred at 45 ° C. for a further 30 minutes, the reaction mixture is then washed with 500 ml each of a 2.5% sodium disulfite solution, a 10% sodium hydroxide solution and water and then dried.
  • a mixture is obtained as the crude product 16% by weight monobromo diethylbenzene 76% by weight of dibromo diethylbenzene and 8% by weight of tribromo-diethylbenzene.
  • the mixture is distilled in vacuo, the fraction passing at 120 to 122 ° C./2.2 mbar being identified as dibromodiethylbenzene.
  • the compound has a density of 1.571 at 20 ° C.
  • ethylbenzene is monobromized analogously to Preparation Example 1.
  • 601.2 g of the distilled bromoethylbenzene, to which a trace of a radical chain initiator was added are heated to 80.degree.
  • 33.3 ml of bromine are added dropwise at this temperature under irradiation with UV light.
  • the reaction mixture is cooled and added dropwise to a mixture of 120 g of bromoethylbenzene and 3.4 g of FeCl3 at a temperature of 33 ° C.
  • the temperature is reduced to 20 ° C.
  • the addition has ended, the mixture is left to react at 45 ° C.
  • a mixture of 40 ml of bromotoluene and 5 ml of H2SO4 is heated to 110 ° C. with stirring.
  • the solution is then introduced at this temperature into a mixture of 3 g of formaldehyde and 20.9 ml of bromotoluene at this temperature.
  • the mixture is left to react for a further hour at 120 to 130 ° C. and washed the reaction mixture with water and distilled in vacuo.
  • the fraction passing at 182 to 198 ° C / 3.6 mbar is identified as bis (bromotolyl) methane.
  • Composition of a flame-retardant insulation liquid 70% 1-bromophenyl-1-bromomethylphenyl ethane 29.5% dibromo diethylbenzene 0.5% epoxy resin as acid acceptor.
  • composition of a flame-retardant hydraulic fluid 45% bis (bromotolyl) methane 40% 1-bromophenyl-1-bromomethylphenyl ethane 1% zinc dialkyldithiophosphate as wear protection additive 8% polymethacrylate as viscosity index improver 1% barium sulfonate as an anti-corrosion agent 5% phosphate ester
  • composition of a flame-retardant hydraulic fluid 70% 1-bromophenyl-1-bromomethylphenyl ethane 19% dibromo diethylbenzene 10% viscosity index improver 0.7% triphenyl phosphorothionate as wear protection additive 0.2% alkylated diphenylamine 0.1% amine phosphate
  • composition of a flame-retardant hydraulic fluid 88% 1-bromophenyl-1-bromomethylphenyl ethane 11% viscosity index improver 0.5% triphenyl phosphorothionate as wear protection additive 0.3% alkylated diphenylamine 0.2% amine phosphate
  • composition of a flame-retardant hydraulic fluid 80% dibromo diethylbenzene 19% viscosity index improver 0.6% triphenyl phosphorothionate as wear protection additive 0.2% alkylated diphenylamine

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Fireproofing Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP86110311A 1985-07-26 1986-07-25 Dérivés d'alkylbenzène bromé comme base pour des fluides fonctionnels difficilement inflammables et biodégradables Withdrawn EP0210612A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853526873 DE3526873A1 (de) 1985-07-26 1985-07-26 Bromierte alkylbenzolderivate als basis schwerentflammbarer, biologisch abbaubarer funktioneller fluessigkeiten
DE3526873 1985-07-26

Publications (2)

Publication Number Publication Date
EP0210612A2 true EP0210612A2 (fr) 1987-02-04
EP0210612A3 EP0210612A3 (fr) 1988-03-09

Family

ID=6276905

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86110311A Withdrawn EP0210612A3 (fr) 1985-07-26 1986-07-25 Dérivés d'alkylbenzène bromé comme base pour des fluides fonctionnels difficilement inflammables et biodégradables

Country Status (4)

Country Link
EP (1) EP0210612A3 (fr)
AU (1) AU6049886A (fr)
DE (1) DE3526873A1 (fr)
ZA (1) ZA865549B (fr)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2257903A (en) * 1940-02-21 1941-10-07 Dow Chemical Co Mixture of isomeric ethyl dibromobenzenes
IL24342A (en) * 1964-09-21 1969-03-27 Monsanto Co Functional fluid compositions
IL39567A0 (en) * 1971-06-15 1972-07-26 Du Pont Substituted terephthalonitriles and isophthalonitriles and their use as herbicides
GB2100740B (en) * 1981-06-19 1985-03-06 James Edward Stangroom Electric field responsive (electroviscous) fluids
DE3402863A1 (de) * 1984-01-27 1985-08-01 Hydrocor-Forschungs- und Analytik GmbH, 1000 Berlin Bromhaltige benzyltoluol-derivate, verfahren zu ihrer herstellung und deren verwendung

Also Published As

Publication number Publication date
DE3526873A1 (de) 1987-01-29
EP0210612A3 (fr) 1988-03-09
AU6049886A (en) 1987-01-29
ZA865549B (en) 1987-03-25

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