CA1244054A - Substantially non-flammable biologically degradable functional fluid - Google Patents
Substantially non-flammable biologically degradable functional fluidInfo
- Publication number
- CA1244054A CA1244054A CA000472977A CA472977A CA1244054A CA 1244054 A CA1244054 A CA 1244054A CA 000472977 A CA000472977 A CA 000472977A CA 472977 A CA472977 A CA 472977A CA 1244054 A CA1244054 A CA 1244054A
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- Prior art keywords
- bromine
- benzyltoluene
- functional fluid
- flammable
- fluids
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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
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- 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
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- 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
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- 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
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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
- 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
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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
- C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2211/06—Perfluorinated compounds
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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
- 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
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- 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
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- 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
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/26—Amines
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/28—Amides; Imides
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- 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
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- 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
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- 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
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- 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
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- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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- Measurement And Recording Of Electrical Phenomena And Electrical Characteristics Of The Living Body (AREA)
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Abstract
Abstract:
The invention provides a substantially non-flammable biologically degradable functional fluid consisting of or containing at least one bromine-containing benzyltoluene derivative of general formula I
The invention provides a substantially non-flammable biologically degradable functional fluid consisting of or containing at least one bromine-containing benzyltoluene derivative of general formula I
Description
~f~
Substantially non flammable biologically degradable functional fluid The invention relates to a substantially non-flammable, biologically degradable functional liquid, particularly a hydraulic fluid or an insulating fluid for electrical apparatus, which comprises a bromine containing benzyl-toluene derivative as the essential component.
Chlorinated aromatic compounds, particularly chlori-nated biphenyls, have taken an important place in various fields of technology in the last few decades. The poly-chlorinated biphenyls, in particular, have been used to a large extent as hydraulic fluids r as insulating fluids for electrical equipment and as flame suppressing addi-tives for plastics and the like. However, in the last few years, these compounds have been the subject of considerable dispute. It has been determined that these products exert harmful effects on health and the environment and they have potentially catastrophic dangers in that, when burned, highly poisonous dioxin and dibenzofuran may be formed. This has already lead in part to the complete banning of the manufacture or at least the ~se of such compounds by the state supervisory organizations and in part to the imposition of serious limitations to the use of these substances.
To overcome these disadvantages it has been proposed in European Patent No. 88 650 granted September 14, 1983 to use instead chlorinated benzyltoluenes and chlorinated benzylxylenes as lubricants and also as hydraulic fluids because these compounds are substantially inflammable and resist oxidation and are also biologically degradable and are advantageous in view of their low toxic properties.
GB-PS 1 504 655 granted March 22, 1978 describes electrical equipment which contains biologically easily degradable dielectric fluids, namely halogina~ed diphenyl-methane, which are characterized in that the halogensubstituents and possibly alkyl substituents are located only in one of the two phenyl rings, while the other phenyl ring remains ùnsubstituted, since only such haloginated diphenylmethanes having an unsubstituted phenyl group are easily biologically degradable, while the diphenylmethanes substituted on both phenyl residues are resistant to microbiological degradation.
European Patent No. 8251 granted February 20, 1980 discloses fluid dielectrics which can be used, for example, as insulating ~luids for transformers or as impregnating materials for insulating layers using capacitors. It is concerned with alkyl aromatic compounds which are chlor-inated on the aromatic nucleus and which may be obtained from chlorotoluene and/or chloroxylene, for example tetra-chlorobenzyltoluene, and it is indicated that these com-pounds have advantages over the multichlorinated biphenyls previously used for the same purpose. The absence of the biphenyl nucleus and the presence of the alkyl groups on the aromatic nucleus are accordingly credited with the favourable action on the biological degradative behaviour.
Finally, European Patent No. 71 338 granted February 9, 1983 describes electroviscous fluids which consist of hydro-phobic liquids in which solid hydrophilic particles are dispersed. Upon application of an electrical field to such a suspension the viscosity of this mixture rises drastic-ally. This change is reversible and rapid so that such suspensions can be used, for example, in electronically controllable clutches. It is indicated that the hydrophobic liquids in the mixture have a high boiling point, a low viscosity, suitable electrical properties and chemical stability and low toxicity and are preferably biologically degradable. For this purpose, according to this European Patent Application, halogenated diaryl derivatives are suitable as the hydrophobic fluids, the aromatic nuclei of which are combined with one another via various bridges and have fluorine, chlorine or bromine atoms as the halogen substituents. It is stated that these diaryl derivatives should be asymmetrically substituted because then a lower solidification point of the fluid and an improvement of the ability to be biologically degraded is obtained.
The conventional functional liquids are not satis-factory in all respects because they either do not fulfil the criterion of non-flammability required by hydraulic and insulating fluids or they have disadvantageous pro-perties resulting from their inflammability such as poor biodegradability, toxicity of the fulids or their decom-position products, unfavourable viscosity-temperature properties or incompatibility with sealing elements.
The object of the present invention is to provide a functional fluid which has physical properties necessary for the intended use and while having high chemical sta-bility nevertheless can be biologically degraded and is nontoxic and does not give rise to highly toxic products, such as dioxin for example, upon improper treatment.
It has been surprisingly found that a particular group of halogenated diaryl derivatives not only, on the one hand, exhibits valuable technical properties, but also, on the other hand, does not exhibit the dangerous and the environmentally hazardous properties of the conventional compounds, so that the compounds are especially suitable as or for functional fluids.
The invention provides a non-flammable biologically degradable func~ional fluid consisting of or containing at least one bromine containing benzyltoluene derivative of general formula I~
(CH~) (CH3)z~
(Cl)~, (I) (Br)x (Br)x, in which x is 1 or 2, x' is 0 or 1, y is 0, 1 or 2, y' is 0, 1 or 2, ~ is 0, or 1, and zl is 1 or 2 with the proviso that the relationship y + y' = 0, 1 or 2 and x ~ xl ~ y + y' = 1, 2 or 3 is fulfilled.
~.rhe bromine-containing benzyltoluene derivatives used according to the invention as or in functional fluids are thus compounds whiah are substituted on both nuclei wherein at least one bromine substituent and one methyl group must be present. Both the nuclei can however carry several bromine atoms and several methyl groups and the positions of these substituents are not important so that, according to the invention, all of the positional isomers of these bromine-containing benzyltoluene derivatives of formula I
given above can be used in or as functional fluids.
In addition one or both of the phenyl groups may contain chlorine atoms as substituents.
It has surprisingly been found that these bromine-containing benzyltoluene derivatives used according to the invention possess a more advantageous compatibility with ; 30 the environment than ~he conventional halogenated diaryl derivatives, and at the same time possess excellent physical properties which make them particularly suitable for use as functional fluids such as hydrulic fluids or insulating fluids for electrical equipment.
Surprisingly, it has also been found that the substituted bromine-containing benzyltoluene derivatives of the invention of general formula I given above, which are substituted on both phenyl rings, can be biologically degraded without further treatment which appears sur-prising in view of European Patent No. 71 338 and GB-PS 1 504 655 discussed above. Moreover, the bromine-containing benzyltoluene derivatives of general formula I above used in accordance with the invention have the further surprising advantage that in normal working conditions they are fluid and exhibit a particularly favourable viscosity-temperature relationship. Moreover they possess a high flame point, are of low toxicity and low corrosiveness and do not produce highly toxic dioxin products when improperly overheated, which can occur accidentally in the case of polychlorinated biphenyls.
Moreover it has been found that the bromine-containing benzyltoluene derivatives used according to the invention are compatible with sealing elements to an excellent extent, so that the group of compounds of the invention have unexpectedly proved advantageous for the uses discussed above.
Particularly preferred are substantially non-flammable, biologically degradable functional fluids which, as the bromine-containing benzyltoluene derivatives, contain a compound of general formula II
(CH3)z tCH3)z.
~ CH2 ~ (II) Br (Br)x, in which x' is O or 1, z is O or 1 and z' is 1 or 2.
- 6 ~
Even more preferred are functional fluids according to the invention which contain a bromine-containing benzyltoluene derivative according to formula III, IV
or V below.
~ CM2 ~ (III) Br Br ~H3CH3 CH2 ~ (IV~
Br CH3 CH2- ~ (V) Br Na~urally the functional fluids according to the invention may contain the bromine-containing benzyltoluene derivatives defined above alone, but preferably however they are used in the form of mixtures, especially in the form of mixtures of the individual positional isomers of these compounds.
The bromine-containing benzyltoluene derivatives according to the invention of the formulae given above and used in the invention in or as functional fluids are partially known, for example in the general formula of European Patent No. 71 338 mentioned above and also in the generic definition of DE-OS 23 36 289 published 1975. The former reference discloses an enormously large group of compounds, and mentions the use of the invention neither expressly nor in the examples. DE-OS 23 36 289 describes essentially chlorinated o-benzyltoluene, which is described as a valuable starting material for the preparation of anthracene and anthraquinone and its derivatives. The '; compounds of the invention of the general formula given above and their uses differ from the biologically degradable bromine-containing benzyltoluene derivatives described in GB-PS 1 504 655 in that they are not just asymmetric but rathe are substituted on both phenyl rings and nevertheless surprisingly have advantageous properties.
The preparation of the bromine-containing benzyltoluene derivatives of the invention takes place in a conventional manner either by the halogenation of the,non-halogen substituted corresponding benzyltoluene with elemental bromine or a mixture of bromine and chlorine in the presence of a known halogenation catalyst such as iron, FeC13, FeBr3, AlC13, ~iC14 and the like. In this way the reaction can take place at room temperature or, depending on the catalyst employed, at temperatures between -5 and ~40C.
A further preferred method for the preparation of the bromine-containing benzyltoluene derivatives of the invention of general formula I above involves the condensation of a compound of general formula VI
(CH3~zl ~ (VI) (Cl) (Br~x,, in which x', y' and z' are as disclosed above, with a compound of general formula VII
1~
(CH3)z ~ (Cl)y (VII) Hal-CH2~-~
(Br)x in which Hal represents bromine or chlorine and x, y, z are as disclosed above. The condensation can be carried out, if necessary, in the presence of a Friedel-Crafts 5catalyst, such as FeC1~, FeBr3, AlC13 and/or TiCl4, in the presence of an excess of the compound of general formula VI.
The bromine-containing benzyltoluene derivatives according to the invention exhibit a substantially improved flame resistance than the chlorine substituted compounds known from European Patent Application No.
88 650 while at the same time exhibiting improved viscosity-temperature relationships.
The known asymetrically substituted dibromobenzyl-toluene of GB-PSl 504 655 are solid at room temperature, while the isomer brominated on both phenyl rings solidifies at -25C, which is particularly advantageous when using these compounds as hydraulic fluids or insulating fluids.
The bromine-containing benzyltoluene derivatives of the invention have proved useful not only as hydraulic fluids but also as insulating fluids for electrical equipment, such as for example condensers, transformers and the like, not only on the basis of their favourable viscosity-temperature relationships, but also on account of their very favourable flame resisting effect. The functional fluids of the invention can in consequence of this be used, in particular, as non-flammable hydraulic or insulating fluids which, on the basis of their low toxicity, their low inclination to form poisonous de-composition products and their biological degradability, .~
represent a considerable contribution to technology.
As already explained the bromine-containiny benzyltoluene derivatives mentioned above can be contained individual'~y or also in the form of mixtures, preferably in the form of isomer mixtures, in the functional fluids of the invention instead of being used alone as said fluids.
The invention is described in more detail in the following examples.
Preparation Example Preparation of dibromobenzyltoluene by condensation of bromotoluene with bromobenzylbromide.
For the preparation of dibromobenzyltoluene, bromo-toluene was first prepared by the bromination of toluene with elemental bromine in the presence of anhydrous FeC13, and this was then brominated at the side chain.
With this 8.3 Mol of bromotoluene were heated in the presence of 0.5g of a radical chain initiator ~ zobisisobutyronitrile) to a temperature of 80C.
1.66 Mol of bromine were added drop-wise with cooling under irradiation with an ultra-violet lamp having a power of 300 W. The resulting hydrogenbromide was absorbed in a wash bottle containing cooled water.
The cooled mixture was then dropped into a suspension of 6g FeC13 in 1.6 Mol of bromotoluene at a temperature 30C to bring about the condensation reaction. The re-sulting gaseous hydrogenbromide was absorbed into cooled water in a wash bottle in the same manner as described above. The formation of by-products (brominated dibenzyl-toluene), was suppressed during this condensatlon reaction by the presence of a large excess of bromotoluene.
After the termination of the addition the mixture was heated to 50C for 30 minutes, after which the cooled reaction mixture was washed with one liter of water, then with one liter of 10~ sodium hydroxide solution and finally once again with one liter of water. The organic phase was dried and the excess bromotoluene was distilled off.
The remaining fluid was distilled under 0.4 mbar, and 395g of a main fraction boiling between 155 and 166C at 0.4 mbar was obtained and this was identified by mass spectrometry as dibromobenzyltoluene. Thereby an investigation of the isomers was foregone.
The electron stream mass spectrum of the resulting dibromobenzyltoluene is given in the Table below.
, :
TAB LE
Electron Impact Mass Spectr~m of Dibromobenzyltoluene m/x Relative Tot~l lon Intensity m/x Relative Totdl Ion Intenslty Int~nsity(~) Stream(o) Intensity(~) Stream(~) IS,ool,os 0,05 118133,00 0,7d ' 0,07 94 37,003,65 0,~4~0 139,00 3,19 0,~ 445 ~-,00I ~o o,ll IS7~O,oo 0,93 0,01 Il~
3g,0012,4B 1,10 1506141,C0 0,70 0,06 g4 sO~oo9,~3 0,52 ~2~14~,oo 0,69 0,06 83 S~.00~,2~ 1,03 1476lSO,Oo ~,o~ o,lB ~/13 52,00~,62 0,23 316151,00 4,t~ 0,41 S30 S~,oO1,75 o,ls 211152,00 ~,41 0,74 IOIS
t1,001.96 0,17 ~36~S3,U0 ~,~4 0,20 ' 270 t~,00~,91 0,s2 713163,00 4,~9 o,~7 sos 61,00~7,97 ~,5a ~60164,00 s,o~ 0,44 60S
64,0~4,9~ 0,44 601165,00 IOo,oo 0,79 1~06~
6S,00~ 93 0,~6 ~s~1~6,00 14,41 1,~7 1731 ~9 000 ~7 0,0~ 1OS167,00 I,z~ 0,~ 7 74.004,95 0,44 s9~~69,00 8,s~ 0,7s ~o~o 75 0010 79 0,9S 1~0~170,00 1,4~ 0,13 172 7~,003S,01 3,01 42~4171,00 7,~ 0,69 94~
71,oo14,y7 I,3z IR06175,00 0,5t 0,OS 75 71,00S,46 0,4d 659176,00 6,45 0,s7 779 79,001,l~ o,lo 1~6~71,00 5,88 0,5~ 709 91 002, 6~ 0, ~4 J~4 1 79, 00 32, 56 ~, 86 3~23 1~,007,07 0,6~ ~5~179,00 46,55 4.09 5616 .00 3,61 0,01 321~0,00 76,1~ 6,69 9114 ~5 000,7~ 0,06 allal,oo ll,as l,OS 14~4 16,001,91 o,l7 2381~2,00 IS,63 1,37 1886 ~7,003,~6 0,3~ ~s41a3,ao S,10 0,qS 615 1~2,00 16,00 1,411930 114,00 14,79 1,30 17B4 as,;70 8~,79 7,8310132 105,00 4,~0 o 43 591 90,003a~.s9 3,~9 465C~43,00 1,42 o,l~ 17~
91,oo ~ o,I9 ~S6~44,oO 0,6Y 0,06 63 9a 001,41 0,~1 ~70~4S,00 I,4s u,l3 175 gg,oo1,16 o,lo 140146,00 o 67 0,06 a~
~01 00 ~.0~ o,la244 2s~,oO o,a~ 0 07 93 0~ oo4,~9 o,~s s42259,00 90,64 7,09 9728 103,00 9,75 0,361176 ~60,00 ~3 44 ~13 ~6~1 10~,00 s,ai o s~70~ ~61,00 18,7a 5,93 9S0~
110,00 0,63 0,0676 ~6~,00 1~,61 1,11 Is~4 Ill,Oo 0,64 0,0677 263,oo o,y9 o,0~ 119 I 1 3, 00 1, 27 0, 1 1 ~ s3 323, oo 4,5~ 0,40 547 II~ 00 ~ 93 o,~7~ 3~4,oO o,77 0,o6 8 7 ~IS,00 4,~8 o,~ss~29 32s,00 8,S9 0,7~ 103~
1~6,00 1,26 0,11~52 3~6,00 ~,7~ '~l lu6 ,00 o,70 0,06 8S3~7,~o 4,~o 0 ~7 507 ZZ,000,75 o,o7 90~7,00 o,ss o oa ~S
~6,002,09 0,~0 2S1338,o0 34 sS ~,07 ~I~C
1~7 00 ~ ~1 o,~l287 139,00 7,39 0,6S 991 121,00 3,74 0,~bS1 ~40,00 68,43 6,C~ a~s6 1~9,00 ~,~1 0,3z ~3s 34~,00 ~1,47 1,Ol lla4 ~30,00 ~ ~6 o,~s 26~ 34~,oo ~,9~ ~,98 4092 1)7,00 0,61 o,os 74 3~,oo S,Z3 0,4~ 6~
The remaining bromine-containing benzyltoluene derivatives according to the invention can be obtained in an analogous manner to the above described reaction scheme by using conventional methods or also by direct bromination S or bromination and chlorination of benzyltoluene, in which case of course reaction mixtures are obtained which in suitable ways, for example by gas chromatography, must be separated into the bromine-containing benzyltoluene derivatives of the general formula given above according to the invention.
The non-flammable, biologically degradable functional fluids of the invention may contain in addition to the bromine-containing benzyltoluene derivatiaves additional components and additives normally used in functional fluids, for example corrosion inhibitors such as alkaline earth sulfonates, stabilizers such as amine derivatives or phenolic products, wear reducing additives such as zinc dialkyldithiphosphate, acid acceptors such as epoxide compounds, tin tetraphenyl etc., as well as anti-foaming agents such as soap, silicone, glycol, phosphate esters, and viscosity index enhancers such as polymeth-acrylate, polyisobutylene. Further the bromine-containing benzyltoluene derivatives used according to the invention can be modified with various suitable products such as mineral oil, glycols, etc.
The following examples serve to further clarify the non-flammable biologically degradable functional fluids of the invention.
Example 1 Investigation of the properties of the dibromobenzyl-toluenes which are preferred as the bromine-containing benzyltoluene derivatives of the invention.
a) Biological Degradability The investigation of the biological degradability was carried out by means of a known measuring procedure for ~c~
the determination of the biological degradability anionic and non-ionic synthetic tensides (surface-active substances) namely the OECD-screening test (Federal Law Publication l (1977), page 245) (modified) for non-ionic tensides.
Aerobic polyvalent microorganisms from the outlet of a biological sewage plant were used as an innoculating suspension. In this method the first sample was taken after seven days, the second sample after 14 days and the third sample after l9 days. The samples thus taken were treated according to the directions of the tests indicated above and the decomposition rate was determined by gas chromatography.
The following results were obtained in this way:
sample after 7 days : 49.3% degraded sample after 14 days : 69.1% degraded sample after l9 days : 82.9% degraded Surprisingly the dibromobenzyltoluene, which is a preferred compound of the invention was biologically degraded by more than 80%.
b) Combustion Test A combustion test was carried out according to "the 6th Luxemburg Report on the requirements and tests of non-flammable fluids for hydraulic power transmission and control."
By this means it was shown that dibromobenzyltoluene has a better combustion behaviour than tetrachloro-benzyltoluene or polychlorinated biphenyl for example.
c) Investigation of corrosiveness The corrosiveness of dibromobenzyltoluene was investigated according to the methods of the 6th Luxemburg Report mentioned above.
This involved immersing the metals steel, copper, brass, aluminum, cadmium and zinc as well as the metal pairs copper-zinc, steel-aluminum, steel-cadmium and -~ ~7 aluminum-zinc to two-thirds of their length in the fluid to be examined (dibromobenzyltoluene) and were left therein for 28 days at a temperature of 35C.
This experiment showed that in the case of all of the test pieces the differences in weight resulting from corrosion was less than l mg (the permissible difference in weight was 20 mg)~
d) Compatability with Sealing Elements For the investigation of the compatability with sealing elements, a sealing element made from sealing material 83 FKM 575 (Viton) was submerged in the fluid under investigation and was kept for 21 days at 60C, 80C, 100C, 120C and 150C. Then the variation in volume of the sealing element and the variation of its Shore hardness were determined.
This investigation showed that the preferred bromine-containing benzyltoluene derivative of the invention, namely dibromobenzyltoluene used as such and also in prepared hydraulic fluids had a particularly good performance, in that it produced a volume alteration in the sealing of between less than l and 2~ and a variation in the Shore hardness of -3 degrees. The permissible volume change and variation in the Shore hardness in this testing method is up to 20~ and from -lO degrees, respectively. Comparative tests using polychLorinated biphenyls and tetrachlorobenzyltoluenes showed values of volume change of ~0~ at a testing temperature of 150C.
In the case of these known products, care must be taken when using them as hydraulic fluids not to exceed temperatures of 100C because then the sealing material is attacked to too great an extent so that it can be damaged.
e) Investiqation of Pyrolysis __ ~
Dibromobenzyltoluene was pyrolysed at temperatures between 150 and 700C in order to see if highly toxic decomposition products are produced. The operation of the 5~
test was carried out according to EPA - method No. 613.
Upon analysis with GCMS no highly toxic dioxin or dibenzofuran (tri - and tetrabromo) could be determined within the detection limits (0.5 ppb).
f) Investigation of the Viscosity-Temperature Relationship The hydraulic fluid according ~o the invention of example 2 below showed the following viscosity-temperature relationships:
- 20C 8320 cSt 10 0C 430 cSt 20C 83 cSt 50C 21. cSt ~100C 6.6 cSt A hydraulic fluid consisting of tetrachlorobenzyl-toluene had the following relationships:
- 20Csolid, not measurable 0C 9730 cSt + 20C 320 cSt ~ 50C 25 cSt 20+100C 4 cSt The foLowin~ examples 2 to 8 provide further description of the invention and are concerned with the formulation of non-flammable hydraulic fluids (examples 2 to 6) and insulating fluids (examples 7 and 8).
ExamPle 2 Formulation of a non-flammable hydraulic fluid:
93% Dibromobenzyltoluene 6% Viscosity index enhancer (polymethacrylate) 0.5% Corrosion inhibitor (barium sulfonate) 0.5% Antiwear additive (zinc dialkyldithiophosphate) Example 3 Formulation of a non-flammable hydraulic fluid:
75% Dibromobenzyltoluene 23% Isopropyl triphenylphosphate 1% Corrosion inhibitor (alkylsulfamidocarboxylic acid) 1~ Acid acceptor (epoxide resin) ~d~
-Example 4 Formulation of a non-flammable hydraulic fluid:
88% Dibromobenzyltoluene 10% Butile stearate 1% Corrosion inhibitor (fatty acid alkanolamide) 0.5~ Oxidation Stabilizer (amine derivative) 0.5% Antiwear additive (zinc dialkyldithiophosphate) Example 5 Formulation of a non-flammable hydraulic fluid:
65% Dibromobenzyltoluene 25% Monobrominated benzyltoluene 9% Viscosity index enhancer (polyisobutylene) 1% Corrosion inhibitor (stearin amine derivative) Example 6 Formulation of a non-flammable hydraulic fluid:
50% Dibromobenzyltoluene 45% Monobrominated xylylxylol 4.5% Viscosity index enhancer (polyisobutylene) 0.5% Corrosion inhibitor (stearin amine derivative) Example 7 Formulation of an insulating fluid for electrical equipment:
99.5% Dibromobenzyltoluene 0.3% Corrosion inhibitor (stearin amine derivative) 0.2% Epoxy resin Example 8 Formulation of an insulating fluid for electrical equipment:
50% Dibromobenzyltoluene 49.5% Monobrominated benzyltoluene 0.3% Corrosion inhibitor (stearin amine derivative) 0.2% Epoxy resin
Substantially non flammable biologically degradable functional fluid The invention relates to a substantially non-flammable, biologically degradable functional liquid, particularly a hydraulic fluid or an insulating fluid for electrical apparatus, which comprises a bromine containing benzyl-toluene derivative as the essential component.
Chlorinated aromatic compounds, particularly chlori-nated biphenyls, have taken an important place in various fields of technology in the last few decades. The poly-chlorinated biphenyls, in particular, have been used to a large extent as hydraulic fluids r as insulating fluids for electrical equipment and as flame suppressing addi-tives for plastics and the like. However, in the last few years, these compounds have been the subject of considerable dispute. It has been determined that these products exert harmful effects on health and the environment and they have potentially catastrophic dangers in that, when burned, highly poisonous dioxin and dibenzofuran may be formed. This has already lead in part to the complete banning of the manufacture or at least the ~se of such compounds by the state supervisory organizations and in part to the imposition of serious limitations to the use of these substances.
To overcome these disadvantages it has been proposed in European Patent No. 88 650 granted September 14, 1983 to use instead chlorinated benzyltoluenes and chlorinated benzylxylenes as lubricants and also as hydraulic fluids because these compounds are substantially inflammable and resist oxidation and are also biologically degradable and are advantageous in view of their low toxic properties.
GB-PS 1 504 655 granted March 22, 1978 describes electrical equipment which contains biologically easily degradable dielectric fluids, namely halogina~ed diphenyl-methane, which are characterized in that the halogensubstituents and possibly alkyl substituents are located only in one of the two phenyl rings, while the other phenyl ring remains ùnsubstituted, since only such haloginated diphenylmethanes having an unsubstituted phenyl group are easily biologically degradable, while the diphenylmethanes substituted on both phenyl residues are resistant to microbiological degradation.
European Patent No. 8251 granted February 20, 1980 discloses fluid dielectrics which can be used, for example, as insulating ~luids for transformers or as impregnating materials for insulating layers using capacitors. It is concerned with alkyl aromatic compounds which are chlor-inated on the aromatic nucleus and which may be obtained from chlorotoluene and/or chloroxylene, for example tetra-chlorobenzyltoluene, and it is indicated that these com-pounds have advantages over the multichlorinated biphenyls previously used for the same purpose. The absence of the biphenyl nucleus and the presence of the alkyl groups on the aromatic nucleus are accordingly credited with the favourable action on the biological degradative behaviour.
Finally, European Patent No. 71 338 granted February 9, 1983 describes electroviscous fluids which consist of hydro-phobic liquids in which solid hydrophilic particles are dispersed. Upon application of an electrical field to such a suspension the viscosity of this mixture rises drastic-ally. This change is reversible and rapid so that such suspensions can be used, for example, in electronically controllable clutches. It is indicated that the hydrophobic liquids in the mixture have a high boiling point, a low viscosity, suitable electrical properties and chemical stability and low toxicity and are preferably biologically degradable. For this purpose, according to this European Patent Application, halogenated diaryl derivatives are suitable as the hydrophobic fluids, the aromatic nuclei of which are combined with one another via various bridges and have fluorine, chlorine or bromine atoms as the halogen substituents. It is stated that these diaryl derivatives should be asymmetrically substituted because then a lower solidification point of the fluid and an improvement of the ability to be biologically degraded is obtained.
The conventional functional liquids are not satis-factory in all respects because they either do not fulfil the criterion of non-flammability required by hydraulic and insulating fluids or they have disadvantageous pro-perties resulting from their inflammability such as poor biodegradability, toxicity of the fulids or their decom-position products, unfavourable viscosity-temperature properties or incompatibility with sealing elements.
The object of the present invention is to provide a functional fluid which has physical properties necessary for the intended use and while having high chemical sta-bility nevertheless can be biologically degraded and is nontoxic and does not give rise to highly toxic products, such as dioxin for example, upon improper treatment.
It has been surprisingly found that a particular group of halogenated diaryl derivatives not only, on the one hand, exhibits valuable technical properties, but also, on the other hand, does not exhibit the dangerous and the environmentally hazardous properties of the conventional compounds, so that the compounds are especially suitable as or for functional fluids.
The invention provides a non-flammable biologically degradable func~ional fluid consisting of or containing at least one bromine containing benzyltoluene derivative of general formula I~
(CH~) (CH3)z~
(Cl)~, (I) (Br)x (Br)x, in which x is 1 or 2, x' is 0 or 1, y is 0, 1 or 2, y' is 0, 1 or 2, ~ is 0, or 1, and zl is 1 or 2 with the proviso that the relationship y + y' = 0, 1 or 2 and x ~ xl ~ y + y' = 1, 2 or 3 is fulfilled.
~.rhe bromine-containing benzyltoluene derivatives used according to the invention as or in functional fluids are thus compounds whiah are substituted on both nuclei wherein at least one bromine substituent and one methyl group must be present. Both the nuclei can however carry several bromine atoms and several methyl groups and the positions of these substituents are not important so that, according to the invention, all of the positional isomers of these bromine-containing benzyltoluene derivatives of formula I
given above can be used in or as functional fluids.
In addition one or both of the phenyl groups may contain chlorine atoms as substituents.
It has surprisingly been found that these bromine-containing benzyltoluene derivatives used according to the invention possess a more advantageous compatibility with ; 30 the environment than ~he conventional halogenated diaryl derivatives, and at the same time possess excellent physical properties which make them particularly suitable for use as functional fluids such as hydrulic fluids or insulating fluids for electrical equipment.
Surprisingly, it has also been found that the substituted bromine-containing benzyltoluene derivatives of the invention of general formula I given above, which are substituted on both phenyl rings, can be biologically degraded without further treatment which appears sur-prising in view of European Patent No. 71 338 and GB-PS 1 504 655 discussed above. Moreover, the bromine-containing benzyltoluene derivatives of general formula I above used in accordance with the invention have the further surprising advantage that in normal working conditions they are fluid and exhibit a particularly favourable viscosity-temperature relationship. Moreover they possess a high flame point, are of low toxicity and low corrosiveness and do not produce highly toxic dioxin products when improperly overheated, which can occur accidentally in the case of polychlorinated biphenyls.
Moreover it has been found that the bromine-containing benzyltoluene derivatives used according to the invention are compatible with sealing elements to an excellent extent, so that the group of compounds of the invention have unexpectedly proved advantageous for the uses discussed above.
Particularly preferred are substantially non-flammable, biologically degradable functional fluids which, as the bromine-containing benzyltoluene derivatives, contain a compound of general formula II
(CH3)z tCH3)z.
~ CH2 ~ (II) Br (Br)x, in which x' is O or 1, z is O or 1 and z' is 1 or 2.
- 6 ~
Even more preferred are functional fluids according to the invention which contain a bromine-containing benzyltoluene derivative according to formula III, IV
or V below.
~ CM2 ~ (III) Br Br ~H3CH3 CH2 ~ (IV~
Br CH3 CH2- ~ (V) Br Na~urally the functional fluids according to the invention may contain the bromine-containing benzyltoluene derivatives defined above alone, but preferably however they are used in the form of mixtures, especially in the form of mixtures of the individual positional isomers of these compounds.
The bromine-containing benzyltoluene derivatives according to the invention of the formulae given above and used in the invention in or as functional fluids are partially known, for example in the general formula of European Patent No. 71 338 mentioned above and also in the generic definition of DE-OS 23 36 289 published 1975. The former reference discloses an enormously large group of compounds, and mentions the use of the invention neither expressly nor in the examples. DE-OS 23 36 289 describes essentially chlorinated o-benzyltoluene, which is described as a valuable starting material for the preparation of anthracene and anthraquinone and its derivatives. The '; compounds of the invention of the general formula given above and their uses differ from the biologically degradable bromine-containing benzyltoluene derivatives described in GB-PS 1 504 655 in that they are not just asymmetric but rathe are substituted on both phenyl rings and nevertheless surprisingly have advantageous properties.
The preparation of the bromine-containing benzyltoluene derivatives of the invention takes place in a conventional manner either by the halogenation of the,non-halogen substituted corresponding benzyltoluene with elemental bromine or a mixture of bromine and chlorine in the presence of a known halogenation catalyst such as iron, FeC13, FeBr3, AlC13, ~iC14 and the like. In this way the reaction can take place at room temperature or, depending on the catalyst employed, at temperatures between -5 and ~40C.
A further preferred method for the preparation of the bromine-containing benzyltoluene derivatives of the invention of general formula I above involves the condensation of a compound of general formula VI
(CH3~zl ~ (VI) (Cl) (Br~x,, in which x', y' and z' are as disclosed above, with a compound of general formula VII
1~
(CH3)z ~ (Cl)y (VII) Hal-CH2~-~
(Br)x in which Hal represents bromine or chlorine and x, y, z are as disclosed above. The condensation can be carried out, if necessary, in the presence of a Friedel-Crafts 5catalyst, such as FeC1~, FeBr3, AlC13 and/or TiCl4, in the presence of an excess of the compound of general formula VI.
The bromine-containing benzyltoluene derivatives according to the invention exhibit a substantially improved flame resistance than the chlorine substituted compounds known from European Patent Application No.
88 650 while at the same time exhibiting improved viscosity-temperature relationships.
The known asymetrically substituted dibromobenzyl-toluene of GB-PSl 504 655 are solid at room temperature, while the isomer brominated on both phenyl rings solidifies at -25C, which is particularly advantageous when using these compounds as hydraulic fluids or insulating fluids.
The bromine-containing benzyltoluene derivatives of the invention have proved useful not only as hydraulic fluids but also as insulating fluids for electrical equipment, such as for example condensers, transformers and the like, not only on the basis of their favourable viscosity-temperature relationships, but also on account of their very favourable flame resisting effect. The functional fluids of the invention can in consequence of this be used, in particular, as non-flammable hydraulic or insulating fluids which, on the basis of their low toxicity, their low inclination to form poisonous de-composition products and their biological degradability, .~
represent a considerable contribution to technology.
As already explained the bromine-containiny benzyltoluene derivatives mentioned above can be contained individual'~y or also in the form of mixtures, preferably in the form of isomer mixtures, in the functional fluids of the invention instead of being used alone as said fluids.
The invention is described in more detail in the following examples.
Preparation Example Preparation of dibromobenzyltoluene by condensation of bromotoluene with bromobenzylbromide.
For the preparation of dibromobenzyltoluene, bromo-toluene was first prepared by the bromination of toluene with elemental bromine in the presence of anhydrous FeC13, and this was then brominated at the side chain.
With this 8.3 Mol of bromotoluene were heated in the presence of 0.5g of a radical chain initiator ~ zobisisobutyronitrile) to a temperature of 80C.
1.66 Mol of bromine were added drop-wise with cooling under irradiation with an ultra-violet lamp having a power of 300 W. The resulting hydrogenbromide was absorbed in a wash bottle containing cooled water.
The cooled mixture was then dropped into a suspension of 6g FeC13 in 1.6 Mol of bromotoluene at a temperature 30C to bring about the condensation reaction. The re-sulting gaseous hydrogenbromide was absorbed into cooled water in a wash bottle in the same manner as described above. The formation of by-products (brominated dibenzyl-toluene), was suppressed during this condensatlon reaction by the presence of a large excess of bromotoluene.
After the termination of the addition the mixture was heated to 50C for 30 minutes, after which the cooled reaction mixture was washed with one liter of water, then with one liter of 10~ sodium hydroxide solution and finally once again with one liter of water. The organic phase was dried and the excess bromotoluene was distilled off.
The remaining fluid was distilled under 0.4 mbar, and 395g of a main fraction boiling between 155 and 166C at 0.4 mbar was obtained and this was identified by mass spectrometry as dibromobenzyltoluene. Thereby an investigation of the isomers was foregone.
The electron stream mass spectrum of the resulting dibromobenzyltoluene is given in the Table below.
, :
TAB LE
Electron Impact Mass Spectr~m of Dibromobenzyltoluene m/x Relative Tot~l lon Intensity m/x Relative Totdl Ion Intenslty Int~nsity(~) Stream(o) Intensity(~) Stream(~) IS,ool,os 0,05 118133,00 0,7d ' 0,07 94 37,003,65 0,~4~0 139,00 3,19 0,~ 445 ~-,00I ~o o,ll IS7~O,oo 0,93 0,01 Il~
3g,0012,4B 1,10 1506141,C0 0,70 0,06 g4 sO~oo9,~3 0,52 ~2~14~,oo 0,69 0,06 83 S~.00~,2~ 1,03 1476lSO,Oo ~,o~ o,lB ~/13 52,00~,62 0,23 316151,00 4,t~ 0,41 S30 S~,oO1,75 o,ls 211152,00 ~,41 0,74 IOIS
t1,001.96 0,17 ~36~S3,U0 ~,~4 0,20 ' 270 t~,00~,91 0,s2 713163,00 4,~9 o,~7 sos 61,00~7,97 ~,5a ~60164,00 s,o~ 0,44 60S
64,0~4,9~ 0,44 601165,00 IOo,oo 0,79 1~06~
6S,00~ 93 0,~6 ~s~1~6,00 14,41 1,~7 1731 ~9 000 ~7 0,0~ 1OS167,00 I,z~ 0,~ 7 74.004,95 0,44 s9~~69,00 8,s~ 0,7s ~o~o 75 0010 79 0,9S 1~0~170,00 1,4~ 0,13 172 7~,003S,01 3,01 42~4171,00 7,~ 0,69 94~
71,oo14,y7 I,3z IR06175,00 0,5t 0,OS 75 71,00S,46 0,4d 659176,00 6,45 0,s7 779 79,001,l~ o,lo 1~6~71,00 5,88 0,5~ 709 91 002, 6~ 0, ~4 J~4 1 79, 00 32, 56 ~, 86 3~23 1~,007,07 0,6~ ~5~179,00 46,55 4.09 5616 .00 3,61 0,01 321~0,00 76,1~ 6,69 9114 ~5 000,7~ 0,06 allal,oo ll,as l,OS 14~4 16,001,91 o,l7 2381~2,00 IS,63 1,37 1886 ~7,003,~6 0,3~ ~s41a3,ao S,10 0,qS 615 1~2,00 16,00 1,411930 114,00 14,79 1,30 17B4 as,;70 8~,79 7,8310132 105,00 4,~0 o 43 591 90,003a~.s9 3,~9 465C~43,00 1,42 o,l~ 17~
91,oo ~ o,I9 ~S6~44,oO 0,6Y 0,06 63 9a 001,41 0,~1 ~70~4S,00 I,4s u,l3 175 gg,oo1,16 o,lo 140146,00 o 67 0,06 a~
~01 00 ~.0~ o,la244 2s~,oO o,a~ 0 07 93 0~ oo4,~9 o,~s s42259,00 90,64 7,09 9728 103,00 9,75 0,361176 ~60,00 ~3 44 ~13 ~6~1 10~,00 s,ai o s~70~ ~61,00 18,7a 5,93 9S0~
110,00 0,63 0,0676 ~6~,00 1~,61 1,11 Is~4 Ill,Oo 0,64 0,0677 263,oo o,y9 o,0~ 119 I 1 3, 00 1, 27 0, 1 1 ~ s3 323, oo 4,5~ 0,40 547 II~ 00 ~ 93 o,~7~ 3~4,oO o,77 0,o6 8 7 ~IS,00 4,~8 o,~ss~29 32s,00 8,S9 0,7~ 103~
1~6,00 1,26 0,11~52 3~6,00 ~,7~ '~l lu6 ,00 o,70 0,06 8S3~7,~o 4,~o 0 ~7 507 ZZ,000,75 o,o7 90~7,00 o,ss o oa ~S
~6,002,09 0,~0 2S1338,o0 34 sS ~,07 ~I~C
1~7 00 ~ ~1 o,~l287 139,00 7,39 0,6S 991 121,00 3,74 0,~bS1 ~40,00 68,43 6,C~ a~s6 1~9,00 ~,~1 0,3z ~3s 34~,00 ~1,47 1,Ol lla4 ~30,00 ~ ~6 o,~s 26~ 34~,oo ~,9~ ~,98 4092 1)7,00 0,61 o,os 74 3~,oo S,Z3 0,4~ 6~
The remaining bromine-containing benzyltoluene derivatives according to the invention can be obtained in an analogous manner to the above described reaction scheme by using conventional methods or also by direct bromination S or bromination and chlorination of benzyltoluene, in which case of course reaction mixtures are obtained which in suitable ways, for example by gas chromatography, must be separated into the bromine-containing benzyltoluene derivatives of the general formula given above according to the invention.
The non-flammable, biologically degradable functional fluids of the invention may contain in addition to the bromine-containing benzyltoluene derivatiaves additional components and additives normally used in functional fluids, for example corrosion inhibitors such as alkaline earth sulfonates, stabilizers such as amine derivatives or phenolic products, wear reducing additives such as zinc dialkyldithiphosphate, acid acceptors such as epoxide compounds, tin tetraphenyl etc., as well as anti-foaming agents such as soap, silicone, glycol, phosphate esters, and viscosity index enhancers such as polymeth-acrylate, polyisobutylene. Further the bromine-containing benzyltoluene derivatives used according to the invention can be modified with various suitable products such as mineral oil, glycols, etc.
The following examples serve to further clarify the non-flammable biologically degradable functional fluids of the invention.
Example 1 Investigation of the properties of the dibromobenzyl-toluenes which are preferred as the bromine-containing benzyltoluene derivatives of the invention.
a) Biological Degradability The investigation of the biological degradability was carried out by means of a known measuring procedure for ~c~
the determination of the biological degradability anionic and non-ionic synthetic tensides (surface-active substances) namely the OECD-screening test (Federal Law Publication l (1977), page 245) (modified) for non-ionic tensides.
Aerobic polyvalent microorganisms from the outlet of a biological sewage plant were used as an innoculating suspension. In this method the first sample was taken after seven days, the second sample after 14 days and the third sample after l9 days. The samples thus taken were treated according to the directions of the tests indicated above and the decomposition rate was determined by gas chromatography.
The following results were obtained in this way:
sample after 7 days : 49.3% degraded sample after 14 days : 69.1% degraded sample after l9 days : 82.9% degraded Surprisingly the dibromobenzyltoluene, which is a preferred compound of the invention was biologically degraded by more than 80%.
b) Combustion Test A combustion test was carried out according to "the 6th Luxemburg Report on the requirements and tests of non-flammable fluids for hydraulic power transmission and control."
By this means it was shown that dibromobenzyltoluene has a better combustion behaviour than tetrachloro-benzyltoluene or polychlorinated biphenyl for example.
c) Investigation of corrosiveness The corrosiveness of dibromobenzyltoluene was investigated according to the methods of the 6th Luxemburg Report mentioned above.
This involved immersing the metals steel, copper, brass, aluminum, cadmium and zinc as well as the metal pairs copper-zinc, steel-aluminum, steel-cadmium and -~ ~7 aluminum-zinc to two-thirds of their length in the fluid to be examined (dibromobenzyltoluene) and were left therein for 28 days at a temperature of 35C.
This experiment showed that in the case of all of the test pieces the differences in weight resulting from corrosion was less than l mg (the permissible difference in weight was 20 mg)~
d) Compatability with Sealing Elements For the investigation of the compatability with sealing elements, a sealing element made from sealing material 83 FKM 575 (Viton) was submerged in the fluid under investigation and was kept for 21 days at 60C, 80C, 100C, 120C and 150C. Then the variation in volume of the sealing element and the variation of its Shore hardness were determined.
This investigation showed that the preferred bromine-containing benzyltoluene derivative of the invention, namely dibromobenzyltoluene used as such and also in prepared hydraulic fluids had a particularly good performance, in that it produced a volume alteration in the sealing of between less than l and 2~ and a variation in the Shore hardness of -3 degrees. The permissible volume change and variation in the Shore hardness in this testing method is up to 20~ and from -lO degrees, respectively. Comparative tests using polychLorinated biphenyls and tetrachlorobenzyltoluenes showed values of volume change of ~0~ at a testing temperature of 150C.
In the case of these known products, care must be taken when using them as hydraulic fluids not to exceed temperatures of 100C because then the sealing material is attacked to too great an extent so that it can be damaged.
e) Investiqation of Pyrolysis __ ~
Dibromobenzyltoluene was pyrolysed at temperatures between 150 and 700C in order to see if highly toxic decomposition products are produced. The operation of the 5~
test was carried out according to EPA - method No. 613.
Upon analysis with GCMS no highly toxic dioxin or dibenzofuran (tri - and tetrabromo) could be determined within the detection limits (0.5 ppb).
f) Investigation of the Viscosity-Temperature Relationship The hydraulic fluid according ~o the invention of example 2 below showed the following viscosity-temperature relationships:
- 20C 8320 cSt 10 0C 430 cSt 20C 83 cSt 50C 21. cSt ~100C 6.6 cSt A hydraulic fluid consisting of tetrachlorobenzyl-toluene had the following relationships:
- 20Csolid, not measurable 0C 9730 cSt + 20C 320 cSt ~ 50C 25 cSt 20+100C 4 cSt The foLowin~ examples 2 to 8 provide further description of the invention and are concerned with the formulation of non-flammable hydraulic fluids (examples 2 to 6) and insulating fluids (examples 7 and 8).
ExamPle 2 Formulation of a non-flammable hydraulic fluid:
93% Dibromobenzyltoluene 6% Viscosity index enhancer (polymethacrylate) 0.5% Corrosion inhibitor (barium sulfonate) 0.5% Antiwear additive (zinc dialkyldithiophosphate) Example 3 Formulation of a non-flammable hydraulic fluid:
75% Dibromobenzyltoluene 23% Isopropyl triphenylphosphate 1% Corrosion inhibitor (alkylsulfamidocarboxylic acid) 1~ Acid acceptor (epoxide resin) ~d~
-Example 4 Formulation of a non-flammable hydraulic fluid:
88% Dibromobenzyltoluene 10% Butile stearate 1% Corrosion inhibitor (fatty acid alkanolamide) 0.5~ Oxidation Stabilizer (amine derivative) 0.5% Antiwear additive (zinc dialkyldithiophosphate) Example 5 Formulation of a non-flammable hydraulic fluid:
65% Dibromobenzyltoluene 25% Monobrominated benzyltoluene 9% Viscosity index enhancer (polyisobutylene) 1% Corrosion inhibitor (stearin amine derivative) Example 6 Formulation of a non-flammable hydraulic fluid:
50% Dibromobenzyltoluene 45% Monobrominated xylylxylol 4.5% Viscosity index enhancer (polyisobutylene) 0.5% Corrosion inhibitor (stearin amine derivative) Example 7 Formulation of an insulating fluid for electrical equipment:
99.5% Dibromobenzyltoluene 0.3% Corrosion inhibitor (stearin amine derivative) 0.2% Epoxy resin Example 8 Formulation of an insulating fluid for electrical equipment:
50% Dibromobenzyltoluene 49.5% Monobrominated benzyltoluene 0.3% Corrosion inhibitor (stearin amine derivative) 0.2% Epoxy resin
Claims (7)
1. A non-flammable biologically degradable functional fluid consisting of or containing at least one bromine-containing benzyltoluene derivative of general formula I
(I) in which 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, with the proviso that the following relationships are fulfilled y + y' = 0, 1 or 2, and x + x' + y + y' = 1, 2 or 3.
(I) in which 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, with the proviso that the following relationships are fulfilled y + y' = 0, 1 or 2, and x + x' + y + y' = 1, 2 or 3.
2. A functional fluid according to claim 1 characterized in that it contains as said bromine-containing benzyltoluene derivative, a compound of general formula II
(II) in which x' is 0 or 1, z is 0 or 1, and z' is 1 or 2,
(II) in which x' is 0 or 1, z is 0 or 1, and z' is 1 or 2,
3. A functional fluid according to claim 1 characterized in that it contains, as said bromine-containing benzyltoluene derivative, a dibromobenzyltoluene of general formula III
(III)
(III)
4. A functional fluid according to claim 1, characterized in that it contains, as said bromine-containing benzyltoluene derivative, a monobromxylylxylol of general formula IV
(IV)
(IV)
5. A functional fluid according to claim 1 characterized in that it contains, as said bromine-containing benzyltoluene derivative, a monobromo-benzyltoluene of formula V
(V)
(V)
6. A functional fluid according to claim 1, claim 2 or claim 3 characterized in that it is formulated as a hydraulic fluid containing at least 35% by weight of the bromine-containing benzyltoluene derivative(s) and optionally conventional additives for hydraulic fluids.
7. A functional fluid according to claim 1, claim 2 or claim 3 characterized in that it is formulated as an insulating fluid for electrical equipment and contains at least 35% by weight of the bromine-containing benzyltoluene derivatives and optionally conventional additives for electrical insulating fluids.
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 |
| DEP3402863.3 | 1984-01-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1244054A true CA1244054A (en) | 1988-11-01 |
Family
ID=6226101
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000472977A Expired CA1244054A (en) | 1984-01-27 | 1985-01-28 | Substantially non-flammable biologically degradable functional fluid |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0150826B1 (en) |
| JP (1) | JPS61501035A (en) |
| AT (1) | ATE43628T1 (en) |
| AU (1) | AU573782B2 (en) |
| CA (1) | CA1244054A (en) |
| DE (2) | DE3402863A1 (en) |
| DK (1) | DK418785A (en) |
| FI (1) | FI78499C (en) |
| HU (1) | HU194300B (en) |
| WO (1) | WO1985003306A1 (en) |
| ZA (1) | ZA85638B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 | |
| ES448228A1 (en) * | 1975-05-30 | 1977-12-01 | Monsanto Co | Electrical devices containing readily biodegradable dielectric fluids |
| 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 |
| JPS58501178A (en) * | 1981-06-19 | 1983-07-21 | ナシヨナル・リサ−チ・デイベロツプメント・コ−ポレイシヨン | Electric field responsive (electrorheological) fluid |
| FR2522334B1 (en) * | 1982-02-26 | 1986-01-10 | Ugine Kuhlmann | APPLICATION TO THE LUBRICATION OF POLYCHLOROBENZYL POLYCHLOROTOLUENES |
-
1984
- 1984-01-27 DE DE19843402863 patent/DE3402863A1/en not_active Withdrawn
-
1985
- 1985-01-25 AT AT85100772T patent/ATE43628T1/en not_active IP Right Cessation
- 1985-01-25 EP EP85100772A patent/EP0150826B1/en not_active Expired
- 1985-01-25 WO PCT/DE1985/000020 patent/WO1985003306A1/en active IP Right Grant
- 1985-01-25 JP JP60500653A patent/JPS61501035A/en active Pending
- 1985-01-25 HU HU851051A patent/HU194300B/en not_active IP Right Cessation
- 1985-01-25 AU AU39308/85A patent/AU573782B2/en not_active Ceased
- 1985-01-25 DE DE8585100772T patent/DE3570692D1/en not_active Expired
- 1985-01-28 ZA ZA85638A patent/ZA85638B/en unknown
- 1985-01-28 CA CA000472977A patent/CA1244054A/en not_active Expired
- 1985-09-16 DK DK418785A patent/DK418785A/en not_active Application Discontinuation
- 1985-09-26 FI FI853708A patent/FI78499C/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0150826A3 (en) | 1985-11-06 |
| AU573782B2 (en) | 1988-06-23 |
| EP0150826B1 (en) | 1989-05-31 |
| ZA85638B (en) | 1985-09-25 |
| HU194300B (en) | 1988-01-28 |
| FI853708A0 (en) | 1985-09-26 |
| WO1985003306A1 (en) | 1985-08-01 |
| HUT37646A (en) | 1986-01-23 |
| DK418785D0 (en) | 1985-09-16 |
| FI78499C (en) | 1989-08-10 |
| DK418785A (en) | 1985-09-16 |
| JPS61501035A (en) | 1986-05-22 |
| FI78499B (en) | 1989-04-28 |
| EP0150826A2 (en) | 1985-08-07 |
| AU3930885A (en) | 1985-08-09 |
| FI853708L (en) | 1985-09-26 |
| DE3570692D1 (en) | 1989-07-06 |
| DE3402863A1 (en) | 1985-08-01 |
| ATE43628T1 (en) | 1989-06-15 |
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