DE4204200A1 - Liq. useful as heat transfer and insulating media - comprises mixt. of poly-alpha-olefin(s) and/or isoparaffin(s) with poly:di:methyl:siloxane(s) and/or poly:alkyl -/poly:aryl:siloxane(s) - Google Patents

Liq. useful as heat transfer and insulating media - comprises mixt. of poly-alpha-olefin(s) and/or isoparaffin(s) with poly:di:methyl:siloxane(s) and/or poly:alkyl -/poly:aryl:siloxane(s)

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Publication number
DE4204200A1
DE4204200A1 DE4204200A DE4204200A DE4204200A1 DE 4204200 A1 DE4204200 A1 DE 4204200A1 DE 4204200 A DE4204200 A DE 4204200A DE 4204200 A DE4204200 A DE 4204200A DE 4204200 A1 DE4204200 A1 DE 4204200A1
Authority
DE
Germany
Prior art keywords
poly
liquid according
mixture
indicates
siloxane
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.)
Ceased
Application number
DE4204200A
Other languages
German (de)
Inventor
Josef L Dipl Chem Dr Re Jostan
Georg Dipl Ing Braun
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.)
Airbus Defence and Space GmbH
Original Assignee
Daimler Benz AG
Deutsche Aerospace AG
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 Daimler Benz AG, Deutsche Aerospace AG filed Critical Daimler Benz AG
Priority to DE4204200A priority Critical patent/DE4204200A1/en
Publication of DE4204200A1 publication Critical patent/DE4204200A1/en
Ceased legal-status Critical Current

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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
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/008—Lubricant compositions compatible with refrigerants
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
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    • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
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    • 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
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Abstract

Liquid (I) comprises a mixt. of poly-alpha-olefins and/or equiv. isoparaffins on the one hand with polydimethylsiloxanes and/or polyalkyl-/polyarylsiloxanes on the other hand. The vol.- and/or wt. pts. of the components of the mixt. are chosen depending on the required electrical properties of the liq. USE/ADVANTAGE - (I) can be used as heat transfer and insulating media in electrical high voltage appts., as cooling and insulating media for the high voltage part of a radar appts., or as hydraulic fluids for hydraulic systems in an aeroplane and as cooling and insulating media in on-board radar of the same aeroplane. (I) has good thermal, calorific, rheological and hydraulic properties.

Description

Die Erfindung betrifft eine Flüssigkeit und deren Verwen­ dung nach den Oberbegriffen der Patentansprüche 1 und 6.The invention relates to a liquid and its use dung according to the preambles of claims 1 and 6.

Bei vielen technischen Anwendungen, z. B. Heiz- oder Kühl­ aggregaten sowie hydraulisch betätigten Geräten oder Anla­ gen, werden an den Anwendungsfall angepaßte Flüssigkeiten verwendet. Diese enthalten in vielen Fällen Polychlorbi­ phenyle (PCB′s) oder Trichlor-Benzol-Isomere (TCB′s), Mi­ neralöle, höhermolekulare organische Ester, Kieselsäure­ ester, Siliconöle oder halogenierte Ethylenoligomere. Ins­ besondere aus ersteren dieser chemischen Verbindungen her­ gestellte Flüssigkeiten sind in nachteiliger Weise toxisch (giftig) und/oder umweltschädlich, da diese Flüssigkeiten zum Teil äußerst schwierig entsorgt werden können. Bei ei­ ner beispielhaften Entsorgung durch Verbrennen der Flüs­ sigkeit können z. B. hochgiftige und beständige Dioxine entstehen. Außerdem sind diese Flüssigkeiten in vielen Fällen nicht für bestimmte anspruchsvolle elektrische An­ wendungen geeignet. Beispielsweise sind Kieselsäureester hydrolyseempfindlich und zersetzen sich bei Feuchteeinwir­ kung unter Bildung von störenden Kieselsäure-Partikeln und dem entsprechenden Alkohol, der den Flamm- und Entzün­ dungspunkt jeweils herabsetzt, so daß erhöhte Brandgefahr entsteht.In many technical applications, e.g. B. heating or cooling units as well as hydraulically operated devices or systems gen, are liquids adapted to the application used. In many cases these contain polychlorobi phenyls (PCB's) or trichlorobenzene isomers (TCB's), Mi mineral oils, high molecular weight organic esters, silica esters, silicone oils or halogenated ethylene oligomers. Ins especially from the former of these chemical compounds provided liquids are disadvantageously toxic (toxic) and / or environmentally harmful as these liquids  sometimes extremely difficult to dispose of. With egg exemplary disposal by burning the rivers liquid can B. highly toxic and stable dioxins arise. Besides, these liquids are in many Cases not for certain demanding electrical applications suitable. Examples are silicic acid esters sensitive to hydrolysis and decompose when exposed to moisture kung with formation of disruptive silica particles and the corresponding alcohol, which is the flame and ignition each point so that there is an increased risk of fire arises.

Der Erfindung liegt daher die Aufgabe zugrunde, eine gat­ tungsgemäße Flüssigkeit anzugeben, die zusätzlich zu vor­ gebbaren thermischen, kalorischen, rheologischen sowie hydraulischen Eigenschaften vorgebbare elektrische Eigen­ schaften besitzt und außerdem eine hohe chemische Stabili­ tät bei toxikologischer Unbedenklichkeit und ökologischer Verträglichkeit. Der Erfindung liegt außerdem die Aufgabe zugrunde, Verwendungsmöglichkeiten einer solchen Flüssig­ keit anzugeben.The invention is therefore based on the object of a gat appropriate liquid to specify, in addition to before definable thermal, caloric, rheological and hydraulic properties predeterminable electrical Eigen has high chemical stability act with toxicological harmlessness and ecological Compatibility. The invention also has the object underlying, uses of such a liquid to specify.

Diese Aufgabe wird gelöst durch die in den kennzeichnenden Teilen der Patentansprüche 1 und 6 angegebenen Merkmale. Zweckmäßige Ausgestaltungen und/oder Weiterbildungen sind den Unteransprüchen entnehmbar.This problem is solved by the in the characterizing Parts of claims 1 and 6 specified features. Appropriate refinements and / or further training are the dependent claims.

Die Erfindung wird im folgenden anhand von Ausführungsbei­ spielen näher erläutert.The invention is described below with reference to exemplary embodiments play explained in more detail.

Soll beispielsweise bei einem Hochleistungs-Hochspannungs­ transformator, der z. B. eine Hochspannung von größer 20 kV erzeugt, die entstehende Verlustwärme abgeführt werden, so muß eine dafür geeignete Flüssigkeit auch bestimmte selektrische Eigenschaften besitzen, beispielsweise eine gute Durchschlagfestigkeit, und außerdem chemisch inert und alterungsbeständig sein. Solche Flüssigkeiten müssen Eigenschaften besitzen, die beispielhaft in einer nachfol­ genden Tabelle zusammengestellt sind.For example, for a high-performance high-voltage transformer, the z. B. a high voltage of greater than 20 kV  generated, the resulting heat loss is dissipated, a suitable liquid must also determine certain have electrical properties, for example good dielectric strength and also chemically inert and be resistant to aging. Such liquids must Have properties that are exemplary in a successor table.

Für derartige Anwendungsfälle sind vorzugsweise zwei Stoffklassen geeignet, nämlich Siliconöle auf der Basis von Polymethylsiloxan sowie Poly-α-olefine, die auch un­ ter dem Sammelnamen Isoparaffine bekannt sind. Erstere können auch modifiziert sein, so daß darunter auch die allgemeinen Stoffklassen Polyalkyl- oder Polyarylsiloxane zu verstehen sind. Letztere werden meist gezielt sytheti­ siert, und zwar durch katalytische Oligomerisation von beispielsweise 1-Decen mit anschließender katalytischer Hydrierung. Beide Stoffklassen erfüllen in bestimmten niedrigviskosen Fraktionen die gestellten Anforderungen weitgehend, aber doch nicht vollständig. Poly-α-olefine haben sogar in ihrer derzeit niedrigviskosesten Fraktion eine noch zu hohe störende kinematische Viskosität bei tiefen Temperaturen, einen nachteilig zu hoch liegenden Fließ- bzw. Stockpunkt und zu niedrige Flamm-, Brenn- und Selbstentzündungstemperaturen. Andererseits weisen die Po­ ly-α-olefine die Vorteile einer geringeren Wärmeausde­ hnung, einer geringeren maximalen Luft- und geringeren ma­ ximalen Wasserlöslichkeit auf.For such applications, there are preferably two Suitable classes of substances, namely silicone oils based of polymethylsiloxane and poly-α-olefins, which also un ter the collective name isoparaffins are known. The former can also be modified so that the general classes of polyalkyl or polyarylsiloxanes are to be understood. The latter are mostly targeted sytheti siert, by catalytic oligomerization of for example 1-decene with subsequent catalytic Hydrogenation. Both classes of substances meet in certain low-viscosity fractions meet the requirements largely, but not completely. Poly-α-olefins have even in their currently lowest viscosity fraction a disruptive kinematic viscosity low temperatures, a disadvantageously too high Flow or pour point and too low flame, burning and Autoignition temperatures. On the other hand, the Po ly-α-olefins the advantages of a lower heat emission guess, a lower maximum air and lower ma ximal water solubility.

Niedrigviskose Siliconöle dagegen weisen im vergleichbaren Tieftemperaturbereich eine um den Faktor 5 bis 10 gerin­ gere kinematische Viskosität, einen um bis zu 30 K niedri­ geren Fließ- bzw. Stockpunkt und höhere Flamm-, Brenn- und Selbstentzündungstemperaturen auf. Allerdings ist bei Si­ liconölen die Wärmeausdehnung um 20 bis 3% höher, ebenso die Luft- und Wasseraufnahme.Low-viscosity silicone oils, on the other hand, have comparable results Low temperature range one by a factor of 5 to 10 lower kinematic viscosity, up to 30 K lower  lower pour point and higher flame, burning and Autoignition temperatures. However, with Si licon oils increase the thermal expansion by 20 to 3%, as well the air and water intake.

Es ist nun in überraschender Weise möglich, geeignete Fraktionen der beiden Stoffklassen in entsprechend abge­ stimmtem Verhältnis zu mischen, so daß sich die jeweiligen Vor- und Nachteile weitgehend kompensieren. Es entsteht ein Gemisch, das die erwähnten Vorteile vereint und die Nachteile der jeweiligen Stoffklasse allein nicht mehr aufweist, sondern allenfalls in stark abgeschwächter, nicht mehr störender Form. Besonders vorteilhaft ist, daß die Mischung durch Wahl des Mischungsverhältnisses und der einzelnen Poly-α-olefin- oder Siliconölfraktionen auf die Belange des jeweiligen Anwendungsgebietes gezielt aus­ gerichtet werden kann. Damit läßt sich das verfügbare Ei­ genschaftsspektrum von inerten dielektrischen Flüssigkei­ ten beträchtlich erweitern und das jeweils benötigte Pro­ dukt maßschneidern.It is now surprisingly possible to find suitable ones Fractions of the two substance classes in abge accordingly to mix the correct ratio so that the respective To a large extent compensate for advantages and disadvantages. It arises a mixture that combines the advantages mentioned and the Disadvantages of the respective class of substances no longer alone has, but at most in a much weakened, no longer disturbing form. It is particularly advantageous that the mixture by choosing the mixing ratio and the individual poly-α-olefin or silicone oil fractions the needs of the respective area of application can be directed. This allows the available egg property spectrum of inert dielectric liquids expand considerably and the required pro tailor-made.

Eine Mischung beider Stoffklassen ist nicht naheliegend, weil sowohl deren chemische Strukturen als auch deren Her­ stellungsprozesse völlig unterschiedlich sind. Die Misch­ barkeit ist aber - wie eine experimentelle Überprüfung zeigte - lückenlos gegeben. Eine störende chemische Wech­ selwirkung zwischen beiden Stoffklassen tritt nicht ein. Vorteilhaft für die Oxidationsstabilität des Gemisches ist es außerdem, die Oxidationsempfindlichkeit insbesondere der Poly-α-olefine durch Zusatz eines Antioxidans, z. B. von 0,2-0,5% 2,6-Di-tert-butyl-p-kresol oder 2,5 Di-tert- butylhydrochinon herabzusetzen. Dadurch werden die Lager­ stabilität und die Konstanz der Eigenschaften gesteigert, und zwar auch unter erhöhter Temperatur, Druck- oder Wechselklimabeanspruchung.A mixture of both substance classes is not obvious, because both their chemical structures and their origin positional processes are completely different. The mixed However, availability is - like an experimental check showed - completely given. An annoying chemical change There is no interaction between the two classes of substances. It is advantageous for the oxidation stability of the mixture it also, the sensitivity to oxidation in particular the poly-α-olefins by adding an antioxidant, e.g. B. of 0.2-0.5% 2,6-di-tert-butyl-p-cresol or 2.5 di-tert- to reduce butylhydroquinone. This will make the bearings  stability and consistency of properties increased, and even under elevated temperature, pressure or Alternating climatic stress.

Die Erfindung wird anhand der Tabelle exemplarisch be­ schrieben, ohne darauf beschränkt zu sein. The invention is based on the table as an example wrote without being limited to it.  

Eigenschaften einer beispielhaften Mischung von niedrig­ viskosem Poly-α-olefin auf 1-Decen-Basis mit niedrig­ viskosem Siliconöl auf Polydimethylsiloxan-BasisCharacteristics of an exemplary mix of low viscous poly-α-olefin based on 1-decene with low viscous silicone oil based on polydimethylsiloxane

Claims (10)

1. Flüssigkeit mit in vorgebbaren Bereichen wählbaren thermischen, kalorischen, rheologischen sowie hydrauli­ schen Eigenschaften, dadurch gekennzeichnet, daß ein Ge­ misch aus Poly-α-olefinen und/oder äquivalenten Isopa­ raffinen einerseits mit Polydimethylsiloxanen und/oder Po­ lyalkyl-/Polyarylsiloxanen andererseits vorhanden ist und daß die Volumen- und/oder Gewichtsanteile der Komponenten des Gemisches in Abhängigkeit von den geforderten elektri­ schen Eigenschaften der Flüssigkeit gewählt sind.1. Liquid with selectable ranges of thermal, caloric, rheological and hydraulic properties, characterized in that a mixture of poly-α-olefins and / or equivalent isopa raffins on the one hand with polydimethylsiloxanes and / or polyalkyl- / polyarylsiloxanes on the other hand is and that the volume and / or weight proportions of the components of the mixture are selected depending on the required electrical properties of the liquid. 2. Flüssigkeit nach Anspruch 1, dadurch gekennzeichnet, daß ein Gemisch von Poly-α-olefinen mit Polydimethylsi­ loxanen im Volum- oder Gewichtsverhältnis von 1 : 99 bis 99 : 1, vorzugsweise aber von 20 : 80 bis 80 : 20 vorhanden ist. 2. Liquid according to claim 1, characterized in that a mixture of poly-α-olefins with polydimethylsi loxanes in a volume or weight ratio of 1:99 to 99: 1, but preferably from 20:80 to 80:20 is present.   3. Flüssigkeit nach Anspruch 1 oder 2, dadurch gekenn­ zeichnet, daß ein Gemisch von synthetischen Poly-α-ole­ finen, bevorzugt auf der Ausgangsbasis von 1-Decen und/oder dessen hydrierten Oligomeren mit einer kinemati­ schen Viskosität von 1 bis 100 mm2/s bei 100°C und einem Fließpunkt von -75 bis -20°C und Polydimethylsiloxanen mit einer kinematischen Viskosität von 0,6 bis 100 mm2/s bei 25°C und einem Fließpunkt von -100 bis -40°C vor­ handen ist.3. Liquid according to claim 1 or 2, characterized in that a mixture of synthetic poly-α-ols finen, preferably on the basis of 1-decene and / or its hydrogenated oligomers with a kinematic viscosity of 1 to 100 mm 2 / s at 100 ° C and a pour point of -75 to -20 ° C and polydimethylsiloxanes with a kinematic viscosity of 0.6 to 100 mm 2 / s at 25 ° C and a pour point of -100 to -40 ° C before is. 4. Flüssigkeit nach einem der vorherigen Ansprüche, da­ durch gekennzeichnet, daß das Gemisch zusätzlich einen Oxidationsstabilisator (Antioxidans) enthält.4. Liquid according to one of the preceding claims, since characterized in that the mixture additionally has a Contains oxidation stabilizer (antioxidant). 5. Flüssigkeit nach einem der vorherigen Ansprüche, da­ durch gekennzeichnet, daß der Oxidationstabilisator zumin­ dest 2,6-Di-tert-butyl-p-kresol oder 2,5 Di-tert-butyl-hy­ drochinon in einer Konzentration von 0,2 bis 0,5 Gewichts­ prozenten enthält.5. Liquid according to one of the preceding claims, there characterized in that the oxidation stabilizer at least least 2,6-di-tert-butyl-p-cresol or 2.5 di-tert-butyl-hy droquinone in a concentration of 0.2 to 0.5 weight contains percentages. 6. Flüssigkeit nach einem der vorherigen Ansprüche, ge­ kennzeichnet zur Verwendung als Wärmeübertragungs- und Isolationsmittel in einem elektrischen Hochspannungs-Ge­ rät.6. Liquid according to one of the preceding claims, ge indicates for use as heat transfer and Insulating agent in a high voltage electrical ge advises. 7. Flüssigkeit nach einem der vorherigen Ansprüche, ge­ kennzeichnet zur Verwendung als Hydraulikflüssigkeit.7. Liquid according to one of the preceding claims, ge indicates for use as hydraulic fluid. 8. Flüssigkeit nach einem der vorherigen Ansprüche, ge­ kennzeichnet zur Verwendung als Kühl- und Isolationsmittel für den Hochspannungsteil eines Radargerätes. 8. Liquid according to one of the preceding claims, ge indicates for use as a coolant and insulation for the high voltage part of a radar.   9. Flüssigkeit nach einem der vorherigen Ansprüche, ge­ kennzeichnet zur gleichzeitigen Verwendung als Hydraulik­ flüssigkeit für hydraulische Systeme in einem Flugzeug und als Kühl und Isolationsmittel im Bordradar des gleichen Flugzeuges.9. Liquid according to one of the preceding claims, ge indicates for simultaneous use as hydraulics fluid for hydraulic systems in an aircraft and as a coolant and insulation in the on-board radar of the same Aircraft. 10. Flüssigkeit nach einem der vorherigen Ansprüche, ge­ kennzeichnet zur gleichzeitigen Verwendung als Hydraulik­ flüssigkeit für hydraulische Systeme in einem Flugzeug und als kühl und Isolationsmittel im Bordradar des gleichen Flugzeuges im Bypass.10. Liquid according to one of the preceding claims, ge indicates for simultaneous use as hydraulics fluid for hydraulic systems in an aircraft and as cool and isolating agent in the onboard radar of the same Airplane in the bypass.
DE4204200A 1992-02-13 1992-02-13 Liq. useful as heat transfer and insulating media - comprises mixt. of poly-alpha-olefin(s) and/or isoparaffin(s) with poly:di:methyl:siloxane(s) and/or poly:alkyl -/poly:aryl:siloxane(s) Ceased DE4204200A1 (en)

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DE4204200A DE4204200A1 (en) 1992-02-13 1992-02-13 Liq. useful as heat transfer and insulating media - comprises mixt. of poly-alpha-olefin(s) and/or isoparaffin(s) with poly:di:methyl:siloxane(s) and/or poly:alkyl -/poly:aryl:siloxane(s)

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WO2004031615A3 (en) * 2002-09-30 2004-07-15 Ulrich Rohs Epicyclic gear
US7574935B2 (en) 2002-09-30 2009-08-18 Ulrich Rohs Transmission
CN100529469C (en) * 2002-09-30 2009-08-19 乌尔里克·罗斯 Rotary transmission mechanism

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