EP0085949A2 - Stabilized trichloroethene and means for stabilizing trichloroethene - Google Patents

Stabilized trichloroethene and means for stabilizing trichloroethene Download PDF

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EP0085949A2
EP0085949A2 EP83101002A EP83101002A EP0085949A2 EP 0085949 A2 EP0085949 A2 EP 0085949A2 EP 83101002 A EP83101002 A EP 83101002A EP 83101002 A EP83101002 A EP 83101002A EP 0085949 A2 EP0085949 A2 EP 0085949A2
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ppm
tert
weight
epoxybutane
hydroxyanisole
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German (de)
French (fr)
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EP0085949A3 (en
EP0085949B1 (en
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Klaus Dr. Dipl.-Chem. Blum
Rudolf Dr. Dipl.-Chem. Strasser
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Wacker Chemie AG
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Wacker Chemie AG
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/261—Alcohols; Phenols
    • C11D7/262—Alcohols; Phenols fatty or with at least 8 carbon atoms in the alkyl or alkenyl chain
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5018—Halogenated solvents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/02—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents
    • D06L1/04—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents combined with specific additives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/24—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/266—Esters or carbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/28—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3281—Heterocyclic compounds

Definitions

  • trichlorethylene must be stabilized against the decomposing influences of heat, light, air, moisture and metals.
  • a commonly used, well stabilizing additive for trichlorethylene is butylene oxide.
  • Stabilizing mixtures containing nitriles, such as propionitrile, acrylonitrile and the like, have also proven useful for trichlorethylene, which is used as an auxiliary for paints.
  • the object of the invention was to provide means for stabilizing trichlorethylene and thus stabilized trichlorethylene which does not contain the stabilizing additives mentioned above. Furthermore, it was an object of the invention to find agents for stabilizing trichlorethylene which can make appropriately formulated trichlorethylene suitable both as an auxiliary for paints and as a degreasing agent.
  • the invention furthermore relates to stabilized trichlorethylene which contains the stabilizer mixture according to the invention.
  • the amount of stabilizer is generally between 3,200 and 25,000 ppm by weight, preferably 5,000 to 10,000 ppm by weight, in each case based on the total amount of stabilized trichloroethene.
  • Amines boiling between 1 and 110 ° C at 1 bar are equivalent to diisopropylamine in the context of the invention. Examples of these are triethylamine and dimethylisobutylamine.
  • the proportion of epoxides is preferably 4,000 to 6,000 ppm by weight.
  • the stability criterion used was the time that the stabilized trichlorethylene had to be exposed to the above test conditions until an HCl content of 0.02% by weight was reached.
  • the HCl content was determined by regular sampling and subsequent titration with 0.1 nNaOH against phenolphthalein.
  • DKH test The test arrangement described above was used, with the modification that steel strips were used instead of the aluminum strips.
  • the BAM test was unresponsive.
  • the accelerated oxidation text according to MIL-T-81533 A resulted in a service life of 1920 hours.
  • the pH was 9.5 after 48 hours.
  • the test liquid was colorless.
  • the service life until the acidity limit of 0.02% by weight of HC1 was reached was 240 hours.
  • the results are summarized in the following table.
  • the results according to Examples 1 to 11 and the comparative examples show the excellent stability of the trichlorethylene according to the invention against light metals, such as aluminum, which is reflected in the extremely long service life.
  • the DKH tests further prove that the trichloroethene stabilized according to the invention is not only suitable as a degreasing agent, but also meets the requirements which are to be placed on trichloroethene as an auxiliary for paints.
  • the comparative experiments illustrate that when the phenolic components to be used according to the invention are replaced by structurally similar phenolic compounds, the task according to the invention is not achieved.

Abstract

1. Agent for stabilizing trichloroethene characterized by the combination of the following components : a) N-methylpyrrole and/or 2-tert-butylphenol and/or 2.4-ditert-butylphenol and/or 4-hydroxyanisole and/or 2-tert-butyl-4-hydroxyanisole and/or 3-tert-butyl-4-hydroxyanisole and/or 2.6-dimethylphenol b) 2-methyl-2.3-epoxybutane and/or 2.3-dimethyl-2.3-epoxybutane and/or 3.3-dimethyl-1.2-epoxybutane and/or 1.2-epoxypentane and/or cyclopentene oxide c) diisobutylene d) ethyl acetate and/or propyl acetate e) at least one amine which at 1 bar boils between 70 and 110 degrees C.

Description

Bekanntlich muß Trichlorethen gegen die zersetzenden Einflüsse von Wärme, Licht, Luft, Feuchtigkeit und Metallen stabilisiert werden.As is known, trichlorethylene must be stabilized against the decomposing influences of heat, light, air, moisture and metals.

Ein häufig eingesetzter, gut stabilisierender Zusatz für Trichlorethen ist Butylenoxid. Für Trichlorethen, das als Hilfsstoff für Lacke eingesetzt wird, haben sich ferner stabilisierende Mischungen, die Nitrile, wie Propionitril, Acrylnitril und dergleichen enthalten, bewährt.A commonly used, well stabilizing additive for trichlorethylene is butylene oxide. Stabilizing mixtures containing nitriles, such as propionitrile, acrylonitrile and the like, have also proven useful for trichlorethylene, which is used as an auxiliary for paints.

Es wurden nun in jüngster Zeit toxikologische Untersuchungen bekannt, die es angeraten sein lassen, Nitrile und namentlich Butylenoxid als stabilisierende Zusätze für Trichlorethen nicht mehr zu verwenden.Recently, toxicological studies have become known which make it advisable not to use nitriles and especially butylene oxide as stabilizing additives for trichloroethene.

Aufgabe der Erfindung war es, Mittel zur Stabilisierung von Trichlorethen und somit stabilisiertes Trichlorethen zur Verfügung zu stellen, das die obengenannten Stabilisierungszusätze nicht enthält. Weiterhin war es Aufgabe der Erfindung, Mittel zur Stabilisierung von Trichlorethen aufzufinden, die entsprechend formuliertes Trichlorethen sowohl als Hilfsstoff für Lacke als auch als Entfettungsmittel geeignet machen können.The object of the invention was to provide means for stabilizing trichlorethylene and thus stabilized trichlorethylene which does not contain the stabilizing additives mentioned above. Furthermore, it was an object of the invention to find agents for stabilizing trichlorethylene which can make appropriately formulated trichlorethylene suitable both as an auxiliary for paints and as a degreasing agent.

Gegenstand der Erfindung ist ein Mittel zur Stabilisierung von Trichlorethen, das durch die Kombination der folgenden Bestandteile gekennzeichnet ist:

  • a) N-Methylpyrrol und/oder 2-tert.-Butylphenol und/oder 2.4-Ditert.-Butylphenol und/oder 4-Hydroxyanisol und/oder 2-tert.-Butyl-4-hydroxyanisol und/oder 3-tert.-Butyl-4-hydroxyanisol und/oder 2.6-Dimethylphenol
  • b) 2-Methyl-2.3-epoxybutan und/oder 2.3-Dimethyl-2.3-epoxybutan und/oder 3.3-Dimethyl-1.2-epoxybutan und/ oder 1.2-Epoxypentan und/oder Cyclopentenoxid
  • c) Diisobutylen
  • d) Ethylacetat und/oder Propylacetat
  • e) Diisopropylamin
The invention relates to an agent for stabilizing trichlorethylene, which is characterized by the combination of the following constituents:
  • a) N-methylpyrrole and / or 2-tert-butylphenol and / or 2,4-ditert.-butylphenol and / or 4-hydroxyanisole and / or 2-tert-butyl-4-hydroxyanisole and / or 3-tert-butyl-4-hydroxyanisole and / or 2,6-dimethylphenol
  • b) 2-methyl-2,3-epoxybutane and / or 2,3-dimethyl-2,3-epoxybutane and / or 3,3-dimethyl-1,2-epoxybutane and / or 1,2-epoxypentane and / or cyclopentene oxide
  • c) diisobutylene
  • d) ethyl acetate and / or propyl acetate
  • e) diisopropylamine

Gegenstand der Erfindung ist weiterhin stabilisiertes Trichlorethylen, das die erfindungsgemäße Stabilisatormischung enthält. Die Stabilisatormenge liegt in der Regel zwischen 3.200 und 25.000 Gew.ppm, vorzugsweise bei 5.000 bis 10.000 Gew.ppm, jeweils bezogen auf die Gesamtmenge stabilisierten Trichlorethens.The invention furthermore relates to stabilized trichlorethylene which contains the stabilizer mixture according to the invention. The amount of stabilizer is generally between 3,200 and 25,000 ppm by weight, preferably 5,000 to 10,000 ppm by weight, in each case based on the total amount of stabilized trichloroethene.

Vorzugsweise enthält das erfindungsgemäß stabilisierte Trichlorethen

  • a) 0 - 500 Gew.ppm N-Methylpyrrol
  • b) 0 - 500 Gew.ppm 2-tert.-Butylphenol und/oder 2.4-Ditert.-Butylphenol und/oder 4-Hydroxyanisol und/oder 2-tert.-Butyl-4-hydroxyanisol und/oder 3-tert.-Butyl-4-hydroxyanisol und/oder 2.6-Dimethylphenol

mit der Maßgabe, daß die Komponenten gemäß a) und b) zumindest in einer Menge von 10 Gew.ppm vorliegen,
  • c) 1.000 - 8.000 Gew.ppm 2-Methyl-2.3-epoxybutan und/oder 2.3-Dimethyl-2.3-epoxybutan und/ oder 3.3-Dimethyl-1.2-epoxybutan und/oder 1.2-Epoxypentan und/oder Cyclopentenoxid
  • d ) - 100 i -, 4.000 Gew.ppm Diisobutylen
  • e) 2.000 - 3.000 Gew.ppm Ethylacetat und/oder Propylacetat
  • f) 10 - 100 Gew.ppm Diisopropropylamin
The trichlorethylene stabilized according to the invention preferably contains
  • a) 0-500 ppm by weight of N-methylpyrrole
  • b) 0-500 ppm by weight of 2-tert-butylphenol and / or 2,4-di-tert-butylphenol and / or 4-hydroxyanisole and / or 2-tert.-butyl-4-hydroxyanisole and / or 3-tert.- Butyl-4-hydroxyanisole and / or 2,6-dimethylphenol

with the proviso that the components according to a) and b) are present at least in an amount of 10 ppm by weight,
  • c) 1,000-8,000 ppm by weight of 2-methyl-2,3-epoxybutane and / or 2,3-dimethyl-2,3-epoxybutane and / or 3,3-dimethyl-1,2-epoxybutane and / or 1,2-epoxypentane and / or cyclopentene oxide
  • d) - 100 i -, 4,000 ppm by weight diisobutylene
  • e) 2,000 - 3,000 ppm by weight of ethyl acetate and / or propyl acetate
  • f) 10-100 ppm by weight diisopropropylamine

Amine, die bei 1 bar zwischen und 110 °C sieden, sind Diisopropylamin im Rahmen der Erfindung äquivalent. Beispiele hierfür sind Triethylamin und Dimethylisobutylamin.Amines boiling between 1 and 110 ° C at 1 bar are equivalent to diisopropylamine in the context of the invention. Examples of these are triethylamine and dimethylisobutylamine.

Vorzugsweise beträgt der Anteil an Epoxiden (gemäß c)) 4.000 bis 6.000 Gew.ppm.The proportion of epoxides (according to c)) is preferably 4,000 to 6,000 ppm by weight.

Bei erfindungsgemäßem Trichlorethen als Hilfsstoff für Lacke beträgt der Anteil an N-Methylpyrrol vorzugsweise maximal 10 Gew.ppm, besonders bevorzugt 0 oder 0 bis 5 Gew.ppm. Vorteilhafterweise wird die Menge eingesetzten Diisobutylens auf Menge und Art des Phenols abgestimmt:

  • Bei 1.000 bis 3.000 Gew.ppm Diisobutylen beträgt die optimale Konzentration für
  • 2-tert.-Butylphenol und 2.4-Ditert.-Butylphenol 200 bis 500 Gew.ppm und für
  • 4-Hydroxyanisol 50 bis 100 Gew.ppm.
  • Bei Einsatz von 2-tert.-Butyl-4-hydroxyanisol werden vorzugsweise lediglich 10 bis 50 Gew.ppm neben 100 bis 200 Gew.ppm Diisobutylen zugegeben.
In trichloroethene according to the invention as an auxiliary for paints, the proportion of N-methylpyrrole is preferably at most 10 ppm by weight, particularly preferably 0 or 0 to 5 ppm by weight. The amount of diisobutylene used is advantageously matched to the amount and type of phenol:
  • At 1,000 to 3,000 ppm by weight diisobutylene, the optimal concentration for
  • 2-tert-butylphenol and 2.4-di-tert-butylphenol 200 to 500 ppm by weight and for
  • 4-hydroxyanisole 50 to 100 ppm by weight.
  • When using 2-tert-butyl-4-hydroxyanisole, preferably only 10 to 50 ppm by weight in addition to 100 to 200 ppm by weight of diisobutylene are preferably added.

Zur Prüfung auf Stabilität wurde das erfindungsgemäße Trichlorethen den drei folgenden Tests unterworfen:

  • 1. Es wurde der beschleunigte Oxidationstest nach MIL-T-81533 A durchgeführt. Als Testapparatur diente ein mit 200 ml erfindungsgemäß stabilisierten Trichlorethens gefülltes Siedegefäß mit Rückflußkühler, das mittels einer 150-Watt-Glühlampe beheizt wurde. In die Testflüssigkeit wurde ein stetiger wasserdampfgesättigter Sauerstoffstrom (10 bis 12 Blasen pro Minute) geleitet.
To test for stability, the trichlorethylene according to the invention was subjected to the following three tests:
  • 1. The accelerated oxidation test according to MIL-T-81533 A was carried out. A boiling vessel filled with 200 ml of trichlorethylene stabilized according to the invention and with a reflux condenser was used as the test apparatus and was heated by means of a 150 watt incandescent lamp. A steady stream of oxygen saturated with water vapor (10 to 12 bubbles per minute) was passed into the test liquid.

Weiter war ein Streifen aus metallischem Aluminium so angeordnet, daß er zur Hälfte in die Testflüssigkeit eintauchte. Ein zweiter Aluminiumstreifen befand sich am Gefäßboden.Furthermore, a strip of metallic aluminum was arranged so that half of it was immersed in the test liquid. A second aluminum strip was on the bottom of the vessel.

Als Stabilitätskriterium wurde die Zeit herangezogen, die das stabilisierte Trichlorethen den obigen Testbedingungen ausgesetzt werden mußte, bis ein HCl-Gehalt von 0,02 Gew.% erreicht war.. Der HCl-Gehalt wurde durch regelmäßige Probeentnahme und anschließende Titration mit 0,1 nNaOH gegen Phenolphthalein ermittelt.The stability criterion used was the time that the stabilized trichlorethylene had to be exposed to the above test conditions until an HCl content of 0.02% by weight was reached. The HCl content was determined by regular sampling and subsequent titration with 0.1 nNaOH against phenolphthalein.

2. DKH-Test: Es wurde die oben beschriebene Testanordnung benutzt, mit der Abänderung, daß anstatt der Aluminiumstreifen Stahlstreifen eingesetzt wurden.2. DKH test: The test arrangement described above was used, with the modification that steel strips were used instead of the aluminum strips.

Nach 48 Stunden wurde auf pH-Wert und Farbe der Testflüssigkeit bonitiert. Ferner wurde die Standzeit bis zum Erreichen der Aciditätsgrenze von 0,02 Gew.% HCl-Gehalt ermittelt.After 48 hours, the pH and color of the test liquid were assessed. Furthermore, the service life until the acidity limit of 0.02% by weight HCl content was reached.

3. Als weitere Qualitätsprüfung diente eine von der Bundesanstalt für Materialprüfung vorgeschlagene Testmethode (BAM-Test): Hierzu wurden 100 ml erfindungsgemäß stabilisierten Trichlorethens mit 100 ml Toluol vermischt und zusammen mit 18 g Aluminiumflitter einer Teilchengröße < 0,5 mm und zusammen mit 0,7 g wasserfreien Aluminiumchlorids 18 Stunden am Rückfluß gekocht. Eine zweite, im übrigen gleiche Probe enthielt zusätzlich 1 g Zinkstearat und eine dritte Probe zusätzlich 10 ml Ölsäure. Schließlich wurden die drei beschriebenen Tests noch mit Destillaten des erfindungsgemäß stabilisierten Trichlorethens wiederholt. Das Prüfverfahren galt als bestanden, wenn bei keinem der beschriebenen Einzeltests exotherme Reaktionen auftraten.3. A test method proposed by the Federal Institute for Material Testing (BAM test) served as a further quality test: For this purpose, 100 ml of trichloroethene stabilized according to the invention were mixed with 100 ml of toluene and together with 18 g of aluminum flakes with a particle size of <0.5 mm and together with 0, 7 g of anhydrous aluminum chloride are refluxed for 18 hours. A second sample, which was otherwise the same, additionally contained 1 g zinc stearate and a third sample additionally 10 ml oleic acid. Finally, the three tests described were repeated with distillates of the trichlorethylene stabilized according to the invention. The test procedure was considered to be passed if none of the individual tests described resulted in exothermic reactions.

Die Erfindung wird nun anhand von Beispielen und Vergleichsbeispielen näher erläutert. Die Daten beziehen sich auf die Ergebnisse der drei oben beschriebenen Tests. Das Zeichen (-) steht für keine Reaktion während des BAM-Tests.The invention will now be explained in more detail by means of examples and comparative examples. The data refer to the results of the three tests described above. The sign (-) stands for no reaction during the BAM test.

Beispiel 1example 1

3 kg Trichlorethen wurden mit 0,9 g N-Methylpyrrol, 15 g 2-Methyl-2.3-epoxybutan, 8,3 g Diisobutylen,. 8,3 g Ethylacetat und 0,08 g Diisopropylamin versetzt..3 kg of trichlorethylene were mixed with 0.9 g of N-methylpyrrole, 15 g of 2-methyl-2,3-epoxybutane, 8.3 g of diisobutylene. 8.3 g of ethyl acetate and 0.08 g of diisopropylamine are added.

Der BAM-Test verlief ohne Reaktion. Der beschleunigte Oxidationstext nach MIL-T-81533 A ergab eine Standzeit von 1920 Stunden.The BAM test was unresponsive. The accelerated oxidation text according to MIL-T-81533 A resulted in a service life of 1920 hours.

Weitere Ergebnisse von Tests, die analog Beispiel 1 durchgeführt wurden, werden in der nun folgenden Tabelle aufgeführt.

Figure imgb0001
Further results of tests which were carried out analogously to Example 1 are listed in the following table.
Figure imgb0001

Beispiel 5Example 5

Es wurden 3 kg Trichlorethylen mit 0,66 g 2.4-Ditert.-Butylphenol, 13,5 g 2-Methyl-2.3-epoxybutan, 6 g Diisobutylen, 8,4 g Ethylacetat und 0,06 g Diisopropylamin versetzt.3 kg of trichlorethylene were mixed with 0.66 g of 2,4-di-tert-butylphenol, 13.5 g of 2-methyl-2,3-epoxybutane, 6 g of diisobutylene, 8.4 g of ethyl acetate and 0.06 g of diisopropylamine.

Das derart stabilisierte Trichlorethen wurde dem beschriebenen DKH-Test unterworfen.The trichloroethene stabilized in this way was subjected to the described DKH test.

Der pH-Wert betrug nach 48 Stunden 9,5. Die Testflüssigkeit war farblos. Die Standzeit bis zum Erreichen der Aciditätsgrenze von 0,02 Gew.% HC1 betrug 240 Stunden.The pH was 9.5 after 48 hours. The test liquid was colorless. The service life until the acidity limit of 0.02% by weight of HC1 was reached was 240 hours.

Weitere Ergebnisse von Tests, die analog Beispiel 5 durchgeführt wurden, sind in der nachfolgenden Tabelle aufgeführt.

Figure imgb0002
Figure imgb0003
Sämtliche Proben gemäß den Beispielen 5 bis 11 erfüllen ferner die Kriterien des BAM-Tests.Further results of tests which were carried out analogously to Example 5 are listed in the table below.
Figure imgb0002
Figure imgb0003
 All samples according to Examples 5 to 11 also meet the criteria of the BAM test.

Vergleichsbeispiel 1Comparative Example 1

Es wurde die gemäß Beispiel 5 beschriebene Formulierung dem DKH-Test unterworfen, mit der Abänderung, daß anstatt 220 ppm 2.4-Ditert.Butylphenol

  • a) 220 ppm 2.6-Ditert.-Butylphenol
  • b) 220 ppm Anisol
  • c) 220 ppm 2.6-Dimethyl-p-Kresol
  • d) 220 ppm 4-tert.-Amylphenol
  • e) 220 ppm 2.6-ditert.-butyl-p-kresol
  • f) 220 ppm 4-tert.-Butylphenol

eingesetzt wurden.The formulation described in Example 5 was subjected to the DKH test, with the modification that instead of 220 ppm, 2,4-ditert.butylphenol
  • a) 220 ppm of 2,6-di-tert-butylphenol
  • b) 220 ppm anisole
  • c) 220 ppm 2,6-dimethyl-p-cresol
  • d) 220 ppm 4-tert-amylphenol
  • e) 220 ppm 2,6-di-tert-butyl-p-cresol
  • f) 220 ppm 4-tert-butylphenol

were used.

Die Ergebnisse sind in der folgenden Tabelle zusammengestellt.

Figure imgb0004
Die Ergebnisse gemäß den Beispielen 1 bis 11 und den Vergleichsbeispielen zeigen die ausgezeichnete Stabilität des erfindungsgemäßen Trichlorethens gegenüber Leichtmetallen, wie Aluminium, die sich in den extrem hohen Standzeiten wiederspiegelt. Die DKH-Tests beweisen ferner, daß das erfindungsgemäß stabilisierte Trichlorethen nicht nur als Entfettungsmittel geeignet ist, sondern ebenso dew Anforderungen gerecht wird, die an Trichlorethen als Hilfsstoff für Lacke zu stellen sind. Die Vergleichsversuche veranschaulichen, daß beim Ersatz der erfindungsgemäß einzusetzenden phenolischen Komponenten gegen strukturell ähnliche phenolische Verbindungen die erfindungsgemäße Aufgabenstellung nicht erreicht wird.The results are summarized in the following table.
Figure imgb0004
 The results according to Examples 1 to 11 and the comparative examples show the excellent stability of the trichlorethylene according to the invention against light metals, such as aluminum, which is reflected in the extremely long service life. The DKH tests further prove that the trichloroethene stabilized according to the invention is not only suitable as a degreasing agent, but also meets the requirements which are to be placed on trichloroethene as an auxiliary for paints. The comparative experiments illustrate that when the phenolic components to be used according to the invention are replaced by structurally similar phenolic compounds, the task according to the invention is not achieved.

Claims (4)

1. Mittel zur Stabilisierung von Trichlorethen, gekennzeichnet durch die Kombination folgender Bestandteile: a) N-Methylpyrrol und/oder 2-tert.-Butylphenol und/ oder 2.4-Ditert.-Butylphenol und/oder 4-Hydroxyanisol und/oder 2-tert.-Butyl-4-hydroxyanisol und/oder 3-tert.-Butyl-4-hydroxyanisol und/oder 2.6-Dimethylphenol b) 2-Methyl- -epoxybutan und/oder 2.3-Dimethyl-2.3-epoxybutan und/oder 3.3-Dimethyl-1.2-epoxybutan und/oder 1.2-Epoxypentan und/oder Cyclo-. pentenoxid c ) Diisobutylen d) Ethylacetat und/oder Propylacetat e)' mindestens ein Amin. das bei 1 bar zwischen 70 und 110 °C siedet. 1. Agent for stabilizing trichlorethylene, characterized by the combination of the following components: a) N-methylpyrrole and / or 2-tert-butylphenol and / or 2,4-di-tert-butylphenol and / or 4-hydroxyanisole and / or 2-tert.-butyl-4-hydroxyanisole and / or 3-tert.- Butyl-4-hydroxyanisole and / or 2,6-dimethylphenol b) 2-methyl-epoxybutane and / or 2,3-dimethyl-2,3-epoxybutane and / or 3,3-dimethyl-1,2-epoxybutane and / or 1,2-epoxypentane and / or cyclo-. pentene oxide c) diisobutylene d) ethyl acetate and / or propyl acetate e) 'at least one amine. that boils between 70 and 110 ° C at 1 bar. 2. Stabilisiertes Trichlorethen, dadurch ge- kennzeichnet , daß es ein Mittel nach Anspruch 1 enthält.2. Stabilized trichlorethylene, characterized in that it contains an agent according to claim 1. 3. Trichlorethen nach Anspruch 2, dadurch ge- kennzeichnet, daß es 3.200 bis 25.000 Gew.ppm Stabilisierungsmittel enthält.3. Trichloroethene according to claim 2, characterized in that it contains 3,200 to 25,000 ppm by weight of stabilizing agent. 4. Trichlorethen nach Anspruch 3, enthaltend a) 0 - 500 Gew.ppm N-Methylpyrrol b) 0 - 500 Gew.ppm 2-tert.-Butylphenol und/oder 2.4-Ditert.-Butylphenol und/oder 4-Hydroxyanisol und/oder 2-tert.-Butyl-4-hydroxyanisol und/oder 3-tert.-Butyl-4-hydroxyanisol und/oder 2.6-Dimethylphenol mit der Maßgabe, daß die Komponenten gemäß a) und b.) zumindest in einer Menge yon 20 Gew.ppm vorliegen, c) 1.000 - 8.000 Gew.ppm 2-Methyl-2.3-epoxybutan und/oder. 2.3-Dimethyl-2.3-epoxybutan und/ oder 3.3-Dimethyl-1.2-epoxybutan und/oder 1.2-Epoxypentan und/oder Cyclopentenoxid d) 100- 4.000 Gew.ppm Diisobutylen e) 2.000 - 3.000 Gew.ppm Ethylacetat und/oder Propylacetat f) 10 - 100 Gew.ppm Diisopropylamin und/oder Triethylamin und/oder Dimethylisobutylamin. 4. Trichlorethylene according to claim 3, containing a) 0-500 ppm by weight of N-methylpyrrole b) 0-500 ppm by weight of 2-tert-butylphenol and / or 2,4-di-tert-butylphenol and / or 4-hydroxyanisole and / or 2-tert.-butyl-4-hydroxyanisole and / or 3-tert.- Butyl-4-hydroxyanisole and / or 2,6-dimethylphenol with the proviso that the components according to a) and b.) are present at least in an amount of 20 ppm by weight, c) 1,000-8,000 ppm by weight of 2-methyl-2,3-epoxybutane and / or. 2,3-dimethyl-2,3-epoxybutane and / or 3,3-dimethyl-1,2-epoxybutane and / or 1,2-epoxypentane and / or cyclopentene oxide d) 100-4,000 ppm by weight diisobutylene e) 2,000 - 3,000 ppm by weight of ethyl acetate and / or propyl acetate f) 10-100 ppm by weight of diisopropylamine and / or triethylamine and / or dimethylisobutylamine.
EP83101002A 1982-02-05 1983-02-03 Stabilized trichloroethene and means for stabilizing trichloroethene Expired - Lifetime EP0085949B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83101002T ATE53565T1 (en) 1982-02-05 1983-02-03 STABILIZED TRIHLORETHENE AND TRIHLORETHENE STABILIZING AGENT.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19823203907 DE3203907A1 (en) 1982-02-05 1982-02-05 STABILIZED TRICHLORETHEN AND AGENT FOR STABILIZING TRICHLORETHEN
DE3203907 1982-02-05

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EP0085949A2 true EP0085949A2 (en) 1983-08-17
EP0085949A3 EP0085949A3 (en) 1984-07-18
EP0085949B1 EP0085949B1 (en) 1990-06-13

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JP (1) JPS58135827A (en)
AT (1) ATE53565T1 (en)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002036531A2 (en) * 2000-11-03 2002-05-10 Dow Global Technologies Inc. Stabilizer and solvent compositions
KR100754721B1 (en) * 2002-04-26 2007-09-03 삼성전자주식회사 Apparatus and method for transmitting and receiving multiplexed data in an orthogonal frequency division multiplexing communication system

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2861390B1 (en) * 2003-10-24 2006-01-21 Arkema STABILIZATION OF TRANS-1,2-DICHLORETHYLENE

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Publication number Priority date Publication date Assignee Title
US2797250A (en) * 1954-05-13 1957-06-25 Du Pont Stabilization of chlorinated hydrocarbons
FR1205056A (en) * 1957-11-09 1960-01-29 Solvay Process for the stabilization of chlorinated hydrocarbons
FR1233249A (en) * 1958-08-15 1960-10-12 Canadian Ind Stabilization of halohydrocarbons, in particular to prevent the decomposition of trichlorethylene
DE1136695B (en) * 1957-11-15 1962-09-20 Sicedison Spa Stabilizing trichlorethylene against decomposition
GB932138A (en) * 1960-10-27 1963-07-24 Canadian Ind Stabilization of halogenated hydrocarbons used as metal degreasing solvents
FR2119014A1 (en) * 1970-12-23 1972-08-04 Central Glass Co Ltd

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2797250A (en) * 1954-05-13 1957-06-25 Du Pont Stabilization of chlorinated hydrocarbons
FR1205056A (en) * 1957-11-09 1960-01-29 Solvay Process for the stabilization of chlorinated hydrocarbons
DE1136695B (en) * 1957-11-15 1962-09-20 Sicedison Spa Stabilizing trichlorethylene against decomposition
FR1233249A (en) * 1958-08-15 1960-10-12 Canadian Ind Stabilization of halohydrocarbons, in particular to prevent the decomposition of trichlorethylene
GB932138A (en) * 1960-10-27 1963-07-24 Canadian Ind Stabilization of halogenated hydrocarbons used as metal degreasing solvents
FR2119014A1 (en) * 1970-12-23 1972-08-04 Central Glass Co Ltd

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002036531A2 (en) * 2000-11-03 2002-05-10 Dow Global Technologies Inc. Stabilizer and solvent compositions
WO2002036531A3 (en) * 2000-11-03 2002-07-25 Dow Global Technologies Inc Stabilizer and solvent compositions
KR100754721B1 (en) * 2002-04-26 2007-09-03 삼성전자주식회사 Apparatus and method for transmitting and receiving multiplexed data in an orthogonal frequency division multiplexing communication system

Also Published As

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ATE53565T1 (en) 1990-06-15
EP0085949A3 (en) 1984-07-18
CA1175220A (en) 1984-10-02
DE3381638D1 (en) 1990-07-19
DE3203907A1 (en) 1983-08-11
JPS58135827A (en) 1983-08-12
JPS6121604B2 (en) 1986-05-28
EP0085949B1 (en) 1990-06-13

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