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EP1697277A1 - Thermal pre-ignition agents - Google Patents

Thermal pre-ignition agents

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Publication number
EP1697277A1
EP1697277A1 EP04820421A EP04820421A EP1697277A1 EP 1697277 A1 EP1697277 A1 EP 1697277A1 EP 04820421 A EP04820421 A EP 04820421A EP 04820421 A EP04820421 A EP 04820421A EP 1697277 A1 EP1697277 A1 EP 1697277A1
Authority
EP
European Patent Office
Prior art keywords
weight
thermal pre
nitrate
ignition device
ignition
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.)
Granted
Application number
EP04820421A
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German (de)
French (fr)
Other versions
EP1697277B1 (en
Inventor
Rainer Hagel
Ulrich Bley
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RWS GmbH
Original Assignee
RUAG Ammotec GmbH
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Publication of EP1697277A1 publication Critical patent/EP1697277A1/en
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Publication of EP1697277B1 publication Critical patent/EP1697277B1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/04—Compositions containing a nitrated organic compound the nitrated compound being an aromatic
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
    • C06C7/00—Non-electric detonators; Blasting caps; Primers
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
    • C06C9/00—Chemical contact igniters; Chemical lighters

Definitions

  • the present invention relates to pre-ignition devices which can be used, for example, as thermal fuses in gas generators for motor vehicle safety systems.
  • Thermal pre-ignition devices are pyrotechnic substances or mixtures. Among other things, they have the task of igniting the generally very thermally stable gas-generating mixtures of the gas generator in the event of a vehicle fire.
  • nitrocellulose, propellant powder derived therefrom or the mixtures based on nitrotriazolone and guanidine nitrate described in patent application DE 197 30 873 A1 are used as the thermal pre-ignition means. These mixtures show ignition temperatures of approx. 160 ° C and are only insufficiently long-term stable in the case of nitrocellulose.
  • the object of the present invention was to provide pyrotechnic mixtures with ignition temperatures around 200 ° C. and sufficient long-term stability, which can be used as thermal pre-igniters for gas generators in motor vehicle safety systems.
  • the object on which the invention is based was achieved by using 2- [bis- (2,4,6-trinitrophenyl)] aminoethyl nitrate, briefly referred to as dipicrylaminoethyl nitrate (DPN). This substance can be used either alone or in mixtures with other components.
  • DPN can be prepared from 2,4-dinitrochlorobenzene and ethanolamine with subsequent nitration (Lit: RV Clark, Ind. Eng. Chem., 25, 1385 (1933)).
  • the structural formula is as follows:
  • the deflagration point of pure DPN is around 200 ° C. Surprisingly, it was found that, in the case of mixtures of DPN with selected components as additives, the deflagration point can be controlled in the range from 178 ° C. to 208 ° C. and the deflagration temperatures of the mixtures may be lower than that of the individual components. Deflagration temperatures below 200 ° C are particularly interesting for pre-ignition devices. The mixtures according to the invention meet this requirement with excellent long-term stability.
  • Nitrogen-containing compounds (individually or in mixtures) nitroguanidine, nitroaminoguanidine, nitrotriazolone, derivatives of tetrazole, such as 5-aminotetrazole, ditetrazolylamine, ditetrazole and their salts, nitraminotetrazole and its salts, such as ammonium-nitraminotetrazole and aminoguanidinium-nitramidino-dinogranidino-nitramino-nitroglammonitaminoguanidium, Triaminoguanidine nitrate, guanidine nitrate, dicyandiamidine nitrate, diaminoguanidine azotetrazolate.
  • tetrazole such as 5-aminotetrazole, ditetrazolylamine, ditetrazole and their salts
  • nitraminotetrazole and its salts such as ammonium-nitraminotetrazole and aminoguani
  • Oxidizing agents (individually or in mixtures) nitrates of alkali or alkaline earth metals or ammonium such as sodium nitrate or potassium nitrate, perchlorates of alkali or alkaline earth metals or ammonium, peroxides of alkaline earth metals or zinc.
  • Reducing agents (individually or in mixtures) aluminum, titanium, titanium hydride, boron, borohydride, zircon, zircon hydride, silicon, graphite, activated carbon, carbon black.
  • Binder (individually or in mixtures) cellulose and its derivatives, polyvinyl butyrals, polynitropolyphenylene, polynitrophphenyl ether, perspex, polyvinyl acetate and copolymers.
  • Energy-rich supplements (individually or in mixtures) hexogen, octogen and nitrocellulose.
  • Burning moderators and processing aids (individually or in mixtures) ferrocene and derivatives, acetony acetates, salicylates, silicates, silica gels, boron nitride.
  • the production and processing takes place according to known and customary methods. These include kneading, extruding, extrusion, tableting or granulating.
  • Table 1 shows the compositions of twelve different mixtures. The components were weighed in the stated weight ratios (data in percent by weight (% by weight)) into plastic containers and homogenized in a tumble mixer for 30 minutes.
  • Table 2 shows the heat of explosion, the sensitivity to friction and impact of the mixtures.
  • the friction and impact sensitivities were measured using methods of the Federal Institute for Materials Research (BAM), while the heat of explosion was measured using a calorimeter from EKA.
  • Table 3 summarizes the deflagration points before and after thermal stress (400 h, 110 ° C) and the weight loss after 72 h and 400 h thermal stress at 110 ° C.
  • the deflagration points were determined using thermogravimetry analysis (Mettler) at a heating rate of 10 ° C. per minute. Weight loss was measured analogously to the Holland test. After 400 h, only slight weight losses of 0.2 to 0.5% by weight can be seen and no significant change in the deflagration temperature after thermal stress.
  • Table 3 Overview of weight losses and deflagration temperatures
  • the present invention specifically relates to:
  • Thermal pre-ignition devices that contain dipicrylaminoethyl nitrate (DPN) in a proportion by weight of 10 to 100%.
  • DPN dipicrylaminoethyl nitrate
  • Thermal pre-ignition agents which, in addition to DPN, contain nitrogen-containing compounds, individually or in mixtures, in parts by weight of 0 to 90%, such as, for example, nitroguanidine, nitroaminoguanidine, nitrotriazolone, derivatives of tetrazole such as 5-aminotetrazole, ditetrazolylamine, ditetrazole and its salts, nitraminotetrazole and its salts such as ammonium-nitraminotetrazole and aminoguanidinium-nitraminotetrazole, aminoguanidine nitrate, diaminoguanidine nitrate, triaminoguanidine nitrate, guanidinediamine dinitrate, guanidinediamine dinitrate, guanidinediamine dinitrate, guanidinediaminitride.
  • nitrogen-containing compounds individually or in mixtures, in parts by weight of 0 to 90%
  • nitrogen-containing compounds such as, for example, nitrogu
  • Thermal pre-ignition agents which, in addition to DPN and the above-mentioned nitrogen-containing compounds, individually or in mixtures, contain oxidizing agents, individually or in mixtures, in proportions by weight of 10 to 90%, such as, for example, nitrates of the alkali or alkaline earth metals or of ammonium, such as sodium nitrate or potassium nitrate, Perchlorates of alkali or alkaline earth metals or ammonium, peroxides of alkaline earth metals or zinc.
  • oxidizing agents individually or in mixtures, in proportions by weight of 10 to 90%, such as, for example, nitrates of the alkali or alkaline earth metals or of ammonium, such as sodium nitrate or potassium nitrate, Perchlorates of alkali or alkaline earth metals or ammonium, peroxides of alkaline earth metals or zinc.
  • Thermal pre-ignition agents which, in addition to DPN, the above-mentioned nitrogen-containing compounds, individually or in mixtures and / or the above-mentioned oxidizing agents, individually or in mixtures, contain reducing agents, individually or in mixtures, in parts by weight of 1 to 80%, such as aluminum, Titan, titanium hydride, boron, borohydride, zircon, zircon hydride, silicon, graphite, activated carbon, carbon black.
  • Thermal pre-ignition agents which, in addition to DPN, the above-mentioned nitrogen-containing compounds, individually or in mixtures, the above-mentioned oxidizing agents, individually or in mixtures and / or the above-mentioned reducing agents, individually or in mixtures, binders, individually or in mixtures Containing parts by weight from 1 to 80%, such as cellulose and its derivatives, polyvinyl butyrals, polynitropolyphenylene, polynitrophenyl ether, plexigum, polyvinyl acetate and copolymers.
  • Thermal pre-ignition agents which, in addition to DPN, the above-mentioned nitrogen-containing compounds, individually or in mixtures, the above-mentioned oxidizing agents, individually or in mixtures, the above-mentioned reducing agents, individually or in mixtures and / or the above-mentioned binders, individually or in mixtures, energetic additives, individually or in mixtures, in proportions by weight of 10 to 80%, such as. Hexogen, octogen and nitrocellulose.
  • Thermal pre-ignition agents which, in addition to DPN, the above-mentioned nitrogen-containing compounds, individually or in mixtures, the above-mentioned oxidizing agents, individually or in mixtures, the above-mentioned reducing agents, individually or in Mixtures, the abovementioned binders, individually or in mixtures and / or the abovementioned energetic additives, individually or in mixtures, combustion moderators and processing aids, individually or in mixtures, in parts by weight of 0.1 to 20%, such as ferrocene and derivatives , Acetonylacetates, salicylates, silicates, silica gels, boron nitride.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Air Bags (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
  • Primary Cells (AREA)
  • Impact Printers (AREA)
  • Springs (AREA)

Abstract

The invention relates to thermal pre-ignition agents and to their use as thermal fuses, in particular for use in gas generators of motor-vehicle safety systems.

Description

Thermische Frühzündmittel Thermal pre-ignition devices
Gegenstand der vorliegenden Erfindung sind Frühzündmittel, die beispielsweise als thermische Sicherungen in Gasgeneratoren für Kraftfahrzeugsicherheitssysteme eingesetzt werden können.The present invention relates to pre-ignition devices which can be used, for example, as thermal fuses in gas generators for motor vehicle safety systems.
Thermische Frühzündmittel sind pyrotechnische Substanzen bzw. Mischungen. Sie haben unter anderem die Aufgabe, die in der Regel thermisch sehr stabilen gaserzeugenden Mischungen des Gasgenerators im Falle eines Fahrzeugbrandes kontrolliert anzuzünden.Thermal pre-ignition devices are pyrotechnic substances or mixtures. Among other things, they have the task of igniting the generally very thermally stable gas-generating mixtures of the gas generator in the event of a vehicle fire.
Als thermische Frühzündmittel werden beispielsweise Nitrocellulose, daraus abge- leitete Treibladungspulver oder die in der Patentanmeldung DE 197 30 873 A1 beschriebenen Mischungen auf Basis von Nitrotriazolon und Guanidinnitrat eingesetzt. Diese Mischungen zeigen Entzündungstemperaturen von ca. 160°C und sind im Falle der Nitrocellulose nur unzureichend langzeitstabil.For example, nitrocellulose, propellant powder derived therefrom or the mixtures based on nitrotriazolone and guanidine nitrate described in patent application DE 197 30 873 A1 are used as the thermal pre-ignition means. These mixtures show ignition temperatures of approx. 160 ° C and are only insufficiently long-term stable in the case of nitrocellulose.
Aufgabe der vorliegenden Erfindung war die Bereitstellung von pyrotechnischen Mischungen mit Entzündungstemperaturen um 200°C und ausreichender Langzeitstabilität, die als thermische Frühzündmittel für Gasgeneratoren in Kraftfahrzeugsicherheitssystemen eingesetzt werden können. Gelöst wurde die der Erfindung zu Grunde liegende Aufgabe durch den Einsatz von 2-[Bis-(2,4,6-trinitrophenyl)] aminoethylnitrat, kurz als Dipikrylaminoethylnitrat (DPN) bezeichnet. Diese Substanz kann entweder alleine oder in Mischungen mit weiteren Komponenten verwendet werden. DPN kann aus 2,4-Dinitrochlorbenzol und Ethanolamin mit anschließender Nitrierung hergestellt werden (Lit: R.V. Clark, Ind. Eng. Chem., 25, 1385 (1933)). Die Strukturformel ist wie folgt: The object of the present invention was to provide pyrotechnic mixtures with ignition temperatures around 200 ° C. and sufficient long-term stability, which can be used as thermal pre-igniters for gas generators in motor vehicle safety systems. The object on which the invention is based was achieved by using 2- [bis- (2,4,6-trinitrophenyl)] aminoethyl nitrate, briefly referred to as dipicrylaminoethyl nitrate (DPN). This substance can be used either alone or in mixtures with other components. DPN can be prepared from 2,4-dinitrochlorobenzene and ethanolamine with subsequent nitration (Lit: RV Clark, Ind. Eng. Chem., 25, 1385 (1933)). The structural formula is as follows:
HsNsOlδ HsNsOlδ
Der Verpuffungspunkt von reinem DPN liegt bei ca. 200°C. Überraschenderweise wurde gefunden, dass sich bei Mischungen von DPN mit ausgewählten Komponenten als Zusatzstoffe der Verpuffungspunkt im Bereich von 178°C bis 208°C steuern lässt und die Verpuffungstemperaturen der Mischungen tiefer liegen können als die der Einzelkomponenten. Für Frühzündmittel sind Verpuffungstemperaturen unter 200°C besonders interessant. Die erfindungsgemäßen Mischungen erfüllen diese Forderung bei ausgezeichneter Langzeitstabilität.The deflagration point of pure DPN is around 200 ° C. Surprisingly, it was found that, in the case of mixtures of DPN with selected components as additives, the deflagration point can be controlled in the range from 178 ° C. to 208 ° C. and the deflagration temperatures of the mixtures may be lower than that of the individual components. Deflagration temperatures below 200 ° C are particularly interesting for pre-ignition devices. The mixtures according to the invention meet this requirement with excellent long-term stability.
Als Zusatzstoffe können verwendet werden:The following additives can be used:
1. Stickstoffhaltige Verbindungen (einzeln oder in Mischungen) Nitroguanidin, Nitroaminoguanidin, Nitrotriazolon, Derivate des Tetrazols wie 5- Aminotetrazol, Ditetrazolylamin, Ditetrazol und deren Salze, Nitraminotetrazol und seine Salze wie Ammonium-Nitraminotetrazol und Aminoguanidinium-Nitramino- tetrazol, Aminoguanidinnitrat, Diaminoguanidinnitrat, Triaminoguanidinnitrat, Gua- nidinnitrat, Dicyandiamidinnitrat, Diaminoguanidin-Azotetrazolat.1. Nitrogen-containing compounds (individually or in mixtures) nitroguanidine, nitroaminoguanidine, nitrotriazolone, derivatives of tetrazole, such as 5-aminotetrazole, ditetrazolylamine, ditetrazole and their salts, nitraminotetrazole and its salts, such as ammonium-nitraminotetrazole and aminoguanidinium-nitramidino-dinogranidino-nitramino-nitroglammonitaminoguanidium, Triaminoguanidine nitrate, guanidine nitrate, dicyandiamidine nitrate, diaminoguanidine azotetrazolate.
2. Oxidationsmittel (einzeln oder in Mischungen) Nitrate der Alkali- oder Erdalkalimetalle oder des Ammoniums wie Natriumnitrat oder Kaliumnitrat, Perchlorate der Alkali- oder Erdalkalimetalle oder des Ammoniums, Peroxide der Erdalkalimetalle oder des Zinks. 3. Reduktionsmittel (einzeln oder in Mischungen) Aluminium, Titan, Titanhydrid, Bor, Borhydrid, Zirkon, Zirkonhydrid, Silicium, Graphit, Aktivkohle, Ruß.2. Oxidizing agents (individually or in mixtures) nitrates of alkali or alkaline earth metals or ammonium such as sodium nitrate or potassium nitrate, perchlorates of alkali or alkaline earth metals or ammonium, peroxides of alkaline earth metals or zinc. 3. Reducing agents (individually or in mixtures) aluminum, titanium, titanium hydride, boron, borohydride, zircon, zircon hydride, silicon, graphite, activated carbon, carbon black.
4. Bindemittel (einzeln oder in Mischungen) Cellulose sowie deren Derivate, Polyvinylbutyrale, Polynitropolyphenylen, Polyni- trophenylether, Plexigum, Polyvinylacetat und Copolymere.4. Binder (individually or in mixtures) cellulose and its derivatives, polyvinyl butyrals, polynitropolyphenylene, polynitrophphenyl ether, perspex, polyvinyl acetate and copolymers.
5. Energiereiche Zuschläge (einzeln oder in Mischungen) Hexogen, Oktogen und Nitrocellulose.5. Energy-rich supplements (individually or in mixtures) hexogen, octogen and nitrocellulose.
6. Abbrandmoderatoren und Verarbeitungshilfen (einzeln oder in Mischungen) Ferrocen und Derivate , Acetonylacetate, Salicylate, Silikate, Kieselgele, Bornitrid.6. Burning moderators and processing aids (individually or in mixtures) ferrocene and derivatives, acetony acetates, salicylates, silicates, silica gels, boron nitride.
Die Herstellung und Verarbeitung findet nach an sich bekannten und üblichen Verfahren statt. Hierzu zählen beispielsweise Kneten, Extrudieren, Strangpressen, Tablettieren oder Granulieren.The production and processing takes place according to known and customary methods. These include kneading, extruding, extrusion, tableting or granulating.
Die folgenden Beispiele sollen die Erfindung näher erläutern, ohne sie ein- zuschränken.The following examples are intended to explain the invention in more detail without restricting it.
In Tabelle 1 sind die Zusammensetzungen von zwölf verschiedenen Mischungen dargestellt. Die Komponenten wurden in den angegebenen Gewichtsverhältnissen (Angaben in Gewichtsprozent (Gew.%)) in Plastikbehälter eingewogen und 30 Minuten im Taumelmischer homogenisiert. Table 1 shows the compositions of twelve different mixtures. The components were weighed in the stated weight ratios (data in percent by weight (% by weight)) into plastic containers and homogenized in a tumble mixer for 30 minutes.
Tabelle 1 : BeispieleTable 1: Examples
In Tabelle 2 sind die Explosionswärmen, Reib- und Schlagempfindlichkeiten der Mischungen dargestellt. Die Messung der Reib- und Schlagempfindlichkeiten erfolgte nach Methoden der Bundesanstalt für Materialforschung (BAM), während die Messung der Explosionswärmen mit einem Kalorimeter der Fa. EKA durchgeführt wurden. Table 2 shows the heat of explosion, the sensitivity to friction and impact of the mixtures. The friction and impact sensitivities were measured using methods of the Federal Institute for Materials Research (BAM), while the heat of explosion was measured using a calorimeter from EKA.
Tabelle 2 Übersicht der Explosionswärmen, Reib- und SchlagempfindlichkeitenTable 2 Overview of the heat of explosion, sensitivity to friction and impact
In Tabelle 3 sind die Verpuffungspunkte vor und nach thermischer Belastung (400 h, 110°C) und die Gewichtsverluste nach 72 h und 400 h thermischer Belastung bei 110°C zusammengefasst. Die Bestimmung der Verpuffungspunkte erfolgte mit der Thermogravimetrie-Analyse (Fa. Mettler) bei einer Aufheizrate von 10°C pro Minute. Die Messung des Gewichtsverlustes erfolgte analog dem Holland Test. Man erkennt nach 400 h nur geringe Gewichtsverluste von 0,2 bis 0,5 Gew.% und keine signfikante Änderung der Verpuffungstemperatur nach thermischer Belastung. Tabelle 3 Übersicht der Gewichtsverluste und VerpuffungstemperaturenTable 3 summarizes the deflagration points before and after thermal stress (400 h, 110 ° C) and the weight loss after 72 h and 400 h thermal stress at 110 ° C. The deflagration points were determined using thermogravimetry analysis (Mettler) at a heating rate of 10 ° C. per minute. Weight loss was measured analogously to the Holland test. After 400 h, only slight weight losses of 0.2 to 0.5% by weight can be seen and no significant change in the deflagration temperature after thermal stress. Table 3 Overview of weight losses and deflagration temperatures
Die Beispiele zeigen, dass die erfindungsgemäß definierten Mischungen Verpuffungstemperaturen im Bereich von 178 bis 208°C aufweisen und gemäß den Forderungen der Automobilindustrie als stabil anzusehen sind.The examples show that the mixtures defined according to the invention have deflagration temperatures in the range from 178 to 208 ° C. and can be regarded as stable in accordance with the requirements of the automotive industry.
Gegenstand der vorliegenden Erfindung sind im Einzelnen:The present invention specifically relates to:
Thermische Frühzündmittel, die als Komponente Dipikrylaminoethylnitrat (DPN) in Gewichtsanteilen von 10 bis100 % enthalten.Thermal pre-ignition devices that contain dipicrylaminoethyl nitrate (DPN) in a proportion by weight of 10 to 100%.
Thermische Frühzündmittel, die neben DPN stickstoffhaltige Verbindungen, einzeln oder in Mischungen, in Gewichtsanteilen von 0 bis 90 % enthalten, wie beispiels- weise Nitroguanidin, Nitroaminoguanidin, Nitrotriazolon, Derivate des Tetrazols wie 5-Aminotetrazol, Ditetrazolylamin, Ditetrazol und deren Salze, Nitraminotetrazol und seine Salze wie Ammonium-Nitraminotetrazol und Aminoguanidinium-Nitraminotetra- zol, Aminoguanidinnitrat, Diaminoguanidinnitrat, Triaminoguanidinnitrat, Guanidinni- trat, Dicyandiamidinnitrat, Diaminoguanidin-Azotetrazolat.Thermal pre-ignition agents which, in addition to DPN, contain nitrogen-containing compounds, individually or in mixtures, in parts by weight of 0 to 90%, such as, for example, nitroguanidine, nitroaminoguanidine, nitrotriazolone, derivatives of tetrazole such as 5-aminotetrazole, ditetrazolylamine, ditetrazole and its salts, nitraminotetrazole and its salts such as ammonium-nitraminotetrazole and aminoguanidinium-nitraminotetrazole, aminoguanidine nitrate, diaminoguanidine nitrate, triaminoguanidine nitrate, guanidinediamine dinitrate, guanidinediamine dinitrate, guanidinediamine dinitrate, guanidinediaminitride.
Thermische Frühzündmittel, die neben DPN und den oben genannten stickstoffhaltigen Verbindungen, einzeln oder in Mischungen, Oxidationsmittel, einzeln oder in Mischungen, in Gewichtsanteilen von 10 bis 90 % enthalten, wie beispielsweise Nitrate der Alkali- oder Erdalkalimetalle oder des Ammoniums wie Natriumnitrat oder Kaliumnitrat, Perchlorate der Alkali- oder Erdalkalimetalle oder des Ammoniums, Peroxide der Erdalkalimetalle oder des Zinks.Thermal pre-ignition agents which, in addition to DPN and the above-mentioned nitrogen-containing compounds, individually or in mixtures, contain oxidizing agents, individually or in mixtures, in proportions by weight of 10 to 90%, such as, for example, nitrates of the alkali or alkaline earth metals or of ammonium, such as sodium nitrate or potassium nitrate, Perchlorates of alkali or alkaline earth metals or ammonium, peroxides of alkaline earth metals or zinc.
Thermische Frühzündmittel, die neben DPN, den oben genannten stickstoffhaltigen Verbindungen, einzeln oder in Mischungen und/oder den oben genannten Oxidationsmitteln, einzeln oder in Mischungen, Reduktionsmittel, einzeln oder in Mischungen, in Gewichtsanteilen von 1 bis 80 % enthalten, wie beispielsweise Aluminium, Titan, Titanhydrid, Bor, Borhydrid, Zirkon, Zirkonhydrid, Silicium, Graphit, Aktivkohle, Ruß.Thermal pre-ignition agents which, in addition to DPN, the above-mentioned nitrogen-containing compounds, individually or in mixtures and / or the above-mentioned oxidizing agents, individually or in mixtures, contain reducing agents, individually or in mixtures, in parts by weight of 1 to 80%, such as aluminum, Titan, titanium hydride, boron, borohydride, zircon, zircon hydride, silicon, graphite, activated carbon, carbon black.
Thermische Frühzündmittel, die neben DPN, den oben genannten stickstoffhaltigen Verbindungen, einzeln oder in Mischungen, den oben genannten Oxidationsmitteln, einzeln oder in Mischungen und/oder den oben genannten Reduktionsmitteln, ein- zeln oder in Mischungen, Bindemittel, einzeln oder in Mischungen, in Gewichtsanteilen von 1 bis 80 % enthalten, wie beispielsweise Cellulose sowie deren Derivate, Polyvinylbutyrale, Polynitropolyphenylen, Polynitrophenylether, Plexigum, Polyvi- nylacetat und Copolymere.Thermal pre-ignition agents which, in addition to DPN, the above-mentioned nitrogen-containing compounds, individually or in mixtures, the above-mentioned oxidizing agents, individually or in mixtures and / or the above-mentioned reducing agents, individually or in mixtures, binders, individually or in mixtures Containing parts by weight from 1 to 80%, such as cellulose and its derivatives, polyvinyl butyrals, polynitropolyphenylene, polynitrophenyl ether, plexigum, polyvinyl acetate and copolymers.
Thermische Frühzündmittel, die neben DPN, den oben genannten stickstoffhaltigen Verbindungen, einzeln oder in Mischungen, den oben genannten Oxidationsmitteln, einzeln oder in Mischungen, den oben genannten Reduktionsmitteln, einzeln oder in Mischungen und/oder den oben genannten Bindemitteln, einzeln oder in Mischungen, energetische Zusätze, einzeln oder in Mischungen, in Gewichtsanteilen von 10 bis 80 % enthalten, wie beispielsweise. Hexogen, Oktogen und Nitrocellulose.Thermal pre-ignition agents which, in addition to DPN, the above-mentioned nitrogen-containing compounds, individually or in mixtures, the above-mentioned oxidizing agents, individually or in mixtures, the above-mentioned reducing agents, individually or in mixtures and / or the above-mentioned binders, individually or in mixtures, energetic additives, individually or in mixtures, in proportions by weight of 10 to 80%, such as. Hexogen, octogen and nitrocellulose.
Thermische Frühzündmittel, die neben DPN, den oben genannten stickstoffhaltigen Verbindungen, einzeln oder in Mischungen, den oben genannten Oxidationsmitteln, einzeln oder in Mischungen, den oben genannten Reduktionsmitteln, einzeln oder in Mischungen, den oben genannten Bindemitteln, einzeln oder in Mischungen und/oder den oben genannten energetischen Zusätzen, einzeln oder in Mischungen, Abbrandmoderatoren und Verarbeitungshilfen, einzeln oder in Mischungen, in Gewichtsanteilen von 0,1 bis 20 % enthalten, wie beispielsweise Ferrocen und Derivate, Acetonylacetate, Salicylate, Silikate, Kieselgele, Bornitrid. Thermal pre-ignition agents which, in addition to DPN, the above-mentioned nitrogen-containing compounds, individually or in mixtures, the above-mentioned oxidizing agents, individually or in mixtures, the above-mentioned reducing agents, individually or in Mixtures, the abovementioned binders, individually or in mixtures and / or the abovementioned energetic additives, individually or in mixtures, combustion moderators and processing aids, individually or in mixtures, in parts by weight of 0.1 to 20%, such as ferrocene and derivatives , Acetonylacetates, salicylates, silicates, silica gels, boron nitride.

Claims

Patentansprüche claims
1. Thermische Frühzündmittel für Gasgeneratoren, dadurch gekennzeichnet, dass sie 10 bis 100 Gew.% Dipikrylaminoethylnitrat enthalten.1. Thermal pre-ignition means for gas generators, characterized in that they contain 10 to 100 wt.% Dipikrylaminoethylnitrrat.
2. Thermische Frühzündmittel nach Anspruch 1 , dadurch gekennzeichnet, dass sie 0 bis 90 Gew.% eines Zusatzstoffes oder mehrerer Zusatzstoffe enthalten.2. Thermal pre-ignition device according to claim 1, characterized in that it contains 0 to 90% by weight of one or more additives.
3. Thermische Frühzündmittel nach Anspruch 2, dadurch gekennzeichnet, dass die Zusatzstoffe ausgewählt sind aus: Nitroguanidin, Nitroaminoguanidin, Nitrotriazo- lon, Derivate des Tetrazols und/oder deren Salze, Nitraminotetrazol und/oder seine Salze, Aminoguanidinnitrat, Diaminoguanidinnitrat, Triaminoguanidinnitrat, Guanidinnitrat, Dicyandiamidinnitrat, Diaminoguanidin-Azotetrazolat; Nitrate der Alkali- und/oder Erdalkalimetalle und/oder des Ammoniums, Perchlorate der Alkali- und/oder Erdalkalimetalle und/oder des Ammoniums, Peroxide der Erdalkalimetalle und/oder des Zinks; Aluminium, Titan, Titanhydrid, Bor, Borhydrid, Zirkon, Zirkonhydrid, Silicium, Graphit, Aktivkohle, Ruß; Cellulose und/oder deren Derivate, Polyvinylbutyrale, Polynitropolyphenylen, Polynitrophenylether, Plexi- gum, Polyvinylacetat und Copolymere; Hexogen, Oktogen; Ferrocen und/oder deren Derivate, Acetonylacetate, Salicylate, Silikate, Kieselgele, Bornitrid.3. Thermal pre-ignition device according to claim 2, characterized in that the additives are selected from: nitroguanidine, nitroaminoguanidine, nitrotriazo-lon, derivatives of tetrazole and / or their salts, nitraminotetrazole and / or its salts, aminoguanidine nitrate, diaminoguanidine nitrate, triaminoguanidine nitrate, guanan Dicyandiamidine nitrate, diaminoguanidine azotetrazolate; Nitrates of alkali and / or alkaline earth metals and / or ammonium, perchlorates of alkali and / or alkaline earth metals and / or ammonium, peroxides of alkaline earth metals and / or zinc; Aluminum, titanium, titanium hydride, boron, borohydride, zirconium, zirconium hydride, silicon, graphite, activated carbon, carbon black; Cellulose and / or its derivatives, polyvinyl butyrals, polynitropolyphenylene, polynitrophenyl ether, perspex, polyvinyl acetate and copolymers; Hexogen, octogen; Ferrocene and / or their derivatives, acetonylacetates, salicylates, silicates, silica gels, boron nitride.
4. Thermische Frühzündmittel nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass sie 10 bis 90 Gew.%, vorzugsweise 25 bis 75 Gew.%, besonders bevorzugt 40 bis 60 Gew.% Dipikrylaminoethylnitrat und 10 bis 90 Gew.%, vorzugsweise 25 bis 75 Gew.%, besonders bevorzugt 40 bis 60 Gew.% eines Oxidationsmittels enthalten.4. Thermal pre-ignition agent according to one or more of claims 1 to 3, characterized in that it contains 10 to 90% by weight, preferably 25 to 75% by weight, particularly preferably 40 to 60% by weight of dipicrylaminoethyl nitrate and 10 to 90% by weight , preferably 25 to 75% by weight, particularly preferably 40 to 60% by weight of an oxidizing agent.
5. Thermische Frühzündmittel nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass sie 10 bis 90 Gew.%, vorzugsweise 10 bis 50 Gew.%, besonders bevorzugt 10 bis 30 Gew.% Dipikrylaminoethylnitrat, 10 bis 90 Gew.%, vorzugsweise 10 bis 60 Gew.%, besonders bevorzugt 20 bis 40 Gew.% einer stickstoffhaltigen Verbindung und 10 bis 90 Gew.%, vorzugsweise 25 bis 75 Gew.%, besonders bevorzugt 40 bis 60 Gew.% eines Oxidationsmittels enthalten.5. Thermal pre-ignition device according to one or more of claims 1 to 4, characterized in that it contains 10 to 90 wt.%, Preferably 10 to 50 wt.%, Particularly preferably 10 to 30 wt.% Dipicrylaminoethyl nitrate, 10 to 90 wt.% , preferably 10 to 60% by weight, particularly preferably 20 to 40% by weight of a nitrogen-containing compound and 10 to 90% by weight, preferably 25 to 75% by weight, particularly preferably 40 to 60% by weight of an oxidizing agent.
6. Thermische Frühzündmittel nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das Oxidationsmittel ausgewählt ist aus einem oder mehreren der Nitrate der Alkali- und/oder Erdalkalimetalle und/oder des Ammoniums, der Perchlorate der Alkali- und/oder Erdalkalimetalle und/oder des Ammoniums, der Peroxide der Erdalkalimetalle und/oder des Zinks.6. Thermal pre-ignition device according to one or more of claims 1 to 5, characterized in that the oxidizing agent is selected from one or more of the nitrates of the alkali and / or alkaline earth metals and / or of ammonium, the perchlorates of the alkali and / or alkaline earth metals and / or of ammonium, the peroxides of the alkaline earth metals and / or zinc.
7. Thermische Frühzündmittel nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die stickstoffhaltige Verbindung ausgewählt ist aus einem oder mehreren von Nitroguanidin, Nitroaminoguanidin, Nitrotriazolon, Derivate des Tetrazols und/oder deren Salze, Nitraminotetrazol und/oder seine Salze, Aminoguanidinnitrat, Diaminoguanidinnitrat, Triaminoguanidinnitrat, Guanidinni- trat, Dicyandiamidinnitrat, Diaminoguanidin-azotetrazolat.7. Thermal pre-ignition device according to one or more of claims 1 to 6, characterized in that the nitrogen-containing compound is selected from one or more of nitroguanidine, nitroaminoguanidine, nitrotriazolone, derivatives of tetrazole and / or their salts, nitraminotetrazole and / or its salts, Aminoguanidine nitrate, diaminoguanidine nitrate, triaminoguanidine nitrate, guanidine nitrate, dicyandiamidine nitrate, diaminoguanidine azotetrazolate.
8. Thermische Frühzündmittel nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass sie 1 bis 80 Gew.%, vorzugsweise 1 bis 40 Gew.%, besonders bevorzugt I bis 15 Gew.% eines Reduktionsmittel enthalten.8. Thermal pre-ignition means according to one or more of claims 1 to 7, characterized in that they contain 1 to 80% by weight, preferably 1 to 40% by weight, particularly preferably I to 15% by weight, of a reducing agent.
9. Thermische Frühzündmittel nach einem oder mehreren der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass das Reduktionsmittel ausgewählt ist aus einem oder mehreren von Aluminium, Titan, Titanhydrid, Bor, Borhydrid, Zirkon, Zirkon- hydrid, Silicium, Graphit, Aktivkohle, Ruß.9. Thermal pre-ignition device according to one or more of claims 1 to 8, characterized in that the reducing agent is selected from one or more of aluminum, titanium, titanium hydride, boron, borohydride, zirconium, zirconium hydride, silicon, graphite, activated carbon, carbon black ,
10. Thermische Frühzündmittel nach einem oder mehreren der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass sie 1 bis 80 Gew.%, vorzugsweise 1 bis 40 Gew.%, besonders bevorzugt 1 bis 20 Gew.% eines Bindemittels enthalten.10. Thermal pre-ignition means according to one or more of claims 1 to 9, characterized in that they contain 1 to 80 wt.%, Preferably 1 to 40 wt.%, Particularly preferably 1 to 20 wt.% Of a binder.
11. Thermische Frühzündmittel nach einem oder mehreren der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass das Bindemittel ausgewählt ist aus einem oder mehreren von Cellulose und deren Derivate, Polyvinylbutyrale, Polynitropolyphe- nylen, Polynitrophenylether, Plexigum, Polyvinylacetat und Copolymere.11. Thermal pre-ignition device according to one or more of claims 1 to 10, characterized in that the binder is selected from one or more of cellulose and its derivatives, polyvinyl butyrals, polynitropolyphenylene, polynitrophenyl ether, plexigum, polyvinyl acetate and copolymers.
12. Thermische Frühzündmittel nach einem oder mehreren der Ansprüche 1 bis 11 , dadurch gekennzeichnet, dass sie 10 bis 80 Gew.%, vorzugsweise 10 bis 50 Gew.%, besonders bevorzugt 10 bis 30 Gew.% energetische Zusätze enthalten. 12. Thermal pre-ignition means according to one or more of claims 1 to 11, characterized in that they contain 10 to 80 wt.%, Preferably 10 to 50 wt.%, Particularly preferably 10 to 30 wt.% Energetic additives.
13. Thermische Frühzündmittel nach einem oder mehreren der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass die energetischen Zusätze ausgewählt sind aus einem oder mehreren von Hexogen, Oktogen und Nitrocellulose.13. Thermal pre-ignition device according to one or more of claims 1 to 12, characterized in that the energetic additives are selected from one or more of hexogen, octogen and nitrocellulose.
14. Thermische Frühzündmittel nach einem oder mehreren der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass sie 0,1 bis 20 Gew.%, vorzugsweise 0,1 bis 10 Gew.% Abbrandmoderatoren und Verarbeitungshilfen enthalten.14. Thermal pre-ignition means according to one or more of claims 1 to 13, characterized in that they contain 0.1 to 20% by weight, preferably 0.1 to 10% by weight, of combustion moderators and processing aids.
15. Thermische Frühzündmittel nach einem oder mehreren der Ansprüche 1 bis 14, dadurch gekennzeichnet, dass die Abbrandmoderatoren und Verarbeitungshilfen ausgewählt sind aus einem oder mehreren von Ferrocen und dessen Derivate, Acetonylacetate, Salicylate, Silikate, Kieselgele und Bornitrid.15. Thermal pre-ignition device according to one or more of claims 1 to 14, characterized in that the combustion moderators and processing aids are selected from one or more of ferrocene and its derivatives, acetonylacetates, salicylates, silicates, silica gels and boron nitride.
16. Verwendung eines thermischen Frühzündmittels nach einem oder mehreren der Ansprüche 1 bis 15 als thermische Sicherung in Gasgeneratoren für Kraftfahrzeugsicherheitssysteme. 16. Use of a thermal pre-ignition device according to one or more of claims 1 to 15 as a thermal fuse in gas generators for motor vehicle safety systems.
EP04820421A 2003-12-17 2004-12-07 Thermal pre-ignition agents Expired - Lifetime EP1697277B1 (en)

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US1935495A (en) * 1931-01-22 1933-11-14 Atlas Powder Co Slow match composition
US3320882A (en) 1964-09-01 1967-05-23 Du Pont High velocity ignition-propagating cord
US3734476A (en) * 1971-09-13 1973-05-22 United Aircraft Corp Cutting torch
US4379007A (en) * 1981-03-16 1983-04-05 The United States Of America As Represented By The Secretary Of The Army Catalysts for nitramine propellants
JPH07232613A (en) * 1993-12-28 1995-09-05 Nippon Kayaku Co Ltd Gas generator for air bag and squib

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AU2004299219A1 (en) 2005-06-30
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NO337562B1 (en) 2016-05-09
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WO2005058775A1 (en) 2005-06-30
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US20080043385A1 (en) 2008-02-21
JP5044219B2 (en) 2012-10-10
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IL176299A0 (en) 2006-10-05
NO20063259L (en) 2006-09-14

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