EP3218330A1 - Thermal pre-ignition agent - Google Patents

Thermal pre-ignition agent

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Publication number
EP3218330A1
EP3218330A1 EP15801695.6A EP15801695A EP3218330A1 EP 3218330 A1 EP3218330 A1 EP 3218330A1 EP 15801695 A EP15801695 A EP 15801695A EP 3218330 A1 EP3218330 A1 EP 3218330A1
Authority
EP
European Patent Office
Prior art keywords
thermal
ignition
nitrate
thermal pre
frühzündmittels
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP15801695.6A
Other languages
German (de)
French (fr)
Inventor
Aleksej Hoschenko
Ulrich Bley
Peter Simon Lechner
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.)
RWS GmbH
Original Assignee
RUAG Ammotec GmbH
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Filing date
Publication date
Application filed by RUAG Ammotec GmbH filed Critical RUAG Ammotec GmbH
Publication of EP3218330A1 publication Critical patent/EP3218330A1/en
Withdrawn legal-status Critical Current

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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
    • C06B25/04—Compositions containing a nitrated organic compound the nitrated compound being an aromatic
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D273/00—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00
    • C07D273/02—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00 having two nitrogen atoms and only one oxygen atom

Definitions

  • the subject of the present invention is a thermal pre-ignition agent.
  • Thermal ignition agents in the context of the invention are pyrotechnic substances or mixtures which have ignition temperatures below 200 ° C. Areas of application of such thermal pre-ignition agents are, for example, safety systems, preferably thermal fuses in gas generators or separating elements for batteries. Such security systems are again preferably used in motor vehicles.
  • the thermal pre-ignition agents are used to ignite the generally thermally very stable gas-generating mixtures of a gas generator in the event of a vehicle fire controlled.
  • Thermal pre-ignition agents are also used as a pyrotechnic set in separating elements, preferably for battery terminals. These dividing elements should interrupt the power supply in the event of a fire, in particular a vehicle fire, or in a motor vehicle accident in which the gas generator is triggered.
  • nitrocellulose-containing thermal ignition agent and derived propellant charge powder have ignition temperatures of about 160 ° C and are insufficiently long-term stability.
  • the document DE 197 30 873 A1 describes mixtures based on nitrotriazolone and guanidine nitrate which are nitrocellulose-free.
  • WO 99/41213 discloses early ignition powders which, even after hot storage for 400 hours at 107 ° C., show a weight loss of ⁇ 3% by weight and an autoignition temperature (decomposition temperature) in the range between 150 ° C. and 200 ° C. to sit.
  • Object of the present invention is to provide an alternative thermal ignition agent with a deflagration ⁇ 180 ° C, a friction sensitivity> 250 N, a shock sensitivity> 3 J and a long-term stability expressed as weight loss ⁇ 1 wt .-% after hot storage at 125 ° C 1000 hours.
  • ignition temperature, autoignition temperature, decomposition temperature and deflagration temperature are used as synonyms for the purposes of the present invention.
  • a further object of the present invention was to provide a thermal pre-ignition agent which can be used for gas generators in motor vehicle safety systems or in separator elements for battery terminals.
  • this object is surprisingly achieved by the features of the main claim.
  • Preferred embodiments can be found in the subclaims.
  • mixtures of 20 to 50 wt .-% dinitrobenzofuroxan (DNBF) with 50 to 80 wt .-% of an oxidizing agent and a nitrogen-containing compound can control the deflagration temperatures in the range of 140 ° C to 175 ° C.
  • the deflagration temperatures of the mixtures may be lower than those of individual components.
  • the melting point or decomposition point of pure DNBF is for example about 170 ° C.
  • the oxidants and nitrogenous compounds are selected from the groups consisting of: 1. Oxidizing agents (individually or in mixtures)
  • Nitrates of alkali or alkaline earth metals or ammonium such as sodium, potassium or ammonium nitrate, perchlorates of alkali or alkaline earth metals or of ammonium, peroxides of alkali or alkaline earth metals or zinc.
  • Nitrogen-containing compounds (individually or in mixtures)
  • tetrazole such as 5-aminote
  • additives may be included, selected from the groups consisting of: 3. Reducing agents (individually or in mixtures)
  • Binders (individually or in mixtures)
  • Burn-off moderators, stabilizers and processing aids (individually or in mixtures)
  • Ferrocene and derivatives acetonyl acetates, salicylates, barium carbonate, strontium carbonate, magnesium carbonate, melamine, zinc oxide, zinc carbonate, silicates, silica gels, silicas, boron nitride.
  • the production and processing takes place according to known and customary methods. These include, for example, kneading, extrusion, extrusion, tableting or granulation.
  • the subject of the present invention is: a thermal pre-ignition agent containing as components 20 to 50% by weight of dinitrobenzofuroxan and 50 to 80% by weight of an oxidizing agent and a nitrogen-containing compound;
  • thermal preignition agent containing from 30 to 70% by weight of an oxidizing agent selected from one or more of the nitrates of the alkali and / or alkaline earth metals and / or ammonium, the perchlorates of the alkali and / or alkaline earth metals and / or of the Ammonium, the peroxides of the alkali and / or alkaline earth metals and / or zinc; a thermal preignition agent containing from 10 to 50% by weight of a nitrogenous compound selected from one or more of ammonium picrate, aminoguanidinium picrate, guanidinium picrate, aminoguanidinium stannate, guanidinium styrenate, nitroguanidine, nitroaminoguanidine, nitrotriazolone, derivatives of tetrazole and / or their salts, nitraminotetrazole and / or its salts, amino guanidine nitrate, diamino-gu
  • thermal preignition agent containing from 1 to 15% by weight of a reducing agent selected from one or more of aluminum, titanium, titanium hydride, boron, borohydride, zirconium, zirconium hydride, silicon, graphite, activated carbon, carbon black;
  • thermal pre-ignition agent containing from 1 to 20% by weight of a binder selected from one or more of cellulose and derivatives thereof, polyvinyl butyrals, polynitropolyphenylene, polynitrophenyl ether, plexigum, polyvinyl acetate and its copolymers; a thermal pre-ignition agent containing from 0.1 to 15% by weight, more preferably from 1 to 10% by weight, of burnout moderators and processing aids selected from one or more of ferrocene and its derivatives, acetonylacetates, salicylates, barium carbonate, strontium carbonate , Magnesium carbonate, melamine, zinc oxide, zinc carbonate, silicates, silica gels and / or boron nitride; - Use of the thermal Appelzündffens invention as a thermal fuse;
  • Table 1 lists the compositions of 6 different mixtures of thermal pre-ignition agent. The components were weighed in the stated weight ratios (in percent by weight (% by weight)) in plastic containers and homogenized in a tumble mixer for 30 minutes.
  • Table 2 shows the deflagration points, friction and impact sensitivities of the mixtures.
  • the measurement of the friction and impact sensitivities was carried out according to methods of the Federal Institute for Materials Research (BAM), while the measurement of the deflagration points was carried out with the thermogravimetric analysis (Mettler) at a heating rate of 10 ° C. per minute.
  • Table 2 Overview of the deflagration temperatures, friction and impact sensitivities
  • Table 3 summarizes the weight losses and deflagration points after thermal stress (24 h, 125 ° C and 400 h, 110 ° C) of some of the mixtures selected from the examples.
  • the weight loss was measured analogously to the Holland test.
  • the measurement of the deflagration points was carried out by thermogravimetric analysis (Mettler) at a heating rate of 10 ° C. per minute.

Abstract

The invention relates to a thermal pre-ignition agent which contains as components 20 to 50 wt.% of dinitrobenzofuroxane and 50 to 80 wt.% of an oxidizing agent and a nitrogen-containing compound.

Description

Thermisches Frühzündmittel  Thermal pre-ignition agent
Gegenstand der vorliegenden Erfindung ist ein thermisches Frühzündmittel. The subject of the present invention is a thermal pre-ignition agent.
Thermische Frühzündmittel im Sinne der Erfindung sind pyrotechnische Stoffe oder Stoffgemische, die Entzündungstemperaturen unterhalb 200°C besitzen. Anwendungsbereiche solcher thermischen Frühzündmittel sind beispielsweise Sicherheitssysteme, vorzugsweise thermische Sicherungen in Gasgeneratoren oder Trennelemente für Batterien. Solche Sicherheitssysteme werden wiederum vorzugsweise in Kraftfahrzeugen eingesetzt. Thermal ignition agents in the context of the invention are pyrotechnic substances or mixtures which have ignition temperatures below 200 ° C. Areas of application of such thermal pre-ignition agents are, for example, safety systems, preferably thermal fuses in gas generators or separating elements for batteries. Such security systems are again preferably used in motor vehicles.
Die thermischen Frühzündmittel werden eingesetzt, um die in der Regel thermisch sehr stabilen Gas erzeugenden Mischungen eines Gasgenerators im Falle eines Fahrzeugbrandes kontrolliert anzuzünden. The thermal pre-ignition agents are used to ignite the generally thermally very stable gas-generating mixtures of a gas generator in the event of a vehicle fire controlled.
Thermische Frühzündmittel werden auch verwendet als pyrotechnischer Satz in Trennelementen, vorzugsweise für Batterieklemmen. Diese Trennelemente sollen im Falle eines Brandes, insbesondere eines Fahrzeugbrandes, oder bei einem Kraft- fahrzeugunfall, bei dem der Gasgenerator ausgelöst wird, die Stromversorgung unterbrechen. Thermal pre-ignition agents are also used as a pyrotechnic set in separating elements, preferably for battery terminals. These dividing elements should interrupt the power supply in the event of a fire, in particular a vehicle fire, or in a motor vehicle accident in which the gas generator is triggered.
Der Nachteil Nitrocellulose enthaltener thermischer Frühzündmittel und daraus abgeleitete Treibladungspulver besteht darin, dass diese Mischungen Entzündungstemperaturen von ca. 160°C besitzen und unzureichend langzeitstabil sind. Im Dokument DE 197 30 873 A1 werden Mischungen auf Basis von Nitrotriazolon und Guanidin- nitrat beschrieben, die nitrocellulosefrei sind. Weiterhin sind aus dem Dokument WO 99/41213 Frühzündpulver bekannt, die selbst nach Warmlagerung über 400 Stunden bei 107°C einen Gewichtsverlust < 3 Gew.-% zeigen und eine Selbstentzündungstemperatur (Zersetzungstemperatur) im Bereich zwischen 150°C und 200°C be- sitzen. The disadvantage of nitrocellulose-containing thermal ignition agent and derived propellant charge powder is that these mixtures have ignition temperatures of about 160 ° C and are insufficiently long-term stability. The document DE 197 30 873 A1 describes mixtures based on nitrotriazolone and guanidine nitrate which are nitrocellulose-free. Furthermore, WO 99/41213 discloses early ignition powders which, even after hot storage for 400 hours at 107 ° C., show a weight loss of <3% by weight and an autoignition temperature (decomposition temperature) in the range between 150 ° C. and 200 ° C. to sit.
Aufgabe der vorliegenden Erfindung ist die Bereitstellung eines alternativen thermischen Frühzündmittels mit einer Verpuffungstemperatur < 180°C, einer Reibempfindlichkeit > 250 N, einer Schlagempfindlichkeit > 3 J und einer Langzeitstabilität ausgedrückt als Gewichtsverlust < 1 Gew.-% nach Warmlagerungen bei 125°C über 1000 Stunden. Die Begriffe Entzündungstemperatur, Selbstentzündungstemperatur, Zersetzungstemperatur und Verpuffungstemperatur werden im Sinne der vorliegenden Erfindung als Synonyme gebraucht. Object of the present invention is to provide an alternative thermal ignition agent with a deflagration <180 ° C, a friction sensitivity> 250 N, a shock sensitivity> 3 J and a long-term stability expressed as weight loss <1 wt .-% after hot storage at 125 ° C 1000 hours. The terms ignition temperature, autoignition temperature, decomposition temperature and deflagration temperature are used as synonyms for the purposes of the present invention.
Eine weitere Aufgabe der vorliegenden Erfindung war die Bereitstellung eines ther- mischen Frühzündmittels, das für Gasgeneratoren in Kraftfahrzeugsicherheitssystemen oder in Trennelementen für Batterieklemmen eingesetzt werden kann. A further object of the present invention was to provide a thermal pre-ignition agent which can be used for gas generators in motor vehicle safety systems or in separator elements for battery terminals.
Erfindungsgemäß wird diese Aufgabe überraschenderweise durch die Merkmale des Hauptanspruchs gelöst. Vorzugsweise Ausgestaltungen finden sich in den Unteransprüchen. Überraschenderweise wurde gefunden, dass sich bei Mischungen von 20 bis 50 Gew.-% Dinitrobenzofuroxan (DNBF) mit 50 bis 80 Gew.-% eines Oxidationsmittels und einer stickstoffhaltigen Verbindung die Verpuffungstemperaturen im Bereich von 140°C bis 175°C steuern lassen. Die Verpuffungstemperaturen der Mischungen können tiefer liegen als die von Einzel komponenten. Der Schmelzpunkt bzw. Zersetzungpunkt von reinen DNBF beträgt beispielsweise ca. 170°C. According to the invention, this object is surprisingly achieved by the features of the main claim. Preferred embodiments can be found in the subclaims. Surprisingly, it has been found that mixtures of 20 to 50 wt .-% dinitrobenzofuroxan (DNBF) with 50 to 80 wt .-% of an oxidizing agent and a nitrogen-containing compound can control the deflagration temperatures in the range of 140 ° C to 175 ° C. The deflagration temperatures of the mixtures may be lower than those of individual components. The melting point or decomposition point of pure DNBF is for example about 170 ° C.
Die Oxidationsmittel und stickstoffhaltigen Verbindunge werden ausgewählt aus den Gruppen bestehend aus: 1. Oxidationsmittel (einzeln oder in Mischungen) The oxidants and nitrogenous compounds are selected from the groups consisting of: 1. Oxidizing agents (individually or in mixtures)
Nitrate der Alkali- oder Erdalkalimetalle oder des Ammoniums wie Natrium-, Kalium- oder Ammoniumnitrat, Perchlorate der Alkali- oder Erdalkalimetalle oder des Ammoniums, Peroxide der Alkali- oder Erdalkalimetalle oder des Zinks.  Nitrates of alkali or alkaline earth metals or ammonium such as sodium, potassium or ammonium nitrate, perchlorates of alkali or alkaline earth metals or of ammonium, peroxides of alkali or alkaline earth metals or zinc.
2. Stickstoffhaltige Verbindungen (einzeln oder in Mischungen) 2. Nitrogen-containing compounds (individually or in mixtures)
Ammoniumpikrat, Aminoguanidiniumpikrat, Guanidiniumpikrat, Aminoguanidini- umstyphnat, Guanidiniumstyphnat, Nitroguanidin, Nitroaminoguanidin, Nitrotri- azolon, Derivate des Tetrazols wie 5-Aminotetrazol, Ditetrazolylamin, Ditetrazol und dessen Salze, Nitraminotetrazol und dessen Salze wie Ammonium-Nitrami- notetrazolat und Aminoguanidinium-Nitraminotetrazolat, Aminoguanidinnitrat, Di- aminoguanidinnitrat, Triaminoguanidinnitrat, Guanidinnitrat, Dicyandiamidinnitrat, Diaminoguanidin-Azotetrazolat, Triam inoguanidin-Azotetrazolat oder Ammonium- Azotetrazolat. Ammonium picrate, aminoguanidinium picrate, guanidinium picrate, aminoguanidinium metyphenate, guanidinium typhnate, nitroguanidine, nitroaminoguanidine, nitrotriazolone, derivatives of tetrazole such as 5-aminotetrazole, ditetrazolylamine, ditetrazole and its salts, nitraminotetrazole and its salts such as ammonium nitramethytetrazolate and aminoguanidinium nitraminotetrazolate, Aminoguanidine nitrate, diaminoguanidine nitrate, triaminoguanidine nitrate, guanidine nitrate, dicyandiamide nitrate, Diaminoguanidine azotetrazolate, triamine inoguanidine azotetrazolate or ammonium azotetrazolate.
Weitere Zusatzstoffe können enthalten sein, ausgewählt aus den Gruppen bestehend aus: 3. Reduktionsmittel (einzeln oder in Mischungen) Other additives may be included, selected from the groups consisting of: 3. Reducing agents (individually or in mixtures)
Aluminium, Titan, Titanhydrid, Bor, Borhydrid, Zirkon, Zirkonhydrid, Silicium, Graphit, Aktivkohle, Ruß.  Aluminum, titanium, titanium hydride, boron, borohydride, zirconium, zirconium hydride, silicon, graphite, activated carbon, carbon black.
4. Bindemittel (einzeln oder in Mischungen) 4. Binders (individually or in mixtures)
Cellulose sowie deren Derivate, Polyvinylbutyrale, Polynitropolyphenylen, Poly- nitrophenylether, Plexigum, Polyvinylacetat, Copolymere.  Cellulose and derivatives thereof, polyvinyl butyrals, Polynitropolyphenylen, poly nitrophenyl ether, Plexigum, polyvinyl acetate, copolymers.
5. Abbrandmoderatoren, Stabilisatoren und Verarbeitungshilfen (einzeln oder in Mischungen) 5. Burn-off moderators, stabilizers and processing aids (individually or in mixtures)
Ferrocen und Derivate, Acetonylacetate, Salicylate, Bariumcarbonat, Stron- tiumcarbonat, Magnesiumcarbonat, Melamin, Zinkoxid, Zinkcarbonat, Silikate, Kieselgele, Kieselsäuren, Bornitrid.  Ferrocene and derivatives, acetonyl acetates, salicylates, barium carbonate, strontium carbonate, magnesium carbonate, melamine, zinc oxide, zinc carbonate, silicates, silica gels, silicas, 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, for example, kneading, extrusion, extrusion, tableting or granulation.
Gegenstand der vorliegenden Erfindung ist im Einzelnen: - ein thermisches Frühzündmittel, welches als Komponenten 20 bis 50 Gew.-% Dinitrobenzofuroxan und 50 bis 80 Gew.-% eines Oxidationsmittels und einer stickstoffhaltigen Verbindung enthält; Specifically, the subject of the present invention is: a thermal pre-ignition agent containing as components 20 to 50% by weight of dinitrobenzofuroxan and 50 to 80% by weight of an oxidizing agent and a nitrogen-containing compound;
- ein thermisches Frühzündmittel, das 30 bis 70 Gew.-% eines Oxidationsmittels enthält, ausgewählt 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 Alkali- und/oder Erdalkalimetalle und/oder des Zinks; - ein thermisches Frühzündmittel, das 10 bis 50 Gew.-% einer stickstoffhaltigen Verbindung enthält, ausgewählt aus einem oder mehreren von Ammoniumpikrat, Aminoguanidiniumpikrat, Guanidiniumpikrat, Aminoguanidiniumstyphnat, Guanidi- niumstyphnat, Nitrogua-'nidin, Nitroaminoguanidin, Nitrotriazolon, Derivate des Tetrazols und/oder deren Salze, Nitraminotetrazol und/oder dessen Salze, Amino- guanidinnitrat, Diamino-'guanidinnitrat, Triaminoguanidinnitrat, Guanidinnitrat, Dicyandiamidinnitrat, Diaminoguanidin-azotetrazolat; a thermal preignition agent containing from 30 to 70% by weight of an oxidizing agent selected from one or more of the nitrates of the alkali and / or alkaline earth metals and / or ammonium, the perchlorates of the alkali and / or alkaline earth metals and / or of the Ammonium, the peroxides of the alkali and / or alkaline earth metals and / or zinc; a thermal preignition agent containing from 10 to 50% by weight of a nitrogenous compound selected from one or more of ammonium picrate, aminoguanidinium picrate, guanidinium picrate, aminoguanidinium stannate, guanidinium styrenate, nitroguanidine, nitroaminoguanidine, nitrotriazolone, derivatives of tetrazole and / or their salts, nitraminotetrazole and / or its salts, amino guanidine nitrate, diamino-guanidine nitrate, triaminoguanidine nitrate, guanidine nitrate, dicyandiamidine nitrate, diaminoguanidine azotetrazolate;
- ein thermisches Frühzündmittel, welches 1 bis 15 Gew.-% eines Reduktionsmittel enthält, ausgewählt aus einem oder mehreren von Aluminium, Titan, Titanhydrid, Bor, Borhydrid, Zirkon, Zirkonhydrid, Silicium, Graphit, Aktivkohle, Ruß; a thermal preignition agent containing from 1 to 15% by weight of a reducing agent selected from one or more of aluminum, titanium, titanium hydride, boron, borohydride, zirconium, zirconium hydride, silicon, graphite, activated carbon, carbon black;
- ein thermisches Frühzündmittel, das 1 bis 20 Gew.-% eines Bindemittels enthält, ausgewählt aus einem oder mehreren von Cellulose und deren Derivaten, Poly- vinylbutyrale, Polynitropolyphenylen, Polynitrophenylether, Plexigum, Poly- vinylacetat und dessen Copolymere; - ein thermisches Frühzündmittel, welches 0,1 bis 15 Gew.-%, besonders bevorzugt 1 bis 10 Gew.-% Abbrandmoderatoren und Verarbeitungshilfen enthält, ausgewählt aus einem oder mehreren von Ferrocen und dessen Derivaten, Ace- tonylacetaten, Salicylaten, Bariumcarbonat, Strontiumcarbonat, Magnesiumcarbo- nat, Melamin, Zinkoxid, Zinkcarbonat, Silikaten, Kieselgelen und/oder Bornitrid; - Verwendung des erfindungsgemäßen thermischen Frühzündmittels als thermische Sicherung; a thermal pre-ignition agent containing from 1 to 20% by weight of a binder selected from one or more of cellulose and derivatives thereof, polyvinyl butyrals, polynitropolyphenylene, polynitrophenyl ether, plexigum, polyvinyl acetate and its copolymers; a thermal pre-ignition agent containing from 0.1 to 15% by weight, more preferably from 1 to 10% by weight, of burnout moderators and processing aids selected from one or more of ferrocene and its derivatives, acetonylacetates, salicylates, barium carbonate, strontium carbonate , Magnesium carbonate, melamine, zinc oxide, zinc carbonate, silicates, silica gels and / or boron nitride; - Use of the thermal Frühzündmittels invention as a thermal fuse;
- Verwendung des erfindungsgemäßen thermischen Frühzündmittels in Kraftfahrzeugsicherheitssystemen; - Use of the thermal Frühzündmittels invention in automotive safety systems;
- Verwendung des erfindungsgemäßen thermischen Frühzündmittels in Gasgeneratoren; - Use of the thermal Frühzündmittels invention in gas generators;
Verwendung des erfindungsgemäßen thermischen Frühzündmittels in Trennelementen, vorzugsweise für Batterieklemmen. Die Erfindung wird durch die folgenden Beispiele näher erläutert, ohne sie darauf einzuschränken: Use of the thermal Frühzündmittels invention in separating elements, preferably for battery terminals. The invention is explained in more detail by the following examples, without limiting them:
In Tabelle 1 sind die Zusannnnensetzungen von 6 verschiedenen Mischungen des thermischen Frühzündmittels aufgeführt. Die Komponenten wurden in den angege- benen Gewichtsverhältnissen (Angaben in Gewichtsprozent (Gew.-%)) in Plastikbehälter eingewogen und 30 Minuten im Taumelmischer homogenisiert. Table 1 lists the compositions of 6 different mixtures of thermal pre-ignition agent. The components were weighed in the stated weight ratios (in percent by weight (% by weight)) in plastic containers and homogenized in a tumble mixer for 30 minutes.
Tabelle 1 : Mischungen Table 1: Mixtures
Triaminoguanidinnitrat  triaminoguanidine
Aminoguanidinnitrat  aminoguanidine
Nitroguanidin  nitroguanidine
Dicyanodiamindinnitrat  Dicyanodiamindinnitrat
In Tabelle 2 sind die Verpuffungspunkte, Reib- und Schlagempfindlichkeiten der Mi- schungen dargestellt. Die Messung der Reib- und Schlagempfindlichkeiten erfolgte nach Methoden der Bundesanstalt für Materialforschung (BAM), während die Messung der Verpuffungspunkte mit der Thermogravimetrie-Analyse (Fa. Mettler) bei einer Aufheizrate von 10°C pro Minute erfolgte. Table 2 shows the deflagration points, friction and impact sensitivities of the mixtures. The measurement of the friction and impact sensitivities was carried out according to methods of the Federal Institute for Materials Research (BAM), while the measurement of the deflagration points was carried out with the thermogravimetric analysis (Mettler) at a heating rate of 10 ° C. per minute.
Tabelle 2: Ubersicht der Verpuffungstemperaturen, Reib- und Schlagempfindlichkeiten Table 2: Overview of the deflagration temperatures, friction and impact sensitivities
Mischung Verpuffungs- Reibempfind- Schlagern pfind- temperatur [°C] lichkeit [N] lichkeit [J] Mixture Deflagration Friction Sensitivity pfind- temperature [° C] sensitivity [N] [J]
1 158 >360 5 2 167 >360 5 1 158> 360 5 2 167> 360 5
3 145 >360 5  3 145> 360 5
4 150 >360 5  4 150> 360 5
5 172 >360 5  5 172> 360 5
6 170 >360 5  6 170> 360 5
In Tabelle 3 sind die Gewichtsverluste und Verpuffungspunkte nach thermischer Belastung (24 h, 125°C und 400 h, 1 10°C) einiger aus den Beispielen ausgewählter Mischungen zusammengefasst. Die Messung des Gewichtsverlustes erfolgte analog dem Holland Test. Die Messung der Verpuffungspunkte erfolgte mit der Thermogra- vimetrie-Analyse (Fa. Mettler) bei einer Aufheizrate von 10°C pro Minute. Table 3 summarizes the weight losses and deflagration points after thermal stress (24 h, 125 ° C and 400 h, 110 ° C) of some of the mixtures selected from the examples. The weight loss was measured analogously to the Holland test. The measurement of the deflagration points was carried out by thermogravimetric analysis (Mettler) at a heating rate of 10 ° C. per minute.
Man erkennt nach 400 h nur geringe Gewichtsverluste von 0,1 bis 0,7 Gew.-% und keine signifikante Änderung der Verpuffungstemperatur nach thermischer Belastung. It can be seen after 400 h only small weight losses of 0.1 to 0.7 wt .-% and no significant change in the deflagration temperature after thermal stress.
Tabelle 3: Übersicht der Gewichtsverluste und Verpuffungstennperaturen Table 3: Overview of weight loss and deflagration temperatures
Die Ergebnisse zeigen, dass die erfindungsgemäß definierten pyrotechnischen Mittel Verpuffungstemperaturen im Bereich von 172 bis 191 °C aufweisen und gemäß den Forderungen der Automobilindustrie als stabil anzusehen sind. The results show that the pyrotechnic means defined according to the invention have deflagration temperatures in the range of 172 to 191 ° C and are to be regarded as stable according to the requirements of the automotive industry.

Claims

Patentansprüche claims
1 . Thermisches Frühzündmittel, dadurch gekennzeichnet, dass es 20 bis 50 Gew.-% Dinitrobenzofuroxan und 50 bis 80 Gew.-% eines Oxidationsmittels und einer stickstoffhaltigen Verbindung enthält. 1 . Thermal pre-ignition agent, characterized in that it contains 20 to 50 wt .-% dinitrobenzofuroxan and 50 to 80 wt .-% of an oxidizing agent and a nitrogen-containing compound.
2. Thermisches Frühzündmittel nach Anspruch 1 , dadurch gekennzeichnet, dass es 30 bis 70 Gew.-% eines Oxidationsmittels enthält, ausgewählt 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 Alkali- und/oder Erdalkalimetalle und/oder des Zinks. 2. Thermal pre-ignition agent according to claim 1, characterized in that it contains 30 to 70 wt .-% of an oxidizing agent selected from one or more of the nitrates of the alkali and / or alkaline earth metals and / or ammonium, the perchlorates of the alkali and / or alkaline earth metals and / or ammonium, the peroxides of the alkali and / or alkaline earth metals and / or zinc.
3. Thermisches Frühzündmittel nach Anspruch 1 , dadurch gekennzeichnet, dass es 10 bis 50 Gew.-% einer stickstoffhaltigen Verbindung enthält, ausgewählt aus einem oder mehreren von Ammoniumpikrat, Aminoguanidiniumpikrat, Guanidi- niumpikrat, Aminoguanidiniumstyphnat, Guanidiniumstyphnat, Nitroguanidin, Nitroaminoguanidin, Nitrotriazolon, Derivate des Tetrazols und/oder deren Salze, Nitraminotetrazol und/oder dessen Salze, Aminoguanidinnitrat, Diaminoguani- dinnitrat, Triaminoguanidinnitrat, Guanidinnitrat, Dicyandiamidinnitrat, Diamino- guanidin-azotetrazolat. 3. Thermal pre-ignition agent according to claim 1, characterized in that it contains 10 to 50 wt .-% of a nitrogen-containing compound selected from one or more of ammonium picrate, Aminoguanidiniumpikrat, Guanidi- niumpikrat, Aminoguanidiniumstyphnat, Guanidiniumstyphnat, nitroguanidine, nitroaminoguanidine, nitrotriazolone, derivatives of the tetrazole and / or salts thereof, nitraminotetrazole and / or its salts, aminoguanidine nitrate, diaminoguanidine dinitrate, triaminoguanidine nitrate, guanidine nitrate, dicyandiamide nitrate, diamino guanidine azotetrazolate.
4. Thermisches Frühzündmittel nach Anspruch 1 , dadurch gekennzeichnet, dass es 1 bis 15 Gew.-% eines Reduktionsmittel enthält, ausgewählt aus einem oder mehreren von Aluminium, Titan, Titanhydrid, Bor, Borhydrid, Zirkon, Zirkonhydrid, Silicium, Graphit, Aktivkohle, Ruß. 4. Thermal pre-ignition composition according to claim 1, characterized in that it contains 1 to 15 wt .-% of a reducing agent selected from one or more of aluminum, titanium, titanium hydride, boron, borohydride, zirconium, zirconium hydride, silicon, graphite, activated carbon, Soot.
5. Thermisches Frühzündmittel nach Anspruch 1 , dadurch gekennzeichnet, dass es 1 bis 20 Gew.-% eines Bindemittels enthält, ausgewählt aus einem oder mehreren von Cellulose und deren Derivaten, Polyvinylbutyrale, Polynitropolyphenylen, Polynitrophenylether, Plexigum, Polyvinylacetat und dessen Copolymere. 5. Thermal pre-ignition composition according to claim 1, characterized in that it contains 1 to 20 wt .-% of a binder selected from one or more of cellulose and derivatives thereof, polyvinyl butyrals, Polynitropolyphenylen, Polynitrophenylether, Plexigum, polyvinyl acetate and its copolymers.
6. Thermisches Frühzündmittel nach Anspruch 1 , dadurch gekennzeichnet, dass es 0,1 bis 15 Gew.-%, besonders bevorzugt 1 bis 10 Gew.-% Abbrandmoderatoren und Verarbeitungshilfen enthält, ausgewählt aus einem oder mehreren von Fer- rocen und dessen Derivaten, Acetonylacetaten, Salicylaten, Bariumcarbonat, Strontiumcarbonat, Magnesiumcarbonat, Melamin, Zinkoxid, Zinkcarbonat, Silikaten, Kieselgelen und/oder Bornitrid. 6. Thermal pre-ignition composition according to claim 1, characterized in that it contains 0.1 to 15 wt .-%, particularly preferably 1 to 10 wt .-% Abbrandmoderatoren and processing aids selected from one or more of Fer- rocen and its derivatives, Acetonyl acetates, salicylates, barium carbonate, Strontium carbonate, magnesium carbonate, melamine, zinc oxide, zinc carbonate, silicates, silica gels and / or boron nitride.
7. Verwendung eines thermischen Frühzündmittels nach einem oder mehreren der Ansprüche 1 bis 6 als thermische Sicherung. 7. Use of a thermal Frühzündmittels according to one or more of claims 1 to 6 as a thermal fuse.
8. Verwendung eines thermischen Frühzündmittels nach einem oder mehreren der Ansprüche 1 bis 6 in Kraftfahrzeugsicherheitssystemen. 8. Use of a thermal Frühzündmittels according to one or more of claims 1 to 6 in motor vehicle safety systems.
9. Verwendung eines thermischen Frühzündmittels nach einem oder mehreren der Ansprüche 1 bis 6 in Gasgeneratoren. 9. Use of a thermal Frühzündmittels according to one or more of claims 1 to 6 in gas generators.
10. Verwendung eines thermischen Frühzündmittels nach einem oder mehreren der Ansprüche 1 bis 6 in Trennelementen, vorzugsweise für Batterieklemmen. 10. Use of a thermal Frühzündmittels according to one or more of claims 1 to 6 in separating elements, preferably for battery terminals.
EP15801695.6A 2014-11-10 2015-11-10 Thermal pre-ignition agent Withdrawn EP3218330A1 (en)

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EP3523266A4 (en) * 2016-10-05 2020-06-10 Olin Corporation Pyrotechnic compositions
DE102017118416A1 (en) * 2017-08-11 2019-02-14 Ruag Ammotec Gmbh Pyrotechnic separator, system for electrically charging an electric power cell, mobile device and charger
CN114539011B (en) * 2022-02-21 2023-03-28 张延松 Safe and efficient high-energy expanding agent and preparation method and application thereof

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FR2693721B1 (en) * 1992-07-20 1994-10-21 Ncs Pyrotechnie Technologies Priming charge with annular percussion and its manufacturing process.
US20010001970A1 (en) * 1995-10-28 2001-05-31 Rainer Hagel Lead- and barium-free propellant charges
DE19540278A1 (en) * 1995-10-28 1997-04-30 Dynamit Nobel Ag Lead- and barium-free igniters
DE59711752D1 (en) 1996-07-20 2004-08-05 Dynamit Nobel Ag THERMAL FUSE
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