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EP3164375B1 - Pyrotechnisches anzündmittel - Google Patents

Pyrotechnisches anzündmittel Download PDF

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Publication number
EP3164375B1
EP3164375B1 EP15734332.8A EP15734332A EP3164375B1 EP 3164375 B1 EP3164375 B1 EP 3164375B1 EP 15734332 A EP15734332 A EP 15734332A EP 3164375 B1 EP3164375 B1 EP 3164375B1
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EP
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Prior art keywords
additive
pyrotechnic
igniting agent
alkali
agent according
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English (en)
French (fr)
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EP3164375A1 (de
Inventor
Ulrich Bley
Aleksej Hoschenko
Ulf Lawrentz
Peter Simon Lechner
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RWS GmbH
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RUAG Ammotec GmbH
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Priority to HRP20192094TT priority Critical patent/HRP20192094T1/hr
Priority to PL15734332T priority patent/PL3164375T3/pl
Priority to SI201531000T priority patent/SI3164375T1/sl
Priority to RS20191481A priority patent/RS60020B1/sr
Publication of EP3164375A1 publication Critical patent/EP3164375A1/de
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B43/00—Compositions characterised by explosive or thermic constituents not provided for in groups C06B25/00 - C06B41/00
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
    • C06C7/00—Non-electric detonators; Blasting caps; Primers

Definitions

  • the present invention is a pyrotechnic igniter.
  • Pyrotechnic igniters in the context of the invention are substances or mixtures which can develop a pyrotechnic effect.
  • the subject of the present invention is a pyrotechnic igniting agent which can be used in mechanical, electrical or opto-electric ignition systems.
  • a 5,5'-azotetrazolate explosive which comprises an iron, cobalt, nickel, copper, cadmium or guanyl urea salt of a 5,5'-azotetrazole or a mixture of at least one 5,5'-azotetrazolate and at least one bistetrazolyl triazenate or at least one further metal salt or guanyl urea salt of a 5,5'-azotetrazole.
  • the salts described therein are neutral, ie neither acidic nor basic.
  • Zinc and chromium salts of 5,5'-azotetrazole are according to the document DE 102010025104 A1 not storable.
  • tetracene-containing pyrotechnic mixtures are thermally not sufficiently stable, since tetrazene decomposes already at 120 ° C.
  • DE 10 2010 036 950 A1 discloses the use of basic 5,5'-azotetrazolate salts of general formula ([ML m X n ] p + ) q (C 1 N 4 R 1 - ) r , where M is an element of the third-twelfth group of the periodic table in the range of 21-80, as initial explosive.
  • the object of the present invention was to provide a further pyrotechnic igniter.
  • Another object of the present invention was to provide a pyrotechnic igniter which can be used in mechanical, electrical or opto-electric ignition systems.
  • this object is surprisingly achieved by the features of the main claim.
  • novel basic azotetrazolate compounds according to the invention have defoaming temperatures in the range from 180 ° C to 240 ° C, friction sensitivities of 0.1 N to 1.0 N and impact sensitivity of 0.1 J to 0.5 J.
  • the pyrotechnic igniter is one which contains as an additive 10 to 60 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 the ammonium, the peroxides of the alkali and / or alkaline earth metals and / or zinc.
  • 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 the ammonium, the peroxides of the alkali and / or alkaline earth metals and / or zinc.
  • the pyrotechnic igniting agent contains as additive 0 to 10 wt .-% of a sensitizer, preferably tetracene.
  • the pyrotechnic igniting agent according to the invention preferably contains as an additive 0 to 20 wt .-% of a reducing agent selected from one or more of aluminum, antimony sulfide, calcium silicide, titanium, titanium hydride, boron, borohydride, zirconium, zirconium hydride, silicon, graphite, activated carbon, carbon black or Friction agent preferably glass breakage.
  • a reducing agent selected from one or more of aluminum, antimony sulfide, calcium silicide, titanium, titanium hydride, boron, borohydride, zirconium, zirconium hydride, silicon, graphite, activated carbon, carbon black or Friction agent preferably glass breakage.
  • the pyrotechnic igniting agent contains as additive 0.1 to 5 wt .-% of a binder selected from one or more of cellulose and derivatives thereof, polyvinyl butyrals, Polynitropolyphenylen, Polynitrophenylether, Plexigum, polyvinyl acetate and copolymers.
  • a binder selected from one or more of cellulose and derivatives thereof, polyvinyl butyrals, Polynitropolyphenylen, Polynitrophenylether, Plexigum, polyvinyl acetate and copolymers.
  • the pyrotechnic igniting agents according to the invention are used in mechanical, electrical or opto-electric ignition systems.
  • the substances are characterized by lead and barium freedom, a high ignition power, short reaction times and corresponding sensitivities. These features enable a reduction in the mass of explosives needed for safe ignition.
  • Table 1 shows decomposition temperatures, friction and impact sensitivities of selected examples.
  • the measurement of the friction and impact sensitivities was carried out according to methods of the Federal Institute for Materials Research (BAM) in the BAM Report 142 (1987), while the measurement of the decomposition temperatures by differential scanning calorimetry (DSC) (Mettler) at a heating rate of 10 K. per minute took place.
  • BAM Federal Institute for Materials Research
  • DSC differential scanning calorimetry
  • Table 1 lists the compositions of 5 different basic salts of 5,5'-azotetrazole. ⁇ b> Table 1 ⁇ / b> Compositions, deflagration temperatures and friction and impact sensitivities of selected basic salts of 5,5'-azotetrazole. No. Molecular formula T Verp .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Air Bags (AREA)
  • Glass Compositions (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Description

  • Gegenstand der vorliegenden Erfindung ist ein pyrotechnisches Anzündmittel.
  • Pyrotechnische Anzündmittel im Sinne der Erfindung sind Stoffe oder Stoffgemische, die eine pyrotechnische Wirkung entfalten können.
  • Insbesondere Gegenstand der vorliegenden Erfindung ist ein pyrotechnisches Anzündmittel, das in mechanischen, elektrischen oder opto-elektrischen Anzündsystemen eingesetzt werden kann.
  • Aus dem Dokument DE 102010025104 A1 ist ein 5,5'-Azotetrazolat-Sprengstoff bekannt, der ein Eisen-, Kobalt-, Nickel-, Kupfer-, Cadmium- oder Guanylharnstoffsalz eines 5,5'-Azotetrazols oder ein Gemisch aus mindestens einem 5,5'-Azotetrazolat und mindestens einem Bistetrazolyltriazenat oder mindestens einem weiteren Metallsalz oder Guanylharnstoffsalz eines 5,5'-Azotetrazols umfasst. Die dort beschriebenen Salze sind neutral, d.h. weder sauer noch basisch. Zink- und Chromsalze des 5,5'-Azotetrazols sind gemäß dem Dokument DE 102010025104 A1 nicht lagerbeständig. Weiterhin besteht das Problem, dass Tetrazen enthaltende pyrotechnische Gemische thermisch nicht hinreichend stabil sind, da sich Tetrazen bereits bei 120 °C zersetzt.
  • DE 10 2010 036 950 A1 offenbart die Verwendung von basischen 5,5'-Azotetrazolatsalzen mit allgemeiner Summenformel ([MLmXn]p +)q(C1N4R1 -)r, wobei M ein Element der dritten-zwölften Gruppe des Periodensystems mit einer Ordnungszahl im Bereich von 21-80 ist, als Initialsprengstoff.
  • Aufgabe der vorliegenden Erfindung war die Bereitstellung eines weiteren pyrotechnischen Anzündmittels. Eine weitere Aufgabe der vorliegenden Erfindung war die Bereitstellung eines pyrotechnischen Anzündmittels, das in mechanischen, elektrischen oder opto-elektrischen Anzündsystemen eingesetzt werden kann.
  • Erfindungsgemäß wird diese Aufgabe überraschenderweise durch die Merkmale des Hauptanspruchs gelöst.
  • Weitere Ausgestaltungen der Erfindung sind in den Unteransprüchen dargelegt.
  • Überraschenderweise wurde ein pyrotechnisches Anzündmittel gefunden, wobei es
    Zn2+ 2(C2N10 2-)(CO3 2-), Zn2+ 3(C2N10 2-)2(CO3 2-), Zn2+ 4(C2N10 2-)2(CO3 2-)(OH-)2, Zn2+ 2(C2N10 2-)(OH-)2 oder Zn2+ 3(C2N10 2-)2(OH-)2.
    enthält, wobei gilt:
    (C2N10 2-) Azotetrazolatdianion mit der Struktur
    Figure imgb0001
     wobei der Anteil der basischen Azotetrazolatkomponente 30 bis 100 Gew.-% beträgt und 0 bis 70 Gew.-% eines Zusatzstoffes oder Mischungen mehrerer Zusatzstoffe enthalten sind. Die erfindungsgemäßen neuen basischen Azotetrazolatverbindungen besitzen Verpuffungstemperaturen im Bereich von 180 °C bis 240 °C, Reibempfindlichkeiten von 0,1 N bis 1,0 N und Schlagempfindlichkeit von 0,1 J bis 0,5 J. Die thermische Stabilität der erfindungsgemäßen basischen Azotetrazolatverbindungen ist gegeben. Lagerungen bei 71 °C zeigen nach 28 Tagen keine Zersetzung der erfindungsgemäßen basischen Azotetrazolatverbindung.
    Vorzugsweise ist das pyrotechnische Anzündmittel eines, welches als Zusatzstoff 10 bis 60 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.
  • Besonders bevorzugt enthält das pyrotechnische Anzündmittel als Zusatzstoff 0 bis 10 Gew.-% eines Sensibilisators, vorzugsweise Tetrazen.
  • Das erfindungsgemäße pyrotechnische Anzündmittel enthält vorzugsweise als Zusatzstoff 0 bis 20 Gew.-% eines Reduktionsmittels, ausgewählt aus einem oder mehreren von Aluminium, Antimonsulfid, Calciumsilicid, Titan, Titanhydrid, Bor, Borhydrid, Zirkon, Zirkonhydrid, Silicium, Graphit, Aktivkohle, Ruß oder Friktionsmittel vorzugsweise Glasbruch.
  • Besonders bevorzugt enthält das pyrotechnische Anzündmittel als Zusatzstoff 0,1 bis 5 Gew.-% eines Bindemittels, ausgewählt aus einem oder mehreren von Cellulose und deren Derivaten, Polyvinylbutyrale, Polynitropolyphenylen, Polynitrophenylether, Plexigum, Polyvinylacetat und Copolymeren.
  • Die erfindungsgemäßen pyrotechnischen Anzündmittel finden Verwendung in mechanischen, elektrischen oder opto-elektrischen Anzündsystemen.
  • Als Zusatzstoffe können verwendet werden:
    1. 1. Oxidationsmittel (einzeln oder in Mischungen) ausgewählt aus der Gruppe bestehend aus:
      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.
    2. 2. Energiereiche Zuschläge (einzeln oder in Mischungen) von Hexogen, Oktogen , Nitrocellulose.
    3. 3. Reduktionsmittel (einzeln oder in Mischungen) ausgewählt aus der Gruppe bestehend aus:
      Aluminium, Titan, Titanhydrid, Bor, Borhydrid, Zirkon, Zirkonhydrid, Silicium, Gra-phit, Aktivkohle, Ruß.
    4. 4. Bindemittel (einzeln oder in Mischungen) ausgewählt aus der Gruppe bestehend aus:
      Cellulose sowie deren Derivate, Polyvinylbutyrale, Polynitropolyphenylen, Polynitrophenylether, Plexigum, Polyvinylacetat, Copolymere.
    5. 5. Abbrandmoderatoren, Stabilisatoren und Verarbeitungshilfen (einzeln oder in Mischungen) ausgewählt aus der Gruppe bestehend aus:
      Zinkoxid, Zinkcarbonat, Silikate, Kieselgele, Kieselsäuren, beispielsweise Aerosil (Fa. Degussa), Bornitrid.
  • Die Substanzen zeichnen sich durch Blei- und Bariumfreiheit aus, einer hohen Anzündleistung, kurzen Reaktionszeiten und entsprechenden Empfindlichkeiten. Diese Eigenschaften ermöglichen eine Reduzierung der zur sicheren Anzündung benötigten Masse an Explosivstoffen.
  • In Tabelle 1 sind Zersetzungstemperaturen, Reib- und Schlagempfindlichkeiten ausgewählter Beispiele dargestellt. Die Messung der Reib- und Schlagempfindlichkeiten erfolgte nach Methoden der Bundesanstalt für Materialforschung (BAM) angeben im BAM-Bericht 142 (1987), während die Messung der Zersetzungstemperaturen mit der Dynamischen Differenzkalorimetrie (DSC) (Fa. Mettler) bei einer Aufheizrate von 10 K pro Minute erfolgte.
  • Gegenstand der vorliegenden Erfindung ist im Einzelnen:
    • ein pyrotechnisches Anzündmittel, wobei es
      Zn2+ 2(C2N10 2-)(CO3 2-), Zn2+ 3(C2N10 2-)2(CO3 2-), Zn2+ 4(C2N10 2-)2(CO3 2-)(OH-)2, Zn2+ 2(C2N10 2-)(OH-)2 oder Zn2+ 3(C2N10 2-)2(OH-)2.
      enthält, wobei gilt:
      (C2N10 2-) Azotetrazolatdianion mit der Struktur
      Figure imgb0002
       wobei der Anteil der basischen Azotetrazolatkomponente 30 bis 100 Gew.-% beträgt und 0 bis 70 Gew.-% eines Zusatzstoffes oder Mischungen mehrerer Zusätzstoffe enthalten sind.
    • ein pyrotechnisches Anzündmittel, welches als Zusatzstoff 10 bis 60 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 pyrotechnisches Anzündmittel, welches als Zusatzstoff 0 bis 10 Gew.-% eines Sensibilisators, vorzugsweise Tetrazen enthält;
    • ein pyrotechnisches Anzündmittel, welches als Zusatzstoff 0 bis 20 Gew.-% eines Reduktionsmittels enthält, ausgewählt aus einem oder mehreren von Aluminium, Antimonsulfid, Calciumsilicid, Titan, Titanhydrid, Bor, Borhydrid, Zirkon, Zirkonhydrid, Silicium, Graphit, Aktivkohle, Ruß oder Friktionsmittel vorzugsweise Glasbruch;
    • ein pyrotechnisches Anzündmittel, welches als Zusatzstoff 0,1 bis 5 Gew.-% eines Bindemittels enthält, ausgewählt aus einem oder mehreren von Cellulose und deren Derivaten, Polyvinylbutyrale, Polynitropolyphenylen, Polynitrophenylether, Plexigum, Polyvinylacetat und Copolymeren;
    • die Verwendung eines pyrotechnischen Anzündmittels in mechanischen, elektrischen oder opto-elektrischen Anzündsystemen.
  • Die Erfindung wird durch die folgenden Beispiele näher erläutert, ohne sie darauf einzuschränken:
    In Tabelle 1 sind die Zusammensetzungen von 5 verschiedenen basischen Salze des 5,5'-Azotetrazols aufgeführt. Tabelle 1 Zusammensetzungen, Verpuffungstemperaturen und Reib- und Schlagempfindlichkeiten ausgewählter basischer Salze des 5,5'-Azotetrazols.
    Nr. Summenformel T Verp.[a] in °C F Reib [b] in N E Schlag [c] in J
    1 Zn2+ 2(C2N10 2-)(CO3 2-) 227 0,7 0,3
    2 Zn2+ 3(C2N10 2-)2(CO3 2-) 223 0,5 0,1
    3 Zn2+ 4(C2N10 2-)2(CO3 2-) 215 0,7 0,3
    4 Zn2+ 2(C2N10 2-)(OH-)2 210 0,5 0,2
    5 Zn2+ 3(C2N10 2-)2(OH-)2 207 0,3 0,1
    [a]: Verpuffungstemperatur; [b]: Reibempfindlichkeit; [c]: Schlagempfindlichkeit.

Claims (6)

  1. Pyrotechnisches Anzündmittel, dadurch gekennzeichnet, dass es
    Zn2+ 2(C2N10 2-)(CO3 2-), Zn2+ 3(C2N10 2-)2(CO3 2-), Zn2+ 4(C2N10 2-)2(CO3 2-)(OH-)2,Zn2+ 2(C2N10 2-)(OH-)2 oder Zn2+ 3(C2N10 2-)2(OH-)2.
    enthält, wobei gilt:
    (C2N10 2-) Azotetrazolatdianion mit der Struktur
    Figure imgb0003
     wobei der Anteil der basischen Azotetrazolatkomponente 30 bis 100 Gew.-% beträgt und o bis 70 Gew.-% eines Zusatzstoffes oder Mischungen mehrerer Zusatzstoffe enthalten sind.
  2. Pyrotechnisches Anzündmittel nach Anspruch 1, dadurch gekennzeichnet, dass es als Zusatzstoff 10 bis 60 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.
  3. Pyrotechnisches Anzündmittel nach Anspruch 1, dadurch gekennzeichnet, dass es als Zusatzstoff o bis 10 Gew.-% eines Sensibilitsators, vorzugsweise Tetrazen enthält.
  4. Pyrotechnisches Anzündmittel nach Anspruch 1, dadurch gekennzeichnet, dass es als Zusatzstoff o bis 20 Gew.-% eines Reduktionsmittels enthält, ausgewählt aus einem oder mehreren von Aluminium, Antimonsulfid, Calciumsilicid, Titan, Titanhydrid, Bor, Borhydrid, Zirkon, Zirkonhydrid, Silicium, Graphit, Aktivkohle, Ruß oder Friktionsmittel vorzugsweise Glasbruch.
  5. Pyrotechnisches Anzündmittel nach Anspruch 1, dadurch gekennzeichnet, dass es als Zusatzstoff 0,1 bis 5 Gew.-% eines Bindemittels enthält, ausgewählt aus einem oder mehreren von Cellulose und der Derivaten, Polyvinylbutyrale, Polynitropolyphenylen, Polynitrophenylether, Plexigum, Polyvinylacetat und Copolymeren.
  6. Verwendung eines pyrotechnischen Anzündmittels nach einem oder mehreren der Ansprüche 1 bis 5 in mechanischen, elektrischen oder opto-elektrischen Anzündsystemen.
EP15734332.8A 2014-07-03 2015-06-29 Pyrotechnisches anzündmittel Active EP3164375B1 (de)

Priority Applications (4)

Application Number Priority Date Filing Date Title
HRP20192094TT HRP20192094T1 (hr) 2014-07-03 2015-06-29 Pirotehničko sredstvo za paljenje
PL15734332T PL3164375T3 (pl) 2014-07-03 2015-06-29 Pirotechniczny środek zapłonowy
SI201531000T SI3164375T1 (sl) 2014-07-03 2015-06-29 Pirotehnično vžigalno sredstvo
RS20191481A RS60020B1 (sr) 2014-07-03 2015-06-29 Pirotehničko sredstvo za paljenje

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DE102014009807 2014-07-03
PCT/EP2015/064729 WO2016001161A1 (de) 2014-07-03 2015-06-29 Pyrotechnisches anzündmittel

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EP3164375B1 true EP3164375B1 (de) 2019-08-21

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US (1) US20170137339A1 (de)
EP (1) EP3164375B1 (de)
JP (1) JP6559164B2 (de)
CN (1) CN107074674B (de)
AU (1) AU2015282658B2 (de)
BR (1) BR112016030839B1 (de)
DK (1) DK3164375T3 (de)
ES (1) ES2757934T3 (de)
HR (1) HRP20192094T1 (de)
HU (1) HUE046300T2 (de)
LT (1) LT3164375T (de)
PL (1) PL3164375T3 (de)
PT (1) PT3164375T (de)
RS (1) RS60020B1 (de)
RU (1) RU2695200C2 (de)
SI (1) SI3164375T1 (de)
WO (1) WO2016001161A1 (de)

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CN108456126B (zh) * 2017-02-20 2020-02-21 比亚迪股份有限公司 一种气体发生器的传火药及其制备方法和一种汽车安全气囊用气体发生器
CN110937962A (zh) * 2019-12-03 2020-03-31 北京理工大学 一种合金型洋红色冷烟花药剂及其制备方法

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FR2228043B1 (de) * 1972-10-17 1977-03-04 Poudres & Explosifs Ste Nale
US4566921A (en) * 1985-02-08 1986-01-28 L'etat Francais Represente Par Le Delegue Ministeriel Pour L'armement Priming composition which is sensitive to percussion and a method for preparing it
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US10968147B2 (en) * 2005-06-02 2021-04-06 Ruag Ammotec Gmbh Pyrotechnic agent
CN101434617A (zh) * 2008-08-20 2009-05-20 西北大学 基于偶氮四唑的含能配合物及其应用
DE102010025104B4 (de) 2010-04-14 2015-06-11 Diehl Bgt Defence Gmbh & Co. Kg Initialsprengstoff
DE202010018123U1 (de) * 2010-08-11 2014-04-01 Nammo Germany Gmbh Explosive Metallkomplexe, deren Herstellung und Verwendung, sowie Zündmittel
CN102731425A (zh) * 2011-04-12 2012-10-17 南京理工大学 5,5’-偶氮四唑锌的制备方法
CZ2013858A3 (cs) * 2013-11-07 2015-09-02 Sellier & Bellot Energetické materiály na bázi bismutu

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BR112016030839B1 (pt) 2022-04-19
DK3164375T3 (da) 2019-11-25
PL3164375T3 (pl) 2020-06-01
PT3164375T (pt) 2019-12-02
AU2015282658B2 (en) 2019-10-10
HUE046300T2 (hu) 2020-02-28
RU2017103493A (ru) 2018-08-03
LT3164375T (lt) 2019-12-10
SI3164375T1 (sl) 2020-07-31
CN107074674A (zh) 2017-08-18
US20170137339A1 (en) 2017-05-18
WO2016001161A1 (de) 2016-01-07
RS60020B1 (sr) 2020-04-30
BR112016030839A2 (de) 2017-08-22
RU2695200C2 (ru) 2019-07-22
ES2757934T3 (es) 2020-04-30
HRP20192094T1 (hr) 2020-02-21
JP2017524638A (ja) 2017-08-31
CN107074674B (zh) 2020-12-08
JP6559164B2 (ja) 2019-08-14
RU2017103493A3 (de) 2019-02-08
EP3164375A1 (de) 2017-05-10
AU2015282658A1 (en) 2017-02-02

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EP2548857B1 (de) Verwendung eines Salzes von Bistetrazolylamin

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