EP2548857A1 - Use of a bistetrazolyl amine salt - Google Patents

Use of a bistetrazolyl amine salt Download PDF

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Publication number
EP2548857A1
EP2548857A1 EP12005052A EP12005052A EP2548857A1 EP 2548857 A1 EP2548857 A1 EP 2548857A1 EP 12005052 A EP12005052 A EP 12005052A EP 12005052 A EP12005052 A EP 12005052A EP 2548857 A1 EP2548857 A1 EP 2548857A1
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Prior art keywords
salt
bta
use according
mixture
explosive
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German (de)
French (fr)
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EP2548857B1 (en
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Arno Dr. Hahma
Eero Karvinen
Jörg Dr. Stierstorfer
Thomas Prof. Dr. Klapötke
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Diehl BGT Defence GmbH and Co KG
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Diehl BGT Defence GmbH and Co KG
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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 invention relates to the use of a salt of bistetrazolylamine (BTA) or a mixture containing such a salt.
  • BTA bistetrazolylamine
  • BTA is also referred to as di (1H-tetrazol-5-yl) amine.
  • BTA salts have the potential to be used as additives in pyrotechnics and fuels.
  • ammonium perchlorate is the common oxidant in compound solid propellants and the thermal decomposition characteristics of ammonium perchlorate directly affect the combustion behavior of solid fuels.
  • the paper describes the investigation of the effect of the lead (II) salt of BTA on the thermal decomposition of ammonium perchlorate.
  • the object of the present invention is to provide an alternative use of a BTA salt. Furthermore, an igniter is to be provided.
  • the use of a salt of BTA or of a mixture containing such a salt is provided as initial explosive.
  • BTA salts can be ignited by introducing a small amount of energy, for example by irradiation with a laser beam having a power of less than 350, in particular less than 300, in particular less than 250 milliwatts.
  • BTA salts have high thermal stability and are insensitive to mechanical stress could be characterized as secondary explosive by the sensitivity. When ignited with a laser beam, focusing of the laser beam is not required.
  • the salts are very high in energy and thus able to enable a single stage construction of a detonator and / or a miniaturization of a detonator.
  • the energy of a conventional initial explosive is not always enough to ignite a secondary explosive directly.
  • an initial explosive is first ignited, which subsequently ignites a secondary explosive which is compressed in direct contact with the initial explosive in the same igniter.
  • a three- or more stages of construction is chosen, especially if it is a detonator with small dimensions.
  • the initial explosive initially ignites a mixture of the initial and secondary explosives and this mixture then further secondary explosive in the igniter.
  • an igniter By being able to build a single-stage detonator, by means of the use of BTA salt according to the invention as an initial explosive, an igniter can be manufactured much more favorably than with an initiating explosive which requires a two-stage or multi-stage structure.
  • a multi-stage structure can be omitted because BTA salts have a sufficient energy density to ignite a secondary explosive directly.
  • the ignition of a BTA salt can also be done electrically. Due to the low ignition power required for ignition, a very thin ignition wire can be used. Both by a laser beam as well as by such a thin ignition wire can be a milliseconds to microseconds accurate ignition. At the same time, the high thermal stability and the insensitivity to mechanical influences in comparison to conventional lnitialsprengstoffe to be ignited by laser beams ensure a high level of safety against accidental ignition. The higher the thermal stability of an initial explosive, the greater its shelf life. In combination with the avoidance of corrosive perchlorate can be provided with BTA salt as initial explosive very storable igniter.
  • initial explosives to be ignited with laser radiation require a power of the laser in the range of at least several hundred milliwatts.
  • ignition of such initial explosive for example tetrammine bis (5-nitro-2H-tetrazolato-N 2 ) cobalt (III) perchlorate, causes only one deflagration and no detonation favorable for the ignition of a secondary explosive.
  • the salt is a metal salt.
  • Metal salts of BTA absorb laser radiation particularly well, so that their ignition a laser beam of relatively low power is sufficient.
  • the metal ions of the metal salt in particular exclusively, comprise ions of at least one metal from the 4th or 5th period of the periodic table of the elements or of a transition metal or of an internal transition metal.
  • These metal salts can be prepared relatively easily and have a high sensitivity to laser radiation.
  • the salt can be a salt of silver, cobalt, chromium, copper, iron or nickel, in particular Ag 2 BTA, CoBTA, Cr 2 BTA 3 , CuBTA, Cu 2 BTA, FeBTA, Fe 2 BTA 3 or NiBTA ,
  • the initial explosive preferably does not comprise any ions of lead or any other toxic element.
  • the salt is not a salt of lead or other toxic element.
  • the initial explosive preferably comprises no nitrate, no halogenate, in particular no chlorate, and / or no perchlorate. Nitrate, halogenate or perchlorate-containing initial explosives are often thermally unstable and react with other explosives over time. They are therefore not storage stable and cause strong corrosion of metals. With the use according to the invention, these disadvantages can be avoided.
  • the mixture comprises at least two different of the salts specified above.
  • the sensitivity of the initial explosive can be adjusted.
  • the initial explosive may comprise only the said mixture of different salts.
  • a mixture consisting exclusively of said salts has the great advantage that only ion exchange reactions can take place in the mixture which do not alter the overall composition of the mixture. Such a mixture allows the adjustment of a desired sensitivity by the mixing ratio and is at the same time extremely storage-stable.
  • the initial explosive may additionally comprise a 5,5-azotetrazolate.
  • the 5,5-azotetrazolate the initial explosive can be made more sensitive to mechanical influences, for example if ignition by impact or friction is desired.
  • the salt is selected or the mixture is composed such that it is thermally stable up to 270.degree. C., in particular 305.degree. C., in particular 345.degree. C., in particular 355.degree. C., in particular 360.degree.
  • the ignition of the initial explosive can be done electrically or by means of at least one laser beam. Because of its high energy density, a salt from BTA can directly ignite a secondary explosive. An initiator containing the initial explosive can therefore be constructed in one stage. Such an igniter is cheaper and easier to manufacture than a multistage igniter.
  • an igniter containing an above-specified salt or mixture is provided.
  • Fig. 1 shows the structural formula of Bistetrazolylamin (Di (1 H -tetrazol-5-yl) amine), a salt thereof according to the invention is used as the initiating explosive.
  • BTA salts used according to the invention can be prepared, for example, as follows:
  • Bistetrazolylamine is prepared from sodium dicyanamide and sodium azide using hydrochloric acid as catalyst as in Klapötke, TM et al., J. Mater. Chem., 2008, 18, 5248-5258 described prepared. 15.3 g (0.10 mol) of bistetrazolylamine are dissolved in 50 ml of distilled water. To this is added 8.0 g (0.2 mol) of sodium hydroxide as a solid. The solution is stirred until fully dissolved. To ensure that no free hydroxide ions that would precipitate with metal ions as insoluble hydroxides are present in the solution, 100 mg of bistetrazolylamine is added. The solution is then filtered to remove free bistetrazolylamine. The solution is diluted to 100 ml with distilled water so that the sodium bistetrazolylamine concentration in the solution is 1 molar. The solution obtained is referred to below as the basic solution.
  • 1 ml of the base solution is placed in a 25 ml beaker on a 75 ° C hot plate of a magnetic stirrer with a 15 mm stirrer at 350 revolutions per Minute stirred.
  • 2.5 ml of 1 molar silver nitrate solution is added dropwise.
  • the silver nitrate is used in excess to reliably precipitate the BTA salt.
  • the beaker is placed after a minute on a second magnetic stirrer with a non-heated hot plate and allowed to cool with stirring. This forms a white precipitate, which is filtered and washed with 5 ml of ice-cold water and then with 5 ml of cold ethanol. Subsequently, the precipitate is dried in an oven at 40 ° C overnight.
  • Example 2 The procedure is as described in Example 1, wherein instead of 2.5 ml of 1 molar silver nitrate solution, 1.5 ml of 1-molar cobalt (II) chloride solution are used. The resulting pink precipitate is separated as described in Example 1 and dried.
  • II 1-molar cobalt
  • Example 2 The procedure is as described in Example 1, wherein instead of 2.5 ml of 1 molar silver nitrate solution 1 ml of 1 molar chromium (III) chloride solution is used. The resulting pink precipitate is separated as described in Example 1 and dried.
  • Example 2 The procedure is as described in Example 1, wherein instead of 2.5 ml of 1 molar silver nitrate solution, 1.5 ml of 1 molar copper sulfate solution are used. The resulting dark green precipitate is separated as described in Example 1 and dried.
  • the friction sensitivity was determined by means of a standardized friction apparatus of the Federal Institute for Materials Testing (BAM), small version.
  • BAM Federal Institute for Materials Testing
  • the values each indicate the force exerted by a pin contained in the friction apparatus on a friction surface contained in the friction apparatus, on which a sample of the substance to be examined is applied.
  • the impact sensitivity was determined by means of a falling on a sample of the substance to be examined standard hammer of the Federal Institute for Materials Testing, small version, determined. In each case, the drop height and the weight of the drop hammer were varied.

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Abstract

Use of a salt of bistetrazolylamine (BTA) or its mixture as a primary explosive is claimed.

Description

Die Erfindung betrifft die Verwendung eines Salzes von Bistetrazolylamin (BTA) oder eines Gemischs, welches ein solches Salz enthält. BTA wird auch als Di(1 H-tetrazol-5-yl)amin bezeichnet. Aus Wang, W. et al., Eur. J. Inorg. Chem. 2009, 3475-3480 ist ein Bleisalz von BTA bekannt. Gemäß dieser Druckschrift wird vorhergesagt, dass BTA-Salze das Potential aufweisen als Additive in pyrotechnischen Stoffen und Treibstoffen verwendet zu werden. Weiterhin wird ausgeführt, dass Ammoniumperchlorat das übliche Oxidationsmittel in zusammengesetzten Festtreibstoffen ist und die thermischen Zerfallscharakteristika von Ammoniumperchlorat direkt das Verbrennungsverhalten fester Treibstoffe beeinflussen. In der Veröffentlichung wird die Untersuchung der Wirkung des Blei(II)-Salzes von BTA auf den thermischen Zerfall von Ammoniumperchlorat beschrieben.The invention relates to the use of a salt of bistetrazolylamine (BTA) or a mixture containing such a salt. BTA is also referred to as di (1H-tetrazol-5-yl) amine. Out Wang, W. et al., Eur. J. Inorg. Chem. 2009, 3475-3480 is a lead salt known by BTA. According to this document, it is predicted that BTA salts have the potential to be used as additives in pyrotechnics and fuels. Furthermore, it is stated that ammonium perchlorate is the common oxidant in compound solid propellants and the thermal decomposition characteristics of ammonium perchlorate directly affect the combustion behavior of solid fuels. The paper describes the investigation of the effect of the lead (II) salt of BTA on the thermal decomposition of ammonium perchlorate.

Aufgabe der vorliegenden Erfindung ist es, eine alternative Verwendung eines BTA-Salzes anzugeben. Weiterhin soll ein Zünder bereitgestellt werden.The object of the present invention is to provide an alternative use of a BTA salt. Furthermore, an igniter is to be provided.

Die Aufgabe wird durch die Merkmale der Ansprüche 1 und 11 gelöst. Zweckmäßige Ausgestaltungen ergeben sich aus den Merkmalen der Ansprüche 2 bis 10.The object is solved by the features of claims 1 and 11. Advantageous embodiments emerge from the features of claims 2 to 10.

Erfindungsgemäß ist die Verwendung eines Salzes von BTA oder eines Gemischs, welches ein solches Salz enthält, als Initialsprengstoff vorgesehen.According to the invention, the use of a salt of BTA or of a mixture containing such a salt is provided as initial explosive.

Überraschenderweise hat es sich gezeigt, dass sich BTA-Salze durch Einbringen einer geringen Energiemenge, beispielsweise durch Bestrahlung mit einem Laserstrahl einer Leistung von weniger als 350, insbesondere weniger als 300, insbesondere weniger als 250 Milliwatt, zünden lassen. Gleichzeitig weisen BTA-Salze eine hohe thermische Stabilität auf und sind gegenüber mechanischer Belastung so unempfindlich, dass sie von der Empfindlichkeit her als Sekundärsprengstoff zu charakterisieren wären. Bei Zündung mit einem Laserstrahl ist eine Fokussierung des Laserstrahls nicht erforderlich.Surprisingly, it has been shown that BTA salts can be ignited by introducing a small amount of energy, for example by irradiation with a laser beam having a power of less than 350, in particular less than 300, in particular less than 250 milliwatts. At the same time, BTA salts have high thermal stability and are insensitive to mechanical stress could be characterized as secondary explosive by the sensitivity. When ignited with a laser beam, focusing of the laser beam is not required.

Gleichzeitig sind die Salze sehr energiereich und somit in der Lage, einen einstufigen Aufbau eines Zünders und/oder eine Miniaturisierung eines Zünders zu ermöglich. Die Energie eines herkömmlichen Initialsprengstoffs reicht nicht immer aus, um einen Sekundärsprengstoff direkt zu zünden. Bei einem herkömmlichen Zünder wird daher zuerst ein Initialsprengstoff gezündet, der nachfolgend einen Sekundärsprengstoff zündet, der in direktem Kontakt mit dem Initialsprengstoff in demselben Zünder verpresst ist. Häufig wird auch ein drei- oder mehrstufiger Aufbau gewählt, insbesondere wenn es sich um einen Zünder mit kleinen Dimensionen handelt. Bei einem solchen Zünder zündet beispielsweise der Initialsprengstoff zunächst ein Gemisch aus dem Initialstrengstoff und dem Sekundärsprengstoff und dieses Gemisch dann weiteren Sekundärsprengstoff im Zünder. Die Energiedichte des Sekundärsprengstoffs reicht dann aus, den Sekundärsprengstoff im Sprengkörper zu zünden. Derartige Zünder sind aufwändig herzustellen und in Bezug auf ihre Zusammensetzung verhältnismäßig empfindlich gegenüber geringen Abweichungen im Verhältnis der Komponenten der Zusammensetzung. Die Sicherstellung der genauen Einhaltung der gewünschten Zusammensetzung bedingt zusätzlichen Aufwand beim Herstellen eines solchen Zünders.At the same time, the salts are very high in energy and thus able to enable a single stage construction of a detonator and / or a miniaturization of a detonator. The energy of a conventional initial explosive is not always enough to ignite a secondary explosive directly. In a conventional igniter, therefore, an initial explosive is first ignited, which subsequently ignites a secondary explosive which is compressed in direct contact with the initial explosive in the same igniter. Often, a three- or more stages of construction is chosen, especially if it is a detonator with small dimensions. In such an igniter, for example, the initial explosive initially ignites a mixture of the initial and secondary explosives and this mixture then further secondary explosive in the igniter. The energy density of the secondary explosive then suffices to ignite the secondary explosive in the explosive device. Such igniters are expensive to manufacture and are relatively sensitive in composition to minor variations in the ratio of components of the composition. Ensuring the exact compliance with the desired composition requires additional effort in producing such a fuse.

Durch die Möglichkeit, einen einstufigen Zünder zu bauen, kann mittels der erfindungsgemäßen Verwendung von BTA-Salz als Initialsprengstoff ein Zünder wesentlich günstiger gefertigt werden als mit einem Initialsprengstoff, welcher einen zwei- oder mehrstufigen Aufbau erfordert. Bei der erfindungsgemäßen Verwendung kann ein mehrstufiger Aufbau entfallen, weil BTA-Salze eine ausreichende Energiedichte aufweisen, um einen Sekundärsprengstoff direkt zu zünden.By being able to build a single-stage detonator, by means of the use of BTA salt according to the invention as an initial explosive, an igniter can be manufactured much more favorably than with an initiating explosive which requires a two-stage or multi-stage structure. In the use according to the invention, a multi-stage structure can be omitted because BTA salts have a sufficient energy density to ignite a secondary explosive directly.

Herkömmliche Laserzündstoffe enthalten Komplexsalze mit Perchlorat, um die für eine Zündung durch einen Laserstrahl erforderliche Empfindlichkeit bereitzustellen. Perchlorat verträgt sich jedoch auf Dauer nicht mit den sonstigen üblichen Bestandteilen von Initialsprengstoffen. Die Lagerstabilität solcher Laserzündstoffe ist daher gering. Weiterhin kann Perchlorat eine starke Korrosion an unedlen Metallen verursachen, die mit dem Sprengstoff oder nach einer Detonation mit den daraus entstandenen Schwaden in Kontakt kommen. Das erfindungsgemäß verwendete BTA-Salz ist jedoch so leicht zu zünden, dass sogar ein mit einem Laserstrahl geringer Leistung zu zündender Zünder bereitgestellt werden kann, der kein Perchlorat enthält. Dadurch können die mit Perchlorat einhergehenden Nachteile vermieden werden. Ebenfalls vermieden werden kann der Einsatz des üblicherweise zur Erhöhung der Zündleistung eingesetzten Bleiazids und/oder Bleitrizinats. Ein Zusatz der genannten Salze zu einem Initialsprengstoff macht diesen einerseits thermisch instabil und andererseits bleihaltig. Die erfindungsgemäße Verwendung ermöglicht dagegen die Bereitstellung eines thermisch stabilen bleifreien Initialsprengstoffs. Die Verwendung von Bleisalzen sollte generell aus Umweltschutzgründen und wegen der Gefährdung der Gesundheit der Arbeiter bei der Produktion vermieden werden.Conventional laser igniters contain complex salts with perchlorate to provide the sensitivity required for ignition by a laser beam. However, perchlorate can not be tolerated in the long term with the other usual constituents of initial explosives. The storage stability of such laser igniters is therefore low. Furthermore, perchlorate can cause severe corrosion of base metals that come in contact with the explosive or after detonation with the resulting swaths. However, the BTA salt used in the invention is so easy to ignite that even one with a laser beam less Power can be provided to igniting igniter containing no perchlorate. As a result, the disadvantages associated with perchlorate can be avoided. It is also possible to avoid the use of the lead azide and / or lead-intrinate usually used to increase the ignition power. An addition of said salts to an initial explosive makes this one hand thermally unstable and on the other hand leaded. By contrast, the use according to the invention makes it possible to provide a thermally stable lead-free initial explosive. The use of lead salts should generally be avoided for environmental reasons and because of the endangerment of workers' health during production.

Die Zündung eines BTA-Salzes kann auch elektrisch erfolgen. Durch die geringe Zündleistung, die zur Zündung erforderlich ist, kann dazu ein sehr dünner Zünddraht verwendet werden. Sowohl durch einen Laserstrahl als auch durch einen derartig dünnen Zünddraht kann eine Millisekunden- bis Mikrosekunden-genaue Zündung erfolgen. Gleichzeitig ist durch die hohe thermische Stabilität und die Unempfindlichkeit gegenüber mechanischen Einflüssen im Vergleich zu herkömmlichen mit Laserstrahlen zu zündenden lnitialsprengstoffen eine hohe Sicherheit gegenüber einer unbeabsichtigten Zündung gewährleistet. Je höher die thermische Stabilität eines Initialsprengstoffs ist, desto größer ist seine Lagerbeständigkeit. In Kombination mit der Vermeidung korrosiven Perchlorats lassen sich mit BTA-Salz als Initialsprengstoff sehr lagerbeständige Zünder bereitstellen.The ignition of a BTA salt can also be done electrically. Due to the low ignition power required for ignition, a very thin ignition wire can be used. Both by a laser beam as well as by such a thin ignition wire can be a milliseconds to microseconds accurate ignition. At the same time, the high thermal stability and the insensitivity to mechanical influences in comparison to conventional lnitialsprengstoffe to be ignited by laser beams ensure a high level of safety against accidental ignition. The higher the thermal stability of an initial explosive, the greater its shelf life. In combination with the avoidance of corrosive perchlorate can be provided with BTA salt as initial explosive very storable igniter.

Weiterhin besteht durch das Vermeiden korrosiver Bestandteile bei der Verwendung von BTA-Salz als Initialsprengstoff mehr Freiheit im Hinblick auf die Wahl des Sekundärsprengstoffs und bei der Wahl von den Initialsprengstoff direkt kontaktierenden Materialien, wie Hülsen oder Zündmechanismen.Furthermore, by avoiding corrosive constituents in the use of BTA salt as the initial explosive, there is more freedom with regard to the choice of secondary explosive and the choice of materials directly contacting the initial explosive, such as sleeves or ignition mechanisms.

Bekannte mit Laserstrahlung zu zündende Initialsprengstoffe benötigen eine Leistung des Lasers im Bereich von zumindest mehreren Hundert Milliwatt. Häufig bewirkt die Zündung eines solchen Initialsprengstoffs, beispielsweise Tetramminbis(5-nitro-2H-tetrazolato-N2)kobalt(III)perchlorat, nur eine Deflagration und keine für die Zündung eines Sekundärsprengstoffs günstige Detonation.Known initial explosives to be ignited with laser radiation require a power of the laser in the range of at least several hundred milliwatts. Frequently, the ignition of such initial explosive, for example tetrammine bis (5-nitro-2H-tetrazolato-N 2 ) cobalt (III) perchlorate, causes only one deflagration and no detonation favorable for the ignition of a secondary explosive.

Bei einer vorteilhaften Ausgestaltung der Erfindung handelt es sich bei dem Salz um ein Metallsalz. Metallsalze von BTA absorbieren Laserstrahlung besonders gut, so dass zu deren Zündung ein Laserstrahl verhältnismäßig geringer Leistung ausreichend ist.In an advantageous embodiment of the invention, the salt is a metal salt. Metal salts of BTA absorb laser radiation particularly well, so that their ignition a laser beam of relatively low power is sufficient.

Bei einer weiteren Ausgestaltung der Erfindung umfassen die Metallionen des Metallsalzes, insbesondere ausschließlich, Ionen mindestens eines Metalls aus der 4. oder 5. Periode des Periodensystems der Elemente oder eines Übergangsmetalls oder eines inneren Übergangsmetalls. Diese Metallsalze lassen sich verhältnismäßig einfach herstellen und weisen eine hohe Empfindlichkeit gegenüber Laserstrahlung auf. Bei dem Salz kann es sich um ein Salz von Silber, Kobalt, Chrom, Kupfer, Eisen oder Nickel, insbesondere Ag2BTA, CoBTA, Cr2BTA3, CuBTA, Cu2BTA, FeBTA, Fe2BTA3 oder NiBTA, handeln.In a further embodiment of the invention, the metal ions of the metal salt, in particular exclusively, comprise ions of at least one metal from the 4th or 5th period of the periodic table of the elements or of a transition metal or of an internal transition metal. These metal salts can be prepared relatively easily and have a high sensitivity to laser radiation. The salt can be a salt of silver, cobalt, chromium, copper, iron or nickel, in particular Ag 2 BTA, CoBTA, Cr 2 BTA 3 , CuBTA, Cu 2 BTA, FeBTA, Fe 2 BTA 3 or NiBTA ,

Vorzugsweise umfasst der Initialsprengstoff bei der erfindungsgemäßen Verwendung keine Ionen von Blei oder einem sonstigen giftigen Element. Insbesondere ist das Salz kein Salz von Blei oder eines sonstigen giftigen Elements. Der Initialsprengstoff umfasst vorzugsweise kein Nitrat, kein Halogenat, insbesondere kein Chlorat, und/oder kein Perchlorat. Nitrat, Halogenat oder Perchlorat enthaltende lnitialsprengstoffe sind thermisch häufig instabil und reagieren mit der Zeit mit anderen Sprengstoffen. Sie sind dadurch nicht lagerungsstabil und verursachen starke Korrosion an Metallen. Mit der erfindungsgemäßen Verwendung können diese Nachteile vermieden werden.In the use according to the invention, the initial explosive preferably does not comprise any ions of lead or any other toxic element. In particular, the salt is not a salt of lead or other toxic element. The initial explosive preferably comprises no nitrate, no halogenate, in particular no chlorate, and / or no perchlorate. Nitrate, halogenate or perchlorate-containing initial explosives are often thermally unstable and react with other explosives over time. They are therefore not storage stable and cause strong corrosion of metals. With the use according to the invention, these disadvantages can be avoided.

In einer bevorzugten Ausgestaltung umfasst das Gemisch mindestens zwei verschiedene der oben spezifizierten Salze. Durch das Mengenverhältnis der verschiedenen Salze kann die Empfindlichkeit des Initialsprengstoffs eingestellt werden. Der Initialsprengstoff kann ausschließlich das genannte Gemisch verschiedener Salze umfassen. Ein Gemisch, das ausschließlich aus den genannten Salzen besteht, weist den großen Vorteil auf, dass in dem Gemisch nur lonenaustauschreaktionen stattfinden können, welche die Gesamtzusammensetzung des Gemischs nicht verändern. Ein solches Gemisch ermöglicht die Einstellung einer gewünschten Sensitivität durch das Mischungsverhältnis und ist dabei gleichzeitig äußerst lagerungsstabil.In a preferred embodiment, the mixture comprises at least two different of the salts specified above. By the ratio of the various salts, the sensitivity of the initial explosive can be adjusted. The initial explosive may comprise only the said mixture of different salts. A mixture consisting exclusively of said salts has the great advantage that only ion exchange reactions can take place in the mixture which do not alter the overall composition of the mixture. Such a mixture allows the adjustment of a desired sensitivity by the mixing ratio and is at the same time extremely storage-stable.

Der Initialsprengstoff kann zusätzlich ein 5,5-Azotetrazolat umfassen. Durch das 5,5-Azotetrazolat kann der Initialsprengstoff sensibler gegenüber mechanischen Einflüssen gemacht werden, beispielsweise wenn eine Zündung durch Schlag oder Reibung gewünscht ist.The initial explosive may additionally comprise a 5,5-azotetrazolate. Through the 5,5-azotetrazolate the initial explosive can be made more sensitive to mechanical influences, for example if ignition by impact or friction is desired.

Bei einer Ausgestaltung der erfindungsgemäßen Verwendung ist das Salz so gewählt oder das Gemisch so zusammengesetzt, dass es bis zu 270°C, insbesondere 305°C, insbesondere 345°C, insbesondere 355°C, insbesondere 360°C, thermisch stabil ist. Je höher die thermische Stabilität des Gemischs oder des Salzes ist, desto lagerungsstabiler und sicherer handhabbar ist es.In one embodiment of the use according to the invention, the salt is selected or the mixture is composed such that it is thermally stable up to 270.degree. C., in particular 305.degree. C., in particular 345.degree. C., in particular 355.degree. C., in particular 360.degree. The higher the thermal stability of the mixture or the salt, the storage stable and safer it is manageable.

Die Zündung des Initialsprengstoffs kann elektrisch oder mittels mindestens eines Laserstrahls erfolgen. Wegen dessen hoher Energiedichte kann ein Salz von BTA einen Sekundärsprengstoff direkt zünden. Ein den Initialsprengstoff enthaltender Zünder kann daher einstufig aufgebaut sein. Ein solcher Zünder ist kostengünstiger und einfacher herzustellen als ein mehrstufiger Zünder.The ignition of the initial explosive can be done electrically or by means of at least one laser beam. Because of its high energy density, a salt from BTA can directly ignite a secondary explosive. An initiator containing the initial explosive can therefore be constructed in one stage. Such an igniter is cheaper and easier to manufacture than a multistage igniter.

Weiterhin ist erfindungsgemäß ein ein oben spezifiziertes Salz oder Gemisch enthaltender Zünder vorgesehen.Furthermore, according to the invention, an igniter containing an above-specified salt or mixture is provided.

Nachfolgend wird die Erfindung anhand der Fig. 1 und von Ausführungsbeispielen näher erläutert.The invention will be described below with reference to FIG Fig. 1 and explained in more detail by exemplary embodiments.

Fig. 1 zeigt die Strukturformel von Bistetrazolylamin (Di(1H-tetrazol-5-yl)amin), dessen Salz erfindungsgemäß als Initialsprengstoff verwendet wird. Fig. 1 shows the structural formula of Bistetrazolylamin (Di (1 H -tetrazol-5-yl) amine), a salt thereof according to the invention is used as the initiating explosive.

Erfindungsgemäß verwendete BTA-Salze können beispielsweise wie folgt hergestellt werden:BTA salts used according to the invention can be prepared, for example, as follows:

Bistetrazolylamin wird aus Natriumdicyanamid und Natriumazid mit Salzsäure als Katalysator wie in Klapötke, T. M. et al., J. Mater. Chem., 2008, 18, 5248-5258 beschrieben hergestellt. 15,3 g (0,10 mol) Bistetrazolylamin werden in 50 ml destilliertem Wasser gelöst. Dazu werden 8,0 g (0,2 mol) Natriumhydroxid als Feststoff zugesetzt. Die Lösung wird bis zu dessen vollständiger Auflösung gerührt. Um sicherzustellen, dass keine freien Hydroxidionen, die mit Metallionen als unlösliche Hydroxide ausfallen würden, in der Lösung vorhanden sind, werden noch 100 mg Bistetrazolylamin zugesetzt. Anschließend wird die Lösung filtriert, um freies Bistetrazolylamin zu entfernen. Die Lösung wird auf 100 ml mit destilliertem Wasser verdünnt, so dass die Natriumbistetrazolylamin-Konzentration in der Lösung 1 molar ist. Die erhaltene Lösung wird im Folgenden als Basislösung bezeichnet.Bistetrazolylamine is prepared from sodium dicyanamide and sodium azide using hydrochloric acid as catalyst as in Klapötke, TM et al., J. Mater. Chem., 2008, 18, 5248-5258 described prepared. 15.3 g (0.10 mol) of bistetrazolylamine are dissolved in 50 ml of distilled water. To this is added 8.0 g (0.2 mol) of sodium hydroxide as a solid. The solution is stirred until fully dissolved. To ensure that no free hydroxide ions that would precipitate with metal ions as insoluble hydroxides are present in the solution, 100 mg of bistetrazolylamine is added. The solution is then filtered to remove free bistetrazolylamine. The solution is diluted to 100 ml with distilled water so that the sodium bistetrazolylamine concentration in the solution is 1 molar. The solution obtained is referred to below as the basic solution.

1. Herstellung von Silberbistetrazolylamin1. Preparation of silver bistetrazolylamine

1 ml der Basislösung wird in einem 25 mi-Becherglas auf einer 75°C warmen Heizplatte eines Magnetrührers mit einem 15 mm-Rührkern bei 350 Umdrehungen pro Minute gerührt. Zu dieser Lösung werden 2,5 ml 1-molare Silbernitratlösung tropfenweise hinzugefügt. Das Silbernitrat wird im Überschuss eingesetzt, um das BTA-Salz zuverlässig auszufällen. Das Becherglas wird nach einer Minute auf einen zweiten Magnetrührer mit einer nicht erwärmten Heizplatte gestellt und unter Rühren abkühlen gelassen. Dabei bildet sich ein weißer Niederschlag, der filtriert und mit 5 ml eiskaltem Wasser und anschließend mit 5 ml kaltem Ethanol gewaschen wird. Anschließend wird der Niederschlag im Trockenschrank bei 40°C über Nacht getrocknet.1 ml of the base solution is placed in a 25 ml beaker on a 75 ° C hot plate of a magnetic stirrer with a 15 mm stirrer at 350 revolutions per Minute stirred. To this solution, 2.5 ml of 1 molar silver nitrate solution is added dropwise. The silver nitrate is used in excess to reliably precipitate the BTA salt. The beaker is placed after a minute on a second magnetic stirrer with a non-heated hot plate and allowed to cool with stirring. This forms a white precipitate, which is filtered and washed with 5 ml of ice-cold water and then with 5 ml of cold ethanol. Subsequently, the precipitate is dried in an oven at 40 ° C overnight.

2. Herstellung von Kobalt(II)bistetrazolylamin2. Preparation of cobalt (II) bistetrazolylamine

Es wird wie in Beispiel 1 beschrieben vorgegangen, wobei statt 2,5 ml 1-molare Silbernitratlösung 1,5 ml 1-molare Kobalt(II)chloridlösung eingesetzt werden. Der dabei gebildete rosa Niederschlag wird wie in Beispiel 1 beschrieben abgesondert und getrocknet.The procedure is as described in Example 1, wherein instead of 2.5 ml of 1 molar silver nitrate solution, 1.5 ml of 1-molar cobalt (II) chloride solution are used. The resulting pink precipitate is separated as described in Example 1 and dried.

3. Herstellung von Chrom(III)bistetrazolyiamin3. Preparation of chromium (III) bistetrazolyiamine

Es wird wie in Beispiel 1 beschrieben vorgegangen, wobei statt 2,5 ml 1-molare Silbernitratlösung 1 ml 1-molare Chrom(III)chloridlösung eingesetzt wird. Der dabei gebildete rosa Niederschlag wird wie in Beispiel 1 beschrieben abgesondert und getrocknet.The procedure is as described in Example 1, wherein instead of 2.5 ml of 1 molar silver nitrate solution 1 ml of 1 molar chromium (III) chloride solution is used. The resulting pink precipitate is separated as described in Example 1 and dried.

4. Herstellung von Kupfer(II)bistetrazolylamin4. Preparation of copper (II) bistetrazolylamine

Es wird wie in Beispiel 1 beschrieben vorgegangen, wobei statt 2,5 ml 1-molare Silbernitratlösung 1,5 ml 1-molare Kupfersulfatlösung eingesetzt werden. Der dabei gebildete dunkelgrüne Niederschlag wird wie in Beispiel 1 beschrieben abgesondert und getrocknet.The procedure is as described in Example 1, wherein instead of 2.5 ml of 1 molar silver nitrate solution, 1.5 ml of 1 molar copper sulfate solution are used. The resulting dark green precipitate is separated as described in Example 1 and dried.

Zur Untersuchung der mechanischen Eigenschaften von BTA-Salzen wurde deren Zerfallstemperatur mittels "Differential Scanning Calorimetry" (DSC) bestimmt. Bei den in Tabelle 1 mit "*" gekennzeichneten Werten erfolgte die Bestimmung nur durch einen Heizplattentest, d. h. bei einer Maximaltemperatur von 360°C erfolgte keine Umsetzung. Ein "-" kennzeichnet einen nicht gemessenen Wert.To investigate the mechanical properties of BTA salts, their decay temperature was determined by differential scanning calorimetry (DSC). For the values marked with "*" in Table 1, the determination was made only by a hot plate test, ie at a maximum temperature of 360 ° C, no reaction took place. A "-" indicates an unmeasured value.

Die Reibempfindlichkeit wurde mittels eines genormten Reibeapparats der Bundesanstalt für Materialprüfung (BAM), kleine Ausführung, ermittelt. Die Werte geben jeweils die Kraft an, die ein in dem Reibeapparat enthaltener Stift auf eine in dem Reibeapparat enthaltene Reibefläche, auf der eine Probe des zu untersuchenden Stoffs aufgebracht ist, ausübt. Die Schlagempfindlichkeit wurde mittels eines auf eine Probe des zu untersuchenden Stoffs fallenden genormten Fallhammers der Bundesanstalt für Materialprüfung, kleine Ausführung, ermittelt. Dabei wurden jeweils die Fallhöhe und das Gewicht des Fallhammers variiert.The friction sensitivity was determined by means of a standardized friction apparatus of the Federal Institute for Materials Testing (BAM), small version. The values each indicate the force exerted by a pin contained in the friction apparatus on a friction surface contained in the friction apparatus, on which a sample of the substance to be examined is applied. The impact sensitivity was determined by means of a falling on a sample of the substance to be examined standard hammer of the Federal Institute for Materials Testing, small version, determined. In each case, the drop height and the weight of the drop hammer were varied.

Es wurden die folgenden Werte ermittelt: Tabelle 1 Stoff Zerfall/°C (DSC) Schlag[J] Reibung[N] BTA 230 >1 >20 Ag2BTA 360 >1 >20 CoBTA 310 >1 >20 Cr2BTA3 >360* >1 >20 CuBTA 275 >1 >20 Cu2BTA - >1 >20 FeBTA - >1 >20 NiBTA - >1 >20 The following values were determined: Table 1 material Decay / ° C (DSC) Impact [J] Friction [N] BTA 230 > 1 > 20 Ag 2 BTA 360 > 1 > 20 CoBTA 310 > 1 > 20 Cr 2 BTA 3 > 360 * > 1 > 20 CuBTA 275 > 1 > 20 Cu 2 BTA - > 1 > 20 FeBTA - > 1 > 20 NiBTA - > 1 > 20

Zur Untersuchung der Laserempfindlichkeit der genannten Salze wurden diese mit einem 0,5 mm Durchmesser aufweisenden Laserstrahl der jeweils angegebenen Wellenlänge und Leistung bestrahlt. Dabei sind die folgenden Reaktionen ermittelt worden: Tabelle 2 Stoff 532 nm, 20 mW 532 nm, 200 mW 630 nm, 200 mW BTA keine Reaktion keine Reaktion keine Reaktion Ag2BTA keine Reaktion Detonation keine Reaktion CoBTA keine Reaktion Detonation Verpuffung Cr2BTA3 keine Reaktion keine Reaktion Verpuffung CuBTA keine Reaktion keine Reaktion Verpuffung Cu2BTA keine Reaktion keine Reaktion Detonation FeBTA keine Reaktion Verpuffung Verpuffung Fe2BTA3 keine Reaktion Verpuffung Verpuffung NiBTA keine Reaktion keine Reaktion Verpuffung To investigate the laser sensitivity of the salts mentioned, they were irradiated with a laser beam having a diameter of 0.5 mm and the wavelength and power specified in each case. The following reactions have been determined: Table 2 material 532 nm, 20 mW 532 nm, 200 mW 630 nm, 200 mW BTA no reaction no reaction no reaction Ag 2 BTA no reaction blast no reaction CoBTA no reaction blast deflagration Cr 2 BTA 3 no reaction no reaction deflagration CuBTA no reaction no reaction deflagration Cu 2 BTA no reaction no reaction blast FeBTA no reaction deflagration deflagration Fe 2 BTA 3 no reaction deflagration deflagration NiBTA no reaction no reaction deflagration

Die obigen Versuchsergebnisse zeigen, dass die untersuchten BTA-Salze eine hohe Zerfallstemperatur aufweisen und relativ unempfindlich gegenüber Schlag und Reibung sind, sich jedoch bereits mit einem Laserstrahl geringer Leistung zünden lassen.The above test results show that the investigated BTA salts have a high decomposition temperature and are relatively insensitive to impact and friction, but can already be ignited with a low-power laser beam.

Claims (11)

Verwendung eines Salzes von Bistetrazolylamin (BTA) oder eines Gemischs, welches ein solches Salz enthält, als Initialsprengstoff.Use of a salt of bistetrazolylamine (BTA) or a mixture containing such a salt as initial explosive. Verwendung nach Anspruch 1,
wobei das Salz ein Metallsalz ist.Use according to claim 1,
wherein the salt is a metal salt. Verwendung nach Anspruch 2,
wobei die Metallionen des Metallsalzes, insbesondere ausschließlich, Ionen mindestens eines Metalls aus der 4. oder 5. Periode des Periodensystems der Elemente oder eines Übergangsmetalls oder eines inneren Übergangsmetalls umfassen.Use according to claim 2,
wherein the metal ions of the metal salt, in particular exclusively, ions of at least one metal from the 4th or 5th period of the Periodic Table of the Elements or a transition metal or an inner transition metal. Verwendung nach einem der vorherigen Ansprüche,
wobei das Salz ein Salz von Silber, Kobalt, Chrom, Kupfer, Eisen oder Nickel, insbesondere Ag2BTA, CoBTA, Cr2BTA3, CuBTA, Cu2BTA, FeBTA, Fe2BTA3 oder NiBTA, umfasst.Use according to one of the preceding claims,
wherein the salt comprises a salt of silver, cobalt, chromium, copper, iron or nickel, in particular Ag 2 BTA, CoBTA, Cr 2 BTA 3 , CuBTA, Cu 2 BTA, FeBTA, Fe 2 BTA 3 or NiBTA. Verwendung nach einem der vorherigen Ansprüche,
wobei das Salz kein Salz von Blei oder eines sonstigen giftigen Elements ist und/oder der Initialsprengstoff kein Nitrat, kein Halogenat, insbesondere kein Chlorat, und/oder kein Perchlorat umfasst.Use according to one of the preceding claims,
wherein the salt is not a salt of lead or other toxic element and / or the initial explosive comprises no nitrate, no halogenate, in particular no chlorate, and / or no perchlorate. Verwendung nach einem der vorherigen Ansprüche,
wobei das Gemisch mindestens zwei verschiedene der gemäß einem der vorherigen Ansprüche spezifizierten Salze umfasst.Use according to one of the preceding claims,
wherein the mixture comprises at least two different salts specified according to one of the preceding claims. Verwendung nach einem der vorherigen Ansprüche,
wobei der Initialsprengstoff ausschließlich das Gemisch gemäß Anspruch 6 oder zusätzlich ein 5,5'-Azotetrazolat umfasst.Use according to one of the preceding claims,
wherein the initial explosive exclusively comprises the mixture according to claim 6 or additionally a 5,5'-azotetrazolate. Verwendung nach einem der vorherigen Ansprüche,
wobei das Salz so gewählt ist oder das Gemisch so zusammengesetzt ist, dass es bis zu 270°C, insbesondere 305°C, insbesondere 345°C, insbesondere 355°C, insbesondere 360°C, thermisch stabil ist.Use according to one of the preceding claims,
wherein the salt is selected or the mixture is so composed that it is up to 270 ° C, in particular 305 ° C, in particular 345 ° C, in particular 355 ° C, in particular 360 ° C, thermally stable. Verwendung nach einem der vorherigen Ansprüche,
wobei die Zündung des Initialsprengstoffs elektrisch oder mittels mindestens eines Laserstrahls erfolgt.Use according to one of the preceding claims,
wherein the ignition of the initial explosive takes place electrically or by means of at least one laser beam. Verwendung nach einem der vorherigen Ansprüche,
wobei ein den Initialsprengstoff enthaltender Zünder einstufig aufgebaut ist.Use according to one of the preceding claims,
wherein a primer containing the initiator is constructed in one stage. Zünder, enthaltend ein gemäß einem der Ansprüche 1 bis 8 spezifiziertes Salz oder Gemisch.An igniter containing a salt or mixture specified according to any one of claims 1 to 8.
EP12005052.1A 2011-07-20 2012-07-07 Use of a bistetrazolyl amine salt Not-in-force EP2548857B1 (en)

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GB185555A (en) * 1921-06-27 1922-09-14 Hans Rathsburg Initial primers and a process for their manufacture
US1511771A (en) * 1921-08-22 1924-10-14 Rathsburg Hans Explosive compound for primers and detonators
US5501823A (en) * 1993-08-02 1996-03-26 Thiokol Corporation Preparation of anhydrous tetrazole gas generant compositions
WO1997041403A1 (en) * 1996-04-26 1997-11-06 Dynamit Nobel Gmbh Explosivstoff- Und Systemtechnik Firing mixtures
US20010042577A1 (en) * 1996-07-20 2001-11-22 Klaus Redecker Temperature fuse
US20100261912A1 (en) * 2009-02-17 2010-10-14 Toshiyuki Toda Bis-(1(2)h-tetrazol-5-yl)amine and production method therefor

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NL9775C (en) * 1921-02-01

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Publication number Priority date Publication date Assignee Title
GB185555A (en) * 1921-06-27 1922-09-14 Hans Rathsburg Initial primers and a process for their manufacture
US1511771A (en) * 1921-08-22 1924-10-14 Rathsburg Hans Explosive compound for primers and detonators
US5501823A (en) * 1993-08-02 1996-03-26 Thiokol Corporation Preparation of anhydrous tetrazole gas generant compositions
WO1997041403A1 (en) * 1996-04-26 1997-11-06 Dynamit Nobel Gmbh Explosivstoff- Und Systemtechnik Firing mixtures
US20010042577A1 (en) * 1996-07-20 2001-11-22 Klaus Redecker Temperature fuse
US20100261912A1 (en) * 2009-02-17 2010-10-14 Toshiyuki Toda Bis-(1(2)h-tetrazol-5-yl)amine and production method therefor

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Title
ANTON HAMMERL ET AL: "Salts of 5,5 -Azotetrazolate", EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, WILEY-VCH VERLAG, WEINHEIM, DE, vol. 2002, no. 4, 1 March 2002 (2002-03-01), pages 834 - 845, XP002653887, ISSN: 1434-1948, [retrieved on 20020228], DOI: 10.1002/1099-0682(200203) *
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WANG, W. ET AL., EUR. J. INORG. CHEM., 2009, pages 3475 - 3480

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IL220783A (en) 2015-01-29
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DE102011108146B4 (en) 2014-03-20
EP2679567A3 (en) 2017-10-04

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