EP2450329A2 - Explosive containing a tetrazole compound - Google Patents
Explosive containing a tetrazole compound Download PDFInfo
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- EP2450329A2 EP2450329A2 EP11008768A EP11008768A EP2450329A2 EP 2450329 A2 EP2450329 A2 EP 2450329A2 EP 11008768 A EP11008768 A EP 11008768A EP 11008768 A EP11008768 A EP 11008768A EP 2450329 A2 EP2450329 A2 EP 2450329A2
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- explosive
- ligand
- explosives
- ion
- complex salt
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
- C06C7/00—Non-electric detonators; Blasting caps; Primers
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B41/00—Compositions containing a nitrated metallo-organic compound
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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
Definitions
- the invention relates to an explosive comprising a tetrazole compound.
- the EP 0 733 520 A1 discloses a gas generator for an airbag comprising a tetrazole compound such as 5-aminotetrazole, tetrazole, bitetrazole and metal salts of these compounds and an oxidizing agent such as a nitrogen oxide or a metal or metal oxide such as copper oxide.
- a preferred composition comprises aminotetrazole combined with copper oxide, sodium nitrate, guanidine nitrate, mica and calcium stearate.
- B2 is a lead-free initial explosive of the formula [M II (A) R (B X ) S ] (C Y ) T known.
- M is cobalt, copper, iron, manganese, nickel or zinc.
- A is 1,5-diaminotetrazole ("DAT”).
- B is water, 5-aminotetrazole ("AT”), 5-aminotetrazolate ("AT - “), 5-nitrotetrazolate ("NT - "), 3,5-dinitro-1,2,4-triazolate (“DNT - "), 5-azido-3-nitro-1,2,4-triazolate (“ ANT - "), azide (“ N 3 - ”) or nitrate (“ NO 3 - ").
- C is AT -, ANT -, DNT -, NO 3 -, N 3 -, NT -, perchlorate, Tetraazidoborat, dinitramide, nitro format, 5,5'-diazido-2,2'-azo-1,3,4- triazolate, 5,5'-dinitro-2,2'-azo-1,3,4-triazolate, 4,4 ', 5,5'-tetranitro-2,2'-biimidazolate or 5,5'-azotetrazolate.
- R is 5 or 6, S is 0 or 1, T is 1 or 2; X is 0 or -1; Y is -1 or -2, X + Y is -2 and R + S is 6.
- detonators are always multi-level. They have at least two, but usually three to five stages. Each of these stages must be assembled and pressed separately. As a result, the number of possible errors in the production and the cost and cost of production are relatively high. However, there are so far no initial explosives known whose ignition performance would be sufficient to provide a single-stage igniter can.
- tetracene is thermally very unstable. It already decomposes at 120 ° C. 2 to 5% of the tetrazole per year decomposes under normal storage conditions of an explosive. This changes the properties of a explosive containing tetracene.
- the addition of tetracene reduces the ignition performance of an explosive. If lead azide and / or lead ricinate are added to make up the balance, the explosive becomes thermally unstable and contains lead. Tetrazene therefore does not allow the production of a lead-free initial explosive. Even the diazole used as a substitute decomposes at 150 ° C. When stored, it decomposes in such a way that it is no longer possible to guarantee safe use after 5 to 10 years.
- the object of the present invention is to provide an explosive which can be used as an initial explosive and which in particular can provide a sufficient ignition performance to enable a single-stage igniter structure.
- the explosive should not require tetrazene or complex compound mixtures to achieve the required sensitivity and ignition performance.
- the explosives should be more stable in storage than hitherto known, in particular tetracene-containing, explosives.
- a use of the explosive should be specified.
- an explosive comprising a complex salt which is 5-aminotetrazole as a ligand, a ligand potentially oxidizing or a energetic ion and a ligand complexed counterion
- a ligand potentially oxidizing ion is an ion that is capable of oxidizing the ligand in a redox reaction.
- the inventors of the explosive of the present invention have found that said complex salt exhibits very high performance.
- the explosive according to the invention can be used both as an initial explosive and as a secondary explosive. It is high energy and more energetic than many conventional initiators and secondary explosives.
- the density of the complex salt can exceed 2000 kg / m 3 and the detonation pressure of the explosive according to the invention in individual cases even the detonation pressure of hexogen.
- the ignition performance of the explosive according to the invention is relatively high. It is higher than the ignition performance of lead azide and enables the provision of a single-stage lead-free igniter. Due to the high ignition performance can be provided with the explosive even a miniaturized single-stage igniter.
- the explosive according to the invention also has an extremely small critical diameter. The critical diameter is the minimum diameter of an explosive in which it still detonates.
- the explosive of the invention is neutral, d. H. neither sour nor basic. Therefore, it is compatible with both acidic and basic compounds, especially secondary explosives, d. H. There are no decomposition reactions with other explosives during storage. The complex salt is also extremely difficult to dissolve. This also avoids an unwanted decomposition reaction with other explosives.
- the explosive according to the invention in particular in comparison to tetrazene, can be mixed or brought into contact with a large number of conventional explosives, in particular secondary explosives, without causing a decomposition reaction. In the design of explosives this results in greater freedom in terms of their composition.
- Another significant advantage of the explosive according to the invention is that it can be prepared very easily and from aqueous solution by precipitation. As a result, the investment costs for production plants are low.
- the explosive according to the invention if it does not contain a silver-containing complex salt, is not photosensitive. It can therefore be handled without major precautions. This makes its production easy. In addition, the shelf life of the explosive-containing active agents according to the invention is high.
- the explosive according to the invention has proven to be laser-sensitive. This makes it suitable for the construction of so-called laser igniter, d. H. Igniter, in which the initial explosive is ignited by a laser beam.
- an explosive containing the explosive of the present invention can be adjusted by the choice of the amount of explosive, the choice of counterion and the choice of the ligand potentially oxidizing or the energetic ion.
- the sensitivity of the explosive according to the invention can also be adjusted by the choice of counterion and the choice of the ligand potentially oxidizing or of the energetic ion.
- the sensitivity in particular the laser sensitivity, can be adapted to the intended application. It is not necessary to add potassium chlorate, any other chlorate or perchlorate, as is customary with conventional sensitivity-adjusting explosives.
- the explosive is preferably an initial explosive, in particular one-stage. Since the explosive according to the invention is laser-sensitive, it is particularly suitable as an explosive to be ignited by a laser beam.
- the counterion can be a Na, K, Ca, Mg, Sr, Ba, La, Cu, Ni, Fe, Zn, Co, Mn, Cd, In, Al, Cr, Ag, Yb, Y, Gd, hydrazine, guanidine or ammonia ion act.
- the ligand potentially oxidizing or the energetic ion can be a perchlorate, chlorate, bromate, iodate, periodate, persulphate, trinitromethanate, dinitromethanate, chromate, dichromate, nitrate, dinitramine, permanganate, Nitrotetrazolate, nitriminotetrazolate, bistetrazolate, bistetrazolyltriazenate, bistetrazolylamine, azotetrazolate or azide ion.
- an explosive which comprises a mixture of at least two different explosives, each of the different explosives being one of the abovementioned explosives according to the invention. Mixing these different explosives makes it easy to adjust the sensitivity and performance of primers without the addition of foreign matter. It is advantageous if each of the different explosives is such a complex salt, as specified for the explosive according to the invention. Then, the overall composition of the mixture does not change by ion exchange reactions occurring over time. As a result, the properties of the mixture, such as sensitivity and ignition performance, remain constant even during long storage. As a result, the reliability of the explosive compared to an explosive mixture of very different substances is significantly increased.
- the invention relates to the use of a complex salt which comprises 5-aminotetrazole as ligands, a ligand potentially oxidizing or an energetic ion and a ligand complexed counterion as explosive.
- the counterion can be a Na, K, Ca, Mg, Sr, Ba, La, Cu, Ni, Fe, Zn, Co, Mn, Cd, In, Al, Cr, Ag, Yb, Y, Gd, hydrazine, guanidine or ammonia ion.
- the ligand potentially oxidizing or the energetic ion may be a perchlorate, chlorate, bromate, iodate, periodate, persulphate, trinitromethanate, dinitromethanate, chromate, dichromate, nitrate, dinitramine, , Permanganate, nitrotetrazolate, nitriminotetrazolate, bistetrazolate, bistetrazolyltriazenate, bistetrazolylamine, azotetrazolate or azide ion.
- a mixture as an explosive, wherein the mixture comprises at least two different explosives, each of the different explosives is an explosive according to the invention.
- each of the different explosives is such a complex salt as specified for the explosive of the present invention.
- the explosive may be a, in particular single-stage, initial explosive.
- the explosive is preferably an explosive for ignition by a laser beam.
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Abstract
Description
Die Erfindung betrifft einen Sprengstoff umfassend eine Tetrazolverbindung.The invention relates to an explosive comprising a tetrazole compound.
Die
Aus der
Derzeit sind Zünder stets mehrstufig aufgebaut. Sie weisen mindestens zwei, üblicherweise aber drei bis fünf Stufen auf. Jede dieser Stufen muss separat zusammengesetzt und gepresst werden. Dadurch sind die Zahl der Fehlermöglichkeiten bei der Herstellung sowie der Aufwand und die Kosten der Herstellung verhältnismäßig hoch. Es sind bisher jedoch keine Initialsprengstoffe bekannt, deren Zündleistung ausreichen würde, um einen einstufigen Zünder bereitstellen zu können.At the moment detonators are always multi-level. They have at least two, but usually three to five stages. Each of these stages must be assembled and pressed separately. As a result, the number of possible errors in the production and the cost and cost of production are relatively high. However, there are so far no initial explosives known whose ignition performance would be sufficient to provide a single-stage igniter can.
Zur Einstellung der Empfindlichkeit von Initialsprengstoffen wird üblicherweise Tetrazen eingesetzt. Tetrazen ist jedoch thermisch sehr instabil. Es zerfällt bereits bei 120°C. Pro Jahr zersetzen sich 2 bis 5% des Tetrazens unter normalen Lagerungsbedingungen eines Sprengstoffs. Dadurch verändern sich die Eigenschaften eines Tetrazen enthaltenden Sprengstoffs. Darüber hinaus setzt der Zusatz von Tetrazen die Zündleistung eines Sprengstoffs herab. Wird zum Ausgleich Bleiazid und/oder Bleitrizinat beigemischt, wird der Sprengstoff thermisch instabil und bleihaltig. Tetrazen ermöglicht daher nicht die Herstellung eines bleifreien Initialsprengstoffs. Auch das ersatzweise eingesetzte Diazol zerfällt bereits bei 150°C. Bei Lagerung zersetzt es sich so, dass eine sichere Einsatzfähigkeit nach 5 bis 10 Jahren nicht mehr gewährleistet werden kann.To set the sensitivity of initial explosives usually tetracene is used. However, tetracene is thermally very unstable. It already decomposes at 120 ° C. 2 to 5% of the tetrazole per year decomposes under normal storage conditions of an explosive. This changes the properties of a explosive containing tetracene. In addition, the addition of tetracene reduces the ignition performance of an explosive. If lead azide and / or lead ricinate are added to make up the balance, the explosive becomes thermally unstable and contains lead. Tetrazene therefore does not allow the production of a lead-free initial explosive. Even the diazole used as a substitute decomposes at 150 ° C. When stored, it decomposes in such a way that it is no longer possible to guarantee safe use after 5 to 10 years.
Als Ersatz für Tetrazen ist ein Bleisalz von bis-Tetrazolyltriazenat bekannt. Die Verwendung von Bleisalzen sollte jedoch generell aus Umweltschutzgründen und wegen der Gefährdung der Gesundheit der an der Produktion beteiligten Personen vermieden werden.As a substitute for tetracene, a lead salt of bis-tetrazolyl triazenate is known. However, the use of lead salts should generally be avoided for environmental reasons and because of the health hazards involved in production.
Zur Einstellung der Empfindlichkeit eines Sprengstoffs werden oft Gemische mit so vielen Komponenten eingesetzt, dass nicht vorherzusagen ist, wie sich ein solches Gemisch bei längerer Lagerung verändert und wie sich dadurch die Zündeigenschaften des Sprengstoffs ändern.To adjust the sensitivity of an explosive often mixtures are used with so many components that it can not be predicted how such a mixture changes during prolonged storage and how this changes the ignition properties of the explosive.
Aufgabe der vorliegenden Erfindung ist es, einen Sprengstoff bereitzustellen, der als Initialsprengstoff verwendet werden kann und der insbesondere eine ausreichende Zündleistung bereitstellen kann, um einen einstufigen Zünderaufbau zu ermöglichen. Bei dem Sprengstoff sollen weder Tetrazen noch kompliziert zusammengesetzte Gemische zum Erreichen der erforderlichen Empfindlichkeit und Zündleistung erforderlich sein. Darüber hinaus soll der Sprengstoff lagerstabiler sein als bisher bekannte, insbesondere Tetrazen enthaltende, Sprengstoffe. Weiterhin soll eine Verwendung des Sprengstoffs angegeben werden.The object of the present invention is to provide an explosive which can be used as an initial explosive and which in particular can provide a sufficient ignition performance to enable a single-stage igniter structure. The explosive should not require tetrazene or complex compound mixtures to achieve the required sensitivity and ignition performance. In addition, the explosives should be more stable in storage than hitherto known, in particular tetracene-containing, explosives. Furthermore, a use of the explosive should be specified.
Die Aufgabe wird durch die Merkmale der Patentansprüche 1 und 8 gelöst. Zweckmäßige Ausgestaltungen ergeben sich aus den Merkmalen der Ansprüche 2 bis 7 und 9 bis 14.The object is solved by the features of claims 1 and 8. Advantageous embodiments emerge from the features of claims 2 to 7 and 9 to 14.
Erfindungsgemäß ist ein Sprengstoff umfassend ein Komplexsalz, welches 5-Aminotetrazol als Liganden, ein den Liganden potentiell oxidierendes oder ein energetisches Ion und ein vom Liganden komplexiertes Gegenion umfasst, vorgesehen. Bei einem den Liganden potentiell oxidierenden Ion handelt es sich um ein Ion, dass dazu in der Lage ist, den Liganden in einer Redoxreaktion zu oxidieren.According to the invention, an explosive comprising a complex salt which is 5-aminotetrazole as a ligand, a ligand potentially oxidizing or a energetic ion and a ligand complexed counterion includes provided. A ligand potentially oxidizing ion is an ion that is capable of oxidizing the ligand in a redox reaction.
Die Erfinder des erfindungsgemäßen Sprengstoffs haben festgestellt, dass das genannte Komplexsalz eine sehr hohe Leistung zeigt. Der erfindungsgemäße Sprengstoff kann sowohl als Initialsprengstoff als auch als Sekundärsprengstoff eingesetzt werden. Er ist hochenergetisch und energetischer als viele herkömmliche Initialsprengstoffe und Sekundärsprengstoffe. Die Dichte des Komplexsalzes kann 2000 kg/m3 und der Detonationsdruck des erfindungsgemäßen Sprengstoffs in Einzelfällen sogar den Detonationsdruck von Hexogen übersteigen.The inventors of the explosive of the present invention have found that said complex salt exhibits very high performance. The explosive according to the invention can be used both as an initial explosive and as a secondary explosive. It is high energy and more energetic than many conventional initiators and secondary explosives. The density of the complex salt can exceed 2000 kg / m 3 and the detonation pressure of the explosive according to the invention in individual cases even the detonation pressure of hexogen.
Die Zündleistung des erfindungsgemäßen Sprengstoffs ist verhältnismäßig hoch. Sie ist höher als die Zündleistung von Bleiazid und ermöglicht die Bereitstellung eines einstufigen bleifreien Zünders. Aufgrund der hohen Zündleistung kann mit dem Sprengstoff sogar ein miniaturisierter einstufiger Zünder bereitgestellt werden. Der erfindungsgemäße Sprengstoff weist außerdem einen außerordentlich kleinen kritischen Durchmesser auf. Der kritische Durchmesser ist der minimale Durchmesser eines Sprengstoffs, bei dem dieser noch detoniert.The ignition performance of the explosive according to the invention is relatively high. It is higher than the ignition performance of lead azide and enables the provision of a single-stage lead-free igniter. Due to the high ignition performance can be provided with the explosive even a miniaturized single-stage igniter. The explosive according to the invention also has an extremely small critical diameter. The critical diameter is the minimum diameter of an explosive in which it still detonates.
Weiterhin ist der erfindungsgemäße Sprengstoff neutral, d. h. weder sauer noch basisch. Daher verträgt er sich sowohl mit sauren als auch mit basischen Verbindungen, insbesondere Sekundärsprengstoffen, d. h. es kommt nicht zu Zersetzungsreaktionen mit anderen Sprengstoffen während der Lagerung. Das Komplexsalz ist darüber hinaus äußerst schwerlöslich. Auch dadurch wird eine ungewollte Zersetzungsreaktion mit anderen Sprengstoffen vermieden.Furthermore, the explosive of the invention is neutral, d. H. neither sour nor basic. Therefore, it is compatible with both acidic and basic compounds, especially secondary explosives, d. H. There are no decomposition reactions with other explosives during storage. The complex salt is also extremely difficult to dissolve. This also avoids an unwanted decomposition reaction with other explosives.
Durch die gute Verträglichkeit kann der erfindungsgemäße Sprengstoff, insbesondere im Vergleich zu Tetrazen, mit einer großen Zahl herkömmlicher Sprengstoffe, insbesondere Sekundärsprengstoffe, gemischt oder in Kontakt gebracht werden, ohne dass es zu einer Zersetzungsreaktion kommt. Bei der Gestaltung von Sprengsätzen ergibt sich dadurch eine größere Gestaltungsfreiheit im Hinblick auf deren Zusammensetzung.Due to the good compatibility, the explosive according to the invention, in particular in comparison to tetrazene, can be mixed or brought into contact with a large number of conventional explosives, in particular secondary explosives, without causing a decomposition reaction. In the design of explosives this results in greater freedom in terms of their composition.
Ein weiterer wesentlicher Vorteil des erfindungsgemäßen Sprengstoffs besteht darin, dass dieser sehr einfach und aus wässriger Lösung durch Ausfällen hergestellt werden kann. Dadurch sind die Investitionskosten für Produktionsanlagen gering.Another significant advantage of the explosive according to the invention is that it can be prepared very easily and from aqueous solution by precipitation. As a result, the investment costs for production plants are low.
Im Gegensatz zu anderen Initialsprengstoffen ist der erfindungsgemäße Sprengstoff, sofern er kein Silber enthaltendes Komplexsalz enthält, nicht lichtempfindlich. Er kann daher ohne größere Vorsichtsmaßnahmen gehandhabt werden. Dadurch ist dessen Herstellung einfach. Darüber hinaus ist die Lagerfähigkeit von den erfindungsgemäßen Sprengstoff enthaltenden Wirkmitteln hoch.In contrast to other initial explosives, the explosive according to the invention, if it does not contain a silver-containing complex salt, is not photosensitive. It can therefore be handled without major precautions. This makes its production easy. In addition, the shelf life of the explosive-containing active agents according to the invention is high.
Weiterhin hat sich der erfindungsgemäße Sprengstoff als laserempfindlich erwiesen. Dadurch eignet er sich für den Bau sogenannter Laserzünder, d. h. Zünder, bei denen der Initialsprengstoff durch einen Laserstrahl gezündet wird.Furthermore, the explosive according to the invention has proven to be laser-sensitive. This makes it suitable for the construction of so-called laser igniter, d. H. Igniter, in which the initial explosive is ignited by a laser beam.
Darüber hinaus haben die Erfinder festgestellt, dass die Eigenschaften eines Sprengsatzes, der den erfindungsgemäßen Sprengstoff enthält, durch die Wahl der Sprengstoffmenge, die Wahl des Gegenions und die Wahl des den Liganden potentiell oxidierenden oder des energetischen Ions eingestellt werden können. Auch die Empfindlichkeit des erfindungsgemäßen Sprengstoffs kann durch die Wahl des Gegenions und die Wahl des den Liganden potentiell oxidierenden oder des energetischen Ions eingestellt werden. Dadurch kann die Empfindlichkeit, insbesondere auch die Laserempfindlichkeit, an die vorgesehene Anwendung angepasst werden. Ein Zusatz von Kaliumchlorat, einem anderen Chlorat oder Perchlorat, wie er bei herkömmlichen Sprengsätzen zur Einstellung der Empfindlichkeit üblich ist, ist nicht erforderlich.In addition, the inventors have found that the properties of an explosive containing the explosive of the present invention can be adjusted by the choice of the amount of explosive, the choice of counterion and the choice of the ligand potentially oxidizing or the energetic ion. The sensitivity of the explosive according to the invention can also be adjusted by the choice of counterion and the choice of the ligand potentially oxidizing or of the energetic ion. As a result, the sensitivity, in particular the laser sensitivity, can be adapted to the intended application. It is not necessary to add potassium chlorate, any other chlorate or perchlorate, as is customary with conventional sensitivity-adjusting explosives.
Vorzugsweise handelt es sich bei dem Sprengstoff um einen, insbesondere einstufigen, Initialsprengstoff. Da der erfindungsgemäße Sprengstoff laserempfindlich ist, eignet er sich besonders gut als ein durch einen Laserstrahl zu zündender Sprengstoff.The explosive is preferably an initial explosive, in particular one-stage. Since the explosive according to the invention is laser-sensitive, it is particularly suitable as an explosive to be ignited by a laser beam.
Bei dem Gegenion kann es sich um ein Na-, K-, Ca-, Mg-, Sr-, Ba-, La-, Cu-, Ni-, Fe-, Zn-, Co-, Mn-, Cd-, In-, Al-, Cr-, Ag-, Yb-, Y-, Gd-, Hydrazin-, Guanidin- oder Ammoniak-Ion handeln.The counterion can be a Na, K, Ca, Mg, Sr, Ba, La, Cu, Ni, Fe, Zn, Co, Mn, Cd, In, Al, Cr, Ag, Yb, Y, Gd, hydrazine, guanidine or ammonia ion act.
Das den Liganden potentiell oxidierende oder das energetische Ion kann ein Perchlorat-, Chlorat-, Bromat-, Jodat-, Perjodat-, Persulphat-, Trinitromethanat-, Dinitromethanat-, Chromat-, Dichromat-, Nitrat-, Dinitramin-, Permanganat-, Nitrotetrazolat-, Nitriminotetrazolat-, Bistetrazolat-, Bistetrazolyltriazenat-, Bistetrazolylamin-, Azotetrazolat- oder Azid-Ion sein.The ligand potentially oxidizing or the energetic ion can be a perchlorate, chlorate, bromate, iodate, periodate, persulphate, trinitromethanate, dinitromethanate, chromate, dichromate, nitrate, dinitramine, permanganate, Nitrotetrazolate, nitriminotetrazolate, bistetrazolate, bistetrazolyltriazenate, bistetrazolylamine, azotetrazolate or azide ion.
Besonders vorteilhaft ist ein Sprengstoff, der ein Gemisch aus mindestens zwei unterschiedlichen Sprengstoffen umfasst, wobei jeder der unterschiedlichen Sprengstoffe einer der bisher genannten erfindungsgemäßen Sprengstoffe ist. Durch das Mischen dieser unterschiedlichen Sprengstoffe lässt sich die Empfindlichkeit und die Leistung von Zünd- und Anzündsätzen ohne den Zusatz von Fremdstoffen einfach einstellen. Vorteilhaft ist es dabei, wenn jeder der unterschiedlichen Sprengstoffe ein solches Komplexsalz ist, wie es für den erfindungsgemäßen Sprengstoff spezifiziert wurde. Dann ändert sich die Gesamtzusammensetzung des Gemischs durch mit der Zeit darin stattfindende Ionenaustauschreaktionen nicht. Dadurch bleiben die Eigenschaften des Gemischs, wie Empfindlichkeit und Zündleistung, auch bei langer Lagerung konstant. Dadurch ist die Zuverlässigkeit des Sprengstoffs gegenüber einem Sprengstoffgemisch aus ganz verschiedenen Stoffen erheblich erhöht.Particularly advantageous is an explosive which comprises a mixture of at least two different explosives, each of the different explosives being one of the abovementioned explosives according to the invention. Mixing these different explosives makes it easy to adjust the sensitivity and performance of primers without the addition of foreign matter. It is advantageous if each of the different explosives is such a complex salt, as specified for the explosive according to the invention. Then, the overall composition of the mixture does not change by ion exchange reactions occurring over time. As a result, the properties of the mixture, such as sensitivity and ignition performance, remain constant even during long storage. As a result, the reliability of the explosive compared to an explosive mixture of very different substances is significantly increased.
Weiterhin betrifft die Erfindung die Verwendung eines Komplexsalzes, welches 5-Aminotetrazol als Liganden, ein den Liganden potentiell oxidierendes oder ein energetisches Ion und ein vom Liganden komplexiertes Gegenion umfasst, als Sprengstoff. Das Gegenion kann dabei ein Na-, K-, Ca-, Mg-, Sr-, Ba-, La-, Cu-, Ni-, Fe-, Zn-, Co-, Mn-, Cd-, In-, Al-, Cr-, Ag-, Yb-, Y-, Gd-, Hydrazin-, Guanidin- oder Ammoniak-Ion sein. Bei dem den Liganden potentiell oxidierenden oder dem energetischen Ion kann es sich um ein Perchlorat-, Chlorat-, Bromat-, Jodat-, Perjodat-, Persulphat-, Trinitromethanat-, Dinitromethanat-, Chromat-, Dichromat-, Nitrat-, Dinitramin-, Permanganat-, Nitrotetrazolat-, Nitriminotetrazolat-, Bistetrazolat-, Bistetrazolyltriazenat-, Bistetrazolylamin-, Azotetrazolat- oder Azid-Ion handeln. Besonders vorteilhaft ist die Verwendung eines Gemischs als Sprengstoff, wobei das Gemisch mindestens zwei unterschiedliche Sprengstoffe umfasst, wobei jeder der unterschiedlichen Sprengstoffe ein erfindungsgemäßer Sprengstoff ist. Vorzugsweise ist jeder der unterschiedlichen Sprengstoffe ein solches Komplexsalz, wie es für den erfindungsgemäßen Sprengstoff spezifiziert wurde. Der Sprengstoff kann ein, insbesondere einstufiger, Initialsprengstoff sein. Bevorzugt ist der Sprengstoff ein Sprengstoff zum Zünden durch einen Laserstrahl.Furthermore, the invention relates to the use of a complex salt which comprises 5-aminotetrazole as ligands, a ligand potentially oxidizing or an energetic ion and a ligand complexed counterion as explosive. The counterion can be a Na, K, Ca, Mg, Sr, Ba, La, Cu, Ni, Fe, Zn, Co, Mn, Cd, In, Al, Cr, Ag, Yb, Y, Gd, hydrazine, guanidine or ammonia ion. The ligand potentially oxidizing or the energetic ion may be a perchlorate, chlorate, bromate, iodate, periodate, persulphate, trinitromethanate, dinitromethanate, chromate, dichromate, nitrate, dinitramine, , Permanganate, nitrotetrazolate, nitriminotetrazolate, bistetrazolate, bistetrazolyltriazenate, bistetrazolylamine, azotetrazolate or azide ion. Particularly advantageous is the use of a mixture as an explosive, wherein the mixture comprises at least two different explosives, each of the different explosives is an explosive according to the invention. Preferably, each of the different explosives is such a complex salt as specified for the explosive of the present invention. The explosive may be a, in particular single-stage, initial explosive. The explosive is preferably an explosive for ignition by a laser beam.
Nachfolgend wird die Erfindung anhand von Ausführungsbeispielen erläutert.The invention will be explained below with reference to exemplary embodiments.
Der Komplexbilder (= Ligand) 5-Aminotetrazol wird in kaltem Wasser aufgeschlämmt und die Konzentration, wenn nicht anders angegeben, auf 1 mol/l eingestellt. Das zu komplexierende Metallsalz mit den Komplexbilder potentiell oxidierendem Anion, wie zum Beispiel Nitrat oder Perchlorat, wird als Lösung, wenn nicht anders angegeben mit einer Konzentration von 0,4 mol/l, auf einmal zugegeben. Die resultierende Lösung wird für fünf Minuten gekocht und danach bei Raumtemperatur mindestens vier Stunden stehen gelassen. Die dabei entstandenen Kristalle werden filtriert, mit einer kleinen Menge destilliertem Wasser und anschließend zwei Mal mit Ethanol gewaschen und bei 30°C getrocknet.The complex (= ligand) 5-aminotetrazole is slurried in cold water and the concentration, unless otherwise stated, adjusted to 1 mol / l. That too Complexing metal salt with the complex images of potentially oxidizing anion, such as nitrate or perchlorate, is added as a solution at a concentration of 0.4 mol / l, all at once, unless otherwise specified. The resulting solution is boiled for five minutes and then allowed to stand at room temperature for at least four hours. The resulting crystals are filtered, washed with a small amount of distilled water and then twice with ethanol and dried at 30 ° C.
Es wurde nach der allgemeinen Arbeitsvorschrift vorgegangen. Dabei wurden 1,67 g (16,7 mmol) 5-Aminotetrazolmonohydrat in 5 ml Wasser und 1,0 g (2,7 mmol) Kupfer(II)perchlorathexahydrat in 5 ml Wasser eingesetzt. Die aus dem Vermischen der Lösungen resultierende Lösung ist anfänglich blau und nach Abschluss der Komplexbildung dunkelgrün. Die Lösung wird im Wärmeschrank bei 40 bis 50°C durch Verdunsten solange eingeengt bis das Komplexsalz auskristallisiert. Die Ausbeute ist quantitativ. Der Stoff verpufft bei 240°C. Bei Untersuchung der Laserempfindlichkeit zeigte sich, dass der Sprengstoff gegenüber 630 nm-Strahlung sehr laserempfindlich ist und mittels Laserstrahlung von 630 nm Wellenlängen zur Detonation gebracht werden kann.It was proceeded according to the general work instructions. Here, 1.67 g (16.7 mmol) of 5-aminotetrazole monohydrate in 5 ml of water and 1.0 g (2.7 mmol) of copper (II) perchlorate hexahydrate in 5 ml of water were used. The solution resulting from the mixing of the solutions is initially blue and dark green after completion of the complex formation. The solution is concentrated in the oven at 40 to 50 ° C by evaporation until the complex salt crystallizes out. The yield is quantitative. The substance evaporates at 240 ° C. Examination of the laser sensitivity revealed that the explosive is very laser-sensitive to 630 nm radiation and that it can be detonated by means of laser radiation of 630 nm.
Es wurde nach der allgemeinen Arbeitsvorschrift vorgegangen. Dabei wurden 1,67 g (16,7 mmol) 5-Aminotetrazolmonohydrat in 5 ml Wasser und 1,0 g (2,7 mmol) Nickelperchlorathexahydrat in 5 ml Wasser eingesetzt. Die aus dem Vermischen der Lösungen resultierende Lösung ist anfänglich grün und nach Abschluss der Komplexbildung dunkelviolett. Die Lösung wird im Wärmeschrank bei 40 bis 50°C durch Verdunstung solange eingeengt bis sie sirupös ist und anschließend bei Raumtemperatur auskristallisieren gelassen. Die Ausbeute ist quantitativ. Der Stoff detoniert heftig mit schrillem Knall bei 280°C. Er ist sehr laserempfindlich gegenüber 532 nm-Strahlung und weniger laserempfindlich gegenüber 630 nm-Strahlung. Der Stoff kann sowohl mittels Laserstrahlung von 532 nm als auch mittels Laserstrahlung von 630 nm Wellenlängen zur Detonation gebracht werden.It was proceeded according to the general work instructions. In this case, 1.67 g (16.7 mmol) of 5-aminotetrazole monohydrate in 5 ml of water and 1.0 g (2.7 mmol) of nickel perchlorate hexahydrate in 5 ml of water were used. The solution resulting from the mixing of the solutions is initially green and dark violet upon completion of the complex formation. The solution is concentrated in the oven at 40 to 50 ° C by evaporation until it is syrupy and then allowed to crystallize out at room temperature. The yield is quantitative. The substance detonates violently with a shrill bang at 280 ° C. It is very laser sensitive to 532 nm radiation and less laser sensitive to 630 nm radiation. The substance can be detonated by laser radiation of 532 nm as well as by laser radiation of 630 nm wavelengths.
Claims (14)
wobei der Sprengstoff ein, insbesondere einstufiger, Initialsprengstoff ist.Explosive according to claim 1,
wherein the explosive is a, in particular single-stage, initial explosive.
wobei der Sprengstoff ein durch einen Laserstrahl zu zündender Sprengstoff ist.Explosive according to claim 1 or 2,
wherein the explosive is an explosive to be ignited by a laser beam.
wobei das Gegenion ein Na-, K-, Ca-, Mg-, Sr-, Ba-, La-, Cu-, Ni-, Fe-, Zn-, Co-, Mn-, Cd-, In-, Al-, Cr-, Ag-, Yb-, Y-, Gd-, Hydrazin-, Guanidin- oder Ammoniak-Ion ist.Explosives according to one of the preceding claims,
wherein the counterion is a Na, K, Ca, Mg, Sr, Ba, La, Cu, Ni, Fe, Zn, Co, Mn, Cd, In, Al -, Cr, Ag, Yb, Y, Gd, hydrazine, guanidine or ammonia ion.
wobei das den Liganden potentiell oxidierende oder das energetische Ion ein Perchlorat-, Chlorat-, Bromat-, Jodat-, Perjodat-, Persulphat-, Trinitromethanat-, Dinitromethanat-, Chromat-, Dichromat-, Nitrat-, Dinitramin-, Permanganat-, Nitrotetrazolat-, Nitriminotetrazolat-, Bistetrazolat-, Bistetrazolyltriazenat-, Bistetrazolylamin-, Azotetrazolat- oder Azid-lon ist.Explosives according to one of the preceding claims,
wherein the ligand is potentially oxidizing or the energetic ion is a perchlorate, chlorate, bromate, iodate, periodate, persulphate, trinitromethanate, dinitromethanate, chromate, dichromate, nitrate, dinitramine, permanganate, Nitrotetrazolate, nitriminotetrazolate, bistetrazolate, bistetrazolyltriazenate, bistetrazolylamine, azotetrazolate or azide ion.
wobei jeder der unterschiedlichen Sprengstoffe ein wie in den Ansprüchen 1 bis 5 spezifiziertes Komplexsalz ist.Explosive according to claim 6,
wherein each of the different explosives is a complex salt as specified in claims 1 to 5.
wobei das Gegenionen ein Na-, K-, Ca-, Mg-, Sr-, Ba-, La-, Cu-, Ni-, Fe-, Zn-, Co-, Mn-, Cd-, In-, Al-, Cr-, Ag-, Yb-, Y-, Gd-, Hydrazin-, Guanidin- oder Ammoniak-Ion ist.Use according to claim 8,
where the counterions are a Na, K, Ca, Mg, Sr, Ba, La, Cu, Ni, Fe, Zn, Co, Mn, Cd, In, Al -, Cr, Ag, Yb, Y, Gd, hydrazine, guanidine or ammonia ion.
wobei das den Liganden potentiell oxidierende oder das energetische Ion ein Perchlorat-, Chlorat-, Bromat-, Jodat-, Perjodat-, Persulphat-, Trinitromethanat-, Dinitromethanat-, Chromat-, Dichromat-, Nitrat-, Dinitramin-, Permanganat-, Nitrotetrazolat-, Nitriminotetrazolat-, Bistetrazolat-, Bistetrazolyltriazenat-, Bistetrazolylamin-, Azotetrazolat- oder Azid-Ion ist.Use according to claim 8 or 9,
wherein the ligand is potentially oxidizing or the energetic ion is a perchlorate, chlorate, bromate, iodate, periodate, persulphate, trinitromethanate, dinitromethanate, chromate, dichromate, nitrate, dinitramine, permanganate, Nitrotetrazolate, nitriminotetrazolate, bistetrazolate, bistetrazolyltriazenate, bistetrazolylamine, azotetrazolate or azide ion.
wobei das Gemisch mindestens zwei unterschiedliche Sprengstoffe umfasst, wobei jeder der unterschiedlichen Sprengstoffe ein Sprengstoff nach einem der Ansprüche 1 bis 5 ist.Using a mixture as an explosive,
wherein the mixture comprises at least two different explosives, each of the different explosives being an explosive according to any one of claims 1 to 5.
wobei jeder der unterschiedlichen Sprengstoffe ein wie in den Ansprüchen 1 bis 5 spezifiziertes Komplexsalz ist.Use according to claim 11,
wherein each of the different explosives is a complex salt as specified in claims 1 to 5.
wobei der Sprengstoff ein, insbesondere einstufiger, Initialsprengstoff ist.Use according to any one of claims 8 to 12,
wherein the explosive is a, in particular single-stage, initial explosive.
wobei der Sprengstoff ein Sprengstoff zum Zünden durch einen Laserstrahl ist.Use according to one of claims 8 to 13,
wherein the explosive is an explosive for igniting by a laser beam.
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DE102010050862A DE102010050862A1 (en) | 2010-11-09 | 2010-11-09 | Explosive comprising a tetrazole compound |
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EP2450329A2 true EP2450329A2 (en) | 2012-05-09 |
EP2450329A3 EP2450329A3 (en) | 2015-12-16 |
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EP (1) | EP2450329B1 (en) |
DE (1) | DE102010050862A1 (en) |
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WO2018011134A1 (en) * | 2016-07-11 | 2018-01-18 | Dynitec Gmbh | Lead-free initiating agents or initiating agent mixtures |
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CN103319291B (en) * | 2013-06-26 | 2015-12-02 | 北京理工大学 | A kind of preparation method of green priming explosive nitrine hydrazine copper |
CN112280055A (en) * | 2020-10-30 | 2021-01-29 | 中国工程物理研究院化工材料研究所 | Cadmium-based energetic metal organic framework directly initiated by 1064nm laser, preparation method and application |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0733520A1 (en) | 1995-03-24 | 1996-09-25 | Morton International, Inc. | An airbag inflator having a housing protected from high-temperature, reactive generated gases |
US7592462B2 (en) | 2007-02-15 | 2009-09-22 | Los Alamos National Security, Llc | Explosive complexes |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3734789A (en) * | 1969-11-28 | 1973-05-22 | Us Navy | Gas generating solid propellant containing 5-aminotetrazole nitrate |
US5197758A (en) * | 1991-10-09 | 1993-03-30 | Morton International, Inc. | Non-azide gas generant formulation, method, and apparatus |
US6077371A (en) * | 1997-02-10 | 2000-06-20 | Automotive Systems Laboratory, Inc. | Gas generants comprising transition metal nitrite complexes |
US6277221B1 (en) * | 1999-04-13 | 2001-08-21 | Atlantic Research Corporation | Propellant compositions with salts and complexes of lanthanide and rare earth elements |
JP2001278868A (en) * | 2000-03-29 | 2001-10-10 | Otsuka Chem Co Ltd | Compound containing neutral ligand |
US6958101B2 (en) * | 2003-04-11 | 2005-10-25 | Autoliv Asp, Inc. | Substituted basic metal nitrates in gas generation |
US20060289096A1 (en) * | 2003-07-25 | 2006-12-28 | Mendenhall Ivan V | Extrudable gas generant |
FR2891822B1 (en) * | 2005-10-11 | 2008-02-15 | Snpe Materiaux Energetiques Sa | OXYGEN-RICH BI-METALLIC COMPLEXES, PREPARATION THEREOF AND PYROTECHNIC COMPOSITIONS COMPRISING THE SAME |
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2010
- 2010-11-09 DE DE102010050862A patent/DE102010050862A1/en not_active Withdrawn
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- 2011-11-03 NO NO11008768A patent/NO2450329T3/no unknown
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0733520A1 (en) | 1995-03-24 | 1996-09-25 | Morton International, Inc. | An airbag inflator having a housing protected from high-temperature, reactive generated gases |
US7592462B2 (en) | 2007-02-15 | 2009-09-22 | Los Alamos National Security, Llc | Explosive complexes |
Cited By (2)
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WO2018011134A1 (en) * | 2016-07-11 | 2018-01-18 | Dynitec Gmbh | Lead-free initiating agents or initiating agent mixtures |
US11535575B2 (en) | 2016-07-11 | 2022-12-27 | Dynitec Gmbh | Lead-free initiating agents or initiating agent mixtures |
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DE102010050862A1 (en) | 2012-05-10 |
NO2450329T3 (en) | 2018-06-02 |
IL216208B (en) | 2018-10-31 |
ZA201108145B (en) | 2012-07-25 |
EP2450329A3 (en) | 2015-12-16 |
IL216208A0 (en) | 2012-02-29 |
EP2450329B1 (en) | 2018-01-03 |
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