EP2450330A2 - Explosive containing an aminoguanidine compound - Google Patents

Abstract

Explosive comprises a complex salt comprising mono-, di- or triaminoguanidine as a ligand, a potentially oxidizing or an energetic ion, and a counter ion complexed with the ligand. Independent claims are also included for: (1) the explosive comprising a mixture of at least two different explosives, where each of the different explosives is the explosive mentioned above; (2) the use of the complex salt as the explosive; and (3) the use of the mixture as the explosive, where mixture comprises at least two different explosives, and each of the different explosives is the explosive mentioned above.

Description

The invention relates to an explosive comprising an aminoguanidine compound.

Out Jensen, KA and Nygaard, B., Acta Chemica Scandinavica 3 (1949), pages 481-486 Nickel compounds of aminoguanidine, diaminoguanidine and triaminoguanidine are known.

From the WO 2006/128910 For example, a pyrotechnic agent is known which contains as component a aminoguanidine-5,5'-azotetrazolate.

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.

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 storing it decomposes in such a way that a safe operational capability can no longer be guaranteed after 5 to 10 years.

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.

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.

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.

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.

According to the invention, an explosive comprising a complex salt which comprises mono-, di- or triaminoguanidine as ligands, a ligand potentially oxidizing or an energetic ion and a ligand complexed counterion is provided. 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. Its density can exceed 2000 kg / m3. Thus, 90% of the theoretical density of a monoaminoguanidine complex salt with a nickel ion as the counter ion and a perchlorate ion as the ligand is potentially oxidizing or energetic 2130 kg / m3, while 90% of the theoretical density of hexogen is only 1625 kg / m3. The detonation pressure of said complex salt is 330 kbar at 90% theoretical density and the detonation velocity is 8175 m / s. The detonation pressure of hexogen at 90% of the theoretical density is 265 kbar and the detonation speed 8260 m / s. 90% of the theoretical density is taken as a rough estimate of the achievable press density.

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. In some cases, the detonation pressure of the explosive according to the invention may even exceed 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.

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.

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.

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.

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.

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.

In addition, the inventors have found that the properties of an explosive containing the explosive according to the invention, by the choice of explosive, the choice of the counterion, the choice of a mono-, di- or triaminoguanidine and the choice of the ligand potentially oxidizing or energetic ions can be adjusted. The sensitivity of the explosive according to the invention can also be adjusted by the choice of the counterion, the choice of a mono-, di- or triaminoguanidine 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.

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 may be a perchlorate, chlorate, bromate, iodate, periodate, persulphate, trinitromethanate, dinitromethanate, chromate, dichromate, dinitramine, permanganate, nitrotetrazolate, Nitriminotetrazolate, bistetrazolate, bistetrazolyltriazenate, bistetrazolylamine, azotetrazolate or azide ion.

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 due to 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.

Furthermore, the invention relates to the use of a complex salt which comprises mono-, di- or triaminoguanidine 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, 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.

Fig. 1

zeigt zum Größenvergleich links ein Streichholz und rechts einen Zentimetermaßstab. In der Mitte ist eine Glaskapillare mit einer schwarzen Zündschnur zu sehen. Im unteren Teil der Glaskapillare befindet sich ein erfindungsgemäßer Sprengstoff.

The invention will be described below with reference to FIG Fig. 1 and explained by exemplary embodiments.

Fig. 1

shows to size comparison on the left a match and right a centimeter scale. In the middle is a glass capillary with a black fuse. In the lower part of the glass capillary is an explosive according to the invention.

At the in Fig. 1 The explosive shown in the glass capillary is uncompressed nickel di (aminoguanidine) diperchlorate. The capillary contains less than 3 mg of the explosive. Even this small amount of explosive was able to ignite a secondary charge of Nitropenta when ignited by a glowing flame of the fuse and thus serve as an igniter. The critical diameter of the explosive is very small. A comparable igniter with lead azide would require about 20 mg of lead azide.

1. General working instructions for the production of the explosive 1.1 General working procedure 1 (AAV 1)

The complex (= ligand) mono-, di- or triaminoguanidine is slurried in cold water and the concentration, unless otherwise stated, adjusted to 1 mol / l. The metal salt to be complexed 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 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.

1.2 General Working Procedure 2 (AAV 2)

The procedure is as in general working procedure 1, wherein instead of the complexed image complexing salt solution, unless otherwise stated in a concentration of 1 mol / l, is used. The salt consists of the Komplexbildkation and the complex images potentially oxidizing anion. The salt may be, for example, monoaminoguanidine perchlorate. The Saline solution is prepared from complexed hydrogencarbonate and corresponding acid in the correct molar ratio directly in solution, whereby the resulting carbon dioxide escapes.

1.3 General Working Procedure 3 (AAV 3)

The procedure is as in general procedure 1, wherein instead of the metal salt, a solid Metallamminkomplexsalz and instead of the slurried complexing complex complexing salt solution is used. For example, to produce metal monoaminoguanidine perchlorate, monoaminoguanidine perchlorate is provided as a solution as described in General Procedure 2 and solid metal ammine perchlorate, for example, nickel ammine perchlorate, is added to this solution.

2. Production of explosives 2.1 Preparation of nickel (II) di (monoaminoguanidine) diperchlorate by a first method

AAV 1 was used. In this case, 1.36 g (10.0 mmol) of monoaminoguanidine hydrogencarbonate and 1.4 g (4.0 mmol) of nickel perchlorate hexahydrate were used. The yield was 40% in the form of orange crystals.

2.2 Preparation of nickel (II) di (monoaminoguanidine) diperchlorate by a second method

It was proceeded to AAV 2. In this case, 1.6 g (12.0 mmol) of monoaminoguanidine hydrogencarbonate and 2.0 g of 60% perchloric acid in 25 ml of water and 1.4 g (4.0 mmol) of nickel perchlorate hexahydrate were used. The yield was 70% in the form of orange crystals.

2.3 Preparation of nickel (II) di (monoaminoguanidine) diperchlorate by a third method

It was proceeded to AAV 3. In this case, 1.6 g (12.0 mmol) of monoaminoguanidine hydrogen carbonate, 2.0 g of 60% perchloric acid in 25 ml of water and 1.0 g (2.8 mmol) of hexaammonium perchlorate were used. The yield was 89% (2.5 mmol) in the form of dark orange crystals. The crystals have proven to be a very powerful initial explosive. In the Trauzl lead-block bulking used to examine the working capacity, the nickel (II) di (monoaminoguanidine) diperchlorate exhibited a bulge of 39.6 cm 3 / g. In comparison, the lead block bulking of lead azide is 11.0 cc / g, of lead neurite 13.0 cc / g, of TNT 30.0 cc / g and of hexogen 48.0 cc / g. Examination of the laser sensitivity revealed that the explosive could be detonated using 532 nm radiation and 630 nm radiation.

2.4 Preparation of copper (II) di (monoaminoguanidine) diperchlorate

It was prepared according to AAV 1. 1.5 g (11 mmol) of monoaminoguanidine hydrogencarbonate in 10 ml of water and 2.0 g (5.4 mmol) of copper perchlorate hexahydrate in 10 ml of water were used. Unlike the AAV 1, the solution was not boiled. The reaction was carried out at room temperature. The yield was 72% = 1.6 g (3.9 mmol) in the form of dark purple crystals. The formed material represents a very high-performance initial explosive. The Bleiblockausbauchung after Trauzl amounts to 38,2 cm3 / g. The fabric is laser sensitive. It can be brought to deflagration by means of 630 nm radiation.

2.5 Preparation of cobalt (II) di (monoaminoguanidine) diperchlorate

The preparation was carried out according to AAV 1. There were used 1.36 g (10 mmol) of monoaminoguanidine hydrogencarbonate in 10 ml of water and 1.46 g (4 mmol) of cobalt (II) perchlorate hexahydrate in 10 ml of water. The cobalt carbonate formed in the reaction is filtered off from the hot solution and the filtrate was concentrated. The result is a dark brown, almost black syrup, which explodes at 200 ° C strong. Crystal formation did not occur.

2.6 Preparation of cobalt (II) di (monoaminoguanidine) dinitrate

The preparation was carried out according to AAV 1. There were used 1.36 g (10 mmol) of monoaminoguanidine hydrogencarbonate in 10 ml of water and 1.2 g (4 mmol) of cobalt (II) nitrate hexahydrate in 10 ml of water. The formed cobalt carbonate is filtered off from the hot solution and the filtrate is concentrated. The result is a dark brown syrup. Crystal formation did not occur. The substance decomposes at 150 ° C under gasification.

Claims (14)

An explosive comprising a complex salt which comprises mono-, di- or triaminoguanidine as ligands, a ligand potentially oxidizing or an energetic ion and a ligand complexed counterion. Explosive according to claim 1,
wherein the explosive is a, in particular single-stage, initial explosive. Explosive according to claim 1 or 2,
wherein the explosive is an explosive to be ignited by a laser beam. 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. 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, dinitramine, permanganate, nitrotetrazolate, Nitriminotetrazolate, bistetrazolate, bistetrazolyltriazenate, bistetrazolylamine, azotetrazolate or azide ion. An explosive comprising a mixture of at least two different explosives, each of the different explosives being an explosive according to any one of the preceding claims. Explosive according to claim 6,
wherein each of the different explosives is a complex salt as specified in claims 1 to 5. Use of a complex salt which comprises mono-, di- or triaminoguanidine as ligands, a ligand potentially oxidizing or an energetic ion and a ligand complexed counterion as explosive. 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. 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, dinitramine, permanganate, nitrotetrazolate, Nitriminotetrazolate, bistetrazolate, bistetrazolyltriazenate, bistetrazolylamine, azotetrazolate or azide ion. 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. Use according to claim 11,
wherein each of the different explosives is a complex salt as specified in claims 1 to 5. Use according to any one of claims 8 to 12,
wherein the explosive is a, in particular single-stage, initial explosive. 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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