EP0697385B1 - Metal complex compounds - Google Patents

Metal complex compounds Download PDF

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Publication number
EP0697385B1
EP0697385B1 EP95110885A EP95110885A EP0697385B1 EP 0697385 B1 EP0697385 B1 EP 0697385B1 EP 95110885 A EP95110885 A EP 95110885A EP 95110885 A EP95110885 A EP 95110885A EP 0697385 B1 EP0697385 B1 EP 0697385B1
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dadpyox
metal complex
stands
complex compounds
compounds according
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French (fr)
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EP0697385A1 (en
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Nikolaus Dr. Fiederling
Cornelius Dr. Ruloff
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Dynamit Nobel GmbH Explosivstoff und Systemtechnik
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Dynamit Nobel AG
Dynamit Nobel GmbH Explosivstoff und Systemtechnik
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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
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine

Definitions

  • the present invention relates to new metal complex compounds of the general formula Me (DADPyOx) x , in which Me is a transition metal ion and x is 1, 2, 3 or 4, processes for their preparation and their use.
  • the object of the present invention was therefore to provide new compounds in a simple manner, which, inter alia, can be used as insensitive, high-energy explosives.
  • DADPyOx 2,6-diamino-3,5-dinitro-pyridine-1-oxide, hereinafter called DADPyOx
  • DADPyOx can be produced, for example, by dinitration of the 2,6-diaminopyridine and subsequent oxidation of the 2,6-diamino-3,5-dinitropyridine formed with hydrogen peroxide.
  • DADPyOx is an explosive that is high in energy and is relatively temperature stable (cf. DE-OS 39 20 336). Because of its structure DADPyOx can be complexed with transition metal ions. Copper, nickel, cobalt, iron, silver or zinc are used as transition metals in their respective possible oxidation states.
  • the new compounds according to the invention are prepared in such a way that DADPyOx is suspended in a suitable suspension medium, for example glacial acetic acid, dimethylformamide or water, particularly preferably in glacial acetic acid, and the corresponding transition metal salt, for example the corresponding chloride, sulfate, carbonate or nitrate, preferably the corresponding one Solid metal transition metal nitrate is added in portions.
  • a suitable suspension medium for example glacial acetic acid, dimethylformamide or water, particularly preferably in glacial acetic acid
  • the corresponding transition metal salt for example the corresponding chloride, sulfate, carbonate or nitrate, preferably the corresponding one Solid metal transition metal nitrate is added in portions.
  • the reaction mixture can be heated to boiling. In view of the best possible yields, stoichiometric amounts of the reactants are preferred.
  • the amount of suspending agent to be used 100 ml suspending agent per 1 g DADPyOx. If necessary
  • Me stands for copper, nickel, cobalt, iron, silver or zinc in their respective possible oxidation states and x for 1, 2, 3 or 4.
  • the new compounds are extremely temperature-stable, while the other properties that are decisive for a high-energy explosive are essentially not adversely affected.
  • metal ion additives are generally regarded as ballast in explosives, which can be expected to significantly reduce the speed of detonation.
  • compounds are obtained according to the invention which, under the same measuring conditions, have detonation speeds of approximately the same order of magnitude as those of the starting compound.
  • Table II shows the surprisingly high temperature stability: Table II Decomposition point Cu (DADPyOx) 2 364 ° C Ni (DADPyOx) 2 370 ° C DADPyOx 355 ° C TNT 300 ° C
  • the approximate detonation speed was determined on a laboratory scale using a simple experimental setup with SIP pressure transducers ("shock wave-induced polarization") (FE Allison; J.Appl.Phys. 36 (1965), 211; GE. Hauver; J.Appl.Phys. 36 (1966 ), 2113).
  • the selected method has the advantage that it can be carried out with amounts of substance up to 2 g.
  • the detonation pressure can also be roughly estimated.
  • 150 kbar were determined for Cu (DADPyOx) 2 at a press density of 1.46 g / ml; for Ni (DADPyOx) 2 there was a detonation speed of approx. 5,400 m / s.
  • the maximum density was determined in a pycnometer for Cu (DADPyOx) 2 to 2.07 g / ml and for Ni (DADPyOx) 2 to 2.03 g / ml. Under the same measuring conditions, DADPyOx showed a detonation speed of approx. 5,900 m / s.
  • the compounds of the invention are new. Due to their properties, they can be used as explosives and used, for example, in detonators. Among other things, you can replace the secondary explosives common in detonators.
  • the compounds according to the invention can also be used as combustion moderators e.g. be used in solid fuels.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Gegenstand der vorliegenden Erfindung sind neue Metallkomplexverbindungen der allgemeinen Formel Me(DADPyOx)x, worin Me für ein Übergangsmetallion und x für 1, 2, 3 oder 4 steht, Verfahren zu deren Herstellung, sowie deren Verwendung.The present invention relates to new metal complex compounds of the general formula Me (DADPyOx) x , in which Me is a transition metal ion and x is 1, 2, 3 or 4, processes for their preparation and their use.

Unfälle mit Waffen und Waffensystemen, die auf die Empfindlichkeit der Explosivstoffe zurückzuführen waren, haben die Suche nach unempfindlichen, aber dennoch leistungsstarken Sprengstoffen in den letzten Jahren verstärken lassen. Während im Rahmen des LoVA-Konzepts ("Low Vulnerable Ammunition") dabei die Suche nach unempfindlichen Waffensystemen im Vordergrund steht, werden im Rahmen eines Teilaspektes dieses Konzeptes sogenannte IHE ("Insensitive High Explosive") erforscht. Zur Realisierung dieses Teilaspektes werden dabei im wesentlichen zwei Wege beschritten:

  • a) gezielte Synthese neuer, energiereicher, insensitiver Verbindungen;
  • b) Phlegmatisierung möglichst energiereicher, sensitiver Explosivstoffe; beispielsweise Einbinden von RDX, HMX in Wachs oder Kunststoff-Matrices.
Accidents involving weapons and weapon systems, which were attributable to the sensitivity of the explosives, have intensified the search for insensitive yet powerful explosives in recent years. While the LoVA concept ("Low Vulnerable Ammunition") focuses on the search for insensitive weapon systems, so-called IHE ("Insensitive High Explosive") is researched as part of this concept. There are two main ways of realizing this aspect:
  • a) targeted synthesis of new, high-energy, insensitive compounds;
  • b) desensitization of explosives which are as energetic as possible and sensitive; for example incorporating RDX, HMX in wax or plastic matrices.

Die gezielte Herstellung energiereicher, insensitiver Explosivstoffe ist häufig nur über komplizierte, mit geringen Ausbeuten ablaufenden und damit teuren Synthesewegen möglich. Verbindungen, die auf diese Weise hergestellt werden, sind daher im allgemeinen von geringer wirtschaftlicher Bedeutung. Vom wirtschaftlichen Gesichtspunkt her bietet zwar die Phlegmatisierung bekannter, auch in ihrer wirtschaftlichen Bedeutung einschätzbarer, energiereicher Explosivstoffe Vorteile, doch ist sie auf der anderen Seite mit allen bekannten Problemen von Mehrphasensystemen wie beispielsweise Grenzflächenproblemen, Homogenität u.a. behaftet und erfordert oftmals einen erheblichen technischen Aufwand.The targeted production of high-energy, insensitive explosives is often only possible via complicated, low-yielding and therefore expensive synthetic routes. Compounds made in this way are therefore generally of little economic importance. From the economic point of view, the desensitization of known, high-energy explosives, which can also be estimated in their economic importance, offers advantages, but on the other hand it is homogeneous with all known problems of multiphase systems, such as, for example, interface problems inter alia afflicted and often requires considerable technical effort.

Aufgabe der vorliegenden Erfindung war es daher, auf einfache Weise neue Verbindungen bereitzustellen, die u.a. als insensitive, energiereiche Explosivstoffe Verwendung finden können.The object of the present invention was therefore to provide new compounds in a simple manner, which, inter alia, can be used as insensitive, high-energy explosives.

Gelöst wurde diese Aufgabe durch Verbindungen gemäß Anspruch 1, die nach dem Verfahren gemäß Anspruch 5 hergestellt werden können. Durch die Komplexierung bestimmter Liganden mit bestimmten Komplexbildnern ändert sich die elektronische Umgebung der Ausgangssubstanz; Bindungskräfte lassen sich auf diese Weise variieren. Eine Variation der Bindungskräfte bedingt auf der anderen Seite aber auch eine Eigenschaftsveränderung der Ausgangssubstanz. In diesem Zusammenhang sei auf das System Cyclopentadien/Ferrocen verwiesen. Während Cyclopentadien einen Siedepunkt von 40 °C hat, zersetzt sich dessen Komplexverbindung mit Fe(II), das Ferrocen, erst oberhalb von 500 °C.This object was achieved by compounds according to claim 1, which can be prepared by the method according to claim 5. By complexing certain ligands with certain complexing agents, the electronic environment of the starting substance changes; Binding forces can be varied in this way. On the other hand, a variation in the binding forces also causes a change in the properties of the starting substance. In this context, reference is made to the cyclopentadiene / ferrocene system. While cyclopentadiene has a boiling point of 40 ° C, its complex compound with Fe (II), the ferrocene, only decomposes above 500 ° C.

Von entscheidender Bedeutung für die erfindungsgemäße Lösung ist die Wahl bestimmter Ausgangsverbindungen, die aufgrund ihrer Struktur als Liganden für komplexbildende Metalle dienen können. Nur bei der Auswahl bestimmter Liganden läßt sich das erfindungsgemäße Ziel, neue, insensitive, energiereiche Explosivstoffe bereitzustellen, auch erreichen. Aminonitroguanidin (ANQ) läßt sich zwar mit dem Komplexbildner Cu2+ zum Kupfer-bis-Aminonitroguanidin-nitrat umsetzen, doch zersetzt sich der Komplex bereits bei ca. 90 °C, während die Ausgangsverbindung, das ANQ, sich erst bei 184 °C zersetzt.Of decisive importance for the solution according to the invention is the choice of certain starting compounds which, because of their structure, can serve as ligands for complex-forming metals. The aim of the invention to provide new, insensitive, high-energy explosives can only be achieved when certain ligands are selected. Aminonitroguanidine (ANQ) can be converted to the copper bis-aminonitroguanidine nitrate with the complexing agent Cu 2+ , but the complex decomposes at approx. 90 ° C, while the starting compound, the ANQ, only decomposes at 184 ° C .

Erfindungsgemäß wurde das 2,6-Diamino-3,5-dinitro-pyridin-1-oxid, im folgenden DADPyOx genannt, ausgewählt und komplexiert. DADPyOx kann beispielsweise durch Dinitrierung des 2,6-Diaminopyridins und anschließender Oxidation des entstandenen 2,6-Diamino-3,5-dinitropyridins mit Wasserstoffperoxid hergestellt werden. DADPyOx stellt einen Explosivstoff dar, der energiereich und relativ temperaturstabil ist (vgl. DE-OS 39 20 336). Aufgrund seiner Struktur

Figure imgb0001
läßt sich DADPyOx mit Übergangsmetallionen komplexieren. Als Übergangsmetalle werden Kupfer, Nickel, Kobalt, Eisen, Silber oder Zink in ihren jeweils möglichen Oxidationsstufen eingesetzt.According to the invention, the 2,6-diamino-3,5-dinitro-pyridine-1-oxide, hereinafter called DADPyOx, was selected and complexed. DADPyOx can be produced, for example, by dinitration of the 2,6-diaminopyridine and subsequent oxidation of the 2,6-diamino-3,5-dinitropyridine formed with hydrogen peroxide. DADPyOx is an explosive that is high in energy and is relatively temperature stable (cf. DE-OS 39 20 336). Because of its structure
Figure imgb0001
 DADPyOx can be complexed with transition metal ions. Copper, nickel, cobalt, iron, silver or zinc are used as transition metals in their respective possible oxidation states.

Die Herstellung der neuen, erfindungsgemäßen Verbindungen erfolgt in der Weise, daß DADPyOx in einem geeigneten Suspensionsmittel, beispielsweise Eisessig, Dimethylformamid oder Wasser, besonders bevorzugt in Eisessig suspendiert und das entsprechende Übergangsmetallsalz, beispielsweise das entsprechende Chlorid, Sulfat, Carbonat oder Nitrat, vorzugsweise das entsprechende Übergangsmetallnitrat in fester Form portionsweise zugegeben wird. Gegebenenfalls kann die Reaktionsmischung zum Sieden erhitzt werden. Im Hinblick auf möglichst optimale Ausbeuten werden stöchiometrische Mengen der Reaktionspartner bevorzugt. Als Anhaltspunkt für die einzusetzende Menge an Suspensionsmittel kann gelten: 100 ml Suspensionsmittel pro 1 g DADPyOx. Falls erforderlich, wird eine eventuell gebildete Säure neutralisiert. Nach Beendigung der Reaktion wird der entstandene Feststoff abgesaugt, gewaschen und getrocknet.The new compounds according to the invention are prepared in such a way that DADPyOx is suspended in a suitable suspension medium, for example glacial acetic acid, dimethylformamide or water, particularly preferably in glacial acetic acid, and the corresponding transition metal salt, for example the corresponding chloride, sulfate, carbonate or nitrate, preferably the corresponding one Solid metal transition metal nitrate is added in portions. If necessary, the reaction mixture can be heated to boiling. In view of the best possible yields, stoichiometric amounts of the reactants are preferred. As a guideline for the amount of suspending agent to be used: 100 ml suspending agent per 1 g DADPyOx. If necessary, any acid formed is neutralized. After the reaction has ended, the solid formed is filtered off with suction, washed and dried.

Auf diese Weise war es überraschenderweise möglich, neue, insensitive, energiereiche Verbindungen der Formel Me(DADPyOx)x bereitzustellen. Hierbei steht Me für Kupfer, Nickel, Kobalt, Eisen, Silber oder Zink in ihren jeweils möglichen Oxidationsstufen und x für 1, 2, 3 oder 4. Die neuen Verbindungen sind äußerst temperaturstabil, während die für einen energiereichen Explosivstoff entscheidenden anderen Eigenschaften im wesentlichen nicht nachteilig beeinflußt werden. Dies ist umso überraschender, als im allgemeinen Metallionenzusätze bei Explosivstoffen als Ballast betrachtet werden, die eine wesentliche Verringerung der Detonationsgeschwindigkeit erwarten lassen. Überraschenderweise werden erfindungsgemäß Verbindungen erhalten, die unter gleichen Meßbedingungen Detonationsgeschwindigkeiten in etwa gleicher Größenordnung wie die der Ausgangsverbindung aufweisen.In this way it was surprisingly possible to provide new, insensitive, high-energy compounds of the formula Me (DADPyOx) x . Me stands for copper, nickel, cobalt, iron, silver or zinc in their respective possible oxidation states and x for 1, 2, 3 or 4. The new compounds are extremely temperature-stable, while the other properties that are decisive for a high-energy explosive are essentially not adversely affected. This is all the more surprising since metal ion additives are generally regarded as ballast in explosives, which can be expected to significantly reduce the speed of detonation. Surprisingly, compounds are obtained according to the invention which, under the same measuring conditions, have detonation speeds of approximately the same order of magnitude as those of the starting compound.

Die neuen Verbindungen sind in ihren mechanischen Eigenschaften denen von TNT vergleichbar. Für die erfindungsgemäßen Verbindungen Ni(DADPyOx)2 und Cu(DADPyOx)2 ergaben sich die in der Tabelle I angegebenen Werte: Tabelle I Schlag- Reibempfindlicheit Cu (DADPyOx)2 15 J > 360 N Ni (DADPyOx)2 15 J 240 N DADPyOx 15 J > 360 N TNT 15 J > 360 N The mechanical properties of the new connections are comparable to those of TNT. The values given in Table I resulted for the compounds Ni (DADPyOx) 2 and Cu (DADPyOx) 2 according to the invention: Table I Blow Sensitivity to friction Cu (DADPyOx) 2 15 y > 360 N. Ni (DADPyOx) 2 15 y 240 N. DADPyOx 15 y > 360 N. TNT 15 y > 360 N.

Die überraschend hohe Temperaturstabilität zeigt Tabelle II: Tabelle II Zersetzungspunkt Cu (DADPyOx)2 364 °C Ni (DADPyOx)2 370 °C DADPyOx 355 °C TNT 300 °C Table II shows the surprisingly high temperature stability: Table II Decomposition point Cu (DADPyOx) 2 364 ° C Ni (DADPyOx) 2 370 ° C DADPyOx 355 ° C TNT 300 ° C

Die Detonationsfähigkeit wurde im sogenannten "Grenzinitialtest" (H. Jobelius, H. Zöllner; 22. Int. Jahrestagung des Fraunhoferinstitutes f. Treibmittel- und Explosivstoffe, ICT, Karlsruhe; (1991), Seite 79-1 bis 79-13) bestimmt. Dabei wurden in einem Standard-Kapselaufbau, mit Kapseldurchmessern von 7 bis 8 mm, zwischen 50 und 100 mg der zu testenden Substanz mit verschiedenen Mengen Bleiazid überschichtet und initiiert. Als Nachweis einer Detonation wurde der Durchschlag durch eine Bleiplatte verwendet. Als Vergleichssubstanzen wurden PETN, Tetryl und HMX verwendet. Die Ergebnisse zeigt die Tabelle III. Überraschenderweise sind die erfindungsgemäßen Verbindungen, wie sich im Grenzinitialtest zeigen ließ, bereits in relativ geringen Durchmessern detonationsfähig. Tabelle III Grenzinitial Cu (DADPyOx)2 30 mg Ni (DADPyOx)2 20 mg PETN 10 mg Tetryl 20 mg HMX 40 mg The detonation ability was tested in the so-called "limit initial test" (H. Jobelius, H. Zöllner; 22nd International Annual Meeting of the Fraunhofer Institute for Propellants and Explosives, ICT, Karlsruhe; (1991), pages 79-1 to 79-13). In a standard capsule structure with capsule diameters of 7 to 8 mm, between 50 and 100 mg of the substance to be tested were overlaid with different amounts of lead azide and initiated. Penetration through a lead plate was used as evidence of a detonation. PETN, Tetryl and HMX were used as reference substances. The results are shown in Table III. Surprisingly, the compounds according to the invention can be detonated even in relatively small diameters, as was shown in the limit initial test. Table III Limit initial Cu (DADPyOx) 2 30 mg Ni (DADPyOx) 2 20 mg PETN 10 mg Tetryl 20 mg HMX 40 mg

Die ungefähre Detonationsgeschwindigkeit wurde im Labormaßstab mit einem einfachen Versuchsaufbau mit SIP-Druckaufnehmern ("Stoßwelleninduzierte Polarisation") (F.E. Allison; J.Appl.Phys. 36 (1965), 211; GE. Hauver; J.Appl.Phys. 36 (1966), 2113) durchgeführt. Das gewählte Verfahren bietet den Vorteil, daß es bereits mit Substanzmengen bis zu 2 g durchzuführen ist. Neben dem Nachweis der Detonationsfähigkeit und einer Abschätzung der Detonationsgeschwindigkeit läßt sich auch der Detonationsdruck grob abschätzen. Für Cu(DADPyOx)2 wurde eine Detonationsgeschwindigkeit von ca. 5.500 m/s und ein Detonationsdruck von ca. 150 kbar, bei einer Pressdichte von 1,46 g/ml bestimmt; für Ni(DADPyOx)2 ergab sich eine Detonationsgeschwindigkeit von ca. 5.400 m/s. Die maximale Dichte wurde in einem Pyknometer für Cu(DADPyOx)2 zu 2,07 g/ml, für Ni(DADPyOx)2 zu 2,03 g/ml bestimmt. Unter gleichen Meßbedingungen ergab DADPyOx eine Detonationsgeschwindigkeit von ca. 5.900 m/s.The approximate detonation speed was determined on a laboratory scale using a simple experimental setup with SIP pressure transducers ("shock wave-induced polarization") (FE Allison; J.Appl.Phys. 36 (1965), 211; GE. Hauver; J.Appl.Phys. 36 (1966 ), 2113). The selected method has the advantage that it can be carried out with amounts of substance up to 2 g. In addition to the detection of the detonation ability and an estimate of the detonation speed, the detonation pressure can also be roughly estimated. A detonation speed of approx. 5,500 m / s and a detonation pressure of approx. 150 kbar were determined for Cu (DADPyOx) 2 at a press density of 1.46 g / ml; for Ni (DADPyOx) 2 there was a detonation speed of approx. 5,400 m / s. The maximum density was determined in a pycnometer for Cu (DADPyOx) 2 to 2.07 g / ml and for Ni (DADPyOx) 2 to 2.03 g / ml. Under the same measuring conditions, DADPyOx showed a detonation speed of approx. 5,900 m / s.

Die erfindungsgemäßen Verbindungen sind neu. Sie lassen sich aufgrund ihrer Eigenschaften als Explosivstoffe verwenden und beispielsweise in Sprengkapseln einsetzen. Sie können u.a. die in Sprengkapseln üblichen Sekundärsprengstoffe ersetzen. Außerdem können die erfindungsgemäßen Verbindungen auch als Abbrandmoderatoren z.B. in Festtreibstoffen verwendet werden.The compounds of the invention are new. Due to their properties, they can be used as explosives and used, for example, in detonators. Among other things, you can replace the secondary explosives common in detonators. In addition, the compounds according to the invention can also be used as combustion moderators e.g. be used in solid fuels.

Die nachfolgenden Beispiele sollen die vorliegende Erfindung erläutern, ohne sie einzuschränken.The following examples are intended to illustrate the present invention without restricting it.

Beispiel 1: Example 1 :

2,273 g (10,57 mmol) DADPyOx werden in 200 ml Eisessig suspendiert. - Dazu werden unter Rühren 1,289 g (5,34 mmol) Cu(NO3)2·3H2O als Feststoff portionsweise gegeben. Die Farbe schlägt dabei von gelb nach grün um. Der Feststoff wird abgesaugt und dreimal mit 30 ml Eisessig gewaschen. Nach Trocknung über Nacht an der Luft wird bei 1,3 Pa (10-2 Torr) weiter getrocknet. Die Ausbeute beträgt 2,00 g (76 % d. Th.).

C10H8CuN10O10
M = 491,776 g/mol
Zersetzungspunkt
keine Zersetzung bis 360 °C
Farbe
ockergelb
Elementaranalyse: C H N Cu ber. 24,42 % 1,64 % 28,48 % 12,92 % gef. 25,14 % 1,80 % 28,69 % 12,41 % 2.273 g (10.57 mmol) of DADPyOx are suspended in 200 ml of glacial acetic acid. - 1.289 g (5.34 mmol) of Cu (NO 3 ) 2 .3H 2 O are added in portions as a solid with stirring. The color changes from yellow to green. The solid is filtered off and washed three times with 30 ml of glacial acetic acid. After drying overnight in air, drying is continued at 1.3 Pa (10 -2 torr). The yield is 2.00 g (76% of theory).
C 10 H 8 CuN 10 O 10
M = 491.776 g / mol
Decomposition point
no decomposition up to 360 ° C
colour
ocher yellow
Elemental analysis: C. H N Cu about. 24.42% 1.64% 28.48% 12.92% found 25.14% 1.80% 28.69% 12.41%

Beispiel 2:Example 2:

5,022 g (23,35 mmol) DADPyOx werden in 500 ml Eisessig suspendiert. Dazu werden bei Raumtemperatur unter Rühren 3,394 g (11,67 mmol) Ni(NO3)2·6H2O als Feststoff portionsweise gegeben. Die Suspension hat eine leuchtend gelbe Farbe. Es wird unter Rühren bis zum Rückfluß erhitzt und 1,5 h gehalten. Bei einer Innentemperatur oberhalb von 100 °C schlägt die Farbe innerhalb kurzer Zeit dabei in rötlich-braun um. Nach dem Abkühlen wird der Feststoff abgesaugt und dreimal mit 50 ml Eisessig gewaschen. Nach Trocknung über Nacht an der Luft wird bei 1,3 Pa (10-2 Torr) weiter getrocknet. Die Ausbeute beträgt 3,39 g (60 % d. Th.).

C10H8NiN10O10
M = 486,930 g/mol
Zersetzungspunkt
keine Zersetzung bis 360 °C
Farbe
rötlich-braun
Elementaranalyse: C H N Cu ber. 24,67 % 1,66 % 28,77 % 12,06 % gef. 25,14 % 1,66 % 28,44 % 11,73 % 5.022 g (23.35 mmol) of DADPyOx are suspended in 500 ml of glacial acetic acid. To this, 3.394 g (11.67 mmol) of Ni (NO 3 ) 2 .6H 2 O are added in portions as a solid at room temperature with stirring. The suspension has a bright yellow color. The mixture is heated to reflux with stirring and held for 1.5 hours. If the interior temperature is above 100 ° C, the color will beat within a short time in reddish-brown. After cooling, the solid is filtered off and washed three times with 50 ml of glacial acetic acid. After drying overnight in air, drying is continued at 1.3 Pa (10 -2 torr). The yield is 3.39 g (60% of theory).
C 10 H 8 NiN 10 O 10
M = 486.930 g / mol
Decomposition point
no decomposition up to 360 ° C
colour
reddish brown
Elemental analysis: C. H N Cu about. 24.67% 1.66% 28.77% 12.06% found 25.14% 1.66% 28.44% 11.73%

Claims (10)

  1. Metal complex compound of the general formula Me(DADPyOx)x, wherein Me stands for a transition metal ion, DADPyOx stands for 2,6-diamino-3,5-dinitro-pyridine-1-oxide and x stands for 1, 2, 3 or 4.
  2. Metal complex Compound according to claim 1, characterised in that Me stands for copper, nickel, cobalt, iron, silver or zinc in their respective oxidation stages and x corresponds to the respective oxidation stages.
  3. Metal complex compound according to claim 1 or 2, characterized in that it corresponds to the formula Cu(DADPyOx)2.
  4. Metal complex compound according to claim 1 or 2, characterised in that it corresponds to the formula Ni[DADPyOx)2.
  5. Process for the preparation of metal complex compounds of the general formula Me(DADPyOx)x, wherein Me stands for a transition metal ion, DADPyOx stands for 2,6-diamino-3,5-dinitro-pyridine-1-oxide and x stands for 1, 2, 3 or 4, characterised in that DADPyOx is caused to react with the corresponding transition metal salt, preferably with the corresponding transition metal chloride, sulphate, carbonate or nitrate, in a suitable dispersing agent.
  6. Process for the preparation of metal complex compounds according to claim 5, characterised in that glacial acetic acid, dimethyl formamide or water, preferably glacial acetic acid, is used as dispersing agent.
  7. Process for the preparation of metal complex compounds according to claim 5 or 6, characterised in that Ni(NO3)2.6H2O or Cu(NO3)2.3H2O is used as transition metal salts.
  8. Use of the metal complex compounds according to one of claims 1 to 4, as insensitive explosive substances with high temperature stability.
  9. Use of the metal complex compounds according to one of claims 1 to 4, in detonators.
  10. Use of the metal complex compounds according to one of claims 1 to 4, as burn-off moderators.
EP95110885A 1994-07-12 1995-07-12 Metal complex compounds Expired - Lifetime EP0697385B1 (en)

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DE4424088 1994-07-12
DE4424088 1994-07-12
US08/501,342 US5578785A (en) 1994-07-12 1995-07-12 Metal complex compounds

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EP0697385A1 EP0697385A1 (en) 1996-02-21
EP0697385B1 true EP0697385B1 (en) 1997-10-01

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DE3920336C2 (en) * 1989-06-21 1997-01-09 Deutsch Franz Forsch Inst Explosive mass with low sensitivity

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DE19525265A1 (en) 1996-01-18

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