EP0503341A1 - Stable nitrogen-rich compound - Google Patents
Stable nitrogen-rich compound Download PDFInfo
- Publication number
- EP0503341A1 EP0503341A1 EP92103023A EP92103023A EP0503341A1 EP 0503341 A1 EP0503341 A1 EP 0503341A1 EP 92103023 A EP92103023 A EP 92103023A EP 92103023 A EP92103023 A EP 92103023A EP 0503341 A1 EP0503341 A1 EP 0503341A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- use according
- azotetrazolate
- mixture
- added
- diguanidinium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 12
- 150000001875 compounds Chemical class 0.000 title description 8
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 4
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 4
- 231100000252 nontoxic Toxicity 0.000 claims abstract description 3
- 230000003000 nontoxic effect Effects 0.000 claims abstract description 3
- 239000002341 toxic gas Substances 0.000 claims abstract description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 238000002485 combustion reaction Methods 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 150000004686 pentahydrates Chemical class 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims description 5
- 229910001385 heavy metal Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 235000010333 potassium nitrate Nutrition 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 3
- JVSMPWHQUPKRNV-UHFFFAOYSA-N 2h-tetrazol-5-amine;hydrate Chemical compound O.NC=1N=NNN=1 JVSMPWHQUPKRNV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 238000007084 catalytic combustion reaction Methods 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000013980 iron oxide Nutrition 0.000 claims description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000002269 spontaneous effect Effects 0.000 abstract 1
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002360 explosive Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000003536 tetrazoles Chemical class 0.000 description 2
- JGZAFSFVZSXXCJ-ONEGZZNKSA-N (E)-bis(2H-tetrazol-5-yl)diazene Chemical compound N(=N\C1=NN=NN1)/C1=NN=NN1 JGZAFSFVZSXXCJ-ONEGZZNKSA-N 0.000 description 1
- -1 Battery acid Chemical class 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 238000006418 Brown reaction Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001149 cognitive effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- MJFQUUWPZOGYQT-UHFFFAOYSA-O diaminomethylideneazanium;nitrate Chemical compound NC(N)=[NH2+].[O-][N+]([O-])=O MJFQUUWPZOGYQT-UHFFFAOYSA-O 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000003721 gunpowder Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
- C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
-
- 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 a stable, nitrogen-rich organic compound and its use as a pyrotechnic mixture.
- Nitrogen-rich organic compounds are widely used in chemistry and technology, be they as reactants in chemical processes or as gas, especially inert gas-generating substances.
- the problem is that the direct coupling of N atoms to one another is only slightly stable in nitrogen-rich compounds and such compounds are therefore out of the question for many applications.
- tetrazole for example, is known as a very stable compound, but has a relatively low nitrogen content. This in turn could be significantly increased by connecting two tetrazole rings via an azo bridge to form the 5,5 'azotetrazole. This compound is not very stable as a free acid.
- Salts of 5,5'-azotetrazole have also been proposed as substances which generate inert gas.
- a bis (triaminoguanidinium) -5,5'-azotetrazolate is known (US Pat. No. 4,601,344) for use in fire extinguishing agents.
- this compound has such a high sensitivity to friction and impact that it falls into the category of initial explosives is classified.
- the thermal stability is also so low that the connection has only a short life at elevated temperature.
- the still known aminoguanidinium-5,5'-azotetrozolate has the same disadvantage (DE-B-2 004 620 with DE-A-34 22 433).
- the intermediate product sodium 5,5'-azotetrazolate pentahydrate can be prepared by dissolving 5-aminotetrazole monohydrate in NaOH, adding powdery KMnO4 to the solution, filtering off the reaction mixture and sodium 5,5'-azotetrazolate pentahydrate from the filtrate is crystallized out.
- the pentahydrate is then reacted in aqueous solution with guanidinium chloride or nitrate to diguanidinium 5,5'-azotetrazolate. With this conversion, the diguanidinium-5,5'-azotetrazolate is obtained as an easily filterable yellow precipitate with a good yield.
- the pyrotechnic kits used to inflate air cushions for occupant protection devices in motor vehicles also called “airbags", as used in practice (DE-A-22 36 175), contain the highly toxic sodium azide. With the constant increase in motor vehicles with such occupant protection devices, considerable environmental problems arise from this. Because of the good water solubility of sodium azide, there is a risk of soil and groundwater contamination in scrap yards. When exposed to acids, e.g. Battery acid, the highly explosive hydrochloric acid forms. In contact with heavy metals such as lead, copper, brass, highly explosive heavy metal azides can occur.
- the compound according to the invention is outstandingly suitable as a basis for a pyrotechnic mixture for the production of environmentally friendly and non-toxic gases which, despite the required liveliness, is stable even under extreme operating conditions and has a long service life by using diguanidinium-5,5'-azotetrazolate (GZT) a powdery, chemically stable oxidizer is mixed.
- GZT diguanidinium-5,5'-azotetrazolate
- the CCT used according to the invention can be processed as a powdery substance.
- a powdery, chemically stable oxidizer which in particular must not be hygroscopic, a mixture can be produced in which the oxygen balance is largely balanced.
- These mixtures are very stable thermally and are insensitive to impact and friction.
- the invention thus proposes an azide-free, in particular sodium azide-free product which is consequently considerably more environmentally friendly.
- KNO3 is preferably used as an oxidizer.
- a mixture made from this with GZT can also be finely ground in larger batches due to its high handling safety - as can be seen from the characteristic values given further below.
- a particle size spectrum can be produced in which over 50% of the particles in the mixture have a particle diameter of ⁇ 15 ⁇ m.
- the grain size distribution and the grain size itself largely determine the liveliness of such a gas generator mixture, whereby it is naturally necessary to ensure a homogeneous mixture.
- Shaped bodies can be produced from the powder mixture by adding organic or inorganic binders.
- the proportion of binders should not exceed 5% by weight.
- the combustion behavior can be significantly influenced by different geometries of the shaped bodies.
- Findings about the combustion behavior and the gas generation can be gathered from the pressure development (pressure-time curves) during ignition attempts in a ballistic bomb.
- the pressure-time behavior of a GZT-KNO3 formulation without a binder is shown at a loading density of 10 g to 100 cm3.
- Decisive for a specific application can e.g. B. the ignition delay, the edge steepness and the time until the maximum pressure is reached.
- the 30/80 time gives an important cognitive value for the liveliness of gas generation, i.e. the slope of the burn-up curve in the range between 30% and 80% of the maximum pressure.
- the shape of the curve in the pressure-time diagram can also be influenced, among other things, by the geometry of the shaped bodies. Of course, any inorganic or organic binders that are present also exert an influence on the slope.
- catalytic combustion controllers can be used in a proportion of 0.1 to 5% by weight.
- organic or inorganic salts of these metals can also be used as the combustion controller.
- a measure of the thermal stability can be determined by measuring the weight loss at 130 ° C in loosely closed test tubes. In a GZT-KNO3 formulation, it is only 0.3% by weight after 34 days.
- the ignition temperature of this formulation is between 251 and 253 ° C with a weight of 0.2 g and a heating rate of 20 K / min.
- the impact sensitivity determined according to the BAM drop hammer method (Koenen and Ide "Explosivstoffe” 9 (1961) page 4, 30), is over 10 kpm, which means that the 10 kg drop hammer could not react at a drop height of 1 m to be watched.
- the determination of the friction sensitivity did not result in a reaction with a pin load of 36 kp.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Air Bags (AREA)
Abstract
Es wird eine stabile, stickstoffreiche organische Verbindung in Form des Diguanidinium-5,5'-azotetrazolat der Summenformel C4H12N16, ein Verfahren zu dessen Herstellung und dessen Verwendung in Mischung mit einem pulverförmigen, chemisch stabilen Oxidator als pyrotechnische Mischung zur spontanen Erzeugung umweltverträglicher, ungiftiger Gase beschrieben.It becomes a stable, nitrogen-rich organic compound in the form of diguanidinium-5,5'-azotetrazolate of the formula C4H12N16, a process for its production and its use in a mixture with a powdery, chemically stable oxidizer as a pyrotechnic mixture for the spontaneous generation of environmentally compatible, non-toxic gases described.
Description
Die Erfindung betrifft eine stabile, stickstoffreiche organische Verbindung und deren Verwendung als pyrotechnische Mischung.The invention relates to a stable, nitrogen-rich organic compound and its use as a pyrotechnic mixture.
Stickstoffreiche organische Verbindungen finden in der Chemie und Technik vielfache Verwendung, sei es als Reaktionspartner in chemischen Prozessen oder als gas-, insbesondere innertgaserzeugende Substanzen. Problematisch ist, daß bei stickstoffreichen Verbindungen die direkte Kopplung von N-Atomen miteinander nur wenig stabil ist und solche Verbindungen deshalb für viele Anwendungszwecke nicht in Frage kommen. So ist zwar beispielsweise Tetrazol als sehr stabile Verbindung geläufig, weist jedoch einen relativ geringen Stickstoffgehalt auf. Dieser wiederum ließe sich nennenswert dadurch erhöhen, daß zwei Tetrazolringe über eine Azo-Brücke zum 5,5' Azotetrazol verbunden werden. Diese Verbindung ist als freie Säure aber wenig stabil.Nitrogen-rich organic compounds are widely used in chemistry and technology, be they as reactants in chemical processes or as gas, especially inert gas-generating substances. The problem is that the direct coupling of N atoms to one another is only slightly stable in nitrogen-rich compounds and such compounds are therefore out of the question for many applications. For example, tetrazole, for example, is known as a very stable compound, but has a relatively low nitrogen content. This in turn could be significantly increased by connecting two tetrazole rings via an azo bridge to form the 5,5 'azotetrazole. This compound is not very stable as a free acid.
Auch Salze des 5,5'-Azotetrazol sind als Innertgas erzeugende Substanzen schon vorgeschlagen worden. So ist ein Bis (-triaminoguanidinium)-5,5'-azotetrazolat bekannt (US-A-4 601 344) zur Verwendung in Feuerlöschmitteln bekannt. Diese Verbindung weist jedoch eine so hohe Reib- und Schlagempfindlichkeit auf, daß sie in die Kategorie der Initialsprengstoffe einzuordnen ist. Auch die thermische Stabilität ist so gering, daß die Verbindung bei erhöhter Temperatur nur eine kurze Lebensdauer hat. Den gleichen Nachteil hat das weiterhin bekannte Aminoguanidinium-5,5'-azotetrozolat (DE-B-2 004 620 mit DE-A-34 22 433).Salts of 5,5'-azotetrazole have also been proposed as substances which generate inert gas. A bis (triaminoguanidinium) -5,5'-azotetrazolate is known (US Pat. No. 4,601,344) for use in fire extinguishing agents. However, this compound has such a high sensitivity to friction and impact that it falls into the category of initial explosives is classified. The thermal stability is also so low that the connection has only a short life at elevated temperature. The still known aminoguanidinium-5,5'-azotetrozolate has the same disadvantage (DE-B-2 004 620 with DE-A-34 22 433).
Erfindungsgemäß wird mit Diguanidinium-5,5'-azotetrazolat eine Verbindung vorgeschlagen, die, wie ihre Summenformel C₄H₁₂N₁₆ zeigt, einen hohen Stickstoffgehalt, nämlich 78,7 % bei einem Molekulargewicht von 284,5, aufweist. Sie ist als Salz des 5,5'-Azotetrazols sehr stabil und in den üblichen organischen Lösungsmitteln mit Ausnahme von Methanol, Dimetyhlformamid und Dimethylsulfoxid bei Zimmertemperatur praktisch unlöslich. Auch die Löslichkeit in Wasser ist nur sehr mäßig. Die thermische Beständigkeit ergibt sich aus dem festgestellten, relativ hohen Schmelzpunkt zwischen 238 und 239 °C. Ferner zeigt sich bei einer Einlagerungstemperatur von 130°C nach 50 Tagen nur ein Gewichtsverlust von 1%, der also praktisch vernachlässigbar ist. Der Vorteil der Verbindung insbesondere für technische Einsätze ergibt sich daraus, daß die bei der Zersetzung entwickelten Gase für den Menschen unschädlich sind, so das ein Einsatz in der Nähe von Menschen, insbesondere auch in geschlossenen Räumen möglich ist.According to the invention with diguanidinium 5,5'-azotetrazolate a compound is proposed which, as its empirical formula C₄H₁₂N₁₆ shows, has a high nitrogen content, namely 78.7% with a molecular weight of 284.5. As the salt of 5,5'-azotetrazole, it is very stable and practically insoluble in the usual organic solvents with the exception of methanol, dimetyhlformamide and dimethyl sulfoxide at room temperature. Solubility in water is also only very moderate. The thermal resistance results from the relatively high melting point between 238 and 239 ° C. Furthermore, at a storage temperature of 130 ° C after 50 days there is only a weight loss of 1%, which is practically negligible. The advantage of the connection, in particular for technical applications, arises from the fact that the gases developed during the decomposition are harmless to humans, so that use in the vicinity of humans, in particular also in enclosed spaces, is possible.
Bei der Darstellung von Diguanidinium-5,5'-azotetrazolat wird zweckmäßigerweise von handelsüblichen Substanzen ausgegangen. So wird erfindungsgemäß vorgeschlagen, daß 5-Aminotetrazol durch Oxidation zu Natrium-5,5'-azotetrazolat-Pentahydrat umgewandelt und in wässriger Lösung mit Guanidiniumchlorid oder -nitrat zu Diguanidinium-5,5'-azotetrazolat umgesetzt wird.When preparing diguanidinium-5,5'-azotetrazolate, it is expedient to start from commercially available substances. It is proposed according to the invention that 5-aminotetrazole is converted to sodium 5,5'-azotetrazolate pentahydrate by oxidation and converted to diguanidinium 5,5'-azotetrazolate in aqueous solution with guanidinium chloride or nitrate.
Sowohl Aminotetrazol, als auch Guanidiniumchlorid oder -nitrat sind im Handel erhältlich, so daß sich der erfindungsgemäße Stoff auch preisgünstig herstellen läßt.Both aminotetrazole and guanidinium chloride or nitrate are commercially available, so that the substance according to the invention can also be produced inexpensively.
Das Zwischenprodukt Natrium-5,5'-azotetrazolat-Pentahydrat läßt sich dadurch herstellen, daß 5-Aminotetrazol-Monohydrat in NaOH gelöst, der Lösung pulveriges KMnO₄ zugegeben, das Reaktionsgemisch abfiltriert und aus dem Filtrat Natrium-5,5'-azotetrazolat-Pentahydrat auskristallisiert wird. Das Pentahydrat wird anschließend in wässriger Lösung mit Guanidiniumchlorid oder -nitrat zu Diguanidinium-5,5'-azotetrazolat umgesetzt. Bei diesem Umsatz fällt das Diguanidinium-5,5'-azotetrazolat als leicht filtrierbarer gelber Niederschlag mit guter Ausbeute an.The intermediate product sodium 5,5'-azotetrazolate pentahydrate can be prepared by dissolving 5-aminotetrazole monohydrate in NaOH, adding powdery KMnO₄ to the solution, filtering off the reaction mixture and sodium 5,5'-azotetrazolate pentahydrate from the filtrate is crystallized out. The pentahydrate is then reacted in aqueous solution with guanidinium chloride or nitrate to diguanidinium 5,5'-azotetrazolate. With this conversion, the diguanidinium-5,5'-azotetrazolate is obtained as an easily filterable yellow precipitate with a good yield.
50 g 5-Aminotetrazol-Monohydrat werden in 500 ml 15 %iger Natronlauge bei Siedetemperatur unter Rühren gelöst. In einem Zeitraum von ca. einer halben Stunde werden 65 g im Mörser pulverisiertes Kaliumpermanganat eingetragen. Überschüssiges KMnO₄ wird, beispielsweise mit Äthanol, reduziert. Nach einer 1-stündigen Nachreaktion wird das siedend heiße dunkelbraune Reaktionsgemisch über einen beheizten Filtertrichter abfiltriert. Im Filtrat kristallisiert das gelbe Natrium-5,5'-azotretazolat-Pentahydrat aus. Nach Umkristallisation und 48-stündigem Trocknen über Phosphorpentoxid werden 37,5 g Ausbeute (51,2 % des theoretischen Wertes) erhalten. Durch Einengen der Mutterlauge und gründliches Waschen des Braunsteins kann die Ausbeute bis auf 75 % gesteigert werden.50 g of 5-aminotetrazole monohydrate are dissolved in 500 ml of 15% sodium hydroxide solution at boiling temperature with stirring. Over a period of about half an hour, 65 g of potassium permanganate powdered in the mortar are introduced. Excess KMnO₄ is reduced, for example with ethanol. After a 1-hour post-reaction, the boiling hot dark brown reaction mixture is filtered off through a heated filter funnel. The yellow sodium 5,5'-azotretazolate pentahydrate crystallizes out in the filtrate. After recrystallization and drying over phosphorus pentoxide for 48 hours, 37.5 g of yield (51.2% of the theoretical value) are obtained. The yield can be increased to 75% by concentrating the mother liquor and washing the manganese dioxide thoroughly.
12,0 g des so erhaltenen Na-5,5'-azotetrazol-Pentahydrats (0,04 Mol) werden bei 50°C in 100 ml Wasser gelöst und unter kräftigem Rühren in eine Lösung von 9,76 g Guanidiniumnitrat (0,08 Mol) eingegeben. Dabei bildet sich ein dicker gelber Niederschlag, der nach Filtration, einmaliger Umkristallisation aus Wasser von 100°C und 48-stündigem Trocknen über P₂O₅ im Vakuumtrockenschrank eine Ausbeute von 9,5 g Diguanidinium-5,5'-azotetrazolat (84,1 % d. Th.) liefert.
- Analyse berechnet für C₄H₁₂H₁₆:
- 16,9 % C; 4,26 % H; 78,8 % N
- Analyse gefunden:
- 16,8 % C; 4,13 % H; 78,2 % N
- Analysis calculated for C₄H₁₂H₁₆:
- 16.9% C; 4.26% H; 78.8% N
- Analysis found:
- 16.8% C; 4.13% H; 78.2% N
Die Erzeugung von großen Gasmengen aus Festkörpern mit relativ kleinem Volumen spielt in vielen Bereichen der Technik eine große Rolle. Hier sei beispielsweise auf sicherheitstechnische Rückhaltesysteme in Kraftfahrzeugen (Airbags) verwiesen, die im Ausgangszustand ein den Komfort der Fahrzeuginsassen, wie auch das äußere Erscheinungsbild des Fahrzeugs nicht beeinträchtigendes, geringes Volumen aufweisen, aus dem bei einem Aufprallunfall spontan große Mengen Gas erzeugt werden, um die Fahrzeuginsassen vor gefährdenden Teilen des Kraftfahrzeugs abzufangen bzw. abzustützen. Weitere Anwendungsgebiete solcher pyrotechnischen Sätze sind aufblasbare Rettungssysteme, wie Schlauchboote, Flöße, Fluchtleitern. Ferner können sie zum Beschleunigen von Wurfkörpern, zum schnellen Transport von Elektrolytflüssigkeiten aus Vorratsbehältern in Akkumulatoren zur Aktivierung derselben im Bedarfsfall, wie auch zum Verbessern von Raketen-Festtreibstoffen oder Rohrwaffenpulvern dienen.The generation of large amounts of gas from solids with a relatively small volume plays a major role in many areas of technology. Reference is made here, for example, to safety-related restraint systems in motor vehicles (airbags) which, in the initial state, have a small volume which does not impair the comfort of the vehicle occupants or the external appearance of the vehicle, from which large amounts of gas are spontaneously generated in the event of an impact in order to To intercept or support vehicle occupants in front of dangerous parts of the motor vehicle. Other areas of application of such pyrotechnic sets are inflatable rescue systems, such as inflatable boats, rafts and escape ladders. Furthermore, they can for accelerating throwing objects, for quickly transporting electrolyte liquids from storage containers in accumulators for activating them if necessary, and also for improving rocket solid propellants or gun powder.
Die bislang zum Aufblasen von Luftkissen für Insassenschutzvorrichtungen in Kraftfahrzeugen, auch "Airbags" genannt, angewendeten pyrotechnischen Sätze, wie sie in der Praxis zum Einsatz kommen (DE-A-22 36 175), enthalten das hochtoxische Natriumazid. Bei der ständigen Zunahme von Kraftfahrzeugen mit solchen Insassenschutzvorrichtungen entstehen daraus erhebliche Umweltprobleme. Auf Schrottplätzen besteht wegen der guten Wasserlöslichkeit von Natriumazid die Gefahr der Boden- und Grundwasserverseuchung. Bei Einwirkung von Säuren, z.B. Batteriesäure, bildet sich die hochexplosive Stickstoffwasserstoffsäure. Im Kontakt mit Schwermetallen wie Blei, Kupfer, Messing können hochexplosive Schwermetallazide entstehen.The pyrotechnic kits used to inflate air cushions for occupant protection devices in motor vehicles, also called "airbags", as used in practice (DE-A-22 36 175), contain the highly toxic sodium azide. With the constant increase in motor vehicles with such occupant protection devices, considerable environmental problems arise from this. Because of the good water solubility of sodium azide, there is a risk of soil and groundwater contamination in scrap yards. When exposed to acids, e.g. Battery acid, the highly explosive hydrochloric acid forms. In contact with heavy metals such as lead, copper, brass, highly explosive heavy metal azides can occur.
Daher werden Anstrengungen unternommen, den hohen gewichtsprozentualen Anteil von Natriumazid in solchen gaserzeugenden Mischungen wenigstens zu reduzieren, wenn es schon nicht gelingt, ganz auf Natriumazid zu verzichten (DE-A-3 733 176 und JP-A-02 184 590).Efforts are therefore being made to at least reduce the high percentage by weight of sodium azide in such gas-generating mixtures if it is not possible to completely do without sodium azide (DE-A-3 733 176 and JP-A-02 184 590).
Die erfindungsgemäße Verbindung ist in hervorragender Weise als Grundlage für eine pyrotechnische Mischung zur Erzeugung umweltfreundlicher und ungiftiger Gase geeignet, die trotz der geforderten Lebhaftigkeit auch unter extremen Einsatzbedingungen beständig und eine lange Lebensdauer aufweist, indem Diguanidinium-5,5'-azotetrazolat (GZT) mit einem pulverförmigen, chemisch stabilen Oxidator gemischt wird.The compound according to the invention is outstandingly suitable as a basis for a pyrotechnic mixture for the production of environmentally friendly and non-toxic gases which, despite the required liveliness, is stable even under extreme operating conditions and has a long service life by using diguanidinium-5,5'-azotetrazolate (GZT) a powdery, chemically stable oxidizer is mixed.
Das erfindungsgemäß verwendete GZT kann als pulverförmige Substanz verarbeitet werden. In Verbindung mit einem pulverförmigen, chemisch stabilen Oxidator, der insbesondere auch nicht hygroskopisch sein darf, läßt sich eine Mischung herstellen, bei der die Sauerstoffbilanz weitgehend ausgeglichen ist. Diese Mischungen sind thermisch sehr stabil sowie schlag- und reibunempfindlich. Mit der Erfindung wird also ein azidfreies, insbesondere natriumazidfreies Produkt vorgeschlagen, das demzufolge wesentlich umweltfreundlicher ist.The CCT used according to the invention can be processed as a powdery substance. In conjunction with a powdery, chemically stable oxidizer, which in particular must not be hygroscopic, a mixture can be produced in which the oxygen balance is largely balanced. These mixtures are very stable thermally and are insensitive to impact and friction. The invention thus proposes an azide-free, in particular sodium azide-free product which is consequently considerably more environmentally friendly.
Als Oxidator wird vorzugsweise KNO₃ verwendet. Eine hieraus mit GZT hergestellte Mischung läßt sich aufgrund ihrer hohen Handhabungssicherheit - wie aus den weiter hinten angegebenen Kennwerten ersichtlich - auch in größeren Chargen fein mahlen. So läßt sich insbesondere ein Korngrößenspektrum herstellen, bei dem über 50 % der Partikel der Mischung einen Teilchendurchmesser < 15 µm aufweisen. Die Korngrößenverteilung und die Korngröße selbst bestimmen sehr maßgeblich die Lebhaftigkeit einer solchen Gasgeneratormischung, wobei naturgemäß auf eine homogene Mischung zu achten ist.As an oxidizer, KNO₃ is preferably used. A mixture made from this with GZT can also be finely ground in larger batches due to its high handling safety - as can be seen from the characteristic values given further below. In particular, a particle size spectrum can be produced in which over 50% of the particles in the mixture have a particle diameter of <15 μm. The grain size distribution and the grain size itself largely determine the liveliness of such a gas generator mixture, whereby it is naturally necessary to ensure a homogeneous mixture.
Durch Zusatz organischer oder anorganischer Bindemittel lassen sich aus der Pulvermischung Formkörper herstellen. Dabei sollte der Anteil der Bindemittel 5 Gew% nicht übersteigen. Durch unterschiedliche Geometrie der Formkörper läßt sich das Abbrandverhalten wesentlich beeinflussen.Shaped bodies can be produced from the powder mixture by adding organic or inorganic binders. The proportion of binders should not exceed 5% by weight. The combustion behavior can be significantly influenced by different geometries of the shaped bodies.
Erkenntnisse über das Abbrandverhalten und die Gaserzeugung lassen sich anhand der Druckentwicklung (Druck-Zeit-Kurven) bei Zündversuchen in einer ballistischen Bombe sammeln. In dem beigefügten Diagramm ist das Druck-Zeit-Verhalten einer GZT-KNO₃-Formulierung ohne Binder bei einer Ladedichte von 10 g auf 100 cm³ wiedergegeben. Zur Anzündung wurden 0,7 g Anzündmischung aus Bor und KNO₃ verwendet. Entscheidend für einen bestimmten Einsatzzweck können z. B. der Zündverzug, die Flankensteilheit und die Zeitdauer bis zum Erreichen des Maximaldrucks sein. Einen wichtigen Erkenntniswert für die Lebhaftigkeit der Gaserzeugung gibt die 30/80-Zeit, das heißt die Steigung der Abbrandkurve im Bereich zwischen 30 % und 80 % des Maximaldrucks. Der Kurvenverlauf im Druck-Zeit-Diagramm läßt sich bei Formkörpern unter anderem auch durch deren Geometrie beeinflussen. Selbstverständlich üben auch eventuell vorhandene anorganische oder organische Bindemittel einen Einfluß auf die Flankensteilheit aus.Findings about the combustion behavior and the gas generation can be gathered from the pressure development (pressure-time curves) during ignition attempts in a ballistic bomb. In the attached diagram, the pressure-time behavior of a GZT-KNO₃ formulation without a binder is shown at a loading density of 10 g to 100 cm³. For lighting 0.7 g ignition mixture of boron and KNO₃ were used. Decisive for a specific application can e.g. B. the ignition delay, the edge steepness and the time until the maximum pressure is reached. The 30/80 time gives an important cognitive value for the liveliness of gas generation, i.e. the slope of the burn-up curve in the range between 30% and 80% of the maximum pressure. The shape of the curve in the pressure-time diagram can also be influenced, among other things, by the geometry of the shaped bodies. Of course, any inorganic or organic binders that are present also exert an influence on the slope.
Eine weitere Möglichkeit zur Steuerung der Gaserzeugung bzw. der Erzeugungsgeschwindigkeit ist durch die Verwendung katalytischer Abbrandregler möglich. Sie können mit einem Anteil von 0,1 bis 5 Gew% eingesetzt werden.A further possibility for controlling the gas generation or the generation rate is possible by using catalytic combustion controllers. They can be used in a proportion of 0.1 to 5% by weight.
Als Abbrandregler kommen vornehmlich Oxide der Schwermetalle der Nebengruppen des Periodensystems der Elemente, insbesondere der I. oder VIII. Nebengruppe und hierunter vor allem Eisenoxide in Frage.Oxide of the heavy metals of the subgroups of the periodic table of the elements, in particular of the I or VIII subgroup, and especially iron oxides in particular, come into consideration as the combustion controller.
Statt dessen können als Abbrandregler auch organische oder anorganische Salze dieser Metalle vervendet werden.Instead, organic or inorganic salts of these metals can also be used as the combustion controller.
Für eine GZT-KNO₃-Formulierung ohne Binder konnten folgende Eigenschaften festgestellt werden:
Ein Maß für die thermische Stabilität läßt sich durch Messung des Gewichtsverlustes bei 130 °C in lose verschlossenen Prüfröhren feststellen. Er beträgt bei einer GZT-KNO₃-Formulierung nur 0,3 Gew% nach 34 Tagen.The following properties were found for a GZT-KNO₃ formulation without a binder:
A measure of the thermal stability can be determined by measuring the weight loss at 130 ° C in loosely closed test tubes. In a GZT-KNO₃ formulation, it is only 0.3% by weight after 34 days.
Die Entzündungstemperatur dieser Formulierung liegt zwischen 251 und 253 °C bei einer Einwaage von 0,2 g und einer Aufheizgeschwindigkeit von 20 K/min.The ignition temperature of this formulation is between 251 and 253 ° C with a weight of 0.2 g and a heating rate of 20 K / min.
Die Schlagempfindlichkeit, ermittelt nach der Fallhammermethode der BAM (Koenen und Ide "Explosivstoffe" 9 (1961) Seite 4, 30), liegt bei über 10 kpm, das heißt mit dem 10-kp-Fallhammer konnte bei einer Fallhöhe von 1 m keine Reaktion beobachtet werden. Auch die Bestimmung der Reibempfindlichkeit (a.a.O.) ergab bei einer Stiftbelastung von 36 kp noch keine Reaktion.The impact sensitivity, determined according to the BAM drop hammer method (Koenen and Ide "Explosivstoffe" 9 (1961) page 4, 30), is over 10 kpm, which means that the 10 kg drop hammer could not react at a drop height of 1 m to be watched. The determination of the friction sensitivity (see above) did not result in a reaction with a pin load of 36 kp.
In der nachfolgenden Tabelle II sind die Schlag- und Reibempfindlichkeit von GZT/KNO₃ einerseits, dem reinen GZT und dem bekannten TAGZT und AGZT andererseits gegenübergestellt.
Claims (14)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4108225 | 1991-03-14 | ||
| DE4108225A DE4108225C1 (en) | 1991-03-14 | 1991-03-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0503341A1 true EP0503341A1 (en) | 1992-09-16 |
| EP0503341B1 EP0503341B1 (en) | 1995-07-05 |
Family
ID=6427255
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP92103023A Expired - Lifetime EP0503341B1 (en) | 1991-03-14 | 1992-02-22 | Stable nitrogen-rich compound |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US5198046A (en) |
| EP (1) | EP0503341B1 (en) |
| DE (2) | DE4108225C1 (en) |
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| EP0665201A1 (en) * | 1994-01-18 | 1995-08-02 | Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. | Gas generating mixture |
| EP0666248A1 (en) * | 1994-01-18 | 1995-08-09 | Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. | Gas generating mixture |
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| US5682014A (en) * | 1993-08-02 | 1997-10-28 | Thiokol Corporation | Bitetrazoleamine gas generant compositions |
| CA2167386C (en) * | 1993-08-02 | 1999-10-05 | Alliant Techsystems Inc. | Method for preparing anhydrous tetrazole gas generant compositions |
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| DE4435790A1 (en) * | 1993-10-06 | 1995-04-13 | Contec Chemieanlagen Gmbh | Gas generator propellant |
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| US20050067074A1 (en) * | 1994-01-19 | 2005-03-31 | Hinshaw Jerald C. | Metal complexes for use as gas generants |
| DE4442037C1 (en) * | 1994-11-25 | 1995-12-21 | Fraunhofer Ges Forschung | Non-toxic gas-generating mixt. with low combustion temp. |
| DE4442170C1 (en) | 1994-11-26 | 1995-12-21 | Fraunhofer Ges Forschung | Non-toxic gas-generating mixt. with thermal-mechanical stability |
| DE4442169C1 (en) * | 1994-11-26 | 1995-12-21 | Fraunhofer Ges Forschung | Non-toxic gas-generating mixt. with thermal-mechanical stability |
| DE19505568A1 (en) * | 1995-02-18 | 1996-08-22 | Dynamit Nobel Ag | Gas generating mixtures |
| US5817972A (en) * | 1995-11-13 | 1998-10-06 | Trw Inc. | Iron oxide as a coolant and residue former in an organic propellant |
| EP0864553B1 (en) * | 1995-12-01 | 2013-02-27 | Kabushiki Kaisha Kobeseikosho | Gas generating agent and transfer charge for use in airbag gas generator, and gas generator comprising said gas generating agent and transfer charge |
| US5844164A (en) * | 1996-02-23 | 1998-12-01 | Breed Automotive Technologies, Inc. | Gas generating device with specific composition |
| US5661261A (en) * | 1996-02-23 | 1997-08-26 | Breed Automotive Technology, Inc. | Gas generating composition |
| US5608183A (en) * | 1996-03-15 | 1997-03-04 | Morton International, Inc. | Gas generant compositions containing amine nitrates plus basic copper (II) nitrate and/or cobalt(III) triammine trinitrate |
| JPH09328387A (en) * | 1996-06-03 | 1997-12-22 | Daicel Chem Ind Ltd | Gas producing agent composition |
| EP0958264B1 (en) | 1996-07-25 | 2011-06-01 | Alliant Techsystems Inc. | Metal complexes for use as gas generants |
| US6306232B1 (en) * | 1996-07-29 | 2001-10-23 | Automotive Systems Laboratory, Inc. | Thermally stable nonazide automotive airbag propellants |
| US5872329A (en) * | 1996-11-08 | 1999-02-16 | Automotive Systems Laboratory, Inc. | Nonazide gas generant compositions |
| US5811725A (en) * | 1996-11-18 | 1998-09-22 | Aerojet-General Corporation | Hybrid rocket propellants containing azo compounds |
| US5917146A (en) * | 1997-05-29 | 1999-06-29 | The Regents Of The University Of California | High-nitrogen energetic material based pyrotechnic compositions |
| US6435552B1 (en) * | 1997-12-18 | 2002-08-20 | Atlantic Research Corporation | Method for the gas-inflation articles |
| US5889161A (en) * | 1998-05-13 | 1999-03-30 | Sri International | N,N'-azobis-nitroazoles and analogs thereof as igniter compounds for use in energetic compositions |
| DE29902273U1 (en) | 1999-02-09 | 1999-07-08 | TRW Automotive Safety Systems GmbH, 63743 Aschaffenburg | Airbag propellant |
| US20050257866A1 (en) * | 2004-03-29 | 2005-11-24 | Williams Graylon K | Gas generant and manufacturing method thereof |
| US10968147B2 (en) * | 2005-06-02 | 2021-04-06 | Ruag Ammotec Gmbh | Pyrotechnic agent |
| US9045380B1 (en) | 2007-10-31 | 2015-06-02 | Tk Holdings Inc. | Gas generating compositions |
| DE102010025104B4 (en) * | 2010-04-14 | 2015-06-11 | Diehl Bgt Defence Gmbh & Co. Kg | initiating explosive |
| US20140109551A1 (en) * | 2012-10-23 | 2014-04-24 | Los Alamos National Security, Llc | Solid chemical rocket propulsion system |
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- 1992-02-22 EP EP92103023A patent/EP0503341B1/en not_active Expired - Lifetime
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| US3909322A (en) * | 1970-08-03 | 1975-09-30 | Us Navy | Solid gas generating and gun propellant compositions containing a nitroaminotetrazole salt |
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| EP0666248A1 (en) * | 1994-01-18 | 1995-08-09 | Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. | Gas generating mixture |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0503341B1 (en) | 1995-07-05 |
| DE59202770D1 (en) | 1995-08-10 |
| US5198046A (en) | 1993-03-30 |
| DE4108225C1 (en) | 1992-04-09 |
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