EP0503341B1 - Composé stable, riche en azote - Google Patents

Composé stable, riche en azote Download PDF

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Publication number
EP0503341B1
EP0503341B1 EP92103023A EP92103023A EP0503341B1 EP 0503341 B1 EP0503341 B1 EP 0503341B1 EP 92103023 A EP92103023 A EP 92103023A EP 92103023 A EP92103023 A EP 92103023A EP 0503341 B1 EP0503341 B1 EP 0503341B1
Authority
EP
European Patent Office
Prior art keywords
use according
added
azotetrazolate
mixture
combustion regulators
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.)
Expired - Lifetime
Application number
EP92103023A
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German (de)
English (en)
Other versions
EP0503341A1 (fr
Inventor
Klaus Martin Dr.Rer.Nat/Dipl.Chem. Buccerius
Friedrich-Wilhelm Dr.Rer.Nat./Dipl.Chem. Wasmann
Klaus Dr.Rer.Nat./Dipl.Chem. Menke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Publication of EP0503341A1 publication Critical patent/EP0503341A1/fr
Application granted granted Critical
Publication of EP0503341B1 publication Critical patent/EP0503341B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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 in pyrotechnic mixtures.
  • 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. It is problematic 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, although tetrazole is very common as a stable compound, it 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 is so sensitive 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 (DE-A-2 004 620 with DE-A-34 22 433) has the same disadvantage.
  • Perchlorates of diguanidine are described as explosives in US-A-4340755.
  • guanidinium salt of 5-nitroaminotetrazole is known from US-A-3905322; it can be used as a gas generator.
  • DE-A-3641788 relates to a method for improving the pressure dependence of the burning behavior of solid propellants and gun propellants.
  • a compound is proposed with diguanidinium-5,5'-azotetrazolate which, as its empirical formula C4H12N16 shows, has a high nitrogen content, namely 78.7% with a molecular weight of 284.5.
  • 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 results 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 closed rooms, is possible.
  • the intermediate product sodium 5,5'-azotetrazolate pentahydrate can be prepared by dissolving 5-aminotetrazole monohydrate in NaOH, adding powdery KMn04 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 in good yield.
  • the compound according to the invention is outstandingly suitable as the 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 therefore 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 - see Table 2.
  • 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 important 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 geometry of the shaped bodies.
  • the pressure-time behavior of a GZT-KNO3 formulation without binder can be determined at a loading density of 10 g to 100 cm3.
  • the pressure-time behavior of a GZT-KNO3 formulation without binder can be determined at a loading density of 10 g to 100 cm3.
  • For lighting are, for example, 0.7 g ignition mixture of boron and KNO3.
  • Decisive for a particular application can be B. the ignition delay, the edge steepness and the time until the maximum pressure is reached.
  • the 30/80 time is 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 be influenced, among other things, by the geometry of the shaped bodies. Of course, any inorganic or organic binders present also have 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, that is, with the 10 kg drop hammer, there was no reaction 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)

Claims (14)

  1. Composé organique stable, riche en azote, sous la forme du 5,5'-azotétrazolate de diguanidinium répondant à la formule brute C₄H₁₂N₁₆.
  2. Procédé de préparation de 5,5'-azotétrazolate de diguanidinium, caractérisé en ce qu'on transforme du 5-aminotétrazole, par oxydation, en 5,5'-azotétrazolate sodique pentahydraté, qu'on fait réagir en solution aqueuse avec du chlorure ou du nitrate de guanidinium.
  3. Procédé selon la revendication 2, caractérisé en ce qu'on dissout du 5-aminotétrazole monohydraté dans NaOH, on ajoute du KMnO₄ pulvérulent à la solution, on sépare le mélange de réaction par filtration et on fait cristalliser le 5,5'-azotétrazolate sodique pentahydraté dans le filtrat, qu'on fait réagir ensuite en solution aqueuse avec du chlorure ou du nitrate de guanidinium.
  4. Utilisation du composé selon la revendication 1 mélangé avec un oxydant pulvérulent chimiquement stable, en tant que mélange pyrotechnique pour produire des gaz non toxiques et non polluants.
  5. Utilisation selon la revendication 4, caractérisée en ce qu'on utilise KNO₃ comme oxydant.
  6. Utilisation selon la revendication 4 ou 5, caractérisée en ce qu'on broie finement le mélange.
  7. Utilisation selon l'une des revendications 4 à 6, caractérisée en ce que plus de 50 % des particules du mélange ont un diamètre inférieur à 15 »m.
  8. Utilisation selon l'une des revendications 4 à 7, caractérisée en ce qu'on comprime le mélange en articles moulés.
  9. Utilisation selon la revendication 8, caractérisée en ce qu'on ajoute des liants organiques ou minéraux en une quantité allant jusqu'à 5 % en poids pour former des articles moulés.
  10. Utilisation selon l'une des revendications 1 à 9, caractérisée en ce qu'on ajoute des régulateurs catalytiques de combustion en une quantité de 0,1 à 5 % en poids pour maîtriser la production de gaz.
  11. Utilisation selon la revendication 10, caractérisée en ce qu'on ajoute, comme régulateurs de combustion, des oxydes des métaux lourds des sous-groupes du système périodique.
  12. Utilisation selon la revendication 11, caractérisée en ce qu'on ajoute, comme régulateurs de combustion, des oxydes des métaux lourds du sous-groupe I ou VIII du système périodique des éléments.
  13. Utilisation selon la revendication 11 ou 12, caractérisée en ce qu'on ajoute des oxydes de fer comme régulateurs de combustion.
  14. Utilisation selon l'une des revendications 4 à 13, caractérisée en ce qu'on ajoute, comme régulateurs de combustion, des sels organiques ou des sels minéraux des métaux cités.
EP92103023A 1991-03-14 1992-02-22 Composé stable, riche en azote Expired - Lifetime EP0503341B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4108225A DE4108225C1 (fr) 1991-03-14 1991-03-14
DE4108225 1991-03-14

Publications (2)

Publication Number Publication Date
EP0503341A1 EP0503341A1 (fr) 1992-09-16
EP0503341B1 true EP0503341B1 (fr) 1995-07-05

Family

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Family Applications (1)

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EP92103023A Expired - Lifetime EP0503341B1 (fr) 1991-03-14 1992-02-22 Composé stable, riche en azote

Country Status (3)

Country Link
US (1) US5198046A (fr)
EP (1) EP0503341B1 (fr)
DE (2) DE4108225C1 (fr)

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US5425886A (en) * 1993-06-23 1995-06-20 The United States Of America As Represented By The Secretary Of The Navy On demand, non-halon, fire extinguishing systems
US5682014A (en) * 1993-08-02 1997-10-28 Thiokol Corporation Bitetrazoleamine gas generant compositions
US5472647A (en) 1993-08-02 1995-12-05 Thiokol Corporation Method for preparing anhydrous tetrazole gas generant compositions
WO1995004014A1 (fr) * 1993-08-02 1995-02-09 Thiokol Corporation Procede de preparation de compositions a base de tetrazole anhydre generatrices de gaz
CH685699A5 (de) * 1993-08-25 1995-09-15 Ems Patvag Ag Pyrochemische Zündkette in einem Gasgenerator.
DE4435790A1 (de) * 1993-10-06 1995-04-13 Contec Chemieanlagen Gmbh Gasgeneratortreibstoff
DE4401214C1 (de) * 1994-01-18 1995-03-02 Fraunhofer Ges Forschung Gaserzeugende Mischung
DE4401213C1 (de) * 1994-01-18 1995-03-02 Fraunhofer Ges Forschung Gaserzeugende Mischung
US5583315A (en) * 1994-01-19 1996-12-10 Universal Propulsion Company, Inc. Ammonium nitrate propellants
US6364975B1 (en) 1994-01-19 2002-04-02 Universal Propulsion Co., Inc. Ammonium nitrate propellants
US20050067074A1 (en) * 1994-01-19 2005-03-31 Hinshaw Jerald C. Metal complexes for use as gas generants
DE4442037C1 (de) 1994-11-25 1995-12-21 Fraunhofer Ges Forschung Gaserzeugende Mischung
DE4442169C1 (de) * 1994-11-26 1995-12-21 Fraunhofer Ges Forschung Gaserzeugende Mischung
DE4442170C1 (de) * 1994-11-26 1995-12-21 Fraunhofer Ges Forschung Gaserzeugende Mischung
DE19505568A1 (de) * 1995-02-18 1996-08-22 Dynamit Nobel Ag Gaserzeugende Mischungen
US5817972A (en) * 1995-11-13 1998-10-06 Trw Inc. Iron oxide as a coolant and residue former in an organic propellant
EP0864553B1 (fr) * 1995-12-01 2013-02-27 Kabushiki Kaisha Kobeseikosho Agent generateur de gas et charge de transfert pour air-bag et generateur de gas les utilisant
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 (ja) * 1996-06-03 1997-12-22 Daicel Chem Ind Ltd ガス発生剤組成物
BR9711958A (pt) 1996-07-25 2000-10-24 Thiokol Corp Complexos de metal para uso como geradores de gás
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
US6328906B1 (en) * 1997-12-18 2001-12-11 Atlantic Research Corporation Chemical delivery systems for fire suppression
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 (de) 1999-02-09 1999-07-08 TRW Automotive Safety Systems GmbH, 63743 Aschaffenburg Airbag-Treibsatz
JP2007531684A (ja) * 2004-03-29 2007-11-08 オートモーティブ システムズ ラボラトリィ、 インク． ガス生成物質およびその製造法
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 (de) * 2010-04-14 2015-06-11 Diehl Bgt Defence Gmbh & Co. Kg Initialsprengstoff
US20140109551A1 (en) * 2012-10-23 2014-04-24 Los Alamos National Security, Llc Solid chemical rocket propulsion system
CN114196454B (zh) * 2021-12-07 2023-02-03 中国人民解放军国防科技大学 一种含高氮化合物的固体燃料

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DE2004620C3 (de) * 1970-02-03 1975-07-17 Dynamit Nobel Ag, 5210 Troisdorf Druckgaserzeugende Ladungen
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US4340755A (en) * 1980-10-10 1982-07-20 The United States Of America As Represented By The Secretary Of The Navy Biguanide diperchlorate and process for preparation thereof
US4462910A (en) * 1983-02-03 1984-07-31 Cosden Technology, Inc. Oil slick dispersants using diguanidinium salt
US4601344A (en) * 1983-09-29 1986-07-22 The United States Of America As Represented By The Secretary Of The Navy Pyrotechnic fire extinguishing method
DE3641788A1 (de) * 1986-12-06 1988-06-09 Fraunhofer Ges Forschung Verfahren zum verbessern des abbrandverhaltens derartiger festreibstoffe und festtreibstoff

Also Published As

Publication number Publication date
EP0503341A1 (fr) 1992-09-16
DE59202770D1 (de) 1995-08-10
US5198046A (en) 1993-03-30
DE4108225C1 (fr) 1992-04-09

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