EP0503341A1 - Stable nitrogen-rich compound - Google Patents

Stable nitrogen-rich compound Download PDF

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Publication number
EP0503341A1
EP0503341A1 EP19920103023 EP92103023A EP0503341A1 EP 0503341 A1 EP0503341 A1 EP 0503341A1 EP 19920103023 EP19920103023 EP 19920103023 EP 92103023 A EP92103023 A EP 92103023A EP 0503341 A1 EP0503341 A1 EP 0503341A1
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Prior art keywords
azotetrazolate
added
mixture
diguanidinium
stable
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EP19920103023
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German (de)
French (fr)
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EP0503341B1 (en
Inventor
Klaus Martin Dr.Rer.Nat/Dipl.Chem. Buccerius
Friedrich-Wilhelm Dr.Rer.Nat./Dipl.Chem. Wasmann
Klaus Dr.Rer.Nat./Dipl.Chem. Menke
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Priority to DE19914108225 priority patent/DE4108225C1/de
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    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06DMEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • C06D5/06Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06BEXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B43/00Compositions characterised by explosive or thermic constituents not provided for in groups C06B25/00 - C06B41/00

Abstract

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

  • 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. 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.
  • 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).
  • 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.
  • 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.
  • Both aminotetrazole and guanidinium chloride or nitrate are commercially available, so that the substance according to the invention can also be produced inexpensively.
  • 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.
  • example
  • 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 of the Na-5,5'-azotetrazole pentahydrate (0.04 mol) thus obtained are dissolved in 100 ml of water at 50 ° C. and in a solution of 9.76 g with vigorous stirring Guanidinium nitrate (0.08 mol) was added. This forms a thick yellow precipitate, which after filtration, single recrystallization from water at 100 ° C and drying for 48 hours over P₂O₅ in a vacuum drying cabinet yield 9.5 g diguanidinium-5,5'-azotetrazolate (84.1% of theory . Th.) Delivers.
  • Analysis calculated for C₄H₁₂H₁₆:
    16.9% C; 4.26% H; 78.8% N
    Analysis found:
    16.8% C; 4.13% H; 78.2% N
    The extraordinarily good thermal resistance of the diguanidium-5,5'-azotetrazolate (GZT) to the known bis (-triaminoguanidium) -5,5'-azotetrazolate (TAGZT) and the likewise known aminoguanidium-5,5'-azotetrazolate (AGZT) results can be seen from Table I below, in which the weight loss in% of a weight of 1000 mg at a constant temperature of 130 ° C is compared in two test series for each of the three substances.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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. 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.
  • 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.
  • 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.
  • Instead, organic or inorganic salts of these metals can also be used as the combustion controller.
  • 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.
  • 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 (see above) did not result in a reaction with a pin load of 36 kp.
  • In the following Table II the impact and friction sensitivity of GZT / KNO₃ on the one hand, the pure GZT and the known TAGZT and AGZT on the other hand are compared.
    Figure imgb0001
    Figure imgb0002

Claims (14)

  1. Stable, nitrogen-rich organic compound in the form of the diguanidinium-5,5'-azotetrazolate of the empirical formula C₄H₁₂N₁₆.
  2. Process for the preparation of diguanidinium-5,5'-azotetrazolate, characterized in that 5-aminotetrazole is converted to sodium 5,5'-azotetrazolate pentahydrate by oxidation and in aqueous solution with guanidinium chloride or nitrate to diguanidinium-5,5 ' -azotetrazolate is implemented.
  3. Process according to Claim 2, characterized in that 5-aminotetrazole monohydrate is dissolved in NaOH, powdery KMnO₄ is added to the solution, the reaction mixture is filtered off and sodium 5,5'-azotetrazolate pentahydrate is crystallized out of the filtrate, which is then dissolved in aqueous solution Guanidinium chloride or nitrate is converted to diguanidinium 5,5'-azotetrazolate.
  4. Use of diguanidinium-5,5'-azotetrazolate (GZT) in a mixture with a powdery, chemically stable oxidizer as a pyrotechnic mixture for the generation of environmentally compatible, non-toxic gases.
  5. Use according to claim 4, characterized in that KNO₃ is used as the oxidizer.
  6. Use according to claim 4 or 5, characterized in that the mixture is finely ground.
  7. Use according to one of Claims 4 to 6, characterized in that over 50% of the particles in the mixture have a particle diameter of less than 15 µm.
  8. Use according to one of claims 4 to 7, characterized in that the mixture is compacted into shaped bodies.
  9. Use according to claim 8, characterized in that organic or inorganic binders are added in a proportion of up to 5% by weight to form shaped articles.
  10. Use according to one of Claims 1 to 9, characterized in that catalytic combustion controllers with a proportion of 0.1 to 5% by weight are added to control the gas generation.
  11. Use according to claim 10, characterized in that oxides of the heavy metals of the sub-groups of the periodic system are added as the combustion regulator.
  12. Use according to claim 11, characterized in that oxides of the heavy metals of subgroup I or VIII of the periodic table of the elements are added as the combustion regulator.
  13. Use according to claim 11 or 12, characterized in that iron oxides are added as the combustion regulator.
  14. Use according to one of Claims 4 to 13, characterized in that organic or inorganic salts of the metals mentioned are added as the combustion regulator.
EP19920103023 1991-03-14 1992-02-22 Stable nitrogen-rich compound Expired - Lifetime EP0503341B1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE4108225 1991-03-14
DE19914108225 DE4108225C1 (en) 1991-03-14 1991-03-14

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EP0503341A1 true EP0503341A1 (en) 1992-09-16
EP0503341B1 EP0503341B1 (en) 1995-07-05

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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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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
US5472647A (en) 1993-08-02 1995-12-05 Thiokol Corporation Method for preparing anhydrous tetrazole gas generant compositions
AU7553794A (en) * 1993-08-02 1995-02-28 Thiokol Corporation Method for preparing anhydrous tetrazole gas generant compositions
US5682014A (en) * 1993-08-02 1997-10-28 Thiokol Corporation Bitetrazoleamine gas generant compositions
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US20050067074A1 (en) * 1994-01-19 2005-03-31 Hinshaw Jerald C. Metal complexes for use as gas generants
US5583315A (en) * 1994-01-19 1996-12-10 Universal Propulsion Company, Inc. Ammonium nitrate propellants
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DE4442037C1 (en) 1994-11-25 1995-12-21 Fraunhofer Ges Forschung Non-toxic gas-generating mixt. with low combustion temp.
DE4442169C1 (en) 1994-11-26 1995-12-21 Fraunhofer Ges Forschung Non-toxic gas-generating mixt. with thermal-mechanical stability
DE4442170C1 (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
JP3912689B2 (en) * 1995-12-01 2007-05-09 日本化薬株式会社 Self-igniting explosive composition, explosive, gas generating agent and gas generator
US5661261A (en) * 1996-02-23 1997-08-26 Breed Automotive Technology, Inc. Gas generating composition
US5844164A (en) * 1996-02-23 1998-12-01 Breed Automotive Technologies, Inc. Gas generating device with specific 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
JP2001508751A (en) 1996-07-25 2001-07-03 コーダント・テクノロジーズ・インコーポレーテッド Metal complexes used as gas generating agents
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
US20050257866A1 (en) * 2004-03-29 2005-11-24 Williams Graylon K Gas generant and manufacturing method thereof
US20090133787A1 (en) * 2005-06-02 2009-05-28 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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EP0666248A1 (en) * 1994-01-18 1995-08-09 Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. Gas generating mixture

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DE4108225C1 (en) 1992-04-09
US5198046A (en) 1993-03-30
EP0503341B1 (en) 1995-07-05

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