EP0949225B1 - Composition génératrice de gaz exempt d'azoture - Google Patents

Composition génératrice de gaz exempt d'azoture Download PDF

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Publication number
EP0949225B1
EP0949225B1 EP99105181A EP99105181A EP0949225B1 EP 0949225 B1 EP0949225 B1 EP 0949225B1 EP 99105181 A EP99105181 A EP 99105181A EP 99105181 A EP99105181 A EP 99105181A EP 0949225 B1 EP0949225 B1 EP 0949225B1
Authority
EP
European Patent Office
Prior art keywords
acid
weight
nitrate
composition according
proportion
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
EP99105181A
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German (de)
English (en)
Other versions
EP0949225A1 (fr
Inventor
Achim Dr. Hofmann
Roland Dr. Schropp
Karl-Heinz Rödig
Siegfried Dr. Zeuner
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.)
ZF Airbag Germany GmbH
Original Assignee
TRW Airbag Systems GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by TRW Airbag Systems GmbH filed Critical TRW Airbag Systems GmbH
Publication of EP0949225A1 publication Critical patent/EP0949225A1/fr
Application granted granted Critical
Publication of EP0949225B1 publication Critical patent/EP0949225B1/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

Definitions

  • the present invention relates to an acid-free, gas-generating Composition, in particular for use in security devices for motor vehicles, with one of at least two components existing fuel mixture in a proportion of 20 to 60 wt .-% and an oxidizer mixture consisting of at least three components in a proportion of 40 to 80 wt .-%, each based on the total composition.
  • Gas generating compositions used in safety devices used for motor vehicles mostly consist of a fuel based on sodium azide and an oxidizing agent. However, due to the toxicity of sodium azide, it was premature started looking for alternatives to the azide-containing gas generators To look for mixtures.
  • US-A-5 608 183 describes a gas generating mixture containing between about 30 and 85 percent by weight of a fuel and between about 15 and about 70 percent by weight of an oxidizing agent.
  • At least 60% by weight of the fuel consists of the nitrate of an acidic polyamine or a C 2 -C 3 -alkyldiamine, such as, for example, the nitrates of urea, guanidine, aminoguanidine, diaminoguanidine, semicarbazide, ethylenediamine, 1,3-propanediamine or 1, 2-propanediamine, or mixtures thereof.
  • the oxidizing agent comprises at least 60% by weight of basic copper nitrate and / or cobalt triamine trinitrate. The mixture is processed in a wet process.
  • the present invention provides such a composition ready, the fuel mixture consisting of at least two components in a proportion of 20 to 60 wt .-% and on at least three components existing oxidizer mixture in one Proportion of 40 to 80% by weight, in each case based on the overall composition, includes.
  • the composition is characterized in that the fuel mixture is composed of 5 to 95 wt .-% one Guanidine compound, 5 to 95% by weight of a heterocyclic, organic acid and 0 to 20 wt .-% other fuels, each based on the fuel mixture.
  • the oxidizer mixture is according to the invention composed of 20 to 70% by weight of one or more transition metal oxides, 10 to 50 wt .-% basic copper nitrate and 2 to 30% by weight metal chlorate, metal perchlorate, ammonium perchlorate, alkali nitrate, Alkaline earth nitrate or mixtures thereof, each based on the Oxidizer.
  • the guanidine compound is preferably made of guanidine carbonate, Guanidine nitrate, guanidine perchlorate, aminoguanidine nitrate, diaminoguanidine nitrate, Triaminoguanidine nitrate, nitroguanidine or their Blends existing group selected.
  • the heterocyclic organic acid is preferably selected from the group consisting of cyanuric acid, isocyanuric acid, cyamelid, urazole, uracil, uramine, urazin, alloxan, alloxanic acid, alloxantin, xanthine, allantoin, barbituric acid, orotic acid, dilituric acid, triazolone, violuric acid, succinimidialinic acid, dialuric acid, dialuric acid , Pseudohydantoin, imidazolone, pyrazolone, parabanic acid, furazan, ammeline, creatinine, maleic acid hydrazide, uric acid, pseudouric acid, guanazine, guanazole, melamine and their salts and derivatives existing group.
  • the use of an at least two-component fuel mixture of a guanidine compound and a heterocyclic organic acid has proven to be beneficial for the generation of the lowest possible harmful gas values in the released gas mixture.
  • the compounds mentioned usually have a melting point above 200 ° C. and are therefore extremely thermally stable. They thus meet the requirements for high long-term and temperature stability to be placed on gas generator fuels.
  • the compounds mentioned also generally have high negative standard enthalpies of formation .DELTA.H f , as a result of which the amount of energy released during the combustion of the mixture and thus also the combustion temperature of the mixture remain low.
  • heterocyclic organic acid In addition, too high a proportion of carbon in the heterocyclic organic acid is undesirable since an increased proportion of oxidizing agent is required in this case and the combustion temperature of the mixture also increases undesirably as a result of the highly exothermic formation of CO 2 .
  • Compounds having 5 or 6 ring atoms are therefore particularly suitable as the heterocyclic organic acid.
  • the number of carbon atoms per molecule of the organic heterocyclic acid should preferably not be greater than 4. Compounds which contain at most 3 carbon atoms per molecule are particularly preferred. In individual cases, such as in compounds with fused ring systems, up to 5 carbon atoms can also be present. Examples include guanine, C 5 H 4 N 5 O, or uric acid, C 5 H 4 N 3 O 3 .
  • the retention capacity solid combustion residues by controlling the combustion temperature and in particular the relationship between influences metallic and non-metallic residues.
  • the formation is favorable both firmly adhering to each other and yet sufficient porous residues to escape the combustion gases to allow.
  • the setting of low combustion temperatures of below 1700 Kelvin is desirable for many reasons, in itself, however, not sufficient to provide the necessary restraint to ensure the solid combustion residues. So will for example in Comparative Example 1 described below a burning temperature of 1708 Kelvin and a metallic part a 37% incineration residue that is difficult to filter Residue generated, which is atomized under the burning conditions.
  • the exemplary embodiment according to the invention is used in a comparable Burning temperature of 1680 Kelvin, but with a metallic content of 69% in the combustion residues a solid Clinker formed, which is still in tablet form after burning and can therefore be removed from the gas stream very easily.
  • the in State of the art regarded as cheap education of exclusively Metallic combustion residues result from the slight Atomization and the formation of droplets from molten metal poor retention of combustion residues.
  • the metal content in the solid combustion residues of the invention Composition is preferably about 50 to 90% by weight.
  • compositions according to the invention additionally contain the oxidizers metal oxide and basic copper nitrate Proportion of conventional oxidizers based on chlorates, Perchlorates and / or nitrates.
  • This conventional The burn-up rates of the invention can be oxidized Control mixtures in a wide range.
  • the share of this conventional oxidizers according to the invention is at most 30% by weight, based on the oxidizer mixture, and preferably at most 20 wt .-%, um the combustion temperatures and the proportion of gravely condensable Keep combustion residues as low as possible.
  • a high proportion of potassium perchlorate the combustion temperatures greatly increased and large amounts of potassium chloride releases which is gaseous under the combustion conditions. This gaseous potassium chloride can come from the combustion gases cannot be removed by filters and will result after condensing undesirable smoke formation in the vehicle interior.
  • compositions according to the invention can be processed dry, which is why additional cost-intensive drying steps can be dispensed with in the preparation of the compositions.
  • the calculated burning temperature of the mixture was 1683 Kelvin.
  • the combustion residues had a metallic content of 69.5 % By weight and were in the form of a solid clinker while maintaining the original tablet form.
  • the proportion of carbon monoxide in the combustion gas was 110 ppm and the proportion of nitrous gases was 30 ppm.
  • the mixture showed good ignitability and a sufficiently high burning rate, but atomization of the solid combustion residues occurred.
  • the metallic proportion of the solid combustion residues was 36.8% by weight.
  • the CO concentration in the combustion gas was 190 ppm, the NO x concentration was 20 ppm.
  • Example 1 43.7 parts micronized guanidine nitrate, 48.3 parts finely ground Copper oxide and 8.0 parts of potassium perchlorate were as in Example 1 described processed into fuel tablets. The so Fuel tablets obtained were put into a conventional one Gas generator filled and ignited in a test can.
  • the calculated combustion temperature of the mixture was 1792 Kelvin.
  • the solid combustion residues were in fragments, the metallic portion of the combustion residues was 51.5% by weight.
  • the mixture was easy to ignite and burned quickly.
  • an undesirably high proportion of toxic gases was measured in the combustion gases with a CO concentration of 255 ppm and a NO x concentration of 48 ppm.
  • the mixture was filled into a conventional gas generator and ignited in a test can.
  • the mixture showed one poor willingness to ignite and only a slow burning rate.
  • the can pressure reached was insufficient.
  • the metal part of the solid combustion residue was 100%, the formation of melted droplets could be observed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Chemistry (AREA)
  • Air Bags (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (8)

  1. Composition exempte d'azide engendrant du gaz, en particulier pour être utilisée dans des dispositifs de sécurité pour véhicules automobiles, comportant un mélange de combustible dans une proportion de 20 à 60 % en poids, constitué d'au moins deux composants, et un mélange oxydant dans une proportion de 40 à 80 % en poids, constitué d'au moins trois composants, respectivement par rapport à la composition totale, caractérisée en ce que le mélange de combustible est constitué de:
    5 à 95 % en poids d'un composé guanidine ;
    95 à 5 % en poids d'un acide organique hétérocyclique ; ainsi que
    0 à 20 % % en poids d'autres combustibles, respectivement par rapport au mélange de combustible,
       et en ce que le mélange oxydant est constitué de
    20 à 70 % en poids d'un ou de plusieurs oxydes de métaux transitoires
    10 à 50 % en poids de nitrate de cuivre basique
    2 à 30 % en poids de chlorate de métal, de perchlorate de métal, de perchlorate d'ammonium, de nitrate alcalin, de nitrate alcalinoterreux ou de leurs mélanges, respectivement par rapport au mélange oxydant.
  2. Composition selon la revendication 1, caractérisée en ce que le composé guanidine est choisi parmi le groupe constitué de carbonate de guanidine, de nitrate de guanidine, de perchlorate de guanidine, de nitrate d'aminoguanidine, de nitrate de diaminoguanidine, de nitrate de triaminoguanidine, de nitroguanidine ou de leurs mélanges.
  3. Composition selon l'une des revendications 1 à 2, caractérisée en ce que l'acide organique hétérocyclique est choisi parmi le groupe constitué d'acide cyanurique, d'acide isocyanurique, de cyamélide, d'urazol, d'uracile, d'uramine, d'urazine, d'alloxane, d'acide d'alloxane, d'alloxantine, de xanthine, d'allantoïne, d'acide barbiturique, d'acide orotique, d'acide diliturique, de triazolone, d'acide violurique, de succinimide, d'acide dialurique, d'acide isodialurique, d'hydantoïne, de pseudohydantoïne, d'imidazolone, de pyrazolone, d'acide parabanique, de furazane, d'ammeline, de créatinine, d'hydrazide d'acide maléique, d'acide urique, d'acide pseudo-urique, de guanazine, de guanazole, de mélamine ainsi que leurs sels et dérivés.
  4. Composition selon la revendication 3, caractérisé en ce que les dérivés de l'acide organique hétérocycliques contiennent les groupes fonctionnels =O -OH, NO2, -CO2H, -NH2 ou des combinaisons de ceux-ci.
  5. Composition selon la revendication 1 à 4, caractérisée en ce que l'oxyde de métal transitoire est choisi parmi le groupe constitué de Cr2O3, MnO2, Fe2O3, Fe3O4, CuO, Cu2O ou de leurs mélanges.
  6. Composition selon l'une des revendications 1 à 5, caractérisée en outre par des produits auxiliaires dans une proportion allant jusqu'à 5 % en poids par rapport à la composition totale, les produits auxiliaires étant choisis parmi le groupe constitué de produits auxiliaires de ruissellement, de produits auxiliaires de pressage et/ou de lubrifiants.
  7. Composition selon la revendication 1, constituée de 20 à 40 % en poids de nitrate de guanidine, de 5 à 30 % en poids d'acide cyanurique, de 15 à 35 % en poids de CuO, de 15 à 35 % en poids de nitrate de cuivre basique, et de 4 à 16 % en poids KClO4, respectivement par rapport à la composition totale.
  8. Composition selon l'une des revendications 1 à 7, caractérisé en ce qu'au brûlage de la composition sont formés des produits de combustion condensés qui présentent une proportion de métal de 50 à 90 % en poids.
EP99105181A 1998-04-08 1999-03-31 Composition génératrice de gaz exempt d'azoture Expired - Lifetime EP0949225B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE29806504U DE29806504U1 (de) 1998-04-08 1998-04-08 Azidfreie, gaserzeugende Zusammensetzung
DE29806504U 1998-04-08

Publications (2)

Publication Number Publication Date
EP0949225A1 EP0949225A1 (fr) 1999-10-13
EP0949225B1 true EP0949225B1 (fr) 2002-11-20

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP99105181A Expired - Lifetime EP0949225B1 (fr) 1998-04-08 1999-03-31 Composition génératrice de gaz exempt d'azoture

Country Status (4)

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US (1) US6132537A (fr)
EP (1) EP0949225B1 (fr)
JP (1) JPH11343192A (fr)
DE (2) DE29806504U1 (fr)

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Also Published As

Publication number Publication date
EP0949225A1 (fr) 1999-10-13
DE59903442D1 (de) 2003-01-02
DE29806504U1 (de) 1998-08-06
US6132537A (en) 2000-10-17
JPH11343192A (ja) 1999-12-14

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