EP1051373B1 - Acid-free, gas-generating composition - Google Patents

Acid-free, gas-generating composition Download PDF

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Publication number
EP1051373B1
EP1051373B1 EP99961043A EP99961043A EP1051373B1 EP 1051373 B1 EP1051373 B1 EP 1051373B1 EP 99961043 A EP99961043 A EP 99961043A EP 99961043 A EP99961043 A EP 99961043A EP 1051373 B1 EP1051373 B1 EP 1051373B1
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Prior art keywords
nitrate
weight
composition according
composition
ammonium perchlorate
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EP99961043A
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German (de)
French (fr)
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EP1051373A1 (en
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Siegfried Zeuner
Achim Hofmann
Roland Schropp
Karl-Heinz Rödig
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ZF Airbag Germany GmbH
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TRW Airbag Systems GmbH
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    • 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 azide-free, gas-generating Composition, in particular for use in safety devices for motor vehicles.
  • US-A-5,780,768 describes such a composition which a fuel mixture of the guanidine nitrate, nitroguanidine and their Mixtures existing group and an inorganic oxidizer comprising ceric ammonium nitrate, lithium nitrate, lithium perchlorate, Sodium perchlorate, mixtures of ammonium perchlorate and at least one alkali metal salt, as well as mixtures thereof is.
  • Ammonium perchlorate is in these mixtures over the Alkali metal salts present in deficit.
  • the oxidizer-fuel mixture has an oxygen balance of between + 4% and -4%. Of the Share of solid combustion residues of the mixture should not be greater than 30 wt .-%.
  • the known gas-generating compositions have in general combustion temperatures of well over 2200 K.
  • the high combustion temperatures favor the formation of Carbon monoxide and nitrogen oxides and thus have higher emissions of harmful gases result.
  • problems arise with the newly used uncoated airbag materials.
  • the to catch the hydrochloric acid released from the ammonium perchlorate used high In addition, amounts of alkali metal salts cause a high Fine dust content in the generated gas mixture.
  • Post-published European application EP 1 037 864 discloses gas-generating pyrotechnic compositions comprising a crosslinkable reducing binder in a proportion of at most 10% by weight of the composition which may contain as oxidizers mixtures of ammonium perchlorate and sodium nitrate ,
  • weight ratios of ammonium perchlorate to sodium nitrate of between 1.42 and 2.1, corresponding to a molar ratio of ammonium perchlorate to nitrate ions (NO 3 - ) of 1.02 and 1.51 described.
  • the latter composition contains a high proportion of lithium carbonate for trapping hydrochloric acid formed from the ammonium perchlorate.
  • compositions with a crosslinkable reducing binder in a proportion of at most 10% by weight the composition.
  • the fuel has an enthalpy of formation of less than -3.35 kJ / g and an oxygen balance greater than -90% on.
  • the oxygen balance of the composition is preferably between 0 and -4%.
  • the combustion temperature is preferred below 2200K, and more preferably below 2000K.
  • the oxygen balance of a compound or a mixture is understood to mean that amount of oxygen in percent by weight which becomes free upon complete reaction of the compound or the mixture with, for example, CO 2 , H 2 O, Al 2 O 3 , B 2 O 3 (O 2 over- balancing). , If the available oxygen is insufficient for this purpose, the shortage of oxygen with a negative sign required for complete conversion is indicated (O 2 sub-balancing).
  • the oxygen balance of the fuel is preferably greater than - 80%.
  • the fuel is that of cyanuric acid, Urea, oxamide, uracol, dialuric acid, biurea, alloxan, Alloxantine, parabanic acid and their mixtures existing group selected. Most preferred is cyanuric acid.
  • the inorganic oxidizer is preferably a mixture of ammonium perchlorate and an alkali metal nitrate, wherein the alkali metal nitrate from sodium nitrate, lithium nitrate, potassium nitrate or whose mixtures existing group is selected.
  • Way can also be a mixture of ammonium perchlorate and alkaline earth metal nitrates such as strontium nitrate as an oxidizer be used.
  • the molar ratio of ammonium perchlorate to alkali metal nitrate can be preferred between 1.5: 1 and 3.5: 1, vary.
  • the molar ratio of ammonium perchlorate and alkaline earth metal nitrate is accordingly preferably between 1.5: 0.5 and 3.5: 0.5.
  • the gas generating composition according to the invention may further up to 10% by weight, based on the total composition, of one Burnup accelerator, selected from the group guanidine carbonate, Guanidine nitrate, guanidine perchlorate, aminoguanidine nitrate, diaminoguanidine nitrate, Triaminoguanidine nitrate, nitroguanidine and theirs Mixtures is selected.
  • one Burnup accelerator selected from the group guanidine carbonate, Guanidine nitrate, guanidine perchlorate, aminoguanidine nitrate, diaminoguanidine nitrate, Triaminoguanidine nitrate, nitroguanidine and theirs Mixtures is selected.
  • Combustion moderators may also be advantageously added to the composition in an amount of up to 5% by weight, based on the total composition, of the group Cr 2 O 3 , MnO 2 , Fe 2 O 3 , Fe 3 O 4 , CuO, Cu 2 O and mixtures thereof are selected.
  • the mixture may contain conventional processing aids in a proportion of up to 3 wt .-%.
  • the processing aids are preferably selected from the group of flow aids, pressing aids and / or lubricants.
  • compositions of the invention consist essentially of 30 to 45 wt .-% cyanuric acid, 0 to 5 wt .-% guanidine nitrate, 10 to 35 wt .-% sodium nitrate, 20 to 50 wt .-% ammonium perchlorate and each 0 to 2 wt. -% CuO and Fe 2 O 3 .
  • Another, particularly preferred composition consists essentially of 30 to 45 wt .-% cyanuric acid, 0 to 5 wt .-% guanidine nitrate, 10 to 35 wt .-% strontium nitrate, 20 to 50 wt .-% ammonium perchlorate and each 0 to 2 % By weight of CuO and Fe 2 O 3 .
  • compositions of the invention are characterized in Comparison to the compositions described in US 5,780,768 due to extremely low combustion temperatures below 2250 K. as well as a good ignition in conjunction with a sufficient high burn rate.
  • the carbon monoxide and nitrogen oxides in the released gas mixture are also considerably lower.
  • the compositions of the invention also give a increased gas yield with significantly reduced particle emissions.
  • a fuel containing C, H, N and O with an enthalpy of formation ⁇ H f of less than -3.35 kJ / g, whose oxygen balance is at the same time greater than -90, has proved favorable for the generation of combustion temperatures which are as low as possible and thus lower % is. This ensures that the proportion of oxidizer in the composition can be kept low.
  • urea oxamide
  • urazole dialuric acid and biurea
  • Guanidine nitrate or another guanidine compound in small amounts of up to 10 wt .-% as an accelerator.
  • the oxygen balance of the composition can advantageously be set between 0 and -4%, since the limit for the NO x which is preferably formed in the case of oxygen overbalancing is substantially lower as the limit for the carbon monoxide which is preferably produced by under-balancing.
  • the resulting mixture was ignited in a closed 60 liter jug.
  • the maximum can pressure determined in this way was 216 kPa, with a calculated gas yield of 84.7%.
  • the carbon monoxide concentration in the liberated gas mixture, measured in a 2.5 m 3 chamber, was 289 ppm, the NO x concentration was 56 ppm.
  • the emitted particulate matter was 1.05 g.
  • the calculated combustion temperature was 2165 K.
  • the HCl concentration in the gas mixture produced was below the detection limit of 1 ppm.
  • Example 1 the amount of particulate matter discharged was lower at 0.95 g as in Example 1. Although the molar ratio of ammonium perchlorate to potassium nitrate in this example was about 2.27 also in this experiment, no significant amount of hydrochloric acid in the Combustion gases are detected. The HCl concentration was ⁇ 1 ppm below the detection limit of the device used.

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

Description

Die vorliegende Erfindung betrifft eine azidfreie, gaserzeugende Zusammensetzung, insbesondere zur Verwendung in Sicherheitseinrichtungen für Kraftfahrzeuge.The present invention relates to an azide-free, gas-generating Composition, in particular for use in safety devices for motor vehicles.

Die US-A-5,780,768 beschreibt eine derartige Zusammensetzung, die ein Brennstoffgemisch aus der Guanidinnitrat, Nitroguanidin und deren Gemischen bestehenden Gruppe sowie einen anorganischen Oxidator umfaßt, der aus der aus Cerammoniumnitrat, Lithiumnitrat, Lithiumperchlorat, Natriumperchlorat, Gemischen von Ammoniumperchlorat und wenigstens einem Alkalimetallsalz, sowie Mischungen davon, ausgewählt ist. Ammoniumperchlorat ist in diesen Gemischen gegenüber den Alkalimetallsalzen im Unterschuß vorhanden. Das Oxidator-Brennstoff-Gemisch weist eine Sauerstoffbilanz von zwischen +4% und -4% auf. Der Anteil an festen Verbrennungsrückständen des Gemisches soll nicht größer als 30 Gew.-% sein.US-A-5,780,768 describes such a composition which a fuel mixture of the guanidine nitrate, nitroguanidine and their Mixtures existing group and an inorganic oxidizer comprising ceric ammonium nitrate, lithium nitrate, lithium perchlorate, Sodium perchlorate, mixtures of ammonium perchlorate and at least one alkali metal salt, as well as mixtures thereof is. Ammonium perchlorate is in these mixtures over the Alkali metal salts present in deficit. The oxidizer-fuel mixture has an oxygen balance of between + 4% and -4%. Of the Share of solid combustion residues of the mixture should not be greater than 30 wt .-%.

Die bekannten gaserzeugenden Zusammensetzungen weisen jedoch im allgemeinen Verbrennungstemperaturen von weit über 2200 K auf. Die hohen Verbrennungstemperaturen begünstigen aber die Bildung von Kohlenmonoxid und Stickoxiden und haben somit höhere Schadgasemissionen zur Folge. Ferner entstehen Probleme mit den neuerdings verwendeten unbeschichteten Airbag-Materialien. Die zum Auffangen der aus dem Ammoniumperchlorat freigesetzten Salzsäure verwendeten hohen Mengen an Alkalimetallsalzen verursachen darüber hinaus einen hohen Feinstaubgehalt im erzeugten Gasgemisch. However, the known gas-generating compositions have in general combustion temperatures of well over 2200 K. The high combustion temperatures, however, favor the formation of Carbon monoxide and nitrogen oxides and thus have higher emissions of harmful gases result. Furthermore, problems arise with the newly used uncoated airbag materials. The to catch the hydrochloric acid released from the ammonium perchlorate used high In addition, amounts of alkali metal salts cause a high Fine dust content in the generated gas mixture.

Die nach-veröffentlichte europäische Anmeldung EP 1 037 864 (entsprechend WO 99/31029 A) offenbart gaserzeugende pyrotechnische Zusammensetzungen mit einem vernetzbaren reduzierenden Binder in einem Anteil von höchstens 10 Gew.-% der Zusammensetzung, die als Oxidatoren Gemische aus Ammoniumperchlorat und Natriumnitrat enthalten können. In den Ausführungsbeispielen sind Gewichtsverhältnisse von Ammoniumperchlorat zu Natriumnitrat von zwischen 1,42 und 2,1, entsprechend einem molaren Verhältnis von Ammoniumperchlorat zu Nitrationen (NO3 -) von 1,02 bzw. 1,51, beschrieben. Die letztgenannte Zusammensetzung enthält jedoch einen hohen Anteil an Lithiumkarbonat zum Abfangen der aus dem Ammoniumperchlorat entstehenden Salzsäure.Post-published European application EP 1 037 864 (corresponding to WO 99/31029 A) discloses gas-generating pyrotechnic compositions comprising a crosslinkable reducing binder in a proportion of at most 10% by weight of the composition which may contain as oxidizers mixtures of ammonium perchlorate and sodium nitrate , In the embodiments, weight ratios of ammonium perchlorate to sodium nitrate of between 1.42 and 2.1, corresponding to a molar ratio of ammonium perchlorate to nitrate ions (NO 3 - ) of 1.02 and 1.51 described. However, the latter composition contains a high proportion of lithium carbonate for trapping hydrochloric acid formed from the ammonium perchlorate.

Es besteht daher weiterhin Bedarf an gaserzeugenden Zusammensetzungen, mit denen die vorgenannten Nachteile vermieden werden können.There is therefore still a need for gas-generating compositions with where the aforementioned disadvantages can be avoided.

Die Erfindung stellt hierzu eine azidfreie gaserzeugende Zusammensetzung bereit, die einen Brennstoff und einen anorganischen Oxidator umfaßt und deren Vebrennungstemperatur unterhalb von 2250 K liegt. Das erfindungsgemäße Gemisch ist dadurch gekennzeichnet, daß der anorganische Oxidator ein Gemisch aus Ammoniumperchlorat und einem aus der Gruppe der Alkalimetallnitrate und Erdalkalimetallnitrate ausgewählten Nitrat ist, wobei molare Verhältnis von Ammoniumperchlorat zu dem anorganischen Nitrat (NO3 -) größer als 1 ist, so daß

  • (i) das molare Verhältnis von Ammoniumperchlorat zu Alkalimetallnitrat zwischen 1,05:1 und 6:1 liegt, oder
  • (ii) das molare Verhältnis von Ammoniumperchlorat zu Erdalkalimetallnitrat zwischen 1,05:0,5 und 6:0,5 liegt.
    • The invention provides for this an azide-free gas generating composition comprising a fuel and an inorganic oxidizer and whose combustion temperature is below 2250K. The mixture according to the invention is characterized in that the inorganic oxidizer is a mixture of ammonium perchlorate and a nitrate selected from the group of alkali metal nitrates and alkaline earth metal nitrates, wherein molar ratio of ammonium perchlorate to the inorganic nitrate (NO 3 - ) is greater than 1, so that
  • (i) the molar ratio of ammonium perchlorate to alkali metal nitrate is between 1.05: 1 and 6: 1, or
  • (ii) the molar ratio of ammonium perchlorate to alkaline earth metal nitrate is between 1.05: 0.5 and 6: 0.5.

    • Ausgenommen sind jedoch gaserzeugende, azidfreie Zusammensetzungen mit einem vernetzbaren reduzierenden Binder in einem Anteil von höchstens 10 Gew.-% der Zusammensetzung. However, except gas-generating, azide-free compositions with a crosslinkable reducing binder in a proportion of at most 10% by weight the composition.

    Vorzugsweise weist der Brennstoff eine Bildungsenthalpie von kleiner als -3,35 kJ/g und eine Sauerstoffbilanz von größer als -90 % auf. Die Sauerstoffbilanz der Zusammensetzung liegt vorzugsweise zwischen 0 und -4 %. Die Verbrennungstemperatur liegt bevorzugt unterhalb von 2200 K und besonders bevorzugt unterhalb von 2000 K.Preferably, the fuel has an enthalpy of formation of less than -3.35 kJ / g and an oxygen balance greater than -90% on. The oxygen balance of the composition is preferably between 0 and -4%. The combustion temperature is preferred below 2200K, and more preferably below 2000K.

    Unter der Sauerstoffbilanz einer Verbindung oder eines Gemisches wird diejenige Sauerstoffmenge in Gewichtsprozent verstanden, die bei vollständiger Umsetzung der Verbindung oder des Gemisches zu beispielsweise CO2, H2O, Al2O3, B2O3 frei wird (O2-Überbilanzierung). Reicht der vorhandene Sauerstoff hierzu nicht aus, so wird die zum vollständigen Umsatz notwendige Fehlmenge an Sauerstoff mit negativem Vorzeichen angegeben (O2-Unterbilanzierung).The oxygen balance of a compound or a mixture is understood to mean that amount of oxygen in percent by weight which becomes free upon complete reaction of the compound or the mixture with, for example, CO 2 , H 2 O, Al 2 O 3 , B 2 O 3 (O 2 over- balancing). , If the available oxygen is insufficient for this purpose, the shortage of oxygen with a negative sign required for complete conversion is indicated (O 2 sub-balancing).

    Die Sauerstoffbilanz des Brennstoffs ist bevorzugt größer als - 80%. Besonders bevorzugt ist der Brennstoff aus der aus Cyanursäure, Harnstoff, Oxamid, Urazol, Dialursäure, Biurea, Alloxan, Alloxantin, Parabansäure und deren Mischungen bestehenden Gruppe ausgewählt. Am meisten bevorzugt ist Cyanursäure.The oxygen balance of the fuel is preferably greater than - 80%. Most preferably, the fuel is that of cyanuric acid, Urea, oxamide, uracol, dialuric acid, biurea, alloxan, Alloxantine, parabanic acid and their mixtures existing group selected. Most preferred is cyanuric acid.

    Der anorganische Oxidator ist bevorzugt eine Mischung aus Ammoniumperchlorat und einem Alkalimetallnitrat, wobei das Alkalimetallnitrat aus der aus Natriumnitrat, Lithiumnitrat, Kaliumnitrat oder deren Mischungen bestehenden Gruppe ausgewählt ist. In vorteilhafter Weise kann auch eine Mischung aus Ammoniumperchlorat und Erdalkalimetallnitraten wie beispielsweise Strontiumnitrat als Oxidator eingesetzt werden.The inorganic oxidizer is preferably a mixture of ammonium perchlorate and an alkali metal nitrate, wherein the alkali metal nitrate from sodium nitrate, lithium nitrate, potassium nitrate or whose mixtures existing group is selected. In an advantageous manner Way can also be a mixture of ammonium perchlorate and alkaline earth metal nitrates such as strontium nitrate as an oxidizer be used.

    Überraschenderweise wurde gefunden, daß bei Verwendung eines Gemisches aus Ammoniumperchlorat und anorganischen Nitraten, wie Alkalimetallnitraten oder Erdalkalimetallnitraten, als Oxidator der Anteil der Alkali- oder Erdalkalimetallsalze im Oxidatorgemisch auch unter die zum Auffangen der aus dem Ammoniumperchlorat freigesetzten Salzsäure notwendige stöchiometrische Menge verringert werden kann, ohne daß im freigesetzten Gasgemisch nennenswerte Mengen an Salzsäure nachzuweisen wären. Durch die jetzt mögliche Verwendung von Ammoniumperchlorat in Überschuß zu den weiteren anorganischen Nitraten wird der Anteil der entstehenden festen Verbrennungsrückstände weiter reduziert und die Gasausbeute beträchtlich erhöht.Surprisingly, it has been found that when using a Mixture of ammonium perchlorate and inorganic nitrates, such as Alkali metal nitrates or alkaline earth metal nitrates, as the oxidizer of Proportion of alkali or alkaline earth metal salts in the oxidizer mixture also under those for catching the released from the ammonium perchlorate Hydrochloric acid necessary stoichiometric amount can be reduced without that in the released gas mixture significant amounts of hydrochloric acid be demonstrated. By the now possible use of ammonium perchlorate in excess of the other inorganic nitrates the proportion of resulting solid combustion residues on reduced and the gas yield increased considerably.

    Das molare Verhältnis von Ammoniumperchlorat zu Alkalimetallnitrat kann dabei bevorzugt zwischen 1,5:1 und 3,5:1, variieren. Das molare Verhältnis von Ammoniumperchlorat und Erdalkalimetallnitrat liegt entsprechend bevorzugt zwischen 1,5:0,5 und 3,5:0,5.The molar ratio of ammonium perchlorate to alkali metal nitrate can be preferred between 1.5: 1 and 3.5: 1, vary. The molar ratio of ammonium perchlorate and alkaline earth metal nitrate is accordingly preferably between 1.5: 0.5 and 3.5: 0.5.

    Die erfindungsgemäße gaserzeugende Zusammensetzung kann ferner bis zu 10 Gew.-%, bezogen auf die Gesamtzusammensetzung, eines Abbrandbeschleunigers enthalten, der aus der Gruppe Guanidincarbonat, Guanidinnitrat, Guanidinperchlorat, Aminoguanidinnitrat, Diaminoguanidinnitrat, Triaminoguanidinnitrat, Nitroguanidin und deren Mischungen ausgewählt ist.The gas generating composition according to the invention may further up to 10% by weight, based on the total composition, of one Burnup accelerator, selected from the group guanidine carbonate, Guanidine nitrate, guanidine perchlorate, aminoguanidine nitrate, diaminoguanidine nitrate, Triaminoguanidine nitrate, nitroguanidine and theirs Mixtures is selected.

    Der Zusammensetzung können darüber hinaus in vorteilhafter Weise Abbrandmoderatoren in einem Anteil von bis zu 5 Gew.-%, bezogen auf die Gesamtzusammensetzung, zugesetzt werden, die aus der Gruppe Cr2O3, MnO2, Fe2O3, Fe3O4, CuO, Cu2O und deren Mischungen ausgewählt sind. Schließlich kann das Gemisch noch übliche Verarbeitungshilfen in einem Anteil von bis zu 3 Gew.-% enthalten. Die Verarbeitungshilfen sind bevorzugt aus der Gruppe der Rieselhilfen, Preßhilfsmittel und/oder Gleitmittel ausgewählt. Combustion moderators may also be advantageously added to the composition in an amount of up to 5% by weight, based on the total composition, of the group Cr 2 O 3 , MnO 2 , Fe 2 O 3 , Fe 3 O 4 , CuO, Cu 2 O and mixtures thereof are selected. Finally, the mixture may contain conventional processing aids in a proportion of up to 3 wt .-%. The processing aids are preferably selected from the group of flow aids, pressing aids and / or lubricants.

    Besonders bevorzugte erfindungsgemäße Zusammensetzungen bestehen im wesentlichen aus 30 bis 45 Gew.-% Cyanursäure, 0 bis 5 Gew.-% Guanidinnitrat, 10 bis 35 Gew.-% Natriumnitrat, 20 bis 50 Gew.-% Ammoniumperchlorat sowie jeweils 0 bis 2 Gew.-% CuO und Fe2O3. Eine weitere, besonders bevorzugte Zusammensetzung besteht im wesentlichen aus 30 bis 45 Gew.-% Cyanursäure, 0 bis 5 Gew.-% Guanidinnitrat, 10 bis 35 Gew.-% Strontiumnitrat, 20 bis 50 Gew.-% Ammoniumperchlorat sowie jeweils 0 bis 2 Gew.-% CuO und Fe2O3.Particularly preferred compositions of the invention consist essentially of 30 to 45 wt .-% cyanuric acid, 0 to 5 wt .-% guanidine nitrate, 10 to 35 wt .-% sodium nitrate, 20 to 50 wt .-% ammonium perchlorate and each 0 to 2 wt. -% CuO and Fe 2 O 3 . Another, particularly preferred composition consists essentially of 30 to 45 wt .-% cyanuric acid, 0 to 5 wt .-% guanidine nitrate, 10 to 35 wt .-% strontium nitrate, 20 to 50 wt .-% ammonium perchlorate and each 0 to 2 % By weight of CuO and Fe 2 O 3 .

    Die erfindungsgemäßen Zusammensetzungen zeichnen sich im Vergleich zu den in der US 5,780,768 beschriebenen Zusammensetzungen durch äußerst niedrige Verbrennungstemperaturen von unterhalb 2250 K sowie eine gute Anzündwilligkeit in Verbindung mit einer ausreichend hohen Abbrandgeschwindigkeit aus. Die Kohlenmonoxid- und Stickoxidanteile im freigesetzten Gasgemisch sind ebenfalls erheblich niedriger. Die erfindungsgemäßen Zusammensetzungen ergeben zudem eine erhöhte Gasausbeute bei deutlich verringertem Partikelausstoß.The compositions of the invention are characterized in Comparison to the compositions described in US 5,780,768 due to extremely low combustion temperatures below 2250 K. as well as a good ignition in conjunction with a sufficient high burn rate. The carbon monoxide and nitrogen oxides in the released gas mixture are also considerably lower. The compositions of the invention also give a increased gas yield with significantly reduced particle emissions.

    Als günstig für die Erzeugung möglichst niedriger Verbrennungstemperaturen und damit niedrigerer Schadgasemissionen hat sich die Verwendung eines C, H, N und O enthaltenden Brennstoffs mit einer Bildungsenthalpie ΔHf von kleiner als -3,35 kJ/g erwiesen, dessen Sauerstoffbilanz gleichzeitig größer als -90% ist. Damit ist gewährleistet, daß der Anteil an Oxidator in der Zusammensetzung gering gehalten werden kann. Geeignete Brennstoffe, mit denen die Sauerstoffbilanz verbessert oder nur geringfügig beeinflußt werden kann, ohne die Bildungswärmen ΔHf zu stark anzuheben, sind organische Verbindungen, die beispielsweise C=O, -OH, -CO2H, -NH2, nicht jedoch NO2, als Substitutenten enthalten.The use of a fuel containing C, H, N and O with an enthalpy of formation ΔH f of less than -3.35 kJ / g, whose oxygen balance is at the same time greater than -90, has proved favorable for the generation of combustion temperatures which are as low as possible and thus lower % is. This ensures that the proportion of oxidizer in the composition can be kept low. Suitable fuels with which the oxygen balance can be improved or only slightly influenced without excessively raising the formation heat ΔH f are organic compounds which are, for example, C = O, -OH, -CO 2 H, -NH 2 , but not NO 2 , contained as substitutes.

    Guanidinnitrat (ΔHf = -3,18 kJ/g, Sauerstoffbilanz = -26,2%) und Nitroguanidin (ΔHf = -0,88 kJ/g, Sauerstoffbilanz = -30,7%) ergeben bei gleicher Sauerstoffbilanz der Mischung mit einem vorgegebenen Oxidator höhere Verbrennungstemperaturen als die erfindungsgemäß bevorzugten Verbindungen, wie z.B. Cyanursäure (ΔHf = -5,356, Sauerstoffbilanz = -55,8 %), Harnstoff, Oxamid, Urazol, Dialursäure und Biurea, und sind daher weniger bevorzugt. Guanidine nitrate (ΔH f = -3.18 kJ / g, oxygen balance = -26.2%) and nitroguanidine (ΔH f = -0.88 kJ / g, oxygen balance = -30.7%) with the same oxygen balance of the mixture with a given oxidizer higher combustion temperatures than the inventively preferred compounds such as cyanuric acid (ΔH f = -5.356, oxygen balance = -55.8%), urea, oxamide, urazole, dialuric acid and biurea, and are therefore less preferred.

    In manchen Fällen kann es jedoch vorteilhaft sein, beispielsweise Guanidinnitrat oder eine andere Guanidinverbindung in geringen Mengen von bis zu 10 Gew.-% als Beschleuniger zuzusetzen.In some cases, however, it may be advantageous, for example Guanidine nitrate or another guanidine compound in small amounts of up to 10 wt .-% as an accelerator.

    Schließlich wurde gefunden, daß im Gegensatz zu der in den Ausführungsbeispielen der US-A 5,780,768 angegebenen Überbilanzierung an Sauerstoff die Sauerstoffbilanz der Zusammensetzung vorteilhaft zwischen 0 und -4% eingestellt werden kann, da der Grenzwert für das bevorzugt bei Sauerstoffüberbilanzierung entstehende NOx wesentlich niedriger ist als der Grenzwert für das bei bevorzugt bei Unterbilanzierung entstehende Kohlenmonoxid.Finally, it has been found that, in contrast to the over-balancing of oxygen given in the exemplary embodiments of US Pat. No. 5,780,768, the oxygen balance of the composition can advantageously be set between 0 and -4%, since the limit for the NO x which is preferably formed in the case of oxygen overbalancing is substantially lower as the limit for the carbon monoxide which is preferably produced by under-balancing.

    Die Erfindung wird nachfolgend anhand einiger Ausführungsbeispiele beschrieben, die jedoch nicht in einem einschränkenden Sinn zu verstehen sind.The invention will be described below with reference to some embodiments but not in a limiting sense understand.

    Beispiel 1example 1

    228 g gemahlene Cyanursäure, 26,4 g mikronisiertes Guanidinnitrat, 218,5 g Ammoniumperchlorat und 127,1 g Natriumnitrat    wurden gemeinsam in eine Kugelmühle eingewogen, 3 Stunden lang gemahlen und miteinander vermischt. Das erhaltene Gemisch wurde ohne weitere Verarbeitungsschritte direkt zu Tabletten verpreßt. 228 g ground cyanuric acid, 26.4 g micronized guanidine nitrate, 218.5 g Ammonium perchlorate and 127.1 g sodium nitrate were weighed together in a ball mill, ground for 3 hours and mixed together. The resulting mixture was compressed directly into tablets without further processing steps.

    Das so erhaltene Gemisch wurde in einer geschlossenen 60 1-Kanne gezündet. Der auf diese Weise ermittelte maximale Kannendruck betrug 216 kPa, bei einer berechneten Gasausbeute von 84,7 %. Die Kohlenmonoxidkonzentration im freigesetzten Gasgemisch, gemessen in einer 2,5 m3 Kammer, betrug 289 ppm, die NOx-Konzentration betrug 56 ppm. Der ausgestoßene Feinstaub lag bei 1,05 g. Die berechnete Verbrennungstemperatur betrug 2165 K. Die HCl-Konzentration im erzeugten Gasgemisch lag unterhalb der Nachweisgrenze von 1 ppm. The resulting mixture was ignited in a closed 60 liter jug. The maximum can pressure determined in this way was 216 kPa, with a calculated gas yield of 84.7%. The carbon monoxide concentration in the liberated gas mixture, measured in a 2.5 m 3 chamber, was 289 ppm, the NO x concentration was 56 ppm. The emitted particulate matter was 1.05 g. The calculated combustion temperature was 2165 K. The HCl concentration in the gas mixture produced was below the detection limit of 1 ppm.

    Beispiel 2Example 2

    38,7 g gemahlene Cyanursäure 3,4 g mikronisiertes Guanidinnitrat 24,2 g Kaliumnitrat 33,7 g Ammoniumperchlorat 2 g Eisenoxid 2 g Kupferoxid    wurden gemeinsam in eine Kugelmühle eingewogen, 3 Stunden lang gemahlen und miteinander vermischt. Das erhaltene Gemisch wurde ohne weitere Verarbeitungsschritte direkt zu Tabletten verpreßt. 38.7 g ground cyanuric acid 3.4 g micronized guanidine nitrate 24.2 g potassium nitrate 33.7 g ammonium perchlorate 2 g iron oxide 2 g copper oxide were weighed together in a ball mill, ground for 3 hours and mixed together. The resulting mixture was compressed directly into tablets without further processing steps.

    43 g der so erhaltenen Zusammensetzung wurden in einem üblichen Fahrergasgenerator in einer geschlossenen 60 1-Kanne gezündet. Der auf diese Weise ermittelte maximale Kannendruck betrug 216 kPa bei einer berechneten Gasausbeute von 80,4 %. Die Verbrennungstemperatur des Gemischs wurde zu 2097 K berechnet. Die Bestimmung der Schadgase erfolgte in einer 2,5 m3-Testkammer mit einem Infrarotspektrometer über 30 Minuten. Bei dieser Messung wurden die folgenden Gaskonzentrationen ermittelt: Gas Konzentration
    [ppm]         CO 242 NO 6,7 NO2 0,36 NH3 < 1 CO2 1583 SO2 <0,1 HCN <1 HCl <0,5 CH2O <0,8 COCl2 <0,1 C6H6 < 1     43 g of the composition thus obtained were ignited in a conventional driver gas generator in a closed 60 liter jug. The maximum can pressure determined in this way was 216 kPa for a calculated gas yield of 80.4%. The combustion temperature of the mixture was calculated to be 2097K. The determination of the noxious gases took place in a 2.5 m 3 test chamber with an infrared spectrometer over 30 minutes. In this measurement, the following gas concentrations were determined: gas concentration
    [Ppm]     CO 242 NO 6.7 NO 2 0.36 NH 3 <1 CO 2 1583 SO 2 <0.1 HCN <1 HCl <0.5 CH 2 O <0.8 COCl 2 <0.1 C 6 H 6 <1

    Die Verwendung des < -Zeichens in der obigen Tabelle bedeutet, daß die Konzentration der jeweiligen Gase unterhalb der Nachweisgrenze des verwendeten Meßgeräts lag.The use of the <symbol in the above table means that the concentration of the respective gases below the detection limit of the used.

    Aus einer thermodynamischen Berechnung ergibt sich bei einer Verbrennung der obigen Zusammensetzung eine HCl-Konzentration von ca. 170 ppm. Diese theoretisch berechnete HCl-Menge wurde in keinem der durchgeführten Experimente gefunden. Es wurde daher versucht, die fehlende HCl-Menge im Verbrennungsgas durch Kondensation mit Wasser unmittelbar nach der Auslösung des Gasgenerators und vor Beginn der Gasmessung in der Testkanne, (d.h. innerhalb eines Zeitbereichs von 100 ms bis 1 min.) nachzuweisen. Bei diesem Versuch wurde nach dem Auswaschen der Testkanne ein pH-Wert von 8,5 ermittelt. Ein Vergleichsversuch vor Auslösung des Gasgenerators ergab einen pH-Wert von 9,3. Ferner wurde in der Waschlösung ein molarer Überschuß von Chloridionen im Vergleich zu Kaliumionen festgestellt. Die erhaltenen Ergebnisse lassen den Schluß zu, daß die bei der Verbrennungsreaktion entstehende Salzsäure nach dem Auslösen des Gasgenerators sehr schnell kondensiert und somit für den Insassen nicht gefährlich wird. Der in den meisten Herstellerspezifikationen angesetzte Grenzwert von 25 ppm für eine 30minütige Exposition mit Salzsäure wird in jedem Fall wesentlich unterschritten.From a thermodynamic calculation results in a Combustion of the above composition an HCl concentration of about 170 ppm. This theoretically calculated amount of HCl was not in any of the experiments found. It was therefore tried, the lack of HCl in the combustion gas due to condensation with water immediately after the triggering of the gas generator and before the start of the Gas measurement in the test can, (i.e., within a time range of 100 ms to 1 min.). In this experiment was after the Washing out the test can a pH of 8.5 determined. A comparative experiment before triggering the gas generator gave a pH of 9.3. Further, in the washing solution, a molar excess of Chloride ions found in comparison to potassium ions. The obtained Results lead to the conclusion that in the combustion reaction Resulting hydrochloric acid after the triggering of the gas generator very quickly condensed and thus not dangerous for the occupant. The in limit of 25 ppm as set by most manufacturer specifications for a 30-minute exposure to hydrochloric acid will in any case significantly below.

    Beispiel 3Example 3

    37,3 g gemahlene Cyanursäure, 3,2 g mikronisiertes Guanidinnitrat, 45 g Ammoniumperchlorat 14,5 g Natriumnitrat    wurden gemeinsam in eine Kugelmühle eingewogen, 3 Stunden lang gemahlen und miteinander vermischt. Das erhaltene Gemisch wurde ohne weitere Verarbeitungsschritte direkt zu Tabletten verpreßt. 37.3 g ground cyanuric acid, 3.2 g micronized guanidine nitrate, 45 g ammonium perchlorate 14.5 g sodium nitrate were weighed together in a ball mill, ground for 3 hours and mixed together. The resulting mixture was compressed directly into tablets without further processing steps.

    42 g der so erhaltenen Zusammensetzung wurden in einem üblichen Gasgenerator in einer geschlossenen 60 1-Kanne gezündet, wobei ein maximaler Kannendruck von 235 kPa erhalten wurde. Die Gasausbeute lag bei 90 %; die Verbrennungstemperatur des Gemischs betrug 2243 K. Die entstehenden Verbrennungsgase wurden in einer 2,5 m3-Testkammer mit einem Infrarot-Spektrometer analysiert. Nach 30 Minuten betrug die Kohlenmonoxidkonzentration 524 ppm, und die NOx-Konzentration lag bei 61,5 ppm. Die Sauerstoffbilanz dieser Zusammensetzung betrug +0,8 %; dies erklärt die Verschiebung zu höheren Kohlenmonoxidwerten in den Verbrennungsgasen im Vergleich zu den Zusammensetzungen gemäß den Beispielen 1 und 2.42 g of the composition thus obtained were ignited in a conventional gas generator in a closed 60 1-can to obtain a maximum can pressure of 235 kPa was obtained. The gas yield was 90%; the combustion temperature of the mixture was 2243 K. The resulting combustion gases were analyzed in a 2.5 m 3 test chamber with an infrared spectrometer. After 30 minutes, the carbon monoxide concentration was 524 ppm and the NO x concentration was 61.5 ppm. The oxygen balance of this composition was +0.8%; this explains the shift to higher carbon monoxide levels in the combustion gases as compared to the compositions of Examples 1 and 2.

    Die Menge an ausgestoßenem Feinstaub lag mit 0,95 g jedoch niedriger als im Beispiel 1. Obwohl das molare Verhältnis von Ammoniumperchlorat zu Kaliumnitrat in diesem Beispiel bei ca. 2,27 lag, konnte auch bei diesem Versuch keine nennenswerte Menge an Salzsäure in den Verbrennungsgasen festgestellt werden. Die HCl-Konzentration lag mit < 1 ppm unterhalb der Nachweisgrenze des verwendeten Geräts.However, the amount of particulate matter discharged was lower at 0.95 g as in Example 1. Although the molar ratio of ammonium perchlorate to potassium nitrate in this example was about 2.27 also in this experiment, no significant amount of hydrochloric acid in the Combustion gases are detected. The HCl concentration was < 1 ppm below the detection limit of the device used.

    Claims (15)

    1. An azide-free gas-generating composition, in particular for use in safety devices for motor vehicles, comprising a fuel and an inorganic oxidizer, characterized in that the combustion temperature of the composition is below 2250 K and that the inorganic oxidizer is a mixture of ammonium perchlorate and a nitrate selected from the group of alkali metal nitrates and alkaline earth metal nitrates,
      (i) the molar ratio of ammonium perchlorate to alkali metal nitrate being between 1.05:1 and 6:1, or
      (ii) the molar ratio of ammonium perchlorate to alkaline earth metal nitrate being between 1.05:0.5 and 6:0.5,
         except for an azide-free gas-generating composition comprising a crosslinkable reducing binder in a proportion of not more than 10% by weight of the composition.
    2. The composition according to Claim 1, characterized in that the oxygen balance of the fuel is greater than -90% and the formation enthalpy is less than -3.35kJ/g.
    3. The composition according to Claim 1, characterized in that the fuel is selected from the group consisting of cyanuric acid, urea, oxamide, urazol, dialuric acid, biurea, alloxane, alloxantine, parabenic acid and mixtures thereof.
    4. The composition according to Claim 3, characterized in that the fuel is cyanuric acid.
    5. The composition according to any of Claims 1 to 4, characterized in that the oxygen balance of the composition is between 0 and -4%.
    6. The composition according to any of Claims 1 to 5, characterized in that the oxidizer is a mixture of ammonium perchlorate and an alkali metal nitrate, the alkali metal nitrate being selected from the group consisting of sodium nitrate, lithium nitrate, potassium nitrate or mixtures thereof.
    7. The composition according to Claim 6, characterized in that the molar ratio of ammonium perchlorate to alkali metal nitrate is between 1.5:1 and 3.5:1.
    8. The composition according to any of Claims 1 to 5, characterized in that the oxidizer is a mixture of ammonium perchlorate and an alkaline earth metal nitrate.
    9. The composition according to Claim 8, characterized in that the oxidizer is a mixture of ammonium perchlorate and strontium nitrate.
    10. The composition according to Claim 8 or 9, characterized in that the molar ratio of ammonium perchlorate to alkaline earth metal nitrate is between 1.5:0.5 and 3.5:0.5.
    11. The composition according to any of the preceding claims, characterized in that the composition, in relation to the overall composition, contains up to 10 % by weight of burning accelerators, which are selected from the group of guanidine carbonate, guanidine nitrate, guanidine perchlorate, aminoguanidine nitrate, diaminoguanidine nitrate, triaminoguanidine nitrate, nitroguanidine and mixtures thereof.
    12. The composition according to any of the preceding claims, characterized in that the composition contains in addition up to 5 % by weight of burning moderators, which are selected from the group of Cr2O3, MnO2, Fe2O3, Fe3O4, CuO, Cu2O and mixtures thereof.
    13. The composition according to any of the preceding claims, characterized in that the composition contains in addition up to 3 % by weight conventional processing aids from the group of trickling aids, pressure aids and/or lubricants.
    14. The composition according to Claim 1, consisting of 30-45% by weight cyanuric acid, 0 to 5 % by weight guanidine nitrate, 10 to 35 % by weight sodium nitrate or potassium nitrate, 20 to 50 % by weight ammonium perchlorate, 0 to 2 % by weight CuO and 0 to 2 % by weight Fe2O3, as well as 0 to 3 % by weight processing aids and inevitable impurities.
    15. The composition according to Claim 1, consisting of 30 to 45 % by weight cyanuric acid, 0 to 5 % by weight guanidine nitrate, 10 to 35 % by weight strontium nitrate, 20 to 50 % by weight ammonium perchlorate, 0 to 2 % by weight CuO and 0 to 2 % by weight Fe2O3, as well as 0 to 3% by weight processing aids and inevitable impurities.
    EP99961043A 1998-12-02 1999-12-01 Acid-free, gas-generating composition Expired - Lifetime EP1051373B1 (en)

    Applications Claiming Priority (3)

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    DE29821544U DE29821544U1 (en) 1998-12-02 1998-12-02 Azide-free, gas generating composition
    DE29821544U 1998-12-02
    PCT/EP1999/009382 WO2000032541A1 (en) 1998-12-02 1999-12-01 Acid-free, gas-generating composition

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    US5985060A (en) * 1998-07-25 1999-11-16 Breed Automotive Technology, Inc. Gas generant compositions containing guanidines
    EP1218317A2 (en) * 1999-09-13 2002-07-03 Dynamit Nobel GmbH Gas-generating mixtures
    FR2959508B1 (en) * 2010-04-29 2015-01-02 Snpe Materiaux Energetiques PYROTECHNIC COMPOUND GAS GENERATOR; PROCESS FOR OBTAINING

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    WO2000032541A1 (en) 2000-06-08
    EP1051373A1 (en) 2000-11-15

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