WO1996026169A1 - Gas-generating mixtures - Google Patents
Gas-generating mixtures Download PDFInfo
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- WO1996026169A1 WO1996026169A1 PCT/EP1996/000605 EP9600605W WO9626169A1 WO 1996026169 A1 WO1996026169 A1 WO 1996026169A1 EP 9600605 W EP9600605 W EP 9600605W WO 9626169 A1 WO9626169 A1 WO 9626169A1
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- guanidine
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- 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
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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
- Gas generators are being used increasingly, for example in vehicles to save lives.
- the gas-generating mixture usually contains sodium azide.
- Natriu azid in itself is toxic and can easily mix with heavy metals such as.
- B. Implement copper and lead to form extremely dangerous and violently reacting compounds. Special measures must therefore be taken in the manufacture of the raw material, the gas mixture, its processing and quality control. For this reason, the disposal of the sodium azide, for example when replacing defective gas generators or when scrapping the vehicles, is also a particular problem. Misuse must also be prevented.
- EP 0 519 485 describes the use of tetrazole or tetrazole derivative (s) or the use of one or more compounds from the group of cyanic acid derivatives and their salts, one or more compounds from the group of triazine and triazine derivatives of urea, its salts, derivatives and derivatives and salts of these compounds, it being possible for the compounds mentioned to also be present as mixtures.
- Nitrates of ammonium, sodium, potassium, magnesium, calcium and iron and / or peroxides of zinc, calcium, strontium or magnesium can be used as the oxidizing agent. Further gas-generating components, coolants, reducing agents, catalysts and / or porosity generators can be added.
- EP 0 438 851 describes a non-toxic, non-acidic pyrotechnic composition which is suitable for use in the generation of essentially non-toxic combustion Products including a gas is suitable for filling an accident cushion.
- the composition comprises a mixture of at least one tetrazole or triazole compound which contains hydrogen in the molecule, at least one oxygen-containing oxidizing agent and at least one metal oxide selected from cobalt oxide, nickel oxide, chromium oxide, aluminum oxide or boron oxide.
- the combustion produces an essentially non-toxic primary gas mixture and unfilterable solids.
- aminotetrazole is used with oxidizing agents, which in addition to nitrites can also contain perchlorates.
- Oxohalates are understood to mean, for example, chlorates, bromates and their per compounds of the alkali metals.
- combustion-regulating catalysts u. a. mentioned: oxides, chlorides, carbonates, sulfonates of the 4th to 6th rows of the periodic table.
- the gas resulting from the reaction is passed through a Venturi nozzle to improve the yield, so that outside air can be used to inflate the airbag.
- this outside air strongly removes the hot gases. cools.
- the volume loss that occurs as a result of this for inflating the gas bag must be compensated for by the pyrotechnic mixture.
- the increased proportion of toxic swaths inside the vehicle can no longer be reduced sufficiently by thinning.
- the present invention describes non-toxic, azide-free mixtures for gas generation by combustion.
- These gas-generating mixtures can include in safety devices, for example in airbag systems for inflating airbags in vehicles and airplanes. However, they are also suitable for lifting heavy loads by inflating sacks underneath or for driving out z.
- the mixtures according to the invention contain
- a) as nitrogen-containing compound (fuel) at least one compound from the group tetrazoles, triazoles, triazines, cyanic acid, urea, their derivatives, derivatives or their salts,
- combustion moderators which are suitable for influencing the combustion and its speed by heterogeneous or homogeneous catalysis, and, if appropriate
- the mixtures according to the invention are non-toxic and, in contrast to mixtures containing azide, are easy to handle. They therefore require less security effort at the Production of the raw materials and mixtures and their shaping, storage or disposal.
- the nitrogen-containing compounds to be used according to the invention are those which, when mixed with oxidizing agents during their thermal / chemical conversion, form mainly CO2, N 2 ° 2 and H 2 ⁇ , but do not develop gases such as CO or N0 ⁇ in concentrations which are hazardous to health.
- the mixtures according to the invention preferably contain nitrogenous compounds (fuels)
- R, and R 7 or R3 may be the same or different, but either R2 or R3 is present and have the meaning: hydrogen, hydroxy, amino, carboxyl, an alkyl radical having 1 to 7 carbon atoms, an alkenyl radical having 2 to 7 carbon atoms, one Alkylamino radical with 1 to 10 carbon atoms, an aryl radical, optionally substituted with one or more substituents, which can be the same or different and are selected from the amino group, the nitro group, the alkyl radicals with 1 to 4 carbon atoms or an arylamino radical which may optionally be substituted for the aryl radical or the sodium, potassium and guanidinium salts of the tetrazole derivatives mentioned.
- R ⁇ preferably hydrogen, A ino, hydroxy, carboxyl, a methyl, ethyl, propyl or isopropyl, butyl, isobutyl or tert-butyl, n-pentyl, n-hexyl or n-heptyl radical, a methylamino, ethylamino, dimethylamino, n-heptylamino, n-octylamino or n-decylamino radical, a tetrazole radical, a phenylamino radical, a phenyl, nitrophenyl or aminophenyl radical;
- R2 or R3 is preferably hydrogen, a methyl or ethyl radical, a phenyl, nitrophenyl or aminophenyl radical.
- tetrazole derivatives 5-aminotetrazole, lithium, sodium, potassium, zinc, magnesium, strontium or calcium 5-aminotetrazolate, 5-aminotetrazole nitrate, sulfate, perchlorate and similar compounds are particularly preferred, l- (4-aminophenyl) tetrazole, l- (4-nitrophenyl) tetrazole, l-methyl-5-dimethylaminotetrazole, l-methyl-5-methylaminotetrazole, 1-methyltetrazole, l-phenyl- 5-aminotetrazole, l-phenyl-5-hydroxy-tetrazole, 1-phenyltetrazole, 2-ethyl-5-aminotetrazole, 2-methyl-5-aminotetrazole, 2-methyl-5-carboxyltetrazole, 2-methyl- 5- methylaminotetrazole, 2-methyltetrazole, 2-phenyltetrazole, 5- (p-tolyl) -
- 5-Aminotetrazole is used as a particularly preferred component.
- the preferred proportion when using this component in the mixture is 10-40% by weight.
- Its salts are used as derivatives of 5-aminotetrazole, in which the acidic hydrogen atoms on 5-aminotetrazole are replaced like salts by toxicologically harmless elements such as calcium, magnesium or zinc.
- the cation is formed from ammonium, guanidinium and its amino derivatives.
- Oxohalogen compounds of alkali or alkaline earth metals or ammonium particularly preferably potassium perchlorate or ammonium perchlorate.
- the oxidizing agents can be used individually or in mixtures. In order to reduce the nitrogen oxide content in the reaction gases as much as possible, it is advantageous to keep the nitrate content in the oxidant mixtures as low as possible, since some of the nitrates can thermally decompose.
- a preferred combination of the oxidizing agents consists of zinc peroxide, potassium perchlorate and at least one nitrate, preferably sodium nitrate or strontium nitrate in a mixing ratio of 1: 2: 10 and a total proportion of approximately 60% by weight in the gas-generating mixture.
- the chlorine-containing compounds react during the burning to form harmless sodium / potassium chloride.
- Ammonium perchlorate alone or in a mixture with another can also be used as perchlorate Oxohalogen compound are provided, but an excess must be avoided in order to rule out the formation of aggressive hydrochloric acid. If ammonium perchlorate is used, the simultaneous presence of zinc compounds is particularly advantageous since the risk of hydrochloric acid formation can thereby be avoided. An excess of sodium and potassium compounds is harmless since this reacts with the reaction gases to form harmless carbonates.
- the partial or complete replacement of the alkali nitrate with strontium nitrate leads to a significant reduction in the slag content.
- the mixing ratio of the nitrogen-containing compounds, for example the tetrazoles and triazoles, to the oxidizing agents is balanced so that an excess of oxygen is formed when the gas mixture is burned off. This excess of oxygen shifts the CO / CO 2 equilibrium towards carbon dioxide.
- Moderators who intervene in the implementation in the form of heterogeneous catalysis are metals, metal oxides and / or metal carbonates and / or metal sulfides. Boron, silicon, copper, iron, titanium, zinc or molybdenum can preferably be used as metals. Calcium carbonate can also be used. Mixtures of these moderators can also be used.
- Moderators who intervene in the implementation in the form of homogeneous catalysis are, for example, sulfur, boron, silicon or ferrocene and its derivatives. These moderators are vaporized into the gas phase by the temperatures occurring during the reaction and can intervene in the reaction itself or as secondary products. The proportion of these substances in the mixture can be up to approx. 8%.
- the mixture according to the invention for gas production can contain additives which are suitable for the proportion of To reduce harmful gases such as nitrogen oxides and / or carbon monoxide.
- the proportion of these harmful gases in the gas mixture generated is determined by
- additives are used whose chemical properties catalyze the conversion of nitrogen oxides in particular, for example nitrogen dioxide to nitrates or nitrites.
- nitrogen oxides in particular, for example nitrogen dioxide to nitrates or nitrites.
- all more or less strongly reacting substances are suitable. These include, for example, oxides, hydroxides or carbonates of non-toxic elements such as those of the alkali and alkaline earth metals, that of zinc, and mixtures of these compounds.
- oxides, hydroxides or carbonates of non-toxic elements such as those of the alkali and alkaline earth metals, that of zinc, and mixtures of these compounds.
- urea, guanidine and its derivatives compounds with NH 2 groups such as, for example, amidosulfonic acids, amido complexes and the like, and A ide for reaction with NO 2.
- a particularly preferred embodiment provides the use of peroxides in the outflow openings of the generators ren. It is particularly advantageous here that, in addition to the reduction of the nitrogen oxides by the reactions described above, additional oxygen is formed for the subsequent catalytic reaction with carbon monoxide.
- the supplements according to the invention can be introduced alone or together directly into the gas-generating set or can be provided in the outflow ducts of the generator.
- a compressed application form of the additives for example in the form of tablets, pills or granules, is expedient for use in the outflow ducts of the generator.
- the amount of the supplements used is about 10% by weight.
- the amount of the aggregates in the outflow ducts can amount to up to 75% by weight, based on the gas charge.
- a reduction in the CO content can surprisingly also be achieved in that part of the fuel from the salts, preferably from the calcium, magnesium or zinc salts of aminotetrazole, preferably from the corresponding salts of 5-aminotetrazole or from Urea derivatives exist. In these cases, the use of only two oxidizing agents is sufficient.
- Additional additives can be added to influence the reaction rate and temperature.
- Such additives can be, for example, boron or metal powder, for example titanium, aluminum, zirconium, iron, copper, molybdenum, and their stable hydrides. Their share of the surcharges is of the order of 5% by weight.
- the gas charge mixtures according to the invention are produced in a manner known per se.
- the components are, for example, mixed dry, sieved, portioned and compressed into tablets.
- the rate of combustion can be adjusted via the grain shape and size of the bulk material obtained, for example, by breaking and sieving the fragments.
- the bulk material can be produced in large quantities and, by mixing fractions with different dynamic vivacity, can be adapted to the particular requirements during combustion. Premixes with 2 or 3 components can also be used to increase the safety or improve the mixing result.
- a mixture of oxidizing agent and additives can be prepared, for example, before it comes into contact with the nitrogen-containing compounds.
- the mixture can also be kneaded by moist components and subsequent granulation z. B. by passing sieves, extrusions or the like.
- Binders such as water glass, "inorganic rubber” (phosphonitrile chloride) or even small proportions of organic binders such as acrylic resins, PTFE, guar gu can be used. Since the components used are neither toxic nor particularly reactive and can only be brought into reaction with the aid of special igniters, special safety precautions are not necessary.
- the bulk material obtained in this way can be used immediately.
- the bulk material can be coated on the surface. This can be done by means of a varnish coating, which may be provided with additives that support the burning of the bulk material. Oxidation agents such as zinc peroxide, perchlorates and metal powders such as titanium and zircon can be considered as burn-in supports.
- the Aufbring gung can by spraying the solvent-containing coating agents such. B. in a drum with evaporation of the solvent.
- Porous grain structures can be used in the grain for special applications.
- Such porous structures can be produced by customary methods, for example by adding soluble salts and then releasing them with the appropriate solvents or by adding thermally decomposable substances such as ammonium bicarbonate, acetone dicarboxylic acid, blowing agents, peroxides or azobisisobutyronitrile, which then occur in a subsequent step Process step are removed again by heating and tempering at elevated temperature. The characteristic is determined by quantity, grain size and distribution.
- Such gas sets can be used, for example, when gas sets with a strongly progressive reaction are required.
- the ready-made gas set can be ignited using the usual methods. It is important that no additional toxic vapor components are released from the igniter after the reaction.
- the gas set mixture is insensitive to its safety-related characteristics, such as: B. against friction, impact and impact or flammability against flame or cerium / iron sparks under normal pressure. In the inclusion, on the other hand, it burns violently when lit appropriately. This increases safety during manufacture and handling.
- the mixtures according to the invention can be used, for example, in gas generators for automotive safety with the electrically triggered ignition systems customary there.
- the specified components for the gas sets according to the invention are homogenized in the specified weight ratios in plastic containers in a tumble mixer for 30 minutes. The mixtures are then tableted into compacts with a diameter of approximately 6 mm. 3.5 g of the tabletted samples are reacted in a 25 ml stainless steel pressure bomb using 0.2 g boron / potassium nitrate (25:75 parts by weight) as an ignition mixture and an electrically heated iron wire. The pressure-time profile of the reaction is registered via a piezoelectric measuring device. During the exothermic reaction, combustion gases are generated, which are mainly composed of H2O, CO2, N2 and O2 and meet the toxicological requirements.
- the gas set mixtures described in the examples are examined, for example, in a measuring device consisting of a combustion chamber, gas flow deflection and filter chamber under defined mechanical construction conditions with regard to the combustion characteristics.
- the gaseous reaction products are collected and characterized in a 60 1 volume (main components: H 2 0, C0 2 - N 2 and 0 2 )
- composition (% by weight
- Example 1 describes the reaction of 5-aminotetrazole (5-ATZ) with a binary mixture of oxidizing agents.
- the vapor composition shows a proportion of 1800 ppm CO in the reaction vapor after burning in a closed pressure bomb.
- Example 2 the addition of only 1% by weight of zinc peroxide surprisingly leads to a significant reduction in the CO content to 1100 ppm with otherwise unchanged test parameters.
- the changes in the composition of the mixtures in Examples 3 to 5 lead to poorer results.
- composition (% by weight)
- Measurement results in the 60 1 test can:
- reaction time is between 40 and 60% of the maximum pressure in milliseconds
- Examples 6 to 9 show that the addition of the Zn, Ca and Mg salts of 5-aminotetrazole (Me (5-ATZ) 2 ) has a favorable effect on the vapor composition. A clear reduction in the CO content is found. The reaction rate is also influenced. Composition (% by weight)
- reaction time is between 40 and 60% of the maximum pressure in milliseconds
- Examples 10 to 13 differ in the proportion of sodium nitrate / strontium nitrate as the oxidizing agent. With an increasing proportion of strontium nitrate, the mass of the slag emerging into the jug is reduced. This means that the filterability of the slag is improved by adding strontium nitrate - after the reaction - in the filter of the generator. At the same time, the CO content of the reaction gas can be influenced favorably.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Air Bags (AREA)
- Catalysts (AREA)
- Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
- Treating Waste Gases (AREA)
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Abstract
Description
Gaserzeugende MischungenGas generating mixtures
Gasgeneratoren werden in zunehmendem Maße, beispielsweise in Fahrzeugen zur Lebensrettung eingesetzt. Üblicherweise ent¬ hält die gaserzeugende Mischung Natriumazid. Natriu azid an sich ist giftig und kann sich leicht mit Schwermetallen wie z. B. Kupfer und Blei unter Bildung extrem gefährlicher und heftig reagierender Verbindungen umsetzen. Daher sind beson- dere Maßnahmen bei der Herstellung des Rohstoffs, der Gas¬ satzmischung, bei seiner Verarbeitung und bei der Qualitäts¬ kontrolle vorzusehen. Aus diesem Grund stellt auch die Ent¬ sorgung des Natriumazids, beispielsweise beim Austausch de¬ fekter Gasgeneratoren oder bei der Verschrottung der Fahr- zeuge ein besonderes Problem dar. Auch die mißbräuchliche Verwendung muß sicher verhindert werden.Gas generators are being used increasingly, for example in vehicles to save lives. The gas-generating mixture usually contains sodium azide. Natriu azid in itself is toxic and can easily mix with heavy metals such as. B. Implement copper and lead to form extremely dangerous and violently reacting compounds. Special measures must therefore be taken in the manufacture of the raw material, the gas mixture, its processing and quality control. For this reason, the disposal of the sodium azide, for example when replacing defective gas generators or when scrapping the vehicles, is also a particular problem. Misuse must also be prevented.
Es hat nicht an Versuchen gefehlt, anstelle von Natriumazid andere Stoffe einzusetzen. Allen Lösungsvorschlägen für den Ersatz des Natriumazids ist gemeinsam, daß sie organische Kohlenstoff- und in der Regel auch organische Stickstoffver¬ bindungen enthalten. Die EP 0 519 485 beschreibt den Einsatz von Tetrazol oder Tetrazolderivat(en) oder den Einsatz je¬ weils ein oder mehrerer Verbindungen aus der Gruppe der Cyansäurederivate und deren Salzen, ein oder mehrerer Ver¬ bindungen aus der Gruppe der Triazin und Triazinderivate, den Einsatz von Harnstoff, dessen Salzen, Derivaten und Ab¬ kömmlingen und Salze dieser Verbindungen, wobei die genann¬ ten Verbindungen auch als Mischungen vorliegen können. Als Oxidationsmittel können Nitrate von Ammonium, Natrium, Ka¬ lium, Magnesium, Kalzium und Eisen und/oder Peroxide von Zink, Kalzium, Strontium oder Magnesium eingesetzt werden. Weitere gaserzeugende Komponenten, Kühlmittel, Reduktions¬ mittel, Katalysatoren und/oder Porositätserzeuger können zu- gesetzt werden.There has been no shortage of attempts to use other substances instead of sodium azide. All proposed solutions for the replacement of sodium azide have in common that they contain organic carbon and generally also organic nitrogen compounds. EP 0 519 485 describes the use of tetrazole or tetrazole derivative (s) or the use of one or more compounds from the group of cyanic acid derivatives and their salts, one or more compounds from the group of triazine and triazine derivatives of urea, its salts, derivatives and derivatives and salts of these compounds, it being possible for the compounds mentioned to also be present as mixtures. Nitrates of ammonium, sodium, potassium, magnesium, calcium and iron and / or peroxides of zinc, calcium, strontium or magnesium can be used as the oxidizing agent. Further gas-generating components, coolants, reducing agents, catalysts and / or porosity generators can be added.
Die EP 0 438 851 beschreibt eine nicht-toxische, nicht-azide pyrotechnische Zusammensetzung, die zur Verwendung bei der Erzeugung von im wesentlichen nichttoxischen Verbrennungs- Produkten einschließlich eines Gases geeignet ist, um ei Unfallkissen zu befüllen. Die Zusammensetzung umfaßt ein Mischung aus wenigstens einer Tetrazol- oder Triazolverbin dung, die im Molekül Wasserstoff enthält, wenigstens ei Sauerstoff-enthaltendes Oxidationsmittel und wenigstens ei Metalloxid, ausgewählt aus Cobaltoxid, Nickeloxid, Chrom oxid, Aluminiumoxid oder Boroxid. Bei der Verbrennung wir eine im wesentlichen nicht-toxische primäre Gasmischung un filtrierbare Feststoffe erzeugt. Eingesetzt wird beispiels weise Aminotetrazol mit Oxidationsmitteln, die neben Nitra ten auch Perchlorate enthalten können.EP 0 438 851 describes a non-toxic, non-acidic pyrotechnic composition which is suitable for use in the generation of essentially non-toxic combustion Products including a gas is suitable for filling an accident cushion. The composition comprises a mixture of at least one tetrazole or triazole compound which contains hydrogen in the molecule, at least one oxygen-containing oxidizing agent and at least one metal oxide selected from cobalt oxide, nickel oxide, chromium oxide, aluminum oxide or boron oxide. The combustion produces an essentially non-toxic primary gas mixture and unfilterable solids. For example, aminotetrazole is used with oxidizing agents, which in addition to nitrites can also contain perchlorates.
Ein ähnlicher Ansatz wird in dem Europäischen Patent E 0 372 733 offenbart: Verwendung von Tetrazolen und Triazolen in Mischungen mit Ammoniumperchlorat und Alkalinitrat als Oxidationsmittel in Verbindung mit einem Zuschlag zur Steue¬ rung der Verbrennung.A similar approach is disclosed in European Patent E 0 372 733: Use of tetrazoles and triazoles in mixtures with ammonium perchlorate and alkali nitrate as an oxidizing agent in conjunction with an addition to control the combustion.
Die PCT Anmeldung WO 94/01381 beschreibt ein aus organischen Nitroverbindungen und Oxohalogenaten bestehendes Gasentwick¬ lungsmittel für Airbags. Als Oxohalogenate werden beispiels¬ weise Chlorate, Bromate sowie deren Perverbindungen der Al¬ kalimetalle verstanden. Als verbrennungsregelnde Katalysato¬ ren werden u. a. erwähnt: Oxide, Chloride, Carbonate, Sul- fonate der 4. bis 6. Reihe des Periodensystems.PCT application WO 94/01381 describes a gas developing agent for airbags consisting of organic nitro compounds and oxohalates. Oxohalates are understood to mean, for example, chlorates, bromates and their per compounds of the alkali metals. As combustion-regulating catalysts, u. a. mentioned: oxides, chlorides, carbonates, sulfonates of the 4th to 6th rows of the periodic table.
Bei der Umsetzung der oben aufgeführten Gassätze zum Aufbla¬ sen von Airbags für die Kraftfahrzeugsicherheit können neben nichttoxischen Arbeitsgasen wie Stickstoff, Kohlendioxid und Wasserdampf auch Anteile toxischer Gase wie z. B. Kohlen- monoxid oder Stickoxide anwesend sein. Für diese Gase wurden Grenzwerte aufgestellt, wie z. B. die maximale Arbeitsplatz¬ konzentration (MAK) unter Berücksichtigung von Spitzenbela- stungen. Ihre Bildung steht in einem thermodynamischen und kinetischen Zusammenhang und wird im Falle des Kohlenmon- oxids z. B. über das Boudouard-Gleichgewicht gesteuert. Es zeigte sich darüber hinaus, daß Mischungen, die Stickstoff- und kohlenstoffhaltige Verbindungen enthalten und beim Ab¬ brand niedrige NO -Anteile entwickeln, hohe CO-Anteile ent- wickeln und umgekehrt. Diese Gleichgewichtseinstellungen sind temperatur- und druckabhängig. Es ist bekannt, daß eine ausreichend wirksame Beeinflussung der Schwadenzusammen¬ setzung im Sinne einer Bildung nichttoxischer Produkte al- leine durch physikalische Maßnahmen, beispielsweise Steue¬ rung der Reaktion durch Druck und/oder Temperatur nicht er¬ reicht werden kann.When implementing the gas sets listed above for inflating airbags for automotive safety, in addition to non-toxic working gases such as nitrogen, carbon dioxide and water vapor, proportions of toxic gases such as B. carbon monoxide or nitrogen oxides may be present. Limit values were set for these gases, e.g. B. the maximum workplace concentration (MAK) taking peak loads into account. Their formation is in a thermodynamic and kinetic relationship and in the case of carbon monoxide z. B. controlled via the Boudouard balance. It was also found that mixtures which contain nitrogen and carbon-containing compounds and which develop low NO contents when burned off contain high amounts of CO. wrap and vice versa. These equilibrium settings are temperature and pressure dependent. It is known that a sufficiently effective influencing of the swath composition in the sense of the formation of non-toxic products cannot be achieved solely by physical measures, for example control of the reaction by pressure and / or temperature.
Literaturbekannt sind Verfahren, die eine Reduzierung dieser Schwadenkomponenten zum Ziel haben. So kann beispielsweise durch Zugabe alkalischer Schlackebildner zum Gassatz das Gleichgewicht zu Lasten des Kohlenmonoxids durch die Bildung von Carbonaten verschoben werden. Stickoxide werden gleich¬ zeitig in Nitrate bzw. Nitrite überführt.Methods are known from the literature which aim to reduce these vapor components. For example, by adding alkaline slag formers to the gas set, the balance can be shifted at the expense of carbon monoxide through the formation of carbonates. Nitrogen oxides are simultaneously converted into nitrates or nitrites.
Diese Maßnahmen haben jedoch den Nachteil, daß durch den ho¬ hen Schlackeanteil die Gasausbeute wesentlich verschlechtert wird. Zudem muß die Schlacke durch Filter oder andere Rück¬ haltesysteme aufwendig von den gasförmigen Bestandteilen ab- getrennt werden, bevor die Arbeitsgase beispielsweise zum Aufblasen des Airbags verwendet werden können.However, these measures have the disadvantage that the gas yield is significantly deteriorated by the high slag content. In addition, the slag has to be separated from the gaseous constituents by filters or other retention systems before the working gases can be used, for example, to inflate the airbag.
Die Verwendung stickstofffreier Systeme führt zwar zur Bil¬ dung stickoxidfreier Schwaden, doch unter Inkaufnahme einer geringeren Gasausbeute. Dies hat seinen Grund darin, daß zur Verschiebung des Boudouard-Gleichgewichts in Richtung CO2 ein Überschuß an schlackebildendem Sauerstoffträger verwen¬ det werden muß. Es wurden daher bereits Hybridsysteme vorge¬ schlagen, bei denen die zuvor beschriebene Reaktion durch komprimierte Luft anstelle schlackebildender Oxidationsmit¬ tel bewirkt wird. Diese Konzepte leiden jedoch unter dem Nachteil des hohen Systemgewichts und der Notwendigkeit zur Kontrolle bzw. Ergänzung der komprimierten Luft.The use of nitrogen-free systems leads to the formation of nitrogen oxide-free swaths, but with a lower gas yield. The reason for this is that an excess of slag-forming oxygen carrier must be used to shift the Boudouard equilibrium towards CO2. Hybrid systems have therefore already been proposed in which the above-described reaction is brought about by compressed air instead of slag-forming oxidizing agents. However, these concepts suffer from the disadvantage of the high system weight and the need to control or supplement the compressed air.
Gemäß US Patent 3,910,595 wird das bei der Reaktion entste¬ hende Gas zur Verbesserung der Ausbeute durch eine Venturi- Düse geleitet, so daß Außenluft zum Aufblasen des Luftsackes mit herangezogen werden kann. Dabei muß jedoch berücksich¬ tigt werden, daß diese Außenluft die heißen Gase stark ab- kühlt. Insbesondere bei niedriger Außentemperatur muß der dadurch auftretende Volumenverlust zum Aufblasen des Gas¬ sackes durch die pyrotechnische Mischung ausgeglichen wer¬ den. Die dadurch erhöhten Anteile toxischer Schwaden im Fahrzeuginnern können nicht mehr ausreichend durch Verdün¬ nung reduziert werden.According to US Pat. No. 3,910,595, the gas resulting from the reaction is passed through a Venturi nozzle to improve the yield, so that outside air can be used to inflate the airbag. However, it must be taken into account that this outside air strongly removes the hot gases. cools. In particular at low outside temperatures, the volume loss that occurs as a result of this for inflating the gas bag must be compensated for by the pyrotechnic mixture. The increased proportion of toxic swaths inside the vehicle can no longer be reduced sufficiently by thinning.
Die vorliegende Erfindung beschreibt nichttoxische, azid- freie Mischungen zur Gaserzeugung durch Abbrand. Diese gaserzeugenden Mischungen können u.a. in Sicherheitseinrich¬ tungen, beispielsweise in Airbag-Systemen zum Aufblasen von Luftsäcken in Fahr- und Flugzeugen eingesetzt werden . Sie sind jedoch auch geeignet zum Anheben schwerer Lasten durch Aufblasen darunter befindlicher Säcke oder zum Austreiben von z. B. Feuerlöschpulver oder andere Maßnahmen, wo es auf schnelle Bildung von Gasen zur Erzeugung einer Arbeitslei¬ stung ankommt.The present invention describes non-toxic, azide-free mixtures for gas generation by combustion. These gas-generating mixtures can include in safety devices, for example in airbag systems for inflating airbags in vehicles and airplanes. However, they are also suitable for lifting heavy loads by inflating sacks underneath or for driving out z. B. fire extinguishing powder or other measures where it comes to rapid formation of gases to produce a Arbeitslei¬ performance.
Die erfindungsgemäßen Mischungen enthaltenThe mixtures according to the invention contain
a) als stickstoffhaltige Verbindung (Brennstoff) wenigstens eine Verbindung aus der Gruppe Tetrazole, Triazole, Triazine, Cyansäure, Harnstoff, deren Derivate, Abkömmlinge oder deren Salze,a) as nitrogen-containing compound (fuel) at least one compound from the group tetrazoles, triazoles, triazines, cyanic acid, urea, their derivatives, derivatives or their salts,
b) als Oxidationsmittel wenigstens drei Verbindungen aus der Gruppe der Peroxide, Nitrate, Chlorate oder Perchlorate,b) at least three compounds from the group of peroxides, nitrates, chlorates or perchlorates as oxidizing agents,
c) Abbrandmoderatoren die geeignet sind, durch heterogene oder homogene Katalyse den Abbrand und seine Geschwindigkeit zu beeinflussen, sowie gegebenenfallsc) combustion moderators which are suitable for influencing the combustion and its speed by heterogeneous or homogeneous catalysis, and, if appropriate
d) Zuschläge, die geeignet sind, den Anteil der toxischen Gase zu reduzieren.d) Supplements that are suitable for reducing the proportion of toxic gases.
Die erfindungsgemäßen Mischungen sind nicht toxisch und im Gegensatz zu Azid-enthaltenden Mischungen leicht zu handha¬ ben. Sie erfordern daher weniger Sicherheitsaufwand bei der Herstellung der Rohstoffe und Mischungen und bei deren Form¬ gebung, Aufbewahrung oder Entsorgung.The mixtures according to the invention are non-toxic and, in contrast to mixtures containing azide, are easy to handle. They therefore require less security effort at the Production of the raw materials and mixtures and their shaping, storage or disposal.
Die erfindungsgemäß einzusetzenden stickstoffhaltigen Ver- bindungen sind solche, die im Gemisch mit Oxidationsmitteln bei ihrer thermisch/chemischen Umsetzung hauptsächlich CO2, N2' °2 unc H2^ bilden, jedoch keine Gase wie CO oder N0χ in gesundheitsgefährdenden Konzentrationen entwickeln.The nitrogen-containing compounds to be used according to the invention are those which, when mixed with oxidizing agents during their thermal / chemical conversion, form mainly CO2, N 2 ° 2 and H 2 ^, but do not develop gases such as CO or N0 χ in concentrations which are hazardous to health.
Die erfindungsgemäßen Mischungen enthalten als stickstoff¬ haltige Verbindungen (Brennstoffe) vorzugsweiseThe mixtures according to the invention preferably contain nitrogenous compounds (fuels)
ein oder mehrere Tetrazolderivat(e) der Formelone or more tetrazole derivative (s) of the formula
worin R, und R7 oder R3 gleich oder verschieden sein können, jedoch entweder R2 oder R3 vorliegt und die Bedeutung haben: Wasserstoff, Hydroxy, Amino, Carboxyl, einen Alkylrest mit 1 bis 7 Kohlenstoffatomen, einen Alkenylrest mit 2 bis 7 Kohlenstoffatomen, einen Alkylaminorest mit 1 bis 10 Kohlen¬ stoffatomen, einen Arylrest, gegebenenfalls substituiert mit einem oder mehreren Substituenten, die gleich oder verschie¬ den sein können und ausgewählt sind aus der Aminogruppe, der Nitrogruppe, den Alkylresten mit 1 bis 4 Kohlenstoffatomen oder einem Arylaminorest, bei dem der Arylrest gegebenen¬ falls substituiert sein kann oder die Natrium-, Kalium- und Guanidiniumsalze der genannten Tetrazolderivate.wherein R, and R 7 or R3 may be the same or different, but either R2 or R3 is present and have the meaning: hydrogen, hydroxy, amino, carboxyl, an alkyl radical having 1 to 7 carbon atoms, an alkenyl radical having 2 to 7 carbon atoms, one Alkylamino radical with 1 to 10 carbon atoms, an aryl radical, optionally substituted with one or more substituents, which can be the same or different and are selected from the amino group, the nitro group, the alkyl radicals with 1 to 4 carbon atoms or an arylamino radical which may optionally be substituted for the aryl radical or the sodium, potassium and guanidinium salts of the tetrazole derivatives mentioned.
Bei diesen Verbindungen bedeutet:For these connections:
R^ vorzugsweise Wasserstoff, A ino, Hydroxy, Carboxyl, einen Methyl-, Ethyl-, Propyl- oder Isopropyl-, Butyl-, Isobutyl- oder tert.-Butyl, n-Pentyl-, n-Hexyl- oder n-Heptylrest, einen Methylamino-, Ethylamino-, Dimethylamino, n-Heptyl- amino-, n-Octylamino- oder n-Decylaminorest, einen Tetra- zolrest, einen Phenylaminorest, einen Phenyl-, Nitrophenyl- oder Aminophenylrest;R ^ preferably hydrogen, A ino, hydroxy, carboxyl, a methyl, ethyl, propyl or isopropyl, butyl, isobutyl or tert-butyl, n-pentyl, n-hexyl or n-heptyl radical, a methylamino, ethylamino, dimethylamino, n-heptylamino, n-octylamino or n-decylamino radical, a tetrazole radical, a phenylamino radical, a phenyl, nitrophenyl or aminophenyl radical;
R2 oder R3 vorzugsweise Wasserstoff, einen Methyl- oder Ethylrest, einen Phenyl-, Nitrophenyl- oder Aminophenylrest.R2 or R3 is preferably hydrogen, a methyl or ethyl radical, a phenyl, nitrophenyl or aminophenyl radical.
Besonders bevorzugt sind die Tetrazolderivate 5-Aminotetra- zol, Lithium-, Natrium-, Kalium-, Zink-, Magnesium-, Stron¬ tium- oder Kalzium-5-aminotetrazolat, 5-Aminotetrazolnitrat, -sulfat, -perchlorat und ähnliche Verbindungen, l-(4-Amino- phenyl )-tetrazol, l-(4-Nitrophenyl)-tetrazol, l-Methyl-5-di- methylaminotetrazol, l-Methyl-5-methylaminotetrazol, 1-Me- thyltetrazol, l-Phenyl-5-aminotetrazol, l-Phenyl-5-hydroxy- tetrazol, 1-Phenyltetrazol, 2-Ethyl-5-aminotetrazol, 2-Me- thyl-5-aminotetrazol, 2-Methyl-5-carboxyltetrazol, 2-Methyl- 5-methylaminotetrazol, 2-Methyltetrazol, 2-Phenyltetrazol, 5-(p-Tolyl )-tetrazol, 5-Diallylaminotetrazol, 5-Dimethylami- notetrazol, 5-Ethylaminotetrazol, 5-Hydroxytetrazol, 5-Me- thyltetrazol, 5-Methylaminotetrazol, 5-n-Decylaminotetrazol, 5-n-Heptylaminotetrazol, 5-n-Octylaminotetrazol, 5-Phenylte- trazol, 5-Phenylaminotetrazol oder Bis-(aminoguanidin)-azo- tetrazol und Diguanidinium-5,5 '-azotetrazolat, sowie 5,5'- Bitetrazol und dessen Salze, wie die 5,5'-Bi-IH-Tetrazolam- moniumverbindungen.The tetrazole derivatives 5-aminotetrazole, lithium, sodium, potassium, zinc, magnesium, strontium or calcium 5-aminotetrazolate, 5-aminotetrazole nitrate, sulfate, perchlorate and similar compounds are particularly preferred, l- (4-aminophenyl) tetrazole, l- (4-nitrophenyl) tetrazole, l-methyl-5-dimethylaminotetrazole, l-methyl-5-methylaminotetrazole, 1-methyltetrazole, l-phenyl- 5-aminotetrazole, l-phenyl-5-hydroxy-tetrazole, 1-phenyltetrazole, 2-ethyl-5-aminotetrazole, 2-methyl-5-aminotetrazole, 2-methyl-5-carboxyltetrazole, 2-methyl- 5- methylaminotetrazole, 2-methyltetrazole, 2-phenyltetrazole, 5- (p-tolyl) -tetrazole, 5-diallylaminotetrazole, 5-dimethylaminotetrazole, 5-ethylaminotetrazole, 5-hydroxytetrazole, 5-methyltetrazole, 5-methylaminotetrazole, 5- n-decylaminotetrazole, 5-n-heptylaminotetrazole, 5-n-octylaminotetrazole, 5-phenyltetrazole, 5-phenylaminotetrazole or bis- (aminoguanidine) -azotetrazole and diguanidinium-5,5'-azotetrazolate, as well as 5.5 ' - Bitetrazole and its salts, such as d The 5,5'-Bi-IH tetrazole ammonium compounds.
Als Triazinderivate werden 1, 3,5-Triazin, als Triazolderi- vate 1 , 2, 4-Triazol-5-on, 3-Nitro-l, 2,4-triazol-5-on, als Cyansäurederivate Natriumcyanat, Cyanursäure, Cyanursäure- ester, Cyanursäureamid (Melamin), 1-Cyanguanidin, Natriumdi- cyanamid, Dinatriumcyanamid, Dicyandiamidinnitrat, Dicyan- diamidinsulfat, und als Harnstoffderivate Biuret, Guanidin, Nitroguanidin, Guanidinnitrat, Aminoguanidin, Aminoguanidin- nitrat, Thioharnstoff , Tria inoguanidinnitrat, A inogua- nidinhydrogencarbonat, Azodicarbonsäurediamid, Tetrazen, Se- micarbazidnitrat, sowie Urethane, Ureide wie Barbitursäure und ihre Derivate enthalten sind. Als besonders bevorzugte Komponente wird 5-Aminotetrazol eingesetzt. Der bevorzugte Anteil bei Einsatz dieser Kompo¬ nente in der Mischung liegt bei 10-40 Gew%. Als Derivate von 5-Aminotetrazol werden seine Salze eingesetzt, bei denen die aciden Wasserstoffatome am 5-Aminotetrazol salzartig ersetzt sind durch toxikologisch unbedenkliche Elemente wie Kalzium, Magnesium oder Zink. Es sind jedoch auch Verbindungen ein¬ setzbar, bei denen das Kation aus Ammonium, Guanidinium und seinen Amino-Derivaten gebildet wird.1, 3,5-triazine as triazine derivatives, 1, 2, 4-triazol-5-one, 3-nitro-l, 2,4-triazol-5-one as triazole derivatives, sodium cyanate, cyanuric acid, cyanuric acid as cyanic acid derivatives - Ester, cyanuric acid amide (melamine), 1-cyananguanidine, sodium di-cyanamide, disodium cyanamide, dicyandiamidine nitrate, dicyanodiamine sulfate, and as urea derivatives biuret, guanidine, nitroguanidine, guanidine nitrate, aminoguanidine, aminoguanidine nitrate, triaitaminodinohydrogen, thiauridinoguanide , Azodicarboxylic acid diamide, tetrazene, semicarbazide nitrate, and urethanes, ureides such as barbituric acid and their derivatives are contained. 5-Aminotetrazole is used as a particularly preferred component. The preferred proportion when using this component in the mixture is 10-40% by weight. Its salts are used as derivatives of 5-aminotetrazole, in which the acidic hydrogen atoms on 5-aminotetrazole are replaced like salts by toxicologically harmless elements such as calcium, magnesium or zinc. However, it is also possible to use compounds in which the cation is formed from ammonium, guanidinium and its amino derivatives.
Als Oxidationsmittel werden erfindungsgemäß eingesetzt :The following are used as oxidizing agents:
Peroxide der Alkali- und Erdalkalimetalle, Zink¬ peroxid, sowie die Peroxodisulfate der genannten Elemente und des Ammoniums;Peroxides of alkali and alkaline earth metals, zinc peroxide, and the peroxodisulfates of the elements mentioned and of ammonium;
Ammoniumnitrat, Nitrate der Alkali- und Erdalkali¬ metalle, insbesondere Lithium-, Natrium- oder Kaliu nitrat, sowie Strontiumnitrat;Ammonium nitrate, nitrates of the alkali and alkaline earth metals, in particular lithium, sodium or potassium nitrate, and strontium nitrate;
Oxohalogenverbindungen der Alkali- oder Erdal¬ kalimetalle oder des Ammoniums, besonders bevor¬ zugt Kaliumperchlorat oder Ammoniumperchlorat.Oxohalogen compounds of alkali or alkaline earth metals or ammonium, particularly preferably potassium perchlorate or ammonium perchlorate.
Die Oxidationsmittel können einzeln oder in Mischungen ein¬ gesetzt werden. Um die Stickoxidanteile in den Reaktionsga¬ sen möglichst zu reduzieren, ist es vorteilhaft, in den Oxi- dationsmittelmischungen den Nitratanteil möglichst gering zu halten, da sich ein Teil der Nitrate thermisch zersetzen kann.The oxidizing agents can be used individually or in mixtures. In order to reduce the nitrogen oxide content in the reaction gases as much as possible, it is advantageous to keep the nitrate content in the oxidant mixtures as low as possible, since some of the nitrates can thermally decompose.
Eine bevorzugte Kombination der Oxidationsmittel besteht aus Zinkperoxid, Kaliumperchlorat und mindestens einem Nitrat, vorzugsweise Natriumnitrat oder Strontiumnitrat im Mi- schungsverhältnis 1:2:10 und einem Gesamtanteil von ca. 60 Gew.-% in der gaserzeugenden Mischung. Dabei reagieren die chlorhaltigen Verbindungen während des Abbrandes zu unschäd¬ lichem Natrium-/Kaliumchlorid. Als Perchlorat kann auch Am¬ moniumperchlorat allein oder in Mischung mit einer anderen Oxohalogenverbindung vorgesehen werden, doch muß ein Über¬ schuß vermieden werden, um die Bildung von aggressiver Salz¬ säure auszuschließen. Wird Ammoniumperchlorat verwendet, ist die gleichzeitige Anwesenheit von Zinkverbindungen besonders vorteilhaft, da damit die Gefahr der Salzsäurebildung ver¬ mieden werden kann. Ein Überschuß an Natrium- und Kaliumver¬ bindungen ist unbedenklich, da dieser mit den Reaktionsgasen zu unschädlichen Karbonaten reagiert. Der teilweise oder vollständige Ersatz des Alkalinitrats durch Strontiumnitrat führt zu einer deutlichen Reduktion des Schlackenanteils.A preferred combination of the oxidizing agents consists of zinc peroxide, potassium perchlorate and at least one nitrate, preferably sodium nitrate or strontium nitrate in a mixing ratio of 1: 2: 10 and a total proportion of approximately 60% by weight in the gas-generating mixture. The chlorine-containing compounds react during the burning to form harmless sodium / potassium chloride. Ammonium perchlorate alone or in a mixture with another can also be used as perchlorate Oxohalogen compound are provided, but an excess must be avoided in order to rule out the formation of aggressive hydrochloric acid. If ammonium perchlorate is used, the simultaneous presence of zinc compounds is particularly advantageous since the risk of hydrochloric acid formation can thereby be avoided. An excess of sodium and potassium compounds is harmless since this reacts with the reaction gases to form harmless carbonates. The partial or complete replacement of the alkali nitrate with strontium nitrate leads to a significant reduction in the slag content.
Das Mischungsverhältnis der stickstoffhaltigen Verbindungen, beispielsweise der Tetrazole und Triazole, zu den Oxidati¬ onsmitteln ist so bilanziert, daß beim Abbrand der Gassatz- mischung Sauerstoff im Überschuß gebildet wird. Dieser Sau¬ erstoffüberschuß verschiebt das CO/Cθ2~Gleichgewicht in Richtung Kohlendioxid.The mixing ratio of the nitrogen-containing compounds, for example the tetrazoles and triazoles, to the oxidizing agents is balanced so that an excess of oxygen is formed when the gas mixture is burned off. This excess of oxygen shifts the CO / CO 2 equilibrium towards carbon dioxide.
Als Abbrandmoderatoren werden Stoffe oder ihre Gemische ein- gesetzt, die geeignet sind, durch heterogene oder homogene Katalyse den Abbrand und seine Geschwindigkeit zu beeinflus¬ sen. Moderatoren, die in Form einer heterogenen Katalyse in die Umsetzung eingreifen, sind Metalle, Metalloxide und/oder Metallkarbonate und/oder Metallsulfide. Als Metalle können vorzugsweise Bor, Silicium, Kupfer, Eisen, Titan, Zink oder Molybdän eingesetzt werden. Auch Kalziumkarbonat kann einge¬ setzt werden. Mischungen dieser Moderatoren können ebenfalls verwendet werden.Substances or their mixtures are used as combustion moderators which are suitable for influencing the combustion and its speed by heterogeneous or homogeneous catalysis. Moderators who intervene in the implementation in the form of heterogeneous catalysis are metals, metal oxides and / or metal carbonates and / or metal sulfides. Boron, silicon, copper, iron, titanium, zinc or molybdenum can preferably be used as metals. Calcium carbonate can also be used. Mixtures of these moderators can also be used.
Moderatoren, die in Form einer homogenen Katalyse in die Um¬ setzung eingreifen, sind beispielsweise Schwefel, Bor, Sili¬ cium oder Ferrocen und seine Derivate. Diese Moderatoren werden durch die bei der Reaktion auftretenden Temperaturen in die Gasphase verdampft und können so selbst oder als Fol- geprodukte in die Reaktion eingreifen. Der Anteil dieser Stoffe an der Mischung kann bis ca. 8% betragen.Moderators who intervene in the implementation in the form of homogeneous catalysis are, for example, sulfur, boron, silicon or ferrocene and its derivatives. These moderators are vaporized into the gas phase by the temperatures occurring during the reaction and can intervene in the reaction itself or as secondary products. The proportion of these substances in the mixture can be up to approx. 8%.
Weiterhin kann die erfindungsgemäße Mischung zur Gaserzeu¬ gung Zuschläge enthalten, die geeignet sind, den Anteil der Schadgase wie Stickoxide und/oder Kohlenmonoxid zu reduzie¬ ren. Der Anteil dieser Schadgase im erzeugten Gasgemisch wird bestimmt durchFurthermore, the mixture according to the invention for gas production can contain additives which are suitable for the proportion of To reduce harmful gases such as nitrogen oxides and / or carbon monoxide. The proportion of these harmful gases in the gas mixture generated is determined by
- die stöchiometrische Zusammensetzung der Mischung, die Temperatur und den Druck der Reaktion, Additive zur Beeinflussung der Reaktion bzw. der Nach reaktion und durch die- The stoichiometric composition of the mixture, the temperature and the pressure of the reaction, additives to influence the reaction or the after reaction and by
Generatorkonstruktion, in dem die Umsetzung stattfin- det.Generator construction in which the implementation takes place.
Während es relativ leicht gelingt, in einem geschlossenen System, wie z.B. einer Druckbombe, die den thermodynamisehen Berechnungen angenäherte Zusammensetzung des Gasgemisches zu erhalten, gelingt dies nicht mehr unter den realen Abström¬ bedingungen im Generator selbst, da sich während der wenigen Millisekunden dauernden Umsetzung das Gleichgewicht nicht einstellen kann. Erfindungsgemäß werden daher geeignete Stoffe, die einen katalytischen Effekt bewirken können, in die Mischung oder in die Zone der abströmenden Gase einge¬ bracht. Hierzu können die bereits zuvor beschriebenen Ab- brandmoderatoren und Oxide der Edelmetalle verwendet werden. Zusätzliche Möglichkeiten bestehen in der Verwendung von Edelmetallen wie Palladium, Ruthenium, Rhenium, Platin oder Rhodium, die den SauerstoffÜberschuß der Reaktionsgase in einer nachgeschalteten Reaktion zur Umsetzung des Kohlen- monoxids nutzen. Eine bevorzugte Anwendungsform sieht vor, die Zuschlagstoffe auf Keramik aufzutragen oder sie auf Me¬ tallnetzen als Stütze zu galvanisieren. Nach dieser Methode kann insbesondere der Kohlenmonoxidanteil im Gasgemisch ver¬ ringert werden.While it is relatively easy to do it in a closed system, e.g. A pressure bomb, which maintains the composition of the gas mixture approximating the thermodynamic calculations, no longer succeeds under the real outflow conditions in the generator itself, since the equilibrium cannot be established during the few milliseconds of implementation. According to the invention, therefore, suitable substances which can have a catalytic effect are introduced into the mixture or into the zone of the outflowing gases. The fire moderators and oxides of the noble metals described above can be used for this. Additional possibilities exist in the use of noble metals such as palladium, ruthenium, rhenium, platinum or rhodium, which use the oxygen excess of the reaction gases in a subsequent reaction to convert the carbon monoxide. A preferred form of application provides for the additives to be applied to ceramic or to be galvanized as a support on metal networks. In particular, the carbon monoxide content in the gas mixture can be reduced by this method.
Zur Reduzierung des NOχ-Anteils werden Zuschlagstoffe ver¬ wendet, deren chemische Eigenschaften die Umsetzung von ins- besondere Stickoxiden, beispielsweise Stickstoffdioxid zu Nitraten oder Nitriten katalysiert. Geeignet sind im Prinzip alle mehr oder weniger stark basisch reagierenden Stoffe. Hierzu zählen beispielsweise Oxide, Hydroxide oder Carbonate nichttoxischer Elemente wie beispielsweise die der Alkali- und Erdalkalimetalle, der des Zinks, sowie Mischungen dieser Verbindungen. Beim Einsatz dieser Verbindungen bilden sich hauptsächlich Nitrate oder Nitrite der Elemente. Ferner eig¬ nen sich Harnstoff, Guanidin und seine Derivate, Verbindun- gen mit NH2~Gruppen wie beispielsweise Amidosulfonsäuren, Amidokomplexe und ähnliche, sowie A ide zur Umsetzung mit NO2 • Eine besonders bevorzugte Ausführungsform sieht den Einsatz von Peroxiden in den Ausströmöffnungen der Generato¬ ren vor. Hierbei ist von besonderem Vorteil, daß sich neben der Reduzierung der Stickoxide durch die zuvor beschriebenen Reaktionen zusätzlich Sauerstoff für die nachgeschaltete ka- talytische Umsetzung mit Kohlenmonoxid bildet.To reduce the NO χ content, additives are used whose chemical properties catalyze the conversion of nitrogen oxides in particular, for example nitrogen dioxide to nitrates or nitrites. In principle, all more or less strongly reacting substances are suitable. These include, for example, oxides, hydroxides or carbonates of non-toxic elements such as those of the alkali and alkaline earth metals, that of zinc, and mixtures of these compounds. When using these compounds, mainly nitrates or nitrites of the elements are formed. Also suitable are urea, guanidine and its derivatives, compounds with NH 2 groups such as, for example, amidosulfonic acids, amido complexes and the like, and A ide for reaction with NO 2. A particularly preferred embodiment provides the use of peroxides in the outflow openings of the generators ren. It is particularly advantageous here that, in addition to the reduction of the nitrogen oxides by the reactions described above, additional oxygen is formed for the subsequent catalytic reaction with carbon monoxide.
Die erfindungsgemäßen Zuschläge können allein oder gemeinsam unmittelbar in den gaserzeugenden Satz eingebracht werden oder in den Abströmkanälen des Generators vorgesehen werden. Für den Einsatz in den Abströmkanälen des Generators ist eine verdichtete Applikationsform der Zuschläge zweckmäßig, etwa in der Form von Tabletten, Pillen oder Granulat. Die Menge der eingesetzten Zuschläge beträgt im Satz etwa 10 Gew.-%. In den Abströmkanälen kann die Menge der Zuschläge bis 75 Gew.-%, bezogen auf den Gassatz, ausmachen.The supplements according to the invention can be introduced alone or together directly into the gas-generating set or can be provided in the outflow ducts of the generator. A compressed application form of the additives, for example in the form of tablets, pills or granules, is expedient for use in the outflow ducts of the generator. The amount of the supplements used is about 10% by weight. The amount of the aggregates in the outflow ducts can amount to up to 75% by weight, based on the gas charge.
Eine Reduktion des CO-Anteils läßt sich überraschenderweise auch dadurch erreichen, daß ein Teil des Brennstoffs aus den Salzen, vorzugsweise aus den Kalzium-, Magnesium- oder Zink¬ salzen des Aminotetrazols, vorzugsweise aus den entsprechen¬ den Salzen des 5-Aminotetrazols oder aus Harnstoffderivaten besteht. In diesen Fällen ist der Einsatz von nur zwei Oxi- dationsmitteln ausreichend.A reduction in the CO content can surprisingly also be achieved in that part of the fuel from the salts, preferably from the calcium, magnesium or zinc salts of aminotetrazole, preferably from the corresponding salts of 5-aminotetrazole or from Urea derivatives exist. In these cases, the use of only two oxidizing agents is sufficient.
Zur Beeinflussung der Reaktionsgeschwindigkeit und -tempera- tur können weitere Additive zugegeben werden. Solche Addi¬ tive können beispielsweise Bor oder Metallpulver, beispiels- weise Titan, Aluminium, Zirkon, Eisen, Kupfer, Molybdän so¬ wie ihre stabilen Hydride sein. Ihr Anteil an den Zuschlägen liegt in der Größenordnung von 5 Gew.-%. Die Herstellung der erfindungsgemäßen Gassatzmischungen er¬ folgt in an sich bekannter Weise. Die Komponenten werden beispielsweise trocken gemischt, gesiebt, portioniert und zu Tabletten verpreßt. Die Anpassung der Abbrandgeschwindigkeit läßt sich über die Kornform und -große des beispielsweise durch Brechen und Aussieben der Fragmente erhaltenen Schütt¬ gutes erreichen. Das Schüttgut kann in großer Menge herge¬ stellt und durch Mischen von Fraktionen mit unterschiedli¬ cher dynamischer Lebhaftigkeit den jeweiligen Erfordernissen beim Abbrand angepaßt werden. Dabei können auch Vormischun¬ gen mit 2 oder 3 Komponenten zur Erhöhung der Sicherheit oder Verbesserung des Mischergebnisses eingesetzt werden. Eine Mischung aus Oxidationsmittel und Zuschlägen kann bei¬ spielsweise hergestellt werden, bevor sie mit den stick- Stoffhaltigen Verbindungen in Berührung kommt.Additional additives can be added to influence the reaction rate and temperature. Such additives can be, for example, boron or metal powder, for example titanium, aluminum, zirconium, iron, copper, molybdenum, and their stable hydrides. Their share of the surcharges is of the order of 5% by weight. The gas charge mixtures according to the invention are produced in a manner known per se. The components are, for example, mixed dry, sieved, portioned and compressed into tablets. The rate of combustion can be adjusted via the grain shape and size of the bulk material obtained, for example, by breaking and sieving the fragments. The bulk material can be produced in large quantities and, by mixing fractions with different dynamic vivacity, can be adapted to the particular requirements during combustion. Premixes with 2 or 3 components can also be used to increase the safety or improve the mixing result. A mixture of oxidizing agent and additives can be prepared, for example, before it comes into contact with the nitrogen-containing compounds.
Die Mischung kann jedoch auch durch Kneten wasserfeuchter Komponenten und anschließender Granulierung z. B. durch Pas¬ sieren von Sieben, Strangpressen oder ähnlichem hergestellt werden. Dabei können Bindemittel, wie beispielsweise Wasser¬ glas, "anorganischem Kautschuk" (Phosphornitrilchlorid) oder auch geringe Anteile organischer Binder wie Acrylharze, PTFE, Guar Gu eingesetzt werden. Da die verwendeten Kompo¬ nenten weder toxisch noch besonders reaktiv sind und sich nur mit Hilfe von speziellen Anzündern im Einschluß zur Re¬ aktion bringen lassen, sind besondere Sicherheitsvorkehrun¬ gen nicht nötig.However, the mixture can also be kneaded by moist components and subsequent granulation z. B. by passing sieves, extrusions or the like. Binders such as water glass, "inorganic rubber" (phosphonitrile chloride) or even small proportions of organic binders such as acrylic resins, PTFE, guar gu can be used. Since the components used are neither toxic nor particularly reactive and can only be brought into reaction with the aid of special igniters, special safety precautions are not necessary.
Das so erhaltene Schüttgut kann unmittelbar eingesetzt wer- den. Zur Vermeidung von Abrieb des Schüttgutes beim Umgang mit den Generatoren, der zur Veränderung der Abbrandcharak- teristik führen und ein Sicherheitsrisiko durch seinen hef¬ tigen Abbrand darstellen würde, kann das Schüttgut ober¬ flächlich beschichtet werden. Dies kann durch einen Lack- Überzug, der gegebenfalls zur Unterstützung des Anbrandes des Schüttgutes mit anbrandunterstützenden Zuschlägen verse¬ hen sein kann, geschehen. Als anbrandunterstützende Zu¬ schläge kommen Oxidationsmittel wie Zinkperoxid, Perchlorate und Metallpulver wie Titan, Zirkon in Betracht. Die Aufbrin- gung kann durch Aufsprühen der lösungsmittelhaltigen Be- schichtungsmittel z. B. in einer Trommel unter Abdampfen des Lösungsmittels erfolgen.The bulk material obtained in this way can be used immediately. In order to avoid abrasion of the bulk material when handling the generators, which would lead to a change in the erosion characteristics and which would represent a safety risk due to its erosion, the bulk material can be coated on the surface. This can be done by means of a varnish coating, which may be provided with additives that support the burning of the bulk material. Oxidation agents such as zinc peroxide, perchlorates and metal powders such as titanium and zircon can be considered as burn-in supports. The Aufbring gung can by spraying the solvent-containing coating agents such. B. in a drum with evaporation of the solvent.
Für spezielle Einsatzgebiete können poröse Kornstrukturen im Korn eingesetzt werden. Die Erzeugung solcher poröser Struk¬ turen kann nach üblichen Methoden, beispielsweise durch Zugabe löslicher Salze und deren anschließender Auslösung mit den entsprechenden Lösungsmitteln oder durch Zugabe thermisch zersetzbarer Stoffe wie beispielsweise Ammoniumbi¬ karbonat, Acetondicarbonsäure, Blähmittel, Peroxide oder Azobisisobutyronitril, die dann in einem nachfolgenden Pro¬ zeßschritt durch Aufheizen und Tempern bei erhöhter Tempera¬ tur wieder entfernt werden, erfolgen. Die Charakteristik wird bestimmt durch Menge, Korngröße und Verteilung. Solche Gassätze können beispielsweise dann eingesetzt werden, wenn stark progressiv reagierende Gassätze erforderlich sind.Porous grain structures can be used in the grain for special applications. Such porous structures can be produced by customary methods, for example by adding soluble salts and then releasing them with the appropriate solvents or by adding thermally decomposable substances such as ammonium bicarbonate, acetone dicarboxylic acid, blowing agents, peroxides or azobisisobutyronitrile, which then occur in a subsequent step Process step are removed again by heating and tempering at elevated temperature. The characteristic is determined by quantity, grain size and distribution. Such gas sets can be used, for example, when gas sets with a strongly progressive reaction are required.
Die Anzündung des konfektionierten Gassatzes kann mit den üblichen Verfahren erfolgen. Dabei ist wichtig, daß keine zusätzlichen toxischen Schwadenkomponenten aus dem Anzünder nach der Reaktion freigesetzt werden.The ready-made gas set can be ignited using the usual methods. It is important that no additional toxic vapor components are released from the igniter after the reaction.
Die Gassatzmischung ist unempfindlich in Bezug auf ihre si- cherheitstechnischen Kenndaten wie z. B. gegen Reib-, Schlag- und Stoßeinwirkung bzw. Entzündbarkeit gegenüber Flamme oder Cer-/Eisenfunken unter Normaldruck. Im Einschluß dagegen brennt sie heftig bei entsprechender Anzündung. Dies erhöht die Sicherheit bei Herstellung und Umgang.The gas set mixture is insensitive to its safety-related characteristics, such as: B. against friction, impact and impact or flammability against flame or cerium / iron sparks under normal pressure. In the inclusion, on the other hand, it burns violently when lit appropriately. This increases safety during manufacture and handling.
Die erfindungsgemäßen Mischungen können beispielsweise in Gasgeneratoren für die Kraftfahrzeugsicherheit mit den dort üblichen elektrisch ausgelösten Anzündsystemen eingesetzt werden.The mixtures according to the invention can be used, for example, in gas generators for automotive safety with the electrically triggered ignition systems customary there.
Im Gegensatz zu Generatoren auf Azidsatzbasis kann auf eine aufwendige Filterung der Schlacke verzichtet werden, da sie keine toxischen Bestandteile enthält. Sie besteht zur Haupt¬ sache aus Karbonaten und Chloriden von Kalium und Natrium neben sehr wenig Nitraten/Nitriten und Zinkoxid. Die . Aus¬ bringung solcher nichttoxischen Bestandteile wird daher im allgemeinen nur begrenzt durch die bei Emission von Staub festgesetzten Grenzwerte.In contrast to generators based on azide, there is no need to filter the slag because it contains no toxic components. It mainly consists of carbonates and chlorides of potassium and sodium in addition to very little nitrates / nitrites and zinc oxide. The . The application of such non-toxic components is therefore generally limited only by the limit values set for the emission of dust.
Die nachfolgenden Beispiele sollen die Erfindung näher er¬ läutern, ohne sie jedoch einzuschränken.The following examples are intended to explain the invention in greater detail, but without restricting it.
Die spezifizierten Komponenten für die erfindungsgemäßen Gassätze werden in den angegebenen Gewichtsverhältnissen in Plastikbehältern im Taumelmischer 30 Minuten homogenisiert. Anschließend erfolgt die Tablettierung der Mischungen zu Preßlingen mit einem Durchmesser von etwa 6 mm. 3,5 g der tablettierten Proben werden mittels 0,2 g Bor/Kaliumnitrat (25:75 Gew.-Anteile) als Anzündmischung und eines elektrisch aufheizbaren Eisendrahtes in einer 25 ml Edelstahldruckbombe zur Umsetzung gebracht. Registriert wird der Druck-Zeitver¬ lauf der Reaktion über eine piezoelektrische Meßeinrichtung. Bei der exothermen Umsetzung entstehen Abbrandgase, die sich hauptsächlich aus H2O, CO2, N2 und O2 zusammensetzen und den gestellten toxikologischen Anforderungen entsprechen.The specified components for the gas sets according to the invention are homogenized in the specified weight ratios in plastic containers in a tumble mixer for 30 minutes. The mixtures are then tableted into compacts with a diameter of approximately 6 mm. 3.5 g of the tabletted samples are reacted in a 25 ml stainless steel pressure bomb using 0.2 g boron / potassium nitrate (25:75 parts by weight) as an ignition mixture and an electrically heated iron wire. The pressure-time profile of the reaction is registered via a piezoelectric measuring device. During the exothermic reaction, combustion gases are generated, which are mainly composed of H2O, CO2, N2 and O2 and meet the toxicological requirements.
Die in den Beispielen beschriebenen Gassatzmischungen werden beispielsweise in einer Meßeinrichtung, bestehend aus Brenn¬ raum, Gasstromumlenkung und Filterraum unter definierten me¬ chanischen Aufbaubedingungen bezüglich der Abbrandcharakte- riεtik untersucht. Die gasförmigen Reaktionsprodukte werden in einem 60 1 Volumen aufgefangen und charakterisiert (Hauptbestandteile: H20, C02- N2 und 02 )The gas set mixtures described in the examples are examined, for example, in a measuring device consisting of a combustion chamber, gas flow deflection and filter chamber under defined mechanical construction conditions with regard to the combustion characteristics. The gaseous reaction products are collected and characterized in a 60 1 volume (main components: H 2 0, C0 2 - N 2 and 0 2 )
Zusammensetzung (Gew.-%Composition (% by weight
Beispiel Nr. : 1 2 3 4 5Example No.: 1 2 3 4 5
5-Aminotetrazol 33,1 33,1 34,0 33,1 34,25-aminotetrazole 33.1 33.1 34.0 33.1 34.2
Natriumnitrat 52,3 52,3 61,5 52,3 64,8Sodium nitrate 52.3 52.3 61.5 52.3 64.8
Kaliumperchlorat 10,1 10,1 10,1Potassium perchlorate 10.1 10.1 10.1
Zinkoxid 4,0 3,0 1,0Zinc oxide 4.0 3.0 1.0
Zinkperoxid 1,0 3,0 4,0Zinc peroxide 1.0 3.0 4.0
Graphit 0,5 0,5 0,5 0,5 1,0 Beispiel Explosionswärme Reib- SchlagempfindlichkeitGraphite 0.5 0.5 0.5 0.5 1.0 Example of explosion heat, friction, impact sensitivity
(kJ/g) (N) (J)(kJ / g) (N) (J)
1 3,61 > 360 101 3.61> 360 10
2 3,69 > 360 102 3.69> 360 10
3 3,70 > 360 103 3.70> 360 10
4 3,82 > 360 7,54 3.82> 360 7.5
5 3,82 > 360 105 3.82> 360 10
Meßergebnisse in der ballistischen Druckbombe:Measurement results in the ballistic pressure bomb:
Beispiel Druckmaximum Zeitdifferenz1 ' Kaltgas2) CO 40-60% p(max)Example pressure maximum time difference 1 'cold gas 2 ) CO 40-60% p (max)
(bar) (ms) (i/g) (ppm)(bar) (ms) (i / g) (ppm)
1 715 6,7 0,41 18001,715 6.7 0.41 1800
2 707 5,9 0,38 11002,707 5.9 0.38 1100
3 729 6,1 0,41 20003,729 6.1 0.41 2000
4 660 6,5 0,40 18004,660 6.5 0.40 1800
5 730 6,7 0,41 33005 730 6.7 0.41 3300
' angegeben ist die Reaktionsdauer zwischen 40 und 60% des maximalen Druckes in Millisekunden'The reaction time between 40 and 60% of the maximum pressure in milliseconds is specified
2 >. gemessen nach Abkühlung auf Raumtemperatur2>. measured after cooling to room temperature
Beispiel 1 beschreibt die Umsetzung von 5-Aminotetrazol (5- ATZ) mit einem binären Gemisch von Oxidationsmitteln. Die Schwadenzusammensetzung zeigt einen Anteil von 1800 ppm CO in den Reaktionsschwaden nach Abbrand in einer geschlossenen Druckbombe. In Beispiel 2 führt die Zugabe von nur 1 Gew.-% Zinkperoxid überraschenderweise zur deutlichen Reduktion des CO-Anteils auf 1100 ppm bei sonst gleichbleibenden Ver¬ suchsparametern. Die Veränderungen in der Zusammensetzung der Mischungen in den Beispielen 3 bis 5 führen zu schlech¬ teren Ergebnissen.Example 1 describes the reaction of 5-aminotetrazole (5-ATZ) with a binary mixture of oxidizing agents. The vapor composition shows a proportion of 1800 ppm CO in the reaction vapor after burning in a closed pressure bomb. In Example 2, the addition of only 1% by weight of zinc peroxide surprisingly leads to a significant reduction in the CO content to 1100 ppm with otherwise unchanged test parameters. The changes in the composition of the mixtures in Examples 3 to 5 lead to poorer results.
Zusammensetzung (Gew.-%)Composition (% by weight)
Beispiel Nr. : 6(=1) 7 8 9Example No.: 6 (= 1) 7 8 9
5-Aminotetrazol 33,1 25,4 16,6 10,75-aminotetrazole 33.1 25.4 16.6 10.7
Natriumnitrat 52,3 52,7 52,7 52,7Sodium nitrate 52.3 52.7 52.7 52.7
Kaliumperchlorat 10,1 10,2 10,2 10,2Potassium perchlorate 10.1 10.2 10.2 10.2
Zn (5-ATZ)2 11,2 Ca (5-ATZ)2 20,0Zn (5-ATZ) 2 11.2 Ca (5-ATZ) 2 20.0
Mg (5-ATZ)2 25,9 Zinkoxid 4,0Mg (5-ATZ) 2 25.9 zinc oxide 4.0
Graphit 0,5 0,5 0,5 0,5 Graphite 0.5 0.5 0.5 0.5
Meßergebnisse in der ballistischen Druckbombe (25 ml)Measurement results in the ballistic pressure bomb (25 ml)
Beispiel Druckmaximum Zeitdifferenz1 ) Kaltgas2) CO 40-60% p(max)Example pressure maximum time difference 1 ) cold gas 2 ) CO 40-60% p (max)
(bar) (ms) (i/g) (ppm)(bar) (ms) (i / g) (ppm)
6 (=1) 715 6,7 0,41 18006 (= 1) 715 6.7 0.41 1800
7 662 6,8 0,39 2507,662 6.8 0.39 250
8 602 6,6 0,40 1408 602 6.6 0.40 140
9 81 39,2 0,33 1009 81 39.2 0.33 100
Meßergebnisse in der 60 1 Testkanne:Measurement results in the 60 1 test can:
Beispiel CO-Reduktion3) Druckmaximu ) (%) (bar)Example CO reduction 3) pressure maximum ) (%) (bar)
6 (=1) 0 2,2 7 10 2,1 8 40 1,7 9 95 < 1,56 (= 1) 0 2.2 7 10 2.1 8 40 1.7 9 95 <1.5
) angegeben ist die Reaktionsdauer zwischen 40 und 60% des maximalen Druckes in Millisekunden ) the reaction time is between 40 and 60% of the maximum pressure in milliseconds
) gemessen nach Abkühlung auf Raumtemperatur ) measured after cooling to room temperature
) bezogen auf das Ergebnis der Testkanne, Beispiel 1 bzw. 6 ) based on the result of the test can, example 1 or 6
) Lademasse 40 g ) Load mass 40 g
Die Beispiele 6 bis 9 zeigen, daß sich der Zusatz der Zn-, Ca- und Mg-Salze des 5-Aminotetrazols (Me(5-ATZ)2) günstig auf die Schwadenzusammensetzung auswirkt. Es wird eine deut¬ liche Reduktion des CO-Anteils festgestellt. Auch die Reak¬ tionsgeschwindigkeit wird beeinflußt. Zusammensetzung (Gew.-%)Examples 6 to 9 show that the addition of the Zn, Ca and Mg salts of 5-aminotetrazole (Me (5-ATZ) 2 ) has a favorable effect on the vapor composition. A clear reduction in the CO content is found. The reaction rate is also influenced. Composition (% by weight)
Beispiel Nr. : 10 11 12 13Example No.: 10 11 12 13
5-Aminotetrazol 33,0 31,6 30,8 28,95-aminotetrazole 33.0 31.6 30.8 28.9
Guanidinnitrat 8,3 8,0 7,8 7,3Guanidine nitrate 8.3 8.0 7.8 7.3
Natriumnitrat 58,2 39,0 27,1Sodium nitrate 58.2 39.0 27.1
Strontiumnitrat 20,9 33,8 63,3Strontium nitrate 20.9 33.8 63.3
Graphit 0,5 0,5 0,5 0,5Graphite 0.5 0.5 0.5 0.5
Beispiel Explosionswärme Reib¬ Schlag- Rückstands- empfindlichkeit masse^ 'Example of heat of explosion friction, impact, residue sensitivity mass ^ '
(kJ/g) (N) (J) (g)(kJ / g) (N) (J) (g)
10 4,06 > 360 20 1,510 4.06> 360 20 1.5
11 3,90 > 360 15 1,211 3.90> 360 15 1.2
12 3,61 > 360 20 1,012 3.61> 360 20 1.0
13 3,41 > 360 15 0,813 3.41> 360 15 0.8
Meßergebnisse in der ballistischen Druckbombe (25 ml.Measurement results in the ballistic pressure bomb (25 ml.
Beispiel Druckmaximum Zeitdifferenz1) Kaltgas2) 40-60% p(max)Example pressure maximum time difference 1 ) cold gas 2 ) 40-60% p (max)
(bar) (ms) (i/g)(bar) (ms) (i / g)
10 779 6,1 0,4610 779 6.1 0.46
11 767 7,0 0,4111 767 7.0 0.41
12 723 7,3 0,4212 723 7.3 0.42
13 620 8,6 0,3913 620 8.6 0.39
) angegeben ist die Reaktionsdauer zwischen 40 und 60% des maximalen Druckes in Millisekunden ) the reaction time is between 40 and 60% of the maximum pressure in milliseconds
) gemessen nach Abkühlung auf Raumtemperatur 5) Feststoffmasse in der 60 1 Testkanne nach Abbrand von 30 g Gassatz im Versuchsgenerator ) Measured after cooling to room temperature 5) Solid mass in the 60 1 test jug after burning 30 g gas set in the test generator
Beispiele 10 bis 13 unterscheiden sich durch den Anteil an Natriumnitrat/Strontiumnitrat als Oxidationsmittel. Mit zu¬ nehmendem Anteil an Strontiumnitrat reduziert sich die Masse der in die Kanne austretenden Schlacke. Das bedeutet, die Filtrierbarkeit der Schlacke wird durch die Zugabe von Strontiumnitrat - nach der Reaktion - im Filter des Genera¬ tors verbessert. Gleichzeitig läßt sich der CO-Anteil des Reaktionsgases günstig beeinflussen. Examples 10 to 13 differ in the proportion of sodium nitrate / strontium nitrate as the oxidizing agent. With an increasing proportion of strontium nitrate, the mass of the slag emerging into the jug is reduced. This means that the filterability of the slag is improved by adding strontium nitrate - after the reaction - in the filter of the generator. At the same time, the CO content of the reaction gas can be influenced favorably.
Claims
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CZ0262197A CZ298208B6 (en) | 1995-02-18 | 1996-02-13 | Gas-generating propellant from nitrogenous compounds, process for preparing such propellant, life-saving systems formed by a gas generator comprising gas-generating propellant and use of the gas-generating propellant |
| EP96902269A EP0809616A1 (en) | 1995-02-18 | 1996-02-13 | Gas-generating mixtures |
| BR9607444A BR9607444A (en) | 1995-02-18 | 1996-02-13 | Gas-producing mixtures |
| PL96321832A PL183318B1 (en) | 1995-02-18 | 1996-02-13 | Gas generating mixtures |
| MX9706223A MX9706223A (en) | 1995-02-18 | 1996-02-13 | Gas-generating mixtures. |
| JP8525361A JPH11500098A (en) | 1995-02-18 | 1996-02-13 | Gas generating mixture |
| US11/561,128 US20070102076A1 (en) | 1995-02-18 | 2006-11-17 | Gas-producing mixtures |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19505568.3 | 1995-02-18 | ||
| DE19505568A DE19505568A1 (en) | 1995-02-18 | 1995-02-18 | Gas generating mixtures |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US11/561,128 Continuation US20070102076A1 (en) | 1995-02-18 | 2006-11-17 | Gas-producing mixtures |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1996026169A1 true WO1996026169A1 (en) | 1996-08-29 |
Family
ID=7754364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1996/000605 Ceased WO1996026169A1 (en) | 1995-02-18 | 1996-02-13 | Gas-generating mixtures |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US20070102076A1 (en) |
| EP (1) | EP0809616A1 (en) |
| JP (1) | JPH11500098A (en) |
| KR (1) | KR100417454B1 (en) |
| CN (1) | CN1183758A (en) |
| BR (1) | BR9607444A (en) |
| CA (1) | CA2211579A1 (en) |
| CZ (1) | CZ298208B6 (en) |
| DE (1) | DE19505568A1 (en) |
| MX (1) | MX9706223A (en) |
| PL (1) | PL183318B1 (en) |
| RU (1) | RU2250207C2 (en) |
| TR (1) | TR199700813T1 (en) |
| WO (1) | WO1996026169A1 (en) |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2953448A (en) * | 1953-01-14 | 1960-09-20 | Ici Ltd | Compositions for safety heating elements |
| EP0438851A2 (en) * | 1990-01-09 | 1991-07-31 | Automotive Systems Laboratory Inc. | Composition and process for inflating a safety crash bag |
| DE4108225C1 (en) * | 1991-03-14 | 1992-04-09 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung Ev, 8000 Muenchen, De | |
| US5139588A (en) * | 1990-10-23 | 1992-08-18 | Automotive Systems Laboratory, Inc. | Composition for controlling oxides of nitrogen |
| EP0519485A1 (en) * | 1991-06-21 | 1992-12-23 | Dynamit Nobel Aktiengesellschaft | Propellant for gas generators |
| FR2691706A1 (en) * | 1992-06-02 | 1993-12-03 | Livbag Snc | Pyrotechnic gas generator with a safety opening. |
| WO1994001381A1 (en) * | 1992-07-13 | 1994-01-20 | Nippon Koki Co., Ltd. | Gas generating agent for air bags |
| WO1995000462A1 (en) * | 1993-06-22 | 1995-01-05 | Automotive Systems Laboratory, Inc. | Azide-free gas generant compositions and processes |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3404531A (en) * | 1966-07-18 | 1968-10-08 | United Aircraft Corp | Method and compositions for producing condensable combustion products |
| DE2004620C3 (en) * | 1970-02-03 | 1975-07-17 | Dynamit Nobel Ag, 5210 Troisdorf | Compressed gas generating charges |
| US3910595A (en) * | 1970-10-27 | 1975-10-07 | Rocket Research Corp | Aspirating apparatus and method for crash restraint system |
| FR2228043B1 (en) * | 1972-10-17 | 1977-03-04 | Poudres & Explosifs Ste Nale | |
| SU1004327A1 (en) * | 1981-07-06 | 1983-03-15 | Предприятие П/Я Г-4665 | Gas-forming composition |
| US4547235A (en) * | 1984-06-14 | 1985-10-15 | Morton Thiokol, Inc. | Gas generant for air bag inflators |
| US4566921A (en) * | 1985-02-08 | 1986-01-28 | L'etat Francais Represente Par Le Delegue Ministeriel Pour L'armement | Priming composition which is sensitive to percussion and a method for preparing it |
| US4909549A (en) * | 1988-12-02 | 1990-03-20 | Automotive Systems Laboratory, Inc. | Composition and process for inflating a safety crash bag |
| US5197758A (en) * | 1991-10-09 | 1993-03-30 | Morton International, Inc. | Non-azide gas generant formulation, method, and apparatus |
| 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 |
| US5429691A (en) * | 1993-08-10 | 1995-07-04 | Thiokol Corporation | Thermite compositions for use as gas generants comprising basic metal carbonates and/or basic metal nitrates |
| US5472534A (en) * | 1994-01-06 | 1995-12-05 | Thiokol Corporation | Gas generant composition containing non-metallic salts of 5-nitrobarbituric acid |
| US5516377A (en) * | 1994-01-10 | 1996-05-14 | Thiokol Corporation | Gas generating compositions based on salts of 5-nitraminotetrazole |
| CA2160350A1 (en) * | 1994-02-15 | 1995-08-17 | Tadao Yoshida | Gas generator composition, process for producing tablet therefrom, and transportation method |
| US5756929A (en) * | 1996-02-14 | 1998-05-26 | Automotive Systems Laboratory Inc. | Nonazide gas generating compositions |
| US6453816B2 (en) * | 1996-07-20 | 2002-09-24 | Dynamit Nobel Gmbh Explosivstoff-Und Systemtechnik | Temperature fuse with lower detonation point |
-
1995
- 1995-02-18 DE DE19505568A patent/DE19505568A1/en not_active Withdrawn
-
1996
- 1996-02-13 MX MX9706223A patent/MX9706223A/en active IP Right Grant
- 1996-02-13 PL PL96321832A patent/PL183318B1/en not_active IP Right Cessation
- 1996-02-13 CZ CZ0262197A patent/CZ298208B6/en not_active IP Right Cessation
- 1996-02-13 JP JP8525361A patent/JPH11500098A/en active Pending
- 1996-02-13 BR BR9607444A patent/BR9607444A/en not_active IP Right Cessation
- 1996-02-13 CA CA002211579A patent/CA2211579A1/en not_active Abandoned
- 1996-02-13 TR TR97/00813T patent/TR199700813T1/en unknown
- 1996-02-13 EP EP96902269A patent/EP0809616A1/en not_active Withdrawn
- 1996-02-13 RU RU97116160/02A patent/RU2250207C2/en not_active IP Right Cessation
- 1996-02-13 KR KR1019970705691A patent/KR100417454B1/en not_active Expired - Fee Related
- 1996-02-13 WO PCT/EP1996/000605 patent/WO1996026169A1/en not_active Ceased
- 1996-02-13 CN CN96193147A patent/CN1183758A/en active Pending
-
2006
- 2006-11-17 US US11/561,128 patent/US20070102076A1/en not_active Abandoned
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2953448A (en) * | 1953-01-14 | 1960-09-20 | Ici Ltd | Compositions for safety heating elements |
| EP0438851A2 (en) * | 1990-01-09 | 1991-07-31 | Automotive Systems Laboratory Inc. | Composition and process for inflating a safety crash bag |
| US5139588A (en) * | 1990-10-23 | 1992-08-18 | Automotive Systems Laboratory, Inc. | Composition for controlling oxides of nitrogen |
| DE4108225C1 (en) * | 1991-03-14 | 1992-04-09 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung Ev, 8000 Muenchen, De | |
| EP0519485A1 (en) * | 1991-06-21 | 1992-12-23 | Dynamit Nobel Aktiengesellschaft | Propellant for gas generators |
| FR2691706A1 (en) * | 1992-06-02 | 1993-12-03 | Livbag Snc | Pyrotechnic gas generator with a safety opening. |
| WO1994001381A1 (en) * | 1992-07-13 | 1994-01-20 | Nippon Koki Co., Ltd. | Gas generating agent for air bags |
| EP0607446A1 (en) * | 1992-07-13 | 1994-07-27 | Nippon Koki Co., Ltd. | Gas generating agent for air bags |
| WO1995000462A1 (en) * | 1993-06-22 | 1995-01-05 | Automotive Systems Laboratory, Inc. | Azide-free gas generant compositions and processes |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0950040A4 (en) * | 1996-08-12 | 1999-12-22 | Automotive Systems Lab | Selective non-catalytic reduction (sncr) of toxic gaseous effluents in airbag inflators |
| JP2001504432A (en) * | 1996-11-08 | 2001-04-03 | オートモーティブ システムズ ラボラトリー インコーポレーテッド | Non-azide gas generating composition |
| US6291711B2 (en) | 1997-05-21 | 2001-09-18 | Totalforsvarets Forskningsinstitut (Foi) | Guanylurea dinitramide, an explosive, propellant, rocket motor charge and gas generator |
| WO1998055428A1 (en) * | 1997-05-21 | 1998-12-10 | Försvarets Forskningsanstalt | New chemical compound, explosive containing the compound and use of the compound in gas generators |
| JPH11310490A (en) * | 1998-02-25 | 1999-11-09 | Nippon Kayaku Co Ltd | Gas generating agent composition |
| EP0949225A1 (en) * | 1998-04-08 | 1999-10-13 | TRW Airbag Systems GmbH & Co. KG | Non-azide gas generating composition |
| US6132537A (en) * | 1998-04-08 | 2000-10-17 | Trw Airbag Systems Gmbh & Co. Kg | Azide-free gas-producing composition |
| EP1114010A4 (en) * | 1998-07-25 | 2002-07-17 | Breed Automotive Tech | Gas generant compositions containing guanadines |
| EP0995732A3 (en) * | 1998-10-23 | 2000-07-26 | Oea, Inc. | Propellant compositions for gas generating apparatus |
| EP1181262A4 (en) * | 1999-03-01 | 2005-03-16 | Automotive Systems Lab | Gas generant composition |
| US6562087B1 (en) | 1999-07-09 | 2003-05-13 | Nippon Kayaku Kabushiki-Kaisha | Automatically ignitable enhancer agent composition |
| WO2001004074A1 (en) * | 1999-07-09 | 2001-01-18 | Nippon Kayaku Kabushiki-Kaisha | Automatically ignitable enhancer agent composition |
| WO2001051192A1 (en) * | 2000-01-12 | 2001-07-19 | Nippon Kayaku Kabushiki-Kaisha | Gas generator |
| WO2001056953A1 (en) * | 2000-02-04 | 2001-08-09 | Daicel Chemical Industries, Ltd. | Gas-generating agent composition comprising triazine derivative |
| EP2038146A4 (en) * | 2006-05-05 | 2009-09-30 | Tk Holdings Inc | Gas generant compositions |
| RU2634023C1 (en) * | 2016-10-11 | 2017-10-23 | Акционерное общество "Федеральный научно-производственный центр "Научно-исследовательский институт прикладной химии" | Gas-generating pyrotechnical composition |
Also Published As
| Publication number | Publication date |
|---|---|
| DE19505568A1 (en) | 1996-08-22 |
| PL183318B1 (en) | 2002-06-28 |
| CN1183758A (en) | 1998-06-03 |
| PL321832A1 (en) | 1997-12-22 |
| EP0809616A1 (en) | 1997-12-03 |
| US20070102076A1 (en) | 2007-05-10 |
| BR9607444A (en) | 1998-06-30 |
| JPH11500098A (en) | 1999-01-06 |
| MX9706223A (en) | 1998-02-28 |
| TR199700813T1 (en) | 1998-01-21 |
| KR19980702294A (en) | 1998-07-15 |
| CZ262197A3 (en) | 1997-12-17 |
| CZ298208B6 (en) | 2007-07-25 |
| CA2211579A1 (en) | 1996-08-29 |
| RU2250207C2 (en) | 2005-04-20 |
| KR100417454B1 (en) | 2004-03-18 |
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