EP0519485A1 - Propellant for gas generators - Google Patents
Propellant for gas generators Download PDFInfo
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- EP0519485A1 EP0519485A1 EP92110353A EP92110353A EP0519485A1 EP 0519485 A1 EP0519485 A1 EP 0519485A1 EP 92110353 A EP92110353 A EP 92110353A EP 92110353 A EP92110353 A EP 92110353A EP 0519485 A1 EP0519485 A1 EP 0519485A1
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- EP
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- Prior art keywords
- derivatives
- propellant
- nitrate
- salts
- radical
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Classifications
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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
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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
Definitions
- Gas generators are finding increasing interest in saving lives, for example in vehicles.
- the most widely used gas generation mixture in the world contains sodium azide.
- sodium azide is toxic, which requires special measures in the manufacture of the raw material, the gas mixture, its processing, quality control and disposal. This applies in particular to the scrapping of vehicles.
- DE-A-21 42 578 describes a compressed propellant charge for rapidly inflating a hollow body by reacting tetrazylazen with oxygen carriers.
- DE-A-18 06 550 proposes a propellant gas-generating, cool gas-producing propellant based on ammonium nitrate, activated carbon and an endothermic decomposing or sublimating compound.
- this system supplies a large proportion of water vapor, which is disadvantageous because water leads to a sharp increase in temperature due to its high heat of condensation.
- DE-A-12 22 418 describes mixtures which develop pressurized gas on the basis of inorganic perchlorate oxidizers, polymeric fuel binders and a coolant.
- preparations with high levels of chlorate or perchlorate lead to chlorine levels in the reaction gases.
- EP-A-372 733 describes an unsatisfactory mixture since the propellant charge of the proposed airbag contains about 40% ammonium perchlorate.
- Even nitrocellulose and nitroglycerin masses can be found in the literature. Such proposals cannot be used for use in life-saving systems. Nitrocellulose and nitroglycerin mixtures or other carbon-rich, energetic compounds are eliminated due to the formation of carbon monoxide.
- the propellants of DE-A-12 50 318 which contain aminotetrazole, potassium dichromate, calcium resinate and metallic silicon, do not meet today's safety requirements. The same applies to DE-C-20 04 620, whose charge gas-generating charge contains azotetrazole and / or ditetrazole and chlorates or perchlorates.
- the propellants of US Pat. No. 3,734,789 which contain 5-aminotetrazole nitrate and polyisoprene binder, burn off quickly, but also generate carbon monoxide in concentrations which are hazardous to health due to the carbon-rich binder fraction.
- the invention is therefore based on the object of providing gas sets whose production and processing or handling are harmless and whose reaction products are not toxic.
- the nitrogen-containing compounds to be used according to the invention are those which, when mixed with oxidizing agents, form mainly CO2, N2 and H2O in their thermal / chemical reaction, but do not develop gases such as CO or NO x in concentrations which are hazardous to health. It is particularly important that the addition of binders is not absolutely necessary.
- R1 is preferably hydrogen, amino, hydroxy, carboxyl, a methyl, ethyl, propyl or isopropyl, butyl, isobutyl or tert-butyl, n-pentyl, n-hexyl or n-heptyl radical, one Methylamino, ethylamino, dimethylamino, n-heptylamino, n-octylamino or n-decylamino, a phenylamino, a phenyl, nitrophenyl or aminophenyl group.
- R2 or R3 is preferably hydrogen, a methyl or ethyl radical, a phenyl, nitrophenyl or aminophenyl radical.
- the tetrazole derivatives are particularly preferred: 5-aminotetrazole, sodium, potassium or calcium 5-aminotetrazolate, 1- (4-aminophenyl) tetrazole, 1- (4-nitrophenyl) tetrazole, 1-methyl-5-dimethylamino-tetrazole, 1-methyl 5-methylaminotetrazole, 1-methyl-tetrazole, 1-phenyl-5-aminotetrazole, 1-phenyl-5-hydroxy-tetrazole, 1-phenyl-tetrazole, 2-ethyl-5-aminotetrazole, 2-methyl- 5-amino-tetrazole, 2-methyl-5-carboxyl-tetrazole, 2-methyl-5-methylamino-tetrazole, 2-methyl-tetrazole, 2-phenyl-tetrazole, 5- (p-tolyl) -tetrazole, 5- Diallyl-aminotetrazole, 5-dimethylamino-tetrazole
- cyanic acid derivatives 1,3,5-triazine, cyanuric acid ester and / or cyanuric acid amide (melamine) as triazine derivatives and biuret, guanidine, nitroguanidine, guanidine nitrate, aminoguanidine, guanidine nitrate, aminoguanidine as urea derivatives.
- Triaminoguanidine nitrate aminoguanidine hydrogen carbonate, azodicarboxylic acid diamide, dicyandiamidine nitrate, dicyandiamidine sulfate, tetrazene and / or semicarbazide nitrate are used.
- the mixtures according to the invention have high thermal and climatic stability, which is a prerequisite for a perfect effect even after long storage.
- Nitrates of ammonium, sodium, potassium, magnesium, calcium or iron, preferably sodium nitrate or peroxides of zinc, calcium, strontium or magnesium can be used as the oxidizing agent.
- the peroxides are used with an oxygen value that can be obtained from stable compounds. For zinc peroxide, this is about 11 to 14% by weight.
- the corresponding molar ratio of nitrogen-containing compound to peroxide is in the range from 1: 2 to 5.5.
- Calcium peroxide can have an active oxygen value of, for example, 18.62% by weight and grain sizes of 15.5 ⁇ m and is advantageously used in a molar ratio of nitrogenous compound / peroxide of 1: 3.
- the above-mentioned peroxides can be used in a molar ratio of 1: 1 to 20.
- Calcium and / or zinc peroxide is preferably used. Mixtures of the peroxides with one another or with other oxidizing agents can also be used.
- Other oxidizing agents are, for example, the above-mentioned nitrates of ammonium, sodium, potassium, magnesium, calcium or iron, preferably sodium nitrate.
- the alkaline hydrolysis products can cause reactions with the other components of the mixture.
- coating the peroxides with inorganic or organic materials by methods known per se is expedient. Such a coating also offers the advantage of better handling, since the blowing agent treated in this way no longer produces dust.
- the mixtures of the tetrazole or its derivatives to be used according to the invention with the compounds from groups A), B) and / or C) enable the propellants to be graded with respect to their reaction rate and the vapors and gases that develop.
- a gradation that is necessary in order to be able to use the propellants according to the invention as widely as possible.
- the propellant charges according to the invention must be mixed in a targeted manner. This is the only way to find the optimal one To achieve effect.
- the efficiency of the propellants according to the invention is influenced not only by the composition, but also by the ignition, and also by the insulation caused by the construction and by the outflow behavior of the developing swaths and gases.
- the efficiency can be assessed, for example, by determining the gas pressure increase gradient of the respective mixture in the design-related, predetermined external environment and the type of ignition selected.
- the developing gas concentrations, especially those of the gases hazardous to health, must not exceed certain maximum values. These values result from the MAK values (or from the TLV values in the USA). From these values together with the permitted exposure times, technical requirements are created which the respective propellant charges have to meet. When defining these requirements, for example, the different passenger cells are also taken into account. In order to meet these requirements, it is necessary to mix the respective propellant in a targeted manner.
- the gas temperature can be kept low by adding diammonium oxalate, oxalic acid diamide, dicyandiamide or carbonates or bicarbonates. If thermal stability is not important and smoke formation is to be avoided when inorganic carbonates or bicarbonates are added, aminoguanidine bicarbonate can be used as the organic bicarbonate. Additional additives can be oxalic acid or urea, which are generally added in an amount of up to 5% by weight, based on the mixture.
- Metal powders of iron, magnesium, zirconium or titanium can be added as reducing agents, which in contrast to non-metal boron do not have a strong influence on the rate of combustion, but in the latter case they do have a strong influence on the heat of the reaction and the reaction products.
- the proportion of reducing agents can be up to 5% by weight.
- Catalysts are metal complexes, of which ferrocene is mentioned here by way of example, the addition of which increases the reaction rate significantly by up to about 3% by weight.
- the gas sets described in accordance with the invention are produced by mixing the components by methods known per se, if appropriate with the preparation of a harmless premix, to which further components are added.
- This mixture can already be used in powdered form. Demixing due to different density of the components can be countered by granulating the mixture.
- the mixture will be molded by pressing or similar measures.
- pressing aids can be added to the mixture.
- graphite, molybdenum disulfide, Teflon, talc, zinc stearate or boron nitride come into question. These agents work even in the smallest amounts and do not or only slightly influence the properties and the burning behavior.
- One such method is to add additives such as salts to the mixture before the actual molding process, which can be removed by extraction with water or solvents after the molding.
- Another method is to add substances which are not very thermally resistant and which decompose when the molding is heated.
- the surface of the mixture can also be increased by adding hollow microspheres made of glass or plastics to the mixture prior to pressing.
- the density of the compact to be achieved in this way can deviate by up to 20% from that of the untreated compact, this value being intended only as a rough guide and not a limitation. This treatment leads to an extreme acceleration of the burning process.
- a further treatment of the moldings can consist in a surface coating.
- protection against environmental influences is achieved in particular.
- Such a measure can also be used to increase the strength of the molded body.
- suitable fibers for stabilization would also have to be provided here.
- a side effect of the coating is the reduction of the abrasion during the transport stress of the parts.
- the moldings treated in this way can be introduced in bulk or directed into appropriate pressure-resistant containers. They are ignited using conventional methods with the aid of ignition kits or thermal charges, the resulting gases possibly filling the life-saving system in a split second after flowing through a suitable filter.
- the propellants according to the invention are particularly suitable for so-called airbags, impact bags, which are used in motor vehicles or aircraft to protect the occupants.
- the airbag In the event of a motor vehicle crash, the airbag must be filled with gas quantities of approximately 50 to 300 liters within a very short time, depending on the system and car size.
- the propellants according to the invention are also suitable for use in belt tensioners.
- Life saving systems containing the propellants according to the invention are also the subject of the present invention.
- 5-ATZ and ZnO2 as components for non-toxic gas sets, are homogenized together in a weight ratio of 1 to 7 (this corresponds to a molar ratio of approx. 1: 5) in plastic containers in a tumble mixer for 1-2 hours. 3.0 g of the sample are reacted as bulk in a 25 ml stainless steel pressure bomb by means of an electrically heatable Fe wire and the pressure-time profile is recorded by means of a piezoelectric measuring device. After about 30 ms, a maximum gas pressure of about 200 bar arises, which is mainly due to the formation of CO2, N2, O2 and H2O. The reaction has a strongly exothermic character of approx.
- the gas set mixtures described in Examples 1 to 24 can also be used in compressed form.
- Example 1 As described in Example 1, further mixtures of gas-generating components and oxygen suppliers such as zinc peroxide with an active oxygen content of 13.07% by weight and an average grain size of 11.8 ⁇ m or, in the case of sodium nitrate, with an average grain size of ⁇ 45 ⁇ m produced.
- gas-generating components and oxygen suppliers such as zinc peroxide with an active oxygen content of 13.07% by weight and an average grain size of 11.8 ⁇ m or, in the case of sodium nitrate, with an average grain size of ⁇ 45 ⁇ m produced.
- Table 4 below contains further information on the mixtures.
- Table 5 shows the values for the maximum pressure (bar) and the time in ms to the maximum pressure, which are in the range of those described in Example 1 for a gas set consisting of 5-aminotetrazole and zinc peroxide. In addition, the time between 40-60% of the maximum pressure was determined. Table 5 Example No. Maxim Pressure (bar) Time (ms) to maxim. print up to 40-60% of the max. print 26 359 30th 1.2 27th 217 123 13.1 28 352 29 1.5 29 473 39 1.3 30th 549 14 0.5 31 917 7 0.2 32 148 220 20.1
- the parameters required for the respective gas set can be set by coordinating the parameters and adding other components.
- the components are suitable for the production of gas sets due to their miscibility, processability, compressibility for shaping and compatibility with one another and with additional additives as well as their safety-related characteristics.
- the mixtures of Examples 33 to 44 were made of zinc peroxide (active oxygen content 12.8% by weight, average particle size 4.8 ⁇ m), aminotetrazole (average particle size ⁇ 125 ⁇ m), sodium nitrate (particle size ⁇ 45 ⁇ m) and the listed components with a grain size of ⁇ 125 ⁇ m.
- the additionally listed components are described in the literature.
Abstract
Description
Gasgeneratoren finden zunehmendes Interesse zur Lebensrettung beispielsweise in Fahrzeugen. Weltweit enthält die am meisten eingesetzte Mischung zur Erzeugung von Gas Natriumazid. Natriumazid ist jedoch giftig, was besondere Maßnahmen bei der Herstellung des Rohstoffs, der Gassatzmischung, seiner Verarbeitung, Qualitätskontrolle und Entsorgung erfordert. Dies gilt insbesondere bei der Verschrottung von Fahrzeugen.Gas generators are finding increasing interest in saving lives, for example in vehicles. The most widely used gas generation mixture in the world contains sodium azide. However, sodium azide is toxic, which requires special measures in the manufacture of the raw material, the gas mixture, its processing, quality control and disposal. This applies in particular to the scrapping of vehicles.
Es hat nicht an Versuchen gefehlt, anstelle von Natriumazid andere Stoffe einzusetzen. So beschreibt die DE-A-21 42 578 einen verpreßten Treibsatz zum schnellen Aufblasen eines Hohlkörpers durch Umsetzung von Tetrazylazen mit Sauerstoffträgern. Die DE-A-18 06 550 schlägt einen druckgaserzeugenden, kühle Gase liefernden Treibsatz auf der Basis von Ammoniumnitrat, Aktivkohle und einer sich endotherm zersetzenden oder sublimierenden Verbindung vor. Dieses System liefert jedoch einen großen Anteil von Wasserdampf, was nachteilig ist, weil Wasser wegen seiner hohen Kondensationswärme zu einer starken Temperaturerhöhung führt.There has been no shortage of attempts to use other substances instead of sodium azide. For example, DE-A-21 42 578 describes a compressed propellant charge for rapidly inflating a hollow body by reacting tetrazylazen with oxygen carriers. DE-A-18 06 550 proposes a propellant gas-generating, cool gas-producing propellant based on ammonium nitrate, activated carbon and an endothermic decomposing or sublimating compound. However, this system supplies a large proportion of water vapor, which is disadvantageous because water leads to a sharp increase in temperature due to its high heat of condensation.
Die DE-A-12 22 418 beschreibt Druckgas entwickelnde Gemische auf der Basis von anorganischen Perchloratoxidatoren, polymeren Brennstoffbindemitteln und einem Kühlmittel. Zubereitungen mit hohen Anteilen an Chlorat oder Perchlorat führen jedoch zu Chloranteilen in den Reaktionsgasen. So beschreibt auch die EP-A-372 733 ein unbefriedigendes Gemisch, da der Treibsatz des vorgeschlagenen Airbags etwa 40 % Ammoniumperchlorat enthält. Selbst Nitrocellulose und Nitroglycerin-Massen finden sich in der Literatur. Für die Verwendung in Lebensrettungssystemen sind solche Vorschläge nicht brauchbar. Nitrocellulose und Nitroglyceringemische oder auch andere kohlenstoffreiche, energetische Verbindungen scheiden wegen der Bildung von Kohlenmonoxid aus.DE-A-12 22 418 describes mixtures which develop pressurized gas on the basis of inorganic perchlorate oxidizers, polymeric fuel binders and a coolant. However, preparations with high levels of chlorate or perchlorate lead to chlorine levels in the reaction gases. For example, EP-A-372 733 describes an unsatisfactory mixture since the propellant charge of the proposed airbag contains about 40% ammonium perchlorate. Even nitrocellulose and nitroglycerin masses can be found in the literature. Such proposals cannot be used for use in life-saving systems. Nitrocellulose and nitroglycerin mixtures or other carbon-rich, energetic compounds are eliminated due to the formation of carbon monoxide.
Auch die Treibsätze der DE-A-12 50 318, die Aminotetrazol, Kaliumdichromat, Calciumresinat und metallisches Silicium enthalten, genügen den heutigen Sicherheitsanforderungen nicht. Das gleiche gilt für die DE-C-20 04 620, deren Druckgas erzeugende Ladung Azotetrazol und/oder Ditetrazol und Chlorate oder Perchlorate enthalten. Die Treibsätze der US-A-3 734 789, die 5-Aminotetrazolnitrat und Polyisoprenbinder enthalten, brennen zwar schnell ab, erzeugen jedoch durch den kohlenstoffreichen Binderanteil auch Kohlenmonoxid in gesundheitsgefährdenden Konzentrationen.The propellants of DE-A-12 50 318, which contain aminotetrazole, potassium dichromate, calcium resinate and metallic silicon, do not meet today's safety requirements. The same applies to DE-C-20 04 620, whose charge gas-generating charge contains azotetrazole and / or ditetrazole and chlorates or perchlorates. The propellants of US Pat. No. 3,734,789, which contain 5-aminotetrazole nitrate and polyisoprene binder, burn off quickly, but also generate carbon monoxide in concentrations which are hazardous to health due to the carbon-rich binder fraction.
Der Erfindung liegt somit die Aufgabe zugrunde, Gassätze bereitzustellen, deren Herstellung und Verarbeitung bzw. Handhabung unbedenklich und deren Umsetzungsprodukte nicht toxisch sind.The invention is therefore based on the object of providing gas sets whose production and processing or handling are harmless and whose reaction products are not toxic.
Diese Aufgabe wird gelöst durch ein Treibmittel für Gasgeneratoren, die als stickstoffhaltige Verbindung a) ein oder mehrere Tetrazolderivat(e) der Formel
enthalten, worin R₁ und R₂ 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 Kohlenstoffatomen, einen Arylrest, gegebenenfalls substituiert mit einem oder mehreren Substituenten, die gleich oder verschieden sein können, ausgewählt aus der Aminogruppe, der Nitrogruppe, den Alkylresten mit 1 bis 4 Kohlenstoffatomen oder einen Arylaminorest, bei dem der Arylrest gegebenenfalls substituiert sein kann oder deren Natrium-, Kalium- und Guanidiniumsalze
oder die als stickstoffhaltige Verbindungen
b) jeweils ein oder mehrere Verbindungen aus den Gruppen
- A) Cyansäurederivate und deren Salze,
- B) Triazin und Triazinderivate,
- C) Harnstoff, dessen Salze, Derivate und Abkömmlinge und deren Salze enthalten,
und ein Oxidationsmittel aus der Gruppe der Peroxide oder aus der Gruppe der Peroxide zusammen mit Oxidationsmitteln aus der Gruppe der Nitrate enthalten.This object is achieved by a propellant for gas generators which, as nitrogen-containing compound a), has one or more tetrazole derivative (s) of the formula
contain in which R₁ and R₂ or R₃ may be the same or different, but either R₂ or R₃ is present and have the meaning: hydrogen, hydroxyl, amino, carboxyl, an alkyl radical having 1 to 7 carbon atoms, an alkenyl radical having 2 to 7 carbon atoms, one Alkylamino radical having 1 to 10 carbon atoms, an aryl radical, optionally substituted with one or more substituents, which may be the same or different, selected from the amino group, the nitro group, the alkyl radicals having 1 to 4 carbon atoms or one Arylamino radical in which the aryl radical can be optionally substituted or their sodium, potassium and guanidinium salts
or as nitrogenous compounds
b) one or more compounds from the groups
- A) cyanic acid derivatives and their salts,
- B) triazine and triazine derivatives,
- C) urea, its salts, derivatives and derivatives and their salts,
and contain an oxidizing agent from the group of peroxides or from the group of peroxides together with oxidizing agents from the group of nitrates.
Die erfindungsgemäß einzusetzenden stickstoffhaltigen Verbindungen sind solche, die im Gemisch mit Oxidationsmitteln bei ihrer thermisch/chemischen Umsetzung hauptsächlich CO₂, N₂ und H₂O bilden, jedoch keine Gase wie CO oder NOx in gesundheitsgefährdenden Konzentrationen entwickeln. Von besonderer Bedeutung ist, daß der Zusatz von Bindemitteln nicht unbedingt notwendig ist.The nitrogen-containing compounds to be used according to the invention are those which, when mixed with oxidizing agents, form mainly CO₂, N₂ and H₂O in their thermal / chemical reaction, but do not develop gases such as CO or NO x in concentrations which are hazardous to health. It is particularly important that the addition of binders is not absolutely necessary.
R₁ bedeutet vorzugsweise Wasserstoff, Amino, 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-Heptylamino-, n-Octylamino- oder n-Decylaminorest, einen Phenylaminorest, einen Phenyl-, Nitrophenyl- oder Aminophenylrest.R₁ is preferably hydrogen, amino, hydroxy, carboxyl, a methyl, ethyl, propyl or isopropyl, butyl, isobutyl or tert-butyl, n-pentyl, n-hexyl or n-heptyl radical, one Methylamino, ethylamino, dimethylamino, n-heptylamino, n-octylamino or n-decylamino, a phenylamino, a phenyl, nitrophenyl or aminophenyl group.
R₂ oder R₃ bedeutet 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-Aminotetrazol, Natrium-, Kalium- oder Calcium-5-aminotetrazolat, 1-(4-Aminophenyl)-tetrazol,1-(4-Nitrophenyl)-tetrazol, 1-Methyl-5-dimethylamino-tetrazol, 1-Methyl-5-methylaminotetrazol, 1-Methyl-tetrazol, 1-Phenyl-5-amino-tetrazol, 1-Phenyl-5-hydroxy-tetrazol, 1-Phenyl-tetrazol, 2-Ethyl-5-amino-tetrazol, 2-Methyl-5-amino-tetrazol, 2-Methyl-5-carboxyl-tetrazol, 2-Methyl-5-methylamino-tetrazol, 2-Methyl-tetrazol, 2-Phenyl-tetrazol, 5-(p-Tolyl)-tetrazol, 5-Diallyl-amino-tetra-zol, 5-Dimethylamino-tetrazol, 5-Ethylamino-tetrazol, 5-Hydroxy-tetrazol, 5-Methyl-tetrazol, 5-Methyl-amino-tetrazol, 5-Methyl-amino-tetrazol, 5-n-Decylamino-tetrazol, 5-n-Heptyl-amino-tetrazol, 5-n-Octylamino-tetrazol, 5-Phenyltetrazol, 5-Phenyl-amino-tetrazol oder Bis(amino-guanidin)azo-tetrazol.The tetrazole derivatives are particularly preferred:
5-aminotetrazole, sodium, potassium or calcium 5-aminotetrazolate, 1- (4-aminophenyl) tetrazole, 1- (4-nitrophenyl) tetrazole, 1-methyl-5-dimethylamino-tetrazole, 1-methyl 5-methylaminotetrazole, 1-methyl-tetrazole, 1-phenyl-5-aminotetrazole, 1-phenyl-5-hydroxy-tetrazole, 1-phenyl-tetrazole, 2-ethyl-5-aminotetrazole, 2-methyl- 5-amino-tetrazole, 2-methyl-5-carboxyl-tetrazole, 2-methyl-5-methylamino-tetrazole, 2-methyl-tetrazole, 2-phenyl-tetrazole, 5- (p-tolyl) -tetrazole, 5- Diallyl-aminotetrazole, 5-dimethylamino-tetrazole, 5-ethylamino-tetrazole, 5-hydroxy-tetrazole, 5-methyl-tetrazole, 5-methyl-aminotetrazole, 5-methyl-aminotetrazole, 5- n-decylamino-tetrazole, 5-n-heptylamino-tetrazole, 5-n-octylamino-tetrazole, 5-phenyltetrazole, 5-phenylamino-tetrazole or bis (amino-guanidine) azo-tetrazole.
Als Cyansäurederivate werden bevorzugt Natriumcyanat, Cyanursäure, 1-Cyanguanidin, und/oder Dinatriumcyanamid, als Triazinderivate 1,3,5-Triazin, Cyanursäureester und/oder Cyanursäureamid (Melamin) und als Harnstoffderivate Biuret, Guanidin, Nitroguanidin, Guanidinnitrat, Aminoguanidin, Aminoguanidinnitrat, Triaminoguanidinnitrat, Aminoguanidinhydrogencarbonat, Azodicarbonsäurediamid, Dicyandiamidinnitrat, Dicyandiamidinsulfat, Tetrazen und/oder Semicarbazidnitrat eingesetzt.Sodium cyanate, cyanuric acid, 1-cyanguanidine and / or disodium cyanamide are preferred as cyanic acid derivatives, 1,3,5-triazine, cyanuric acid ester and / or cyanuric acid amide (melamine) as triazine derivatives and biuret, guanidine, nitroguanidine, guanidine nitrate, aminoguanidine, guanidine nitrate, aminoguanidine as urea derivatives. Triaminoguanidine nitrate, aminoguanidine hydrogen carbonate, azodicarboxylic acid diamide, dicyandiamidine nitrate, dicyandiamidine sulfate, tetrazene and / or semicarbazide nitrate are used.
Neben der gesundheitlichen Unbedenklichkeit besitzen die erfindungsgemäßen Gemische eine hohe thermische und klimatische Stabilität, die Voraussetzung für eine einwandfreie Wirkung auch nach langer Lagerung ist.In addition to the harmlessness to health, the mixtures according to the invention have high thermal and climatic stability, which is a prerequisite for a perfect effect even after long storage.
Als Oxidationsmittel können Nitrate von Ammonium, Natrium, Kalium, Magnesium, Calcium oder Eisen, vorzugsweise Natriumnitrat oder Peroxide von Zink, Calcium, Strontium oder Magnesium eingesetzt werden.Nitrates of ammonium, sodium, potassium, magnesium, calcium or iron, preferably sodium nitrate or peroxides of zinc, calcium, strontium or magnesium can be used as the oxidizing agent.
Die Peroxide werden dabei mit einem Sauerstoffwert eingesetzt, wie er aus stabilen Verbindungen erhalten werden kann. Für Zinkperoxid liegt dieser bei etwa 11 bis 14 Gew.-%. Das entsprechende Molverhältnis von stickstoffhaltiger Verbindung zu Peroxid liegt dabei im Bereich von 1:2 bis 5,5. Calciumperoxid kann einen aktiven Sauerstoffwert von beispielsweise 18,62 Gew.-% und Korngrößen von 15,5 µm aufweisen und wird vorteilhaft im Molverhältnis stickstoffhaltige Verbindung/Peroxid von 1:3 eingesetzt. Im allgemeinen können die obengenannten Peroxide im Molverhältnis 1:1 bis 20 eingesetzt werden.The peroxides are used with an oxygen value that can be obtained from stable compounds. For zinc peroxide, this is about 11 to 14% by weight. The corresponding molar ratio of nitrogen-containing compound to peroxide is in the range from 1: 2 to 5.5. Calcium peroxide can have an active oxygen value of, for example, 18.62% by weight and grain sizes of 15.5 μm and is advantageously used in a molar ratio of nitrogenous compound / peroxide of 1: 3. In general, the above-mentioned peroxides can be used in a molar ratio of 1: 1 to 20.
Bevorzugt eingesetzt wird Calcium- und/oder Zinkperoxid. Es können auch Mischungen der Peroxide untereinander oder solche mit anderen Oxidationsmitteln eingesetzt werden. Andere Oxidationsmittel sind beispielsweise die oben erwähnten Nitrate von Ammonium, Natrium, Kalium, Magnesium, Calcium oder Eisen, vorzugsweise Natriumnitrat.Calcium and / or zinc peroxide is preferably used. Mixtures of the peroxides with one another or with other oxidizing agents can also be used. Other oxidizing agents are, for example, the above-mentioned nitrates of ammonium, sodium, potassium, magnesium, calcium or iron, preferably sodium nitrate.
Bei Einsatz von Magnesium- und insbesondere Calcium- oder Strontiumperoxid kann es durch die alkalisch wirkenden Hydrolyseprodukte zu Reaktionen mit den übrigen Komponenten des Gemischs kommen. Hier ist eine Beschichtung der Peroxide mit anorganischen oder organischen Materialien nach an sich bekannten Verfahren zweckmäßig. Eine solche Beschichtung bietet darüberhinaus den Vorteil der besseren Handhabbarkeit, da das solchermaßen behandelte Treibmittel nicht mehr staubt.When using magnesium and in particular calcium or strontium peroxide, the alkaline hydrolysis products can cause reactions with the other components of the mixture. Here, coating the peroxides with inorganic or organic materials by methods known per se is expedient. Such a coating also offers the advantage of better handling, since the blowing agent treated in this way no longer produces dust.
Die erfindungsgemäß einzusetzenden Mischungen aus dem Tetrazol bzw. dessen Derivaten mit den Verbindungen aus den Gruppen A), B) und/oder C) ermöglichen eine feingradige Abstufung der Treibmittel in bezug auf ihre Reaktionsgeschwindigkeit und auf die sich entwickelnden Schwaden und Gase. Eine Abstufung, die erforderlich ist, um die erfindungsgemäßen Treibmittel möglichst vielfältig einsetzen zu können. Je nach Vorgabe der Konstruktion des Generatorgehäuses eines, beispielsweise, Airbags oder eines Gurtstrammers müssen die erfindungsgemäßen Treibsätze gezielt gemischt werden. Nur so ist es möglich, eine jeweils optimale Wirkung zu erreichen. Beeinflußt wird der Wirkungsgrad der erfindungsgemäßen Treibsätze nämlich nicht nur durch die Zusammensetzung, sondern weiterhin durch die Anzündung, und auch von der, durch die Konstruktion bedingte Verdämmung und durch das Abströmverhalten der sich entwickelnden Schwaden und Gase. Die Beurteilung des Wirkungsgrades kann beispielsweise erfolgen durch die Ermittlung des Gasdruckanstiegsgradienten der jeweiligen Mischung in der jeweils konstruktiv bedingten, vorgegebenen äußeren Umgebung und der gewählten Art der Anzündung. Die sich entwickelnden Gaskonzentrationen, insbesondere die der gesundheitsgefährdenden Gase dürfen bestimmte Maximalwerte nicht überschreiten. Diese Werte ergeben sich aus den MAK-Werten (bzw. aus den TLV-Werten in den USA). Aus diesen Werten zusammen mit den erlaubten Expositionszeiten werden technische Anforderungen erstellt, die die jeweiligen Treibsätze zu erfüllen haben. Bei der Festlegung dieser Anforderungen gehen beispielsweise auch die unterschiedlichen Fahrgastzellen ein. Um diese Anforderungen zu erfüllen, bedarf es der gezielten Abmischung des jeweiligen Treibsatzes.The mixtures of the tetrazole or its derivatives to be used according to the invention with the compounds from groups A), B) and / or C) enable the propellants to be graded with respect to their reaction rate and the vapors and gases that develop. A gradation that is necessary in order to be able to use the propellants according to the invention as widely as possible. Depending on the specification of the construction of the generator housing of, for example, airbags or a belt tensioner, the propellant charges according to the invention must be mixed in a targeted manner. This is the only way to find the optimal one To achieve effect. The efficiency of the propellants according to the invention is influenced not only by the composition, but also by the ignition, and also by the insulation caused by the construction and by the outflow behavior of the developing swaths and gases. The efficiency can be assessed, for example, by determining the gas pressure increase gradient of the respective mixture in the design-related, predetermined external environment and the type of ignition selected. The developing gas concentrations, especially those of the gases hazardous to health, must not exceed certain maximum values. These values result from the MAK values (or from the TLV values in the USA). From these values together with the permitted exposure times, technical requirements are created which the respective propellant charges have to meet. When defining these requirements, for example, the different passenger cells are also taken into account. In order to meet these requirements, it is necessary to mix the respective propellant in a targeted manner.
Die in den Tabellen angegebenen Werte wurden ermittelt, indem in einem Näpfchen in loser Schüttung 4 g des jeweiligen Treibsatzes in einer Druckbombe von 25 ml Volumen mit einem Glühdraht gezündet wurden. Nach der Anzündung wurde eine Druck-/Zeit-Kurve aufgezeichnet. Die anfallenden Werte wurden folgendermaßen ausgewertet:
- (1) maximaler Druck(bar): bei gleicher Einwaage sind Unterschiede direkt den entstandenen Gasvolumina zuzuschreiben. Diese werden durch Gasausbeute und Wärmetönung der Reaktion bestimmt.
- (2) Gasdruckanstieg für den Bereich von 40-60 % vom maximalen Druck: In diesem Bereich wird die Kurve nicht mehr verfälscht durch den Anbrand bzw. das Abkühlverhalten der Schwaden durch die innere Bombenoberfläche. Die angegebenen Zeiten in Millisekunden (ms) geben den Druckanstieg wieder und bedeuten unterschiedliche Umsetzungsgeschwindigkeiten. Solche Werte erhält man auch in den jeweiligen Anwendungsfällen, beispielsweise in den diversen, konstruktiv veränderten Gasgeneratorgehäusen. Sie erlauben eine präzise Abstimmung der erfindungsgemäßen Treibsätze im Hinblick auf die Leistungsanforderungen. Durch die Angabe der Druckanstiegszeiten im Bereich von 40-60% vom maximalen Druck wird die Umsetzungsgeschwindigkeit der erfindungsgemäßen Treibsätze ausreichend charakterisiert. Die Zeiten für die Umsetzung bis zum Auftreten des maximalen Druckes dienen zur zusätzlichen Information.
- (1) maximum pressure (bar): with the same sample weight, differences can be directly attributed to the resulting gas volumes. These are determined by the gas yield and the heat of the reaction.
- (2) Gas pressure increase for the area of 40-60% of the maximum pressure: In this area the curve is no longer distorted by the burning or the cooling behavior of the swaths through the inner surface of the bomb. The specified times in milliseconds (ms) reflect the pressure increase and mean different implementation speeds. Such values can also be obtained in the respective applications, for example in the various, structurally modified gas generator housings. They allow the propellant charges according to the invention to be precisely coordinated with regard to the performance requirements. The rate at which the propellants according to the invention are implemented is adequately characterized by specifying the pressure rise times in the range of 40-60% of the maximum pressure. The times for the implementation until the maximum pressure occurs serve as additional information.
Ein Niedrighalten der Gastemperatur kann gezielt durch Zugabe von Diammoniumoxalat, Oxalsäurediamid, Dicyandiamid oder Carbonaten bzw. Bicarbonaten erreicht werden. Sofern es auf die thermische Stabilität nicht ankommt und die Rauchbildung bei Zugabe anorganischer Carbonate oder Bicarbonate vermieden werden soll, kann als organisches Bicarbonat Aminoguanidinbicarbonat eingesetzt werden. Weitere Zuschläge können Oxalsäure oder Harnstoff sein, welche im allgemeinen in einer Menge bis zu 5 Gew.-%, bezogen auf das Gemisch, hinzugegeben werden.The gas temperature can be kept low by adding diammonium oxalate, oxalic acid diamide, dicyandiamide or carbonates or bicarbonates. If thermal stability is not important and smoke formation is to be avoided when inorganic carbonates or bicarbonates are added, aminoguanidine bicarbonate can be used as the organic bicarbonate. Additional additives can be oxalic acid or urea, which are generally added in an amount of up to 5% by weight, based on the mixture.
Als Reduktionsmittel können Metallpulver von Eisen, Magnesium, Zirkonium oder Titan zugesetzt werden, die im Gegensatz zum Nichtmetall Bor keinen starken Einfluß auf die Abbrandgeschwindigkeit, bei letzterem wohl aber auf die Wärmetönung der Umsetzung und die Reaktionsprodukte haben. Der Anteil der Reduktionsmittel kann bis zu 5 Gew.-% betragen.Metal powders of iron, magnesium, zirconium or titanium can be added as reducing agents, which in contrast to non-metal boron do not have a strong influence on the rate of combustion, but in the latter case they do have a strong influence on the heat of the reaction and the reaction products. The proportion of reducing agents can be up to 5% by weight.
Als Katalysatoren für eine so heterogen zusammengesetzte Mischung eignen sich Verbindungen, die Einfluß nehmen auf die Zersetzung von Peroxiden wie z.B. Metalle oder ihre Oxide, z.B. Mangandioxid. Zusätze von Vanadiumpentoxid oder Cerdioxid führen zu einer Erhöhung der Umsetzungsgeschwindigkeit. Bei Zugabe bis 5 Gew.-% Molybdän(VI)-oxid wird sie nur wenig verändert, wie auch in Anwesenheit von Cer(III)nitrat- Hexahydrat. Diese Zusätze sind in Mengen bis zu wenigen Gew.-% wirksam. Weitere Katalysatoren sind Metallkomplexe, von denen hier beispielhaft Ferrocen genannt sei, dessen Zusatz bis zu etwa 3 Gew.-% die Umsetzungsgeschwindigkeit deutlich steigert.Compounds which influence the decomposition of peroxides, such as metals or their oxides, for example manganese dioxide, are suitable as catalysts for such a heterogeneously composed mixture. Additions of vanadium pentoxide or cerium dioxide lead to an increase in the reaction rate. With addition of up to 5% by weight of molybdenum (VI) oxide, it is changed only slightly, as well as in the presence of cerium (III) nitrate hexahydrate. These additives are effective in amounts of up to a few% by weight. Further Catalysts are metal complexes, of which ferrocene is mentioned here by way of example, the addition of which increases the reaction rate significantly by up to about 3% by weight.
Die Herstellung der erfindungsgemäß beschriebenen Gassätze erfolgt durch Mischen der Komponenten nach an sich bekannten Verfahren, ggf. unter Herstellung einer ungefährlichen Vormischung, der weitere Komponenten zugefügt werden. Diese Mischung kann bereits in gepulverter Form eingesetzt werden. Entmischung durch unterschiedliche Dichte der Komponenten kann durch Granulieren der Mischung begegnet werden.The gas sets described in accordance with the invention are produced by mixing the components by methods known per se, if appropriate with the preparation of a harmless premix, to which further components are added. This mixture can already be used in powdered form. Demixing due to different density of the components can be countered by granulating the mixture.
In den weitaus häufigsten Anwendungsfällen wird man das Gemisch durch Verpressen oder ähnliche Maßnahmen formen. Zur Vereinfachung dieses Verfahrens können der Mischung Preßhilfen zugesetzt werden. Als solche kommen Graphit, Molybdändisulfid, Teflon, Talkum, Zinkstearat oder Bornitrid in Frage. Diese Mittel wirken bereits in geringsten Mengen und beeinflussen die Eigenschaften und das Abbrandverhalten nicht oder nur geringfügig.In the most common applications, the mixture will be molded by pressing or similar measures. To simplify this process, pressing aids can be added to the mixture. As such, graphite, molybdenum disulfide, Teflon, talc, zinc stearate or boron nitride come into question. These agents work even in the smallest amounts and do not or only slightly influence the properties and the burning behavior.
In manchen Fällen kann es vorteilhaft sein, die Abbrandcharakteristik des Preßlings durch Porositätserzeugung zu beeinflussen. Eine solche Methode besteht darin, vor dem eigentlichen Formvorgang der Mischung Zusätze wie Salze zuzufügen, die durch Extraktion mit Wasser oder Lösungsmitteln nach der Formgebung wieder entfernt werden können. Eine andere Methode besteht in der Zugabe von thermisch wenig widerstandsfähigen Stoffen, die sich beim Ausheizen des Formlings zersetzen. Die Oberfläche des Gemischs kann auch dadurch vergrößert werden, daß der Mischung vor dem Verpressen Mikrohohlkugeln aus Glas oder Kunststoffen zugesetzt werden. Die hierdurch zu erzielende Dichte des Preßlings kann etwa bis zu 20% von der des unbehandelten Preßlings abweichen, wobei dieser Wert nur ein grober Richtwert sein soll und keine Einschränkung bedeutet. Diese Behandlung führt zu einer extremen Beschleunigung des Abbrennvorgangs.In some cases it can be advantageous to influence the burn-up characteristics of the compact by creating porosity. One such method is to add additives such as salts to the mixture before the actual molding process, which can be removed by extraction with water or solvents after the molding. Another method is to add substances which are not very thermally resistant and which decompose when the molding is heated. The surface of the mixture can also be increased by adding hollow microspheres made of glass or plastics to the mixture prior to pressing. The density of the compact to be achieved in this way can deviate by up to 20% from that of the untreated compact, this value being intended only as a rough guide and not a limitation. This treatment leads to an extreme acceleration of the burning process.
Eine weitere Behandlung der Formlinge kann in einer Oberflächenbeschichtung bestehen. Hierbei wird neben der Beeinflussung der Abbrandcharakteristik insbesondere ein Schutz gegen Umwelteinflüsse erreicht. Eine solche Maßnahme kann auch zur Festigkeitssteigerung des Formkörpers angebracht sein. In Extremfällen wäre hier zusätzlich die Verwendung geeigneter Fasern zur Stabilisierung vorzusehen. Ein Nebeneffekt der Beschichtung ist die Verringerung des Abriebs bei der Transportbeanspruchung der Teile.A further treatment of the moldings can consist in a surface coating. In addition to influencing the burning characteristics, protection against environmental influences is achieved in particular. Such a measure can also be used to increase the strength of the molded body. In extreme cases, the use of suitable fibers for stabilization would also have to be provided here. A side effect of the coating is the reduction of the abrasion during the transport stress of the parts.
Die so behandelten Formlinge können in loser Schüttung oder gerichtet in entsprechende druckfeste Behälter eingebracht werden. Sie werden nach üblichen Verfahren mit Hilfe von Anzündsätzen oder thermischen Aufladungen angezündet, wobei die entstehenden Gase ggf. nach Durchströmen eines geeigneten Filters zur Füllung des Lebensrettungssystems in Sekundenbruchteilen führen.The moldings treated in this way can be introduced in bulk or directed into appropriate pressure-resistant containers. They are ignited using conventional methods with the aid of ignition kits or thermal charges, the resulting gases possibly filling the life-saving system in a split second after flowing through a suitable filter.
Die erfindungsgemäßen Treibmittel eignen sich in besonderer Weise für sogenannte Airbags, Prallsäcke, die in Kraftfahrzeugen oder Flugzeugen zum Schutz der Insassen eingesetzt werden. Bei dem Aufprall eines Kraftfahrzeugs muß der Airbag innerhalb kürzester Zeit mit Gasmengen von etwa 50 bis 300 Litern, je nach System und Wagengröße, gefüllt werden. Die erfindungsgemäßen Treibmittel sind auch geeignet für den Einsatz in Gurtstrammern.The propellants according to the invention are particularly suitable for so-called airbags, impact bags, which are used in motor vehicles or aircraft to protect the occupants. In the event of a motor vehicle crash, the airbag must be filled with gas quantities of approximately 50 to 300 liters within a very short time, depending on the system and car size. The propellants according to the invention are also suitable for use in belt tensioners.
Lebensrettungssysteme, die die erfindungsgemäßen Treibmittel enthalten, sind ebenfalls Gegenstand der vorliegenden Erfindung.Life saving systems containing the propellants according to the invention are also the subject of the present invention.
167 g (aus Aminoguanidinsulfat, Natriumnitrit und Salpetersäure dargestelltes) 5-Aminotetrazol (5-ATZ) werden aus ca. 600 ml Wasser unter ständigem Rühren umkristallisiert, nach Filtration bei 110°C getrocknet, gemahlen und mit einem 250 µm Sieb von groben Anteilen abgetrennt (5-ATZ Spezifikation; Schmp./Zers.: > 203°C, mittlere Korngröße 80 µm und H₂O-Anteil < 0,05 %). ZnO₂ wird aus ZnSO₄ x 7H₂O und Wasserstoffperoxid in Ammoniakwasser dargestellt, mit verd. Essigsäure sowie Wasser gewaschen und bei 60°C getrocknet (Spezifikation von ZnO₂: 13,47 Gew.-% akt. Sauerstoff, mittlere Korngröße 10,3 µm).
5-ATZ und ZnO₂, als Komponenten für nicht toxische Gassätze, werden zusammen im Gewichtsverhältnis 1 zu 7 (dies entspricht einem Molverhältnis ca. 1:5) in Plastikbehältern im Taumel-Mischer 1-2 Std. lang homogenisiert. 3,0 g der Probe werden als Schüttgut in einer 25 ml großen Edelstahldruckbombe durch einen elektrisch aufheizbaren Fe-Draht zur Reaktion gebracht und der Druck-Zeitverlauf mittels einer piezoelektrischen Meßeinrichtung aufgenommen. Es entsteht nach ca. 30 ms ein maximaler Gasdruck von etwa 200 bar, der hauptsächlich auf die Bildung von CO₂, N₂, O₂ und H₂O zurückzuführen ist. Die Reaktion hat einen stark exothermem Charakter von ca. 471 cal/g (ca. 1970 J/g). Als Reaktionsrückstand verbleibt ZnO. Der CO-Anteil entspricht der Forderung. Der Verpuffungspunkt liegt bei 219 °C, die Reibempfindlichkeit bei 240 N, die Schlagempfindlichkeit bei 20 J.167 g (from aminoguanidine sulfate, sodium nitrite and nitric acid) 5-aminotetrazole (5-ATZ) are recrystallized from approx. 600 ml of water with constant stirring, after filtration at 110 ° C., ground and separated from coarse fractions with a 250 μm sieve (5-ATZ specification; mp / decomp .:> 203 ° C, average grain size 80 µm and H₂O content <0.05%). ZnO₂ becomes ZnSO₄ x 7H₂O and hydrogen peroxide in ammonia water shown, washed with dil. acetic acid and water and dried at 60 ° C (specification of ZnO₂: 13.47 wt .-% act. oxygen, average grain size 10.3 µm).
5-ATZ and ZnO₂, as components for non-toxic gas sets, are homogenized together in a weight ratio of 1 to 7 (this corresponds to a molar ratio of approx. 1: 5) in plastic containers in a tumble mixer for 1-2 hours. 3.0 g of the sample are reacted as bulk in a 25 ml stainless steel pressure bomb by means of an electrically heatable Fe wire and the pressure-time profile is recorded by means of a piezoelectric measuring device. After about 30 ms, a maximum gas pressure of about 200 bar arises, which is mainly due to the formation of CO₂, N₂, O₂ and H₂O. The reaction has a strongly exothermic character of approx. 471 cal / g (approx. 1970 J / g). ZnO remains as the reaction residue. The CO share corresponds to the requirement. The deflagration point is 219 ° C, the friction sensitivity at 240 N, the impact sensitivity at 20 J.
Die Verwendung von 5-ATZ und ZnO₂ als Komponenten in nicht toxischen Gassätzen entspricht Beispiel 1 unter Verwendung von weiteren Zusätzen. Die folgenden Beispiele 2 bis 24 beschreiben die Umsetzung der in bekannter Weise hergestellten Gemische. Die Ergebnisse sind in den Tabellen 1 bis 4 zusammengefaßt.
Die in den Beispielen 1 bis 24 beschriebenen Gassatzmischungen können auch in gepreßter Form eingesetzt werden. Eine Mischung aus 10 g 5-ATZ (H₂O-Anteil < 0,1 %, Schmelzpunkt (Zers.) > 203°C, Korngröße 200-250 µm), 43,9 g ZnO₂ (12,85 Gew.-% akt. Sauerstoff, Korngröße ca. 14 µm) und 23,5 g NH₄NO₃ (Schmelzpunkt 167 - 169°C, Korngröße 315 - 250 µm), Molverhältnis 1:3:2,5; werden entsprechend Beispiel 1 vermischt und zu Tabletten (Durchmesser = 6 mm, Höhe = 2,77 mm, Dichte = 2,18 g/cm³, Radiale Druckkraft = 155,5 +/- 28,4 N) mit 4 t Preßdruck verpreßt. Das Abbrandverhalten der Preßlinge, entsprechend Beispiel 1 geprüft, ist langsamer als das des Schüttguts und erfordert 0,1 g B/KNO₃ oder Ti/ZnO₂ als Anzündmischung. Die Umsatzgeschwindigkeit steigt mit Senkung des Preßdrucks und fällt mit der Größe des Preßguts. Der Rückstand aus den Umsetzungen bleibt weitgehend in Form der Preßlinge erhalten.The gas set mixtures described in Examples 1 to 24 can also be used in compressed form. A mixture of 10 g 5-ATZ (H₂O content <0.1%, melting point (decomp.)> 203 ° C, grain size 200-250 µm), 43.9 g ZnO₂ (12.85 wt .-% act. Oxygen, particle size approx. 14 µm) and 23.5 g NH₄NO₃ (melting point 167 - 169 ° C, particle size 315 - 250 µm), molar ratio 1: 3: 2.5; are mixed according to Example 1 and pressed into tablets (diameter = 6 mm, height = 2.77 mm, density = 2.18 g / cm³, radial pressure force = 155.5 +/- 28.4 N) with a pressure of 4 t. The burning behavior of the compacts, tested according to Example 1, is slower than that of the bulk material and requires 0.1 g B / KNO₃ or Ti / ZnO₂ as an ignition mixture. The rate of turnover increases with lowering the pressure and falls with the size of the material to be pressed. The residue from the reactions remains largely in the form of the compacts.
Wie in Beispiel 1 beschrieben, wurden weitere Mischungen aus gaserzeugenden Komponenten und Sauerstofflieferanten wie Zinkperoxid mit einem aktiven Sauerstoffanteil von 13,07 Gew.-% und einer mittleren Korngröße von 11,8 µm bzw. im Falle des Natriumnitrats mit einer mittleren Korngröße < 45 µm hergestellt.As described in Example 1, further mixtures of gas-generating components and oxygen suppliers such as zinc peroxide with an active oxygen content of 13.07% by weight and an average grain size of 11.8 μm or, in the case of sodium nitrate, with an average grain size of <45 μm produced.
Die nachfolgende Tabelle 4 enthält weitere Angaben zu den Mischungen.
Die Komponenten wurden in Behältern aus Kunststoff 1/2 h lang mit einem Taumelmischer, 1/2 h mit einem Vibrator und erneut 1/2 h lang mit einem Taumelmischer homogenisiert.
4 g der so homogenisierten Mischung werden wie in Beispiel 1 beschrieben in eine Edelstahldruckbombe eingebracht und unter Verschluß nach Anzündung mit einem Glühdraht zur Umsetzung gebracht. Gemessen wurden
- der entstehende Druck (bar) bis zum Maximalwert
- die Zeit (Millisekunden, ms) bis zum Maximalwert des Druckes
- Der Druckanstiegsgradient (dp/dt) zwischen einem Druck, der 40 bis 60 % vom Maximalwert des Druckes erreicht. Als Maß diente die Anstiegszeit.
4 g of the mixture thus homogenized are introduced into a stainless steel pressure bomb as described in Example 1 and, after being ignited, are reacted with a glow wire to seal them. Were measured
- the resulting pressure (bar) up to the maximum value
- the time (milliseconds, ms) to the maximum value of the pressure
- The pressure rise gradient (dp / dt) between a pressure that reaches 40 to 60% of the maximum value of the pressure. The rise time served as a measure.
Nachfolgende Tabelle 5 zeigt die Werte für den maximalen Druck (bar) und die Zeit in ms bis zum maximalen Druck, die im Bereich derjenigen liegen, wie sie in Beispiel 1 für einen Gassatz aus 5-Aminotetrazol und Zinkperoxid beschrieben werden. Zusätzlich wurde noch die Zeit zwischen 40-60 % des maximalen Druckes bestimmt.
Durch Abstimmung der Parameter und Zumischung weiterer Komponenten lassen sich die für den jeweiligen Gassatz notwendigen Vorgaben einstellen.The parameters required for the respective gas set can be set by coordinating the parameters and adding other components.
Eine weitere Probe der zuvor genannten Mischungen wurde auf physikalische und sicherheitstechnische Eigenschaften untersucht. Die Ergebnisse sind in Tabelle 6 beschrieben.
Die Komponenten sind aufgrund ihrer Mischbarkeit, Verarbeitbarkeit, Verpreßbarkeit zur Formgebung sowie Verträglichkeit untereinander und mit weiteren Zuschlägen sowie ihrer sicherheitstechnischen Kenndaten für die Herstellung von Gassätzen geeignet.The components are suitable for the production of gas sets due to their miscibility, processability, compressibility for shaping and compatibility with one another and with additional additives as well as their safety-related characteristics.
Wie in den Beispielen 26-32 beschrieben, wurden die Mischungen der Beispiele 33 bis 44 aus Zinkperoxid (aktiver Sauerstoffanteil 12,8 Gew.-%, mittlere Korngröße 4,8 µm), Aminotetrazol (mittlere Korngröße ≦ 125 µm), Natriumnitrat (Korngröße ≦ 45 µm) und die aufgelisteten Komponenten mit einer Korngröße ≦ 125 µm hergestellt.As described in Examples 26-32, the mixtures of Examples 33 to 44 were made of zinc peroxide (active oxygen content 12.8% by weight, average particle size 4.8 µm), aminotetrazole (average particle size ≦ 125 µm), sodium nitrate (particle size ≦ 45 µm) and the listed components with a grain size of ≦ 125 µm.
Die Reibempfindlichkeit, gemessen nach der Methode der BAM, war in allen Fällen > 360 N. Die zusätzlich aufgelisteten Komponenten sind in der Literatur beschrieben.The sensitivity to friction, measured according to the BAM method, was> 360 N in all cases. The additionally listed components are described in the literature.
Die nachfolgenden Tabellen 7 und 8 enthalten weitere Angaben zu den Mischungen.
Claims (13)
oder daß sie
und ein Oxidationsmittel aus der Gruppe der Peroxide oder aus der Gruppe der Peroxide zusammen mit Oxidationsmitteln aus der Gruppe der Nitrate enthalten.
or that they
and contain an oxidizing agent from the group of peroxides or from the group of peroxides together with oxidizing agents from the group of nitrates.
oder
R₁ Amino, Hydroxy oder Carboxyl und R₂ oder R₃ Wasserstoff, Methyl oder Phenyl bedeutet.Propellant according to claim 1, characterized in that R₁ and R₂ or R₃ may be the same or different, but either R₂ or R₃ is present and hydrogen, amino, methyl, phenyl, nitrophenyl or aminophenyl
or
R₁ is amino, hydroxy or carboxyl and R₂ or R₃ is hydrogen, methyl or phenyl.
als Cyansäurederivate Natriumcyanat, Cyanursäure, 1-Cyanguanidin, und/oder Dinatriumcyanamid,
als Triazinderivate 1,3,5-Triazin, Cyanursäureester und/oder Cyanursäureamid (Melamin)
und/oder als Harnstoffderivate Biuret, Guanidin, Nitroguanidin, Guanidinnitrat, Aminoguanidin, Aminoguanidinnitrat, Aminoguanidinhydrogencarbonat, Azodicarbonsäurediamid, Dicyandiamidinnitrat, Dicyandiamidinsulfat, Tetrazen und/oder Semicarbazidnitrat enthalten sind.Propellant according to one of claims 1 or 2, characterized in that 5-aminotetrazole, potassium 5-aminotetrazolate and / or bis (aminoguanidine) azotetrazole as derivatives of tetrazole,
as cyanic acid derivatives sodium cyanate, cyanuric acid, 1-cyanguanidine and / or disodium cyanamide,
as triazine derivatives 1,3,5-triazine, cyanuric acid ester and / or cyanuric acid amide (melamine)
and / or as urea derivatives, biuret, guanidine, nitroguanidine, guanidine nitrate, aminoguanidine, aminoguanidine nitrate, aminoguanidine hydrogen carbonate, azodicarboxylic acid diamide, dicyandiamidine nitrate, dicyandiamidine sulfate, tetrazene and / or semicarbazide nitrate are contained.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4120599 | 1991-06-21 | ||
DE4120599 | 1991-06-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0519485A1 true EP0519485A1 (en) | 1992-12-23 |
Family
ID=6434491
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92110353A Withdrawn EP0519485A1 (en) | 1991-06-21 | 1992-06-19 | Propellant for gas generators |
Country Status (4)
Country | Link |
---|---|
US (2) | US20030145923A1 (en) |
EP (1) | EP0519485A1 (en) |
CZ (1) | CZ291570B6 (en) |
DE (1) | DE4220019A1 (en) |
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US6550808B1 (en) | 2000-11-17 | 2003-04-22 | Autoliv Asp. Inc. | Guanylurea nitrate in gas generation |
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WO1998003450A1 (en) * | 1994-12-13 | 1998-01-29 | United Technologies Corporation | Breathable gas generators |
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EP0813512A4 (en) * | 1995-03-03 | 1999-03-17 | Primex Tech Inc | Thermally stable gas generating composition |
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WO1997023434A1 (en) * | 1995-12-23 | 1997-07-03 | Dynamit Nobel Gmbh Explosivstoff- Und Systemtechnik | Priming-explosive-free igniting mixture |
EP0795528A1 (en) * | 1996-03-15 | 1997-09-17 | Morton International, Inc. | Gas generant compositions containing amine nitrates plus basic copper (II) nitrate and/or cobalt(III) triammine trinitrate |
WO1997042142A1 (en) * | 1996-05-02 | 1997-11-13 | Trw Airbag Systems Gmbh & Co. Kg | Gas-generating, azide-free mixture |
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Also Published As
Publication number | Publication date |
---|---|
CZ291570B6 (en) | 2003-04-16 |
US20040226639A1 (en) | 2004-11-18 |
US20030145923A1 (en) | 2003-08-07 |
CZ189792A3 (en) | 1993-01-13 |
DE4220019A1 (en) | 1992-12-24 |
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