EP0722429B1 - Combustible generateur de gaz - Google Patents

Combustible generateur de gaz Download PDF

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Publication number
EP0722429B1
EP0722429B1 EP94928758A EP94928758A EP0722429B1 EP 0722429 B1 EP0722429 B1 EP 0722429B1 EP 94928758 A EP94928758 A EP 94928758A EP 94928758 A EP94928758 A EP 94928758A EP 0722429 B1 EP0722429 B1 EP 0722429B1
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EP
European Patent Office
Prior art keywords
weight
gas generator
component
generator propellant
propellant according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP94928758A
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German (de)
English (en)
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EP0722429A1 (fr
Inventor
Eduard Gast
Peter Semmler
Bernhard Schmid
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Nigu Chemie GmbH
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Nigu Chemie GmbH
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Publication of EP0722429A1 publication Critical patent/EP0722429A1/fr
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Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/06—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires containing gas-producing, chemically-reactive components
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
    • 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
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids

Definitions

  • the invention relates to solid gas generator fuels based on Guanidine compounds on suitable supports.
  • JP H5-254977 is based on gas generator fuels for airbags of triaminoguanidine nitrate (TAGN), which also contains oxidizing agents such as May contain alkali and alkaline earth nitrates, nitrites, chlorates or perchlorates. Molybdenum sulfide can be contained as a further component as a binder.
  • TAGN triaminoguanidine nitrate
  • Molybdenum sulfide can be contained as a further component as a binder.
  • the advantage of using TAGN instead of the known sodium azide is in the non-toxicity and also good stability of TAGN, which is also in Connection with heavy metals, no salts sensitive to friction and impact forms.
  • the rate of combustion of the gas generator fuels is said to vary by Pressing pressure during the production of pellets or tablets from the Component mixture may be possible.
  • the object of the present invention is compared to JP H5-254977 to provide improved gas generator fuels, the Burning behavior can be set in a targeted manner and that is good when burning retain slag and the formation of toxic gases on one Limit the minimum.
  • the gas generator fuels are said to be thermally stable, good ignitable, fast - even at low temperatures - burning and easy to store be and ensure a high gas yield.
  • these should Gas generator fuels reduce the size of the generator housing and thus their weight reduction compared to known with sodium azide enable operated generators.
  • TAGN Carbonates, hydrogen carbonates or nitrates of guanidine, aminoguanidine, diaminoguanidine or triaminoguanidine (TAGN) or mixtures thereof can be used as component (A).
  • TAGN is preferably used.
  • TAGN is practically non-toxic (LD 50 > 3500 mg / kg rat), not hygroscopic, not very water-soluble, thermally stable, burning at low temperature and of low sensitivity to impact and friction.
  • the gas yield from the combustion of TAGN is very high, with a large proportion of nitrogen gas being generated.
  • 1 to 50% by weight of the TAGN can be replaced by nitroguanidine.
  • the cost of component (A) can thus be reduced and favorable combustion behavior can be achieved, since nitroguanidine has a lower combustion rate than TAGN.
  • component (B) alkali metal or alkaline earth metal nitrates, ammonium nitrate and mixtures thereof can be used. Potassium nitrate is preferably used. Potassium nitrate is non-hygroscopic, non-toxic, enables a high gas yield and low burning temperature when burned.
  • Component (A) is in the mixture of (A) and (B) in an amount of about 20 to 55, preferably about 50 to 55% by weight, component (B) in an amount of about 80 to 45, preferably about 50 up to 45% by weight.
  • Component (A) is preferably present in an amount of approximately 50 to 55% by weight and component (B) in an amount of approximately 50 to 45% by weight.
  • component (C) silicon dioxide, alkali metal, alkaline earth metal or aluminosilicates or mixtures thereof are examples of this are Aerosil® 200 and Aerosil® 300, highly disperse silica and diatomaceous earth (Diatomaceous earth).
  • the preferred carrier substance is silica with a pH from about 7.
  • Oxygen-supplying carrier substances such as iron (III) oxide, cobalt oxides, manganese dioxide and copper (II) oxide or mixtures thereof can also be used as component (C).
  • the preferred oxygen-supplying carrier substance is iron (III) oxide.
  • Component (C) is present in an amount of 5 to 45, preferably about 8 to 20% by weight, based on the total amount of components (A) and (B). If iron (III) oxide is used as the oxygen-supplying carrier substance (C), it is present in an amount of about 20 to 40, preferably about 25 to 35,% by weight, based on the total amount of components (A) and (B).
  • Component (C) serves to moderate the burnup, i.e. to adjust the Burning rate At the same time, the slag or Improved melt formation.
  • the slag formation is, for example, at Airbag absolutely necessary.
  • An airbag consists essentially of a gas generator housing that with the gas generator fuel, usually in tablet form, and one Initial igniter (squib) for igniting the gas generator fuel, as well as a Gas bag.
  • Suitable detonators are, for example, in Us-Ps 49 31 111 described.
  • the gas bag which is initially folded into small pieces, is after the initial ignition filled with the gases generated when the gas generator fuel burns and reaches its full volume in a period of about 10-50 ms.
  • the Hot sparks, melts or solids escape from the gas generator in the gas bag must be largely prevented, as it will destroy of the gas bag or injury to vehicle occupants. This is achieved through slag formation.
  • respirable dust-like particles decreased from the gas generator of an airbag could escape.
  • respirable dust particles a diameter of about 6 ⁇ m or less.
  • the oxygen-supplying Carrier substances also suppress the formation of toxic gases such as Carbon monoid when burning.
  • the gas generator fuel may also contain, as component (D), a binder which is soluble in water at room temperature.
  • binders are cellulose compounds or polymers made from one or more polymerizable olefinically unsaturated monomers.
  • cellulose compounds are cellulose ethers, such as carboxymethyl cellulose, methyl cellulose ethers, in particular methyl hydroxyethyl cellulose.
  • a usable methylhydroxyethyl cellulose is CULMINAL (R) MHEC 30000 PR from Firm Aqualon.
  • Suitable binders are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and polycarbonates.
  • Component (D) is based on the total amount of components (A) and (B) in an amount of about 0.1 to 5, preferably about 1.5 to 2.5% by weight in front.
  • the binder (D) serves as a desensitizing agent and as a processing aid in the production of granules or tablets from the gas generator fuel. It also serves to reduce the hydrophilicity and to stabilize the Gas generator fuels.
  • the tablets or pellets used in the gas generators from the Gas generator fuel can be produced by known methods, for example by extrusion, extrusion, in rotary presses or Tableting machines.
  • the size of the pellets or tablets depends on the desired burning time in the respective application.
  • triaminoguanidine nitrate TAGN
  • Nitroguanidine - as well as potassium nitrate and possibly cellulose ether are in possible little water dissolved at 90 ° C and one iron oxide and / or silicon dioxide average grain size of about 1 micron stirred into the solution. After predrying at 60 ° C and 16 hPa with mechanical agitation the mixture is still in crushed wet and then after drying at 60 ° C with a tableting machine for tablets with a diameter of 6 mm and a height of 2 mm pressed.
  • Mix 1 contains no silicon dioxide and Mix 5 contains no iron (III) oxide.
  • Mixture 6 contains neither silicon dioxide nor iron (III) oxide as a comparison mixture.
  • Composition of the mixtures in percent by weight 1 2nd 3rd 4th 5 6 TAGN 39.1 39.1 39.1 29.1 47.3 53.0
  • Nitroguanidine - - - 10.0 - - KNO 3 30.9 30.9 30.9 40.7 47.0 Fe 2 O 3 30.0 20.0 14.0 14.0 - - SiO 2 - 10.0 14.0 14.0 12.0 - Cellulose ether - - 2.0 2.0 - - -
  • Table II shows an overview of the calculated reaction parameters.
  • a high reaction temperature occurs in mixture 5 and especially in mixture 6.
  • Calculated values O 2 balance% + 2.13 + 1.13 - 1.84 - 1.57 + 0.25 + 0.84 Volume ccm 1000 1000 1000 1000 1000 1000 Loading density (g / ccm) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
  • Pressure bar 427 444 470 457 654 810 Temperature K 1973 2116 2116 2116 2468 2666 Mole numbers of the combustion gases Mol / kg 21.1 22.6 23.9 23.4 27.5 28.8 Expl. Heat J / g 3369 3092 2998 2913 3852 4566
  • Table III shows an overview of the reaction products formed during the combustion and their amounts. Reaction products at 298 K, freeze-out temp. 1,500 K. Connection (wt%) 1 2nd 3rd 4th 5 6 CO 2 3,604 10,086 11.538 13,228 12.408 3,768 H 2 O 18.952 18.817 18.828 17.711 22,935 26,692 N 2 27,219 27,219 27.217 26.735 33,383 37,596 CO 0.000 0.134 1,283 1,223 0.000 0.000 H 2 0.000 0.017 0.139 0.109 0.000 0.000 NO 0.001 0.000 0.000 0.009 0.018 O 2 0.001 0.000 0.000 0.000 0.248 0.826 HCN 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 NH 3 0.000 0.000 0.003 0.002 0.000 KOH 0.086 0.000 0.003 0.003 0.053 0.101 K 2 CO 3 21.014 0.000 0.000 0.000 0.150 31.997
  • Table IV shows test results on the sensitivity to decomposition, stability, slag formation and the combustion behavior of the various mixtures.
  • Mixtures 1 to 5 showed good to very good burning behavior, especially with regard to a constant high burning rate.
  • Investigation results mixture 1 2nd 3rd 4th 5 6 Decomposition temp. ° C - 207 178 203 - Measurement conditions: Heating rate 2 ° C / min from 15 ° C below decomposition temp.
  • a trial burn of the mixture 1 was carried out in a normal gas generator housing made of aluminum for a 60 liter airbag, provided with a bore for pressure measurement, in a 60 liter can.
  • the test temperature for test 1 was -35 ° C.
  • the propellant weight was 51.0 g.
  • the propellant consisted of tablets with a diameter of 6 mm and a height of 2 mm.
  • FIG. 1 shows the pressure in the combustion chamber in units of 10 5 Pascals as a function of the time after ignition in milliseconds.
  • the pressure builds up within approx. 1.5 ms and the pressure drop to half the maximum pressure occurs after approx. 27 ms.
  • the maximum pressure is 1.88 * 10 7 Pa, it is reached after 12.3 ms.
  • the test burns of mixture 2 was in a Euro gas generator housing made of aluminum for a 35 liter airbag, provided with a hole for pressure measurement, carried out in a 60 liter jug.
  • the test temperature in test 2 was -35 ° C, in test 3 + 20 ° C.
  • the Propellant weight was 41.0 g in test 2 and 30.0 g in test 3.
  • the Propellant consisted of tablets with a diameter of 6 mm and a height of 2 mm.
  • FIG. 2 shows the pressure in the combustion chamber in units of 10 5 Pascals as a function of the time after ignition in milliseconds.
  • the pressure builds up within approx. 1.5 ms and the pressure drop to half the maximum pressure occurs after approx. 27 ms.
  • the maximum pressure was 1.45 * 10 7 Pa, it was reached after 15.7 ms.
  • FIG. 3 shows the pressure in the combustion chamber in units of 10 5 Pascal as a function of the time after ignition in milliseconds.
  • the pressure builds up within approx. 1.5 ms and the pressure drop to half the maximum pressure occurs after approx. 27 ms.
  • the maximum pressure was 1.33 * 10 7 Pa, it was reached after 7.5 ms.
  • the gas generator fuel according to the invention consists of non-toxic, light producible and inexpensive components, their processing is unproblematic. Their thermal stability ensures good shelf life. In spite of at low combustion temperatures, the ignitability of the mixtures is good. she burn quickly and deliver large gas yields with very low CO and NO contents.
  • the mixtures according to the invention are therefore for use as Gas generating agent in the various airbag systems, as an extinguishing agent or blowing agent particularly suitable.
  • the gas generator fuels are also good recyclable.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Air Bags (AREA)
  • Percussion Or Vibration Massage (AREA)
  • Sampling And Sample Adjustment (AREA)
  • Gas Separation By Absorption (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Medicinal Preparation (AREA)
  • Fats And Perfumes (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)

Claims (12)

  1. Combustible générateur de gaz, comprenant:
    (A) au moins un carbonate, hydrogénocarbonate ou nitrate de guanidine, d'aminoguanidine, de diaminoguanidine ou de triaminoguanidine en une quantité d'environ 20 à 55% en poids, par rapport à la quantité totale de composants (A) et (B),
    (B) au moins un nitrate de métal alcalin ou de métal alcalino-terreux ou nitrate d'ammonium comme agent oxydant en une quantité d'environ 80 à 45% en poids, par rapport à la quantité totale des composants (A) et (B), et
    pour ralentir la combustion et améliorer la production de scories, en une quantité de 5 à 45% en poids, par rapport à la quantité totale des composants (A) et (B),
    (C1) au moins une substance support choisie parmi le dioxyde de silicium, les silicates de métal alcalin, les silicates de métal alcalino-terreux ou les aluminosilicates et/ou
    (C2) au moins une substance support apporteuse d'oxygène choisie parmi l'oxyde de fer(III), les oxydes de cobalt, le dioxyde de manganèse et l'oxyde de cuivre(II).
  2. Combustible générateur de gaz selon la revendication 1, dans lequel le composant (A) est présent en une quantité de 50 à 55% en poids, le composant (B) en une quantité de 50 à 45% en poids et les composants (C1) et/ou (C2), par rapport à la quantité totale des composants (A) et (B), en une quantité de 8 à 20% en poids.
  3. Combustible générateur de gaz selon la revendication 1 ou 2, dans lequel le composant (A) est du nitrate de triaminoguanidine.
  4. Combustible générateur de gaz selon l'une quelconque des revendications 1 à 3, dans lequel le composant (B) est du nitrate de potassium.
  5. Combustible générateur de gaz selon l'une quelconque des revendications 1 à 4, dans lequel le composant (C1) est de l'acide silicique hautement dispersé.
  6. Combustible générateur de gaz selon l'une quelconque des revendications 1 à 5, dans lequel le composant (A) est composé de 99 à 50% en poids de nitrate de triaminoguanidine et de 1 à 50% en poids de nitroguanidine, par rapport à la quantité totale de composé (A).
  7. Combustible générateur de gaz selon l'une quelconque des revendications 1 à 6, dans lequel le composant (C2) est de l'oxyde de fer(III).
  8. Combustible générateur de gaz selon la revendication 7, dans lequel l'oxyde de fer(III) est présent en une quantité de 20 à 40% en poids, de préférence de 25 à 35% en poids, par rapport à la quantité totale des composants (A) et (B).
  9. Combustible générateur de gaz selon l'une quelconque des revendications 1 à 8, comprenant en outre (D) un liant qui est soluble dans l'eau à température ambiante.
  10. Combustible générateur de gaz selon la revendication 9, dans lequel le liant est de l'éther de cellulose tel que de la carboxyméthylcellulose, de la méthylcellulose et de préférence de la méthylhydroxyéthylcellulose, ou un polymère d'un ou plusieurs monomères à insaturation oléfinique polymérisables.
  11. Combustible générateur de gaz selon la revendication 9 ou 10, dans lequel le liant est présent en une quantité de 0,1 à 5% en poids, de préférence de 1,5 à 2,5% en poids, par rapport à la quantité totale des composants (A) et (B).
  12. Utilisation du combustible générateur de gaz selon l'une quelconque des revendications 1 à 11 comme agent générateur de gaz dans des airbags, comme agent d'extinction ou comme agent propulseur.
EP94928758A 1993-10-06 1994-10-06 Combustible generateur de gaz Expired - Lifetime EP0722429B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4334099 1993-10-06
DE4334099 1993-10-06
PCT/DE1994/001184 WO1995009825A1 (fr) 1993-10-06 1994-10-06 Combustible generateur de gaz

Publications (2)

Publication Number Publication Date
EP0722429A1 EP0722429A1 (fr) 1996-07-24
EP0722429B1 true EP0722429B1 (fr) 1999-03-31

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EP94928758A Expired - Lifetime EP0722429B1 (fr) 1993-10-06 1994-10-06 Combustible generateur de gaz

Country Status (15)

Country Link
EP (1) EP0722429B1 (fr)
JP (1) JPH09503195A (fr)
CN (1) CN1132501A (fr)
AT (1) ATE178304T1 (fr)
AU (1) AU687895B2 (fr)
BR (1) BR9407761A (fr)
CA (1) CA2172822A1 (fr)
CZ (1) CZ88796A3 (fr)
DE (2) DE59408048D1 (fr)
ES (1) ES2130448T3 (fr)
HU (1) HUT76867A (fr)
PL (1) PL175606B1 (fr)
RU (1) RU2117649C1 (fr)
SK (1) SK45596A3 (fr)
WO (1) WO1995009825A1 (fr)

Cited By (1)

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Publication number Priority date Publication date Assignee Title
US6454887B1 (en) 1996-07-22 2002-09-24 Daicel Chemical Industries, Ltd. Gas generant for air bag

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CN100395219C (zh) * 2006-04-29 2008-06-18 松原市大和化工有限责任公司 混敏硝铵炸药
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EP2526077B1 (fr) * 2010-01-19 2018-03-14 Clearspark, LLC Procédé pour la fabrication d'une composition pyrotechnique
CN104998367A (zh) * 2014-04-17 2015-10-28 北京众慧诚科技有限公司 一种燃烧型灭火组合物
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DE9416112U1 (de) 1994-12-15
WO1995009825A1 (fr) 1995-04-13
DE59408048D1 (de) 1999-05-06
PL175606B1 (pl) 1999-01-29
SK45596A3 (en) 1997-01-08
ATE178304T1 (de) 1999-04-15
AU7806694A (en) 1995-05-01
BR9407761A (pt) 1997-03-04
HU9600744D0 (en) 1996-05-28
RU2117649C1 (ru) 1998-08-20
CN1132501A (zh) 1996-10-02
HUT76867A (en) 1997-12-29
CZ88796A3 (en) 1996-08-14
AU687895B2 (en) 1998-03-05
JPH09503195A (ja) 1997-03-31
EP0722429A1 (fr) 1996-07-24
ES2130448T3 (es) 1999-07-01
CA2172822A1 (fr) 1995-04-13
PL313943A1 (en) 1996-08-05

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