EP1069096B1 - Composition génératrice de gaz exempt d'azoture - Google Patents

Composition génératrice de gaz exempt d'azoture Download PDF

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Publication number
EP1069096B1
EP1069096B1 EP00113004A EP00113004A EP1069096B1 EP 1069096 B1 EP1069096 B1 EP 1069096B1 EP 00113004 A EP00113004 A EP 00113004A EP 00113004 A EP00113004 A EP 00113004A EP 1069096 B1 EP1069096 B1 EP 1069096B1
Authority
EP
European Patent Office
Prior art keywords
weight
acid
nitrate
composition
set forth
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP00113004A
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German (de)
English (en)
Other versions
EP1069096A1 (fr
Inventor
Siegfried Zeuner
Achim Hofmann
Roland Schropp
Karl-Heinz Rödig
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ZF Airbag Germany GmbH
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TRW Airbag Systems GmbH
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Publication date
Application filed by TRW Airbag Systems GmbH filed Critical TRW Airbag Systems GmbH
Publication of EP1069096A1 publication Critical patent/EP1069096A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/02—Compositions characterised by non-explosive or non-thermic constituents for neutralising poisonous gases from explosives produced during blasting
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids

Definitions

  • the present invention relates to an azide-free gas-generating Composition consisting essentially of at least one organic Fuel, at least one inorganic oxidizer and iron oxide consists.
  • the composition is particularly suitable for use in Gas generators for vehicle occupant restraint systems.
  • Generic gas generating compositions are for example DE 94 16 112 U1 known.
  • This document shows a solid gas generator fuel with at least one organic fuel, at least one inorganic oxidizer and at least one carrier substance and / or at least an oxygen-providing carrier, wherein the oxygen carrier Vehicle can be iron (III) oxide.
  • the oxygen carrier Vehicle can be iron (III) oxide.
  • Gas generating compositions of this type are also known from DE-C2-4411654.
  • the gas-generating mixture described therein consists of 20 to 50 wt .-% of a nitrogen-rich organic compound having a nitrogen content of at least 40 wt .-%, 20 to 70 wt .-% of an inorganic oxidizer, 0 to 40 wt .-% of a transition metal oxide and 0.1 to 20 wt .-% zeolite.
  • Iron oxide with an average particle size of less than 1 ⁇ m and a specific surface area of more than 8 m 2 / g according to BET is mentioned in particular as transition metal oxide.
  • the zeolite addition is intended to bring about a reduction of the carbon monoxide and nitrogen oxide content in the gas mixture resulting from the burning off of the gas-generating composition.
  • an azide-free gas generating mixture for use in gas generators for vehicle occupant restraint systems which consists essentially of at least one organic fuel, at least one inorganic oxidizer and iron oxide and which is characterized in that the iron oxide is brown, ferromagnetic ⁇ -Fe 2 O 3 , and the organic fuel is selected from the group consisting of the nitrogen-rich tetrazole, triazole and guanidine compounds and mixtures thereof, or from the group consisting of the nitrogen-containing heterocyclic organic acids and mixtures thereof.
  • Iron oxide exists in various modifications; For example, a distinction is made between red ⁇ -Fe 2 O 3 (hematite), brown ⁇ -Fe 2 O 3 (maghemite), black Fe 3 O 4 (magnetite), yellow ⁇ -FeOOH (goethite) and yellow ⁇ -FeOOH (lepidocrocite). which can be both natural and synthetic.
  • the preferred iron oxide according to the invention is synthetically produced, brown, ferromagnetic iron oxide ( ⁇ -Fe 2 O 3 , maghemite).
  • the iron oxide particularly preferably has an average particle size of ⁇ 1 ⁇ m and a specific surface area of ⁇ 10 m 2 / g.
  • the core idea of the invention is the use of brown ⁇ -iron oxide instead of the commonly used red iron oxide ( ⁇ -Fe 2 O 3 , hematite) or other iron oxides.
  • ⁇ -iron oxide as a special modification of the available iron oxides, a significant reduction of the noxious gas content, in particular the proportion of nitrogen oxides, can be achieved.
  • the principle underlying the present invention of the exchange of red iron oxide for brown ⁇ -iron oxide is particularly useful for compositions containing iron oxide as an active ingredient anyway.
  • the invention is not limited to such gas-generating compositions, but mutatis mutandis applicable to all acid-free gas-generating mixtures.
  • Fe 3 O 4 is disadvantageous because of its lower oxidation equivalence, since larger amounts of iron oxide are needed to oxidize equal amounts of fuel. This is undesirable because of the associated deterioration in gas yield.
  • the use of FeOOH is not preferred because of the high proportion of bound water, since this water evaporates on burning of the gas-generating mixture and the burning rate is thereby reduced too much.
  • Experiments have also shown that when using Fe 3 O 4 or FeOOH, the reduction of the nitrogen oxide in the gas mixture does not occur to the same extent as in the use of ⁇ -Fe 2 O 3 .
  • the proportion of ⁇ -Fe 2 O 3 in the gas-generating composition of the present invention is preferably 2 to 50% by weight, more preferably about 10 to 40% by weight.
  • Tetrazole Triazole or guanidine compounds and mixtures thereof used.
  • these compounds are 5-aminotetrazole, 1H-tetrazole, Bistetrazole, azotetrazole, triazolone, nitrotriazolone, Guanidine carbonate, guanidine nitrate, guanidine perchlorate, aminoguanidine nitrate, Guanidine perchlorate, diaminoguanidine nitrate, triaminoguanidine nitrate, Nitroguanidine and its salts, derivatives or mixtures thereof.
  • the organic fuel may further be made from nitrogen-containing heterocyclic organic acids and mixtures thereof be selected from the existing group.
  • nitrogenous heterocyclic organic acids are cyanuric acid, Isocyanuric acid, cyamelide, uracol, uracil, uramine, uracin, alloxan, Alloxanoic acid, alloxantine, xanthine, allantoin, barbituric acid, orotic acid, Dilituric acid, triazolone, violuric acid, succinimide, dialuric acid, Isodialuric acid, hydantoin, pseudohydantoin, imidazolone, pyrazolone, Parabanic acid, furazan, ammeline, creatinine, maleic hydrazide, Uric acid, pseudo-uric acid, guanazine, guanazole, melamine, their salts, Derivatives or mixtures thereof.
  • the inorganic gas contained in the gas generating composition Oxidator is preferably from the of the alkali and / or alkaline earth metal nitrates; chlorates, perchlorates and peroxides, and Ammonium nitrate or perchlorate, copper oxide or basic copper nitrate existing group selected. It can also be mixtures of the aforementioned oxidizers are used.
  • the gas generating composition can still the commonly used processing aids, such as Freeze aids, pressing aids and / or lubricants.
  • the processing aids are preferred in a proportion of up to 5 wt .-%, based on the total composition used.
  • An inventively particularly preferred gas-generating composition consists essentially of 15 to 55 wt .-% 5-aminotetrazole, 25 to 65 wt .-% potassium nitrate and 20 to 60 wt .-% ⁇ -Fe 2 O 3 .
  • potassium nitrate instead of potassium nitrate as an inorganic oxidizer, sodium nitrate can also be used.
  • composition according to the invention consists essentially of 30 to 50 wt .-% guanidine nitrate. 15 to 35% by weight of basic copper nitrate, 10 to 25% by weight of copper oxide, 1 to 10% by weight of ammonium perchlorate, 1 to 10% by weight of sodium nitrate and 2 to 20% by weight of ⁇ -Fe 2 O 3 ,
  • test results show that only the replacement of the red ⁇ -iron oxide by brown ⁇ -iron oxide, a reduction of the nitrogen oxide content effected in the released gas mixture.
  • the carbon monoxide content remains almost unaffected.
  • a comparable effect occurs when a conventional gas generating composition, brown ⁇ -iron oxide is added.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Air Bags (AREA)

Claims (10)

  1. Composition exempte d'azide engendrant du gaz, pour être utilisée dans des générateurs de gaz pour systèmes de retenue de passager de véhicule, constituée essentiellement d'au moins un combustible organique, d'au moins un oxydant inorganique ou un oxyde de fer, caractérisée en ce que l'oxyde de fer est du γ-Fe2O3 ferromagnétique brun et le combustible organique est choisi parmi le groupe constitué des composés azotées de tétrazole, de triazole et de guanidine ainsi que de leurs mélanges ou du groupe constitué des acides organiques hétérocycicliques azotées ainsi que de leurs mélanges.
  2. Composition selon la revendication 1, caractérisée en ce que le γ-Fe2O3 présente une taille de particules moyenne de ≤ 1µm et une surface spécifique de ≥ 10 m2/g.
  3. Composition selon la revendication 1 ou 2, caractérisée en ce que l'oxydant inorganique est choisi parmi le groupe constitué des nitrates alcalins et/ou alcalinoterreux, des chlorates alcalins et/ou alcalinoterreux, des perchlorates alcalins et/ou alcalinoterreux et des peroxydes alcalins et/ou alcalinoterreux, du nitrate d'ammonium ou du perchlorate d'ammonium ainsi que de l'oxyde de cuivre ou du nitrate de cuivre basique ou de leurs mélanges.
  4. Composition selon l'une des revendications 1 à 3, caractérisée en ce que les composés de tétrazole, de triazole et de guanidine sont choisis parmi le groupe constitué de 5-aminotétrazole, de 1H-tétrazole, de bistétrazole, de azotétrazole, de triazolone, de nitrotriazolone, de carbonate de guanidine, de nitrate de guanidine, de perchlorate de guanidine, de nitrate d'aminoguanidine, de nitrate de diaminoguanidine, de nitrate de triaminoguanidine, de nitroguanidine ou de leurs sels ou dérivés ainsi que de leurs mélanges.
  5. Composition selon l'une des revendications 1 à 3, caractérisée en ce que les acides organiques hétérocycliques azotés sont choisis parmi le groupe constitué d'acide cyanurique, d'acide isocyanurique, de cyamélide, d'urazol, d'uracile, d'uramine, d'urazine, d'alloxane, d'acide d'alloxane, d'alloxantine, de xanthine, d'allantoïne, d'acide barbiturique, d'acide orotique, d'acide diliturique, de triazolone, d'acide violurique, de succinimide, d'acide dialurique, d'acide isodialurique, d'hydantoïne, de pseudohydantoïne, d'imidazolone, de pyrazolone, d'acide parabanique, de furazane, d'ammeline, de créatinine, d'hydrazide d'acide maléique, d'acide urique, d'acide pseudo-urique, de guanazine, de guanazole, de mélamine, de leurs sels et dérivés ainsi que de leurs mélanges
  6. Composition selon l'une des revendications 1 à 5, caractérisée en ce que le mélange contient additionnellement jusqu'à 5 % en poids de produits auxiliaires.
  7. Composition selon la revendication 1, constituée essentiellement de 15 à 55 % en poids de 5-aminotétrazole, de 25 à 65 % en poids de nitrate de potassium et de 20 à 60 % en poids de γ-Fe2O3.
  8. Composition selon la revendication 1, constituée essentiellement de 15 à 55 % en poids de 5-aminotétrazole, de 25 à 65 % en poids de nitrate de sodium et de 20 à 60 % en poids de γ-Fe2O3.
  9. Composition selon la revendication 1, constituée essentiellement de 30 à 50 % en poids de nitrate de guanidine, de 15 à 35 % en poids de nitrate de cuivre basique, de 10 à 25 % en poids d'oxyde de cuivre, de 1 à 10 % en poids de perchlorate d'ammonium, 1 à 10 % en poids de nitrate de sodium et de 2 à 20 % en poids de γ-Fe2O3.
  10. Utilisation de γ-Fe2O3 pour fabriquer une composition exempte d'azide engendrant du gaz selon l'une des revendications 1 à 9.
EP00113004A 1999-07-12 2000-06-20 Composition génératrice de gaz exempt d'azoture Expired - Lifetime EP1069096B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19932466 1999-07-12
DE19932466A DE19932466A1 (de) 1999-07-12 1999-07-12 Azidfreie gaserzeugende Zusammensetzung

Publications (2)

Publication Number Publication Date
EP1069096A1 EP1069096A1 (fr) 2001-01-17
EP1069096B1 true EP1069096B1 (fr) 2005-05-11

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Family Applications (1)

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EP00113004A Expired - Lifetime EP1069096B1 (fr) 1999-07-12 2000-06-20 Composition génératrice de gaz exempt d'azoture

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EP (1) EP1069096B1 (fr)
DE (2) DE19932466A1 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4500399B2 (ja) * 2000-02-04 2010-07-14 ダイセル化学工業株式会社 トリアジン誘導体を含むガス発生剤組成物
DE10064285C1 (de) * 2000-12-22 2002-10-17 Nigu Chemie Gmbh Gasgeneratortreibstoff-Zusammensetzung und deren Verwendung
DE10230402B4 (de) * 2002-07-05 2007-01-11 Trw Airbag Systems Gmbh & Co. Kg Verfahren zur Herstellung einer gaserzeugenden Zusammensetzung
US20040094250A1 (en) * 2002-11-14 2004-05-20 Estes-Cox Corporation Composite propellant compositions
US20060289096A1 (en) * 2003-07-25 2006-12-28 Mendenhall Ivan V Extrudable gas generant
US20050016646A1 (en) * 2003-07-25 2005-01-27 Barnes Michael W. Chlorine-containing gas generant compositions including a copper-containing chlorine scavenger
JP4767487B2 (ja) * 2003-10-20 2011-09-07 ダイセル化学工業株式会社 ガス発生剤組成物
FR2871457B1 (fr) * 2004-06-10 2006-08-11 Giat Ind Sa Composition pyrotechnique ayant une tenue mecanique amelioree
CN100455553C (zh) * 2004-10-08 2009-01-28 彼得里-蒂恩充气系统两合公司 作为可热引发的引燃混合物的物质混合物
DE102004062168A1 (de) * 2004-10-08 2006-04-13 Petri-Dn Gmbh Inflator Systems Stoffgemisch als thermisch initiierbare Anzündmischung
FR2950624B1 (fr) * 2009-09-25 2013-05-10 Snpe Materiaux Energetiques Compose pyrotechnique generateur de gaz
JP6970190B2 (ja) 2016-05-23 2021-11-24 ジョイソン セーフティー システムズ アクウィジション エルエルシー ガス発生組成物ならびにそれらの製造方法及び使用方法
CN106810410B (zh) * 2016-12-30 2019-10-29 北京理工大学 一种烟火型气体发生剂组合物及其制备方法

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US3074830A (en) * 1960-01-05 1963-01-22 Cecil A Rassier Combustion mixtures containing guanidine nitrate
US3214308A (en) * 1962-12-13 1965-10-26 Thiokol Chemical Corp Thermally stable propellant powders containing powdered polymeric materials and perchlorates
US3617586A (en) * 1963-12-30 1971-11-02 John M Lenoir Burning rate accelerating method
JPS526388A (en) * 1975-07-07 1977-01-18 Matsushita Electric Ind Co Ltd Production process of catalyst for purification of waste gas of combus tion
US4214438A (en) * 1978-02-03 1980-07-29 Allied Chemical Corporation Pyrotechnic composition and method of inflating an inflatable device
EP0543026A4 (en) * 1991-05-28 1995-03-29 Daicel Chem Gas generating agent
US5382050A (en) * 1993-04-08 1995-01-17 Trw Inc. Gas generator for vehicle occupant restraint
CN1132501A (zh) * 1993-10-06 1996-10-02 尼古化学股份公司 气体发生器的推进剂
US5817972A (en) * 1995-11-13 1998-10-06 Trw Inc. Iron oxide as a coolant and residue former in an organic propellant
JP3247929B2 (ja) * 1995-11-14 2002-01-21 ダイセル化学工業株式会社 ガス発生剤組成物

Also Published As

Publication number Publication date
DE19932466A1 (de) 2001-01-18
DE50010265D1 (de) 2005-06-16
EP1069096A1 (fr) 2001-01-17

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