WO2000040523A1 - Matiere liberant du gaz pour dispositifs de securite actionnes par gaz pour automobiles - Google Patents

Matiere liberant du gaz pour dispositifs de securite actionnes par gaz pour automobiles Download PDF

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Publication number
WO2000040523A1
WO2000040523A1 PCT/SE1999/002496 SE9902496W WO0040523A1 WO 2000040523 A1 WO2000040523 A1 WO 2000040523A1 SE 9902496 W SE9902496 W SE 9902496W WO 0040523 A1 WO0040523 A1 WO 0040523A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas
dinitramide
car safety
safety devices
guanidine
Prior art date
Application number
PCT/SE1999/002496
Other languages
English (en)
Inventor
Per Sjöberg
Original Assignee
Nexplo Bofors Ab
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nexplo Bofors Ab filed Critical Nexplo Bofors Ab
Priority to AT99965701T priority Critical patent/ATE237567T1/de
Priority to EP99965701A priority patent/EP1171403B1/fr
Priority to DE69907036T priority patent/DE69907036T2/de
Publication of WO2000040523A1 publication Critical patent/WO2000040523A1/fr

Links

Classifications

    • 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
    • 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

  • pyrotechnical gas-generating substances used in air-bag assemblies are to fill the fabric pouch of the air bag with a gas quickly, in order to provide a flexible protecting medium between the passenger and the equipment in the car.
  • the pyrotechnical gas-generating substances and the gas formed by them must meet a number of requirements in order to ensure the that the air-bag assembly works and is reliable, and that the environment is not harmed.
  • the same requirements are also placed on the pyrotechnical gas-generating substances used in other gas-actuated safety devices in cars, such as safety- belt tighteners, inflatable neck supports, etc.
  • the gas formed in all such car safety devices should not contain any hot solid particles that could burn through the main part of the system and set fire to the gas-filled fabric pouch and injure the passengers or jeopardize the entire operation of the safety device.
  • Sodium azide the most commonly used pyrotechnical gas-generating substance for this purpose nowadays, does not fully meet this requirement and must therefore be employed with specially reinforced fabric pouches to stop the movement of the solid particles formed in the combustion of sodium azide.
  • the need for this extra reinforcement means that such a safety device is larger and weighs more than strictly needed for its operation.
  • the environmental requirements placed on the pyrotechnical gas-generating substances used for the purpose in question stipulate that these substances must not form gaseous mixtures that contain poisonous gases in an amount that is harmful to health.
  • the poisonous gases that are mainly relevant in this context because they are formed in the combustion of the gas-generating substances are nitrous compounds, NO x and carbon monoxide. If the gas-generating substance contains chlorine, hydrochloric acid is also formed.
  • the pyrotechnical gas-generating substances used in a gas-actuated car safety device must have a high efficiency, i.e. they should form a large amount of gas per unit weight or volume of the gas-generating substance.
  • the efficiency of sodium azide is not particularly high, since it only forms gas in an amount of about 40% of the solid substance. This low efficiency makes it difficult to meet the car manufacturers' requirement of car safety devices with a low weight and a small size when sodium azide is employed as a gas-generating substance.
  • a further requirement placed on the said pyrotechnical gas-generating substances is that they should all be thermally stable in the sense that they should not be affected much by the high temperatures that can occur in the dashboard in countries with a warm climate.
  • Nitrocellulose is an example of a substance that does not meet this requirement, but which would otherwise be suitable, and in fact it is used nowadays for this purpose, although it limits the service life of the said car safety devices.
  • the product used in car safety devices as a pyrotechnical gas- generating substance must also meet several requirements concerning its combustion characteristics if a fully satisfactory operation is to be ensured.
  • the ideal pyrotechnical gas-generating substance in this connection should have a high rate of burning and one that does not vary much with the pressure or the temperature.
  • Sodium azide is an ideal substance from this point of view, but it has several disadvantages, as mentioned above.
  • nitramine-based gunpowder compositions such as RDX, which are used e.g. in a mixture with cellulose acetyl butyrate .
  • RDX nitramine-based gunpowder compositions
  • the disadvantage of nitramine-based gunpowders is that their rate of burning depends on the pressure to a large extent. If the pressure to too low, the burning is completely extinguished, while if the pressure is too high, the combustion has an explosive course.
  • US Patent No. 5,695,216 these disadvantages can be corrected by constructing a powerful container for the gas-forming substance and to equip the container with decompression means. However, even if this functions - and functions well, the construction still requires extra parts and costs more.
  • the present invention relates to the use of a pyrotechnical gas-generating substance that is completely new in the application under consideration, namely guanidine dinitramide, which has the following chemical formula and which can be easily prepared from guanidine and ammonium dinitramide.
  • a pyrotechnical gas-generating substance that is completely new in the application under consideration, namely guanidine dinitramide, which has the following chemical formula and which can be easily prepared from guanidine and ammonium dinitramide.
  • guanidine dinitramide can be advantageously used as a pyrotechnical gas- generating substance in gas-actuated car safety devices such as air bags, safety-belt tighteners, inflatable neck supports, etc.
  • the guanidine dinitramide is employed either in the pure form or in a mixture with other gas-releasing or oxygen-releasing substances, such as for example guanyl urea dinitramide, which can modify the burning rate and the rate of gas evolution of the main substance according to each special requirement .
  • the present invention also relates to the mixing of guanidine dinitramide with other substances in order to obtain a mixture whose burning characteristics are optimal for the application in question.
  • guanidine dinitramide and of mixtures in which it features as the main component are that these substances contain both oxidizers and a fuel. They are therefore in principle of the type of single-component gunpowder, which does not need any other substance for combustion or has access to atmospheric oxygen.
  • guanidine dinitramide burns very fast even at a low pressure, and its combustion is not very pressure-dependent, the pressure exponent being about 0.75. At atmospheric pressure, guanidine dinitramide burns faster than nitrocellulose and almost as fast as sodium azide. A significant advantage over sodium azide is, furthermore, that guanidine dinitramide does not form any solid combustion products but is instead fully converted into gases on combustion. This means in turn that, when guanidine dinitramide is used as the gas-generating substance in air-bag assemblies, no extra reinforcement is needed for the gas pouches in order to prevent the substance from burning through them. This fact enables the designers of such car safety devices to reduce the weight and size of the latter without jeopardizing their operation.
  • guanidine dinitramide only contains one carbon atom, so that advantageously little carbon monoxide is formed in its combustion.
  • guanidine dinitramide has an ideal thermal stability, with a melting point in excess of 130°C and a decomposition temperature of over 160°C,
  • the rate of burning of guanidine dinitramide and therefore of course the rate of gas-formation, can be modified by admixing other gas-generating or oxygen-releasing substances to it.
  • a specially suitable additive that can be used in this connection is guanyl urea dinitramide, which has the following chemical formula. O N-H
  • Guanyl urea dinitramide is relatively easy to prepare from guanyl urea by reacting it with ammonium dinitramide. Pure guanyl urea dinitramide burns much less fast than guanidine dinitramide, so that it is not all that suitable for use by itself as a gas-generating substance in car safety devices, at least in certain applications. Furthermore, guanyl urea dinitramide contains an additional carbon atom, so that its combustion gases contain too much carbon monoxide when this compound is used as the main gas-generating substance.
  • Both guanidine dinitramide and guanyl urea dinitramide can be pressed into tablets with a good mechanical strength whether they are used singly or in mixtures with each other. This means that both pure guanidine dinitramide and its mixtures with guanyl urea dinitramide are suitable for use in most applications in the form of pressed tablets. If required, a small amount - preferably not more than 10 wt-% - of a binder may be added to confer an even better mechanical strength on the pressed tablets.
  • the substances according to the invention have the further advantage that, when they finish their service life as potential gas-generating substances in a car safety device, which hopefully has not seen active use, they can be simply recovered for re-use as gas- generating substances in a similar or a different product .
  • guanidine dinitramide and guanyl urea dinitramide are uniform and stable products that can furthermore be easily recrystallized. If, despite everything, they undergo decomposition to some extent, they can still be recycled after recrystallization.
  • Guanidine dinitramide itself is moderately soluble in water at room temperature and is not hygroscopic, whereas guanyl urea dinitramide is fairly insoluble in cold water but moderately soluble in warm water. Both compounds can therefore be recrystallized from water at a low temperature. This is a particularly simple and cheap process, which should make it possible to recover and re-use the gas-generating substances from scrapped but non-deployed air-bag assemblies and similar other pyrotechnically actuated car safety devices.
  • This diagram was constructed on the basis of experimental values obtained as follows. In the case of each mixture, the same amount of sample in the form of pressed tablets was combusted in a hermetically sealed combustion bomb, together with a standard amount of auxiliary gunpowder used as an aid and a pressure- raising additive. The pressure inside the combustion bomb was measured with a manometer, and the rate of burning was determined from the curves obtained for the change in pressure. The experimental values obtained were used to construct the curves shown in the diagram.
  • the letters A and B in this diagram refer to guanyl urea dinitramide and guanidine dinitramide, respectively, and the amounts of both are given in the diagram.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Air Bags (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)

Abstract

Cette invention concerne un procédé de préparation de compositions pyrotechniques à décharge de gaz qui sont destinées principalement à des dispositifs de sécurité actionnés par gaz employés dans des automobiles (coussins d'air, tendeurs pour ceintures de sécurité, appuie-nuque gonflables, notamment) et qui peuvent être récupérés s'ils ne sont pas activement utilisés. L'invention concerne également ces compositions proprement dites. Cette invention se caractérise essentiellement en ce qu'elle fait appel à du guanidine dinitramide, éventuellement combiné à du guanyl urée dinitramide comme agent libérant du gaz pour les produits susmentionnés.
PCT/SE1999/002496 1998-12-30 1999-12-29 Matiere liberant du gaz pour dispositifs de securite actionnes par gaz pour automobiles WO2000040523A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AT99965701T ATE237567T1 (de) 1998-12-30 1999-12-29 Gaserzeugendes material für gasausgelöste sicherheitsvorrichtungen in autos
EP99965701A EP1171403B1 (fr) 1998-12-30 1999-12-29 Matiere liberant du gaz pour dispositifs de securite actionnes par gaz pour automobiles
DE69907036T DE69907036T2 (de) 1998-12-30 1999-12-29 Gaserzeugendes material für gasausgelöste sicherheitsvorrichtungen in autos

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE9804611-3 1998-12-30
SE9804611A SE513315C2 (sv) 1998-12-30 1998-12-30 Sätt att framställa gasbildare för gasdrivna bilsäkerhetsdetaljer och pyrotekiska gasbildare framställd i enlighet med sättet

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US86965001A A-371-Of-International 1998-12-30 2001-10-15
US10/772,246 Division US20040154711A1 (en) 1998-12-30 2004-02-06 Gas-generating material for gas-actuated car safety devices

Publications (1)

Publication Number Publication Date
WO2000040523A1 true WO2000040523A1 (fr) 2000-07-13

Family

ID=20413919

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SE1999/002496 WO2000040523A1 (fr) 1998-12-30 1999-12-29 Matiere liberant du gaz pour dispositifs de securite actionnes par gaz pour automobiles

Country Status (6)

Country Link
EP (1) EP1171403B1 (fr)
AT (1) ATE237567T1 (fr)
DE (1) DE69907036T2 (fr)
ES (1) ES2197707T3 (fr)
SE (1) SE513315C2 (fr)
WO (1) WO2000040523A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003037859A2 (fr) * 2001-10-31 2003-05-08 Arc Automotive, Inc. Compositions gazogenes contenant du guanidine dinitramide et dispositifs gonflables dans lesquels elles sont utilisees
US6599380B2 (en) 2000-06-07 2003-07-29 Trw Airbag Systems Gmbh & Co. Kg Guanidine-thermite igniter composition for use in gas generators
US6764562B1 (en) 1999-05-12 2004-07-20 Bofors Bepab Ab Composite gas-generating material for gas-actuated car safety devices
CZ303225B6 (cs) * 2008-10-23 2012-06-06 Explosia A.S. Pyrotechnická slož pro bezpecnostní systémy pasivní ochrany, zejména pro použití v airbagu ci predpínaci bezpecnostních pásu

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB943991A (en) * 1958-12-11 1963-12-11 Sebel D & Co Ltd Combustion mixtures
GB1126567A (en) * 1965-08-14 1968-09-05 Dynamit Nobel Ag A gas-producing pyrotechnic mixture
GB1210461A (en) * 1967-02-17 1970-10-28 Dynamit Nobel Ag Improvements in or relating to propellent charges for use in switch means
GB1313619A (en) * 1970-02-03 1973-04-18 Dynamit Nobel Ag Gas-producing combustible charges
WO1998055428A1 (fr) * 1997-05-21 1998-12-10 Försvarets Forskningsanstalt Nouveau compose chimique, explosif contenant ce compose et utilisation de ce compose dans des generateurs de gaz

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB943991A (en) * 1958-12-11 1963-12-11 Sebel D & Co Ltd Combustion mixtures
GB1126567A (en) * 1965-08-14 1968-09-05 Dynamit Nobel Ag A gas-producing pyrotechnic mixture
GB1210461A (en) * 1967-02-17 1970-10-28 Dynamit Nobel Ag Improvements in or relating to propellent charges for use in switch means
GB1313619A (en) * 1970-02-03 1973-04-18 Dynamit Nobel Ag Gas-producing combustible charges
WO1998055428A1 (fr) * 1997-05-21 1998-12-10 Försvarets Forskningsanstalt Nouveau compose chimique, explosif contenant ce compose et utilisation de ce compose dans des generateurs de gaz

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6764562B1 (en) 1999-05-12 2004-07-20 Bofors Bepab Ab Composite gas-generating material for gas-actuated car safety devices
US6599380B2 (en) 2000-06-07 2003-07-29 Trw Airbag Systems Gmbh & Co. Kg Guanidine-thermite igniter composition for use in gas generators
WO2003037859A2 (fr) * 2001-10-31 2003-05-08 Arc Automotive, Inc. Compositions gazogenes contenant du guanidine dinitramide et dispositifs gonflables dans lesquels elles sont utilisees
WO2003037859A3 (fr) * 2001-10-31 2004-02-19 Atlantic Res Corp Compositions gazogenes contenant du guanidine dinitramide et dispositifs gonflables dans lesquels elles sont utilisees
CZ303225B6 (cs) * 2008-10-23 2012-06-06 Explosia A.S. Pyrotechnická slož pro bezpecnostní systémy pasivní ochrany, zejména pro použití v airbagu ci predpínaci bezpecnostních pásu

Also Published As

Publication number Publication date
SE9804611D0 (sv) 1998-12-30
DE69907036T2 (de) 2004-01-29
DE69907036D1 (de) 2003-05-22
SE9804611L (sv) 2000-07-01
ES2197707T3 (es) 2004-01-01
EP1171403B1 (fr) 2003-04-16
ATE237567T1 (de) 2003-05-15
EP1171403A1 (fr) 2002-01-16
SE513315C2 (sv) 2000-08-21

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