EP0404651B1 - Feste gaserzeugende Zusammensetzung und deren Anwendung in Gasgeneratoren für Airbags in Kraftfahrzeugen - Google Patents

Feste gaserzeugende Zusammensetzung und deren Anwendung in Gasgeneratoren für Airbags in Kraftfahrzeugen Download PDF

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Publication number
EP0404651B1
EP0404651B1 EP90401697A EP90401697A EP0404651B1 EP 0404651 B1 EP0404651 B1 EP 0404651B1 EP 90401697 A EP90401697 A EP 90401697A EP 90401697 A EP90401697 A EP 90401697A EP 0404651 B1 EP0404651 B1 EP 0404651B1
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EP
European Patent Office
Prior art keywords
azide
composition
composition according
relative
total weight
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
EP90401697A
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English (en)
French (fr)
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EP0404651A1 (de
Inventor
Christian Perotto
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.)
Livbag SAS
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Livbag SAS
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B35/00—Compositions containing a metal azide
    • 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 the field of protection in the event of an impact on the passengers of a motor vehicle by an airbag by means of a pyrotechnic generator of non-toxic cold gases. More specifically, the invention relates to a new solid gas-generating composition based on molybdenum sulfide and alkali or alkaline earth azide and its use in such a gas generator.
  • nitrogen-generating compositions are particularly sought after.
  • the solid compositions based on alkali or alkaline earth azide and on molybdenum sulfide, optionally in the presence of sulfur have been found to meet the first two requirements, namely the high combustion rate, particularly well. and a moderate combustion temperature.
  • Such compositions are for example described in patents US-A-3,741,585, US-A-4,203,787 and US-A-4,547,235. These compositions are entirely satisfactory in terms of the generation of non-toxic cold gases for automobile safety but have certain disadvantages of implementation and storage linked to the presence of metal azides which are explosive bodies and sensitive to humidity, the hydrolysis products of which are themselves dangerous explosives.
  • the azide functional group can be introduced into a composition by certain polymers carrying this group such as, for example, glycidyl polyazide.
  • the object of the present invention is precisely to propose such a composition.
  • the object of the invention relates to a solid composition generating non-toxic cold gases comprising molybdenum sulfide, an alkali or alkaline earth azide, characterized in that it contains between 3% and 6% by weight relative to the weight total of said composition of a binder consisting of the reaction product of a glycidyl polyazide with hydroxyl endings with at least one polyisocyanate chosen from the group consisting of diisocyanates and triisocyanates.
  • the said azide is sodium azide.
  • part of the molybdenum sulphide is replaced by sulfur.
  • the invention also relates to the use of such a composition in a gas generator for an airbag intended for motor vehicles.
  • compositions according to the invention are thus particularly suitable for pyrotechnic gas generators intended to inflate the airbags of motor vehicles.
  • the invention relates to compositions based on molybdenum sulfide and alkali or alkaline earth azide such as for example sodium azide, lithium azide, strontium azide, calcium azide.
  • sodium azide will be used.
  • compositions according to the invention contain between 3% and 6% by weight relative to the total weight of said composition of a binder consisting of the reaction product of a glycidyl polyazide with OH hydroxyl endings with at least a polyisocyanate chosen from the group consisting of diisocyanates and triisocyanates.
  • the glycidyl polyazides with OH hydroxyl endings which can be used in the context of the present invention are polyethers of general formula: in which C, H, O, N represent carbon, hydrogen, oxygen and nitrogen respectively and where n represents an integer between 5 and 100.
  • polymers are generally obtained by reaction of sodium azide on a polyepichlorohydrin as described for example in US Patents 4,268,450, 4,379,894 or 4,486,351.
  • glycidyl polyazides with molecular weights between 600 and 7000 and we prefer those whose molecular mass is between 1500 and 2500.
  • polyisocyanate it is possible to use the usual aliphatic, cycloaliphatic or aromatic diisocyanates and triisocyanates such as, for example, methyl-1 cyclohexane-2,4 diisocyanate, methyl-1 cyclohexane-2,6 diisocyanate, dicyclohexylmethane-4,4'diisocyanate, l isophorone diisocyanate, methylene diisocyanate, hexane-1,6 diisocyanate, trimethyl-2,2,4 hexane-1,6 diisocyanate, toluene diisocyanate, biuret trimer of hexamethylene diisocyanate, polymethylene polyphenyl isocyanate.
  • trimer biuret of hexamethylene diisocyanate of formula: polyisocyanate is preferred: and polymethylene polyphenylisocyanates of formula: in which x represents an integer or zero and which have an average functionality in group NCO of 2.7.
  • the NCO: OH ratio is close to 1: 1.
  • a characteristic of the invention lies in the fact that the weight content of the binder composition is within a very precise range, between 3% and 6% relative to the total weight of the composition , so that the composition retains the advantages of traditional compositions based on molybdenum sulfide and sodium azide in terms of the non-toxicity of the gases while being easier to use and store thanks to the fact that the azide grains are, at least partially, coated with a binder.
  • the weight content of the binder composition is between 4% and 5% relative to the total weight of the composition.
  • the weight content of the azide composition is advantageously between 55% and 71% relative to the total weight of the composition and the weight content of molybdenum sulfide is advantageously between 25% and 40% relative to the total weight of composition.
  • part of the molybdenum sulphide can be replaced by sulfur.
  • the weight content of the sulfur composition must be less than 8% relative to the total weight of the composition, the content overall of the sulfur and molybdenum sulfide composition being between 25% and 40% relative to the total weight of the composition.
  • compositions according to the invention are advantageously carried out in the following manner.
  • the solid constituents namely the azide, the molybdenum sulphide and possibly the sulfur, are mixed.
  • a liquid mixer a solution of glycidyl polyazide and isocyanate in a non-reactive volatile anhydrous solvent such as methylene chloride is prepared.
  • a 50:50 volume solution is produced between the solvent on the one hand and the constituents of the binder on the other hand.
  • the mixture of solid constituents and said solution is then introduced into a kneader, catalysts intended to promote the reaction of the isocyanate on the glycidyl polyazide, such as dibutyltin dilaurate or acetylacetonate, are optionally added and kneaded under vacuum to remove the solvent.
  • a powder is then obtained which can be shaped by tableting or compression.
  • the pellets or blocks thus obtained are then baked in an oven heated to a temperature between 60 ° C and 100 ° C to complete the crosslinking of the binder.
  • pellets or blocks thus obtained burn at a moderate temperature with high combustion rates, releasing a large volume of non-toxic gases within the meaning of the standards imposed by the manufacturers of motor vehicles, these gases being essentially constituted by nitrogen. Furthermore, it has been found that the pellets or blocks of compositions according to the invention are much less sensitive to external aggressions, in particular moisture, than the pellets or blocks of traditional compositions based on alkali or alkaline earth azide and molybdenum sulfide.
  • compositions according to the invention can thus advantageously be used to constitute the pyrotechnic charge of non-toxic cold gas generators intended to inflate the airbags of motor vehicles.
  • the binder was obtained by reaction of a glycidyl polyazide with OH hydroxyl terminations of average molecular weight 2000 on the trimer biuret of hexamethylene diisocyanate.
  • Dibutyltin dilaurate was used as the catalyst.
  • the pellets obtained burn with a speed of 7 mm / s at 7 MPa in a pressure bomb.
  • the combustion temperature is 867 ° K or 594 ° C.

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

Claims (12)

  1. Feste, ungiftige Gase erzeugende Zusammensetzung, die Molybdänsulfid, ein Alkali- oder Erdalkalimetallnitrid aufweist, dadurch gekennzeichnet, daß sie zwischen 3 und 6 Gew.-%, bezogen auf das Gesamtgewicht der Zusammensetzung, eines Bindemittels enthält, das aus dem Reaktionsprodukt eines Glycidolpolynitrids mit Hydroxylendgruppen mit mindestens einem aus der Gruppe der Diisocyanate und Triisocyanate ausgewählten Polyisocyanat gebildet wird.
  2. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß das Nitrid aus der von Natriumnitrid, Lithiumnitrid, Strontiumnitrid, Calciumnitrid gebildeten Gruppe ausgewählt wird.
  3. Zusammensetzung nach Anspruch 2, dadurch gekennzeichnet, daß das Nitrid das Natriumnitrid ist.
  4. Zusammensetzung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß der Gewichtsanteil des Nitrids zwischen 55% und 71%, bezogen auf das Gesamtgewicht der Zusammensetzung, beträgt.
  5. Zusammensetzung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das Glycidolpolynitrid mit Hydroxylendgruppen eine durchschnittliche molare Masse zwischen 1000 und 7000 aufweist.
  6. Zusammensetzung nach Anspruch 5, dadurch gekennzeichnet, daß das Glycidolpolynitrid mit Hydroxylendgruppen eine durchschnittliche molare Masse zwischen 1500 und 2500 aufweist.
  7. Zusammensetzung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das Polyisocyanat aus der Gruppe des trimeren Biurets des Hexamethylendiisocyanats und des Polymethylenpolyphenylisocyanats ausgewählt wird.
  8. Zusammensetzung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß der Gewichtsanteil des Bindemittels zwischen 4% und 5%, bezogen auf das Gesamtgewicht der Zusammensetzung, beträgt.
  9. Zusammensetzung nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß der Gewichtsanteil des Molybdänsulfids zwischen 25% und 40%, bezogen auf das Gesamtgewicht der Zusammensetzung, beträgt.
  10. Zusammensetzung nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß ein Teil des Molybdänsulfids durch Schwefel ersetzt wird.
  11. Zusammensetzung nach Anspruch 10, dadurch gekennzeichnet, daß der Gewichtsanteil an Schwefel unter 8%, bezogen auf das Gesamtgewicht der Zusammensetzung, liegt.
  12. Verwendung einer Zusammensetzung nach einem der Ansprüche 1 bis 11 in einem Gasgenerator für ein für Kraftfahrzeuge bestimmtes, aufblasbares Sicherheitskissen .
EP90401697A 1989-06-21 1990-06-18 Feste gaserzeugende Zusammensetzung und deren Anwendung in Gasgeneratoren für Airbags in Kraftfahrzeugen Expired - Lifetime EP0404651B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8908224A FR2648809B1 (fr) 1989-06-21 1989-06-21 Composition solide generatrice de gaz et son utilisation dans les generateurs de gaz pour coussins gonflables destines a proteger les passagers d'un vehicule automobile
FR8908224 1989-06-21

Publications (2)

Publication Number Publication Date
EP0404651A1 EP0404651A1 (de) 1990-12-27
EP0404651B1 true EP0404651B1 (de) 1994-05-18

Family

ID=9382955

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90401697A Expired - Lifetime EP0404651B1 (de) 1989-06-21 1990-06-18 Feste gaserzeugende Zusammensetzung und deren Anwendung in Gasgeneratoren für Airbags in Kraftfahrzeugen

Country Status (5)

Country Link
US (1) US4976795A (de)
EP (1) EP0404651B1 (de)
JP (1) JPH0725633B2 (de)
DE (1) DE69008934T2 (de)
FR (1) FR2648809B1 (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5743557A (en) * 1996-05-07 1998-04-28 Amphenol-Tuchel Electronics Gmbh Hybrid inflator
DE19821010C1 (de) * 1998-05-11 1999-10-28 Bayern Chemie Gmbh Flugchemie Gasgenerator-Festtreibstoff und dessen Verwendung
WO2003074270A2 (en) * 2002-02-28 2003-09-12 Solutia Inc. Embossed reflective laminates
US6824868B2 (en) * 2002-04-30 2004-11-30 Solutia, Inc. Digital color-design composite for use in laminated glass
FR3027597B1 (fr) * 2014-10-28 2016-12-09 Herakles Produit pyrotechnique composite performant sans pb dans sa composition et sa preparation
FR3027598B1 (fr) * 2014-10-28 2018-05-04 Arianegroup Sas Produit pyrotechnique composite avec charges d'adn et de rdx dans un liant de type pag et sa preparation

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3779823A (en) * 1971-11-18 1973-12-18 R Price Abrasion resistant gas generating compositions for use in inflating safety crash bags
US4405392A (en) * 1975-09-11 1983-09-20 Imperial Metal Industries (Kynoch) Limited Method of making priming composition
US4268450A (en) * 1977-08-08 1981-05-19 Rockwell International Corporation Energetic hydroxy-terminated azido polymer
US4288262A (en) * 1978-03-30 1981-09-08 Rockwell International Corporation Gun propellants containing polyglycidyl azide polymer
CA1087851A (en) * 1978-07-17 1980-10-21 Lechoslaw A.M. Utracki Gas generating composition
US4601344A (en) * 1983-09-29 1986-07-22 The United States Of America As Represented By The Secretary Of The Navy Pyrotechnic fire extinguishing method
US4919737A (en) * 1988-08-05 1990-04-24 Morton Thiokol Inc. Thermoplastic elastomer-based low vulnerability ammunition gun propellants

Also Published As

Publication number Publication date
JPH03141185A (ja) 1991-06-17
FR2648809B1 (fr) 1991-09-13
DE69008934D1 (de) 1994-06-23
FR2648809A1 (fr) 1990-12-28
US4976795A (en) 1990-12-11
DE69008934T2 (de) 1994-09-22
EP0404651A1 (de) 1990-12-27
JPH0725633B2 (ja) 1995-03-22

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