EP0404651A1 - 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 PDFInfo
- Publication number
- EP0404651A1 EP0404651A1 EP90401697A EP90401697A EP0404651A1 EP 0404651 A1 EP0404651 A1 EP 0404651A1 EP 90401697 A EP90401697 A EP 90401697A EP 90401697 A EP90401697 A EP 90401697A EP 0404651 A1 EP0404651 A1 EP 0404651A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- azide
- composition
- composition according
- relative
- 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.)
- Granted
Links
- 0 *CC1(CC(*)CCCC1)C1CCCCC1 Chemical compound *CC1(CC(*)CCCC1)C1CCCCC1 0.000 description 1
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 satisfy the first two requirements, namely the high combustion rate, particularly well. and a moderate combustion temperature.
- Such compositions are for example described in US Patents 3,741,585, 4,203,787 and 4,547,235. These compositions are entirely satisfactory in terms of the generation of cold gases which are non-toxic for motor vehicle safety, but have certain disadvantages of use. and storage associated with the presence of metal azides which are explosive and moisture sensitive bodies, 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 4,268,460, 4,379,894 or 4,486,351.
- glycidyl polyazides with a molecular weight will be used 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.
- 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 the 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 composition of sulfur and molybdenum sulphide 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 optionally 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 humidity, 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 endings 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.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Air Bags (AREA)
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 true EP0404651A1 (de) | 1990-12-27 |
EP0404651B1 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) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19821010C1 (de) * | 1998-05-11 | 1999-10-28 | Bayern Chemie Gmbh Flugchemie | Gasgenerator-Festtreibstoff und dessen Verwendung |
FR3027597A1 (fr) * | 2014-10-28 | 2016-04-29 | Herakles | Produit pyrotechnique composite performant sans pb dans sa composition et sa preparation |
KR20170101898A (ko) * | 2014-10-28 | 2017-09-06 | 에어버스 사프란 론처스 에스아에스 | Gap 결합제에 adn 및 rdx 충전물을 갖는 복합 발화 제품 및 이의 제조 방법 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5743557A (en) * | 1996-05-07 | 1998-04-28 | Amphenol-Tuchel Electronics Gmbh | Hybrid inflator |
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 |
Citations (3)
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 |
US4268450A (en) * | 1977-08-08 | 1981-05-19 | Rockwell International Corporation | Energetic hydroxy-terminated azido polymer |
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 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4405392A (en) * | 1975-09-11 | 1983-09-20 | Imperial Metal Industries (Kynoch) Limited | Method of making priming composition |
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 |
US4919737A (en) * | 1988-08-05 | 1990-04-24 | Morton Thiokol Inc. | Thermoplastic elastomer-based low vulnerability ammunition gun propellants |
-
1989
- 1989-06-21 FR FR8908224A patent/FR2648809B1/fr not_active Expired - Lifetime
-
1990
- 1990-06-04 US US07/533,178 patent/US4976795A/en not_active Expired - Fee Related
- 1990-06-18 EP EP90401697A patent/EP0404651B1/de not_active Expired - Lifetime
- 1990-06-18 DE DE69008934T patent/DE69008934T2/de not_active Expired - Fee Related
- 1990-06-21 JP JP2161468A patent/JPH0725633B2/ja not_active Expired - Lifetime
Patent Citations (3)
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 |
US4268450A (en) * | 1977-08-08 | 1981-05-19 | Rockwell International Corporation | Energetic hydroxy-terminated azido polymer |
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 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19821010C1 (de) * | 1998-05-11 | 1999-10-28 | Bayern Chemie Gmbh Flugchemie | Gasgenerator-Festtreibstoff und dessen Verwendung |
FR3027597A1 (fr) * | 2014-10-28 | 2016-04-29 | Herakles | Produit pyrotechnique composite performant sans pb dans sa composition et sa preparation |
WO2016066945A1 (fr) * | 2014-10-28 | 2016-05-06 | Herakles | PRODUIT PYROTECHNIQUE COMPOSITE PERFORMANT SANS Pb DANS SA COMPOSITION ET SA PREPARATION |
KR20170101897A (ko) * | 2014-10-28 | 2017-09-06 | 에어버스 사프란 론처스 에스아에스 | 조성물에서 Pb를 가지지 않는 고성능 복합 발화 제품 및 이의 제조 방법 |
KR20170101898A (ko) * | 2014-10-28 | 2017-09-06 | 에어버스 사프란 론처스 에스아에스 | Gap 결합제에 adn 및 rdx 충전물을 갖는 복합 발화 제품 및 이의 제조 방법 |
Also Published As
Publication number | Publication date |
---|---|
FR2648809A1 (fr) | 1990-12-28 |
JPH0725633B2 (ja) | 1995-03-22 |
FR2648809B1 (fr) | 1991-09-13 |
DE69008934T2 (de) | 1994-09-22 |
JPH03141185A (ja) | 1991-06-17 |
EP0404651B1 (de) | 1994-05-18 |
DE69008934D1 (de) | 1994-06-23 |
US4976795A (en) | 1990-12-11 |
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