EP2139828B1 - Pyrotechnische verbindung zur gaserzeugung und schutzverfahren dafür - Google Patents

Pyrotechnische verbindung zur gaserzeugung und schutzverfahren dafür Download PDF

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Publication number
EP2139828B1
EP2139828B1 EP08805727A EP08805727A EP2139828B1 EP 2139828 B1 EP2139828 B1 EP 2139828B1 EP 08805727 A EP08805727 A EP 08805727A EP 08805727 A EP08805727 A EP 08805727A EP 2139828 B1 EP2139828 B1 EP 2139828B1
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EP
European Patent Office
Prior art keywords
compound
advantageously
weight
oxygen
plasticizer
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.)
Not-in-force
Application number
EP08805727A
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English (en)
French (fr)
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EP2139828A2 (de
Inventor
Frédéric MARLIN
Bernard Thibieroz
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.)
Safran Ceramics SA
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SME SA
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Publication of EP2139828A2 publication Critical patent/EP2139828A2/de
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Publication of EP2139828B1 publication Critical patent/EP2139828B1/de
Not-in-force legal-status Critical Current
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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B29/00—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate
    • C06B29/22—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate the salt being ammonium perchlorate
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
    • C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
    • C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin

Definitions

  • a composition with a high swelling capacity, a high inflating surface flow rate and without particles has many advantages with respect to the operation and miniaturization of airbag system gas generators. This miniaturization is required for reasons of cost, weight and integration inside the vehicles.
  • compositions based on silicone binder were then proposed.
  • Compositions based on "RTV” binder ("Room Temperature Vulcanizable") and potassium perchlorate have been described in the patent applications FR 2 190 776 and FR 2 213 254 .
  • the patent application FR 2 728 562 describes an improved version of these products, which can be manufactured by a process of continuous mixing and extrusion.
  • the silicone binder is combined with a mixture of ammonium perchlorate and sodium nitrate; said sodium nitrate serving as a chlorine sensor.
  • the compositions according to these documents exhibit an acceptable gas yield, a high combustion temperature and a high rate of combustion. The inflating surface flow rate is therefore relatively high.
  • compositions based on nitrocellulose and nitroglycerine compared with compositions based on nitrocellulose and nitroglycerine, these compositions have the advantage of being very stable in temperature and can be adjusted to "oxygen balance" (balance in oxygen) to meet the standards of toxicity of gaseous effluents.
  • these compositions have the disadvantage of emitting a high level of particles (approximately 30%), especially sodium chloride and silica, which requires the use of a bag having a high thickness and a coating of protection of the internal face of said bag.
  • the patent application EP 1 216 977 discloses an extrudable solvent-free composition essentially comprising a two-component oxygenated hydrocarbon binder (an elastomer (a gum) and a plasticizer), a nitrogenous organic compound and oxidizing charges.
  • the oxidizing charges are ammonium perchlorate and a chlorine sensor which may be sodium nitrate.
  • Sodium nitrate comes into height of about 15 to 20% by weight in the composition. Its role is to capture chlorine from ammonium perchlorate to form sodium chloride.
  • This composition has a high combustion temperature and a swelling capacity and a surface flow of the same order of magnitude as those of the silicone bases, due to a slightly lower combustion rate and a lower particle rate.
  • the gas yield, and therefore the swelling capacity is limited by the presence of the chlorine sensor which induces the formation of a solid chlorine salt.
  • the overall content of solid combustion residues of these compositions is about 14%.
  • the burning rates of these compositions are about 20 to 40 mm / s at a combustion pressure of 20 MPa.
  • compositions with a high combustion temperature generating few particles and toxic effluent (with the aim of increasing the swelling capacity and the inflating surface flow rate, so as to reduce the volumes of These compositions can advantageously be shaped by solvent-free extrusion, which makes it possible to produce a monolithic shape that facilitates loading, improving the charging density of the generator.
  • the absence of solvent avoids the emission of VOCs (volatile organic compounds).
  • the gas generator can be smaller, compact and less expensive.
  • the progressiveness of the control of the flow rate of gas related to the operation of a monolithic block and the moderation of the energy released due to the small mass of pyrotechnic product needed should allow to use bags of moderate or low thickness.
  • the fixed improvement objective has been achieved.
  • the inventors currently offer high performance pyrotechnic compounds, with reference to the above specifications, pyrotechnic compounds that perform better than those corresponding to the compositions of the application. EP 1 216 977 .
  • the pyrotechnic gas-generating compounds of the invention which are suitable for vehicle occupant protection systems, therefore comprise, in their composition, an oxidizing charge (without carbon) and an oxygenated hydrocarbon binding agent, of the above types.
  • Said at least one original oxygenated plasticizer present advantageously consists of at least one plasticizer with the properties stated above. Mixtures of such plasticisers with other oxygenated plasticizers (such as dioctyladipate and / or dioctylazelate) may however also be present.
  • the compounds of the invention generally have the disadvantage of emitting hydrogen chloride. At the end of combustion, said hydrogen chloride condenses with the water formed by the combustion and can be captured by the bag.
  • the level of hydrogen chloride emitted by the compounds according to the invention is approximately 0.2 g / g.
  • the bag can be coated with chlorine sensors.
  • the pyrotechnic gas-generating compounds of the invention are therefore characterized in that their composition does not contain a chlorine sensor (complementary oxidant) but at least one specific oxygenated plasticizer (which compensates for the absence of said complementary oxidant).
  • the oxidizing charge generally represents from 64 to 94% by weight of the total mass of the compound, advantageously from 72 to 82% by weight of said total mass. It is the main constituent of the compounds of the invention.
  • Said oxidizing charge consists of ammonium perchlorate.
  • Said ammonium perchlorate is advantageously used in several granulometries so as to improve the incorporation and distribution in the polymer and to reduce the toxicity of the gaseous effluents during combustion.
  • the crosslinked oxygenated hydrocarbon binder generally represents from 6 to 20% by weight of the total mass of the compound. It advantageously represents from 8 to 16% by weight of the total mass. It comprises the crosslinked elastomer and said at least one original oxygenated plasticizer of the invention.
  • the elastomer in question is a high molecular weight elastomer: Mw> 200,000 g / mol.
  • He is chosen in the family of polyesters and polyacrylates.
  • the polyacrylates may have reactive terminations of the chlorine / carboxyl, chlorine, hydroxyl or epoxy type.
  • the polyesters may have hydroxyl-type reactive terminations. They advantageously have such hydroxyl-type reactive terminations.
  • a crosslinking agent advantageously consists of a diisocyanate or triisocyanate.
  • said at least one elastomer and said at least one crosslinking agent represent from 3 to 10% by weight, advantageously from 4 to 8% by weight, of the total mass of the compounds of the invention; and / or, advantageously and, said at least one plasticizer represents from 3 to 10% by weight, advantageously from 4 to 8% by weight, of the total mass of said compounds.
  • the constituents (oxidizing charge + crosslinked oxygenated hydrocarbon binding agent + optional constituents chosen from those identified above) of the composition of the compounds of the invention, listed above, represent at least 95% by weight of said compounds, generally at least 98 % by weight of said compounds.
  • the complement, if any, is generally composed of additives, such as auxiliaries (aids) manufacturing.
  • the compounds of the invention can be of different types. These are monolithic compounds that can be full, mono- or multiperforated. These compounds typically contain, in their composition, an original oxygenated plasticizer as described above.
  • Said compounds are particularly effective.
  • Their composition is high gaseous (about 36 mol / kg) with combustion temperatures around 3000 K (it is indeed so-called hot compositions).
  • Their burning rate is fast, about 45 mm / s at a pressure of 20 MPa. Because of their composition, they generate very few solid particles ( ⁇ 2%).
  • Their composition is also likely, according to advantageous variants, to have an oxygen balance value of between -2% and -3%, ie that they generate only a very small amount of toxic gas and that they are quite suitable for an application in the field of airbags.
  • the inflating surface flow rates of the compositions of the compounds of the invention are very interesting. They are about 830 mol.K / cm 2 .s.
  • the process for obtaining the compounds of the invention is advantageously a process by analogy, as described in the application EP 1 216 077 . It is very advantageously a process carried out continuously, without solvent, in a twin screw mixer-extruder.
  • said at least one plasticizer consists of or comprises an original plasticizer of the invention.
  • said mixing and extrusion are advantageously carried out in a twin screw mixer-extruder.
  • the twin-screw mixer-extruder includes a mixing and mixing chamber, a compression chamber and an extrusion head.
  • the solid and liquid constituents are introduced into the mixing and kneading compartment by two different feed openings, a solids supply opening and a liquid feed opening, and then transported and kneaded, followed by the homogeneous paste thus formed. is degassed in the compression compartment, then extruded with the aid of an extrusion head in the form of rods, and finally the rods thus formed are cut into loads using a cutting apparatus, and then these loads are crosslinked at a temperature generally between 100 ° C and 150 ° C.
  • the charges thus formed find their preferential application as a pyrotechnic charge in gas generators intended to inflate a protective cushion for occupants of a motor vehicle. Indeed, the burning rate of these loads, as well as the rate of solid residues produced and the rate of carbon monoxide and nitrogen oxides produced are particularly suitable (see above).
  • compositions of pyrotechnic compounds have been evaluated by means of thermodynamic calculations and physical measurements.
  • pellets were prepared.
  • This composition is a composition according to the patent application EP 1 216 077 . It is extruded and crosslinked to generate compounds.
  • the oxygen balance of this composition is -2.3%. Its theoretical density is 1.73 g / cm 3 .
  • the particle content is less than 2%.
  • the burning rate of the compounds (extruded) is between 40 and 50 mm / s at 20 MPa (see table below).
  • the oxygen balance of this composition is -2.4%. Its theoretical density is 1.72 g / cm 3 .
  • the particle content is less than 2%.
  • the burning rate of the compounds (extruded) is between 40 and 50 mm / s at 20 MPa (see table below).
  • compositions A, B, 1 and 2 and those of the corresponding compounds are given in Table 1 below.
  • the much higher burning rate of the compounds of the invention gives a surface flow rate of inflation greater than that of the reference compounds.
  • the characteristic dimension of the object to be burned can be doubled to ensure an equivalent operating time.
  • the extruded block made from the compositions of the invention can therefore be very compact and allow the development of small generators containing a low pyrotechnic mass.
  • the gas generators employing the compounds of the invention may be to some extent devoid of particulate filters. In doing so, the thermal losses of the gases are reduced.
  • the compounds of the invention generally have the disadvantage of emitting hydrogen chloride.
  • said hydrogen chloride condenses with the water formed by the combustion and can be captured by the bag.
  • the level of hydrogen chloride emitted by the compounds of the invention is about 0.2 g / g.
  • the bag can be coated with chlorine sensors.
  • the vents can be reduced to increase the capture rate by condensation of acidified water in the atmosphere. bag. After operation, the bag naturally deflates under the effect of the drop in temperature and condensation of condensables.
  • a conductive airbag (side) gas generator containing a compound according to the invention (14 g) emits 2.8 g of hydrogen chloride.
  • the hydrogen chloride level is of the order of 700 ppm in a cabin of 2.8 m 3 .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Air Bags (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)

Claims (13)

  1. Gaserzeugende pyrotechnische Verbindung, geeignet für Systeme zum Schutz von Fahrzeuginsassen, deren Zusammensetzung enthält:
    - eine oxidierende Ladung aus Ammoniumperchlorat und
    - ein sauerstoffhaltiges, vernetztes Kohlenwasserstoffbindemittel, das durch Vernetzen eines Elastomers in Gegenwart wenigstens eines Vernetzungsmittels und wenigstens eines sauerstoffhaltigen Weichmachers des Elastomers erhalten wird, wobei das Elastomer eine molare Masse von über 200.000 aufweist und aus den Polyestern und den Polyacrylaten ausgewählt ist,
    dadurch gekennzeichnet, daß:
    - die oxidierende Ladung keinen Chlorfänger umfaßt und
    - der wenigstens eine sauerstoffhaltige Weichmacher aus einem Weichmacher, welcher aus den Diestern mit Etherfunktionen, deren molare Masse über 350 g/mol liegt und deren Sauerstoffbilanz gleich oder größer -230 % ist, ausgewählt ist, aus einer Mischung derartiger Weichmacher untereinander oder aus einer Mischung aus wenigstens einem solchen Weichmacher mit wenigstens einem weiteren sauerstoffhaltigen Weichmacher besteht.
  2. Verbindung nach Anspruch 1, dadurch gekennzeichnet, daß der wenigstens eine sauerstoffhaltige Weichmacher ausgewählt ist aus:
    - Dibutoxyethoxyethyladipat,
    - Dibutoxyethoxyethoxyethyladipat,
    - Dibutoxyethoxyethoxyethylglutarat,
    - Dibutoxyethoxyethoxyethylphthalat,
    - Bis(ethylenglykolmonobutylether)adipat,
    - Bis(ethylenglykolmonobutylether)phthalat,
    - den Mischungen der Diester untereinander und
    - den Mischungen aus wenigstens einem der Diester mit Dioctyladipat und/oder Dioctylazelat.
  3. Verbindung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die oxidierende Ladung 64 bis 94 Masse-%, vorteilhafterweise 72 bis 82 Masse-% der Gesamtmasse der Verbindung ausmacht.
  4. Verbindung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das sauerstoffhaltige, vernetzte Kohlenwasserstoffbindemittel 6 bis 20 Masse-%, vorteilhafterweise 8 bis 16 Masse-% der Gesamtmasse der Verbindung ausmacht.
  5. Verbindung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das wenigstens eine Elastomer und das wenigstens eine Vernetzungsmittel zwischen 3 und 10 Masse-%, vorteilhafterweise zwischen 4 und 8 Masse-% der Gesamtmasse der Verbindung ausmachen, und/oder, vorteilhafterweise und, der wenigstens eine Weichmacher 3 bis 10 Masse-%, vorteilhafterweise 4 bis 8 Masse-% der Gesamtmasse der Verbindung ausmacht.
  6. Verbindung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß ihre Zusammensetzung ferner wenigstens eine organische Nitroverbindung enthält, deren Sauerstoffbilanz über -30 % liegt, daß ihre Zusammensetzung vorteilhafterweise ferner wenigstens eine organische Nitroverbindung enthält, die aus den Stickstoffnitraten und den Dinitramiden ausgewählt ist.
  7. Verbindung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß ihre Zusammensetzung ferner wenigstens einen ballistischen Katalysator enthält, der vorteilhafterweise aus Kupferoxid, Eisenoxid, Manganoxid und Kobaltoxid ausgewählt ist.
  8. Verbindung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß ihre Zusammensetzung ferner wenigstens ein Benetzungsmittel enthält, das aus den Organosilanen und den Titanaten, vorteilhafterweise aus Vinyltris-(2-methoxyethoxy)silan, Tris-(3-trimethoxysilylpropyl)isocyanurat, γ-Glycidoxypropyltrimethoxysilan, Diethoxydiacetoxysilan, Diacetoxydiethoxysilan und Dibutoxyethoxymethylsilan ausgewählt ist.
  9. Verbindung nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß ihre Zusammensetzung, in Masse-Prozentsätzen ausgedrückt, umfaßt:
    - 64 bis 94 %, vorteilhafterweise 72 bis 82 %, der oxidierenden Ladung,
    - 6 bis 20 %, vorteilhafterweise 8 bis 16 %, des wenigstens einen sauerstoffhaltigen, vernetzten Kohlenwasserstoffbindemittels,
    - 0 bis 10%, vorteilhafterweise 3 bis 8 %, wenigstens einer organischen Nitroverbindung, deren Sauerstoffbilanz über -30 % liegt,
    - 0 bis 6 %, vorteilhafterweise 1 bis 2 %, wenigstens eines ballistischen Katalysators und
    - 0 bis 4 %, vorteilhafterweise 0,2 bis 3 %, wenigstens eines Benetzungsmittels.
  10. Verbindung nach einem der Ansprüche 1 bis 9, monolithischer, massiver, einfach oder mehrfach perforierter Art.
  11. Verfahren für den Erhalt einer Verbindung nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß es umfaßt:
    - das kontinuierlich vollzogene Mischen ohne Lösungsmittel der oxidierenden Ladung, des Elastomers, des wenigstens einen Vernetzungsmittels und des wenigstens einen Weichmachers sowie eventuell der wenigstens einen organischen Nitroverbindung, deren Sauerstoffbilanz über -30 % liegt und/oder des wenigstens einen ballistischen Katalysators und/oder des wenigstens einen Benetzungsmittels, sowie das Extrudieren der aus dem Mischen hervorgehenden Paste,
    - die Wärmebehandlung der extrudierten Paste, um die Vernetzung des Elastomers sicherzustellen.
  12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß das Mischen und das Extrudieren in einem Zweischnecken-Mischer-Extruder durchgeführt werden.
  13. Verfahren nach einem der Ansprüche 11 oder 12, dadurch gekennzeichnet, daß es das Schneiden der extrudierten Paste in Ladungen und die Wärmebehandlung der Ladungen umfaßt.
EP08805727A 2007-05-02 2008-04-30 Pyrotechnische verbindung zur gaserzeugung und schutzverfahren dafür Not-in-force EP2139828B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0754809A FR2915746B1 (fr) 2007-05-02 2007-05-02 Compose pyrotechnique generateur de gaz; procede d'obtention
PCT/FR2008/050773 WO2008145935A2 (fr) 2007-05-02 2008-04-30 Compose pyrotechnique generateur de gaz; procede d'obtention

Publications (2)

Publication Number Publication Date
EP2139828A2 EP2139828A2 (de) 2010-01-06
EP2139828B1 true EP2139828B1 (de) 2011-10-05

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EP08805727A Not-in-force EP2139828B1 (de) 2007-05-02 2008-04-30 Pyrotechnische verbindung zur gaserzeugung und schutzverfahren dafür

Country Status (7)

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US (1) US20110041969A1 (de)
EP (1) EP2139828B1 (de)
JP (1) JP5483732B2 (de)
CN (1) CN101679139B (de)
AT (1) ATE527227T1 (de)
FR (1) FR2915746B1 (de)
WO (1) WO2008145935A2 (de)

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FR2975097B1 (fr) * 2011-05-09 2015-11-20 Sme Composes pyrotechniques generateurs de gaz
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Publication number Publication date
WO2008145935A3 (fr) 2009-09-17
JP5483732B2 (ja) 2014-05-07
FR2915746B1 (fr) 2009-08-21
CN101679139A (zh) 2010-03-24
ATE527227T1 (de) 2011-10-15
WO2008145935A2 (fr) 2008-12-04
US20110041969A1 (en) 2011-02-24
FR2915746A1 (fr) 2008-11-07
CN101679139B (zh) 2012-09-26
JP2010526010A (ja) 2010-07-29
EP2139828A2 (de) 2010-01-06

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