EP2139828B1 - Gas-generating pyrotechnic compound and production process. - Google Patents

Gas-generating pyrotechnic compound and production process. 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
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Prior art keywords
compound
advantageously
weight
oxygen
plasticizer
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EP08805727A
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German (de)
French (fr)
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EP2139828A2 (en
Inventor
Frédéric MARLIN
Bernard Thibieroz
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Safran Ceramics SA
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SME SA
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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 .

Abstract

The present invention provides pyrotechnic gas generator compounds and a method of obtaining them. Said compounds have a composition which comprises: an oxidizing charge which comprises at least one inorganic perchlorate and which does not comprise a chlorine scavenger; and a crosslinked, oxygen-containing hydrocarbon binder obtained by crosslinking an elastomer in the presence of at least one crosslinking agent and at least one oxygen-containing plasticizer for said elastomer; said elastomer having a molecular weight of more than 200 000 and being preferably selected from polyesters and polyacrylates; said at least one oxygen-containing plasticizer being composed of a plasticizer of which the molecular weight is greater than 350 g/mol and the oxygen balance equal to or greater than −230 %, of a mixture of such plasticizers with one another or of a mixture of at least one such plasticizer with at least one other oxygen-containing plasticizer. Said compounds can be obtained continuously by extrusion.

Description

La présente invention a pour objet des composés pyrotechniques générateurs de gaz ainsi qu'un procédé pour leur obtention. Lesdits composés pyrotechniques présentent :

  • un fort pouvoir gonflant (le pouvoir intrinsèque de gonflage d'une formulation est donné par le produit du rendement molaire de ladite formulation (en mole/kg) par la température T (en K). Ce produit est équivalent au produit de la pression fois le volume et traduit donc la capacité d'une formulation à générer une quantité de gaz) ; et
  • un fort débit surfacique de gonflage (le débit surfacique de gonflage est estimé par le produit p x n x T x Vc, où p est la densité du matériau (en g/cm3), n le rendement molaire gazeux de la combustion (en mole/g), T la température de combustion (en K) et Vc la vitesse de combustion en cm/s. Ainsi, le paramètre de débit surfacique de gonflage est-il exprimé en mol.K/cm2.s.
The present invention relates to pyrotechnic compounds gas generators and a method for obtaining them. Said pyrotechnic compounds present:
  • a high swelling capacity (the intrinsic inflation power of a formulation is given by the product of the molar yield of said formulation (in mol / kg) by the temperature T (in K) This product is equivalent to the product of the pressure times volume and thus translates the capacity of a formulation to generate a quantity of gas); and
  • a high inflating surface flow rate (the inflation surface flow rate is estimated by the product pxnx T x Vc, where p is the density of the material (in g / cm 3 ), n the gaseous molar yield of the combustion (in mole / g ), T is the combustion temperature (in K) and Vc is the combustion rate in cm / s Thus, the parameter of the surface flow rate of inflation is expressed in mol.K / cm 2 .s.

Par ailleurs, la combustion desdits composés pyrotechniques génèrent peu de particules condensées.Moreover, the combustion of said pyrotechnic compounds generate few condensed particles.

La présente invention se situe dans le domaine technique de la génération pyrotechnique de gaz. Elle trouve plus particulièrement application dans les systèmes de protection des occupants de véhicules, protection au moyen de coussins amortissants (dits "airbags"), qui sont gonflés par les gaz de combustion de composés pyrotechniques.

  • • Le domaine technique des airbags gonflés par des générateurs de gaz incluant des composés pyrotechniques à base de compositions pyrotechniques a connu depuis les vingt dernières années un essor très important. Ce domaine arrive aujourd'hui à maturité et la majorité des systèmes produits et vendus s'appuie sur des formulations présentant de fortes similarités. Les compositions pyrotechniques employées dans ces systèmes sont des compositions dites "froides" dont la température de combustion est généralement comprise entre 1800 et 2200 K.
The present invention is in the technical field of pyrotechnic generation of gas. It is particularly applicable in vehicle occupant protection systems, protection by means of damping cushions (so-called "airbags"), which are inflated by the combustion gases of pyrotechnic compounds.
  • • The technical field of airbags inflated by gas generators including pyrotechnic compounds based on pyrotechnic compositions has known for the last twenty years a very important boom. This field is now mature and the majority of systems produced and sold rely on formulations with strong similarities. The pyrotechnic compositions used in these systems are so-called "cold" compositions whose combustion temperature is generally between 1800 and 2200 K.

L'emploi de ce type de compositions présente les avantages suivants :

  • la température basse permet de limiter l'épaisseur du sac ;
  • les effluents gazeux sont généralement de bonne qualité vis-à-vis des normes de toxicité admissibles en vigueur dans le domaine (USCAR).
The use of this type of composition has the following advantages:
  • the low temperature makes it possible to limit the thickness of the bag;
  • the gaseous effluents are generally of good quality with respect to the acceptable toxicity standards in force in the field (USCAR).

Ces compositions induisent par contre des inconvénients qui peuvent pénaliser certaines applications :

  • le rendement gazeux est généralement faible. La masse de produit nécessaire est donc importante;
  • la température étant relativement basse et le rendement gazeux faible, le pouvoir gonflant est limité;
  • la combustion émettant des résidus solides, des filtres sont nécessaires pour réduire l'émission de particules. Ces filtres réduisent encore le pouvoir gonflant du fait des pertes thermiques qu'ils induisent. Les filtres induisent en outre une augmentation du volume et du coût du générateur ;
  • les compositions froides présentent dans la quasi-totalité des cas des vitesses de combustion faibles. Ce point cumulé au faible pouvoir gonflant induit de faibles débits surfaciques de gonflage. Ces faibles débits surfaciques de gonflage sont compensés par l'emploi de pastilles fines et de faibles diamètres qui induisent une forte surface initiale de produit pyrotechnique et une faible densité de chargement.
These compositions, on the other hand, have drawbacks that can penalize certain applications:
  • the gas yield is generally low. The necessary mass of product is therefore important;
  • the temperature being relatively low and the gas yield low, the swelling capacity is limited;
  • As combustion emits solid residues, filters are needed to reduce the emission of particles. These filters further reduce the swelling capacity due to the thermal losses they induce. The filters further induce an increase in the volume and cost of the generator;
  • in almost all cases, the cold compositions have low combustion rates. This cumulative point at low swelling power induces low inflation surface flow rates. These low inflation surface flow rates are compensated for by the use of thin pellets and small diameters which induce a strong initial surface of pyrotechnic product and a low loading density.

D'une manière générale, la forte surface initiale de produit "froid" à basse vitesse de combustion induit, en plus des inconvénients précités, les difficultés suivantes :

  • la combustion du produit s'initie lentement et une forte charge d'allumage est nécessaire ;
  • la fabrication de petites pastilles nécessaires à l'obtention du débit sur la durée de la combustion induit un débit élevé au départ et donc une forte montée en pression en début de combustion dans le sac. Cela est dommageable pour ledit sac dans les premières millisecondes, quand il est plié et ledit sac subit donc fortement les contraintes de mise en position dans la phase de déploiement ;
  • la combustion de pastilles à évolution de surface décroissante induit une diminution du débit au fur et à mesure de l'avancement de la combustion alors que le besoin fonctionnel est au contraire un débit constant voire croissant sur la durée.
  • • Le fort pouvoir gonflant d'une composition étant associé au couple rendement molaire gazeux et température, les compositions répondant à ces exigences présentent une température de combustion élevée et un faible taux de particules produit lors de la combustion. Le faible taux de particules est rendu nécessaire pour disposer du maximum de gaz émis et de manière à éviter les agressions sur les sacs. Des essais en modules airbags ont en effet mis en évidence que l'endommagement des sacs par les produits de combustion est exacerbé par la présence de particules en cas d'utilisation de compositions "chaudes".
In general, the high initial "cold" product surface at low combustion speed induces, in addition to the aforementioned drawbacks, the following difficulties:
  • the combustion of the product is initiated slowly and a high ignition charge is required;
  • the manufacture of small pellets necessary to obtain the flow rate over the duration of the combustion induces a high flow at the start and therefore a large increase in pressure at the beginning of combustion in the bag. This is damaging for said bag in the first milliseconds, when it is folded and said bag is therefore strongly subjected to positioning constraints in the deployment phase;
  • the combustion of pellets with decreasing surface evolution induces a decrease in the flow rate as the combustion progresses while the functional need is on the contrary a constant or even increasing flow over time.
  • • The high swelling capacity of a composition being associated with the molar yield gaseous temperature pair, the compositions meeting these requirements have a high combustion temperature and a low level of particles produced during combustion. The low level of particles is necessary to have the maximum amount of gas emitted and so as to avoid aggression on the bags. Tests in airbag modules have indeed shown that the damage of the bags by the combustion products is exacerbated by the presence of particles in case of use of "hot" compositions.

Pour l'ensemble des raisons précitées, une composition à fort pouvoir gonflant, à fort débit surfacique de gonflage et sans particules présente beaucoup d'avantages vis-à-vis du fonctionnement et de la miniaturisation des générateurs de gaz pour système airbag. Cette miniaturisation est requise pour des raisons de coût, de poids et d'intégration à l'intérieur des véhicules.For all of the above reasons, 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.

Des composés obtenus à partir de compositions extrudables sans solvant à fort pouvoir gonflant ont déjà été employés dans les systèmes airbags. De telles compositions, dites double base, contenant de la nitrocellulose et de la nitroglycérine ont été employées dans les années quatre-vingt-dix sous forme de blocs monolithiques. On trouve des détails de formulations et de composés de propergol double base dans l'ouvrage de Davenas "Technologie des propergols solides", édition Masson 1989 , et on trouve un exemple d'utilisation de ces composés dans la demande de brevet FR 2 853 872 . Les formulations présentent un fort rendement gazeux, une température de combustion relativement élevée et un faible taux de particules. Des tests conduits en modules airbags avec ces composés ont montré que le fonctionnement pouvait être bon en sac non enduit de relativement faible épaisseur (∼ 470 dtex). L'agression sur le sac est acceptable malgré la température élevée du fait du faible taux de particules produit et du fait du fonctionnement induit par le bloc monolithique qui limite l'agression sur le sac en début de déploiement. Ces composés ne sont toutefois plus employés sur les nouveaux équipements car ils ne résistent pas suffisamment aux vieillissements à haute température requis par les constructeurs automobiles. En plus du problème de vieillissement en température, ces composés présentent une balance en oxygène décalée vers les valeurs négatives (déficit en oxygène) qui induit un taux de monoxyde de carbone nettement supérieur aux normes maximales en vigueur pour l'application considérée. La balance en oxygène est le pourcentage massique d'oxygène libéré (valeur positive) ou absorbée (valeur négative) lors de la réaction de combustion d'un constituant. A titre d'exemple, un groupement CH2, élément de base des polymères aliphatiques, présente une balance en oxygène de -343 %. En effet, il faut trois atomes d'oxygène dont la masse molaire est de 48 g pour équilibrer la combustion des 14 g/mole de CH2.Compounds obtained from extrudable, solvent-free, high-swelling compositions have already been employed in airbag systems. Such double base compositions containing nitrocellulose and nitroglycerine have been used in the nineties as monolithic blocks. The details of formulations and dual base propellant compounds are found in Davenas "Solid Propellant Technology", Masson edition 1989 , and there is an example of use of these compounds in the patent application FR 2,853,872 . The formulations have a high gas yield, a relatively high combustion temperature and a low particle level. Tests conducted in modular airbags with these compounds have shown that the operation could be good in uncoated bag of relatively small thickness (~ 470 dtex). Aggression on the bag is acceptable despite the high temperature due to the low level of particles produced and because of the operation induced by the monolithic block which limits aggression on the bag at the beginning of deployment. However, these compounds are no longer used on new equipment because they do not withstand the high-temperature aging required by car manufacturers. In addition to the problem of temperature aging, these compounds have an oxygen balance shifted to negative values (oxygen deficiency) which induces a carbon monoxide level well above the maximum standards in force for the application in question. The oxygen balance is the mass percentage of oxygen released (positive value) or absorbed (negative value) during the combustion reaction of a constituent. By way of example, a CH 2 group, the basic element of aliphatic polymers, has an oxygen balance of 343%. Indeed, it takes three oxygen atoms whose molar mass is 48 g to balance the combustion of 14 g / mole of CH 2 .

Pour pallier ces difficultés, des compositions à base de liant silicone ont ensuite été proposées. Des compositions à base de liant "RTV" ("Room Température Vulcanizable") et de perchlorate de potassium ont été décrites dans les demandes de brevet FR 2 190 776 et FR 2 213 254 . La demande de brevet FR 2 728 562 décrit une version améliorée de ces produits, fabricables par un procédé de malaxage et d'extrusion en continu. Dans ce dernier document, le liant silicone est associé à un mélange de perchlorate d'ammonium et de nitrate de sodium ; ledit nitrate de sodium servant de capteur de chlore. Les compositions suivant ces documents présentent un rendement gazeux acceptable, une température de combustion élevée et une forte vitesse de combustion. Le débit surfacique de gonflage est donc relativement fort. En outre, par rapport aux compositions à base de nitrocellulose et de nitroglycérine, ces compositions présentent l'avantage d'être très stables en température et de pouvoir être réglées en "oxygen balance" (balance en oxygène) de manière à respecter les normes de toxicité des effluents gazeux. Ces compositions présentent par contre l'inconvénient d'émettre un fort taux de particules (environ 30 %), notamment du chlorure de sodium et de la silice, ce qui nécessite l'emploi d'un sac présentant une forte épaisseur et une enduction de protection de la face interne dudit sac.To overcome these difficulties, 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. In the latter document, 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. In addition, 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. However, 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.

La demande de brevet EP 1 216 977 décrit, elle, une composition extrudable sans solvant comprenant essentiellement un liant hydrocarboné oxygéné à deux composants (un élastomère (une gomme) et un plastifiant), un composé organique azoté et des charges oxydantes. Les charges oxydantes sont le perchlorate d'ammonium et un capteur de chlore qui peut être du nitrate de sodium. Le nitrate de sodium entre à hauteur d'environ 15 à 20 % en poids dans la composition. Son rôle est de capter le chlore du perchlorate d'ammonium pour former du chlorure de sodium. Cette composition présente une température de combustion élevée ainsi qu'un pouvoir gonflant et un débit surfacique du même ordre de grandeur que ceux des bases silicone, en raison d'une vitesse de combustion légèrement plus faible et d'un taux de particules plus faible. Malgré ce gain, le rendement gazeux, et donc le pouvoir gonflant, est limité par la présence du capteur de chlore qui induit la formation d'un sel de chlore solide. La teneur globale en résidus de combustion solides de ces compositions est d'environ 14 %. Les vitesses de combustion de ces compositions sont d'environ 20 à 40 mm/s à une pression de combustion de 20 MPa.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. Despite this gain, 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.

L'homme du métier est toujours à la recherche de compositions à température de combustion élevée, générant peu de particules et d'effluent toxique (dans le but d'accroître le pouvoir gonflant et le débit surfacique de gonflage, de manière à réduire les volumes, masses et coûts des générateurs de gaz pour système airbag), ces compositions pouvant avantageusement être mises en forme par extrusion sans solvant, ce qui permet la réalisation de forme monolithique facilitant le chargement, améliorant la densité de chargement du générateur. En outre, l'absence de solvant permet d'éviter l'émission de COV (composés organiques volatils).Those skilled in the art are always looking for 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. In addition, the absence of solvent avoids the emission of VOCs (volatile organic compounds).

En partant de l'enseignement de la demande EP 1 216 977 , les inventeurs ont souhaité proposer des composés pyrotechniques générateurs de gaz améliorés. Ils se sont plus particulièrement fixés pour objectifs :

  • d'accroître le rendement gazeux ;
  • de supprimer les particules (résidus de combustion solides) ;
  • de disposer d'une forte vitesse de combustion permettant d'augmenter l'épaisseur à brûler et donc la compacité du générateur ;
ce, afin de :
  • réduire le volume et la masse de propergol nécessaires, et
  • éliminer les filtres utiles à la filtration desdites particules.
Starting from the teaching of demand EP 1 216 977 the inventors wished to propose improved pyrotechnic gas-generating compounds. In particular, they set themselves the objectives:
  • to increase the gas yield;
  • to remove particles (solid combustion residues);
  • to have a high rate of combustion to increase the thickness to be burned and therefore the compactness of the generator;
this, in order to:
  • reduce the volume and mass of propellant needed, and
  • eliminate the filters useful for the filtration of said particles.

Ainsi le générateur de gaz peut être plus petit, compact et moins coûteux. En outre, malgré une forte température des gaz de combustion, l'absence de particules, la progressivité de la mise en régime du débit de gaz liée au fonctionnement d'un bloc monolithique et la modération de l'énergie libérée du fait de la faible masse de produit pyrotechnique nécessaire devraient permettre d'employer des sacs d'épaisseur modérée ou faible.Thus the gas generator can be smaller, compact and less expensive. In addition, despite a high temperature of the combustion gases, the absence of particles, 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.

L'objectif de perfectionnement fixé a été atteint. Les inventeurs proposent présentement des composés pyrotechniques performants, en référence au cahier des charges ci-dessus, des composés pyrotechniques plus performants que ceux correspondants aux compositions de la demande EP 1 216 977 .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 .

Les composés pyrotechniques de l'invention ont une composition du type de celle des composés selon ladite demande EP 1 216 977 en ce qu'elle renferme :

  • une charge oxydante de perchlorate d'ammonium (i.e. sans carbone) ; et
  • un liant hydrocarboné oxygéné réticulé, obtenu par réticulation d'un élastomère en présence d'au moins un agent réticulant et d'au moins un plastifiant oxygéné dudit élastomère ; ledit élastomère ayant une masse moléculaire supérieure à 200 000 et étant choisi parmi les polyesters et les polyacrylates. Le(s) plastifiant(s) est(sont) évidemment parfaitement miscible(s) dans l'élastomère, de manière à ne pas exsuder en température et à ainsi abaisser la température de transition vitreuse dudit élastomère.
The pyrotechnic compounds of the invention have a composition of the type of compounds according to said application EP 1 216 977 in that it contains:
  • an oxidizing charge of ammonium perchlorate (ie without carbon); and
  • a crosslinked oxygenated hydrocarbon binder obtained by crosslinking an elastomer in the presence of at least one crosslinking agent and at least one oxygenated plasticizer of said elastomer; said elastomer having a molecular weight greater than 200,000 and being selected from polyesters and polyacrylates. The plasticizer (s) is (are) obviously perfectly miscible (s) in the elastomer, so as not to exude temperature and thus lower the glass transition temperature of said elastomer.

Les composés pyrotechniques générateurs de gaz de l'invention, convenant pour les systèmes de protection des occupants de véhicules, comprennent donc, dans leur composition, une charge oxydante (sans carbone) et un liant hydrocarboné oxygéné, des types ci-dessus.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.

De façon caractéristique, la charge oxydante en cause ne comprend pas de capteur de chlore et ledit au moins un plastifiant oxygéné de l'élastomère consiste en :

  • un plastifiant choisi parmi les diesters à fonctions éthers dont la masse moléculaire est supérieure à 350 g/mol (sa tension de vapeur est ainsi négligeable à 120°C) et la balance en oxygène égale ou supérieure à -230 % (ladite balance en oxygène peut ainsi être équilibrée en combustion avec les charges choisies) ; ou
  • un mélange de tels plastifiants entre eux (d'au moins deux plastifiants de ce type) ; ou
  • un mélange d'au moins un tel plastifiant avec au moins un autre plastifiant oxygéné (d'un autre type).
Typically, the oxidizing charge in question does not include a chlorine sensor and said at least one oxygenated plasticizer of the elastomer consists of:
  • a plasticizer chosen from diesters with ether functions whose molecular mass is greater than 350 g / mol (its vapor pressure is thus negligible at 120 ° C.) and the oxygen balance equal to or greater than -230% (said oxygen balance) can be balanced in combustion with the chosen loads); or
  • a mixture of such plasticizers with each other (of at least two plasticizers of this type); or
  • a mixture of at least one such plasticizer with at least one other oxygenated plasticizer (of another type).

Ledit au moins un plastifiant oxygéné original présent consiste avantageusement en au moins un plastifiant aux propriétés énoncées ci-dessus. Des mélanges de tels plastifiants avec d'autres plastifiants oxygénés (tels le dioctyladipate et/ou le dioctylazélate) peuvent toutefois également être présents.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.

Les inventeurs ont démontré qu'il était possible de compenser la suppression de la charge oxydante complémentaire constituée par le capteur de chlore (notamment le nitrate de sodium) selon l'enseignement de la demande EP 1 216 977 , par la présence d'un nouveau plastifiant oxygéné, qui apporte la quantité d'oxygène nécessaire à la bonne combustion, évitant ainsi la production de CO (dont la concentration doit être limitée selon les normes en vigueur, pour le type d'application visée). Ce résultat n'était nullement acquis par avance.The inventors have demonstrated that it is possible to compensate for the suppression of the additional oxidizing charge constituted by the chlorine sensor (in particular sodium nitrate) according to the teaching of the demand. EP 1 216 977 , by the presence of a new oxygenated plasticizer, which brings the quantity of oxygen necessary for the good combustion, thus avoiding the production of CO (whose concentration must be limited according to the standards in force, for the type of application aimed at ). This result was not acquired in advance.

Les composés de l'invention présentent généralement l'inconvénient d'émettre du chlorure d'hydrogène. En fin de combustion, ledit chlorure d'hydrogène se condense avec l'eau formée par la combustion et peut être capté par le sac. Le taux de chlorure d'hydrogène émis par les composés selon l'invention est d'environ 0,2 g/g. De manière à limiter la diffusion du chlorure d'hydrogène dans l'habitacle du véhicule, le sac peut être enduit avec des capteurs de chlore.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. In order to limit the diffusion of hydrogen chloride into the passenger compartment of the vehicle, the bag can be coated with chlorine sensors.

Les composés pyrotechniques générateurs de gaz de l'invention se caractérisent donc en ce que leur composition ne renferme pas de capteur de chlore (oxydant complémentaire) mais au moins un plastifiant oxygéné spécifique (qui compense l'absence dudit oxydant complémentaire).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).

Ledit au moins un plastifiant oxygéné est très avantageusement choisi parmi :

  • le dibutoxyéthoxyéthyl adipate (DBEEA),
  • le dibutoxyéthoxyéthoxyéthyl adipate (DBEEEA),
  • le dibutoxyéthoxyéthoxyéthyl glutarate (DBEEEG),
  • le dibutoxyéthoxyéthoxyéthyl phtalate,
  • le bis(éthylène glycol monobutyl éther) adipate (dibutyl cellosolve® adipate), ,
  • le bis(éthylène glycol monobutyl éther) phtalate (dibutyl cellosolve® phtalate),
  • les mélanges desdits diesters, entre eux, et
  • les mélanges d'au moins un desdits diesters avec le dioctyladipate (DOA) et/ou le dioctylazélate.
Said at least one oxygenated plasticizer is very advantageously chosen from:
  • dibutoxyethoxyethyl adipate (DBEEA),
  • dibutoxyethoxyethoxyethyl adipate (DBEEEA),
  • dibutoxyethoxyethoxyethylglutarate (DBEEEG),
  • dibutoxyethoxyethoxyethyl phthalate,
  • bis (ethylene glycol monobutyl ether) adipate (dibutyl cellosolve ® adipate),,
  • bis (ethylene glycol monobutyl ether) phthalate (dibutyl cellosolve ® phthalate),
  • mixtures of said diesters, with each other, and
  • mixtures of at least one of said diesters with dioctyladipate (DOA) and / or dioctylazelate.

On a ci-dessus précisé la nature originale du second principal composant (plastifiant) du liant hydrocarboné oxygéné réticulé (liant = élastomère réticulé + plastifiant) des composés pyrotechniques de l'invention. On se propose ci-après de donner, de façon nullement limitative, des précisions sur chacun des constituants desdits composés ainsi que sur leur quantité d'intervention respective.The original nature of the second main component (plasticizer) of the crosslinked oxygenated hydrocarbon binder (binder = crosslinked elastomer + plasticizer) of the pyrotechnic compounds of the invention has been specified above. It is proposed hereinafter to give, in no way limiting, details on each of the constituents of said compounds and their respective amount of intervention.

La charge oxydante représente généralement de 64 à 94 % en masse de la masse totale du composé, avantageusement de 72 à 82 % en masse de ladite masse totale. Il s'agit du constituant principal des composés de l'invention.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.

Ladite charge oxydante consiste en du perchlorate d'ammonium. Ledit perchlorate d'ammonium intervient avantageusement sous plusieurs granulométries de manière à améliorer l'incorporation et la distribution dans le polymère et à diminuer la toxicité des effluents gazeux lors de la combustion.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.

Le liant hydrocarboné oxygéné réticulé représente généralement de 6 à 20 % en masse de la masse totale du composé. Il représente avantageusement de 8 à 16 % en masse de la masse totale. Il comprend l'élastomère réticulé et ledit au moins un plastifiant oxygéné original de l'invention. L'élastomère en cause est un élastomère de haute masse moléculaire : Mw > 200 000 g/mol. Il est choisi dans la famille des polyesters et polyacrylates. Les polyacrylates peuvent avoir des terminaisons réactives de type chlore/carboxyle, chlore, hydroxyle ou époxy. Les polyesters peuvent avoir des terminaisons réactives de type hydroxyle. Ils ont avantageusement de telles terminaisons réactives de type hydroxyle. L'élastomère présent dans la composition des composés de l'invention a été réticulé via ses fonctions réactives par au moins un agent réticulant (= agent de réticulation). Un tel agent réticulant consiste avantageusement en un diisocyanate ou triisocyanate.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. The elastomer present in the composition of the compounds of the invention has been crosslinked via its reactive functional groups by at least one crosslinking agent (= crosslinking agent). Such a crosslinking agent advantageously consists of a diisocyanate or triisocyanate.

De manière générale : ledit au moins un élastomère et ledit au moins un agent réticulant représentent de 3 à 10 % en masse, avantageusement de 4 à 8 % en masse, de la masse totale des composés de l'invention ; et/ou, avantageusement et,
ledit au moins un plastifiant représente de 3 à 10 % en masse, avantageusement de 4 à 8 % en masse, de la masse totale desdits composés.In general: 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.

En plus des deux constituants décrits ci-dessus : la charge oxydante et le liant hydrocarboné oxygéné réticulé (élastomère + au moins un agent réticulant + au moins un plastifiant oxygéné original), les composés de l'invention peuvent comprendre, dans leur composition, les constituants additionnels suivants :

  • au moins un composé organique nitré (azoté) dont la balance en oxygène est supérieure à -30 % (qui permet notamment d'augmenter le rendement gazeux). Un tel au moins un composé est avantageusement choisi parmi les nitrates azotés et les dinitramides. Il consiste très avantageusement en le nitrate de guanidine (NG) ou la guanyle urée dinitramide (GUDN). Généralement, un tel au moins un composé intervient entre 0 (1) et 10 %, avantageusement entre 3 et 8 %, en masse au sein des composés de l'invention ;
  • au moins un catalyseur balistique (qui permet entre autres d'améliorer la vitesse de combustion). L'homme du métier sait qu'un tel catalyseur balistique consiste en un oxyde de métal de transition, à haute surface spécifique (qui accélère la décomposition de la charge oxydante). Un tel au moins un catalyseur balistique est avantageusement choisi parmi l'oxyde de cuivre, l'oxyde de fer, l'oxyde de manganèse et l'oxyde de cobalt. Généralement, un tel au moins un catalyseur balistique intervient entre 0 (0,1) et 6 %, avantageusement entre 0 (0,1) et 2 %, très avantageusement entre 1 et 2 %, en masse au sein des composés de l'invention ;
  • au moins un agent mouillant choisi parmi les organosiloxanes et les titanates. Un tel au moins un agent mouillant est avantageusement choisi parmi le vinyltris-(2-méthoxyéthoxy)silane, le tris-(3-triméthoxysilylpropyl)isocyanurate, le γ-glycidoxypropyltriméthoxysilane, le diéthoxydiacétoxysilane, le diacétoxydiéthoxysilane et le dibutoxyéthoxyméthylsilane. Un tel au moins un agent mouillant permet de réduire la viscoélasticité et la porosité résiduelle du composé. Généralement, un tel au moins un agent mouillant intervient entre 0 (0,1) et 4 %, avantageusement entre 0,2 et 3 %, en masse au sein des composés de l'invention.
In addition to the two components described above: the oxidizing charge and the crosslinked oxygenated hydrocarbon binder (elastomer + at least one crosslinking agent + at least one original oxygenated plasticizer), the compounds of the invention may comprise, in their composition, the additional constituents:
  • at least one nitrated organic compound (nitrogen) whose oxygen balance is greater than -30% (which allows in particular to increase the gas yield). Such at least one compound is advantageously chosen from nitrogen nitrates and dinitramides. It consists very advantageously of guanidine nitrate (NG) or guanyl urea dinitramide (GUDN). Generally, such at least one compound is between 0 (1) and 10%, advantageously between 3 and 8%, by weight within the compounds of the invention;
  • at least one ballistic catalyst (which makes it possible, among other things, to improve the combustion rate). The person skilled in the art knows that such a ballistic catalyst consists of a transition metal oxide with a high specific surface area (which accelerates the decomposition of the oxidizing charge). Such at least one ballistic catalyst is advantageously selected from copper oxide, iron oxide, manganese oxide and cobalt oxide. Generally, such at least one ballistic catalyst intervenes between 0 (0.1) and 6%, advantageously between 0 (0.1) and 2%, very advantageously between 1 and 2%, by weight within the compounds of the invention;
  • at least one wetting agent selected from organosiloxanes and titanates. Such at least one wetting agent is advantageously chosen from vinyltris- (2-methoxyethoxy) silane, tris- (3-trimethoxysilylpropyl) isocyanurate, γ-glycidoxypropyltrimethoxysilane, diethoxydiacetoxysilane, diacetoxydiethoxysilane and dibutoxyethoxymethylsilane. Such at least one wetting agent makes it possible to reduce the viscoelasticity and the residual porosity of the compound. Generally, such at least one wetting agent intervenes between 0 (0.1) and 4%, advantageously between 0.2 and 3%, by weight within the compounds of the invention.

Au vu des propos ci-dessus, on a compris que la composition massique des composés de l'invention est généralement de :

  • 64 à 94 %, avantageusement 72 à 82 %, d'une charge oxydante ;
  • 6 à 20 %, avantageusement 8 à 16 %, d'au moins un liant hydrocarboné oxygéné réticulé ;
  • 0 à 10 %, avantageusement 3 à 8 %, d'au moins un composé organique nitré dont l'oxygène balance est supérieure à -30 % ;
  • 0 à 6 %, avantageusement de 1 à 2 %, d'au moins un catalyseur balistique ; et
  • 0 à 4 %, avantageusement 0,2 à 3 %, d'au moins un agent mouillant.
In view of the above, it has been understood that the mass composition of the compounds of the invention is generally:
  • From 64 to 94%, advantageously 72 to 82%, of an oxidizing charge;
  • 6 to 20%, advantageously 8 to 16%, of at least one crosslinked oxygenated hydrocarbon binder;
  • 0 to 10%, advantageously 3 to 8%, of at least one nitrated organic compound whose oxygen balance is greater than -30%;
  • 0 to 6%, preferably 1 to 2%, of at least one ballistic catalyst; and
  • 0 to 4%, advantageously 0.2 to 3%, of at least one wetting agent.

Les constituants (charge oxydante + liant hydrocarboné oxygéné réticulé + éventuels constituants choisis parmi ceux identifiés ci-dessus) de la composition des composés de l'invention, listés ci-dessus, représentent au moins 95 % en masse desdits composés, généralement au moins 98 % en masse desdits composés. Le complément, si complément il y a, est généralement constitué d'additifs, tels des auxiliaires (aides) de fabrication.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.

Les composés de l'invention, dont on précise ci-après le procédé d'obtention, peuvent être de différents types. Il s'agit de composés monolithiques qui peuvent être pleins, mono- ou multiperforés. Lesdits composés renferment dans leur composition, de façon caractéristique, un plastifiant oxygéné original tel que décrit ci-dessus.The compounds of the invention, of which the method of production is specified below, 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.

Lesdits composés sont particulièrement performants. Leur composition est à haut rendement gazeux (environ 36 mol/kg) avec des températures de combustion aux alentours de 3000 K (il s'agit bien de compositions dites chaudes). Leur vitesse de combustion est rapide, environ 45 mm/s à une pression de 20 MPa. De par leur composition, ils génèrent très peu de particules solides (< 2 %). Leur composition est par ailleurs susceptible, selon des variantes avantageuses, de présenter une valeur de balance en oxygène comprise entre -2 % et -3 %, i.e. qu'ils ne génèrent que très peu de gaz toxique et qu'ils conviennent tout à fait pour une application dans le domaine des airbags. Les débits surfaciques de gonflage des compositions des composés de l'invention sont très intéressants. Ils sont d'environ 830 mol.K/cm2.s.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.

Le procédé d'obtention des composés de l'invention est avantageusement un procédé par analogie, tel que décrit dans la demande EP 1 216 077 . Il s'agit très avantageusement d'un procédé mis en oeuvre en continu, sans solvant, dans un mélangeur-extrudeur bi-vis.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.

On indique, de manière plus générale, que ledit procédé comprend :

  • mis en oeuvre en continu, le mélange sans solvant de la charge oxydante, de l'élastomère, du au moins un agent réticulant et du au moins un plastifiant ainsi qu'éventuellement du au moins un composé organique nitré dont l'oxygène balance est supérieure à -30 % et/ou du au moins un catalyseur balistique et/ou du au moins un agent mouillant et l'extrusion de la pâte résultant dudit mélange ;
  • le traitement thermique de ladite pâte extrudée pour assurer la réticulation dudit élastomère.
More generally, said method comprises:
  • implemented continuously, the solvent-free mixture of the oxidizing charge, the elastomer, the at least one crosslinking agent and the at least one plasticizer and optionally at least one nitrated organic compound whose oxygen balance is greater than at -30% and / or at least one ballistic catalyst and / or at least one wetting agent and the extrusion of the paste resulting from said mixture;
  • heat treatment of said extruded paste to ensure crosslinking of said elastomer.

De façon caractéristique, ledit au moins un plastifiant consiste en ou comprend un plastifiant original de l'invention.Typically, said at least one plasticizer consists of or comprises an original plasticizer of the invention.

Comme indiqué ci-dessus, lesdits mélange et extrusion sont avantageusement mis en oeuvre dans un mélangeur-extrudeur bi-vis.As indicated above, said mixing and extrusion are advantageously carried out in a twin screw mixer-extruder.

Par ailleurs, ledit procédé comprend avantageusement la découpe de la pâte extrudée en chargements et le traitement thermique desdits chargements (chargements réticulés = composés de l'invention).Furthermore, said method advantageously comprises cutting the extruded paste in loadings and heat treatment of said loadings (crosslinked loadings = compounds of the invention).

De façon nullement limitative, on peut préciser ci-après une variante de mise en oeuvre du procédé de l'invention.In no way limiting, we can specify below an alternative embodiment of the method of the invention.

Le mélangeur-extrudeur bi-vis comprend un compartiment de mélange et de malaxage, un compartiment de compression et une tête d'extrusion. Les constituants solides et liquides sont introduits dans le compartiment de mélange et de malaxage par deux ouvertures d'alimentation différentes, une ouverture d'alimentation des solides et une ouverture d'alimentation des liquides, puis transportés et malaxés, puis la pâte homogène ainsi formée est dégazée dans le compartiment de compression, puis extrudée à l'aide d'une tête d'extrusion sous forme de joncs, et enfin les joncs ainsi formés sont découpés en chargements à l'aide d'un appareil de découpe, puis ces chargements sont mis à réticuler à une température généralement comprise entre 100°C et 150°C.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.

Les chargements ainsi formés trouvent leur application préférentielle comme chargement pyrotechnique dans les générateurs de gaz destinés à gonfler un coussin de protection pour occupants d'un véhicule automobile. En effet, la vitesse de combustion de ces chargements, ainsi que le taux de résidus solides produits et le taux de monoxyde de carbone et d'oxydes d'azote produits conviennent particulièrement (voir ci-dessus).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).

On se propose maintenant d'illustrer, de façon nullement limitative, l'invention présentement revendiquée.It is now proposed to illustrate, in a non-limiting manner, the presently claimed invention.

Les compositions de composés pyrotechniques ont été évaluées au moyen de calculs thermodynamiques et de mesures physiques.The compositions of pyrotechnic compounds have been evaluated by means of thermodynamic calculations and physical measurements.

Ces compositions et composés correspondent à des compositions et composés de l'art antérieur (compositions A et B ci-après et composés correspondants (respectivement pastilles et chargements extrudés) ou à des compositions et composés de l'invention (compositions 1 et 2 ci-après et composés correspondants = chargements extrudés).These compositions and compounds correspond to compositions and compounds of the prior art (compositions A and B hereinafter and corresponding compounds (respectively pellets and extruded charges) or to compositions and compounds of the invention (compositions 1 and 2 below). after and corresponding compounds = extruded loads).

Composition_A , dite froide, de l'art antérieur Composition_A , so-called cold, of the prior art

Cette composition, sans liant, renferme :

  • 49 % en masse de nitrate de guanidine,
  • 48% en masse de nitrate basique de cuivre, et
  • 3 % en masse d'auxiliaire(s) de fabrication.
This composition, without binder, contains:
  • 49% by weight of guanidine nitrate,
  • 48% by mass of basic nitrate of copper, and
  • 3% by weight of auxiliary (s) of manufacture.

Elle est du type des compositions selon les brevets US 6 143 102 et 5 608 183 .It is of the type of the compositions according to the patents US 6,143,102 and 5,608,183 .

A partir de ladite composition, on a préparé des pastilles.From said composition, pellets were prepared.

Composition B de l'art antérieur Composition B of the prior art

Cette composition, avec liant, renferme :

  • 59 % en masse de perchlorate d'ammonium,
  • 21 % en masse de nitrate de sodium,
  • 5 % en masse de nitrate de guanidine, et
  • 15 % en masse d'élastomère acrylique, de réticulant et de plastifiant.
This composition, with binder, contains:
  • 59% by weight of ammonium perchlorate,
  • 21% by weight of sodium nitrate,
  • 5% by weight of guanidine nitrate, and
  • 15% by weight of acrylic elastomer, crosslinking agent and plasticizer.

Cette composition est une composition selon la demande de brevet EP 1 216 077 . Elle est extrudée et réticulée pour générer des composés.This composition is a composition according to the patent application EP 1 216 077 . It is extruded and crosslinked to generate compounds.

Composition 1 d'un composé de l'invention Composition 1 of a compound of the invention

Elle renferme :

  • 79,9 % en masse de perchlorate d'ammonium,
  • 6,2 % en masse d'élastomère acrylique + agent de réticulation,
  • 6,4 % en masse de DBEEEG (plastifiant),
  • 1 % en masse de vinyltris-(2-méthoxyéthoxy)silane,
  • 5,5 % en masse de nitrate de guanidine, et
  • 1 % en masse d'oxyde ferrique.
It contains:
  • 79.9% by weight of ammonium perchlorate,
  • 6.2% by weight of acrylic elastomer + crosslinking agent,
  • 6.4% by weight of DBEEEG (plasticizer),
  • 1% by weight of vinyltris- (2-methoxyethoxy) silane,
  • 5.5% by weight of guanidine nitrate, and
  • 1% by weight of ferric oxide.

La balance en oxygène de cette composition est de -2,3 %. Sa densité théorique est de 1,73 g/cm3.The oxygen balance of this composition is -2.3%. Its theoretical density is 1.73 g / cm 3 .

Sa température de combustion est d'environ 3000 K, à 20 MPa et son rendement molaire est de 36,1 mol/kg.Its combustion temperature is about 3000 K at 20 MPa and its molar yield is 36.1 mol / kg.

Le taux de particules est inférieur à 2 %.The particle content is less than 2%.

Suivant la granulométrie des charges employées, la vitesse de combustion des composés (extrudés) est comprise entre 40 et 50 mm/s à 20 MPa (voir le tableau ci-après).Depending on the particle size of the charges used, the burning rate of the compounds (extruded) is between 40 and 50 mm / s at 20 MPa (see table below).

Composition 2 d'un composé de l'invention Composition 2 of a compound of the invention

Elle renferme :

  • 79,9 % en masse de perchlorate d'ammonium,
  • 6% en masse d'élastomère acrylique + agent de réticulation,
  • 6 % en masse de DBEEA (plastifiant),
  • 1,6 % en masse de vinyltris-(2-méthoxyéthoxy)silane,
  • 5,5 % en masse de nitrate de guanidine, et
  • 1 % en masse d'oxyde ferrique.
It contains:
  • 79.9% by weight of ammonium perchlorate,
  • 6% by weight of acrylic elastomer + crosslinking agent,
  • 6% by weight of DBEEA (plasticizer),
  • 1.6% by weight of vinyltris- (2-methoxyethoxy) silane,
  • 5.5% by weight of guanidine nitrate, and
  • 1% by weight of ferric oxide.

La balance en oxygène de cette composition est de -2,4 %. Sa densité théorique est de 1,72 g/cm3.The oxygen balance of this composition is -2.4%. Its theoretical density is 1.72 g / cm 3 .

Sa température de combustion est d'environ 3000 K à 20 MPa et son rendement molaire est de 36 mol/kg.Its combustion temperature is about 3000 K to 20 MPa and its molar yield is 36 mol / kg.

Le taux de particules est inférieur à 2 %.The particle content is less than 2%.

Suivant la granulométrie des charges employées, la vitesse de combustion des composés (extrudés) est comprise entre 40 et 50 mm/s à 20 MPa (voir le tableau ci-après).Depending on the particle size of the charges used, the burning rate of the compounds (extruded) is between 40 and 50 mm / s at 20 MPa (see table below).

Les performances des compositions A, B, 1 et 2 et celles des composés correspondants sont données dans le tableau 1 ci-après.The performances of compositions A, B, 1 and 2 and those of the corresponding compounds are given in Table 1 below.

La plupart des valeurs indiquées dans ledit tableau 1 sont des valeurs calculées. Les vitesses de combustion et les porosités ont, elles, été mesurées sur les composés obtenus à partir des compositions. Tableau 1 Art antérieur Invention Compositions A
(sans liant, pastillée) B
(extrudée, selon EP 1 216 077) Exemples 1 et 2
(composés extrudés) Température de combustion à 20 MPa (K) 1870 2800 2900 < T< 3100 Rendement gazeux à 1000 K et 20 MPa (mole/kg) 29,6 31,5 (à 0,1 MPa) 34 < R < 37 Taux de résidus solides à 1000 K et 1 bar (%) 26,7 16 < 2 Vitesse de combustion à 20 MPa (mm/s) 22 38 40 < Vc < 50 Densité (g/cm3) 1,98 1,7 1,68 <p < 1,75 Porosité % 3 / < 0,2 Pouvoir gonflant volumique (mol.K/cm3) 106,3 151 ∼185 Débit surfacique de gonflage (mol.K/cm2s) 233,9 575 830 < D < 840 Most of the values shown in Table 1 are calculated values. The combustion rates and the porosities were measured on the compounds obtained from the compositions. <u> Table 1 </ u> Prior art Invention compositions AT
(without binder, pelletized) B
(extruded, according to EP 1 216 077) Examples 1 and 2
(extruded compounds) Combustion temperature at 20 MPa (K) 1870 2800 2900 <T <3100 Gaseous yield at 1000 K and 20 MPa (mole / kg) 29.6 31.5 (at 0.1 MPa) 34 <R <37 Solid residue rate at 1000 K and 1 bar (%) 26.7 16 <2 Burning rate at 20 MPa (mm / s) 22 38 40 <Vc <50 Density (g / cm 3 ) 1.98 1.7 1.68 <p <1.75 Porosity% 3 / <0.2 Bulking power volume (mol.K / cm 3 ) 106.3 151 ~185 Flow rate of inflation (mol.K / cm 2 s) 233.9 575 830 <D <840

Les résultats du tableau 1 ci-dessus indiquent que le pouvoir de gonflage volumique des compositions des composés de l'invention est environ 45 % à 75 % supérieur à celui des compositions de référence de l'art antérieur. Compte tenu des densités respectives des divers composés, la masse peut être quasiment divisée par deux pour remplir la même fonction de gonflage.The results of Table 1 above indicate that the volume blowing power of the compositions of the compounds of the invention is about 45% to 75% higher than that of the prior art reference compositions. Given the respective densities of the various compounds, the mass can be almost halved to fulfill the same inflation function.

En outre, la vitesse de combustion nettement plus forte des composés de l'invention engendre un débit surfacique de gonflage supérieur à celui des composés de référence. Par rapport aux pastilles de composition A, la dimension caractéristique de l'objet à brûler peut être doublée pour assurer une durée de fonctionnement équivalente. Le bloc extrudé réalisé à partir des compositions de l'invention peut donc être très compact et permettre le développement de générateurs de petite taille contenant une faible masse pyrotechnique.In addition, 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. With respect to the pellets of composition A, 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.

De plus, en l'absence de particules émises par la combustion, les générateurs de gaz employant les composés de l'invention peuvent être dans une certaine mesure dépourvus de filtres à particules. Ce faisant, les pertes thermiques des gaz sont réduites.In addition, in the absence of particles emitted by combustion, 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.

Il convient aussi de noter que la mise en forme de ces compositions sous forme d'un bloc monolithique à très forte vitesse de combustion permet de réaliser un allumage à faible débit. La géométrie monolithique du chargement autorise aussi la conception de formes permettant de délivrer un débit progressif ou constant, ce qui n'est pas possible avec des chargements pastillés usuellement utilisés dans le cas de compositions type A.It should also be noted that the shaping of these compositions in the form of a monolithic block with a very high combustion rate makes it possible to achieve low flow ignition. The monolithic geometry of the loading also allows the design of shapes to deliver a progressive or constant flow, which is not possible with pelletized loads usually used in the case of type A compositions.

Les composés de l'invention présentent généralement l'inconvénient d'émettre du chlorure d'hydrogène. En fin de combustion, ledit chlorure d'hydrogène se condense avec l'eau formée par la combustion et peut être capté par le sac. Le taux de chlorure d'hydrogène émis par les composés de l'invention est d'environ 0,2 g/g. De manière à limiter la diffusion du chlorure d'hydrogène dans l'habitacle du véhicule, le sac peut être enduit avec des capteurs de chlore. De plus, compte tenu de la nature de la composition des gaz qui contiennent 50 % de condensable (H2O) quand la température diminue, les évents peuvent être réduits de manière à accroître le taux de captage par condensation d'eau acidifiée dans le sac. Après le fonctionnement, le sac se dégonfle naturellement sous l'effet de la baisse de température et de la condensation des condensables.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 of the invention is about 0.2 g / g. In order to limit the diffusion of hydrogen chloride into the passenger compartment of the vehicle, the bag can be coated with chlorine sensors. In addition, given the nature of the composition of gases that contain 50% condensable (H 2 O) when the temperature decreases, 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.

Un générateur de gaz pour airbag (côté) conducteur contenant un composé selon l'invention (14 g) émet 2,8 g de chlorure d'hydrogène. En l'absence improbable de captage, le taux de chlorure d'hydrogène est de l'ordre de 700 ppm dans un habitacle de 2,8 m3.A conductive airbag (side) gas generator containing a compound according to the invention (14 g) emits 2.8 g of hydrogen chloride. In the unlikely absence of capture, the hydrogen chloride level is of the order of 700 ppm in a cabin of 2.8 m 3 .

Claims (13)

  1. A pyrotechnic gas generator compound suitable for vehicle occupant protection systems whose composition comprises:
    - an oxidizing charge of ammonium perchlorate; and
    - a crosslinked, oxygen-containing hydrocarbon binder obtained by crosslinking an elastomer in the presence of at least one crosslinking agent and at least one oxygen-containing plasticizer for said elastomer; said elastomer having a molecular weight of more than 200 000 and being selected from polyesters and polyacrylates;
    characterized in that:
    - said oxidizing charge does not contain a chlorine scavenger; and
    - said at least one oxygen-containing plasticizer is composed of a plasticizer selected from diesters having ether functions, of which the molecular weight is greater than 350 g/mol and the oxygen balance equal to or greater than -230%, of a mixture of such plasticizers with one another or of a mixture of at least one such plasticizer with at least one other oxygen-containing plasticizer.
  2. The compound of claim 1, characterized in that said at least one oxygen-containing plasticizer is selected from:
    - dibutoxyethoxyethyl adipate,
    - dibutoxyethoxyethoxyethyl adipate,
    - dibutoxyethoxyethoxyethyl glutarate,
    - dibutoxyethoxyethoxyethyl phthalate,
    - bis(ethylene glycol monobutyl ether) adipate,
    - bis(ethylene glycol monobutyl ether) phthalate
    - mixtures of said diesters with one another, and
    - mixtures of at least one of said diesters with dioctyl adipate and/or dioctyl azelate.
  3. The compound of claim 1 or 2, characterized in that said oxidizing charge represents 64% to 94% by weight, advantageously 72% to 82% by weight, of the total weight of said compound.
  4. The compound of any one of claims 1 to 3, characterized in that said crosslinked, oxygen-containing hydrocarbon binder represents 6% to 20% by weight, advantageously 8% to 16% by weight, of the total weight of said compound.
  5. The compound of any one of claims 1 to 4, characterized in that 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 weight of said compound; 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 weight of said compound.
  6. The compound of any one of claims 1 to 5, characterized in that its composition further comprises at least one organic nitro compound of which the oxygen balance is greater than -30%; in that its composition advantageously further comprises at least one organic nitro compound selected from nitrogenous nitrates and dinitramides.
  7. The compound of any one of claims 1 to 6, characterized in that its composition further comprises at least one ballistic catalyst, advantageously selected from copper oxide, iron oxide, manganese oxide, and cobalt oxide.
  8. The compound of any one of claims 1 to 7, characterized in that its composition further comprises at least one wetting agent selected from organosilanes and titanates, advantageously selected from vinyltris(2-methoxyethoxy)silane, tris(3-trimethoxysilylpropyl) isocyanurate, γ-glycidyloxypropyltrimethoxysilane, diethoxydiacetoxysilane, diacetoxydiethoxysilane, and dibutoxyethoxymethylsilane.
  9. The compound of any one of claims 1 to 8, characterized in that its composition comprises, expressed in percentages by weight:
    - 64% to 94%, advantageously 72% to 82%, of the oxidizing charge;
    - 6% to 20%, advantageously 8% to 16%, of the at least one crosslinked, oxygen-containing hydrocarbon binder;
    - 0% to 10%, advantageously 3% to 8%, of at least one organic nitro compound of which the oxygen balance is greater than -30%;
    - 0% to 6%, advantageously from 1% to 2%, of at least one ballistic catalyst; and
    - 0% to 4%, advantageously 0.2% to 3%, of at least one wetting agent.
  10. The compound of any one of claims 1 to 9, of monolithic type, which is solid or mono- or multi-perforated.
  11. A method for obtaining a compound of any one of claims 1 to 10, characterized in that it comprises:
    - continuously implementing a solventless mixing of said oxidizing charge, said elastomer, said at least one crosslinking agent, and said at least one plasticizer and also, optionally, said at least one organic nitro compound of which the oxygen balance is greater than -30% and/or said at least one ballistic catalyst and/or said at least one wetting agent, and extruding the paste resulting from said mixing;
    - heat-treating said extruded paste to carry out the crosslinking of said elastomer.
  12. The method of claim 11, characterized in that said mixing and said extruding are implemented in a twin-screw mixer-extruder.
  13. The method of either of claims 11 and 12, characterized in that it comprises cutting the extruded paste into charges and heat-treating said charges.
EP08805727A 2007-05-02 2008-04-30 Gas-generating pyrotechnic compound and production process. Not-in-force EP2139828B1 (en)

Applications Claiming Priority (2)

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FR0754809A FR2915746B1 (en) 2007-05-02 2007-05-02 PYROTECHNIC COMPOUND GAS GENERATOR; PROCESS FOR OBTAINING
PCT/FR2008/050773 WO2008145935A2 (en) 2007-05-02 2008-04-30 Gas-generating pyrotechnic compound and production process.

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EP2139828A2 EP2139828A2 (en) 2010-01-06
EP2139828B1 true EP2139828B1 (en) 2011-10-05

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FR2915746B1 (en) 2009-08-21
US20110041969A1 (en) 2011-02-24
CN101679139B (en) 2012-09-26
JP5483732B2 (en) 2014-05-07
ATE527227T1 (en) 2011-10-15
WO2008145935A2 (en) 2008-12-04
EP2139828A2 (en) 2010-01-06
WO2008145935A3 (en) 2009-09-17
JP2010526010A (en) 2010-07-29
CN101679139A (en) 2010-03-24
FR2915746A1 (en) 2008-11-07

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