EP1216977B1 - Hydrocarbon binder containing pyrotechnic gas-generating compositions and method for continuous manufacturing - Google Patents

Hydrocarbon binder containing pyrotechnic gas-generating compositions and method for continuous manufacturing Download PDF

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Publication number
EP1216977B1
EP1216977B1 EP01403255A EP01403255A EP1216977B1 EP 1216977 B1 EP1216977 B1 EP 1216977B1 EP 01403255 A EP01403255 A EP 01403255A EP 01403255 A EP01403255 A EP 01403255A EP 1216977 B1 EP1216977 B1 EP 1216977B1
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Prior art keywords
nitrate
composition
gum
binder
compartment
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EP01403255A
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German (de)
French (fr)
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EP1216977A2 (en
EP1216977A3 (en
Inventor
Dimitri Charrette
Georges Chounet
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Safran Ceramics SA
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SNPE Materiaux Energetiques SA
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • 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
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0033—Shaping the mixture
    • C06B21/0075—Shaping the mixture by extrusion
    • 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
    • C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
    • 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

Definitions

  • the present invention relates to the field technical pyrotechnic generation of gas usable especially in protection systems occupants of a motor vehicle by means of cushions that are inflated by the flue gases of a pyrotechnic loading. More specifically, the invention pyrotechnic compositions generating to acceptable temperatures for automotive safety clean and non-toxic gases. The invention relates to also a continuous manufacturing process of such compositions.
  • pyrotechnic gas generators For different pyrotechnic needs including to ensure proper inflation of the cushions protection, pyrotechnic gas generators must provide in extremely short times, the order of thirty milliseconds, clean gases that is to say free from solid particles likely to constitute hot spots that can damage the wall cushion, and non-toxic that is to say low levels of nitrogen oxides, carbon oxides and chlorinated products.
  • a first family concerns compositions to base of alkaline or alkaline earth azide in the presence a mineral oxidant such as potassium nitrate or of a metal oxide.
  • These compositions that can binder, where appropriate, have major disadvantages. On the one hand, they produce of their combustion a lot of dust that must be filtered by filtration systems relatively large, which increases both the weight and price of the generator.
  • azides are very toxic products that exhibit in addition, the possibility of forming azides of lead or other heavy metals that are explosives primary. These compositions are therefore difficult to keep in good condition for several years in a motor vehicle.
  • compositions to nitrocellulose and nitroglycerin base are very interesting because they burn very quickly and without producing dust. But they have the disadvantage of not to be totally stable over time, and at high temperature.
  • a third family concerns compositions so-called "composites” constituted basically by a organic binder and an oxidizing mineral filler as especially mineral perchlorate. These compositions are a priori very interesting because they present good burning speed and excellent aging stability.
  • compositions have also been proposed constituted by a silicone binder crosslinkable to ambient temperature, still known as RTV (Room Temperature Vulcanizable), and potassium perchlorate, the potassium atom playing the role of internal chlorine sensor.
  • RTV Room Temperature Vulcanizable
  • Such compositions are, for example, described in FR-A-2 190 776 and FR-B-2 213 254 or in their corresponding US-A-3,986,908 and US-A-3,964,256. These compositions, however, the disadvantage of generating very rich oxygen gases that are not sought after by the builders of automobile industry.
  • compositions consisting of a silicone binder and a mixture of ammonium perchlorate and sodium nitrate. Of such compositions do not contain a solvent. They are for example described in the French patent FR-A-2 728 562 or in its American correspondent US-A-5,610,444. These compositions generate many gases clean, high in nitrogen and non-toxic but present the disadvantage of burning at very high temperatures and to produce a high solid residue rate.
  • compositions exist involve the presence of a solvent for adjust the viscosity.
  • a solvent for adjust the viscosity.
  • the use of a solvent has many disadvantages and especially at the level of industrial.
  • the solvent must be removed from the composition and this operation may create porosity in the pyrotechnic charge.
  • the object of the present invention is precisely to propose such compositions and a process allowing them to be implemented.
  • the invention therefore relates to a composition pyrotechnic gas generator comprising a binder, a nitrogenous organic compound, additives and a charge oxidizing agent comprising ammonium perchlorate and a chlorine sensor, said binder being a binder at least two components hydrocarbon, one of the components being constituted by an eraser, characterized in that when the gum is a polyester gum, it is associated with a polyester resin and in that, when the gum is an acrylic gum, it is associated with one of its plasticizers.
  • a gum is called a polymer whose mass molecular weight is greater than 200 000.
  • Acrylic gums used are also called rubbers acrylics or polyacrylates. These erasers may have reactive terminations of the chlorine / carboxyl type, chlorine, hydroxyl or epoxy.
  • polyester gums used are rubbers with ester motives and which may have reactive terminations of the hydroxyl type.
  • the binder is constituted by the combination of an eraser acrylic and one of its plasticizers.
  • the plasticizer of the acrylic gum is chosen from the group consisting of by dioctyl adipate and dioctyl azelate.
  • a crosslinking agent will generally be associated with the binder.
  • the binder is constituted by the combination of an eraser polyester and a polyester resin.
  • the composition further comprises an isocyanate type crosslinking agent.
  • the weight content of the charges is greater than or equal to 85% of the total weight of the composition.
  • the oxidizing charge comprises perchlorate ammonium and a chlorine sensor.
  • the chlorine sensor is selected from the group consisting of nitrate sodium, calcium carbonate, carbonate of lithium, potassium nitrate, nitrate strontium, barium nitrate, chlorate potassium, potassium perchlorate and copper.
  • a preferred chlorine sensor is nitrate sodium.
  • the composition also comprises a compound organic nitrogen.
  • the nitrogenous organic compound is chosen in the group consisting of nitroguanidine, the guanidine nitrate, aminoguanidine nitrate, oxamide, dicyandiamide, guanylurea nitramide and metallic cyanamides.
  • the content weight of this nitrogen compound is between 3 and 15% of the total weight of the composition.
  • the composition further comprises a ballistic catalyst selected from the group consisting of titanium oxide, copper oxide, basic copper nitrate, copper chromite and iron oxide.
  • a ballistic catalyst selected from the group consisting of titanium oxide, copper oxide, basic copper nitrate, copper chromite and iron oxide.
  • the catalyst Ballistic preferred is iron oxide.
  • Content weight of the ballistic catalyst is preferably between 0% and 4% of the weight total of the composition.
  • the The composition further comprises a wetting agent.
  • This wetting agent is selected from the group consisting of organosilanes, titanates and aziridines.
  • the Preferred organosilanes are the trialkoylsilanes the functional group is a vinyl, epoxy, amine group or metacrylic.
  • the weight content of the wetting agent is preferably between 0.5% and 2% by weight total of the composition.
  • This component reduces porosity residual product.
  • the ballistic catalyst and the wetting agent constitute the preferred additives of the compositions according to the invention.
  • the nitrogenous organic compound and gum are premixed and introduced into the mixing and mixing by the feed opening of the solids.
  • the pressure of the compression compartment is less than 50 ⁇ 10 3 Pa, ie 500 mbar.
  • the temperature of the mixing compartment and mixing is between 15 ° C and 75 ° C.
  • the pressure in the extrusion head is between 6.10 6 Pa and 15.10 6 Pa, ie between 60 bars and 150 bars.
  • the hydrocarbon binder comprises a an eraser and a liquid component which is either a resin or a plasticizer.
  • a pasty binder When we incorporate in this binder the oxidizing charge, the nitrogenous organic compound and various additives, this binder has sufficient resistance to be extruded in the form of rushes. So there is no need neither thickening agent nor solvent.
  • the rushes are then cut into loads and the binder structure is definitely frozen by crosslinking in an oven at a temperature between 100 ° C and 150 ° C.
  • Figure 1 represents, in the form of partly cut-off diagram, an installation allowing the implementation of the method according to the invention.
  • the bis-screw extruder-mixer 1 comprises a part upstream 2 in which the operations of mixing and kneading of the composition, a part downstream 3 in which takes place the degassing operation of the composition and an extrusion head 4.
  • a plug is formed of material that separates the downstream part 2 of the part upstream 3.
  • the gum and the nitrogenous organic compound are premixed.
  • the gum will be an eraser acrylic and the nitrogen compound will be nitrate guanidine.
  • the inert constituents namely the plasticizer and the various additives.
  • the various constituents are introduced continuously into the mixing and mixing chamber.
  • Solids A are introduced without solvent by means of a hopper.
  • the B liquids are introduced without solvent by means of a dosing pump 6.
  • the liquids B consist of the plasticizer and the wetting agent.
  • Solids A are the acrylic gum / guanidine nitrate mixture, the charge oxidizing agent comprising ammonium perchlorate and additives other than wetting agent.
  • Ammonium perchlorate particles are used two different grain sizes.
  • the particle size is between 10 ⁇ m and 50 ⁇ m.
  • Ammonium perchlorate producing by combustion chlorinated derivatives it is attached a sensor of chlorine.
  • the preferred chlorine sensor in the context of the invention is sodium nitrate which fixes the chlorine in the form of sodium chloride submicron, so without risk of deterioration of airbag walls.
  • Sodium nitrate will also be introduced by the feed opening of solids A.
  • the ratio between ammonium perchlorate and sodium nitrate is between 1 and 2.
  • the rate of oxidizing charges is preferentially about 80% of the total weight of the composition, for have a fairly balanced composition in balance in oxygen.
  • the weight content of the charges i.e. oxidizing charge, nitrogenous organic compound and additives
  • the weight content of the charges is greater than or equal to 85% of the total weight of composition. These are therefore binder compositions heavily loaded.
  • the content of the composition by binding and crosslinker will advantageously be close to 15%.
  • the preferred additives are the wetting agent and the ballistic catalyst.
  • the preferred ballistic catalyst is iron oxide.
  • the constituents are transported and kneaded in the mixing and mixing compartment 2.
  • the constituents are mixed using the elements of kneading 7 so as to form a homogeneous paste.
  • the temperature within this compartment is included between 15 ° C and 75 ° C.
  • the dough formed in the mixing and mixing compartment 2 is then degassed in the compression compartment 3, at a pressure of less than 30 ⁇ 10 3 Pa, ie 300 mbar.
  • This paste is then extruded, by means of a extrusion head 4, in the form of rods 8.
  • the pressure in the extrusion head is preferably close to 100 bars.
  • These rods are then cut into loads 9 to using a cutting device 10.
  • These loads 9 are recovered by a conveyor belt 11 and conveyed to an oven 12.
  • This oven 12 is heated to a temperature between 100 and 150 ° C. Preferably, this oven is heated to 120 ° C.
  • the loads remain in this oven for about 3 hours in order to complete the crosslinking of the constituents of the binder and to thus freeze the load structure 9.
  • the loads 9 have the shape of hollow cylindrical blocks presenting the more often axial channels.
  • the loads thus formed find their preferential application as loading pyrotechnics in gas generators intended for inflate a protective cushion for occupants of a motor vehicle. Indeed, the speed of combustion of these shipments, as well as the rate of solid residues products and the rate of carbon monoxide and oxides nitrogen products are particularly suitable for automotive safety requirements.
  • the weight content of the charges is 88%.
  • the combustion temperature of this composition is of the order of 2400 ° C.
  • the burning rate is 33mm / s under 20 MPa.
  • the weight content of the charges is 87.9%
  • the combustion temperature of this composition is of the order of 2400 ° C.
  • the burning rate is 43mm / s under 20 MPa.
  • the weight content of the charges is 85%.
  • the combustion temperature of this composition is of the order of 2400 ° C.
  • the burning rate is 20mm / s under 20Mpa.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Air Bags (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The invention is directed to a solvent-free gas-generating pyrotechnic composition, and a method for continuously manufacturing the composition in a twin-screw mixer-extruder, the composition including a binder, a nitrogenous organic compound, an oxidizing filler, and optionally at least one additive; the oxidizing filler including an ammonium perchlorate and a chlorine scavenger; the binder including at least one polymer, having a molecular mass greater than 200,000 and selected from a polyester polymer and an acrylic ester, and wherein the binder uncliding at least one liquid constituent selected from a polyester resin and a plasticizer.

Description

La présente invention se rapporte au domaine technique de la génération pyrotechnique de gaz utilisables notamment dans les systèmes de protection des occupants d'un véhicule automobile au moyen de coussins qui sont gonflés par les gaz de combustion d'un chargement pyrotechnique. Plus précisément l'invention concerne des compositions pyrotechniques générant à des températures acceptables pour la sécurité automobile des gaz propres et non toxiques. L'invention concerne également un procédé de fabrication en continu de telles compositions.The present invention relates to the field technical pyrotechnic generation of gas usable especially in protection systems occupants of a motor vehicle by means of cushions that are inflated by the flue gases of a pyrotechnic loading. More specifically, the invention pyrotechnic compositions generating to acceptable temperatures for automotive safety clean and non-toxic gases. The invention relates to also a continuous manufacturing process of such compositions.

Pour différents besoins pyrotechniques et notamment pour assurer un gonflement correct des coussins de protection, les générateurs pyrotechniques de gaz doivent fournir en des temps extrêmement courts, de l'ordre de trente millisecondes, des gaz propres c'est-à-dire exempts de particules solides susceptibles de constituer des points chauds pouvant endommager la paroi du coussin, et non toxiques c'est-à-dire à faible teneurs en oxydes d'azote, en oxydes de carbone et en produits chlorés.For different pyrotechnic needs including to ensure proper inflation of the cushions protection, pyrotechnic gas generators must provide in extremely short times, the order of thirty milliseconds, clean gases that is to say free from solid particles likely to constitute hot spots that can damage the wall cushion, and non-toxic that is to say low levels of nitrogen oxides, carbon oxides and chlorinated products.

Diverses familles de compositions pyrotechniques ont été développées dans ce but.Various families of pyrotechnic compositions have been developed for this purpose.

Un première famille concerne les compositions à base d'azoture alcalin ou alcalino-terreux en présence d'un oxydant minéral comme le nitrate de potassium ou d'un oxyde métallique. Ces compositions qui peuvent le cas échéant comporter un liant présentent des inconvénients majeurs. D'une part elles produisent lors de leur combustion beaucoup de poussières qui doivent être filtrées par des systèmes de filtration relativement importants, ce qui augmente à la fois le poids et le prix du générateur. D'autre part les azotures sont des produits très toxiques qui présentent de surcroít la possibilité de former des azotures de plomb ou d'autres métaux lourds qui sont des explosifs primaires. Ces compositions sont donc difficiles à conserver dans de bonnes conditions pendant plusieurs années dans un véhicule automobile.A first family concerns compositions to base of alkaline or alkaline earth azide in the presence a mineral oxidant such as potassium nitrate or of a metal oxide. These compositions that can binder, where appropriate, have major disadvantages. On the one hand, they produce of their combustion a lot of dust that must be filtered by filtration systems relatively large, which increases both the weight and price of the generator. On the other hand azides are very toxic products that exhibit in addition, the possibility of forming azides of lead or other heavy metals that are explosives primary. These compositions are therefore difficult to keep in good condition for several years in a motor vehicle.

Une seconde famille concerne les compositions à base de nitrocellulose et de nitroglycérine. Ces compositions, encore connues sous l'appellation de « poudres à double base », sont très intéressantes car elles brûlent très vite et sans produire de poussière. Mais elles présentent toutefois l'inconvénient de ne pas être totalement stables dans le temps, et à haute température.A second family concerns compositions to nitrocellulose and nitroglycerin base. These compositions, still known as "Double-base powders" are very interesting because they burn very quickly and without producing dust. But they have the disadvantage of not to be totally stable over time, and at high temperature.

Une troisième famille concerne les compositions dites « composites » constituées fondamentalement par un liant organique et par une charge minérale oxydante comme notamment un perchlorate minéral. Ces compositions sont à priori très intéressantes car elles présentent une bonne vitesse de combustion et une excellente stabilité au vieillissement.A third family concerns compositions so-called "composites" constituted basically by a organic binder and an oxidizing mineral filler as especially mineral perchlorate. These compositions are a priori very interesting because they present good burning speed and excellent aging stability.

Il a ainsi été proposé par le brevet FR-A-2 137 619 ou par son correspondant US-A-3,723,205 des compositions dont le liant est un chlorure de polyvinyle et dont la charge oxydante est un perchlorate d'ammonium en présence de nitrate de sodium comme capteur interne de chlore. Néanmoins l'emploi d'un liant chloré en présence de charges énergétiques est d'une mise en oeuvre délicate, notamment au plan de la sécurité et de la non toxicité des gaz générés.It has been proposed by FR-A-2 137 619 or by its corresponding US-A-3,723,205 compositions whose binder is a polyvinyl chloride and whose oxidizing charge is an ammonium perchlorate in presence of sodium nitrate as an internal sensor of chlorine. Nevertheless the use of a chlorinated binder in the presence of energy charges is an implementation delicate, particularly in terms of security and non toxicity of the gases generated.

Il a aussi été proposé des compositions composites constituées par un liant silicone réticulable à température ambiante, encore connu sous l'appellation de liant « RTV » (Room Temperature Vulcanizable), et de perchlorate de potassium, l'atome de potassium jouant le rôle de capteur interne de chlore. De telles compositions sont, par exemple, décrites dans les brevets FR-A-2 190 776 et FR-B-2 213 254 ou dans leurs correspondants américains US-A-3,986,908 et US-A-3,964,256. Ces compositions présentent cependant l'inconvénient de générer des gaz très riches en oxygène qui ne sont pas recherchés par les constructeurs de l'industrie automobile.Composite compositions have also been proposed constituted by a silicone binder crosslinkable to ambient temperature, still known as RTV (Room Temperature Vulcanizable), and potassium perchlorate, the potassium atom playing the role of internal chlorine sensor. Such compositions are, for example, described in FR-A-2 190 776 and FR-B-2 213 254 or in their corresponding US-A-3,986,908 and US-A-3,964,256. These compositions, however, the disadvantage of generating very rich oxygen gases that are not sought after by the builders of automobile industry.

Il existe aussi des compositions composites constituées par un liant silicone et par un mélange de perchlorate d'ammonium et de nitrate de sodium. De telles compositions ne contiennent pas de solvant. Elles sont par exemple décrites dans le brevet français FR-A-2 728 562 ou dans son correspondant américain US-A-5 610 444. Ces compositions génèrent bien des gaz propres, riches en azote et non toxiques mais présentent l'inconvénient de brûler à des températures très élevées et de produire un taux de résidus solides élevé.There are also composite compositions consisting of a silicone binder and a mixture of ammonium perchlorate and sodium nitrate. Of such compositions do not contain a solvent. They are for example described in the French patent FR-A-2 728 562 or in its American correspondent US-A-5,610,444. These compositions generate many gases clean, high in nitrogen and non-toxic but present the disadvantage of burning at very high temperatures and to produce a high solid residue rate.

Les procédés de fabrication des compositions existantes impliquent la présence d'un solvant pour ajuster la viscosité. L'emploi d'un solvant présente de nombreux inconvénients et notamment au niveau industriel. Le solvant doit être éliminé de la composition et cette opération risque de créer des porosités dans le chargement pyrotechnique.The methods of making the compositions exist involve the presence of a solvent for adjust the viscosity. The use of a solvent has many disadvantages and especially at the level of industrial. The solvent must be removed from the composition and this operation may create porosity in the pyrotechnic charge.

L'homme du métier est donc toujours à la recherche de compositions pyrotechniques génératrices de gaz, sans solvant, et qui génèrent à des températures acceptables pour l'industrie automobile des gaz propres, non toxiques, avec très peu de résidus solides. L'homme du métier est également à la recherche d'un procédé de fabrication continu de telles compositions, notamment sous forme de blocs.The person skilled in the art is therefore always looking for pyrotechnic gas-generating compositions, without solvent, and that generate at acceptable temperatures for the clean gas car industry, no toxic, with very little solid residues. The man of profession is also looking for a method of continuous manufacture of such compositions, in particular in the form of blocks.

L'objet de la présente invention est précisément de proposer de telles compositions ainsi qu'un procédé permettant de les mettre en oeuvre.The object of the present invention is precisely to propose such compositions and a process allowing them to be implemented.

L'invention concerne donc une composition pyrotechnique génératrice de gaz comprenant un liant, un composé organique azoté, des additifs et une charge oxydante comprenant du perchlorate d'ammonium et un capteur de chlore, ledit liant étant un liant hydrocarboné à au moins deux composants, l'un des composants étant constitué par une gomme, caractérisée en ce que, lorsque la gomme est une gomme polyester, elle est associée à une résine polyester et en ce que, lorsque la gomme est une gomme acrylique, elle est associée à un de ses plastifiants.The invention therefore relates to a composition pyrotechnic gas generator comprising a binder, a nitrogenous organic compound, additives and a charge oxidizing agent comprising ammonium perchlorate and a chlorine sensor, said binder being a binder at least two components hydrocarbon, one of the components being constituted by an eraser, characterized in that when the gum is a polyester gum, it is associated with a polyester resin and in that, when the gum is an acrylic gum, it is associated with one of its plasticizers.

On appelle gomme un polymère dont la masse moléculaire est supérieure à 200 000. Les gommes acryliques utilisées sont aussi appelées caoutchoucs acryliques ou polyacrylates. Ces gommes peuvent avoir des terminaisons réactives de type chlore/carboxyle, chlore, hydroxyl ou époxy.A gum is called a polymer whose mass molecular weight is greater than 200 000. Acrylic gums used are also called rubbers acrylics or polyacrylates. These erasers may have reactive terminations of the chlorine / carboxyl type, chlorine, hydroxyl or epoxy.

Les gommes polyester utilisées sont des caoutchoucs avec des motifs ester et qui peuvent avoir des terminaisons réactives de type hydroxyl.The polyester gums used are rubbers with ester motives and which may have reactive terminations of the hydroxyl type.

On appelle résine un polymère hydrocarboné dont la masse moléculaire est comprise entre 100 et 10 000.A resin called a hydrocarbon polymer whose mass molecular weight is between 100 and 10,000.

Selon un premier mode préféré de réalisation, le liant est constitué par l'association d'une gomme acrylique et d'un de ses plastifiants. Le plastifiant de la gomme acrylique est choisi dans le groupe constitué par l'adipate de dioctyle et l'azélate de dioctyle.According to a first preferred embodiment, the binder is constituted by the combination of an eraser acrylic and one of its plasticizers. The plasticizer of the acrylic gum is chosen from the group consisting of by dioctyl adipate and dioctyl azelate.

Un réticulant sera généralement associé au liant.A crosslinking agent will generally be associated with the binder.

Selon un deuxième mode préféré de réalisation, le liant est constitué par l'association d'une gomme polyester et d'une résine polyester. Selon ce mode préféré de réalisation, la composition comprend en outre un réticulant de type isocyanate.According to a second preferred embodiment, the binder is constituted by the combination of an eraser polyester and a polyester resin. According to this mode preferred embodiment, the composition further comprises an isocyanate type crosslinking agent.

Selon un troisième mode préféré de réalisation, le teneur pondérale des charges est supérieure ou égale à 85% du poids total de la composition. On entend par charges à la fois les charges oxydantes, les composés organiques azotés et les autres additifs.According to a third preferred embodiment, the weight content of the charges is greater than or equal to 85% of the total weight of the composition. We hear by charges both the oxidizing charges, the compounds organic nitrogen and other additives.

La charge oxydante comprend du perchlorate d'ammonium et un capteur de chlore. Le capteur de chlore est choisi dans le groupe constitué par le nitrate de sodium, le carbonate de calcium, le carbonate de lithium, le nitrate de potassium, le nitrate de strontium, le nitrate de barium, le chlorate de potassium, le perchlorate de potassium et l'oxyde de cuivre.The oxidizing charge comprises perchlorate ammonium and a chlorine sensor. The chlorine sensor is selected from the group consisting of nitrate sodium, calcium carbonate, carbonate of lithium, potassium nitrate, nitrate strontium, barium nitrate, chlorate potassium, potassium perchlorate and copper.

Un capteur de chlore préféré est le nitrate de sodium.A preferred chlorine sensor is nitrate sodium.

La composition comprend également un composé organique azoté. Le composé organique azoté est choisi dans le groupe constitué par la nitroguanidine, le nitrate de guanidine, le nitrate d'aminoguanidine, l'oxamide, le dicyandiamide, le guanyluréedinitramide et les cyanamides métalliques. Préférentiellement la teneur pondérale de ce composé azoté est comprise entre 3 et 15% du poids total de la composition.The composition also comprises a compound organic nitrogen. The nitrogenous organic compound is chosen in the group consisting of nitroguanidine, the guanidine nitrate, aminoguanidine nitrate, oxamide, dicyandiamide, guanylurea nitramide and metallic cyanamides. Preferentially the content weight of this nitrogen compound is between 3 and 15% of the total weight of the composition.

Selon un quatrième mode préféré de réalisation, la composition comprend en outre un catalyseur balistique choisi dans le groupe constitué par l'oxyde de titane, l'oxyde de cuivre, le nitrate basique de cuivre, le chromite de cuivre et l'oxyde de fer. Le catalyseur balistique préféré est l'oxyde de fer. La teneur pondérale du catalyseur balistique est préférentiellement comprise entre 0% et 4% du poids total de la composition.According to a fourth preferred embodiment, the composition further comprises a ballistic catalyst selected from the group consisting of titanium oxide, copper oxide, basic copper nitrate, copper chromite and iron oxide. The catalyst Ballistic preferred is iron oxide. Content weight of the ballistic catalyst is preferably between 0% and 4% of the weight total of the composition.

Il permet entre autre d'améliorer la vitesse de combustion.It allows among other things to improve the speed of combustion.

Selon un cinquième mode préféré de réalisation, la composition comprend en outre un agent mouillant. Cet agent mouillant est choisi dans le groupe constitué par les organo-silanes, les titanates et les aziridines. Les organo-silanes préférés sont les trialcoylsilanes dont le groupe fonctionnel est un groupe vinyl, epoxy, amine ou métacrylique.According to a fifth preferred embodiment, the The composition further comprises a wetting agent. This wetting agent is selected from the group consisting of organosilanes, titanates and aziridines. The Preferred organosilanes are the trialkoylsilanes the functional group is a vinyl, epoxy, amine group or metacrylic.

La teneur pondérale de l'agent mouillant est préférentiellement comprise entre 0,5% et 2% du poids total de la composition.The weight content of the wetting agent is preferably between 0.5% and 2% by weight total of the composition.

Ce composant permet de réduire la porosité résiduelle du produit.This component reduces porosity residual product.

Le catalyseur balistique et l'agent mouillant constituent les additifs préférés des compositions selon l'invention.The ballistic catalyst and the wetting agent constitute the preferred additives of the compositions according to the invention.

L'invention concerne également un procédé de fabrication continu et sans solvant dans un mélangeur-extrudeur bi-vis de telles compositions, caractérisé en ce que :

  • le mélangeur-extrudeur bis-vis comprend un compartiment de mélange et de malaxage, un compartiment de compression et une tête d'extrusion, et en ce que,
  • 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, et en ce qu'ils sont, dans ce compartiment, transportés et malaxés, puis, en ce que,
  • 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 en ce que,
  • les joncs ainsi formés sont découpés en chargements à l'aide d'un appareil de découpe, et en ce que ces dits chargements sont mis à réticuler à une température comprise entre 100°C et 150°C.
The invention also relates to a continuous and solvent-free manufacturing process in a twin-screw mixer-extruder of such compositions, characterized in that:
  • the bis-screw mixer-extruder comprises a mixing and kneading compartment, a compression compartment and an extrusion head, and in that
  • the solid and liquid constituents are introduced into the mixing and mixing compartment by two different feed openings, a solids supply opening and a liquid feed opening, and in that they are in this compartment , transported and kneaded, then, in that,
  • the homogeneous paste thus formed is degassed in the compression chamber and then extruded, using an extrusion head in the form of rods, and finally that,
  • the rods thus formed are cut into loadings by means of a cutting apparatus, and in that said loadings are made to crosslink at a temperature of between 100 ° C. and 150 ° C.

Selon une variante préférée de l'invention, le composé organique azoté et la gomme sont prémélangés et introduits dans le compartiment de mélange et de malaxage par l'ouverture d'alimentation des solides.According to a preferred variant of the invention, the nitrogenous organic compound and gum are premixed and introduced into the mixing and mixing by the feed opening of the solids.

Selon une autre variante préférée de l'invention, la pression du compartiment de compression est inférieure à 50.103 Pa, soit 500 mbar.According to another preferred variant of the invention, the pressure of the compression compartment is less than 50 × 10 3 Pa, ie 500 mbar.

La température du compartiment de mélange et de malaxage est comprise entre 15°C et 75°C.The temperature of the mixing compartment and mixing is between 15 ° C and 75 ° C.

La pression dans la tête d'extrusion est comprise entre 6.106Pa et 15.106Pa, soit entre 60 bars et 150 bars. The pressure in the extrusion head is between 6.10 6 Pa and 15.10 6 Pa, ie between 60 bars and 150 bars.

L'originalité fondamentale de l'invention réside dans le fait que le liant hydrocarboné comprend d'une part une gomme et d'autre part un constituant liquide qui est soit une résine, soit un plastifiant. On obtient donc un liant pâteux. Quand on incorpore à ce liant la charge oxydante, le composé organique azoté et les divers additifs, ce liant a suffisamment de tenue pour être extrudé sous forme de joncs. Il n'y a donc besoin ni d'agent épaississant, ni de solvant.The fundamental originality of the invention lies in that the hydrocarbon binder comprises a an eraser and a liquid component which is either a resin or a plasticizer. We obtain therefore a pasty binder. When we incorporate in this binder the oxidizing charge, the nitrogenous organic compound and various additives, this binder has sufficient resistance to be extruded in the form of rushes. So there is no need neither thickening agent nor solvent.

Les joncs sont ensuite découpés en chargements et la structure du liant est définitivement figée par réticulation en étuve à une température comprise entre 100°C et 150°C.The rushes are then cut into loads and the binder structure is definitely frozen by crosslinking in an oven at a temperature between 100 ° C and 150 ° C.

On donne maintenant une description détaillée du mode préféré de réalisation de l'invention en se référant à la figure 1 qui représente, sous forme de schéma partiellement coupé, une installation permettant la mise en oeuvre du procédé selon l'invention.We now give a detailed description of the preferred embodiment of the invention in Referring to Figure 1 which represents, in the form of partly cut-off diagram, an installation allowing the implementation of the method according to the invention.

L'extrudeur-malaxeur bis-vis 1 comprend une partie amont 2 dans laquelle se situent les opérations de mélange et de malaxage de la composition, une partie aval 3 dans laquelle a lieu l'opération de dégazage de la composition et une tête d'extrusion 4.The bis-screw extruder-mixer 1 comprises a part upstream 2 in which the operations of mixing and kneading of the composition, a part downstream 3 in which takes place the degassing operation of the composition and an extrusion head 4.

En cours de fonctionnement, il se forme un bouchon de matière qui sépare la partie aval 2 de la partie amont 3.During operation, a plug is formed of material that separates the downstream part 2 of the part upstream 3.

Dans la suite de la présente description, on appellera la partie amont 2 « compartiment de mélange et de malaxage » et la partie aval 3 « compartiment de compression ».In the remainder of this description, will call the upstream part 2 'mixing compartment and 'and the downstream part 3' compartment of compression ".

La gomme et le composé organique azoté sont prémélangés. The gum and the nitrogenous organic compound are premixed.

Préférentiellement la gomme sera une gomme acrylique et le composé azoté sera du nitrate de guanidine.Preferably the gum will be an eraser acrylic and the nitrogen compound will be nitrate guanidine.

En phase de démarrage, on introduit d'abord les constituants inertes, à savoir le plastifiant et les divers additifs. On introduit ensuite les charges oxydantes et le mélange gomme/composé organique azoté. Une fois la phase de démarrage terminée, les divers constituants sont introduits en continu dans le compartiment de mélange et de malaxage. Les solides A sont introduits sans solvant au moyen d'une trémie. Les liquides B sont introduits sans solvant au moyen d'une pompe doseuse 6. Les liquides B sont constitués par le plastifiant et l'agent mouillant. Les solides A sont le mélange gomme acrylique/nitrate de guanidine, la charge oxydante comprenant du perchlorate d'ammonium et les additifs autres que l'agent mouillant.In the start-up phase, we first introduce the inert constituents, namely the plasticizer and the various additives. We then introduce the charges oxidizing agents and the gum / nitrogenous organic compound mixture. Once the start-up phase has been completed, the various constituents are introduced continuously into the mixing and mixing chamber. Solids A are introduced without solvent by means of a hopper. The B liquids are introduced without solvent by means of a dosing pump 6. The liquids B consist of the plasticizer and the wetting agent. Solids A are the acrylic gum / guanidine nitrate mixture, the charge oxidizing agent comprising ammonium perchlorate and additives other than wetting agent.

On utilise des particules de perchlorate d'ammonium de deux granulométries différentes. La granulométrie est comprise entre 10µm et 50µm.Ammonium perchlorate particles are used two different grain sizes. The particle size is between 10μm and 50μm.

Le perchlorate d'ammonium produisant par combustion des dérivés chlorés, il lui est adjoint un capteur de chlore. Le capteur de chlore préféré dans le cadre de l'invention est le nitrate de sodium qui fixe le chlore sous forme de chlorure de sodium de taille submicronique, donc sans risque de détérioration des parois du coussin gonflable.Ammonium perchlorate producing by combustion chlorinated derivatives, it is attached a sensor of chlorine. The preferred chlorine sensor in the context of the invention is sodium nitrate which fixes the chlorine in the form of sodium chloride submicron, so without risk of deterioration of airbag walls.

Le nitrate de sodium sera également introduit par l'ouverture d'alimentation des solides A. Le ratio entre le perchlorate d'ammonium et le nitrate de sodium est compris entre 1 et 2.Sodium nitrate will also be introduced by the feed opening of solids A. The ratio between ammonium perchlorate and sodium nitrate is between 1 and 2.

Le taux de charges oxydantes est préférentiellement d'environ 80% du poids total de la composition, pour avoir une composition assez équilibrée en balance en oxygène. The rate of oxidizing charges is preferentially about 80% of the total weight of the composition, for have a fairly balanced composition in balance in oxygen.

La teneur pondérale des charges (c'est-à-dire charge oxydante, composé organique azoté et additifs) est supérieure ou égale à 85% du poids total de la composition. Ce sont donc des compositions à liant fortement chargé. La teneur de la composition en liant et réticulant sera avantageusement voisine de 15%.The weight content of the charges (i.e. oxidizing charge, nitrogenous organic compound and additives) is greater than or equal to 85% of the total weight of composition. These are therefore binder compositions heavily loaded. The content of the composition by binding and crosslinker will advantageously be close to 15%.

Les additifs préférés sont l'agent mouillant et le catalyseur balistique. Le catalyseur balistique préféré est l'oxyde de fer.The preferred additives are the wetting agent and the ballistic catalyst. The preferred ballistic catalyst is iron oxide.

Les constituants sont transportés et malaxés dans le compartiment de mélange et de malaxage 2. Les constituants sont malaxés au moyen des éléments de malaxage 7 de manière à former une pâte homogène. La température au sein de ce compartiment est comprise entre 15°C et 75°C.The constituents are transported and kneaded in the mixing and mixing compartment 2. The constituents are mixed using the elements of kneading 7 so as to form a homogeneous paste. The temperature within this compartment is included between 15 ° C and 75 ° C.

La pâte formée dans le compartiment de mélange et de malaxage 2 est ensuite dégazée dans le compartiment de compression 3, sous une pression inférieure à 30.103Pa, soit 300 mbar.The dough formed in the mixing and mixing compartment 2 is then degassed in the compression compartment 3, at a pressure of less than 30 × 10 3 Pa, ie 300 mbar.

Cette pâte est ensuite extrudée, au moyen d'une tête d'extrusion 4, sous forme de joncs 8. La pression dans la tête d'extrusion est de préférence voisine de 100 bars.This paste is then extruded, by means of a extrusion head 4, in the form of rods 8. The pressure in the extrusion head is preferably close to 100 bars.

Ces joncs sont alors découpés en chargements 9 à l'aide d'un appareil de découpe 10. Ces chargements 9 sont récupérés par un tapis transporteur 11 et acheminés vers une étuve 12. Cette étuve 12 est chauffée à une température comprise entre 100 et 150°C. De préférence, cette étuve est chauffée à 120°C. Les chargements restent 3 heures environ dans cette étuve de manière à achever la réticulation des constituants du liant et à figer ainsi la structure des chargements 9.These rods are then cut into loads 9 to using a cutting device 10. These loads 9 are recovered by a conveyor belt 11 and conveyed to an oven 12. This oven 12 is heated to a temperature between 100 and 150 ° C. Preferably, this oven is heated to 120 ° C. The loads remain in this oven for about 3 hours in order to complete the crosslinking of the constituents of the binder and to thus freeze the load structure 9.

De façon particulièrement préférée les chargements 9 ont la forme de blocs cylindriques creux présentant le plus souvent des canaux axiaux.In a particularly preferred way the loads 9 have the shape of hollow cylindrical blocks presenting the more often axial channels.

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 bien aux exigences de la sécurité automobile.The loads thus formed find their preferential application as loading pyrotechnics in gas generators intended for inflate a protective cushion for occupants of a motor vehicle. Indeed, the speed of combustion of these shipments, as well as the rate of solid residues products and the rate of carbon monoxide and oxides nitrogen products are particularly suitable for automotive safety requirements.

Les exemples qui suivent illustrent, à titre non limitatif, certaines possibilités de mise en oeuvre de l'invention.The following examples illustrate, as a non certain possibilities for the implementation of the invention.

Exemple 1Example 1

On a fabriqué selon le procédé représenté à la figure 1 la composition génératrice de gaz suivante :

  • gomme acrylique : 5,5% du poids total de la composition
  • plastifiant (adipate de dioctyle ou azélate de dioctyle) : 6,5% du poids total de la composition.
The following gas generating composition was manufactured according to the process shown in FIG.
  • acrylic gum: 5.5% of the total weight of the composition
  • plasticizer (dioctyl adipate or dioctyl azelate): 6.5% of the total weight of the composition.

La teneur en liant est donc de 12% du poids total de la composition.

  • perchlorate d'ammonium bigranulométrique n'exédant pas 50µm : 60,5% en poids, le perchlorate fin étant en excès pondéral par rapport au perchlorate de plus grosse granulométrie.
  • nitrate de sodium : 20% en poids
The binder content is therefore 12% of the total weight of the composition.
  • ammonium perchlorate bigranulometric not exceeding 50 .mu.m: 60.5% by weight, the fine perchlorate being in excess weight relative to the perchlorate of larger particle size.
  • sodium nitrate: 20% by weight

La teneur en charges oxydantes est de 80,5% en poids.

  • nitrate de guanidine : 5% en poids
  • oxyde de fer : 1,5% en poids
  • agent mouillant (vinyl silane) : 1% en poids
The content of oxidizing charges is 80.5% by weight.
  • guanidine nitrate: 5% by weight
  • iron oxide: 1.5% by weight
  • wetting agent (vinyl silane): 1% by weight

La teneur pondérale des charges est de 88%.The weight content of the charges is 88%.

La température de combustion de cette composition est de l'ordre de 2400°C.The combustion temperature of this composition is of the order of 2400 ° C.

La vitesse de combustion est de 33mm/s sous 20 Mpa.The burning rate is 33mm / s under 20 MPa.

Les caractéristiques des gaz de combustion de 18g d'une telle composition sont les suivantes :

  • teneur globale des gaz en résidus solides à la température de combustion : 15,5%
  • teneur des gaz en monoxyde de carbone, pour un volume de 60 L : 4500 ppm
  • teneur des gaz en oxydes d'azote, pour un volume de 60 L : 1000 ppm.
The characteristics of the 18 g combustion gases of such a composition are as follows:
  • overall gas content in solid residues at the combustion temperature: 15.5%
  • carbon monoxide gas content, for a volume of 60 L: 4500 ppm
  • gas content of nitrogen oxides, for a volume of 60 L: 1000 ppm.

Exemple 2Example 2

On a fabriqué selon le procédé représenté à la figure 1 la composition génératrice de gaz suivante :

  • gomme acrylique : 6,6% du poids total de la composition
  • plastifiant (adipate de dioctyle ou azélate de dioctyle) : 5,5% du poids total de la composition.
The following gas generating composition was manufactured according to the process shown in FIG.
  • acrylic gum: 6.6% of the total weight of the composition
  • plasticizer (dioctyl adipate or dioctyl azelate): 5.5% of the total weight of the composition.

La teneur en liant est donc de 12,1% du, poids total de la compisition

  • perchlorate d'ammonium bigranulométrique n'excédant pas 50µm : 58,5% en poids, le perchlorate de plus grosse granulométrie étant en excès par rapport au perchlorate fin.
  • nitrate de sodium : 15,9% en poids.
  • nitrate basique de cuivre : 6,5% en poids.
The binder content is therefore 12.1% of the total weight of the compisition
  • ammonium perchlorate bigranulometric not exceeding 50 .mu.m: 58.5% by weight, the perchlorate of larger particle size being in excess relative to the fine perchlorate.
  • sodium nitrate: 15.9% by weight.
  • basic nitrate of copper: 6.5% by weight.

La teneur en charges oxydantes est de 80,9% en poids

  • agent mouillant (vinyl silane) : 1% en poids
  • nitrate de guanidine : 6% en poids
The content of oxidizing charges is 80.9% by weight
  • wetting agent (vinyl silane): 1% by weight
  • guanidine nitrate: 6% by weight

La teneur pondérale des charges est de 87,9%The weight content of the charges is 87.9%

La température de combustion de cette composition est de l'ordre de 2400°C .The combustion temperature of this composition is of the order of 2400 ° C.

La vitesse de combustion est de 43mm/s sous 20 Mpa.The burning rate is 43mm / s under 20 MPa.

Les caractéristiques des gaz de combustion de 18g d'une telle composition sont les suivantes :

  • teneur globale des gaz en résidus solides à la température de combustion : 14,6%
  • teneur des gaz en monoxyde de carbone, pour un volume de 60L : 4500ppm
  • teneur des gaz en oxydes d'azote, pour un volume de 60L : 1000ppm.
The characteristics of the 18 g combustion gases of such a composition are as follows:
  • total gas content in solid residues at the combustion temperature: 14.6%
  • Carbon monoxide gas content, for a volume of 60L: 4500ppm
  • gas content of nitrogen oxides, for a volume of 60L: 1000ppm.

Exemple 3Example 3

On a fabriqué selon le procédé représenté à la figure 1 la composition génératrice de gaz suivante :

  • gomme polyester : 3,46% en poids
  • résine polyester : 8,76% en poids
  • agent réticulant (méthylène dicyclohexyl diisocyanate) : 2,78% en poids
The following gas generating composition was manufactured according to the process shown in FIG.
  • polyester gum: 3.46% by weight
  • polyester resin: 8.76% by weight
  • crosslinking agent (methylene dicyclohexyl diisocyanate): 2.78% by weight

La teneur en liant et en réticulant est donc de 15% en poids

  • perchlorate d'ammonium bigranulométrique n'excédant pas 50 µm : 54% en poids, le perchlorate de plus grosse granulométrie étant en excès par rapport au perchlorate fin
  • nitrate de sodium : 15,5% en poids
  • oxyde de cuivre : 7% en poids
The content of binder and crosslinking agent is therefore 15% by weight
  • bigranulometric ammonium perchlorate not exceeding 50 μm: 54% by weight, the larger particle size perchlorate being in excess of the fine perchlorate
  • sodium nitrate: 15.5% by weight
  • copper oxide: 7% by weight

La teneur en charges oxydantes est de 76,5% en poids

  • nitrate de guanidine : 8,5% en poids
The content of oxidizing charges is 76.5% by weight
  • guanidine nitrate: 8.5% by weight

La teneur pondérale des charges est de 85%. The weight content of the charges is 85%.

La température de combustion de cette composition est de l'ordre de 2400°C.The combustion temperature of this composition is of the order of 2400 ° C.

La vitesse de combustion est de 20mm/s sous 20Mpa.The burning rate is 20mm / s under 20Mpa.

Les caractéristiques des gaz de combustion de 18g d'une telle composition sont les suivantes :

  • teneur globale des gaz en résidus solides à la température de combustion : 16,3%
  • teneur des gaz en monoxyde de carbone, pour un volume de 60L : 4500ppm
  • teneur des gaz en oxydes d'azote, pour un volume de 60L : 800ppm.
The characteristics of the 18 g combustion gases of such a composition are as follows:
  • overall gas content in solid residues at the combustion temperature: 16.3%
  • Carbon monoxide gas content, for a volume of 60L: 4500ppm
  • gas content of nitrogen oxides, for a volume of 60L: 800ppm.

Claims (14)

  1. Gas-generating pyrotechnic composition comprising a binder, a nitrogenous organic compound, additives and an oxidizing filler comprising ammonium perchlorate and a chlorine scavenger, the said binder being a hydrocarbonaceous binder with at least two components, one of the components being composed of a polyester or acrylic gum, characterized in that, when the gum is a polyester gum, it is used in combination with a polyester resin and in that, when the gum is an acrylic gum, it is used in combination with one of its plasticizers.
  2. Composition according to claim 1, characterized in that the plasticizer of the acrylic gum is chosen from the group consisting of dioctyl adipate and dioctyl azelate.
  3. Composition according to claim 1, characterized in that, when the binder is composed of the combination of a polyester gum and of a polyester resin, the composition additionally comprises a crosslinking agent of isocyanate type.
  4. Composition according to any one of claims 1 to 3, characterized in that the content by weight of the fillers composed of the nitrogenous organic compound, the additives and the oxidizing filler is greater than or equal to 85% of the total weight of the composition.
  5. Composition according to any one of claims 1 to 4, characterized in that the said chlorine scavenger is chosen from the group consisting of sodium nitrate, calcium carbonate, lithium carbonate, potassium nitrate, strontium nitrate, barium nitrate, potassium chlorate, potassium perchlorate and copper oxide.
  6. Composition according to claim 5, characterized in that the chlorine scavenger is sodium nitrate.
  7. Composition according to any one of claims 1 to 6, characterized in that the said nitrogenous organic compound is chosen from the group consisting of nitroguanidine, guanidine nitrate, aminoguanidine nitrate, oxamide, dicyandiamide, guanylurea dinitramide and metal cyanamides.
  8. Composition according to any one of claims 1 to 7, characterized in that it additionally comprises a ballistic catalyst chosen from the group consisting of titanium oxide, copper oxide, basic copper nitrate, copper chromite and iron oxide.
  9. Composition according to any one of claims 1 to 8, characterized in that it additionally comprises a wetting agent chosen from the group consisting of organosilanes, titanates and aziridines.
  10. Process for the solvent-free continuous manufacture in a twin-screw mixer-extruder (1) of pyrotechnic compositions according to any one of claims 1 to 9, characterized in that:
    the twin-screw mixer-extruder (1) comprises a mixing and kneading compartment (2), a compression compartment (3) and an extrusion head (4), and in that
    the solid (A) and liquid (B) constituents are introduced into the mixing and kneading compartment (2) via two different feed openings, a feed opening for the solids and a feed opening for the liquids, in that they are, in this compartment, conveyed and kneaded, then, in that,
    the homogeneous paste thus formed is degassed in the compression compartment (3) and then extruded, using an extrusion head (4), in the form of rods (8) and, finally, in that,
    the rods thus formed (8) are cut up into charges (9) using a cutting device (10), and in that these said charges (9) are crosslinked at a temperature of between 100°C and 150°C.
  11. Process according to claim 10, characterized in that the nitrogenous organic compound and the gum are premixed and introduced into the mixing and kneading compartment (2) via the feed opening for the solids.
  12. Process according to claim 10 or 11, characterized in that the pressure in the compression compartment (3) is less than 50 x 103 Pa.
  13. Process according to any one of Claims 10 to 12, characterized in that the temperature of the mixing and kneading compartment (2) is between 15°C and 75°C.
  14. Process according to any one of claims 10 to 13, characterized in that the pressure in the extrusion head (4) is between 6 x 106 Pa and 15 x 106 Pa.
EP01403255A 2000-12-22 2001-12-14 Hydrocarbon binder containing pyrotechnic gas-generating compositions and method for continuous manufacturing Expired - Lifetime EP1216977B1 (en)

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EP1216977A3 (en) 2002-09-11
BR0106250B1 (en) 2010-11-16
MXPA01012981A (en) 2002-10-21
KR20020051850A (en) 2002-06-29
DE60112231T2 (en) 2006-05-24
ATE300508T1 (en) 2005-08-15
JP2002255679A (en) 2002-09-11
US6824626B2 (en) 2004-11-30
CA2364135A1 (en) 2002-06-22
CA2364135C (en) 2009-02-03
DE60112231D1 (en) 2005-09-01
FR2818636B1 (en) 2003-02-28
US20020079031A1 (en) 2002-06-27
BR0106250A (en) 2002-08-13
KR100446267B1 (en) 2004-09-01
JP3825316B2 (en) 2006-09-27
FR2818636A1 (en) 2002-06-28

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