WO2019063923A1 - Gas-generating composition - Google Patents

Gas-generating composition Download PDF

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Publication number
WO2019063923A1
WO2019063923A1 PCT/FR2018/052339 FR2018052339W WO2019063923A1 WO 2019063923 A1 WO2019063923 A1 WO 2019063923A1 FR 2018052339 W FR2018052339 W FR 2018052339W WO 2019063923 A1 WO2019063923 A1 WO 2019063923A1
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Prior art keywords
nitrate
composition according
weight
advantageously
group
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PCT/FR2018/052339
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French (fr)
Inventor
Guy Delannoy
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Arianegroup Sas
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Priority to EP18792970.8A priority Critical patent/EP3687962B1/en
Publication of WO2019063923A1 publication Critical patent/WO2019063923A1/en

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    • 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
    • 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

  • the present invention relates to solid gas generating compositions for emergency deballasting in submarines.
  • the submarine Under normal conditions of use, to surface, the submarine must partially empty the ballasts of their water with gas and regain positive buoyancy. It is said that it "ballast hunt”.
  • compositions generating gas For emergency deballasting, it is advantageous to use solid compositions generating gas.
  • Such compositions based on glycidyl polyazide (PAG) and alkaline or alkaline earth nitrate are thus described in the DE19821010 application.
  • PAG glycidyl polyazide
  • alkaline or alkaline earth nitrate are thus described in the DE19821010 application.
  • the advantage of these compositions is that they deliver a large amount of nitrogen, carbon dioxide and oxygen, which ensures the deballasting function, and that the products of combustion are without hydrogen and without monoxide carbon, prohibited gases because toxic and dangerous.
  • Combustion products contain a significant amount of solid residues that result from the oxidation of the alkaline or alkaline earth nitrate, for example strontium oxide (SrO), calcium oxide (CaO ) or sodium oxide (Na2O). Conventionally, these products are in the solid state at the combustion temperature. They can disrupt the ballistic operation of the combustion chamber, possibly with nozzle plugging. • The PAG polymer has a very high cost, a cost that affects the price of the load to the point of making marketing problematic.
  • the PAG azide-based polymer with a polyester having a hydroxy-terminus or a polyether having a hydroxy-terminus, such as polyethylene glycol (PEG) or diethylene glycol polyadipate (PADEG).
  • PEG polyethylene glycol
  • PADEG diethylene glycol polyadipate
  • alkaline or alkaline-earth nitrate by a mixture of ammonium perchlorate or ammonium chlorate with an alkaline or alkaline-earth nitrate selected from the group consisting of sodium nitrate, potassium nitrate, strontium nitrate and barium nitrate.
  • such a composition makes it possible to avoid the formation of solid residues during the generation of gases while avoiding the formation of the acid gas HCl due to the presence of chlorate and perchlorate by the formation of salts of alkali or alkaline chlorides earthy.
  • the present invention therefore relates to a solid gas-generating composition
  • a solid gas-generating composition comprising (advantageously consisting essentially of, in particular consisting of):
  • a binder comprising (advantageously consisting essentially of, in particular consisting of) (a1) a polymer selected from the group consisting of polyesters having a hydroxy terminus, polyethers having a hydroxy terminus and mixtures thereof and (a2) a system crosslinking;
  • an oxidizing charge constituted by a mixture of (bl) ammonium perchlorate or ammonium chlorate or their mixture with (b2) an alkaline or alkaline-earth nitrate selected from the group consisting of sodium nitrate, potassium nitrate, strontium nitrate, barium nitrate and mixtures thereof.
  • composition according to the present invention therefore comprises (a1) a polymer selected from the group consisting of polyesters having a hydroxy terminus, polyethers having a hydroxy terminus and mixtures thereof.
  • the polymer (a1) is chosen from the group consisting of polybutylene oxide, polytetramethylene oxide, polyoxypropylene glycol, polyethylene glycol, diethylene glycol polyadipate and mixtures thereof, advantageously in the group consisting of polyethylene glycol, diethylene glycol polyadipate and their mixture, in particular it is diethylene glycol polyadipate (PADEG).
  • the composition according to the invention further comprises (a2) a crosslinking system.
  • the crosslinking system that can be used in the composition according to the present invention is advantageously liquid and in particular chosen from polyisocyanates such as toluene diisocyanate, in particular alicyclic polyisocyanates, such as dicyclohexylmethylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or biuret triisocyanate.
  • the crosslinking system is generally present in the composition in a content of between 0.4 and 5% by weight relative to the total weight of the composition.
  • composition according to the present invention further comprises (b1) ammonium perchlorate or ammonium chlorate or a mixture thereof.
  • ammonium perchlorate is preferred.
  • the composition according to the present invention furthermore comprises a nitrate (b2) chosen from the group consisting of sodium nitrate, potassium nitrate, strontium nitrate, barium nitrate and their mixtures, advantageously in the group consisting of sodium nitrate, potassium nitrate and their mixture, still more advantageously, it is sodium nitrate.
  • composition according to the present invention comprises (advantageously essentially consists of, in particular is constituted by):
  • a binder comprising (advantageously consisting essentially of, in particular consisting of) (a1) PADEG and (a2) an isocyanate crosslinking system;
  • an oxidizing charge consisting of a mixture of (bl) ammonium perchlorate with (b2) sodium nitrate.
  • the nitrate content (b2) is such that the neutralization of the alkaline by the chlorine of ammonium perchlorate or ammonium chlorate is complete.
  • it is between 40 and 57% by weight relative to the total weight of the filler (b), advantageously between 42 and 56.3% by weight.
  • the nitrate content (b2) is between 44 and 57% by weight relative to the total weight of the filler (b), advantageously between 45.degree. , 6 and 56.3% by weight.
  • the component (b1) is ammonium perchlorate and the nitrate content (b2) is between 40 and 55% by weight relative to the total weight of the filler (b), advantageously between 42 and 52.7% by weight.
  • Table 1 below gives the precise mixtures allowing the neutralization of the alkaline by chlorine.
  • the binder content (a) is sufficient to allow the composition according to the invention to be manufactured, more advantageously castable.
  • this content is at least 10% by weight relative to the total weight of the composition according to the invention.
  • the binder content (a) is not too important to avoid the appearance of carbon monoxide and hydrogen.
  • the binder content (a) is between 10 and 20% by weight, more preferably between 12 and 18% by weight, relative to the total weight of the composition according to the invention.
  • the binder (a) according to the invention is PEG
  • its content is between 11 and 18% by weight, advantageously between 12 and 17% by weight relative to the total weight of the composition according to the invention. 'invention.
  • binder (a) according to the invention is PADEG
  • its content is between 12 and 19% by weight, advantageously between 13 and 18% by weight relative to the total weight of the composition according to the invention.
  • the content of binder (a) is between 11 and 17% by weight, advantageously between 12 and 16% by weight. weight relative to the total weight of the composition according to the invention.
  • the content of binder (a) is between 14 and 19% by weight, advantageously between 15 and 18%. by weight relative to the total weight of the composition according to the invention.
  • Table 2 below gives examples of binder content according to the composition according to the invention.
  • composition according to the present invention may further comprise additives such as, for example, antioxidants, wetting agents, manufacturing additives, chain extenders, polymerization catalysts, combustion modifiers (accelerators or retarders), ballistic additives (eg cooling such as copper or bismuth salt, iron oxide), adhesion agents binder-loads and bridges.
  • additives such as, for example, antioxidants, wetting agents, manufacturing additives, chain extenders, polymerization catalysts, combustion modifiers (accelerators or retarders), ballistic additives (eg cooling such as copper or bismuth salt, iron oxide), adhesion agents binder-loads and bridges.
  • additives are generally present in the binder (a).
  • the additives, if present, are generally present in the composition in a content of between 0.1 and 10% by weight relative to the total weight of the composition.
  • composition according to the present invention advantageously does not comprise aluminum, in particular in the form of powder.
  • nitric esters such as nitroglycerin, BTTN or TMETN.
  • the present invention further relates to a pyrotechnic charge characterized in that it comprises the composition according to the present invention in a structure.
  • the loadings can be full or channel, advantageously they are channel, especially central channel.
  • the structures are conventional structures like propellant structure.
  • the loading is possibly starred or slightly evolutive.
  • the loads are generally incorporated in cylinders. They can have a weight ranging from 50 to 200 kg.
  • the solid composition according to the invention is manufactured according to the methods conventionally used for this type of composition. For example by mixing in a kneader in which the various ingredients are introduced in an appropriate order and carefully and thoroughly kneaded under given pressure and temperature conditions. This mixture, which is in the form of a paste, is cast in a mold with shaping tools. The whole is baked to ensure the hardening of the dough.
  • the present invention finally relates to the use of the composition or the pyrotechnic charge according to the invention for the generation of clean gas for the rapid flushing of submarine ballasts, that is to say for the emergency deballasting of vehicles. submarines.
  • the generator consists of a combustion chamber in which is housed the loading, a sealed nozzle and an igniter.
  • the pressure in the combustion chamber equilibrates around 10 MPa, the combustion flow rate (sensitive to the combustion rate and the combustion surface) evacuating through the neck of the nozzle initiated. After the nozzle exit, the gases are led into the ballast. The pressure rise in the ballast makes it possible to evacuate the water.
  • the gases obtained do not have solid residues and only infinitesimal quantities of HCl.
  • the gases obtained being nitrogen, carbon dioxide and oxygen.

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

Abstract

The present invention relates to a solid gas-generating composition comprising: -a) a polymeric binder selected from the group consisting of polyethylene glycol and diethylene glycol polyadipate;- b) an oxidising charge consisting of a mixture of (b1) ammonium perchlorate or ammonium chlorate with (b2) an alkaline or alkaline-earth nitrate selected from the group consisting of sodium nitrate, potassium nitrate, strontium nitrate and barium nitrate. It also relates to a pyrotechnic charge comprising the composition according to the invention in a structure. Finally, it relates to the use of the composition according to the invention or the pyrotechnic charge according to the invention for generating clean gas for fast flushing of submarine ballasts.

Description

COMPOSITION GENERATRICE DE GAZ  GAS GENERATING COMPOSITION
La présente invention concerne les compositions solides génératrices de gaz destinées au déballastage d'urgence dans les sous-marins. The present invention relates to solid gas generating compositions for emergency deballasting in submarines.
Dans des conditions normales d'utilisation, pour faire surface, le sous- marin doit vider partiellement les ballasts de leur eau à l'aide de gaz et retrouver une flottabilité positive. On dit qu'il "chasse aux ballasts". Under normal conditions of use, to surface, the submarine must partially empty the ballasts of their water with gas and regain positive buoyancy. It is said that it "ballast hunt".
Cependant, en cas de remontée d'urgence, il est nécessaire de vider quasi-instantanément Ces ballasts. On parle alors de chasse rapide aux ballasts. However, in the event of an emergency lift, it is necessary to empty these ballasts almost instantaneously. This is called rapid ballast hunting.
Pour réaliser le déballastage d'urgence, il est avantageux d'utiliser des compositions solides génératrices de gaz. De telles compositions à base de polyazoture de glycidyle (PAG) et de nitrate alcalin ou alcalino-terreux sont ainsi décrites dans la demande DE19821010. L'intérêt de ces compositions est qu'elles délivrent une grande quantité d'azote, de dioxyde de carbone et d'oxygène, ce qui permet d'assurer la fonction de déballastage, et que les produits de combustion sont sans hydrogène et sans monoxyde de carbone, gaz interdits car toxiques et dangereux.  For emergency deballasting, it is advantageous to use solid compositions generating gas. Such compositions based on glycidyl polyazide (PAG) and alkaline or alkaline earth nitrate are thus described in the DE19821010 application. The advantage of these compositions is that they deliver a large amount of nitrogen, carbon dioxide and oxygen, which ensures the deballasting function, and that the products of combustion are without hydrogen and without monoxide carbon, prohibited gases because toxic and dangerous.
Toutefois, ces compositions présentent principalement deux inconvénients: However, these compositions have two main disadvantages:
• Les produits de combustion contiennent une part importante de résidus solides qui proviennent de l'oxydation de l'alcalin ou de l'alcalino-terreux du nitrate, par exemple l'oxyde de strontium (SrO), l'oxyde de calcium (CaO) ou l'oxyde de sodium (Na2O). Classiquement, ces produits sont à l'état solide à la température de combustion. Ils peuvent perturber le fonctionnement balistique de la chambre de combustion, avec éventuellement un bouchage de tuyère. • Le polymère PAG a un coût très élevé, coût qui se répercute sur le prix du chargement au point de rendre sa commercialisation problématique. • Combustion products contain a significant amount of solid residues that result from the oxidation of the alkaline or alkaline earth nitrate, for example strontium oxide (SrO), calcium oxide (CaO ) or sodium oxide (Na2O). Conventionally, these products are in the solid state at the combustion temperature. They can disrupt the ballistic operation of the combustion chamber, possibly with nozzle plugging. • The PAG polymer has a very high cost, a cost that affects the price of the load to the point of making marketing problematic.
Or les inventeurs se sont aperçus de façon surprenante qu'il était possible de résoudre ces différents problèmes en remplaçant:  But the inventors surprisingly realized that it was possible to solve these problems by replacing:
- le polymère à base d'azoture PAG par un polyester ayant une terminaison hydroxy ou un polyéther ayant une terminaison hydroxy tel que le polyéthylène glycol (PEG) ou du polyadipate de diéthylène glycol (PADEG).  the PAG azide-based polymer with a polyester having a hydroxy-terminus or a polyether having a hydroxy-terminus, such as polyethylene glycol (PEG) or diethylene glycol polyadipate (PADEG).
- le nitrate alcalin ou alcalino-terreux par un mélange de perchlorate d'ammonium ou de chlorate d'ammonium avec un nitrate alcalin ou alcalino-terreux choisi dans le groupe constitué par le nitrate de sodium, le nitrate de potassium, le nitrate de strontium et le nitrate de baryum. - the alkaline or alkaline-earth nitrate by a mixture of ammonium perchlorate or ammonium chlorate with an alkaline or alkaline-earth nitrate selected from the group consisting of sodium nitrate, potassium nitrate, strontium nitrate and barium nitrate.
En effet, une telle composition permet d'éviter la formation de résidus solides lors de la génération de gaz tout en évitant la formation du gaz acide HCI dues à la présence de chlorate et de perchlorate grâce à la formation de sels de chlorures alcalins ou alcalino-terreux. Indeed, such a composition makes it possible to avoid the formation of solid residues during the generation of gases while avoiding the formation of the acid gas HCl due to the presence of chlorate and perchlorate by the formation of salts of alkali or alkaline chlorides earthy.
La présente invention concerne donc une composition solide génératrice de gaz comprenant (avantageusement constituée essentiellement de, en particulier constituée par) : The present invention therefore relates to a solid gas-generating composition comprising (advantageously consisting essentially of, in particular consisting of):
-a) un liant comprenant (avantageusement constitué essentiellement de, en particulier constitué par) (al) un polymère choisi dans le groupe constitué par les polyesters ayant une terminaison hydroxy, les polyéthers ayant une terminaison hydroxy et leurs mélanges et (a2) un système réticulant;  a) a binder comprising (advantageously consisting essentially of, in particular consisting of) (a1) a polymer selected from the group consisting of polyesters having a hydroxy terminus, polyethers having a hydroxy terminus and mixtures thereof and (a2) a system crosslinking;
-b) une charge oxydante constituée par un mélange de (bl) perchlorate d'ammonium ou chlorate d'ammonium ou leur mélange avec (b2) un nitrate alcalin ou alcalino-terreux choisi dans le groupe constitué par le nitrate de sodium, le nitrate de potassium, le nitrate de strontium, le nitrate de baryum et leurs mélanges. b) an oxidizing charge constituted by a mixture of (bl) ammonium perchlorate or ammonium chlorate or their mixture with (b2) an alkaline or alkaline-earth nitrate selected from the group consisting of sodium nitrate, potassium nitrate, strontium nitrate, barium nitrate and mixtures thereof.
La composition selon la présente invention comprend donc (al) un polymère choisi dans le groupe constitué par les polyesters ayant une terminaison hydroxy, les polyethers ayant une terminaison hydroxy et leurs mélanges. De façon avantageuse, le polymère (al) est choisi dans le groupe constitué par le polybutylèneoxyde, le polytétraméthylène oxyde, le polyoxypropylène glycol, le polyéthylène glycol, le polyadipate de diéthylène glycol et leurs mélanges, avantageusement dans le groupe constitué par le polyéthylène glycol le polyadipate de diéthylène glycol et leur mélange, en particulier il s'agit du polyadipate de diéthylène glycol (PADEG).  The composition according to the present invention therefore comprises (a1) a polymer selected from the group consisting of polyesters having a hydroxy terminus, polyethers having a hydroxy terminus and mixtures thereof. Advantageously, the polymer (a1) is chosen from the group consisting of polybutylene oxide, polytetramethylene oxide, polyoxypropylene glycol, polyethylene glycol, diethylene glycol polyadipate and mixtures thereof, advantageously in the group consisting of polyethylene glycol, diethylene glycol polyadipate and their mixture, in particular it is diethylene glycol polyadipate (PADEG).
La composition selon l'invention comprend en outre (a2) un système réticulant. Le système réticulant utilisable dans la composition selon la présente invention est avantageusement liquide et en particulier choisi parmi les polyisocyanates tels que le toluène diisocyanate, en particulier les polyisocyanates alicycliques, tels que le dicyclohexylméthylène diisocyanate, l'isophorone diisocyanate, l'hexaméthylène diisocyanate ou le biuret triisocyanate. The composition according to the invention further comprises (a2) a crosslinking system. The crosslinking system that can be used in the composition according to the present invention is advantageously liquid and in particular chosen from polyisocyanates such as toluene diisocyanate, in particular alicyclic polyisocyanates, such as dicyclohexylmethylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or biuret triisocyanate.
Le système réticulant est en général présent dans la composition en une teneur comprise entre 0,4 et 5 % en masse par rapport à la masse totale de la composition.  The crosslinking system is generally present in the composition in a content of between 0.4 and 5% by weight relative to the total weight of the composition.
La composition selon la présente invention comprend de plus (bl) du perchlorate d'ammonium ou du chlorate d'ammonium ou leur mélange. De façon avantageuse, pour des raisons de sécurité le perchlorate d'ammonium est préféré. La composition selon la présente invention comprend par ailleurs un nitrate (b2) choisi dans le groupe constitué par le nitrate de sodium, le nitrate de potassium, le nitrate de strontium, le nitrate de baryum et leurs mélanges, avantageusement dans le groupe constitué par le nitrate de sodium, le nitrate de potassium et leur mélange, encore plus avantageusement, il s'agit du nitrate de sodium. The composition according to the present invention further comprises (b1) ammonium perchlorate or ammonium chlorate or a mixture thereof. Advantageously, for safety reasons, ammonium perchlorate is preferred. The composition according to the present invention furthermore comprises a nitrate (b2) chosen from the group consisting of sodium nitrate, potassium nitrate, strontium nitrate, barium nitrate and their mixtures, advantageously in the group consisting of sodium nitrate, potassium nitrate and their mixture, still more advantageously, it is sodium nitrate.
Ainsi dans un mode de réalisation particulièrement avantageux, la composition selon la présente invention comprend (avantageusement est constituée essentiellement de, en particulier est constituée par) : Thus, in a particularly advantageous embodiment, the composition according to the present invention comprises (advantageously essentially consists of, in particular is constituted by):
-a) un liant comprenant (avantageusement constitué essentiellement de, en particulier constitué par) (al) du PADEG et (a2) un système réticulant isocyanate;  a) a binder comprising (advantageously consisting essentially of, in particular consisting of) (a1) PADEG and (a2) an isocyanate crosslinking system;
-b) une charge oxydante constituée par un mélange de (bl) perchlorate d'ammonium avec (b2) le nitrate de sodium.  -b) an oxidizing charge consisting of a mixture of (bl) ammonium perchlorate with (b2) sodium nitrate.
De façon avantageuse, la teneur en nitrate (b2) est telle que la neutralisation de l'alcalin par le chlore du perchlorate d'ammonium ou du chlorate d'ammonium est totale. Avantageusement elle est comprise entre 40 et 57 % en poids par rapport au poids total de la charge (b), avantageusement entre 42 et 56,3% en poids. Advantageously, the nitrate content (b2) is such that the neutralization of the alkaline by the chlorine of ammonium perchlorate or ammonium chlorate is complete. Advantageously it is between 40 and 57% by weight relative to the total weight of the filler (b), advantageously between 42 and 56.3% by weight.
En particulier, dans le cas où le composant (bl) est du chlorate d'ammonium, la teneur en nitrate (b2) est comprise entre 44 et 57 % en poids par rapport au poids total de la charge (b), avantageusement entre 45,6 et 56,3% en poids.  In particular, in the case where the component (b1) is ammonium chlorate, the nitrate content (b2) is between 44 and 57% by weight relative to the total weight of the filler (b), advantageously between 45.degree. , 6 and 56.3% by weight.
Dans un autre cas particulier, le composant (bl) est du perchlorate d'ammonium et la teneur en nitrate (b2) est comprise entre 40 et 55 % en poids par rapport au poids total de la charge (b), avantageusement entre 42 et 52,7% en poids. Par exemple le tableau 1 ci-dessous donne les mélanges précis permettant la neutralisation de l'alcalin par le chlore. In another particular case, the component (b1) is ammonium perchlorate and the nitrate content (b2) is between 40 and 55% by weight relative to the total weight of the filler (b), advantageously between 42 and 52.7% by weight. For example Table 1 below gives the precise mixtures allowing the neutralization of the alkaline by chlorine.
Tableau 1 : Table 1:
Figure imgf000006_0001
De façon avantageuse la teneur en liant (a) est suffisante pour permettre que la composition selon l'invention soit fabricable, plus avantageusement coulable. En particulier cette teneur est d'au moins 10% en poids par rapport au poids total de la composition selon l'invention.
Figure imgf000006_0001
Advantageously, the binder content (a) is sufficient to allow the composition according to the invention to be manufactured, more advantageously castable. In particular, this content is at least 10% by weight relative to the total weight of the composition according to the invention.
Avantageusement la teneur en liant (a) n'est pas trop importante pour éviter l'apparition de monoxyde de carbone et d'hydrogène. Advantageously the binder content (a) is not too important to avoid the appearance of carbon monoxide and hydrogen.
Plus avantageusement la teneur en liant (a) est comprise entre 10 et 20% en poids, encore plus avantageusement entre 12 et 18% en poids, par rapport au poids total de la composition selon l'invention.  More preferably the binder content (a) is between 10 and 20% by weight, more preferably between 12 and 18% by weight, relative to the total weight of the composition according to the invention.
En particulier, dans le cas où le liant (a) selon l'invention est du PEG, sa teneur est comprise entre 11 et 18% en poids, avantageusement entre 12 et 17% en poids par rapport au poids total de la composition selon l'invention. In particular, in the case where the binder (a) according to the invention is PEG, its content is between 11 and 18% by weight, advantageously between 12 and 17% by weight relative to the total weight of the composition according to the invention. 'invention.
Dans un mode particulier, dans le cas où le liant (a) selon l'invention est du PADEG, sa teneur est comprise entre 12 et 19% en poids, avantageusement entre 13 et 18% en poids par rapport au poids total de la composition selon l'invention. In a particular embodiment, in the case where the binder (a) according to the invention is PADEG, its content is between 12 and 19% by weight, advantageously between 13 and 18% by weight relative to the total weight of the composition according to the invention.
Dans un autre mode particulier, dans le cas où le composé (bl) selon l'invention est du chlorate d'ammonium, la teneur en liant (a) est comprise entre 11 et 17% en poids, avantageusement entre 12 et 16% en poids par rapport au poids total de la composition selon l'invention.  In another particular embodiment, in the case where the compound (b1) according to the invention is ammonium chlorate, the content of binder (a) is between 11 and 17% by weight, advantageously between 12 and 16% by weight. weight relative to the total weight of the composition according to the invention.
Dans encore un autre mode particulier, dans le cas où le composé (bl) selon l'invention est du perchlorate d'ammonium, la teneur en liant (a) est comprise entre 14 et 19% en poids, avantageusement entre 15 et 18% en poids par rapport au poids total de la composition selon l'invention.  In yet another particular embodiment, in the case where the compound (b1) according to the invention is ammonium perchlorate, the content of binder (a) is between 14 and 19% by weight, advantageously between 15 and 18%. by weight relative to the total weight of the composition according to the invention.
Par exemple, le tableau 2 ci-dessous donne des exemples de teneur en liant en fonction de la composition selon l'invention.  For example, Table 2 below gives examples of binder content according to the composition according to the invention.
Tableau 2 :  Table 2:
Figure imgf000007_0001
La composition selon la présente invention peut en outre comprendre des additifs tels que par exemple des anti-oxydants, des agents mouillants, des additifs de fabrication, des extenseurs de chaîne, des catalyseurs de polymérisation, des modificateurs de combustion (accélérateurs ou ralentisseurs), des additifs balistiques (refroidissants par exemple tels que le sel de cuivre ou de bismuth, l'oxyde de fer), des agents d'adhésion liant-charges et des pontants. Les additifs sont en général présents dans le liant (a). Les additifs, s'ils sont présents, sont en général présents dans la composition en une teneur comprise entre 0,1 et 10 % en masse par rapport à la masse totale de la composition.
Figure imgf000007_0001
The composition according to the present invention may further comprise additives such as, for example, antioxidants, wetting agents, manufacturing additives, chain extenders, polymerization catalysts, combustion modifiers (accelerators or retarders), ballistic additives (eg cooling such as copper or bismuth salt, iron oxide), adhesion agents binder-loads and bridges. The additives are generally present in the binder (a). The additives, if present, are generally present in the composition in a content of between 0.1 and 10% by weight relative to the total weight of the composition.
La composition selon la présente invention avantageusement ne comprend pas d'aluminium, en particulier sous forme de poudre. The composition according to the present invention advantageously does not comprise aluminum, in particular in the form of powder.
Elle ne comprend pas non plus avantageusement d'esters nitriques tels que nitroglycérine, BTTN ou TMETN. It also does not advantageously include nitric esters such as nitroglycerin, BTTN or TMETN.
Elle ne comprend pas non plus avantageusement de composé organique azoté tel que la nitroguanidine. It also does not advantageously comprise nitrogenous organic compound such as nitroguanidine.
La présente invention concerne de plus un chargement pyrotechnique caractérisé en ce qu'il comprend la composition selon la présente invention dans une structure. Les chargements peuvent être pleins ou à canal, avantageusement ils sont à canal, en particulier à canal central. Les structures sont des structures classiques type structure à propulseur. Le chargement est éventuellement étoilé ou légèrement évolutive.  The present invention further relates to a pyrotechnic charge characterized in that it comprises the composition according to the present invention in a structure. The loadings can be full or channel, advantageously they are channel, especially central channel. The structures are conventional structures like propellant structure. The loading is possibly starred or slightly evolutive.
Les chargements sont en général incorporés dans des cylindres. Ils peuvent avoir un poids allant de 50 à 200 kg. The loads are generally incorporated in cylinders. They can have a weight ranging from 50 to 200 kg.
La composition solide selon l'invention est fabriquée selon les procédés classiquement utilisés pour ce type de composition. Par exemple par mélange dans un malaxeur dans lequel les différents ingrédients sont introduits selon un ordre approprié et soigneusement et longuement malaxés dans des conditions de pression et de température données. Ce mélange, qui se présente sous la forme d'une pâte, est coulé dans un moule avec des outillages de mise en forme. L'ensemble subit une cuisson pour assurer le durcissement de la pâte. La présente invention concerne enfin l'utilisation de la composition ou du chargement pyrotechnique selon l'invention pour la génération de gaz propre pour la chasse rapide aux ballasts de sous-marin, c'est-à-dire pour le déballastage d'urgence des sous-marins. Le générateur est constitué d'une chambre de combustion dans lequel est logé le chargement, d'une tuyère operculée et d'un allumeur. Classiquement après l'allumage, la pression dans la chambre de combustion s'équilibre autour de 10 MPa, le débit de combustion (sensible à la vitesse de combustion et à la surface en combustion) s'évacuant par le col amorcé de la tuyère. Après la sortie de tuyère, les gaz sont conduits dans le ballast. L'élévation de pression dans le ballast permet d'évacuer l'eau. The solid composition according to the invention is manufactured according to the methods conventionally used for this type of composition. For example by mixing in a kneader in which the various ingredients are introduced in an appropriate order and carefully and thoroughly kneaded under given pressure and temperature conditions. This mixture, which is in the form of a paste, is cast in a mold with shaping tools. The whole is baked to ensure the hardening of the dough. The present invention finally relates to the use of the composition or the pyrotechnic charge according to the invention for the generation of clean gas for the rapid flushing of submarine ballasts, that is to say for the emergency deballasting of vehicles. submarines. The generator consists of a combustion chamber in which is housed the loading, a sealed nozzle and an igniter. Conventionally after ignition, the pressure in the combustion chamber equilibrates around 10 MPa, the combustion flow rate (sensitive to the combustion rate and the combustion surface) evacuating through the neck of the nozzle initiated. After the nozzle exit, the gases are led into the ballast. The pressure rise in the ballast makes it possible to evacuate the water.
L'invention sera mieux comprise à la lumière des exemples qui suivent qui ne sont indiqués qu'à titre d'illustration de l'invention. The invention will be better understood in the light of the examples which follow, which are only given by way of illustration of the invention.
Exemple 1 : fabrication de différentes compositions selon l'invention Example 1 Manufacture of Different Compositions According to the Invention
Les compositions suivantes ont été fabriquées  The following compositions were made
% en Chlorate Perchlorate PADEG + PEG + Nitrate Nitrate de Nitrate de Nitrate poids d'ammonium d'ammonium isocyanate isocyan de potassium strontium de ate sodium baryum % Chlorate Perchlorate PADEG + PEG + Nitrate Nitrate Nitrate Nitrate ammonium ammonium isocyanate potassium isocyanate strontium sodium barium
Comp 45,7 16 38,3 Comp 45.7 16 38.3
1 1
Comp 46,2 15 38,8  Comp 46.2 15 38.8
2 2
Comp 47,6 18 34,4  Comp 47.6 18 34.4
3 3
Comp 48,1 17 34,9  Comp 48.1 17 34.9
4 4
Comp 42,6 15 42,4  Comp 42.6 15 42.4
5 5
Comp 43,1 14 42,9 6 Comp 43.1 14 42.9 6
Comp 44,6 17 38,4  Comp 44.6 17 38.4
7  7
Comp 45,1 16 38,9  Comp 45.1 16 38.9
8 8
Comp 42,1 14 43,9  Comp 42.1 14 43.9
9 9
Comp 42,1 14 43,9  Comp 42.1 14 43.9
10 10
Comp 44,2 16 39,8  Comp 44.2 16 39.8
11 11
Comp 44,2 16 39,8  Comp 44.2 16 39.8
12 12
Comp 38 13 49 13  Comp 38 13 49 13
Comp 38,45 12 49,5 14 5 Comp 38.45 12 49.5 14 5
Comp 40,2 15 44,8 15 Comp 40.2 15 44.8 15
Comp 40,2 15 44,8 16  Comp 40.2 15 44.8 16
En utilisant ces compositions, les gaz obtenus ne présentent pas de résidus solides et uniquement des quantités infinitésimales de HCI. En outre il n'y pas d'apparition de monoxyde de carbone ni d'hydrogène, les seuls gaz obtenus étant de l'azote, du dioxyde de carbone et de l'oxygène. By using these compositions, the gases obtained do not have solid residues and only infinitesimal quantities of HCl. In addition there is no appearance of carbon monoxide or hydrogen, the only gases obtained being nitrogen, carbon dioxide and oxygen.
Enfin les rendements en gaz de ces compositions sont similaires à ceux obtenus avec la composition décrite dans la demande de brevet DE19821010, sans les inconvénients de cet art antérieur. Finally, the gas yields of these compositions are similar to those obtained with the composition described in the patent application DE19821010, without the disadvantages of this prior art.

Claims

REVENDICATIONS
1. Composition solide génératrice de gaz comprenant : A solid gas generating composition comprising:
-a) un liant comprenant (al) un polymère choisi dans le groupe constitué par les polyesters ayant une terminaison hydroxy, les polyéthers ayant une terminaison hydroxy et leurs mélanges et (a2) un système réticulant; -b) une charge oxydante constituée par un mélange de (bl) perchlorate d'ammonium ou chlorate d'ammonium ou leur mélange avec (b2) un nitrate alcalin ou alcali no-terreux choisi dans le groupe constitué par le nitrate de sodium, le nitrate de potassium, le nitrate de strontium, le nitrate de baryum et leurs mélanges.  a) a binder comprising (a1) a polymer selected from the group consisting of polyesters having a hydroxy terminus, polyethers having a hydroxy terminus and mixtures thereof and (a2) a crosslinking system; b) an oxidizing charge consisting of a mixture of (bl) ammonium perchlorate or ammonium chlorate or a mixture thereof with (b2) an alkaline or alkaline earth nitrate selected from the group consisting of sodium nitrate, potassium nitrate, strontium nitrate, barium nitrate and mixtures thereof.
2. Composition selon la revendication 1, caractérisée en ce que la teneur en nitrate (b2) est comprise entre 40 et 57 % en poids par rapport au poids total de la charge (b), avantageusement entre 42 et 56,3% en poids. 2. Composition according to Claim 1, characterized in that the nitrate content (b2) is between 40 and 57% by weight relative to the total weight of the filler (b), advantageously between 42 and 56.3% by weight. .
3. Composition selon l'une quelconque des revendications 1 ou 2, caractérisée en ce que le composant (bl) est du chlorate d'ammonium et en ce que la teneur en nitrate (b2) est comprise entre 44 et 57 % en poids par rapport au poids total de la charge (b), avantageusement entre 45,6 et 56,3% en poids. 3. Composition according to any one of claims 1 or 2, characterized in that the component (bl) is ammonium chlorate and in that the nitrate content (b2) is between 44 and 57% by weight by relative to the total weight of the filler (b), advantageously between 45.6 and 56.3% by weight.
4. Composition selon l'une quelconque des revendications 1 ou 2, caractérisée en ce que le composant (bl) est du perchlorate d'ammonium et en ce que la teneur en nitrate (b2) est comprise entre 40 et 55 % en poids par rapport au poids total de la charge (b), avantageusement entre 42 et 52,7% en poids. 4. Composition according to any one of claims 1 or 2, characterized in that the component (bl) is ammonium perchlorate and in that the nitrate content (b2) is between 40 and 55% by weight by relative to the total weight of the filler (b), advantageously between 42 and 52.7% by weight.
5. Composition selon l'une quelconque des revendications 1 à 4 caractérisée en ce que la teneur en liant (a) est comprise entre 10 et 20% en poids par rapport au poids total de la composition, avantageusement entre 12 et 18% en poids. 5. Composition according to any one of claims 1 to 4 characterized in that the binder content (a) is between 10 and 20% by weight relative to the total weight of the composition, preferably between 12 and 18% by weight .
6. Composition selon l'une quelconque des revendications 1 à 5, caractérisée en ce que le polymère (al) est choisi dans le groupe constitué par le polybutylèneoxyde, le polytétra méthylène oxyde, le polyoxypropylène glycol, le polyéthylène glycol, le polyadipate de diéthylène glycol et leurs mélanges, avantageusement dans le groupe constitué par le polyéthylène glycol, le polyadipate de diéthylène glycol et leur mélange , en particulier il s'agit du polyadipate de diéthylène glycol. 6. Composition according to any one of claims 1 to 5, characterized in that the polymer (a1) is selected from the group consisting of polybutyleneoxide, polytetramethylene oxide, polyoxypropylene glycol, polyethylene glycol, diethylene polyadipate glycol and mixtures thereof, advantageously in the group consisting of polyethylene glycol, diethylene glycol polyadipate and their mixture, in particular it is diethylene glycol polyadipate.
7. Composition selon l'une quelconque des revendications 1 à 6, caractérisée en ce qu'elle comprend : 7. Composition according to any one of claims 1 to 6, characterized in that it comprises:
-a) un liant comprenant (al) du polyadipate de diéthylène glycol et (a2) un système réticulant isocyanate;  a) a binder comprising (a1) diethylene glycol polyadipate and (a2) an isocyanate crosslinking system;
-b) une charge oxydante constituée par un mélange de (bl) perchlorate d'ammonium avec (b2) le nitrate de sodium.  -b) an oxidizing charge consisting of a mixture of (bl) ammonium perchlorate with (b2) sodium nitrate.
8. Composition selon l'une quelconque des revendications 1 à 7, caractérisée ce qu'elle comprend des additifs. 8. Composition according to any one of claims 1 to 7, characterized in that it comprises additives.
9. Chargement pyrotechnique caractérisé en ce qu'il comprend la composition selon l'une quelconque des revendications 1 à 8 dans une structure. 9. Pyrotechnic charge characterized in that it comprises the composition according to any one of claims 1 to 8 in a structure.
10. Utilisation de la composition selon l'une quelconque des revendications 1 à 8 ou du chargement pyrotechnique selon la revendication 9 pour la génération de gaz propre pour la chasse rapide aux ballasts de sous-marin. 10. Use of the composition according to any one of claims 1 to 8 or the pyrotechnic charge according to the claim 9 for the generation of clean gas for rapid flushing of submarine ballasts.
PCT/FR2018/052339 2017-09-29 2018-09-24 Gas-generating composition WO2019063923A1 (en)

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Application Number Priority Date Filing Date Title
FR1759146A FR3071831B1 (en) 2017-09-29 2017-09-29 GAS GENERATING COMPOSITION
FR1759146 2017-09-29

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3215573A (en) * 1963-04-22 1965-11-02 Aerojet General Co Polyurethane-base propellants containing unsaturated hydrocarbons
FR2709488A1 (en) * 1990-08-24 1995-03-10 Hercules Inc Solid propellant with a binder containing a noncrystalline polyether and an energetic plasticiser.
DE19821010C1 (en) 1998-05-11 1999-10-28 Bayern Chemie Gmbh Flugchemie Gas generator solid propellant for submarine emergency surfacing system
US20020020477A1 (en) * 1998-06-01 2002-02-21 John R. Moser, Jr Reduced energy binder for energetic compositions
EP1216977A2 (en) * 2000-12-22 2002-06-26 Snpe Hydrocarbon binder containing pyrotechnic gas-generating compositions and method for continuous manufacturing
WO2011135262A1 (en) * 2010-04-29 2011-11-03 Sme Gas-generating pyrotechnic compound and production process

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3215573A (en) * 1963-04-22 1965-11-02 Aerojet General Co Polyurethane-base propellants containing unsaturated hydrocarbons
FR2709488A1 (en) * 1990-08-24 1995-03-10 Hercules Inc Solid propellant with a binder containing a noncrystalline polyether and an energetic plasticiser.
DE19821010C1 (en) 1998-05-11 1999-10-28 Bayern Chemie Gmbh Flugchemie Gas generator solid propellant for submarine emergency surfacing system
US20020020477A1 (en) * 1998-06-01 2002-02-21 John R. Moser, Jr Reduced energy binder for energetic compositions
EP1216977A2 (en) * 2000-12-22 2002-06-26 Snpe Hydrocarbon binder containing pyrotechnic gas-generating compositions and method for continuous manufacturing
WO2011135262A1 (en) * 2010-04-29 2011-11-03 Sme Gas-generating pyrotechnic compound and production process

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FR3071831A1 (en) 2019-04-05
EP3687962C0 (en) 2024-06-12
FR3071831B1 (en) 2021-06-11
EP3687962B1 (en) 2024-06-12

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