EP1790626B1 - Semicontiunuous process for making an explosive composite charge having a polyurethane matrix by using two components - Google Patents

Semicontiunuous process for making an explosive composite charge having a polyurethane matrix by using two components Download PDF

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Publication number
EP1790626B1
EP1790626B1 EP06124572.6A EP06124572A EP1790626B1 EP 1790626 B1 EP1790626 B1 EP 1790626B1 EP 06124572 A EP06124572 A EP 06124572A EP 1790626 B1 EP1790626 B1 EP 1790626B1
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Prior art keywords
component
pasty
polyol
explosive
charge
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EP06124572.6A
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German (de)
French (fr)
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EP1790626A1 (en
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Bernard Mahe
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Eurenco SA
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Eurenco SA
Eurenco France SA
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    • 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
    • C06B21/0008—Compounding the ingredient
    • C06B21/0025—Compounding the ingredient the ingredient being a polymer bonded explosive or thermic component
    • 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
    • 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
    • C06B21/0058—Shaping the mixture by casting a curable composition, e.g. of the plastisol type

Definitions

  • the present invention is in the military field, more particularly in the field of explosive ordnance, such as bombs and shells.
  • composite explosive conventionally means a functionally detachable pyrotechnic composition consisting of a solid polymeric matrix, generally polyurethane, filled, said charge being pulverulent and containing an organic nitro-explosive charge, for example hexogen, octogen, ONTA (oxynitrotriazole), or a mixture of at least two of these compounds.
  • the dough When mixing is complete, the dough should be used within a short time (pot life).
  • pot life The lengthening of the pot life by a reduction in the level of crosslinking catalyst has as counterpart an increased polymerization time, the temperature being limited, inter alia, by the pyrotechnic nature of certain constituents.
  • JM TAUZIA during a paper titled “Some comments on Processing Energetic Materials” at the symposium “Compatibility and Processing” organized by the American Defense Prepardness Association (ADPA), October 23-25, 1989 in Virginia Beach (USA) is), has suggested, in order to solve this problem, a two-component process in which two chemically stable polymer components having approximately the same filler content and viscosity are first made from the constituents, batchwise in kneaders. .
  • a first disadvantage is that it is very difficult to continuously mix the two pasty components to obtain a homogeneous product.
  • a second disadvantage is that both components are pyrotechnically active (presence of explosive charges) and both must be made and stored in secure facilities.
  • a third drawback is that the solid polymeric matrix of the composite explosive finally obtained is different from that which is obtained with the same constituents in the same proportions, according to the conventional "batch” method.
  • the isocyanate component is polymeric.
  • the fact of preparing, in an intermediate manner, an isocyanate prepolymer from the starting isocyanate monomer results in obtaining a solid polyurethane matrix different from that obtained according to the "batch” process by directly mixing all the isocyanate monomer and any the hydroxyl prepolymer.
  • the crosslinking agent intervenes twice, for the implementation of the polymerization in two stages. It intervenes in a significant amount for the implementation of the first of said two steps; it intervenes in larger quantities for the implementation implementation of said first of said two steps for the implementation of the second of said two steps.
  • the Applicant has already proposed an improvement to the two-component process above. It has proposed a two-component semi-continuous process for obtaining a composite explosive charge with polyurethane matrix, presenting neither the drawbacks of the conventional "batch” method nor the aforementioned drawbacks of the two-component semi-continuous process described by JM TAUZIA. Said method has in particular been described in the patent application EP-A-1 333 015 . It presents, in combination, two original technical characteristics, one relating to the distribution of constituents in the two components, the other relating to the mixing mass ratio of said two components.
  • component A Only component A is pyrotechnically active, which considerably limits the safety constraints, and the mixing of components A and B is easily homogenized.
  • the physicochemical, mechanical, detonation and vulnerability properties of the final product are identical to those of the product obtained according to the conventional "batch" process from the same constituents in the same proportions, which avoids a penalizing requalification of the product. .
  • components A and B are completely independent of the mixing operations of components A and B and casting and can be performed during masked times. These components A and B can be stored if necessary for several weeks before being mixed.
  • EP-A-1 333 015 is also completely independent of the pot life because small amounts of components A and B are rapidly and continuously mixed, which makes it possible to increase the percentage of crosslinking catalyst and consequently to reduce the duration crosslinking the pasty explosive composition in the mold and / or achieving this crosslinking at a lower temperature.
  • the Applicant is presently proposing an improvement to said method according to EP-A-1 333 015 . It proposes, in fact, to incorporate a small amount of polyisocyanate monomer (component B) in component A.
  • the Applicant has, surprisingly, shown that such incorporation - of a small amount of polyisocyanate monomer (often referred to as a crosslinking agent) in component A - makes it possible to reduce, in an extremely significant way, dramatically , the viscosity of said component A.
  • a crosslinking agent polyisocyanate monomer
  • the small amount involved does not initiate crosslinking, therefore has no effect on the shelf life of component A, but exerts, quite unexpectedly, an effect of remarkable intensity on the viscosity of said component A
  • This effect is much more than a simple dilution effect (of a paste by a liquid) because it is of a much stronger intensity than that (not very significant) resulting from the addition of an equivalent quantity of another liquid such as the polyol prepolymer or the plasticizer or that, before any start of the crosslinking, the addition of all the liquid polyisocyanate polymer.
  • the added polyisocyanate monomer acts as a surfactant, which it dramatically modifies the bonds between the binder (the matrix) and the feedstock.
  • the pasty component typically contains from 1 to 10% by weight, preferably from 3 to 7% by weight, of the total amount of polyisocyanate monomer (crosslinking agent) intervention. If it contains less than 1% by weight, the effect on the viscosity is not very sensitive, if it contains more than 10% by weight, the crosslinking is likely to begin within it.
  • the process of the invention reproduces the characteristics of the process according to EP-A-1 333 015 with "transfer” of a small amount of the polyisocyanate monomer of component B (now B ') to component A (now A').
  • the impact of this "transfer” on the viscosity of said resulting component A ' is enormous (see the examples below). In terms of process, this translates into a considerable advantage. This allows access to greatly increased flow rates for the same level of pressure in the installation.
  • the person skilled in the art obviously conceives the interest of the improvement according to the invention.
  • the pasty explosive composition is obtained from the usual constituents or ingredients used according to the prior methods and which are well known to those skilled in the art.
  • These constituents essentially comprise a polyol prepolymer, a polyisocyanate monomer, a plasticizer and a pulverulent filler comprising at least one organic nitrated explosive.
  • the sum of the weight contents of polyol prepolymer, polyisocyanate monomer, plasticizer and pulverulent solid filler represents between 98% and 100% of all the constituents.
  • the physical states, solid, liquid, pasty, constituents and compositions should be understood, in the present description, as the physical states at room temperature (about 20 ° C) and at atmospheric pressure (about 0.1 MPa).
  • organic nitro-explosive is conventionally understood to mean an explosive chosen from the group consisting of aromatic nitro explosives (comprising at least one C-NO 2 group , the carbon atom being part of an aromatic ring) , nitric ester explosives (comprising at least one CO-NO 2 group ) and nitramine explosives (comprising at least one CN-NO 2 group ).
  • the organic nitro explosive is selected from the group consisting of hexogen, octogen, pentrite, oxynitrotriazole (ONTA), triaminotrinitrobenzene, nitroguanidine and mixtures thereof, i.e. all mixtures of at least two of the above compounds.
  • the organic nitrated explosive is selected from the group consisting of hexogen, octogen, ONTA and mixtures thereof.
  • the content of organic nitro explosive is between 15% and 90% by weight relative to the composite explosive and the solid filler content is between 75% and 90% by weight relative to the composite explosive.
  • the pulverulent solid filler consists only of at least one organic nitro explosive.
  • the pulverulent solid filler also comprises at least one other compound than the at least one organic nitro explosive.
  • reducing metal preferably selected from the group consisting of aluminum, zirconium, magnesium, tungsten, boron and mixtures thereof.
  • the reducing metal present is aluminum.
  • the reducing metal content may for example be between 2% and 35% by weight relative to the composite explosive.
  • the pulverulent filler may also comprise, in combination or not with a reducing metal, a mineral oxidant, preferably chosen from the group consisting of ammonium perchlorate, which is particularly preferred, potassium perchlorate, ammonium nitrate, sodium nitrate and mixtures thereof.
  • a mineral oxidant preferably chosen from the group consisting of ammonium perchlorate, which is particularly preferred, potassium perchlorate, ammonium nitrate, sodium nitrate and mixtures thereof.
  • the mineral oxidant content may for example be between 10% and 45% by weight relative to the composite explosive.
  • the pulverulent solid filler comprises at least one other compound than the organic nitro explosive
  • this other compound is preferably selected from the group consisting of ammonium perchlorate, aluminum and mixtures thereof.
  • the polyol prepolymer is a more or less viscous liquid. Its number-average molecular weight (Mn) is preferably between 500 and 10,000 and is preferably selected from the group consisting of polyisobutylene polyols, polybutadiene polyols, polyether polyols, polyester polyols and polysiloxane polyols. We use particularly preferably a hydroxyl terminated polybutadiene.
  • the polyisocyanate monomer is conventionally a liquid, preferably selected from the group consisting of toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), dicyclohexylmethylene diisocyanate (MDCI), hexamethylene diisocyanate (HMDI), biuret trihexane isocyanate (BTHI), 3,5,5-trimethyl-1,6-hexamethylene diisocyanate and mixtures thereof. Particularly preferably, IPDI or MDCI is used.
  • the plasticizer is also a liquid, preferably a monoester such as isodecyl pelargonate (IDP) or a polyester selected from the group consisting of phthalates, adipates, azelates and acetates.
  • a monoester such as isodecyl pelargonate (IDP)
  • a polyester selected from the group consisting of phthalates, adipates, azelates and acetates.
  • a monoester such as isodecyl pelargonate (IDP) or a polyester selected from the group consisting of phthalates, adipates, azelates and acetates.
  • DOP dioctyl phthalate
  • DOZ dioctyl azelate
  • DOA dioctyl adipate
  • all the constituents may also comprise at least one additive selected from the group consisting of crosslinking catalysts (NCO / OH reaction catalysts), wetting agents, antioxidants, binder-filler adhesion and chain extender compounds.
  • additives selected from the group consisting of crosslinking catalysts (NCO / OH reaction catalysts), wetting agents, antioxidants, binder-filler adhesion and chain extender compounds.
  • tin dibutyldilaurate As a crosslinking catalyst, tin dibutyldilaurate (DBTL) is preferably used, but any other catalyst well known to those skilled in the art, especially other organic tin compounds such as a salt, may also be used.
  • a lecithin such as soy lecithin or a siloxane is preferably used.
  • DBPC ditertiobutyl paracresol
  • AO2246 2,2'-methylenebis-4-methyl-6-tert-butylphenol
  • Binder-filler adhesion agent is preferably used triethylene pentamine acrylonitrile (TEPAN), or certain compounds derived from silanols such as triethoxysilyl-3-propylsuccinic anhydride (C 13 H 24 O 6 Si).
  • TEPAN triethylene pentamine acrylonitrile
  • silanols such as triethoxysilyl-3-propylsuccinic anhydride (C 13 H 24 O 6 Si).
  • Said at least one additive chosen from crosslinking catalysts, wetting agents, antioxidants and binder-filler adhesion agents may be equally distributed between the two components A 'and B'. Preferably, it is fully included in component A '.
  • chain extender compound which is also referred to as a bridging agent
  • a low mass polyol monomer of less than about 300, preferably a triol such as trimethylolpropane (TMP). or a diol such as dipropylene glycol. Said compound is imperatively wholly included in component A '.
  • the pasty explosive composition contains at least one additional constitutive ingredient chosen from the additives listed above.
  • the components A 'and B' are independently produced, discontinuously, by simple homogeneous mixing, for example in a kneader, and are chemically stable, that is to say that there is no chemical reaction between the mixed components of each component, and that all the constituents retain their structural identity, both during mixing and during subsequent storage and independently of the components A 'and B'.
  • component A 'and component B' are then continuously mixed in such a way that the mass ratio of component A '/ component B' is constant (at industrial sensitivities close to ) and between 95.05 / 4.95 and 99.55 / 0.45, preferably included between 97/3 and 99/1, for example equal to or close to 98/2. It is thus intended to optimize the constitution of the polyurethane matrix.
  • This continuous mixing between the component A 'and the component B' is for example and preferably carried out in a static mixer, a mixer well known to those skilled in the art, in the form of a pipe containing crosspieces forcing the product which passes to it to become to separate then to remix.
  • the pasty explosive composition is generally obtained with a flow rate of between 0.1 l / min and 5 l / min, more preferably between 0.3 l / min and 1 l / min, for example close to or equal to 0.5 l / min.
  • the components A 'and B' are each contained in a pot equipped with a piston whose setting in motion, using a motor, allows the supply of components A 'and B' d a convergent located upstream of a static mixer, so that the contents of the convergent flows into said static mixer.
  • the pressure on the mixture of components A 'and B' in the convergent is preferably between 1 MPa and 10 MPa. Both pistons are preferably driven by the same engine.
  • the static mixer used is preferably composed of a plurality of pipe-shaped, series-connected elements having a diameter of preferably between 15 mm and 60 mm.
  • a diameter of preferably between 15 mm and 60 mm For example, between 6 and 15 mixing elements, such as those sold commercially and well known to those skilled in the art, are used.
  • the static mixer is usually provided with a double jacket to allow adjustment of the temperature.
  • Pots or bins containing components A 'and B' may also be provided with a heating system.
  • component A 'and component B' are mixed at a temperature of between 40 ° C. and 80 ° C.
  • the pasty explosive composition obtained after mixing the components A 'and B' is introduced into a mold in which it then undergoes thermal crosslinking, in an oven for example.
  • This crosslinking results from the formation of urethane bridges due to the reaction of the hydroxyl functions of the polyol prepolymer and optionally of the chain extender compound with the isocyanate functions of the polyisocyanate monomer.
  • the crosslinking rate increases with temperature and catalyst content.
  • the mold is constituted by the envelope, generally metallic, of a munition, for example a shell.
  • the pasty explosive composition obtained from the mixer is introduced automatically in a large series of molds, for example several hundred d shells envelopes.
  • the crosslinking temperature of the pasty explosive composition introduced into the molds is between 15 ° C. and 80 ° C.
  • ambient temperature approximately 20 ° C.
  • the crosslinking temperature is identical to or close to that at which component A 'and component B' are mixed.
  • the installation of the Applicant in service in Sorgues comprises two feed pots (respectively A or A 'and B or B') each equipped with a piston, feeding (respectively A or A 'and B or B') a convergent opening in a static mixer.
  • feeding at the output of said static mixer, the pasty composition (A + B or A '+ B') is poured into a mold (which can be constituted directly from the object to be loaded).
  • Component A then has a viscosity of between 2 and 2.5 x 10 3 Pa.s (between 20,000 and 25,000 poises).
  • the two components, A 'and B' have the following specific mass compositions: COMPONENT A ' COMPONENT B ' prepolymer PBHT 6.4538% bridging TMP 0.0645% crosslinking IPDI 0.0400% crosslinking IPDI 0.7588% plasticizer DOA 3.9372% plasticizer DOA 0.4529% antioxidant AO2246 0.171% wetting Lecithin 0.171% AALC Tepan 0.0585% Catalyst DBTL 0.0001% Charge hexogen 88.0000%
  • Component A ' contains 5% of the total amount of polyisocyanate monomer.
  • the viscosity of said component A 'is then between 250 and 300 Pa.s (between 2500 and 3000 poise).

Description

La présente invention se situe dans le domaine militaire, plus particulièrement dans celui des munitions explosives, telles que les bombes et les obus.The present invention is in the military field, more particularly in the field of explosive ordnance, such as bombs and shells.

Elle a plus précisément pour objet un nouveau procédé d'obtention de chargements explosifs composites à matrice solide polyuréthanne.More specifically, it relates to a novel process for obtaining explosive composite charges polyurethane solid matrix.

On entend, de façon classique, par explosif composite, une composition pyrotechnique fonctionnellement détonable, constituée d'une matrice polymérique solide, en général polyuréthanne, chargée, ladite charge étant pulvérulente et contenant une charge explosive nitrée organique, par exemple de l'hexogène, de l'octogène, de l'ONTA (oxynitrotriazole), ou un mélange d'au moins deux de ces composés.The term "composite explosive" conventionally means a functionally detachable pyrotechnic composition consisting of a solid polymeric matrix, generally polyurethane, filled, said charge being pulverulent and containing an organic nitro-explosive charge, for example hexogen, octogen, ONTA (oxynitrotriazole), or a mixture of at least two of these compounds.

Les chargements explosifs composites et la façon de les obtenir sont par exemple décrits par J. QUINCHON, "Poudres, Propergols et Explosifs, tome 1, Les explosifs, Technique et Documentation, 1982, pages 190-192 ". La charge pulvérulente est mélangée dans un malaxeur à une résine polymérisable liquide, par exemple un prépolymère à terminaisons hydroxyle. On obtient une pâte que l'on peut couler dans un moule puis faire polymériser par cuisson. Par le choix et le réglage des agents de réticulation de la résine, des catalyseurs et d'autres additifs, on peut obtenir des pièces moulées de caractéristiques variées.Composite explosive shipments and the manner of obtaining them are for example described by J. QUINCHON, "Powders, Propellants and Explosives, Volume 1, Explosives, Technique and Documentation, 1982, pages 190-192 The pulverulent filler is mixed in a kneader with a liquid polymerisable resin, for example a hydroxyl-terminated prepolymer, to obtain a paste which can be cast in a mold and then polymerized by firing. resin crosslinking agents, catalysts and other additives, moldings of various characteristics can be obtained.

Ce procédé classique de malaxage de tous les constituants qui sont introduits et mélangés dans un malaxeur selon une séquence définie présente des inconvénients et limitations.This conventional method of kneading all the constituents that are introduced and mixed in a kneader in a defined sequence has disadvantages and limitations.

Lorsque le mélange est achevé, la pâte doit être utilisée dans un laps de temps assez bref (vie de pot). L'allongement de la vie de pot par une réduction du taux de catalyseur de réticulation a comme contrepartie une durée de polymérisation augmentée, la température étant limitée, entre autres, par la nature pyrotechnique de certains constituants.When mixing is complete, the dough should be used within a short time (pot life). The lengthening of the pot life by a reduction in the level of crosslinking catalyst has as counterpart an increased polymerization time, the temperature being limited, inter alia, by the pyrotechnic nature of certain constituents.

Cette façon d'opérer nécessite donc un compromis technique entre la vie de pot et la durée de cuisson ainsi qu'un enchaînement obligatoire des séquences de malaxage et de coulée de la pâte.This way of operating therefore requires a technical compromise between the pot life and the cooking time as well as an obligatory sequence of the mixing and casting sequences of the dough.

Elle nécessite également un compromis économique entre la taille du malaxeur et la taille de l'objet moulé.It also requires an economic compromise between the size of the mixer and the size of the molded object.

En effet, si ce procédé "batch" s'avère assez bien adapté pour fabriquer des gros objets tels que des mines sous-marines, des torpilles et des bombes, il s'avère par contre très pénalisant et coûteux pour fabriquer une grande quantité de petits objets moulés à forte cadence, par exemple pour fabriquer plusieurs centaines d'obus de diamètre de l'ordre de 50 à 100 mm contenant chacun quelques centaines de grammes à quelques kilos d'explosif composite à partir d'une malaxée de 1 à 3 t de pâte.Indeed, if this process "batch" is quite suitable for making large objects such as submarine mines, torpedoes and bombs, it is very disadvantageous and expensive to make a large amount of small objects molded at a high rate, for example to make several hundred shells of diameter of the order of 50 to 100 mm each containing a few hundred grams to a few kilograms of composite explosive from a kneaded from 1 to 3 t of dough.

Il est nécessaire, dans cette situation, d'avoir une vie de pot élevée pour pouvoir charger de nombreuses munitions avec la même malaxée, ce qui a comme contrepartie une durée de réticulation de la pâte particulièrement longue et un coût très élevé du cycle de fabrication à cause de la durée d'immobilisation du matériel et des personnes.It is necessary, in this situation, to have a high pot life to be able to load many ammunition with the same kneaded, which has as counterpart a duration of crosslinking of the particularly long dough and a very high cost of the manufacturing cycle because of the downtime of equipment and people.

Si on réduit la taille du malaxeur, on réduit le nombre de munitions à remplir par malaxée, ce qui est économiquement pénalisant.If the size of the mixer is reduced, the number of ammunition to be filled by kneading is reduced, which is economically disadvantageous.

L'homme du métier a cherché à sortir de ce carcan vie de pot/durée de cuisson et de cet enchaînement obligatoire et précis des opérations de malaxée et couléeThose skilled in the art have sought to get out of this yoke pot life / cooking time and this binding and precise sequence of kneading and pouring operations

J.M. TAUZIA, lors d'une communication intitulée "Some comments on Processing Energetic Materials" au symposium "Compatibility and Processing" organisé par l'American Defense Prepardness Association (ADPA), les 23-25 octobre 1989 à Virginia Beach (Etats-Un is), a suggéré, pour résoudre ce problème, un procédé bicomposant dans lequel deux composants polymériques chimiquement stables et présentant approximativement le même taux de charge et la même viscosité sont tout d'abord réalisés à partir des constituants, de façon discontinue dans des malaxeurs. JM TAUZIA, during a paper titled "Some comments on Processing Energetic Materials" at the symposium "Compatibility and Processing" organized by the American Defense Prepardness Association (ADPA), October 23-25, 1989 in Virginia Beach (USA) is), has suggested, in order to solve this problem, a two-component process in which two chemically stable polymer components having approximately the same filler content and viscosity are first made from the constituents, batchwise in kneaders. .

Ces deux composants pâteux sont ensuite mélangés de façon continue avec un rapport massique proche de 1.These two pasty components are then mixed continuously with a mass ratio close to 1.

Ce procédé bicomposant, s'il permet bien de s'affranchir du compromis vie de pot/durée de cuisson et rend possible le stockage des deux composants pendant plusieurs semaines, présente plusieurs inconvénients.This two-component process, while it makes it possible to overcome the compromise pot life / cooking time and makes possible the storage of the two components for several weeks, has several disadvantages.

Un premier inconvénient est qu'il s'avère très délicat de mélanger de façon continue les deux composants pâteux pour obtenir un produit homogène.A first disadvantage is that it is very difficult to continuously mix the two pasty components to obtain a homogeneous product.

Un second inconvénient est que les deux composants sont pyrotechniquement actifs (présence de charges explosives) et qu'ils doivent donc tous les deux être réalisés puis stockés dans des installations sécurisées.A second disadvantage is that both components are pyrotechnically active (presence of explosive charges) and both must be made and stored in secure facilities.

Un troisième inconvénient est que la matrice polymérique solide de l'explosif composite finalement obtenu est différente de celle que l'on obtient, avec les mêmes constituants dans les mêmes proportions, selon le procédé "batch" classique. En effet, selon J.M. TAUZIA, le composant isocyanate est polymérique. Le fait de préparer, de façon intermédiaire, un prépolymère isocyanate à partir du monomère isocyanate de départ a pour conséquence l'obtention d'une matrice polyuréthanne solide différente de celle obtenue selon le procédé "batch" en mélangeant directement tout le monomère isocyanate et tout le prépolymère hydroxyle.A third drawback is that the solid polymeric matrix of the composite explosive finally obtained is different from that which is obtained with the same constituents in the same proportions, according to the conventional "batch" method. Indeed, according to J.M. TAUZIA, the isocyanate component is polymeric. The fact of preparing, in an intermediate manner, an isocyanate prepolymer from the starting isocyanate monomer results in obtaining a solid polyurethane matrix different from that obtained according to the "batch" process by directly mixing all the isocyanate monomer and any the hydroxyl prepolymer.

Cette différence de structure de la matrice solide polyuréthanne entraîne des différences indésirables de propriétés mécaniques et/ou détoniques, d'où nécessité d'une requalification très coûteuse et pénalisante du produit final.This difference in structure of the polyurethane solid matrix results in undesirable differences in mechanical and / or detonation properties, hence the need for a very expensive and penalizing requalification of the final product.

Le procédé bicomposant décrit par J.M. TAUZIA n'est donc pas totalement satisfaisant.The two-component process described by J.M. TAUZIA is therefore not totally satisfactory.

On connaît par ailleurs des procédés de fabrication de propergols (et non de chargements explosifs) basés sur l'extrusion. Le procédé selon la demande FR 2 746 389 comprend une polymérisation en deux étapes :

  • une première étape qui fait intervenir une première quantité de l'agent de réticulation (environ 70 % en poids) pour l'obtention d'un produit viscoélastique,
  • une seconde étape qui fait intervenir la quantité complémentaire de l'agent de réticulation (environ 30 % en poids) pour l'obtention d'un produit caoutchouteux.
Methods for manufacturing propellants (and not explosive charges) based on extrusion are also known. The process according to the request FR 2,746,389 comprises a two-step polymerization:
  • a first step which involves a first quantity of the crosslinking agent (approximately 70% by weight) to obtain a viscoelastic product,
  • a second step which involves the complementary amount of the crosslinking agent (about 30% by weight) to obtain a rubbery product.

Dans un tel contexte, différent de celui de l'invention (l'homme du métier conçoit que le malaxeur décrit ne conviendrait pas pour le traitement de molécules explosives), l'agent de réticulation intervient en deux fois, pour la mise en oeuvre de la polymérisation en deux étapes. Il intervient en quantité significative pour la mise en oeuvre de la première desdites deux étapes ; il intervient en plus grande quantité pour la mise en oeuvre de ladite première desdites deux étapes que pour la mise en oeuvre de la seconde desdites deux étapes.In such a context, different from that of the invention (the person skilled in the art understands that the kneader described is not suitable for the treatment of explosive molecules), the crosslinking agent intervenes twice, for the implementation of the polymerization in two stages. It intervenes in a significant amount for the implementation of the first of said two steps; it intervenes in larger quantities for the implementation implementation of said first of said two steps for the implementation of the second of said two steps.

Dans un tel contexte, la Demanderesse a déjà proposé un perfectionnement au procédé bicomposant ci-dessus. Elle a proposé un procédé semi-continu bicomposant d'obtention d'un chargement explosif composite à matrice polyuréthanne, ne présentant ni les inconvénients du procédé "batch" classique, ni les inconvénients précités du procédé semi-continu bicomposant décrit par J.M. TAUZIA. Ledit procédé a notamment été décrit dans la demande de brevet EP-A-1 333 015 . Il présente, en combinaison, deux caractéristiques techniques originales, l'une relative à la répartition des constituants dans les deux composants, l'autre relative au rapport massique de mélange desdits deux composants.In such a context, the Applicant has already proposed an improvement to the two-component process above. It has proposed a two-component semi-continuous process for obtaining a composite explosive charge with polyurethane matrix, presenting neither the drawbacks of the conventional "batch" method nor the aforementioned drawbacks of the two-component semi-continuous process described by JM TAUZIA. Said method has in particular been described in the patent application EP-A-1 333 015 . It presents, in combination, two original technical characteristics, one relating to the distribution of constituents in the two components, the other relating to the mixing mass ratio of said two components.

Ledit procédé est un procédé semi-continu d'obtention d'un chargement explosif composite constitué d'une matrice solide polyuréthanne chargée dont la charge est solide, pulvérulente et comprend au moins un explosif nitré organique, par introduction dans un moule d'une composition explosive pâteuse puis réticulation thermique de cette composition, ladite composition étant obtenue par mélange de constituants comprenant essentiellement un prépolymère polyol, un monomère polyisocyanate, un plastifiant et une charge solide pulvérulente comprenant au moins un explosif nitré organique. Il est caractérisé en ce que, pour obtenir la composition explosive pâteuse :

  • on réalise tout d'abord, de façon discontinue, à partir de l'ensemble des constituants, par simple mélange homogène, deux composants :
    • un composant A pâteux comprenant la totalité du prépolymère polyol et la totalité de la charge solide pulvérulente,
    • un composant B liquide comprenant la totalité du monomère polyisocyanate,
    le plastifiant étant indifféremment réparti entre les deux composants A et B,
  • on mélange ensuite, de façon continue, le composant A et le composant B de telle sorte que le rapport massique composant A/composant B soit constant et compris entre 95/5 et 99,5/0,5.
The method is a semi-continuous process for obtaining a composite explosive charge consisting of a charged solid polyurethane matrix whose charge is solid, pulverulent and comprises at least one organic nitrated explosive, by introduction into a mold of a composition explosive pasty then thermal crosslinking of this composition, said composition being obtained by mixing constituents essentially comprising a polyol prepolymer, a polyisocyanate monomer, a plasticizer and a powdery solid filler comprising at least one organic nitrated explosive. It is characterized in that, to obtain the pasty explosive composition:
  • first, in a discontinuous manner, from the set of constituents, by simple homogeneous mixing, two components are produced:
    • a pasty component A comprising all of the polyol prepolymer and all of the powdery solid filler,
    • a liquid component B comprising all the polyisocyanate monomer,
    the plasticizer being indifferently distributed between the two components A and B,
  • component A and component B are then continuously mixed in such a way that the component A / component B mass ratio is constant and between 95/5 and 99.5 / 0.5.

Il convient de bien noter les deux caractéristiques techniques de ce procédé :

  • le fait que les composants A et B n'ont pas la même viscosité, que l'un est pâteux et comprend la totalité de la charge et du prépolymère polyol, et que l'autre est liquide et comprend la totalité du monomère polyisocyanate, tel que, sans modification chimique, notamment sans prépolymérisation à l'aide d'un polyol ; et
  • le rapport massique comprenant A/composant B bien particulier.
It is important to note the two technical characteristics of this process:
  • the fact that the components A and B do not have the same viscosity, that one is pasty and comprises all of the filler and polyol prepolymer, and that the other is liquid and comprises all of the polyisocyanate monomer, such as that, without chemical modification, in particular without prepolymerization using a polyol; and
  • the specific weight ratio including A / component B.

Cette combinaison de caractéristiques techniques distinctives, comparativement au procédé semi-continu bicomposant selon J.M. TAUZIA, a pour effet technique de supprimer tous les inconvénients précités, et de rendre le procédé particulièrement simple et peu coûteux.This combination of distinctive technical characteristics, compared to the two-component semi-continuous process according to J.M. TAUZIA, has the technical effect of eliminating all the aforementioned drawbacks, and of making the process particularly simple and inexpensive.

Seul le composant A est pyrotechniquement actif, ce qui limite considérablement les contraintes de sécurité, et le mélange des composants A et B s'homogénéise facilement.Only component A is pyrotechnically active, which considerably limits the safety constraints, and the mixing of components A and B is easily homogenized.

Par ailleurs, les propriétés physico-chimiques, mécaniques, détoniques et de vulnérabilité du produit final sont identiques à celles du produit obtenu selon le procédé "batch" classique à partir des mêmes constituants dans les mêmes proportions, ce qui évite une requalification pénalisante du produit.Moreover, the physicochemical, mechanical, detonation and vulnerability properties of the final product are identical to those of the product obtained according to the conventional "batch" process from the same constituents in the same proportions, which avoids a penalizing requalification of the product. .

Les opérations de préparation des composants A et B sont totalement indépendantes des opérations de mélange des composants A et B et de coulée et peuvent être réalisées durant des temps masqués. Ces composants A et B peuvent être stockés si besoin est durant plusieurs semaines avant d'être mélangés.The preparation operations of components A and B are completely independent of the mixing operations of components A and B and casting and can be performed during masked times. These components A and B can be stored if necessary for several weeks before being mixed.

Le procédé selon EP-A-1 333 015 est de plus totalement indépendant de la vie de pot du fait que l'on mélange rapidement et de façon continue de petites quantités des composants A et B, ce qui permet d'augmenter le pourcentage de catalyseur de réticulation et de diminuer en conséquence la durée de réticulation de la composition explosive pâteuse dans le moule et/ou de réaliser cette réticulation à une température inférieure.The process according to EP-A-1 333 015 is also completely independent of the pot life because small amounts of components A and B are rapidly and continuously mixed, which makes it possible to increase the percentage of crosslinking catalyst and consequently to reduce the duration crosslinking the pasty explosive composition in the mold and / or achieving this crosslinking at a lower temperature.

Une réticulation à la température ambiante (20°C) est même possible, ce qui peut être particulièrement avantageux.Crosslinking at ambient temperature (20 ° C.) is even possible, which can be particularly advantageous.

Pour mettre en oeuvre ledit procédé selon EP-A-1 333 015 , on se heurte parfois à une réelle difficulté au niveau de l'alimentation du mélangeur (composant A/composant B, agencé en amont du moule) en le composant A. Ce composant est en effet introduit dans ledit mélangeur, généralement statique, sous la poussée d'un piston et le niveau de pression nécessaire pour mettre en mouvement ledit piston est évidemment proportionnel à la perte de charge, elle-même d'autant plus importante que la viscosité dudit composant A est élevée. Or ledit composant A présente, dans certains cas, une viscosité élevée, du fait qu'il renferme peu de liquide.To implement said method according to EP-A-1 333 015 sometimes there is a real difficulty in feeding the mixer (component A / component B, arranged upstream of the mold) to component A. This component is indeed introduced into said mixer, generally static, under the pressure of a piston and the level of pressure required to move said piston is obviously proportional to the pressure drop, itself all the more important that the viscosity of said component A is high. Or said component A has, in some cases, a high viscosity, because it contains little liquid.

En référence à cette difficulté technique, la Demanderesse propose présentement un perfectionnement audit procédé selon EP-A-1 333 015 . Elle propose, en fait, d'incorporer une faible quantité de monomère polyisocyanate (composant B) dans le composant A.With reference to this technical difficulty, the Applicant is presently proposing an improvement to said method according to EP-A-1 333 015 . It proposes, in fact, to incorporate a small amount of polyisocyanate monomer (component B) in component A.

La Demanderesse a, de façon surprenante, montré qu'une telle incorporation - d'une faible quantité de monomère polyisocyanate (qualifié souvent d'agent de réticulation) dans le composant A - permet d'abaisser, de façon extrêmement significative, de façon spectaculaire, la viscosité dudit composant A.The Applicant has, surprisingly, shown that such incorporation - of a small amount of polyisocyanate monomer (often referred to as a crosslinking agent) in component A - makes it possible to reduce, in an extremely significant way, dramatically , the viscosity of said component A.

La faible quantité en cause n'amorce pas la réticulation, est donc sans effet sur la durée de conservation du composant A, mais exerce, de façon tout à fait inattendue, un effet, d'une intensité remarquable, sur la viscosité dudit composant A. Cet effet est beaucoup plus qu'un simple effet de dilution (d'une pâte par un liquide) car il est d'une intensité beaucoup plus forte que celui (peu significatif) résultant de l'ajout d'une quantité équivalente d'un autre liquide tel le prépolymère polyol ou le plastifiant ou que celui résultant, avant tout début de la réticulation, de l'ajout de la totalité du polymère polyisocyanate liquide. Il semblerait qu'au sein du composant A, le monomère polyisocyanate ajouté agisse comme un agent tensioactif, qu'il modifie, de façon spectaculaire, les liaisons entre le liant (la matrice) et la charge...The small amount involved does not initiate crosslinking, therefore has no effect on the shelf life of component A, but exerts, quite unexpectedly, an effect of remarkable intensity on the viscosity of said component A This effect is much more than a simple dilution effect (of a paste by a liquid) because it is of a much stronger intensity than that (not very significant) resulting from the addition of an equivalent quantity of another liquid such as the polyol prepolymer or the plasticizer or that, before any start of the crosslinking, the addition of all the liquid polyisocyanate polymer. It would appear that within component A, the added polyisocyanate monomer acts as a surfactant, which it dramatically modifies the bonds between the binder (the matrix) and the feedstock.

On se propose maintenant de décrire le procédé de l'invention, qui constitue donc un perfectionnement au procédé selon EP-A-1 333 015 , et pour éviter toute confusion, dans la description qui va suivre, on parle de composant A' (pâteux) et B' (liquide).It is now proposed to describe the process of the invention, which is therefore an improvement to the process according to EP-A-1 333 015 , and to avoid any confusion, in the description that follows, we speak of component A '(pasty) and B' (liquid).

La présente invention concerne donc un procédé semi-continu d'obtention d'un chargement explosif composite constitué d'une matrice solide polyuréthanne chargée dont la charge est pulvérulente et comprend au moins un explosif nitré organique ; ledit procédé comprenant les étapes successives ci-après :

  • l'obtention d'une composition explosive pâteuse constituée essentiellement des ingrédients ci-après :
    • un prépolymère polyol,
    • un monomère polyisocyanate,
    • un plastifiant, et
    • une charge solide pulvérulente comprenant au moins un explosif nitré organique,
    par mélange en continu d'un composant A' pâteux et d'un composant B' liquide, préparés, de façon discontinue, à partir desdits ingrédients constitutifs ;
  • l'introduction dans un moule de ladite composition explosive pâteuse ; et
  • la réticulation thermique de ladite composition dans ledit moule.
En cela, ledit procédé de l'invention est un procédé selon EP-A-1 333 015 .The present invention thus relates to a semi-continuous process for obtaining a composite explosive charge consisting of a filled solid polyurethane matrix whose charge is powdery and comprises at least one organic nitro explosive; said method comprising the following successive steps:
  • obtaining a pasty explosive composition consisting essentially of the following ingredients:
    • a polyol prepolymer,
    • a polyisocyanate monomer,
    • a plasticizer, and
    • a pulverulent solid filler comprising at least one organic nitrated explosive,
    continuously mixing a pasty component and a liquid component B ', prepared discontinuously, from said constituent ingredients;
  • introducing into a mold said pasty explosive composition; and
  • thermal crosslinking of said composition in said mold.
In this, said method of the invention is a method according to EP-A-1 333 015 .

Dans un tel cadre, de façon caractéristique :

  • ledit composant B' liquide comprend 90 à 99 % en poids dudit monomère polyisocyanate ;
  • ledit composant A' pâteux comprend la totalité du prépolymère polyol, la totalité de la charge solide pulvérulente et les 1 à 10 % en poids restants du monomère polyisocyanate ;
le plastifiant étant indifféremment réparti entre lesdits composants A' et B' ; et
le mélange en continu desdits composants A' et B' est mis en oeuvre de sorte que le rapport massique composant A'/composant B' soit constant (aux sensibilités industrielles près), compris entre 95,05/4,95 et 99,55/0,45.In such a setting, typically
  • said liquid component B 'comprises 90 to 99% by weight of said polyisocyanate monomer;
  • said pasty component comprises all of the polyol prepolymer, all of the powdery solid filler and the remaining 1-10 wt.% of the polyisocyanate monomer;
the plasticizer being indifferently distributed between said components A 'and B'; and
the continuous mixing of said components A 'and B' is carried out so that the mass ratio component A '/ component B' is constant (at industrial sensitivities close), between 95.05 / 4.95 and 99.55 / 0.45.

Selon l'invention, de façon caractéristique, le composant pâteux renferme de 1 à 10 % en poids, avantageusement de 3 à 7 % en poids, de la quantité totale d'intervention du monomère polyisocyanate (agent de réticulation). S'il renferme moins de 1 % en poids, l'effet sur la viscosité n'est guère sensible, s'il renferme plus de 10 % en poids, la réticulation est susceptible de s'amorcer en son sein.According to the invention, typically the pasty component contains from 1 to 10% by weight, preferably from 3 to 7% by weight, of the total amount of polyisocyanate monomer (crosslinking agent) intervention. If it contains less than 1% by weight, the effect on the viscosity is not very sensitive, if it contains more than 10% by weight, the crosslinking is likely to begin within it.

Comme explicité ci-dessus, le procédé de l'invention reproduit les caractéristiques du procédé selon EP-A-1 333 015 avec "transfert" d'une faible quantité du monomère polyisocyanate du composant B (devenu B') vers le composant A (devenu A'). L'impact de ce "transfert" sur la viscosité dudit composant A' résultant est énorme (voir les exemples ci-après). En terme de procédé, cela se traduit par un avantage considérable. Cela permet d'accéder à des débits de coulée largement augmentés pour un même niveau de pression dans l'installation. L'homme du métier conçoit de manière évidente l'intérêt du perfectionnement selon l'invention.As explained above, the process of the invention reproduces the characteristics of the process according to EP-A-1 333 015 with "transfer" of a small amount of the polyisocyanate monomer of component B (now B ') to component A (now A'). The impact of this "transfer" on the viscosity of said resulting component A 'is enormous (see the examples below). In terms of process, this translates into a considerable advantage. This allows access to greatly increased flow rates for the same level of pressure in the installation. The person skilled in the art obviously conceives the interest of the improvement according to the invention.

On se propose maintenant de préciser quelque peu, de façon nullement limitative, le cadre de la présente invention (cadre, qui, on l'a compris, correspond à celui de l'invention selon EP-A-1 333 015 ).It is now proposed to clarify somewhat, in no way limiting, the scope of the present invention (frame, which, it is understood, corresponds to that of the invention according to EP-A-1 333 015 ).

Lors de la mise en oeuvre du procédé de l'invention, la composition explosive pâteuse est obtenue à partir des constituants ou ingrédients usuels utilisés selon les procédés antérieurs et qui sont bien connus de l'homme du métier.When carrying out the process of the invention, the pasty explosive composition is obtained from the usual constituents or ingredients used according to the prior methods and which are well known to those skilled in the art.

Ces constituants comprennent essentiellement un prépolymère polyol, un monomère polyisocyanate, un plastifiant et une charge pulvérulente comprenant au moins un explosif nitré organique.These constituents essentially comprise a polyol prepolymer, a polyisocyanate monomer, a plasticizer and a pulverulent filler comprising at least one organic nitrated explosive.

Par "essentiellement", il faut comprendre que les constituants ou ingrédients précités sont toujours présents et représentent globalement plus de 90 % en poids par rapport au poids total de la composition explosive pâteuse.By "essentially" it should be understood that the aforementioned constituents or ingredients are still present and generally represent more than 90% by weight relative to the total weight of the pasty explosive composition.

De façon préférée, la somme des teneurs pondérales en prépolymère polyol, monomère polyisocyanate, plastifiant et charge solide pulvérulente représente entre 98 % et 100 % de l'ensemble des constituants.Preferably, the sum of the weight contents of polyol prepolymer, polyisocyanate monomer, plasticizer and pulverulent solid filler represents between 98% and 100% of all the constituents.

De façon générale, les états physiques, solide, liquide, pâteux, des constituants et des compositions doivent être compris, dans la présente description, comme étant les états physiques à la température ambiante (environ 20°C) et à la pression atmosphérique (environ 0,1 MPa).In general, the physical states, solid, liquid, pasty, constituents and compositions should be understood, in the present description, as the physical states at room temperature (about 20 ° C) and at atmospheric pressure (about 0.1 MPa).

On entend, de façon classique, par "explosif nitré organique", un explosif choisi dans le groupe constitué par les explosifs nitrés aromatiques (comportant au moins un groupement C-NO2, l'atome de carbone faisant partie d'un cycle aromatique), les explosifs esters nitriques (comportant au moins un groupement C-O-NO2) et les explosifs nitramines (comportant au moins un groupement C-N-NO2).The term "organic nitro-explosive" is conventionally understood to mean an explosive chosen from the group consisting of aromatic nitro explosives (comprising at least one C-NO 2 group , the carbon atom being part of an aromatic ring) , nitric ester explosives (comprising at least one CO-NO 2 group ) and nitramine explosives (comprising at least one CN-NO 2 group ).

De façon préférée, l'explosif nitré organique est choisi dans le groupe constitué par l'hexogène, l'octogène, la pentrite, l'oxynitrotriazole (ONTA), le triaminotrinitrobenzène, la nitroguanidine et leurs mélanges, c'est-à-dire tous les mélanges d'au moins deux des composés précités. De façon particulièrement préférée, l'explosif nitré organique est choisi dans le groupe constitué par l'hexogène, l'octogène, l'ONTA et leurs mélanges.Preferably, the organic nitro explosive is selected from the group consisting of hexogen, octogen, pentrite, oxynitrotriazole (ONTA), triaminotrinitrobenzene, nitroguanidine and mixtures thereof, i.e. all mixtures of at least two of the above compounds. Particularly preferably, the organic nitrated explosive is selected from the group consisting of hexogen, octogen, ONTA and mixtures thereof.

Selon une variante préférée, la teneur en explosif nitré organique est comprise entre 15 % et 90 % en poids par rapport à l'explosif composite et la teneur en charge solide pulvérulente est comprise entre 75 % et 90 % en poids par rapport à l'explosif composite.According to a preferred variant, the content of organic nitro explosive is between 15% and 90% by weight relative to the composite explosive and the solid filler content is between 75% and 90% by weight relative to the composite explosive.

Selon une variante, la charge solide pulvérulente n'est constituée que d'au moins un explosif nitré organique.According to one variant, the pulverulent solid filler consists only of at least one organic nitro explosive.

Selon une autre variante, la charge solide pulvérulente comprend également au moins un autre composé que le au moins un explosif nitré organique.According to another variant, the pulverulent solid filler also comprises at least one other compound than the at least one organic nitro explosive.

Elle peut par exemple comprendre un métal réducteur, de préférence choisi dans le groupe constitué par l'aluminium, de zirconium, le magnésium, le tungstène, le bore et leurs mélanges. De façon particulièrement préférée, le métal réducteur présent est l'aluminium. La teneur en métal réducteur peut par exemple être comprise entre 2 % et 35 % en poids par rapport à l'explosif composite.It may for example comprise a reducing metal, preferably selected from the group consisting of aluminum, zirconium, magnesium, tungsten, boron and mixtures thereof. In a particularly preferred manner, the reducing metal present is aluminum. The reducing metal content may for example be between 2% and 35% by weight relative to the composite explosive.

La charge pulvérulente peut également comprendre, en association ou non avec un métal réducteur, un oxydant minéral, de préférence choisi dans le groupe constitué par le perchlorate d'ammonium, qui est particulièrement préféré, le perchlorate de potassium, le nitrate d'ammonium, le nitrate de sodium et leurs mélanges. La teneur en oxydant minéral peut par exemple être comprise entre 10 % et 45 % en poids par rapport à l'explosif composite.The pulverulent filler may also comprise, in combination or not with a reducing metal, a mineral oxidant, preferably chosen from the group consisting of ammonium perchlorate, which is particularly preferred, potassium perchlorate, ammonium nitrate, sodium nitrate and mixtures thereof. The mineral oxidant content may for example be between 10% and 45% by weight relative to the composite explosive.

Lorsque la charge solide pulvérulente comprend au moins un autre composé que l'explosif nitré organique, cet autre composé est de préférence choisi dans le groupe constitué par le perchlorate d'ammonium, l'aluminium et leurs mélanges.When the pulverulent solid filler comprises at least one other compound than the organic nitro explosive, this other compound is preferably selected from the group consisting of ammonium perchlorate, aluminum and mixtures thereof.

Le prépolymère polyol est un liquide plus ou moins visqueux. Sa masse moléculaire moyenne en nombre (Mn) est de préférence comprise entre 500 et 10 000 et il est de préférence choisi dans le groupe constitué par les polyisobutylènes polyols, les polybutadiènes polyols, les polyéthers polyols, les polyesters polyols et les polysiloxanes polyols. On utilise de façon particulièrement préférée un polybutadiène à terminaisons hydroxyle.The polyol prepolymer is a more or less viscous liquid. Its number-average molecular weight (Mn) is preferably between 500 and 10,000 and is preferably selected from the group consisting of polyisobutylene polyols, polybutadiene polyols, polyether polyols, polyester polyols and polysiloxane polyols. We use particularly preferably a hydroxyl terminated polybutadiene.

Le monomère polyisocyanate est classiquement un liquide, de préférence choisi dans le groupe constitué par le toluène diisocyanate (TDI), l'isophorone diisocyanate (IPDI), le dicyclohexylméthylène diisocyanate (MDCI), l'hexaméthylène diisocyanate (HMDI), le biuret trihexane isocyanate (BTHI), le 3,5,5-triméthyl-1,6-hexaméthylène diisocyanate et leurs mélanges. De façon particulièrement préférée, on utilise l'IPDI ou le MDCI.The polyisocyanate monomer is conventionally a liquid, preferably selected from the group consisting of toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), dicyclohexylmethylene diisocyanate (MDCI), hexamethylene diisocyanate (HMDI), biuret trihexane isocyanate (BTHI), 3,5,5-trimethyl-1,6-hexamethylene diisocyanate and mixtures thereof. Particularly preferably, IPDI or MDCI is used.

Le plastifiant est également un liquide, de préférence un monoester tel que le pélargonate d'isodécyle (IDP) ou un polyester choisi dans le groupe constitué par les phtalates, les adipates, les azélates et les acétates. Parmi les polyesters, la triacétine, les phtalates d'alkyle tels que le phtalate de dioctyle (DOP), les azélates d'alkyle tels que l'azélate de dioctyle (DOZ) et les adipates d'alkyle tels que l'adipate de dioctyle (DOA) sont particulièrement préférés.The plasticizer is also a liquid, preferably a monoester such as isodecyl pelargonate (IDP) or a polyester selected from the group consisting of phthalates, adipates, azelates and acetates. Among the polyesters, triacetin, alkyl phthalates such as dioctyl phthalate (DOP), alkyl azelates such as dioctyl azelate (DOZ) and alkyl adipates such as dioctyl adipate (DOA) are particularly preferred.

Outre les constituants essentiels précités, l'ensemble des constituants peut également comprendre au moins un additif choisi dans le groupe constitué par les catalyseurs de réticulation (catalyseurs de la réaction NCO/OH), les agents mouillants, les agents antioxydants, les agents d'adhésion liant-charge et les composés extenseurs de chaîne.In addition to the essential constituents mentioned above, all the constituents may also comprise at least one additive selected from the group consisting of crosslinking catalysts (NCO / OH reaction catalysts), wetting agents, antioxidants, binder-filler adhesion and chain extender compounds.

Comme catalyseur de réticulation, on utilise de préférence le dibutyldilaurate d'étain (DBTL), mais on peut aussi utiliser tout autre catalyseur bien connu de l'homme du métier, notamment d'autres composés organiques de l'étain tels qu'un sel stanneux d'un acide carboxylique, un oxyde de trialkylétain, un dihalogénure de dialkylétain ou un oxyde de dialkylétain. On peut citer par exemple le diacétate de dibutylétain, le diacétate de diéthylétain, le dioxyde de dioctylétain et l'octoate stanneux. On peut aussi utiliser comme catalyseur une amine tertiaire, notamment une trialkylamine, ou bien encore un composé organique du bismuth, tel que le triphénylbismuth.As a crosslinking catalyst, tin dibutyldilaurate (DBTL) is preferably used, but any other catalyst well known to those skilled in the art, especially other organic tin compounds such as a salt, may also be used. stannous carboxylic acid, trialkyltin oxide, dialkyltin dihalide or dialkyltin oxide. Examples that may be mentioned are dibutyltin diacetate, diethyltin diacetate, dioctyltin dioxide and stannous octoate. It is also possible to use as a catalyst a tertiary amine, especially a trialkylamine, or else an organic compound of bismuth, such as triphenylbismuth.

Comme agent mouillant, on utilise de préférence une lécithine telle que la lécithine de soja, ou un siloxane.As the wetting agent, a lecithin such as soy lecithin or a siloxane is preferably used.

Comme agent antioxydant, on utilise de préférence le ditertiobutylparacrésol (DBPC) ou le 2,2'-méthylènebis-4-méthyl-6-tertiobutylphénol (AO2246).As an antioxidant, ditertiobutyl paracresol (DBPC) or 2,2'-methylenebis-4-methyl-6-tert-butylphenol (AO2246) is preferably used.

Comme agent d'adhésion liant-charge, on utilise de préférence le triéthylène pentamine acrylonitrile (TEPAN), ou certains composés dérivés de silanols comme l'anhydride triéthoxysilyl-3-propylsuccinique (C13H24O6Si).Binder-filler adhesion agent is preferably used triethylene pentamine acrylonitrile (TEPAN), or certain compounds derived from silanols such as triethoxysilyl-3-propylsuccinic anhydride (C 13 H 24 O 6 Si).

Ledit au moins un additif choisi parmi les catalyseurs de réticulation, les agents mouillants, les agents antioxydants et les agents d'adhésion liant-charge peut être indifféremment réparti entre les deux composants A' et B'. De préférence, il est intégralement compris dans le composant A'.Said at least one additive chosen from crosslinking catalysts, wetting agents, antioxidants and binder-filler adhesion agents may be equally distributed between the two components A 'and B'. Preferably, it is fully included in component A '.

Comme composé extenseur de chaîne (présentement chaîne polymérique polyuréthanne), que l'on qualifie également d'agent pontant, on utilise en général un monomère polyol de faible masse, inférieure à 300 environ, de préférence un triol tel que le triméthylolpropane (TMP) ou un diol tel que le dipropylèneglycol. Ledit composé est impérativement en totalité compris dans le composant A'.As the chain extender compound (currently polymeric polyurethane chain), which is also referred to as a bridging agent, use is generally made of a low mass polyol monomer of less than about 300, preferably a triol such as trimethylolpropane (TMP). or a diol such as dipropylene glycol. Said compound is imperatively wholly included in component A '.

Selon une variante avantageuse, outre les ingrédients principaux (le prépolymère polyol, le monomère polyisocyanate, le plastifiant et la charge solide pulvérulente), la composition explosive pâteuse ne renferme qu'au moins un ingrédient constitutif additionnel choisi parmi les additifs listés ci-dessus.According to an advantageous variant, in addition to the main ingredients (the polyol prepolymer, the polyisocyanate monomer, the plasticizer and the pulverulent solid filler), the pasty explosive composition contains at least one additional constitutive ingredient chosen from the additives listed above.

Dans le cadre de variantes de réalisation préférées :

  • le composant A' comprend la totalité du plastifiant ; et/ou
  • le composant B' est uniquement constitué des 90 à 99 % en poids de monomère polyisocyanate intervenant.
In the context of preferred embodiments:
  • component A 'comprises all the plasticizer; and or
  • component B 'consists solely of 90 to 99% by weight of intervening polyisocyanate monomer.

Les composants A' et B' sont indépendamment réalisés, de façon discontinue, par simple mélange homogène, par exemple dans un malaxeur, et sont chimiquement stables, c'est-à-dire qu'il n'y a aucune réaction chimique entre les constituants mélangés de chaque composant, et que tous les constituants conservent leur identité structurelle, aussi bien lors du mélange que lors du stockage ultérieur et indépendamment des composants A' et B'.The components A 'and B' are independently produced, discontinuously, by simple homogeneous mixing, for example in a kneader, and are chemically stable, that is to say that there is no chemical reaction between the mixed components of each component, and that all the constituents retain their structural identity, both during mixing and during subsequent storage and independently of the components A 'and B'.

Selon la présente invention, pour obtenir une composition explosive pâteuse, on mélange ensuite, de façon continue, le composant A' et le composant B' de telle sorte que le rapport massique composant A'/composant B' soit constant (aux sensibilités industrielles près) et compris entre 95,05/4,95 et 99,55/0,45, de préférence compris entre 97/3 et 99/1, par exemple égal à ou voisin de 98/2. On vise ainsi à optimiser la constitution de la matrice polyuréthanne.According to the present invention, to obtain a pasty explosive composition, component A 'and component B' are then continuously mixed in such a way that the mass ratio of component A '/ component B' is constant (at industrial sensitivities close to ) and between 95.05 / 4.95 and 99.55 / 0.45, preferably included between 97/3 and 99/1, for example equal to or close to 98/2. It is thus intended to optimize the constitution of the polyurethane matrix.

Ce mélange continu entre le composant A' et le composant B' est par exemple et de préférence réalisé dans un mélangeur statique, mélangeur bien connu de l'homme du métier, en forme de conduite contenant des croisillons obligeant le produit qui y passe à se séparer puis à se remélanger.This continuous mixing between the component A 'and the component B' is for example and preferably carried out in a static mixer, a mixer well known to those skilled in the art, in the form of a pipe containing crosspieces forcing the product which passes to it to become to separate then to remix.

A la sortie du mélangeur, mélangeur statique ou autre mélangeur à faible sollicitation mécanique, générant en particulier un faible taux de cisaillement, on obtient généralement la composition explosive pâteuse avec un débit volumique compris entre 0,1 l/min et 5 l/min, mieux encore compris entre 0,3 l/min et 1 l/min, par exemple voisin de ou égal à 0,5 l/min.At the outlet of the mixer, static mixer or other mixer with low mechanical stress, generating in particular a low shear rate, the pasty explosive composition is generally obtained with a flow rate of between 0.1 l / min and 5 l / min, more preferably between 0.3 l / min and 1 l / min, for example close to or equal to 0.5 l / min.

En référence au dispositif, avantageusement utilisé pour la mise en oeuvre du procédé de l'invention, on peut préciser, de façon nullement limitative, ce qui suit.With reference to the device, advantageously used for the implementation of the method of the invention, it is possible to specify, in no way limiting, the following.

Selon une variante préférée, les composants A' et B' sont chacun contenus dans un pot équipé d'un piston dont la mise en mouvement, à l'aide d'un moteur, permet l'alimentation en composants A' et B' d'un convergent situé en amont d'un mélangeur statique, de sorte que le contenu du convergent se déverse dans ledit mélangeur statique.According to a preferred variant, the components A 'and B' are each contained in a pot equipped with a piston whose setting in motion, using a motor, allows the supply of components A 'and B' d a convergent located upstream of a static mixer, so that the contents of the convergent flows into said static mixer.

La pression sur le mélange des composants A' et B' dans le convergent est de préférence comprise entre 1 MPa et 10 MPa. Les deux pistons sont de préférence mus par le même moteur.The pressure on the mixture of components A 'and B' in the convergent is preferably between 1 MPa and 10 MPa. Both pistons are preferably driven by the same engine.

Compte tenu du rapport massique composant A'/composé B' élevé, il est intéressant de souligner qu'un tel équipement offre la possibilité d'enchaîner plusieurs pots du composant A' pour le même pot de composant B', sans rupture du procédé continu.Given the high mass ratio component A '/ compound B', it is interesting to note that such equipment offers the possibility of linking several pots of the component A 'for the same pot component B', without breaking the continuous process .

Le mélangeur statique utilisé est de préférence constitué de plusieurs éléments montés en série, en forme de conduite, ayant un diamètre de préférence compris entre 15 mm et 60 mm. On utilise par exemple entre 6 et 15 éléments de mélange, tels que ceux vendus dans le commerce et bien connus de l'homme du métier.The static mixer used is preferably composed of a plurality of pipe-shaped, series-connected elements having a diameter of preferably between 15 mm and 60 mm. For example, between 6 and 15 mixing elements, such as those sold commercially and well known to those skilled in the art, are used.

La variante préférée précitée selon laquelle les composants A' et B' sont chacun contenus dans un pot équipé d'un piston permet des dosages très précis et une alimentation très régulière, mais on peut aussi, par exemple, alimenter le mélangeur statique à l'aide de pompes doseuses reliées aux bacs de stockage des composants A' et B'.The aforementioned preferred variant according to which the components A 'and B' are each contained in a pot equipped with a piston allows very precise dosages and a very regular supply, but one can also, for example, supplying the static mixer with metering pumps connected to the storage bins of components A 'and B'.

Le mélangeur statique est en général muni d'une double enveloppe afin de permettre un ajustement de la température.The static mixer is usually provided with a double jacket to allow adjustment of the temperature.

Les pots ou les bacs contenant les composants A' et B' peuvent également être munis d'un système de chauffage.Pots or bins containing components A 'and B' may also be provided with a heating system.

Selon une variante préférée, le composant A' et le composant B' sont mélangés à une température comprise entre 40°C et 80°C.According to a preferred variant, component A 'and component B' are mixed at a temperature of between 40 ° C. and 80 ° C.

La composition explosive pâteuse obtenue après mélange des composants A' et B' est introduite dans un moule dans lequel elle subit ensuite une réticulation thermique, dans un four par exemple.The pasty explosive composition obtained after mixing the components A 'and B' is introduced into a mold in which it then undergoes thermal crosslinking, in an oven for example.

Cette réticulation résulte de la formation de ponts uréthanne du fait de la réaction des fonctions hydroxyle du prépolymère polyol et éventuellement du composé extenseur de chaîne avec les fonctions isocyanate du monomère polyisocyanate. La vitesse de réticulation augmente avec la température et la teneur en catalyseur.This crosslinking results from the formation of urethane bridges due to the reaction of the hydroxyl functions of the polyol prepolymer and optionally of the chain extender compound with the isocyanate functions of the polyisocyanate monomer. The crosslinking rate increases with temperature and catalyst content.

Selon une variante préférée, le moule est constitué par l'enveloppe, en général métallique, d'une munition, par exemple d'un obus.According to a preferred variant, the mold is constituted by the envelope, generally metallic, of a munition, for example a shell.

De façon préférée, et notamment lorsqu'on utilise un mélangeur statique pour mélanger de façon continue les composants A' et B', la composition explosive pâteuse issue du mélangeur est introduite de façon automatisée dans une grande série de moules, par exemple plusieurs centaines d'enveloppes d'obus.Preferably, and especially when a static mixer is used to continuously mix the components A 'and B', the pasty explosive composition obtained from the mixer is introduced automatically in a large series of molds, for example several hundred d shells envelopes.

Selon une variante préférée de l'invention, la température de réticulation de la composition explosive pâteuse introduite dans les moules est comprise entre 15°C et 80°C.According to a preferred variant of the invention, the crosslinking temperature of the pasty explosive composition introduced into the molds is between 15 ° C. and 80 ° C.

On peut notamment opérer à la température ambiante (environ 20°C), ce qui peut être particulièrement avantageux.In particular, it is possible to operate at ambient temperature (approximately 20 ° C.), which can be particularly advantageous.

Selon une variante préférée, la température de réticulation est identique ou voisine de celle à laquelle le composant A' et le composant B' sont mélangés.According to a preferred variant, the crosslinking temperature is identical to or close to that at which component A 'and component B' are mixed.

On se propose maintenant d'illustrer l'invention et de démontrer son grand intérêt.It is now proposed to illustrate the invention and to demonstrate its great interest.

On se situe dans le contexte de la fabrication d'un explosif composite, présentant la composition pondérale ci-après : 6,4538 % de prépolymère polyol (PBHT : polybutadiène hydroxy téléchélique) 0,7988 % de monomère polyisocyanate, réticulant (IPDI : isophorone diisocyanate) 4,3901 % de plastifiant (DOA : adipate de dioctyle) 0,0645 % d'agent pontant (TMP : triméthylolpropane) 0,1171 % d'agent antioxydant (AO2246 : 2,2'-méthylènebis-4-méthyl-6-tertio-butylphénol) 0,1171 % d'agent mouillant (lécithine de soja) 0,0585 % d'agent d'adhésion liant-charge ou AALC (TEPAN : tri-éthylène pentamine acrylonitrile) 0,0001 % de catalyseur (DBTL : dibutyldilaurate d'étain) 88 % de charge pulvérulente (HX : hexogène). It is in the context of the manufacture of a composite explosive, having the following weight composition: 6.4538 % polyol prepolymer (PBHT: telechelic hydroxy polybutadiene) .7988 % of polyisocyanate monomer, crosslinker (IPDI: isophorone diisocyanate) 4.3901 % of plasticizer (DOA: dioctyl adipate) 0.0645 % bridging agent (TMP: trimethylolpropane) .1171 % of antioxidant (AO2246: 2,2'-methylenebis-4-methyl-6-tert-butylphenol) .1171 % wetting agent (soy lecithin) 0.0585 % Binder-Filler Adhesion Agent or AALC (TEPAN: tri-ethylene pentamine acrylonitrile) 0.0001 % of catalyst (DBTL: tin dibutyldilaurate) 88 % powdery charge (HX: hexogen).

On opère successivement selon la technique bicomposante de EP-A-1 333 015 et celle de l'invention avec des rapports massiques (A/B, A'/B') de 98/2.One operates successively according to the two-component technique of EP-A-1 333 015 and that of the invention with mass ratios (A / B, A '/ B') of 98/2.

L'installation de la Demanderesse en service à Sorgues comporte deux pots d'alimentation (respectivement en A ou A' et B ou B') équipés chacun d'un piston, alimentant (respectivement en A ou A' et B ou B') un convergent débouchant dans un mélangeur statique. A la sortie dudit mélangeur statique, la composition pâteuse (A+B ou A'+B') est déversée dans un moule (qui peut être constitué directement de l'objet à charger).
• Selon la technique de EP-A-1 333 015 , les deux composants, A et B, présentent les compositions respectives ci-après : COMPOSANT A COMPOSANT B Prépolymère PBHT 6,4538 % Pontant TMP 0,0645 % Réticulant IPDI 0,7988 % Plastifiant DOA 3,9372 % Plastifiant DOA 0,4529 % Antioxydant AO2246 0,1171 % Mouillant Lécithine 0,1171 % AALC TEPAN 0,0585 % Catalyseur DBTL 0,0001 % Charge Hexogène 88,0000 % The installation of the Applicant in service in Sorgues comprises two feed pots (respectively A or A 'and B or B') each equipped with a piston, feeding (respectively A or A 'and B or B') a convergent opening in a static mixer. At the output of said static mixer, the pasty composition (A + B or A '+ B') is poured into a mold (which can be constituted directly from the object to be loaded).
• According to the technique of EP-A-1 333 015 the two components, A and B, have the following respective compositions: COMPONENT A COMPONENT B prepolymer PBHT 6.4538% bridging TMP 0.0645% crosslinking IPDI 0.7988 % plasticizer DOA 3.9372% plasticizer DOA 0.4529% antioxidant AO2246 0.171% wetting Lecithin 0.171% AALC Tepan 0.0585% Catalyst DBTL 0.0001% Charge hexogen 88.0000%

Le composant A présente alors une viscosité entre 2 et 2,5 x 103 Pa.s (entre 20 000 et 25 000 poises).Component A then has a viscosity of between 2 and 2.5 x 10 3 Pa.s (between 20,000 and 25,000 poises).

Dans l'installation, il faut monter entre 2 et 3 x 106 Pa (entre 20 et 30 bar) de pression sur les pistons pour atteindre des débits de l'ordre de 21 x 10-3 m3/s (350 cm3/min).
• Selon la technique de l'invention, les deux composants, A' et B', présentent les compositions massiques respectives ci-après : COMPOSANT A' COMPOSANT B' Prépolymère PBHT 6,4538 % Pontant TMP 0,0645 % Réticulant IPDI 0,0400 % Réticulant IPDI 0,7588 % Plastifiant DOA 3,9372 % Plastifiant DOA 0,4529 % Antioxydant AO2246 0,1171 % Mouillant Lécithine 0,1171 % AALC TEPAN 0,0585 % Catalyseur DBTL 0,0001 % Charge Hexogène 88,0000 % In the installation, it is necessary to raise between 2 and 3 x 10 6 Pa (between 20 and 30 bar) of pressure on the pistons to reach flow rates of the order of 21 x 10 -3 m 3 / s (350 cm 3 / min).
According to the technique of the invention, the two components, A 'and B', have the following specific mass compositions: COMPONENT A ' COMPONENT B ' prepolymer PBHT 6.4538% bridging TMP 0.0645% crosslinking IPDI 0.0400% crosslinking IPDI 0.7588% plasticizer DOA 3.9372% plasticizer DOA 0.4529% antioxidant AO2246 0.171% wetting Lecithin 0.171% AALC Tepan 0.0585% Catalyst DBTL 0.0001% Charge hexogen 88.0000%

Le composant A' renferme 5 % de la quantité totale de monomère polyisocyanate. La viscosité dudit composant A' est alors comprise entre 250 et 300 Pa.s (entre 2 500 et 3 000 poises).Component A 'contains 5% of the total amount of polyisocyanate monomer. The viscosity of said component A 'is then between 250 and 300 Pa.s (between 2500 and 3000 poise).

Dans l'installation, il suffit alors d'environ 8 x 105 Pa (8 bar) de pression sur les pistons pour atteindre des débits de l'ordre de 2 x 10-2 m3/s (350 cm3/min). Des débits d'environ 5 x 10-2 m3/s (850 cm3/min) sont accessibles avec une pression de seulement 2 x 104 Pa (20 bar).In the installation, it suffices then about 8 x 10 5 Pa (8 bar) of pressure on the pistons to reach flows of the order of 2 x 10 -2 m 3 / s (350 cm 3 / min). Flow rates of about 5 x 10 -2 m 3 / s (850 cm 3 / min) are accessible with a pressure of only 2 x 10 4 Pa (20 bar).

A la considération de ces chiffres, on saisit tout l'intérêt de la présente invention.Considering these figures, the whole point of the present invention is appreciated.

Claims (11)

  1. A semi-continuous method for obtaining a composite explosive charge comprising a solid polyurethane matrix loaded with a charge, said charge being in powder form and comprising at least one nitro-organic explosive, said method comprising the following successive steps:
    - obtaining a pasty explosive composition consisting essentially of the following ingredients:
    • a polyol pre-polymer,
    • a polyisocyanate monomer,
    • a plasticising agent, and
    • a solid charge in powder form comprising at least one nitro-organic explosive,
    by continuously mixing a pasty component A' and a liquid component B', prepared discontinuously from said constituent ingredients,
    - introducing said pasty explosive composition into a mould, and
    - thermal cross-linking said composition in said mould, and
    being characterised in that:
    - said liquid component B' comprises 90 to 99% by weight of said polyisocyanate monomer,
    - said pasty component A' comprises the whole of the polyol pre-polymer, the whole of the solid charge in powder form and the remaining 1 to 10% by weight of the polyisocyanate monomer,
    the plasticising agent being distributed without distinction between said components A' and B', and in that the continuous mixing of said components A' and B' is carried out in such a way that the weight ratio component A'/component B' is constant, comprised between 95.05/4.95 and 99.55/0.45.
  2. The method according to claim 1, characterised in that the sum total of the weight contents of polyol pre-polymer, polyisocyanate monomer, plasticising agent, and solid charge in powder form represents between 98% and 100% of the whole of the ingredients.
  3. The method according to claim 1 or 2, characterised in that the polyol pre-polymer has a number-average molecular mass (Mn) between 500 and 10,000, and is selected from the group consisting of polyol polyisobutylenes, polyol polybutadienes, polyol polyethers, polyol polyesters and polyol polysiloxanes.
  4. The method according to any one of claims 1 to 3, characterised in that the polyisocyanate monomer is selected from the group consisting of toluene diisocyanate, isophorone diisocyanate, dicyclohexylmethylene diisocyanate, hexamethylene diisocyanate, biuret trihexane isocyanate, 3,5,5-trimethyl-1,6-hexamethylene diisocyanate, and mixtures thereof.
  5. The method according to any one of claims 1 to 4, characterised in that said pasty explosive composition also comprises at least one additive selected from the group consisting of cross-linking catalysts, wetting agents, antioxidant agents, binder-charge adhesion agents and chain-extending compounds; said at least one chain-extending compound present being totally contained in the component A' and said at least one additive present, other than a chain-extending compound, being distributed without distinction between the two components A' and B'.
  6. The method according to claim 5, characterised in that said at least one additive is totally contained in the component A'.
  7. The method according to any one of claims 1 to 6, characterised in that the component B' consists solely of the polyisocyanate monomer.
  8. The method according to any one of claims 1 to 7, characterised in that the mixing between the component A' and the component B' takes place in a static mixer.
  9. The method according to any one of claims 1 to 8, characterised in that the cross-linking temperature of the pasty explosive composition is between 15°C and 80°C.
  10. The method according to claim 9, characterised in that the cross-linking temperature of the pasty explosive composition is ambient temperature.
  11. The method according to claim 9 or 10, characterised in that the cross-linking temperature of the pasty explosive composition is identical or close to that at which the component A' and the component B' are mixed.
EP06124572.6A 2005-11-24 2006-11-22 Semicontiunuous process for making an explosive composite charge having a polyurethane matrix by using two components Active EP1790626B1 (en)

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IL191313A (en) 2013-05-30
AU2006319000A1 (en) 2007-05-31
US7887651B1 (en) 2011-02-15
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