EP1333015B1 - 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
EP1333015B1
EP1333015B1 EP03290123A EP03290123A EP1333015B1 EP 1333015 B1 EP1333015 B1 EP 1333015B1 EP 03290123 A EP03290123 A EP 03290123A EP 03290123 A EP03290123 A EP 03290123A EP 1333015 B1 EP1333015 B1 EP 1333015B1
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European Patent Office
Prior art keywords
component
process according
explosive
components
pasty
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EP03290123A
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German (de)
French (fr)
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EP1333015A3 (en
EP1333015A2 (en
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Jean-Paul Augier
Bernard Mahe
Alain Bonnel
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Eurenco SA
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Eurenco SA
Eurenco France SA
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Priority to SI200331729T priority Critical patent/SI1333015T1/en
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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
    • C06B21/0033—Shaping the mixture
    • C06B21/0058—Shaping the mixture by casting a curable composition, e.g. of the plastisol type
    • 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 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.
  • 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 polymerizable resin, for example a hydroxyl-terminated prepolymer.
  • a paste is obtained that can be poured into a mold and then polymerized by cooking.
  • resin crosslinking agents, catalysts and other additives moldings of various characteristics can be obtained.
  • 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 rate of crosslinking catalyst has as counterpart an increased polymerization time, the temperature being limited, inter alia, by the pyrotechnic nature of certain constituents.
  • this "batch" process proves to be well-adapted for making large objects such as submarine mines, torpedoes and bombs, it proves to be very penalizing and expensive to manufacture a large quantity of small objects molded at a high rate, for example to make several hundred shells diameter of about 50 to 100mm each containing a few hundred grams to a few kilograms of composite explosive from a kneaded 1 to 3 t of dough.
  • JM TAUZIA in a communication entitled “Some comments on Processing Energetic Materials” at Symposium “Compatibility and Processing” organized by the American Defense Prepardness Association (ADPA) on 23-25 October 1989 in Virginia Beach (USA) is) suggests, to solve this problem, a two-component process in which 2 chemically stable polymeric components and having approximately the same filler content and viscosity are first made from the constituents, discontinuously in kneaders.
  • a first disadvantage is that it is very difficult to continuously mix the 2 pasty components to obtain a homogeneous product.
  • a second disadvantage is that the 2 components are pyrotechnically active (presence of explosive charges) and must therefore both 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 main subject of the present invention is an improvement of this two-component process and proposes a two-component semi-continuous process for obtaining a composite explosive charge with a polyurethane matrix, presenting neither the disadvantages of the conventional "batch" method nor the aforementioned drawbacks. of the two-component semi-continuous process described by JM TAUZIA.
  • a composite explosive charge with a polyurethane matrix can be obtained by a simple and inexpensive two-component semi-continuous process, which does not require requalification of the final product, thanks to a very precise combination of technical characteristics relating to the distribution of constituents in the 2 components and to the mass ratio of mixing of the 2 components.
  • the subject of the present invention is a semi-continuous process for obtaining composite explosive charges consisting of a filled polyurethane solid matrix whose charge is solid, pulverulent and comprises at least one organic nitrated explosive, by introduction into molds. of a pasty explosive composition and thermal crosslinking of this composition, said composition being obtained by mixing constituents essentially comprising a polyol prepolymer, a plasticizer, a polyisocyanate monomer and a solid filler pulverulent composition comprising at least one organic nitro explosive.
  • the components A and B do not have the same viscosity, that one is pasty and comprises all of the polyol prepolymer and that the other is liquid and comprises all of the polyisocyanate monomer, such as, without modification chemical, especially without prepolymerization using a polyol.
  • 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 casting operations and can be performed during masked times. These components A and B can be stored if necessary for several weeks before being mixed.
  • the process according to the invention is moreover totally 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 to reduce accordingly the crosslinking time of the pasty explosive composition in the mold and / or to achieve this crosslinking at a lower temperature.
  • the pasty explosive composition is obtained from the usual constituents 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 plasticizer, a polyisocyanate monomer and a pulverulent filler comprising at least one organic nitrated explosive.
  • the sum of the contents by weight of polyol prepolymer, plasticizer, polyisocyanate monomer and pulverulent 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 selected 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 nitrated explosive is selected from the group consisting of hexogen, octogen, pentrite, 5-oxo-3-nitro-1,2,4-triazole (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 content of solid powdery charge is between 75% and 90% by weight relative to the explosive. composite.
  • the pulverulent solid filler consists only of organic nitro explosive.
  • the pulverulent solid filler also comprises at least one other compound than the organic nitro explosive.
  • reducing metal preferably selected from the group consisting of aluminum, zirconium, magnesium, tungsten, boron and mixtures thereof.
  • the reducing metal is aluminum.
  • the reducing metal content may for example be between 0% 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 0% 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. Hydroxyl-terminated polybutadiene is particularly preferably used.
  • the polyisocyanate monomer is 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.
  • TDI toluene diisocyanate
  • IPDI isophorone diisocyanate
  • MDCI dicyclohexylmethylene diisocyanate
  • HMDI hexamethylene diisocyanate
  • BTHI biuret trihexane isocyanate
  • IPDI Intra-PDI 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 and agents. binder-load adhesion.
  • additives selected from the group consisting of crosslinking catalysts (NCO / OH reaction catalysts), wetting agents, antioxidants and agents. binder-load adhesion.
  • tin dibutyldilaurate As a crosslinking catalyst, tin dibutyldilaurate (DBTL) is preferably used, but it is also possible to use any other catalyst well known to those skilled in the art, especially other organic compounds of tin such as a salt.
  • stannous carboxylic acid, a trialkyltin oxide, a dialkyltin dihalide or a dialkyltin oxide examples that may be mentioned are dibutyltin diacetate, diethyltin diacetate, dioctyltin dioxide and stannous octoate.
  • a catalyst a tertiary amine, especially a trialkylamine, or else an organic compound of bismuth, such as triphenylbismuth.
  • a lecithin such as soy lecithin or a siloxane is preferably used.
  • ditertiobutyl paracresol Ionol
  • MBP5 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-propyl succinic anhydride (C 13 H 24 O 6 Si).
  • TEPAN triethylene pentamine acrylonitrile
  • silanols such as triethoxysilyl-3-propyl succinic anhydride (C 13 H 24 O 6 Si).
  • the components may also include a polyurethane polymeric chain extender compound.
  • This compound is generally a low molecular weight polyol monomer of less than about 300, preferably a triol such as trimethylolpropane (TMP) or a diol such as dipropylene glycol.
  • TMP trimethylolpropane
  • diol such as dipropylene glycol.
  • component A comprises all of the plasticizer.
  • component B consists solely of the polyisocyanate monomer.
  • component A When the constituents comprise a chain extender compound, it is imperatively completely included in component A.
  • this additive may be distributed equally between the two components A and B, but, preferably, it is wholly included in component A.
  • the other constituents that the polyol prepolymer, the plasticizer, the polyisocyanate monomer and the pulverulent solid filler are exclusively selected from the group consisting of chain extender compounds, crosslinking catalysts, wetting agents, antioxidants and the binder-filler adhesion agents, the chain extender compounds being completely included in the component A, the crosslinking catalysts, the wetting agents, the antioxidants and the binder-filler adhesion agents being able to be indifferently distributed therein between the 2 components A and B.
  • they are preferably included in component A.
  • the components A and B are independently made by simple mixing, for example in a kneader, and are chemically stable, ie 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 subsequent and independent storage of 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, preferably between 98/2 and 99.2 / 0.8, for example close to 99.
  • This continuous mixing between the component A and the component B is carried out in a static mixer, a mixer well known to those skilled in the art, in the form of a pipe containing braces forcing the product which passes there to separate and then remix.
  • 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 of a convergent located upstream of the static mixer, so that the contents of the convergent flows into the static mixer.
  • the pressure on the mixture of components A and B in the convergent is preferably between 1 MPa and 10 MPa and the two pistons are preferably driven by the same engine.
  • the static mixer according to the invention is preferably composed of a plurality of duct-mounted series elements having a diameter of preferably between 15 mm and 60 mm.
  • mixing elements such as those sold commercially and well known to those skilled in the art, are used.
  • the pasty explosive composition is obtained with a flow rate of between 0.1 l / min and 51 / min, better still between 0.3 l / min and 11 l / min, for example close to 0.5 l / min. min.
  • components A and B are each contained in a pot equipped with a piston allows very precise dosages and a very regular supply, but it is also possible, for example, to supply the static mixer with the aid of metering pumps connected to storage bins of components A and B.
  • the static mixer is usually provided with a double jacket to allow adjustment of the temperature.
  • Each element can be regulated at a different temperature.
  • the last element can for example be regulated at the chosen temperature for the subsequent crosslinking of the explosive paste in the molds, the other elements upstream being regulated at a lower 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 functional groups 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 from the mixer is introduced automatically in a large series of molds, for example several hundred shells envelopes.
  • the crosslinking temperature of the pasty explosive composition introduced into the molds is between 15 ° C. and 80 ° C.
  • the crosslinking temperature is identical to or close to that at which component A and component B are mixed.
  • Example 1 Obtaining a composite explosive charge with a polyurethane matrix filled with hexogen A pasty component
  • Component B consists solely of isophorone diisocyanate (IPDI), ie polyisocyanate monomer.
  • the continuous mixing between the component A and the component B is carried out in a static mixer consisting of 13 elements connected in series of length 32 mm and diameter 32 mm, after transfer of each of the components A and B in a pot equipped with a piston.
  • the pot containing component A has a diameter of 300 mm and a height of 250 mm.
  • the pot containing component B has a diameter of 40 mm and a height of 250 mm.
  • the setting in motion of the 2 pistons allows the supply of components A and B of a convergent located upstream of the static mixer, so that on the one hand the component mass ratio A / component B is constant and equal to 99.14 / 0.86, and on the other hand that the content of the convergent flows into the static mixer.
  • the pressure on the mixture of components A and B in the convergent is 2.5 MPa.
  • the entire installation that is to say in particular the 2 pots containing the components A and B, the convergent and the 13 elements of the static mixer, is thermostated at 60 ° C.
  • the pasty explosive composition is obtained with a flow rate of 0.35 l / min.
  • the pasty explosive composition leaving the static mixer is cast, at room temperature, approximately 20 ° C., into metal molds of square section 80 mm ⁇ 80 mm and height 120 mm, previously arranged in a pour box connected to a valve located at the outlet of the static mixer, the box-valve seal being provided by a rubber.
  • the dynamic viscosity of the pasty explosive composition at the outlet of the static mixer is 5800 poises.
  • This mold loading operation is carried out under a partial vacuum of about 15 mmHg in the casing.
  • the molds After loading, the molds are introduced into an oven at 60 ° C. for 7 days, which makes it possible to crosslink the binder of the explosive composition and finally to obtain a composite explosive feed consisting of 12% by weight of polyurethane matrix and of 88% by weight of hexogen, whose density is 1.62 g / cm 3 .
  • the sensitivity to impact is 25 Joules.
  • the dynamic viscosity of the dough is then 4800 poises.
  • the pasty explosive composition obtained has the same weight composition as that obtained for Example 1.
  • This composition is then poured into molds identical to those used for Example 1, and then cured at 60 ° C. in an oven.
  • the composite explosive obtained after crosslinking at 60 ° C. has a density of 1.62 g / cm 3 , the same value as that of the composite explosive obtained in Example 1.
  • the sensitivity to friction and the impact sensitivity of the resulting composite explosive were also determined using the same methods as those used for Example 1.
  • the sensitivity to impact is 21 Joules.

Abstract

Semi-continuous production of a composite explosive charge (I) consisting of a solid polyurethane matrix filled with powder (II) containing nitrated organic explosive(s), by charging a mold with a paste obtained by mixing a polyol prepolymer (III), plasticizer (IV), polyisocyanate monomer (V) and (II) then thermally crosslinking. Semi-continuous production of a composite explosive charge (I) consisting of a solid polyurethane matrix filled with powder (II) containing nitrated organic explosive(s), by charging a mold with a paste obtained by mixing a polyol prepolymer (III), plasticizer (IV), polyisocyanate monomer (V) and (II) then thermally crosslinking, includes: (i) discontinuously forming the following homogeneous mixtures by simple mixing: (a) a paste comprising the whole of (II) and (III); and (b) a liquid comprising the whole of (V) ((IV) being distributed between (a) and/or (b) as required); and (ii) continuously mixing (a) and (b) at a weight ratio of 95-99.5 : 5-0.5.

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, les 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 hydroxyles. On obtient une pâte qu'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 polymerizable resin, for example a hydroxyl-terminated prepolymer. A paste is obtained that can be poured into a mold and then polymerized by cooking. By selection and adjustment of 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 rate 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 50 à 100mm 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 "batch" process proves to be well-adapted for making large objects such as submarine mines, torpedoes and bombs, it proves to be very penalizing and expensive to manufacture a large quantity of small objects molded at a high rate, for example to make several hundred shells diameter of about 50 to 100mm each containing a few hundred grams to a few kilograms of composite explosive from a kneaded 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 coulée.Those 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 Matérials» au symposium «Compatibility and Processing » organisé par l'American Defense Prepardness Association (ADPA) les 23-25 Octobre 1989 à Virginia Beach (Etats-Un is) suggère, pour résoudre ce problème, un procédé bicomposant dans lequel 2 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, in a communication entitled "Some comments on Processing Energetic Materials" at Symposium "Compatibility and Processing" organized by the American Defense Prepardness Association (ADPA) on 23-25 October 1989 in Virginia Beach (USA) is) suggests, to solve this problem, a two-component process in which 2 chemically stable polymeric components and having approximately the same filler content and viscosity are first made from the constituents, discontinuously in kneaders.

Ces 2 composants pâteux sont ensuite mélangés de façon continue avec un rapport massique proche de 1.These 2 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 2 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 2 composants pâteux pour obtenir un produit homogène.A first disadvantage is that it is very difficult to continuously mix the 2 pasty components to obtain a homogeneous product.

Un second inconvénient est que les 2 composants sont pyrotechniquement actifs (présence de charges explosives) et qu'il doivent donc tous les 2 êtres réalisés puis stockés dans des installations sécurisées.A second disadvantage is that the 2 components are pyrotechnically active (presence of explosive charges) and must therefore both 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 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 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 la nécessité d'une requalification très coûteuse et pénalisante du produit final.This difference in structure of the polyurethane solid matrix causes 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.

La présente invention a principalement pour objet un perfectionnement de ce procédé bicomposant et propose 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.The main subject of the present invention is an improvement of this two-component process and proposes a two-component semi-continuous process for obtaining a composite explosive charge with a polyurethane matrix, presenting neither the disadvantages of the conventional "batch" method nor the aforementioned drawbacks. of the two-component semi-continuous process described by JM TAUZIA.

Il a été découvert, de façon inattendue, qu'on pouvait obtenir un chargement explosif composite à matrice polyuréthanne selon un procédé semi-continu bicomposant, simple et peu onéreux, ne nécessitant pas de requalification du produit final, grâce à une combinaison bien précise de caractéristiques techniques relatives à la répartition des constituants dans les 2 composants et au rapport massique de mélange des 2 composants.Unexpectedly, it has been discovered that a composite explosive charge with a polyurethane matrix can be obtained by a simple and inexpensive two-component semi-continuous process, which does not require requalification of the final product, thanks to a very precise combination of technical characteristics relating to the distribution of constituents in the 2 components and to the mass ratio of mixing of the 2 components.

Plus précisément, la présente invention a pour objet un procédé semi-continu d'obtention de chargements explosifs composites constitués d'une matrice solide polyuréthanne chargée dont la charge est solide, pulvérulente et comprend au moins un explosif nitré organique, par introduction dans des moules 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 plastifiant, un monomère polyisocyanate et une charge solide pulvérulente comprenant au moins un explosif nitré organique.More specifically, the subject of the present invention is a semi-continuous process for obtaining composite explosive charges consisting of a filled polyurethane solid matrix whose charge is solid, pulverulent and comprises at least one organic nitrated explosive, by introduction into molds. of a pasty explosive composition and thermal crosslinking of this composition, said composition being obtained by mixing constituents essentially comprising a polyol prepolymer, a plasticizer, a polyisocyanate monomer and a solid filler pulverulent composition comprising at least one organic nitro explosive.

Ce procédé selon l'invention est caractérisé en ce que, pour obtenir la composition explosive pâteuse :

  • on réalise tout d'abord, à partir de l'ensemble des constituants, 2 composants :
    • un composant A pâteux comprenant la totalité du prépolymère polyol et la totalité de la charge pulvérulente,
    • un composant B liquide comprenant la totalité du monomère polyisocyanate, le plastifiant étant indifféremment réparti entre les 2 composants A et B,
  • on mélange ensuite, de façon continue, dans un mélangeur statique, 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 ;
    en ce que :
  • à la sortie dudit mélangeur statique, le mélange composant A / composant B est introduit dans une série de moules ; et,
    en ce que :
  • la teneur en explosif nitré organique dudit chargement explosif est comprise entre 15 et 90 % en poids et la teneur en charge pulvérulente entre 75 et 90 % en poids.
This method according to the invention is characterized in that, to obtain the pasty explosive composition:
  • firstly, from the set of constituents, two components are produced:
    • a pasty component A comprising all of the polyol prepolymer and all of the powdery filler,
    • a liquid component B comprising all of 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 a static mixer so that the component A / component B mass ratio is constant and between 95/5 and 99.5 / 0.5;
    in that :
  • at the outlet of said static mixer, the component A / component B mixture is introduced into a series of molds; and,
    in that :
  • the organic nitrate explosive content of said explosive charge is between 15 and 90% by weight and the filler content between 75 and 90% by weight.

Il faut bien noter, selon l'invention, outre le rapport massique composant A /composant B bien particulier, 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.It should be noted, according to the invention, besides the very particular component A / component B mass ratio, the fact that the components A and B do not have the same viscosity, that one is pasty and comprises all of the polyol prepolymer and that the other is liquid and comprises all of the polyisocyanate monomer, such as, without modification chemical, especially without prepolymerization using a polyol.

Cette combinaison de caractéristiques techniques distinctives comparativement au procédé semi-continu bicomposant de l'état de la technique 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 of the state of the art has the technical effect of eliminating all the aforementioned drawbacks, and 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 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 casting operations 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 l'invention 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 the invention is moreover totally 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 to reduce accordingly the crosslinking time of the pasty explosive composition in the mold and / or to achieve this crosslinking at a lower temperature.

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

Selon la présente invention, la composition explosive pâteuse est obtenue à partir des constituants usuels utilisés selon les procédés antérieurs et qui sont bien connus de l'homme du métier.According to the present invention, the pasty explosive composition is obtained from the usual constituents 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 plastifiant, un monomère polyisocyanate et une charge pulvérulente comprenant au moins un explosif nitré organique.These constituents essentially comprise a polyol prepolymer, a plasticizer, a polyisocyanate monomer and a pulverulent filler comprising at least one organic nitrated explosive.

Par «essentiellement », il faut comprendre que les constituant 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 above-mentioned constituents are still present and generally represent more than 90% by weight per relative to the total weight of the pasty explosive composition.

De façon préférée, la somme des teneurs pondérales en prépolymère polyol, plastifiant, monomère polyisocyanate et charge pulvérulente représente entre 98% et 100% de l'ensemble des constituants.Preferably, the sum of the contents by weight of polyol prepolymer, plasticizer, polyisocyanate monomer and pulverulent 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 selected 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, le 5-oxo 3-nitro 1,2,4-triazole (ONTA), le triaminotrinitrobenzène, la nitroguanidine et leur mélanges, c'est-à-dire tous les mélanges d'au moins deux des composés précités.Preferably, the organic nitrated explosive is selected from the group consisting of hexogen, octogen, pentrite, 5-oxo-3-nitro-1,2,4-triazole (ONTA), triaminotrinitrobenzene, nitroguanidine and mixtures thereof, i.e., all mixtures of at least two of the above compounds.

De façon particulière préférée, l'explosif nitré organique est choisi dans le groupe constitué par l'hexogène, l'octogène, l'ONTA et leurs mélanges.In a particularly preferred manner, the organic nitrated explosive is selected from the group consisting of hexogen, octogen, ONTA and mixtures thereof.

Selon une caractéristique, 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 one characteristic, the content of organic nitro explosive is between 15% and 90% by weight relative to the composite explosive and the content of solid powdery charge is between 75% and 90% by weight relative to the explosive. composite.

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

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

Elle peut par exemple comprendre un métal réducteur, de préférence choisi dans le groupe constitué par l'aluminium, le zirconium, le magnésium, le tungstène, le bore et leurs mélanges. De façon particulièrement préférée, le métal réducteur est l'aluminium.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 is aluminum.

La teneur en métal réducteur peut par exemple être comprise entre 0% et 35% en poids par rapport à l'explosif composite.The reducing metal content may for example be between 0% 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 préférée, le perchlorate de potassium, le nitrate d'ammonium, le nitrate de sodium et leurs mélanges.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.

La teneur en oxydant minéral peut par exemple être comprise entre 0% et 45% en poids rapport à l'explosif composite.The mineral oxidant content may for example be between 0% 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.

Selon la présente invention, 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 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 hydroxyles.According to the present invention, 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. Hydroxyl-terminated polybutadiene is particularly preferably used.

Le monomère polyisocyanate est 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.The polyisocyanate monomer is 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.

De façon particulièrement préférée, on utilise l'IPDI ou le MDCI.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 azelates et les acétates. Parmi les polyesters, la triacétine, les phtalates d'alkyle tel que le phtalate de dioctyle (DOP), les azélates d'alkyle tel que l'azélate de dioctyle (DOZ) et les adipates d'alkyle tel 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 et les agents d'adhésion liant-charge.In addition to the abovementioned essential constituents, 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 and agents. binder-load adhesion.

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 tel 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.As a crosslinking catalyst, tin dibutyldilaurate (DBTL) is preferably used, but it is also possible to use any other catalyst well known to those skilled in the art, especially other organic compounds of tin such as a salt. stannous carboxylic acid, a trialkyltin oxide, a dialkyltin dihalide or a dialkyltin oxide. Examples that may be mentioned are dibutyltin diacetate, diethyltin diacetate, dioctyltin dioxide and stannous octoate.

On peut aussi utiliser comme catalyseur une amine tertiaire, notamment une trialkylamine, ou bien encore un composé organique du bismuth, tel que le triphénylbismuth.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 (Ionol) ou le 2,2'-méthylène bis 4-méthyl 6-tertiobutylphénol (MBP5).As an antioxidant, ditertiobutyl paracresol (Ionol) or 2,2'-methylenebis-4-methyl-6-tert-butylphenol (MBP5) 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-propyl succinique (C13H24O6Si).Binder-filler adhesion agent is preferably used triethylene pentamine acrylonitrile (TEPAN), or certain compounds derived from silanols such as triethoxysilyl-3-propyl succinic anhydride (C 13 H 24 O 6 Si).

Les constituants peuvent également comprendre un composé extenseur de chaîne polymérique polyuréthanne.The components may also include a polyurethane polymeric chain extender compound.

Ce composé est 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.This compound is generally a low molecular weight polyol monomer of less than about 300, preferably a triol such as trimethylolpropane (TMP) or a diol such as dipropylene glycol.

Selon la présente invention, on réalise tout d'abord, à partir de l'ensemble des constituants, 2 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 2 composants A et B.
According to the present invention, firstly, from the set of constituents, 2 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 2 components A and B.

De façon préférée, le composant A comprend la totalité du plastifiant.Preferably, component A comprises all of the plasticizer.

De façon particulièrement préférée, le composant B est uniquement constitué du monomère polyisocyanate.Particularly preferably, component B consists solely of the polyisocyanate monomer.

Lorsque les constituants comprennent un composé extenseur de chaîne, celui-ci est impérativement en totalité compris dans le composant A.When the constituents comprise a chain extender compound, it is imperatively completely included in component A.

Lorsque les constituants comprennent au moins un additif choisi dans le groupe constitué par les catalyseurs de réticulation, les agents mouillants, les agents antioxydants et les agents d'adhésion liant-charge, cet additif peut être indifféremment réparti entre les 2 composants A et B, mais, de préférence, il est en totalité compris dans le composant A.When the constituents comprise at least one additive chosen from the group consisting of crosslinking catalysts, wetting agents, antioxidants and binder-filler adhesion agents, this additive may be distributed equally between the two components A and B, but, preferably, it is wholly included in component A.

Selon une variante préférée, les autres constituants que le prépolymère polyol, le plastifiant, le monomère polyisocyanate et la charge solide pulvérulente sont exclusivement choisis dans le groupe constitué par les composés extenseurs de chaîne, les catalyseurs de réticulation, les agents mouillants, les agents antioxydants et les agents d'adhésion liant-charge, les composés extenseurs de chaîne étant en totalité compris dans le composant A, les catalyseurs de réticulation, les agents mouillants, les agents antioxydants et les agents d'adhésion liant-charge pouvant eux être indifféremment répartis entre les 2 composants A et B. Ils sont toutefois de préférence compris dans le composant A.According to a preferred variant, the other constituents that the polyol prepolymer, the plasticizer, the polyisocyanate monomer and the pulverulent solid filler are exclusively selected from the group consisting of chain extender compounds, crosslinking catalysts, wetting agents, antioxidants and the binder-filler adhesion agents, the chain extender compounds being completely included in the component A, the crosslinking catalysts, the wetting agents, the antioxidants and the binder-filler adhesion agents being able to be indifferently distributed therein between the 2 components A and B. However, they are preferably included in component A.

Les composants A et B sont indépendamment réalisés par simple mélange, 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 indépendant des composants A et B.The components A and B are independently made by simple mixing, for example in a kneader, and are chemically stable, ie 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 subsequent and independent storage of 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 et compris entre 95/5 et 99,5/0,5, de préférence compris entre 98/2 et 99,2/0,8, par exemple voisin de 99.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 component A / component B mass ratio is constant and between 95/5 and 99, 5 / 0.5, preferably between 98/2 and 99.2 / 0.8, for example close to 99.

Ce mélange continu entre le composant A et le composant B est 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 carried out in a static mixer, a mixer well known to those skilled in the art, in the form of a pipe containing braces forcing the product which passes there to separate and then remix.

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 du mélangeur statique, de sorte que le contenu du convergent se déverse dans le 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 of a convergent located upstream of the static mixer, so that the contents of the convergent flows into the static mixer.

La pression sur le mélange des composants A et B dans le convergent est de préférence comprise entre 1MPa et 10MPa et les 2 pistons sont de préférence mûs 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 and the two 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.Considering the high component A / compound B mass ratio, it is interesting to note that such equipment offers the possibility of linking several pots of component A for the same pot of component B, without breaking the continuous process.

Le mélangeur statique, selon l'invention, 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.The static mixer according to the invention is preferably composed of a plurality of duct-mounted series elements having a diameter of preferably between 15 mm and 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.For example, between 6 and 15 mixing elements, such as those sold commercially and well known to those skilled in the art, are used.

Selon une autre variante préférée, on obtient la composition explosive pâteuse avec un débit volumique compris entre 0,1l/min et 51/min, mieux encore compris entre 0,3l/min et 1l/min, par exemple voisin de 0,5l/min.According to another preferred variant, the pasty explosive composition is obtained with a flow rate of between 0.1 l / min and 51 / min, better still between 0.3 l / min and 11 l / min, for example close to 0.5 l / min. min.

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 components A and B are each contained in a pot equipped with a piston allows very precise dosages and a very regular supply, but it is also possible, for example, to supply the static mixer with the aid of metering pumps connected to 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.

Chaque élément peut être régulé à une température différente. Le dernier élément peut par exemple être régulé à la température choisie pour la réticulation ultérieure de la pâte explosive dans les moules, les autres éléments situés en amont étant régulés à une température inférieure.Each element can be regulated at a different temperature. The last element can for example be regulated at the chosen temperature for the subsequent crosslinking of the explosive paste in the molds, the other elements upstream being regulated at a lower 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.

Selon la présente invention, 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.According to the present invention, 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 uréthannes du fait de la réaction des fonctions hydroxyles du prépolymère polyol et éventuellement du composé extenseur de chaîne avec les fonctions isocyanates 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 functional groups 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, 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, the pasty explosive composition from the mixer is introduced automatically in a large series of molds, for example several hundred 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 est particulièrement avantageux.In particular, it is possible to operate at ambient temperature (approximately 20 ° C.), which is particularly advantageous.

Selon une autre 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 another preferred variant, the crosslinking temperature is identical to or close to that at which component A and component B are mixed.

L'exemple non limitatif suivant illustre l'invention.The following nonlimiting example illustrates the invention.

Exemple 1 : Example 1 Obtention d'un chargement explosif composite à matrice polyuréthanne chargée en hexogène Composant A pâteux Obtaining a composite explosive charge with a polyurethane matrix filled with hexogen A pasty component

Dans un malaxeur vertical en acier inoxydable de capacité 35 litres, on réalise un composant A pâteux, par mélange, à 60°C durant 4 h, des constituants suivants, dans les proportions relatives mentionnées :

  • 7,49 parties en poids du polybutadiène à terminaisons hydroxyles de masse moléculaire moyenne en nombre environ 2500 et de fonctionnalité environ 2,2 en fonctions hydroxyles commercialisé par la Société Atochem sous la dénomination R45HT (prépolymère polyol).
  • 0,08 partie en poids de triméthylolpropane (composé extenseur de chaîne).
  • 3,37 parties en poids d'adipate de dioctyle (plastifiant)
  • 0,12 partie en poids de MBP5 (agent antioxydant)
  • 0,12 partie en poids de lécithine de soja (agent mouillant)
  • 0,06 partie en poids de TEPAN (agent d'adhésion liant-charge)
  • 0,0001 partie en poids de dibutyldilaurate d'étain (catalyseur de réticulation)
  • 88,76 parties en poids d'hexogène pulvérulent (charge en explosif nitré organique).
In a stainless steel vertical mixer with a capacity of 35 liters, a pasty component A is produced by mixing, at 60 ° C. for 4 hours, the following constituents, in the relative proportions mentioned:
  • 7.49 parts by weight of the hydroxyl-terminated polybutadiene of number average molecular weight about 2500 and of functionality about 2.2 in hydroxyl functions marketed by the company Atochem under the name R45HT (polyol prepolymer).
  • 0.08 parts by weight of trimethylolpropane (chain extender compound).
  • 3.37 parts by weight of dioctyl adipate (plasticizer)
  • 0.12 parts by weight of MBP5 (antioxidant)
  • 0.12 parts by weight of soy lecithin (wetting agent)
  • 0.06 parts by weight of TEPAN (binder-filler adhesion agent)
  • 0.0001 parts by weight of tin dibutyldilaurate (crosslinking catalyst)
  • 88.76 parts by weight of powdered hexogen (charge in organic nitro explosive).

Composant B liquideLiquid component B

Le composant B est uniquement constitué d'isophorone diisocyanate (IPDI), c'est à dire du monomère polyisocyanate.Component B consists solely of isophorone diisocyanate (IPDI), ie polyisocyanate monomer.

Obtention d'une composition explosive pâteuse, par mélange, de façon continue, des composants A et BObtaining a pasty explosive composition, by mixing, in a continuous manner, components A and B

Le mélange continu entre le composant A et le composant B est réalisé dans un mélangeur statique constitué de 13 éléments montés en série de longueur 32 mm et de diamètre 32 mm, après transfert de chacun des composants A et B dans un pot équipé d'un piston. Le pot contenant le composant A a un diamètre de 300 mm et une hauteur de 250 mm. Le pot contenant le composant B a un diamètre de 40 mm et une hauteur de 250 mm.The continuous mixing between the component A and the component B is carried out in a static mixer consisting of 13 elements connected in series of length 32 mm and diameter 32 mm, after transfer of each of the components A and B in a pot equipped with a piston. The pot containing component A has a diameter of 300 mm and a height of 250 mm. The pot containing component B has a diameter of 40 mm and a height of 250 mm.

La mise en mouvement des 2 pistons, à l'aide d'un même moteur, permet l'alimentation en composants A et B d'un convergeant situé en amont du mélangeur statique, de sorte que d'une part le rapport massique composant
A / composant B soit constant et égal 99,14/0,86, et d'autre part que le contenu du convergent se déverse dans le mélangeur statique.The setting in motion of the 2 pistons, using the same engine, allows the supply of components A and B of a convergent located upstream of the static mixer, so that on the one hand the component mass ratio
A / component B is constant and equal to 99.14 / 0.86, and on the other hand that the content of the convergent flows into the static mixer.

La pression sur le mélange des composants A et B dans le convergent est de 2,5 MPa.The pressure on the mixture of components A and B in the convergent is 2.5 MPa.

L'ensemble de l'installation, c'est-à-dire notamment les 2 pots contenant les composants A et B, le convergent et les 13 éléments du mélangeur statique, est thermostaté à 60°C.The entire installation, that is to say in particular the 2 pots containing the components A and B, the convergent and the 13 elements of the static mixer, is thermostated at 60 ° C.

A la sortie du mélangeur statique, on obtient la composition explosive pâteuse avec un débit de 0,35 1/min.At the outlet of the static mixer, the pasty explosive composition is obtained with a flow rate of 0.35 l / min.

Cette composition explosive pâteuse a la composition pondérale suivante :

  • prépolymère polyol : 7,42%
  • extenseur de chaîne : 0,07%
  • monomère polyisocyanate : 0,86%
  • plastifiant : 3,35%
  • agent antioxydant : 0,12%
  • agent mouillant : 0,12%
  • agent d'adhésion liant-charge : 0,06%
  • catalyseur de réticulation : 0,0001%
  • hexogène : 88,00%
This explosive pasty composition has the following composition by weight:
  • polyol prepolymer: 7.42%
  • chain extender: 0.07%
  • Polyisocyanate monomer: 0.86%
  • plasticizer: 3.35%
  • antioxidant agent: 0.12%
  • wetting agent: 0.12%
  • binder-filler adhesion agent: 0.06%
  • crosslinking catalyst: 0.0001%
  • hexogen: 88.00%

Obtention du chargement explosif composite par coulée dans un moule puis réticulation de la composition explosive.Obtaining the composite explosive charge by casting in a mold and then crosslinking the explosive composition.

La composition explosive pâteuse sortant du mélangeur statique est coulée, à la température ambiante, 20°C environ, dans des moules métalliques de section carrée 80mm x 80 mm et de hauteur 120 mm, préalablement disposés dans un caisson de coulée relié à une vanne située à la sortie du mélangeur statique, l'étanchéité caisson-vanne étant assurée par un caoutchouc.The pasty explosive composition leaving the static mixer is cast, at room temperature, approximately 20 ° C., into metal molds of square section 80 mm × 80 mm and height 120 mm, previously arranged in a pour box connected to a valve located at the outlet of the static mixer, the box-valve seal being provided by a rubber.

La viscosité dynamique de la composition explosive pâteuse à la sortie du mélangeur statique est de 5800 poises.The dynamic viscosity of the pasty explosive composition at the outlet of the static mixer is 5800 poises.

Cette opération de chargement des moules est effectuée sous vide partiel de 15 mm Hg environ dans le caisson de coulée.This mold loading operation is carried out under a partial vacuum of about 15 mmHg in the casing.

Après chargement, les moules sont introduits dans un four à 60°C pendant 7 jours, ce qui permet de réticuler le liant de la composition explosive et d'obtenir finalement un chargement en explosif composite constitué de 12% en poids de matrice polyuréthanne et de 88% en poids d'hexogène, dont la masse volumique est 1,62 g/cm3.After loading, the molds are introduced into an oven at 60 ° C. for 7 days, which makes it possible to crosslink the binder of the explosive composition and finally to obtain a composite explosive feed consisting of 12% by weight of polyurethane matrix and of 88% by weight of hexogen, whose density is 1.62 g / cm 3 .

Lors de la réticulation à 60°C de la composition dans les moules, on a suivi l'évolution en fonction du temps de la viscosité dynamique de cette composition :

  • Après 2h : 6900 poises
  • Après 4h : 7900 poises
  • Après 6h : 9100 poises.
During crosslinking at 60 ° C. of the composition in the molds, the evolution as a function of time of the dynamic viscosity of this composition was followed:
  • After 2h: 6900 poises
  • After 4h: 7900 poises
  • After 6h: 9100 poises.

Les propriétés mécaniques en traction de l'explosif composite obtenu ont été déterminées à l'aide d'une machine de traction classique, à 20°C, avec une vitesse de traction de 50 mm/min, à partir d'éprouvettes monodimentionnelles normalisées, selon une méthode bien connue de l'homme du métier (moyenne de 6 mesures) :

  • Contrainte maximale (Sm) : 0,8 MPa
  • Module d'élasticité (E) : 15 MPa
  • Allongement à la contrainte maximale (em) : 9%
  • Contrainte à la rupture (Sr) : 0,8 MPa
  • Allongement à la rupture (er) : 10%
The tensile mechanical properties of the composite explosive obtained were determined using a conventional tensile machine at 20 ° C with a tensile speed of 50 mm / min, from standardized single-sample test pieces, according to a method that is well known to those skilled in the art (average of 6 measurements):
  • Maximum stress (Sm): 0.8 MPa
  • Modulus of elasticity (E): 15 MPa
  • Elongation at maximum stress (e m ): 9%
  • Breaking stress (Sr): 0.8 MPa
  • Elongation at break (e r ): 10%

Ces propriétés mécaniques sont satisfaisantes pour ce type de chargement.These mechanical properties are satisfactory for this type of loading.

On a par ailleurs déterminé, selon les méthodes et les appareillages Julius Peters bien connus de l'homme du métier, la sensibilité au frottement et la sensibilité à l'impact de l'explosif composite obtenu.According to Julius Peters methods and apparatus well known to those skilled in the art, the sensitivity to friction and the impact sensitivity of the composite explosive obtained have been determined.

La sensibilité à l'impact est de 25 Joules.The sensitivity to impact is 25 Joules.

Pour la sensibilité au frottement, on constate 20 essais positifs sur 30 à 353 N, limite maximale de l'appareillage.For the sensitivity to friction, there are 20 positive tests on 30 to 353 N, maximum limit of the apparatus.

Exemple comparatifComparative example

Cet exemple comparatif ne fait pas partie de l'invention. Il a été réalisé dans le seul but de montrer que les propriétés physico-chimiques et mécaniques de l'explosif composite obtenu selon le procédé semi-continu bicomposant objet de l'invention sont identiques à celles de l'explosif composite obtenu à partir des mêmes constituants, dans les mêmes proportions, selon le procédé « batch » classique jusqu'alors utilisé par l'homme du métier.This comparative example does not form part of the invention. It was realized for the sole purpose of showing that the physicochemical and mechanical properties of the composite explosive obtained according to the two-component semi-continuous process of the invention are identical to those of the composite explosive obtained from the same constituents, in the same proportions, according to the conventional "batch" method hitherto used by those skilled in the art.

Selon cet exemple comparatif, on introduit, dans un malaxeur vertical de 135 litres :

  • 7,42 parties en poids du prépolymère polyol utilisé pour l'exemple 1
  • 0,07 partie en poids de triméthylolpropane
  • 3,35 parties en poids d'adipate de dioctyle
  • 0,12 partie en poids de MBP5
  • 0,12 partie en poids de lécithine de soja
  • 0,06 partie en poids de TEPAN
  • 0,0001 partie en poids de dibutyldilaurate d'étain
  • 88,00 parties en poids d'hexogène pulvérulent.
According to this comparative example, a vertical mixer of 135 liters is introduced:
  • 7.42 parts by weight of the polyol prepolymer used for Example 1
  • 0.07 parts by weight of trimethylolpropane
  • 3.35 parts by weight of dioctyl adipate
  • 0.12 parts by weight of MBP5
  • 0.12 parts by weight of soy lecithin
  • 0.06 parts by weight of TEPAN
  • 0.0001 parts by weight of tin dibutyldilaurate
  • 88.00 parts by weight of powdery hexogen.

Tous ces constituants sont identiques à ceux utilisés pour l'exemple 1 (même provenance et mêmes caractéristiques).All these constituents are identical to those used for Example 1 (same source and same characteristics).

Après mélange durant 4 h à 60°C, on réalise dans le malaxeur un vide partiel d'environ 15 mm Hg, puis on poursuit l'agitation de nouveau durant 4 h à 60°C.After mixing for 4 hours at 60 ° C., a partial vacuum of about 15 mmHg is produced in the kneader, followed by stirring again for 4 hours at 60.degree.

La viscosité dynamique de la pâte est alors de 4800 poises.The dynamic viscosity of the dough is then 4800 poises.

On ajoute alors 0,86 partie en poids d'IPDI (même provenance et mêmes caractéristiques que celui utilisé pour l'exemple 1), puis on agite 30 min à 60°C, sous vide partiel de 15 mm Hg environ.0.86 part by weight of IPDI (same source and same characteristics as that used for Example 1) are then added, followed by stirring for 30 min at 60 ° C. under a partial vacuum of approximately 15 mmHg.

La composition explosive pâteuse obtenue a la même composition pondérale que celle obtenue pour l'exemple 1.The pasty explosive composition obtained has the same weight composition as that obtained for Example 1.

Cette composition est ensuite coulée dans des moules identiques à ceux utilisés pour l'exemple 1, puis réticulée 7 j à 60°C dans un four.This composition is then poured into molds identical to those used for Example 1, and then cured at 60 ° C. in an oven.

Lors de la réticulation à 60°C de la composition, on a suivi l'évolution en fonction du temps de la viscosité, le point de départ du temps étant le moment de l'introduction de l'IPDI dans le malaxeur :

  • Après 2h : 7300 poises
  • Après 4h : 9900 poises
  • Après 6h : 12500 poises.
During the crosslinking at 60 ° C. of the composition, the evolution as a function of time of the viscosity was followed, the starting point of the time being the moment of introduction of the IPDI in the kneader:
  • After 2h: 7300 poises
  • After 4h: 9900 poises
  • After 6h: 12500 poises.

On constate que l'évolution de la viscosité de la composition pâteuse n'est pas significativement différente de celle mesurée pour l'exemple 1.It can be seen that the evolution of the viscosity of the pasty composition is not significantly different from that measured for Example 1.

L'explosif composite obtenu après réticulation 7 j à 60°C a une masse volumique de 1,62 g/cm3, soit la même valeur que celle de l'explosif composite obtenu à l'exemple 1.The composite explosive obtained after crosslinking at 60 ° C. has a density of 1.62 g / cm 3 , the same value as that of the composite explosive obtained in Example 1.

Les propriétés mécaniques de l'explosif composite obtenu selon cet exemple comparatif ont été déterminées dans les mêmes conditions que celles décrites pour l'exemple 1 :

  • Contrainte maximale (Sm) : 1,0 MPa
  • Module d'élasticité (E) :18 MPa
  • Allongement à la contrainte maximale (em) : 10%
  • Contrainte à la rupture (Sr) : 1,0 MPa
  • Allongement à la rupture (er) : 11%
The mechanical properties of the composite explosive obtained according to this comparative example were determined under the same conditions as those described for Example 1:
  • Maximum stress (Sm): 1.0 MPa
  • Modulus of elasticity (E): 18 MPa
  • Elongation at the maximum stress (e m ): 10%
  • Breaking stress (Sr): 1.0 MPa
  • Elongation at break (e r ): 11%

Toutes ces valeurs ne sont pas significativement différentes de celles obtenues pour l'explosif composite de l'exemple 1.All these values are not significantly different from those obtained for the composite explosive of Example 1.

On a également déterminé, selon les mêmes méthodes que celles utilisées pour l'exemple 1, la sensibilité au frottement et la sensibilité à l'impact de l'explosif composite obtenu.The sensitivity to friction and the impact sensitivity of the resulting composite explosive were also determined using the same methods as those used for Example 1.

La sensibilité à l'impact est de 21 Joules.The sensitivity to impact is 21 Joules.

Pour la sensibilité au frottement, on constate 16 essais positifs sur 30 à 353 N, limite maximale de l'appareillage.For the sensitivity to friction, there are 16 positive tests on 30 to 353 N, maximum limit of the equipment.

Ces valeurs ne sont pas significativement différentes de celles obtenues pour l'explosif composite de l'exemple 1.These values are not significantly different from those obtained for the composite explosive of Example 1.

Claims (20)

  1. A semi-continuous process for producing composite explosive charges composed of a charged solid polyurethane matrix, the charge of which is pulverulent and comprises at least one nitro-organic explosive, by introduction into moulds of a pasty explosive composition and then thermal crosslinking of this composition; said pasty explosive composition being obtained by fixing constituents essentially comprising a polyol prepolymer, a plasticizer, a polyisocyanate monomer and a pulverulent solid charge comprising at least one nitro-organic explosive, characterized in that:
    to obtain the pasty explosive composition:
    - 2 components:
    . a pasty component A comprising all the polyol prepolymer and all the pulverulent solid charge,
    . a liquid component B comprising all the polyisocyanate monomer, the plasticizer being distributed without distinction between the 2 components A and B,
    are first of all prepared under batchwise condition from all the constituents by simple homogeneous mixing,
    the component A and the component B are subsequently mixed under continuous conditions in a static mixer such that the component A/component B weight ratio is constant and between 95/5 and 99.5/0.5; in that:
    at the cutlet of said static mixer, the component A/component B mixture is introduced in a series of moulds; and in that:
    the content of nitro-organic explosive of said explosive charges is between 15 and 90% by weight and the content of pulverulent solid charge is between 75 and 90% by weight.
  2. The process according to claim 1, characterized in that the sum of the contents by weight of polyol prepolymer, plasticizer, polyisocyanate monomer and pulverulent solid charge represents between 98% and 100% of all the constituents.
  3. The process according to claim 1 or 2,
    characterized in that the constituents also comprise a chain-extending compound and in that this compound is entirely included in the component A.
  4. The process according to any one of claims 1 to 3, characterized in that the constituents also comprise at least one additive chosen from the group consisting of crosslinking catalysts, wetting agents, antioxidants and agents for binder-charge adhesion; thins at least one additive being distributed without distinction between the 2 components A and B.
  5. The process according to claim 4, characterized in that the additive is entirely included in the component A.
  6. The process to any one of claims 1 to 5, characterized in that the other constituents are chosen exclusively from the group consisting of chain-extending compounds, crosslinking catalysts, wetting agents, antioxidants and agents for binder-charge adhesion; the chain-extending compounds being entirely included in the component A, the crosslinking catalysts, the wetting agents, the antioxidants and the agents for binder-charge adhesion being distributed without distinction between the 2 components A and B.
  7. The process according to any one of claims 1 to 6, characterized in that the component B is composed solely of the polyisocyanate monomer.
  8. The process according to any one of claims 1 to 7, characterized in that the component A/component B weight ratio is between 98/2 and 99.2/0.8.
  9. The process according to any one of claims 1 to 8, characterized in that the pasty explosive composition is obtained with a throughout by volume of between 0.1 and 5 l/min.
  10. The process according to any one of claims 1 to 9, characterized in that the components A and B are each present in a vessel equipped with a piston, the moving of which by means of a motor makes it possible to feed, with components A and B, a convergent mixer head situated upstream of the static mixer.
  11. The process according to claim 10,
    characterized in that the pressure on the mixture of the components A and B in the mixer head is between 1 MPa and 10 MPa.
  12. The process according to claim 10 or 11, characterized in that the 2 pistons are driven by the same motor.
  13. The process according to any one of claims 1 to 12, characterized in that the static mixer is composed of several mixing elements mounted in series.
  14. The process according to any one of claims 1 to 13, characterized in that the temperature for crosslinking the pasty explosive composition is between 15°C and 80°C.
  15. The process according to any one of claims 1 to 14, characterized in that the component A and the component B are mixed at a temperature of between 40°C and 80°C.
  16. The process according to claim 15,
    characterized in that the temperature for crosslinking the pasty explosive composition is identical or similar to that at which the component A and the component B are mixed.
  17. The process according to claim 15 or 16,
    characterized in that the temperature for crosslinking the pasty explosive composition is ambient temperature.
  18. The process according to any one of claims 1 to 17, characterized in that the polyol prepolymer has a number-average molecular mass (Mn) of between 500 and 10 000 and is chosen from the group consisting of polyisobutylene polyols, polybutadiene polyols, polyether polyols, polyester polyols and polysiloxane polyols.
  19. The process according to any one of claims 1 to 18, characterized in that the polyisocyanate monomer is Chosen 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 their mixtures.
  20. The process according to any one of claims 1 to 19, characterized in that, at the outlet of said static mixer, the component A/component B mixture is introduced in a large series of moulds in an automatised manner.
EP03290123A 2002-02-01 2003-01-17 Semicontiunuous process for making an explosive composite charge having a polyurethane matrix by using two components Expired - Lifetime EP1333015B1 (en)

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SG105568A1 (en) 2004-08-27
JP3740128B2 (en) 2006-02-01
EP1333015A3 (en) 2005-09-21
IL153983A (en) 2005-09-25
CA2418319C (en) 2008-11-04
NO20030488D0 (en) 2003-01-30
US20050115652A1 (en) 2005-06-02
ES2333948T3 (en) 2010-03-03
BR0300166B1 (en) 2013-10-01
FR2835519B1 (en) 2004-11-19
NO20030488L (en) 2003-08-04
EP1333015A2 (en) 2003-08-06
BR0300166A (en) 2003-09-09
AU2003200305B2 (en) 2008-04-03
SI1333015T1 (en) 2010-02-26
KR100952063B1 (en) 2010-04-13
TW593213B (en) 2004-06-21
TW200302815A (en) 2003-08-16
KR20030066413A (en) 2003-08-09
US6916390B2 (en) 2005-07-12
FR2835519A1 (en) 2003-08-08
PT1333015E (en) 2010-02-02
ZA200300557B (en) 2003-08-22
DK1333015T3 (en) 2010-03-22
NO329572B1 (en) 2010-11-15
IL153983A0 (en) 2003-07-31
JP2004035390A (en) 2004-02-05
DE60329878D1 (en) 2009-12-17
AU2003200305A1 (en) 2003-08-21
ATE447545T1 (en) 2009-11-15
CA2418319A1 (en) 2003-08-01

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