Classifications

• • 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 field military, particularly in the area of explosive ordnance, such as bombs and shells.
• a pyrotechnic composition functionally detonable consisting of a matrix solid polymer, in general polyurethane, charged, said filler being pulverulent and containing a filler explosive nitrate organic, for example hexogen, octogen, ONTA (oxynitrotriazole), or mixture of at least two of these compounds.
• the dough When the mixture is complete, the dough should be used in a rather short period of time (pot life).
• pot life The lengthening of pot life by a reduction in the rate of crosslinking catalyst has as a counterpart a increased polymerization time, the temperature being limited, inter alia, by the pyrotechnic nature of certain constituents.
• J.M. TAUZIA in a communication entitled “Some comments on Processing Energetic Materials” at Symposium “Compatibility and Processing” organized by the American Defense Prepardness Association (ADPA) October 23-25, 1989 in Virginia Beach (United States) suggests, to solve this problem, a method two-component in which 2 polymeric components chemically stable and approximately same charge rate and the same viscosity are all first made from the constituents, so discontinuous in kneaders.
• a first drawback is that it turns out to be very delicate to continuously mix the 2 components pasty to obtain a homogeneous product.
• a second disadvantage is that the 2 components are pyrotechnically active (presence of explosive) and therefore must all 2 beings made and stored in secure facilities.
• a third disadvantage is that the matrix solid polymeric composite explosive eventually obtained is different from what we obtain, with the same constituents in the same proportions, according to the classic "batch” process. Indeed, according to TAUZIA, the isocyanate component is polymeric. The fact of to prepare, intermediately, a prepolymer isocyanate from the starting isocyanate monomer a as a consequence, obtaining a polyurethane matrix solid different from that obtained by the process "Batch” by directly mixing all the monomer isocyanate and all the hydroxyl prepolymer.
• the main object of the present invention is an improvement of this two-component process and proposes a two-component semi-continuous process for obtaining a explosive composite charge with polyurethane matrix, presenting neither the disadvantages of the "batch" process conventional or the aforementioned disadvantages of the method semi-continuous two-component system described by J.M. TAUZIA.
• the present invention object a semi-continuous process of obtaining a composite explosive charge consisting of a matrix solid polyurethane loaded with a solid charge, powdery and comprises at least one nitrated explosive organic, by introducing into a mold a pasty explosive composition then crosslinking of this composition, said composition being obtained by mixing constituents comprising essentially a polyol prepolymer, a plasticizer, a polyisocyanate monomer and a solid filler powder comprising at least one nitrated explosive organic.
• components A and B do not have the same viscosity, that one is pasty and includes the total charge and polyol prepolymer, and that the other is liquid and includes all the monomer polyisocyanate, such as, without chemical modification, especially without prepolymerization using a polyol.
• the physicochemical properties, mechanical, detonation and product vulnerability are identical to those of the product obtained according to the classic "batch" process from the same constituents in the same proportions, which avoids a penalizing requalification of the product.
• Preparation operations for components A and B are totally independent of mixing operations components A and B and casting and can be performed during masked times. These components A and B can be stored if needed for several weeks before being mixed.
• the process according to the invention is moreover totally independent of pot life from the fact that we mix quickly and continuously small amounts of components A and B, which increases the percentage of crosslinking catalyst and decrease accordingly the crosslinking duration of the pasty explosive composition in the mold and / or carry out this crosslinking at a temperature lower.
• composition explosive paste is obtained from the constituents used according to the previous methods and which are well known to those skilled in the art.
• These constituents essentially comprise a polyol prepolymer, a plasticizer, a monomer polyisocyanate and a powdery filler comprising at least less an organic nitro explosive.
• the sum of the contents of weight in polyol prepolymer, plasticizer, monomer polyisocyanate and powdery filler represents between 98% and 100% of all constituents.
• 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 nitro 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, that is all mixtures of at least two of the above compounds.
• the nitrated explosive organic is selected from the group consisting of hexogen, octogen, ONTA and mixtures thereof.
• the explosive content organic nitrate is between 15% and 90% by weight compared to the composite explosive and the powdery solid charge is between 75% and 90% by weight relative to the composite explosive.
• the powdery solid filler consists only of organic nitro explosive.
• the solid charge powder also includes at least one other compound as the organic nitrate explosive.
• a metal reducing agent preferably selected from the group consisting of by aluminum, zirconium, magnesium, tungsten, boron and their mixtures.
• 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 powdery filler may also comprise in combination or not with a reducing metal, a mineral oxidant, preferably selected from the group constituted by ammonium perchlorate, which is particularly preferred, potassium perchlorate, ammonium nitrate, sodium nitrate and their mixtures.
• a mineral oxidant preferably selected from the group constituted by ammonium perchlorate, which is particularly preferred, potassium perchlorate, ammonium nitrate, sodium nitrate and their mixtures.
• the mineral oxidant content may for example be between 0% and 45% by weight compared to the explosive composite.
• the powdery solid charge comprises at least least one compound other than the organic nitro explosive
• this other compound is preferably chosen from group consisting of ammonium perchlorate, aluminum and their mixtures.
• the polyol prepolymer is a more or less viscous liquid.
• His mass number-average molecular weight (Mn) is preferably between 500 and 10,000 and is preferably chosen in the group consisting of polyisobutylenes polyols, polybutadienes polyols, polyethers polyols, polyesters polyols and polysiloxanes polyols. It is particularly preferred to use a polybutadiene with hydroxyl endings.
• the polyisocyanate monomer is a liquid of chosen from the group consisting of the toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), dicyclohexylmethylene diisocyanate (MDCI), hexamethylene diisocyanate (HMDI), trihexane biuret 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 trihexane biuret isocyanate
• IPDI In a particularly preferred manner, IPDI or MDCI.
• the plasticizer is also a liquid, preferably a monoester such as pelargonate isodecyl (IDP) or a polyester selected from the group consisting of phthalates, adipates, azelates and acetates.
• a monoester such as pelargonate isodecyl (IDP)
• a polyester selected from the group consisting of phthalates, adipates, azelates and acetates.
• phthalates preferably dioctyl phthalate (DOP)
• alkyl azelates such as azelate dioctyl (DOZ)
• DOA dioctyl adipate
• all the constituents may also include least one additive selected from the group consisting of crosslinking catalysts (reaction catalysts NCO / OH), wetting agents, antioxidants and binder-filler adhesion agents.
• crosslinking catalysts reaction catalysts NCO / OH
• wetting agents antioxidants
• binder-filler adhesion agents binder-filler adhesion agents
• DBTL dibutyldilaurate tin
• any other well known catalyst of the skilled person including other compounds organic tin such as a stannous salt of an acid carboxylic acid, a trialkyltin oxide, a dihalide of dialkyltin or a dialkyltin oxide.
• organic tin such as a stannous salt of an acid carboxylic acid, a trialkyltin oxide, a dihalide of dialkyltin or a dialkyltin oxide.
• an amine as catalyst tertiary, including trialkylamine, or an organic compound of bismuth, such as Triphenylbismuth.
• the wetting agent preferably a lecithin such as soy lecithin, or a siloxane.
• antioxidant preferably ditertiobutylparacresol (Ionol) or 2,2'-methylene 4-methyl-6-tert-butylphenol (MBP5).
• 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).
• Constituents may also include a extender compound polyurethane polymer chain.
• This compound is generally a polyol monomer of low mass, less than about 300, preferably one triol such as trimethylolpropane (TMP) or a diol such than dipropylene glycol.
• TMP trimethylolpropane
• diol such than dipropylene glycol.
• component A comprises the all the plasticizer.
• component B consists solely of the polyisocyanate monomer.
• component A When the constituents comprise a compound chain expander, this one is imperatively necessary all included in component A.
• constituents include at least one additive selected from the group consisting of crosslinking catalysts, wetting agents, antioxidants and binder-filler adhesion agents
• this additive can be indifferently distributed between the 2 components A and B, but preferably it is completely included in component A.
• the others components that the polyol prepolymer, the plasticizer, the polyisocyanate monomer and the solid charge powder are exclusively selected from the group consisting of the chain extender compounds, the crosslinking catalysts, wetting agents, antioxidants and binder-filler adhesion agents, the chain extensor compounds being in totality included in component A, the catalysts of crosslinking, wetting agents, agents antioxidants and binding-load adhesion agents can they be indifferently distributed between the 2 components A and B. However, they are preferably included in component A.
• Components A and B are independently made, discontinuously, by simple homogeneous mixing, by example in a kneader, and are chemically stable, that is, there is no chemical reaction between the mixed constituents of each component, and that all constituents retain their identity structural, both during mixing and during subsequent and independent storage of components A and B.
• component A and component B of such that the mass ratio component A / component B is constant and between 95/5 and 99.5 / 0.5, preferably between 98/2 and 99.2 / 0.8, for example neighbor of 99.
• component A and component B are for example and preferably made in a static mixer, well-known mixer of the person skilled in the art, in the form of a pipe containing braces forcing the product passing through to to separate then to remix.
• the components A and B are each contained in a pot equipped with a piston whose the 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 convergent content pours into the mixer static.
• the pressure on the mixture of components A and B in the convergent is preferably between 1MPa and 10MPa and the 2 pistons are preferably moved by the same engine.
• the static mixer according to the invention is preferably consisting of several elements mounted in series, shaped like a pipe, having a diameter of preferably between 15mm and 60mm.
• the explosive pasty composition with volume flow between 0.1l / min and 5l / min, better understood between 0.3l / min and 1l / min, for example near 0,5l / min.
• 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 diet, but one can also, by For example, power the static mixer using metering pumps connected to the storage bins of components A and B.
• the static mixer is generally provided with a double envelope to allow adjustment of the temperature.
• Each element can be regulated at a temperature different.
• the last element can for example be regulated at the temperature chosen for the crosslinking subsequent explosive paste in the molds, other upstream elements being regulated at a lower temperature.
• Pots or bins containing components A and B may also be equipped with a heater.
• component A and component B are mixed at a temperature included between 40 ° C and 80 ° C.
• the composition explosive paste obtained after mixing the components A and B is introduced into a mold in which it undergoes then a thermal crosslinking, in a furnace by example.
• This crosslinking results from the formation of bridges urethanes because of the reaction of the functions hydroxyls of the polyol prepolymer and optionally chain extender compound with functions isocyanates of the polyisocyanate monomer.
• the speed of crosslinking increases with temperature and grade as a catalyst.
• 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 hundreds of shells envelopes.
• the crosslinking temperature of the explosive composition pastry introduced into the molds is included between 15 ° C and 80 ° C.
• the temperature crosslinking is identical or similar to that to which component A and component B are mixed.
• Example 1 Obtaining a composite explosive charge with polyurethane matrix loaded with hexogen
• Component B is made up of only isophorone diisocyanate (IPDI), that is to say polyisocyanate monomer.
• IPDI isophorone diisocyanate
• the continuous mixing between component A and component B is made in a static mixer consists of 13 elements mounted in series of length 32mm and diameter 32mm, after transfer of each of components A and B in a pot equipped with a piston.
• the pot containing component A has a diameter of 300mm and a height of 250mm.
• the pot containing component B has a 40mm diameter and a height of 250mm.
• the setting in motion of the 2 pistons allows the supply of components A and B 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 contents of the convergent pours in the static mixer.
• the pressure on the mixture of components A and B in the convergent is 2.5 MPa.
• the whole installation ie including the 2 pots containing components A and B, the convergent and the 13 elements of the static mixer, is thermostated at 60 ° C.
• the pasty explosive composition coming out of static mixer is poured, at the temperature about 20 ° C in metal molds of square section 80mm x 80mm and height 120mm, previously arranged in a casing connected to a valve located at the outlet of the static mixer, the sealing box-valve being ensured by a rubber.
• the dynamic viscosity of the explosive composition pasty at the outlet of the static mixer is 5800 poise.
• This mold loading operation is carried out under partial vacuum of about 15mm Hg 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.
• This comparative example is not part of the invention. It was made for the sole purpose of show that the physico-chemical properties and mechanical properties of the composite explosive obtained according to bicomponent semi-continuous process object of the invention are identical to those of the composite explosive obtained from the same constituents, in the same proportions, according to the classic batch process hitherto used by those skilled in the art.
• the dynamic viscosity of the dough is then 4800 poise.
• the pasty explosive composition obtained has the same weight composition as obtained for the example 1.
• This composition is then poured into molds identical to those used for Example 1, then crosslinked at 60 ° C in an oven.
• the composite explosive obtained after crosslinking 7j 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 impact is 21 Joules.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Dispersion Chemistry (AREA)
• Molecular Biology (AREA)
• Crystallography & Structural Chemistry (AREA)
• Polyurethanes Or Polyureas (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Processes Of Treating Macromolecular Substances (AREA)
• Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

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