EP0210881A1 - Use of 5-oxo-3-nitro-1,2,4-triazole as a secondary explosive and pyrotechnical compositions comprising 5-oxo-3-nitro-1,2,4-triazole - Google Patents

Use of 5-oxo-3-nitro-1,2,4-triazole as a secondary explosive and pyrotechnical compositions comprising 5-oxo-3-nitro-1,2,4-triazole Download PDF

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EP0210881A1
EP0210881A1 EP86401282A EP86401282A EP0210881A1 EP 0210881 A1 EP0210881 A1 EP 0210881A1 EP 86401282 A EP86401282 A EP 86401282A EP 86401282 A EP86401282 A EP 86401282A EP 0210881 A1 EP0210881 A1 EP 0210881A1
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composition according
explosive
binder
triazole
oxo
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EP0210881B1 (en
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Alain Becuwe
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Societe Nationale des Poudres et Explosifs
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B43/00—Compositions characterised by explosive or thermic constituents not provided for in groups C06B25/00 - C06B41/00
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine

Definitions

  • the present invention relates to a new secondary explosive and to new pyrotechnic compositions, in particular new explosive compositions.
  • Secondary explosives and pyrotechnic compositions such as explosive compositions, powders for weapons, propellants are very commonly used both in the armaments industries and in the civil space technical field, mining and quarrying, public works, etc.
  • the secondary explosives satisfying these two conditions used to date are mainly cyclotetramethylene tetranitramine, also called octogen or HMX, cyclotrimethylene trinitramine, also called hexogen or RDX.
  • the sensitivity of explosives depends, among other things, on the commercial variety. With regard to hexogen, the results are given for two of them (B and CH).
  • the sensitivity to impact and the sensitivity to friction are determined using Julius Peters apparatus, according to the method described by HDMALLORY (The development of impact sensitivity tests at the Explosive Research Laboratory, Bruceton, PENNSYLVANIA during the years 1941-1945 US Naval Ordnance Lab. White Oak, MARYLAND, 1956, report 4236).
  • octogen and hexogen have the advantage major to have a density and a detonation speed significantly higher.
  • these compounds have the disadvantage of being very much more sensitive to impact and friction than tolite, hence certain difficulties or constraints of use.
  • a binder either plastic and inert, or active, such as molten tolite, has been incorporated into the compositions.
  • active such as molten tolite
  • TATB and tolite have a low sensitivity to external aggressions (shock, friction, temperature rise) which makes it possible to reduce the vulnerability of the compositions at the cost, however, of a drop in performance.
  • 5-oxo 3-nitro 1,2,4-triazole (commonly called oxynitrotriazole) has interesting properties which make it possible to use it as a secondary explosive in place of octogen or hexogen, while having a sensitivity as low as that of tolite.
  • Oxynitrotriazole has the enormous advantage of having explosive performances close to those of hexogen, given its high density without having the sensitivity of hexogen or octogen (see Table 1).
  • substitution of all or part of the hexogen by oxynitrotriazole makes it possible to reduce the vulnerability of the explosive compositions while maintaining practically the same level of performance.
  • substitution of part of the octogen by oxynitrotriazole makes it possible, while maintaining a satisfactory level of performance, to reduce the vulnerability of the explosive compositions in order to meet a need of users, a need which loading with octogen alone does not not allow to answer.
  • oxynitrotriazole can be used as an oxidizing charge in place of the explosive substances usually used in gun powders such as triple base powders and composite powders as well as in composite propellants.
  • oxynitrotriazole to replace ammonium nitrate in composite gas-generating propellants has several advantages, the most important of which is the fact that oxynitrotriazole is significantly less hygroscopic than ammonium nitrate.
  • the present invention therefore relates to the use of 5-oxo 3-nitro 1,2,4-triazole as a secondary explosive. It also aims to provide new pyrotechnic compositions, and in particular new explosive compositions, characterized in that they contain 5-oxo 3-nitro 1,2,4-triazole. Among these new pyrotechnic compositions one can also mention new powders for weapons and new propellants.
  • Oxynitrotriazole is for example obtained in 2 stages from two common raw materials: semicarbazide hydrochloride and formic acid.
  • the second step consists in nitrating the oxytriazole thus obtained, for example with 98% nitric acid, at ambient temperature, for a few hours.
  • Oxynitrotriazole is isolated from the medium according to a conventional technique well known to those skilled in the art, with an overall yield, for all of the 2 stages, close to 65%.
  • Oxynitrotriazole has a detonation speed close to that of hexogen and the sensitivities on impact and friction are very much lower than those of octogen and hexogen, the sensitivities obtained for oxynitrotriazole being close to those obtained for tolite.
  • Crystallization tests in particular in water with slow stirring (regular, almost spherical crystals with an average diameter of about 100 to 150 ⁇ m) and in water with stirring but with programmed cooling to 0 ° C, have shown the possibility of obtaining crystals large enough to be easily used in formulations.
  • oxynitrotriazole in addition to its use as a secondary explosive in the form of a pure product, oxynitrotriazole can be used in pyrotechnic compositions and in particular explosive compositions.
  • It can also be used as a secondary explosive in mixture with a compound in which it is practically insoluble and allowing loading in the molten state (use with molten tolite for example).
  • Oxynitrotriazole can also be used as a secondary explosive in mixture with waxes or more generally with plastics allowing loading by compression.
  • Oxynitrotriazole can also be used as an oxidizing charge in powders for weapons, in particular triple base powders and composite powders as well as in composite propellants.
  • the new explosive compositions according to the invention are characterized in that they contain 5-oxo 3-nitro 1,2,4-triazole. They are obtained according to conventional methods well known to those skilled in the art by substituting all or part of the secondary explosives usually used by oxynitrotriazole.
  • the explosive compositions are explosive compositions with a plastic binder used by compression.
  • Such compositions are produced according to conventional methods well known to those skilled in the art for obtaining explosive plastic binder compositions used by compression. We can for example cite those described in French patents 1 602 614 and 1 469 198.
  • the basic material consists of granules in which the crystals of explosives are coated with a plastic material. These granules are most often obtained according to a dry coating process, the oxynitrotriazole being soluble in water. They are then compressed under high pressure (of the order of 10 8 Pa), after heating the molding powder in the case of thermoplastic binders, at room temperature in the case of thermosetting binders (for example polyester binders).
  • the explosive compositions according to this first preferred variant of the invention one can distinguish those containing no other secondary explosive than 5-oxo 3-nitro 1,2,4-triazole and those which, on the contrary, contain at least another secondary explosive than 5-oxo 3-nitro 1,2,4-triazole such as for example HMX, RDX, TATB, HNS or PETN.
  • those containing at least one secondary explosive chosen from the group formed by octogen and hexogen are preferred.
  • the plastic binder is chosen from the group consisting of fluorinated binders, polyurethane binders and polyester binders.
  • the other binders usually used in explosive compositions with plastic binder used by compression are also suitable. Mention may for example be made of binders based on butadiene-styrene copolymers.
  • the explosive compositions are explosive compositions with a plastic binder used by casting.
  • Such compositions are produced according to conventional methods well known to those skilled in the art for obtaining explosive compositions used by casting. These include, for example, those described in French patents 2,124,038, 2,225,979 and 2,086,881.
  • the secondary explosive (s) and a liquid polymerizable resin are firstly mixed and then the paste obtained is poured into a mold. The dough is then polymerized.
  • the crosslinking agents catalysts, wetting agents, explosive molded compositions of various characteristics are obtained.
  • the explosive compositions according to this second preferred variant one can distinguish those containing no other secondary explosive than 5-oxo 3-nitro 1,2,4-triazole and those which, on the contrary, contain at least one other explosive secondary than 5-oxo 3-nitro 1,2,4-triazole, preferably chosen from the group formed by octogen and hexogen.
  • the weight content of the binder in the explosive composition being between 12 and 20%.
  • the other binders usually used in explosive compositions with plastic binder used by casting are also suitable. Mention may for example be made of silicone binders and polyester binders, in particular those obtained by reaction of an epoxide with a carboxy-telechelic polybutadiene (PBCT).
  • PBCT carboxy-telechelic polybutadiene
  • the explosive compositions are mixtures based on tolite. These mixtures, used by casting, are produced according to the conventional methods for obtaining mixtures based on tolite currently known as hexolites, pentolites or octolites by replacing all or part of the secondary explosive usually associated with tolite (to namely hexogen, pentrite or octogen) by oxynitrotriazole.
  • mixtures consist of suspensions of grains of oxynitrotriazole in molten tolite. They can, for example, be obtained by direct mixing of oxynitrotriazole in molten tolite.
  • the weight content of oxynitrotriazole in these mixtures is between 50 and 90%.
  • the new gun powders according to the invention are characterized in that they contain 5-oxo 3-nitro 1,2,4-triazole. They are obtained according to conventional processes and well known to those skilled in the art by substituting all or part of the secondary explosives usually used as an oxidizing charge in powders with 5-oxo 3-nitro 1,2,4-triazole.
  • the powders for weapons are triple base powders, the 3 bases of which are nitrocellulose, nitroglycerin and oxynitrotriazole.
  • the nitrocellulose and nitroglycerin contents are those usually present in the triple base powders containing them, such as for example in the nitrocellulose-nitroglycerine-nitroguanidine triple base powders, the oxynitrotriazole contents being close to those usually present in nitroguanidine.
  • triple base powders may contain the additives conventionally used, namely in particular stabilizers (2-nitrodiphenylamine for example), plasticizers, and antiluents.
  • the powders for weapons are composite powders with an inert binder. They are mainly constituted by a synthetic resin and by one or more explosive substances playing the role of oxidizing charge.
  • oxidizing charges which can be associated with oxynitrotriazole in powders for weapons according to this second preferred variant, mention may be made, without limitation, of triaminoguanidine nitrate, ammonium nitrate, alkali nitrates or alkaline earth.
  • the inert binder is preferably a polyurethane binder but it can also for example and without limitation be a polyester binder.
  • polyurethane binders those obtained by reacting a hydroxylated polybutadiene with a diisocyanate are preferred.
  • the level of binder is of the order of 20% by weight.
  • the composite powders according to the invention also generally contain the usual additives known to those skilled in the art, such as in particular plasticizers, anti-oxidant, anti-glow, anti-erosive agents.
  • the powders with an inert binder for weapons according to the invention can be obtained according to the conventional methods for obtaining this type of powder, and in particular by the "global” technique which is very widely used and which has already been previously described for the production. explosive compositions with plastic binder used by casting.
  • the new composite propellants according to the invention are characterized in that they contain 5-oxo 3-nitro 1,2,4-triazole. They are obtained according to conventional methods and well known to those skilled in the art by substituting all or part of the explosive substances usually used as an oxidizing charge in propellants with 5-oxo 3-nitro 1,2,4-triazole. They can be obtained according to the conventional methods for obtaining composite propellants and in particular by the "global” technique called “casting" which is very widely used and which has already been described previously.
  • binder-filler adhesion agents antioxidants, catalysts.
  • the composite propellants according to the invention are gas-generating propellants in which the oxynitrotriazole substitutes all or part of the ammonium nitrate usually used in these compositions.
  • such composite gas-generating propellants consisting of those consisting of a polyurethane binder loaded with oxynitrotriazole.
  • the content by weight of binder is of the order of 20% and that of oxynitrotriazole of the order of 80%.
  • the composite propellants according to the invention contain at least one other secondary explosive than oxynitrotriazole chosen from the group consisting of hexogen and octogen, the binder preferably being a polyurethane binder.
  • the content by weight of binder is for example of the order of 20% and that of the total charges of about 80%.
  • oxytriazole 170 g of oxytriazole are introduced into 750 ml of 98% nitric acid while maintaining the temperature at 5-10 ° C. The addition lasts 2 hours. Then stirred for 3 hours at room temperature. This nitric bath is then slowly poured into 600 ml of ice water and left to stand for a dozen hours. After filtration, spinning and drying, 208 g of oxynitrotriazole are obtained, which is in the form of a white solid identified by its IR, NMR and mass spectra. The overall yield of all 2 stages is 64%.
  • the detonation speed of such an oxynitrotriazole cord is 7,400 m / s.
  • the detonation speed of this cord is 7,770 m / s.
  • This composition consists of 7% by weight of the fluorinated binder sold under the trade name "Kel F 800" by the company 3M and 93 % by weight of fillers.
  • the charges are oxynitrotriazole and octogen in the relative proportions by weight 50/50.
  • the binder is introduced in solution in ethyl acetate in a mixer with the solid fillers. After mixing under reduced pressure, which makes it possible to remove the solvent, the granules thus obtained are dried under vacuum and then compressed at 110 ° C. under a pressure of 1.5 ⁇ 10 8 Pa .
  • the explosive characteristics of this composition are grouped in Table 2, compared with those of 2 known compositions containing 7% by weight of the same binder KelF 800 and 93% by weight of fillers; for one of them, these charges are TATB and octogen in the relative proportions by weight 60/40 respectively and for the other octogen only. It can be seen that the composition with oxynitrotriazole is less sensitive to shock and friction than that with TATB while the detonation speed is higher and that the initiation by detonation wave remains entirely satisfactory.
  • All the elements are mounted inside a plastic tube 5 mm inside diameter.
  • the barrier thickness is then determined by the known Bruceton method, which allows 50% positive priming over 30 tests. Examples 5 to 11 - Other explosive compositions with a plastic binder
  • Example 5 the same composition is made as in Example 4, but the filler consists only of oxynitrotriazole.
  • the binder is a polyurethane binder, sold under the trade name ESTANE by the company GOODRICH.
  • the binder is a polyamide (nylon) binder.
  • the binder is a polyvinyl acetate binder, sold under the trade name RHODO HV2 by the company RHONE-POULENC.
  • compositions of Examples 5 to 11 contain as fillers a mixture of octogen and oxynitrotriazole; they were carried out according to the same method as that of Example 4.
  • Example 5 The explosive characteristics of the composition of Example 5 are grouped in Table 3 compared with those of 2 known compositions, one charged with octogen, the other with TATB.
  • compositions with oxynitrotriazole on the one hand and with TATB on the other hand are very little sensitive to shock, friction and shock wave compared to that of octogen.
  • the weight percentage by binder, the relative weight proportions of the charges and the explosive characteristics of the compositions of Examples 6 to 11 are grouped in Table 4.
  • compositions consist of 19.4% by weight of a polyurethane binder obtained by reaction of the hydroxylated polyester sold under the trade name T1271 by the company ISEL with isophorore diisocyanate (IPDI) and 80.6% by weight of fillers. .
  • the fillers are oxynitrotriazole and octogen in the relative proportions by weight 44/56 respectively for Example 12 and 58/42 respectively for Example 13.
  • successively are introduced, with intermediate kneading under pressure reduced, hydroxylated polyester, fillers and isocyanate.
  • the paste obtained is poured into molds and then polymerized by baking at 40 ° C for 8 days.
  • the explosive characteristics of these compositions are grouped in Table 5, compared with those of 2 known compositions containing 19.4% by weight of the same binder and 80.6% by weight of fillers. For one of them, the charges are TATB and octogen in the relative proportions by weight 44/56 respectively and for the other octogen only.
  • the mechanical properties of the compositions are similar.
  • the detonation speed of the compositions containing on the one hand the TATB and on the other hand the oxynitrotriazole are close to and slightly lower than that of the composition solely charged with octogen.
  • shock wave sensitivity is lowered by the substitution of part of the octogen by TATB or by oxynitrotriazole. Unexpectedly, however, the drop is significantly greater with oxynitrotriazole than with TATB.
  • the initiability (sensitivity to the BRISKA detonator, possibly with plastic relay) is lowered by the substitution of part of the octogen by TATB or by oxynitrotriazole.
  • the solvent couple used is acetone-ethanol in the 50/50 mass ratio and the watering rate is 70% compared to dry nitrocellulose.
  • the triple base monotubular powder obtained does not show any particular sensitivity. It has a sensitivity to friction of 309 N, ignition by an electric spark greater than 726 mJ and ignition by capacitive discharges in a confined environment greater than 15.6 J.
  • the dimensions of the powder after finishing are as follows: length (L): 3.87 mm; External diameter (D): 3.31 mm; Hole diameter (d): 0.56 mm; Powder thickness (Web): 1.38 mm.
  • Firing in a 200 cm 3 gauge bomb at several loading densities (0.12; 0.15; 0.18; 0.20 and 0.23 g / cm 3 ) made it possible to determine the combustion speed curve. It is very regular. There is a speed of 110 mm / s at 100 MPa.
  • the flame temperature is low (3600 K) compared to that of a double base nitrocellulose nitroglycerine 60/40 powder (about 3900 K) while the density is close. It is, however, superior to that of a triple base powder with nitroguanidine (around 3000 K).
  • the theoretical strength (1.15 MJ / kg) is on the other hand greater than that of a triple base powder with nitroguanidine (1.08 MJ / kg) but slightly less than that of a double base (1.19 MJ / kg).
  • the powder produced is in the form of cylindrical grains having 7 channels parallel to the axis of the grains. It is used for large caliber ammunition.
  • composition by weight is as follows:
  • the mixture of the various ingredients of the composition except for the isocyanate, is firstly homogenized in a kneader, at 60 ° C. under reduced pressure. Part of the isocyanate is then added so that the NCO / OH ratio is 0.72. After homogenization, the dough is pre-crosslinked at 60 ° C for 5 days, then it is introduced into an extruder mixer. The remainder of the isocyanate is then added and the paste is extruded through a die having the desired final geometry of the powder.
  • the strands obtained are then heated at 60 ° C for 2 days, then cut into grains.
  • Manometric bombs were used to measure a combustion speed of 40 mm / s at 100 MPa and a force of 0.97 MJ / kg.
  • the flame temperature is 2211 K.
  • the powder containing the oxynitrotriazole according to the invention has a lower flame temperature. (2211 K instead of 2430 K) and a lower concentration of reducing gases such as H 2 and CO.
  • a gas-generating composite propellant consisting of 81% by weight of oxynitrotriazole and 19% by weight of a polyurethane binder was produced.
  • the basic constituents of this binder are hydroxylated polybutadiene R45M and methylenedicyclohexyldiisocyanate.
  • This binder also contains a plasticizer (dioctyl azelate), an antioxidant (ionol) and lecithin.
  • This composite propellant was produced according to the conventional so-called "global” or “casting” method using an NCO / OH ratio of 1.

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Abstract

L'invention concerne l'utilisation du 5-oxo 3-nitro 1,2,4-triazole (oxynitrotriazole) comme explosif secondaire. Elle concerne également de nouvelles compositions pyrotechniques contenant du 5-oxo 3-nitro 1,2,4-triazole et notamment de nouvelles compositions explosives comme par exemple des explosifs comprimés ou des explosifs composites, de nouvelles poudres pour armes comme par exemple des poudres triple base ou des poudres composites à liant inerte, et de nouveaux propergols composites.The invention relates to the use of 5-oxo 3-nitro 1,2,4-triazole (oxynitrotriazole) as a secondary explosive. It also relates to new pyrotechnic compositions containing 5-oxo 3-nitro 1,2,4-triazole and in particular new explosive compositions such as for example compressed explosives or composite explosives, new powders for weapons such as for example triple powders base or inert binder composite powders, and new composite propellants.

Description

La présente invention est relative à un nouvel explosif secondaire et à de nouvelles compositions pyrotechniques, notamment de nouvelles compositions explosives.The present invention relates to a new secondary explosive and to new pyrotechnic compositions, in particular new explosive compositions.

Les explosifs secondaires et les compositions pyrotechniques telles que les compositions explosives, les poudres pour armes, les propergols sont très couramment utilisées aussi bien dans les industries d'armement que dans le domaine civil technique spatiale, exploitation des mines et des carrières, travaux publics, etc.Secondary explosives and pyrotechnic compositions such as explosive compositions, powders for weapons, propellants are very commonly used both in the armaments industries and in the civil space technical field, mining and quarrying, public works, etc.

De très nombreux explosifs secondaires et compositions explosives sont connues. D'après J. QUINCHON, les poudres, propergols et explosifs, tome 1 : les explosifs, Technique et Documentation, 1982, on peut par exemple citer :

  • - comme explosifs secondaires le trinitrotoluène (tolite ou TNT), le trinitrophénol, le trinitrotriaminobenzène (TATB), l'hexanitrostil- bène (HNS), la pentrite, la nitroglycérine, l'hexogène (RDX), l'octogène (HMX), le tétryl, la nitroguanidine (NGu), le dinitroglycol- urile, le tétranitroglycolurile,
  • - comme compositions explosives :
    • " les explosifs industriels comme notamment les dynamites et les explosifs nitratés,
    • * les compositions explosives militaires comme notamment les mélanges explosifs-cires (hexocires, octocires, etc), les mélanges à base de tolite (hexolites, pentolites, etc) et les mélanges à liant plastique parmi lesquels on peut dis tinguer ceux mis en oeuvre par compression (explosifs comprimés) et ceux mis en oeuvre par coulée (explosifs composites).
Many secondary explosives and explosive compositions are known. According to J. QUINCHON, powders, propellants and explosives, volume 1: explosives, Technique et Documentation, 1982, we can for example quote:
  • - as secondary explosives trinitrotoluene (tolite or TNT), trinitrophenol, trinitrotriaminobenzene (TATB), hexanitrostilbene (HNS), pentrite, nitroglycerin, hexogen (RDX), octogen (HMX), tetryl, nitroguanidine (NGu), dinitroglycol-urile, tetranitroglycolurile,
  • - as explosive compositions:
    • "industrial explosives such as dynamites and nitrate explosives in particular,
    • * military explosive compositions such as, in particular, explosive-wax mixtures (hexocires, octocires, etc.), mixtures based on tolite (hexolites, pentolites, etc.) and mixtures with a plastic binder among which we can distinguish those used by compression (compressed explosives) and those used by casting (composite explosives).

Il est également connu d'utiliser les explosifs secondaires, par exemple HMX, RDX, NGu, comme charge oxydante dans les poudres pour armes ou dans les propergols.It is also known to use secondary explosives, for example HMX, RDX, NGu, as an oxidizing charge in powders for weapons or in propellants.

On peut citer notamment, de façon non limitative :

  • - les poudres triple base pour armes nitrocellulose-nitroglycérine, nitroguanidine ou hexogène,
  • - les poudres composites à liant inerte pour armes qui comprennent essentiellement un liant organique (polyuréthanne par exemple) et un explosif secondaire jouant le rôle de charge oxydante (hexogène par exemple),
  • - les propergols composites chargés par exemple à l'octogène ou au nitrate d'ammonium (cas des propergols générateurs de gaz).
We can cite in particular, without limitation:
  • - triple base powders for nitrocellulose-nitroglycerin, nitroguanidine or hexogen weapons,
  • - composite powders with an inert binder for weapons which essentially comprise an organic binder (polyurethane for example) and a secondary explosive acting as an oxidizing charge (hexogen for example),
  • - composite propellants loaded for example with octogen or ammonium nitrate (case of propellants generating gas).

Il est bien connu dans la technologie des explosifs que, pour certaines applications, il est nécessaire d'utiliser des explosifs secondaires ayant à la fois une masse volumique et une vitesse de détonation élevées.It is well known in explosives technology that, for certain applications, it is necessary to use secondary explosives having both a high density and a high detonation rate.

Les explosifs secondaires satisfaisant à ces deux conditions utilisés à ce jour sont principalement la cyclotétraméthylène tétranitramine, aussi appelée octogène ou HMX, la cyclotriméthylène trinitramine, aussi appelée hexogène ou RDX.The secondary explosives satisfying these two conditions used to date are mainly cyclotetramethylene tetranitramine, also called octogen or HMX, cyclotrimethylene trinitramine, also called hexogen or RDX.

Les caractéristiques explosives de ces produits sont connues ; les principales sont regroupées dans le tableau 1, comparativement à celles de la tolite.

Figure imgb0001
The explosive characteristics of these products are known; the main ones are grouped in table 1, compared with those for tolite.
Figure imgb0001

La vitesse de détonation variant avec la masse volumique, les résultats sont accompagnés de la masse volumique correspondante.As the detonation rate varies with the density, the results are accompanied by the corresponding density.

La sensibilité des explosifs dépend entre autres de la variété commerciale. En ce qui concerne l'hexogène, les résultats sont donnés pour deux d'entre elles (B et CH).The sensitivity of explosives depends, among other things, on the commercial variety. With regard to hexogen, the results are given for two of them (B and CH).

La sensibilité à l'impact et la sensibilité à la friction sont déterminées à l'aide de l'appareillage Julius Peters, selon la méthode décrite par H.D.MALLORY (The development of impact sensitivity tests at the Explosive Research Laboratory, Bruceton, PENNSYLVANIA during the years 1941-1945 US Naval Ordnance Lab. White Oak, MARYLAND, 1956, report 4236).The sensitivity to impact and the sensitivity to friction are determined using Julius Peters apparatus, according to the method described by HDMALLORY (The development of impact sensitivity tests at the Explosive Research Laboratory, Bruceton, PENNSYLVANIA during the years 1941-1945 US Naval Ordnance Lab. White Oak, MARYLAND, 1956, report 4236).

Lorsque l'énergie maximale de l'appareil d'essai est atteinte, on indique le pourcentage de détonations des essais à cette énergie.When the maximum energy of the test apparatus is reached, the percentage of detonations of the tests at this energy is indicated.

Comparativement à la tolite, l'octogène et l'héxogène ont l'intérêt majeur de posséder une masse volumique et une vitesse de détonation nettement supérieures. Ces composés présentent toutefois l'inconvénient d'être très nettement plus sensibles à l'impact et à la friction que la tolite, d'où certaines difficultés ou contraintes d'utilisation.Compared to tolite, octogen and hexogen have the advantage major to have a density and a detonation speed significantly higher. However, these compounds have the disadvantage of being very much more sensitive to impact and friction than tolite, hence certain difficulties or constraints of use.

La mise en oeuvre des explosifs secondaires dans les chargements de munitions nécessite de les présenter sous forme de compositions appropriées : il est de plus en plus rare d'utiliser directement l'explosif secondaire de base ; on le formule dans des compositions explosives variées mieux appropriées aux contraintes de l'emploi et à ses exigences opérationnelles.The use of secondary explosives in ammunition loads requires presenting them in the form of appropriate compositions: it is increasingly rare to use the basic secondary explosive directly; it is formulated in various explosive compositions better suited to the constraints of the job and its operational requirements.

Compte-tenu de la sensibilité de certaines compositions, il a fallu mettre au point des compositions explosives désensibilisées, afin de faciliter le chargement et la manutention de ces compositions.Given the sensitivity of certain compositions, it was necessary to develop desensitized explosive compositions in order to facilitate the loading and handling of these compositions.

Dans ce but on a par exemple incorporé dans les compositions un liant soit plastique et inerte, soit actif comme la tolite fondue. Toutefois, vis-à-vis de certaines agressions comme par exemple l'impact de balles, ces compositions sont encore trop vulnérables ce qui a conduit à rechercher des solutions au niveau de l'explosif secondaire lui-même en plus de l'enrobage par un liant moins sensible.For this purpose, for example, a binder, either plastic and inert, or active, such as molten tolite, has been incorporated into the compositions. However, with regard to certain aggressions such as for example the impact of bullets, these compositions are still too vulnerable which has led to the search for solutions at the level of the secondary explosive itself in addition to the coating by a less sensitive binder.

Dans ce but il est par exemple connu de substituer une partie de HMX ou RDX par le TATB dans les compositions explosives.For this purpose, it is for example known to substitute part of HMX or RDX with TATB in explosive compositions.

Le TATB et la tolite ont une faible sensibilité aux agressions extérieures (choc, frottement, élévation de température) ce qui permet de diminuer la vulnérabilité des compositions au prix cependant d'une baisse des performances.TATB and tolite have a low sensitivity to external aggressions (shock, friction, temperature rise) which makes it possible to reduce the vulnerability of the compositions at the cost, however, of a drop in performance.

La Demanderesse a maintenant découvert que, de façon inattendue, le 5-oxo 3-nitro 1,2,4-triazole (couramment appelé oxynitrotriazole) présente des propriétés intéressantes qui permettent de l'utiliser comme explosif secondaire en lieu et place de l'octogène ou de l'hexogène, tout en ayant une sensibilité aussi faible que celle de la tolite.The Applicant has now discovered that, unexpectedly, 5-oxo 3-nitro 1,2,4-triazole (commonly called oxynitrotriazole) has interesting properties which make it possible to use it as a secondary explosive in place of octogen or hexogen, while having a sensitivity as low as that of tolite.

Ces propriétés intéressantes sont les suivantes :

  • masse volumique (p) : 1,91 g/cm 3
  • vitesse de détonation : 7770 m/s à p = 1,71 g/cm
  • sensibilité à l'impact : 22 J
  • sensibilité à la friction : 7 % à 353 N.
These interesting properties are:
  • density (p) : 1.91 g / cm 3
  • detonation speed: 7770 m / s at p = 1.71 g / cm
  • impact sensitivity: 22 J
  • friction sensitivity: 7% at 353 N.

La vitesse de détonation calculée à p = 1,91 g/cm3 est de 8 590 m/s.The detonation speed calculated at p = 1.91 g / cm 3 is 8,590 m / s.

Les méthodes utilisées sont les mêmes que celles utilisées pour obtenir les résultats présentés au tableau 1.The methods used are the same as those used to obtain the results presented in Table 1.

L'oxynitrotriazole présente l'énorme avantage de posséder des performances explosives voisines de celles de l'hexogène compte tenu de sa masse volumique élevée sans avoir la sensibilité de l'hexogène ou de l'octogène (se reporter au tableau 1).Oxynitrotriazole has the enormous advantage of having explosive performances close to those of hexogen, given its high density without having the sensitivity of hexogen or octogen (see Table 1).

La substitution de tout ou partie de l'hexogène par l'oxynitrotriazole permet de diminuer la vulnérabilité des compositions explosives tout en conservant pratiquement le même niveau de performances. La substitution d'une partie de l'octogène par l'oxynitrotriazole permet, tout en conservant un niveau satisfaisant de performances, de diminuer la vulnérabilité des compositions explosives pour répondre à un besoin des utilisateurs, besoin auquel le chargement avec l'octogène seul ne permettait pas de répondre.The substitution of all or part of the hexogen by oxynitrotriazole makes it possible to reduce the vulnerability of the explosive compositions while maintaining practically the same level of performance. The substitution of part of the octogen by oxynitrotriazole makes it possible, while maintaining a satisfactory level of performance, to reduce the vulnerability of the explosive compositions in order to meet a need of users, a need which loading with octogen alone does not not allow to answer.

Ces résultats inattendus procurent un progrès technique considérable dans le domaine des compositions explosives.These unexpected results provide considerable technical progress in the field of explosive compositions.

Il a également été découvert que l'oxynitrotriazole pouvait être utilisé comme charge oxydante en lieu et place des substances explosives habituellement utilisées dans les poudres pour armes comme par exemple les poudres triple base et les poudres composites ainsi que dans les propergols composites.It has also been discovered that oxynitrotriazole can be used as an oxidizing charge in place of the explosive substances usually used in gun powders such as triple base powders and composite powders as well as in composite propellants.

De façon inattendue, l'utilisation de l'oxynitrotriazole dans les poudres pour armes entraine, comparativement à l'utilisation des poudres actuellement connues, une baisse de la température de flamme, donc une baisse de l'érosion du canon de l'arme, ce qui est très important en pratique.Unexpectedly, the use of oxynitrotriazole in powders for weapons causes, compared to the use of powders currently known, a drop in the flame temperature, therefore a drop in the erosion of the barrel of the weapon, which is very important in practice.

Par ailleurs, l'utilisation de l'oxynitrotriazole en remplacement du nitrate d'ammonium dans les propergols composites générateurs de gaz présente plusieurs avantages dont le plus important est le fait que l'oxynitrotriazole est nettement moins hygroscopique que le nitrate d'ammonium.Furthermore, the use of oxynitrotriazole to replace ammonium nitrate in composite gas-generating propellants has several advantages, the most important of which is the fact that oxynitrotriazole is significantly less hygroscopic than ammonium nitrate.

La présente invention a donc pour objet l'utilisation du 5-oxo 3-nitro 1,2,4-triazole comme explosif secondaire. Elle a également pour objet de fournir de nouvelles compositions pyrotechniques, et notamment de nouvelles compositions explosives, caractérisées en ce qu'elles contiennent du 5-oxo 3-nitro 1,2,4-triazole. Parmi ces nouvelles compositions pyrotechniques on peut également mentionner de nouvelles poudres pour armes et de nouveaux propergols.The present invention therefore relates to the use of 5-oxo 3-nitro 1,2,4-triazole as a secondary explosive. It also aims to provide new pyrotechnic compositions, and in particular new explosive compositions, characterized in that they contain 5-oxo 3-nitro 1,2,4-triazole. Among these new pyrotechnic compositions one can also mention new powders for weapons and new propellants.

Le 5-oxo 3-nitro 1,2,4-triazole, composé de formule

Figure imgb0002
, couramment appelé oxynitrotriazole, est également parfois appelé oxonitrotriazole ou nitrotriazolone.5-oxo 3-nitro 1,2,4-triazole, compound of formula
Figure imgb0002
 , commonly called oxynitrotriazole, is also sometimes called oxonitrotriazole or nitrotriazolone.

L'oxynitrotriazole est par exemple obtenu en 2 étapes à partir de deux matières premières courantes : le chlorhydrate de semicarbazide et l'acide formique.Oxynitrotriazole is for example obtained in 2 stages from two common raw materials: semicarbazide hydrochloride and formic acid.

Le schéma réactionnel de ce procédé est le suivant :

Figure imgb0003
Figure imgb0004
 The reaction scheme for this process is as follows:
Figure imgb0003
Figure imgb0004

Lors de la lère étape, la réaction du chlorhydrate de semicarbazide et de l'acide formique en milieu aqueux pendant quelques heures à 85-90°C permet de former, puis d'isoler avec un rendement de l'ordre de 80 %, le 5-oxo 1,2,4-triazole (couramment appelé oxytriazole).During the 1st stage, the reaction of semicarbazide hydrochloride and formic acid in an aqueous medium for a few hours at 85-90 ° C. makes it possible to form and then to isolate with a yield of the order of 80%, the 5-oxo 1,2,4-triazole (commonly called oxytriazole).

La 2ème étape consiste à nitrer l'oxytriazole ainsi obtenu, par exemple par l'acide nitrique à 98 %, à la température ambiante, pendant quelques heures. L'oxynitrotriazole est isolé du milieu selon une technique classique bien connue de l'homme de métier, avec un rendement global, pour l'ensemble des 2 étapes, voisin de 65%.The second step consists in nitrating the oxytriazole thus obtained, for example with 98% nitric acid, at ambient temperature, for a few hours. Oxynitrotriazole is isolated from the medium according to a conventional technique well known to those skilled in the art, with an overall yield, for all of the 2 stages, close to 65%.

L'oxynitrotriazole possède une vitesse de détonation proche de celle de l'hexogène et les sensibilités à l'impact et à la friction sont très nettement inférieures à celles de l'octogène et de l'hexogène, les sensibilités obtenues pour l'oxynitrotriazole étant voisines de celles obtenues pour la tolite.Oxynitrotriazole has a detonation speed close to that of hexogen and the sensitivities on impact and friction are very much lower than those of octogen and hexogen, the sensitivities obtained for oxynitrotriazole being close to those obtained for tolite.

L'oxynitrotriazole possède également d'autres caractéristiques intéressantes rendant intéressant et particulièrement avantageux son emploi comme explosif secondaire :

  • - Il se décompose sans fondre vers 270°C (par analyse thermique différentielle on constate une décomposition de 268 à 286°C avec un maximum à 279°C). Cette température est relativement élevée (l'hexogène par exemple se décompose entre 160 et 200°C).
  • - Il a une masse volumique élevée : P = 1,91 g/cm3
  • - Il possède une stabilité sous vide intéressante ; l'épreuve consistant à chauffer le produit sous vide à température donnée et à mesurer le volume de gaz émis en fonction du temps donne le résultat suivant :
    • 100°C : 1,4 cm3/g en 193 H
    • 130°C : 1,5 cm3/g en 193 H
    • 150°C : 1,7 cm3/g en 193 H
  • - La chaleur de formation Hf est de - 828 J/g soit - 107,7 kJ/mol.
  • - Il est notamment compatible avec l'octogène et les liants habituels des explosifs à liant plastique, des poudres et propergols composites.
Oxynitrotriazole also has other interesting characteristics which make it interesting and particularly advantageous to use it as a secondary explosive:
  • - It decomposes without melting around 270 ° C (by thermal analysis differential there is a decomposition from 268 to 286 ° C with a maximum at 279 ° C). This temperature is relatively high (hexogen for example decomposes between 160 and 200 ° C).
  • - It has a high density: P = 1.91 g / cm 3
  • - It has an interesting vacuum stability; the test consisting of heating the product under vacuum to a given temperature and measuring the volume of gas emitted as a function of time gives the following result:
    • 100 ° C: 1.4 cm 3 / g in 193 H
    • 130 ° C: 1.5 cm 3 / g in 193 H
    • 150 ° C: 1.7 cm 3 / g in 193 H
  • - The heat of formation Hf is - 828 J / g or - 107.7 kJ / mol.
  • - It is in particular compatible with octogen and the usual binders of explosives with plastic binders, powders and composite propellants.

Des essais de cristallisation, notamment dans l'eau sous agitation lente (cristaux réguliers, presque sphériques de diamètre moyen de l'ordre de 100 à 150 µm) et dans l'eau sous agitation mais avec refroidissement programmé jusqu'à 0°C, ont montré la possibilité d'obtenir des cristaux suffisamment gros pour être utilisés facilement dans les formulations.Crystallization tests, in particular in water with slow stirring (regular, almost spherical crystals with an average diameter of about 100 to 150 μm) and in water with stirring but with programmed cooling to 0 ° C, have shown the possibility of obtaining crystals large enough to be easily used in formulations.

En plus de son utilisation comme explosif secondaire à l'état de produit pur, l'oxynitrotriazole peut être utilisé dans les compositions pyrotechniques et notamment les compositions explosives.In addition to its use as a secondary explosive in the form of a pure product, oxynitrotriazole can be used in pyrotechnic compositions and in particular explosive compositions.

Il peut également être utilisé comme explosif secondaire en mélange avec un composé dans lequel il est pratiquement insoluble et permettant le chargement à l'état fondu (utilisation avec de la tolite fondue par exemple).It can also be used as a secondary explosive in mixture with a compound in which it is practically insoluble and allowing loading in the molten state (use with molten tolite for example).

On peut également utiliser l'oxynitrotriazole comme explosif secondaire en mélange avec des cires ou plus généralement avec des matières plastiques permettant le chargement par compression.Oxynitrotriazole can also be used as a secondary explosive in mixture with waxes or more generally with plastics allowing loading by compression.

On peut aussi utiliser l'oxynitrotriazole comme charge oxydante dans les poudres pour armes, notamment les poudres triple base et les poudres composites ainsi que dans les propergols composites.Oxynitrotriazole can also be used as an oxidizing charge in powders for weapons, in particular triple base powders and composite powders as well as in composite propellants.

Les nouvelles compositions explosives selon l'invention sont caractérisées en ce qu'elles contiennent du 5-oxo 3-nitro 1,2,4-triazole. Elles sont obtenues selon les procédés classiques et bien connus de l'homme de métier en substituant tout ou partie des explosifs secondaires habituellement utilisés par l'oxynitrotriazole.The new explosive compositions according to the invention are characterized in that they contain 5-oxo 3-nitro 1,2,4-triazole. They are obtained according to conventional methods well known to those skilled in the art by substituting all or part of the secondary explosives usually used by oxynitrotriazole.

Selon une première variante préférée, les compositions explosives sont des compositions explosives à liant plastique mises en oeuvre par compression. De telles compositions sont réalisées selon les procédés classiques et bien connus de l'homme de métier d'obtention des compositions explosives à liant plastique mises en oeuvre par compression. On peut par exemple citer ceux décrits dans les brevets français 1 602 614 et 1 469 198. La matière de base est constituée par des granulés dans lesquels les cristaux d'explosifs sont enrobés d'une matière plastique. Ces granulés sont le plus souvent obtenus selon un procédé d'enrobage à sec, l'oxynitrotriazole étant soluble dans l'eau. Ils sont ensuite comprimés sous pression élevée (de l'ordre de 108 Pa), après réchauffement de la poudre à mouler dans le cas des liants thermoplastiques, à la température ambiante dans le cas de liants thermodurcissables (par exemple les liants polyesters).According to a first preferred variant, the explosive compositions are explosive compositions with a plastic binder used by compression. Such compositions are produced according to conventional methods well known to those skilled in the art for obtaining explosive plastic binder compositions used by compression. We can for example cite those described in French patents 1 602 614 and 1 469 198. The basic material consists of granules in which the crystals of explosives are coated with a plastic material. These granules are most often obtained according to a dry coating process, the oxynitrotriazole being soluble in water. They are then compressed under high pressure (of the order of 10 8 Pa), after heating the molding powder in the case of thermoplastic binders, at room temperature in the case of thermosetting binders (for example polyester binders).

Parmi les compositions explosives selon cette première variante préférée de l'invention on peut distinguer celles ne contenant pas d'autre explosif secondaire que le 5-oxo 3-nitro 1,2,4-triazole et celles qui, au contraire, contiennent au moins un autre explosif secondaire que le 5-oxo 3-nitro 1,2,4-triazole comme par exemple HMX, RDX, TATB, HNS ou PETN. Parmi ces dernières compositions explosives, on préfère celles contenant au moins un explosif secondaire choisi dans le groupe formé par l'octogène et l'hexogène.Among the explosive compositions according to this first preferred variant of the invention, one can distinguish those containing no other secondary explosive than 5-oxo 3-nitro 1,2,4-triazole and those which, on the contrary, contain at least another secondary explosive than 5-oxo 3-nitro 1,2,4-triazole such as for example HMX, RDX, TATB, HNS or PETN. Among these last explosive compositions, those containing at least one secondary explosive chosen from the group formed by octogen and hexogen are preferred.

Parmi les compositions explosives à liant plastique mises en oeuvre par compression selon l'invention, on préfère celles dont le liant plastique est choisi dans le groupe constitué par les liants fluorés, les liants polyuréthannes et les liants polyesters. Bien entendu les autres liants habituellement utilisés dans les compositions explosives à liant plastique mises en oeuvre par compression conviennent également. On peut par exemple citer les liants à base de copolymères butadiène-styrène.Among the explosive compositions with a plastic binder used by compression according to the invention, preference is given to those in which the plastic binder is chosen from the group consisting of fluorinated binders, polyurethane binders and polyester binders. Of course, the other binders usually used in explosive compositions with plastic binder used by compression are also suitable. Mention may for example be made of binders based on butadiene-styrene copolymers.

Selon une deuxième variante préférée, les compositions explosives sont des compositions explosives à liant plastique mises en oeuvre par coulée. De telles compositions sont réalisées selon les procédés classiques et bien connus de l'homme de métier d'obtention de compositions explosives mises en oeuvre par coulée. On peut citer par exemple ceux décrits dans les brevets français 2 124 038, 2 225 979 et 2 086 881.According to a second preferred variant, the explosive compositions are explosive compositions with a plastic binder used by casting. Such compositions are produced according to conventional methods well known to those skilled in the art for obtaining explosive compositions used by casting. These include, for example, those described in French patents 2,124,038, 2,225,979 and 2,086,881.

De façon générale, pour préparer ces compositions explosives à liant plastique mises en oeuvre par coulée, on mélange tout d'abord, 1' (ou les) explosif secondaire et une résine polymérisable liquide puis on coule la pâte obtenue dans un moule. On fait ensuite polymériser la pâte. Selon le choix et le règlage des agents de réticulation, des catalyseurs, des mouillants, on obtient des compositions explosives moulées de caractéristiques variées.In general, to prepare these explosive compositions with a plastic binder used by casting, the secondary explosive (s) and a liquid polymerizable resin are firstly mixed and then the paste obtained is poured into a mold. The dough is then polymerized. Depending on the choice and adjustment of the crosslinking agents, catalysts, wetting agents, explosive molded compositions of various characteristics are obtained.

Parmi les compositions explosives selon cette deuxième variante préférée, on peut distinguer celles ne contenant pas d'autre explosif secondaire que le 5-oxo 3-nitro 1,2,4-triazole et celles qui, au contraire, contiennent au moins un autre explosif secondaire que le 5-oxo 3-nitro 1,2,4-triazole, de préférence choisie dans le groupe formé par l'octogène et l'hexogène.Among the explosive compositions according to this second preferred variant, one can distinguish those containing no other secondary explosive than 5-oxo 3-nitro 1,2,4-triazole and those which, on the contrary, contain at least one other explosive secondary than 5-oxo 3-nitro 1,2,4-triazole, preferably chosen from the group formed by octogen and hexogen.

Parmi les compositions explosives à liant plastique mises en oeuvre par coulée selon l'invention, on préfère celles dont le liant plastique est un liant polyuréthanne, la teneur pondérale du liant dans la composition explosive étant comprise entre 12 et 20 %. Bien entendu, les autres liants habituellement utilisés dans les compositions explosives à liant plastique mises en oeuvre par coulée conviennent également. On peut par exemple citer les liants silicones et les liants polyesters, notamment ceux obtenus par réaction d'un époxyde avec un polybutadiène carboxytéléchélique (PBCT).Among the explosive compositions with a plastic binder used by casting according to the invention, those whose plastic binder is a polyurethane binder are preferred, the weight content of the binder in the explosive composition being between 12 and 20%. Of course, the other binders usually used in explosive compositions with plastic binder used by casting are also suitable. Mention may for example be made of silicone binders and polyester binders, in particular those obtained by reaction of an epoxide with a carboxy-telechelic polybutadiene (PBCT).

Selon une troisième variante préférée de l'invention, les compositions explosives sont des mélanges à base de tolite. Ces mélanges, mis en oeuvre par coulée, sont réalisés selon les procédés classiques d'obtention des mélanges à base de tolite actuellement connus comme les hexolites, pentolites ou octolites en remplaçant tout ou partie de l'explosif secondaire habituellement associé à la tolite (à savoir l'hexogène, la pentrite ou l'octogène) par l'oxynitrotriazole.According to a third preferred variant of the invention, the explosive compositions are mixtures based on tolite. These mixtures, used by casting, are produced according to the conventional methods for obtaining mixtures based on tolite currently known as hexolites, pentolites or octolites by replacing all or part of the secondary explosive usually associated with tolite (to namely hexogen, pentrite or octogen) by oxynitrotriazole.

Ces mélanges, au dessus de 80°C, sont constitués par des suspensions de grains d'oxynitrotriazole dans la tolite fondue. On peut par exemple les obtenir par mélange direct de l'oxynitrotriazole dans de la tolite fondue.These mixtures, above 80 ° C., consist of suspensions of grains of oxynitrotriazole in molten tolite. They can, for example, be obtained by direct mixing of oxynitrotriazole in molten tolite.

De façon préférée, la teneur pondérale de l'oxynitrotriazole dans ces mélanges est comprise entre 50 et 90%.Preferably, the weight content of oxynitrotriazole in these mixtures is between 50 and 90%.

Les nouvelles poudres pour armes selon l'invention sont caractérisées en ce qu'elles contiennent du 5-oxo 3-nitro 1,2,4-triazole. Elles sont obtenues selon les procédés classiques et bien connus de l'homme de métier en substituant tout ou partie des explosifs secondaires habituellement utilisés comme charge oxydante dans les poudres par du 5-oxo 3-nitro 1,2,4-triazole.The new gun powders according to the invention are characterized in that they contain 5-oxo 3-nitro 1,2,4-triazole. They are obtained according to conventional processes and well known to those skilled in the art by substituting all or part of the secondary explosives usually used as an oxidizing charge in powders with 5-oxo 3-nitro 1,2,4-triazole.

Selon une première variante préférée, les poudres pour armes sont des poudres triple base dont les 3 bases sont la nitrocellulose, la nitroglycérine et l'oxynitrotriazole. Les teneurs en nitrocellulose et nitroglycérine sont celles habituellement présentes dans les poudres triple base les contenant, comme par exemple dans les poudres triple base nitrocellulose-nitroglycérine-nitroguanidine, les teneurs en oxynitrotriazole étant voisines de celles habituellement présentes en nitroguanidine.According to a first preferred variant, the powders for weapons are triple base powders, the 3 bases of which are nitrocellulose, nitroglycerin and oxynitrotriazole. The nitrocellulose and nitroglycerin contents are those usually present in the triple base powders containing them, such as for example in the nitrocellulose-nitroglycerine-nitroguanidine triple base powders, the oxynitrotriazole contents being close to those usually present in nitroguanidine.

A titre d'exemple on peut citer les poudres triple base suivantes :

  • - nitrocellulose (20%) nitroglycérine (20%) oxynitrotriazole (60%)
  • - nitrocellulose (22%) nitroglycérine (28%) oxynitrotriazole (50%)
  • - nitrocellulose (30 %) nitroglycérine (30 %) oxynitrotriazole (40 %)
By way of example, the following triple base powders may be mentioned:
  • - nitrocellulose (20%) nitroglycerin (20%) oxynitrotriazole (60 % )
  • - nitrocellulose (22%) nitroglycerin (28%) oxynitrotriazole (50%)
  • - nitrocellulose (30%) nitroglycerin (30%) oxynitrotriazole (40%)

Ces poudres triple base peuvent contenir les additifs classiquement utilisés à savoir notamment des stabilisants (2-nitrodiphénylamine par exemple), des plastifiants, et des antilueurs.These triple base powders may contain the additives conventionally used, namely in particular stabilizers (2-nitrodiphenylamine for example), plasticizers, and antiluents.

Elles sont obtenues par exemple, selon un procédé à solvants, classique pour les formulations de poudre triple base.They are obtained for example, according to a solvent process, conventional for triple base powder formulations.

Selon une deuxième variante préférée, les poudres pour armes sont des poudres composites à liant inerte. Elles sont principalement constituées par une résine synthétique et par une ou plusieurs substances explosives jouant le rôle-de charge oxydante.According to a second preferred variant, the powders for weapons are composite powders with an inert binder. They are mainly constituted by a synthetic resin and by one or more explosive substances playing the role of oxidizing charge.

Parmi les poudres pour armes selon cette deuxième variante préférée on peut distinguer celles ne contenant pas d'autre explosif secondaire que le 5-oxo 3-nitro 1,2,4-triazole et celles qui, au contraire, contiennent au moins un autre explosif secondaire que le 5-oxo 3-nitro 1,2,4-triazole, de préférence choisi dans le groupe constitué par l'hexogène, l'octogène et la pentrite.Among the powders for weapons according to this second preferred variant, one can distinguish those containing no other secondary explosive than 5-oxo 3-nitro 1,2,4-triazole and those which, on the contrary, contain at least one other explosive secondary than 5-oxo 3-nitro 1,2,4-triazole, preferably chosen from the group consisting of hexogen, octogen and pentrite.

A titre d'exemples d'autres charges oxydantes pouvant être associées à l'oxynitrotriazole dans les poudres pour armes selon cette deuxième variante préférée, on peut citer de façon non limitative le nitrate de triaminoguanidine, le nitrate d'ammonium, les nitrates alcalins ou alcalino-terreux.As examples of other oxidizing charges which can be associated with oxynitrotriazole in powders for weapons according to this second preferred variant, mention may be made, without limitation, of triaminoguanidine nitrate, ammonium nitrate, alkali nitrates or alkaline earth.

Le liant inerte est de façon préférée un liant polyuréthanne mais il peut aussi par exemple et de façon non limitative être un liant polyester. Parmi les liants polyuréthannes on préfère ceux obtenus par réaction d'un polybutadiène hydroxylé avec un diisocyanate.The inert binder is preferably a polyurethane binder but it can also for example and without limitation be a polyester binder. Among the polyurethane binders, those obtained by reacting a hydroxylated polybutadiene with a diisocyanate are preferred.

De façon préférée le taux de liant est de l'ordre de 20% en poids. Les poudres composites selon l'invention contiennent également en général les additifs usuels connus de l'homme de métier tels que notamment des plastifiants, des agents anti-oxydant, anti-lueur, anti-érosif.Preferably, the level of binder is of the order of 20% by weight. The composite powders according to the invention also generally contain the usual additives known to those skilled in the art, such as in particular plasticizers, anti-oxidant, anti-glow, anti-erosive agents.

Les poudres à liant inerte pour armes selon l'invention peuvent être obtenues selon les procédés classiques d'obtention de ce type de poudre, et notamment par la technique "globale" qui est très largement utilisée et qui a déjà été précédemement décrite pour la réalisation des compositions explosives à liant plastique mises en oeuvre par coulée.The powders with an inert binder for weapons according to the invention can be obtained according to the conventional methods for obtaining this type of powder, and in particular by the "global" technique which is very widely used and which has already been previously described for the production. explosive compositions with plastic binder used by casting.

Les nouveaux propergols composites selon l'invention sont caractérisés en ce qu'ils contiennent du 5-oxo 3-nitro 1,2,4-triazole. Ils sont obtenus selon les procédés classiques et bien connus de l'homme de métier en substituant tout ou partie des substances explosives habituellement utilisées comme charge oxydante dans les propergols par du 5-oxo 3-nitro 1,2,4-triazole. On peut les obtenir selon les procédés classiques d'obtention des propergols composites et notamment par la technique "globale" dite "de coulée" qui est très largement utilisée et qui a déjà été précédemment décrite.The new composite propellants according to the invention are characterized in that they contain 5-oxo 3-nitro 1,2,4-triazole. They are obtained according to conventional methods and well known to those skilled in the art by substituting all or part of the explosive substances usually used as an oxidizing charge in propellants with 5-oxo 3-nitro 1,2,4-triazole. They can be obtained according to the conventional methods for obtaining composite propellants and in particular by the "global" technique called "casting" which is very widely used and which has already been described previously.

Ils peuvent contenir les additifs usuels connus de l'homme de métier, tels que notamment des agents d'adhésion liant-charge, des antioxydants, des catalyseurs.They may contain the usual additives known to those skilled in the art, such as, in particular, binder-filler adhesion agents, antioxidants, catalysts.

Selon une première variante préférée, les propergols composites selon l'invention sont des propergols générateurs de gaz dans lesquels l'oxynitrotriazole substitue tout ou partie du nitrate d'ammonium habituellement utilisé dans ces compositions.According to a first preferred variant, the composite propellants according to the invention are gas-generating propellants in which the oxynitrotriazole substitutes all or part of the ammonium nitrate usually used in these compositions.

A titre d'exemple de tels propergols composites générateurs de gaz selon l'invention, on peut citer ceux constitués d'un liant polyuréthanne chargé en oxynitrotriazole. Par exemple la teneur pondérale en liant est de l'ordre de 20 % et celle en oxynitrotriazole de l'ordre de 80 %.By way of example of such composite gas-generating propellants according to the invention, mention may be made of those consisting of a polyurethane binder loaded with oxynitrotriazole. For example, the content by weight of binder is of the order of 20% and that of oxynitrotriazole of the order of 80%.

Selon une deuxième variante préférée, les propergols composites selon l'invention contiennent au moins un autre explosif secondaire que l'oxynitrotriazole choisi dans le groupe constitué par l'hexogène et l'octogène, le liant étant de préférence un liant polyuréthanne.According to a second preferred variant, the composite propellants according to the invention contain at least one other secondary explosive than oxynitrotriazole chosen from the group consisting of hexogen and octogen, the binder preferably being a polyurethane binder.

La teneur pondérale en liant est par exemple de l'ordre de 20 % et celle du total des charges de 80 % environ.The content by weight of binder is for example of the order of 20% and that of the total charges of about 80%.

Les exemples non limitatifs suivants illustrent l'invention et mettent en évidence les nombreux avantages qu'elle procure.The following nonlimiting examples illustrate the invention and demonstrate the numerous advantages which it provides.

Exemple 1 - Synthèse de l'oxynitrotriazoleExample 1 Synthesis of Oxynitrotriazole * Synthèse de l'oxytriazole (5-oxo 1,2,4-triazole) * Synthesis of oxytriazole (5-oxo 1,2,4-triazole)

Dans un réacteur de 500 ml équipé d'un agitateur, d'un réfrigérant, d'un thermomètre et d'un système de chauffage, on place 115 ml d'acide formique à 85%. On agite et on porte à 70-75°C. On introduit par portions 111,5 g de chlorhydrate de semicarbazide. On observe un dégagement d'HCl. L'introduction terminée, on chauffe le milieu réactionnel à 85-90°C pendant 6 à 8 heures. Après refroidissement, on évapore à sec. Le produit est repris par 200 ml d'eau puis à nouveau évaporé à sec ; on répète une fois cette opération puis le produit est repris par 140 ml d'eau à 90°C. Après refroidissement à 10°C le produit est filtré et lavé à l'aide d'eau glacée. Le rendement en oxytriazole est de 80%. L'oxytriazole obtenu a été identifié par IR et RMN du carbone 13. Son point de fusion est de 234°C et son analyse élémentaire donne le résultat suivant :

Figure imgb0005
115 ml of 85% formic acid are placed in a 500 ml reactor equipped with an agitator, a condenser, a thermometer and a heating system. Stir and bring to 70-75 ° C. 111.5 g of semicarbazide hydrochloride are introduced in portions. A release of HCl is observed. When the introduction is complete, the reaction medium is heated to 85-90 ° C for 6 to 8 hours. After cooling, it is evaporated to dryness. The product is taken up in 200 ml of water and then again evaporated to dryness; this operation is repeated once, then the product is taken up in 140 ml of water at 90 ° C. After cooling to 10 ° C the product is filtered and washed with ice water. The yield of oxytriazole is 80%. The oxytriazole obtained was identified by IR and carbon 13 NMR. Its melting point is 234 ° C. and its elemental analysis gives the following result:
Figure imgb0005

* Synthèse de l'oxynitrotriazole (5-oxo 3-nitro 1,2,4-triazole) * Synthesis of oxynitrotriazole (5-oxo 3-nitro 1,2,4-triazole)

On introduit 170 g d'oxytriazole dans 750 ml d'acide nitrique à 98% en maintenant la température à 5-100C. L'addition dure 2 heures. On agite ensuite 3 heures à température ambiante. On verse alors lentement ce bain nitrique dans 600 ml d'eau glacée et on laisse reposer une douzaine d'heures. Après filtration, essorage et séchage, on obtient 208 g d'oxynitrotriazole qui se présente sous la forme d'un solide blanc identifié par ses spectres IR, RMN et de masse. Le rendement global de l'ensemble des 2 étapes est de 64%.170 g of oxytriazole are introduced into 750 ml of 98% nitric acid while maintaining the temperature at 5-10 ° C. The addition lasts 2 hours. Then stirred for 3 hours at room temperature. This nitric bath is then slowly poured into 600 ml of ice water and left to stand for a dozen hours. After filtration, spinning and drying, 208 g of oxynitrotriazole are obtained, which is in the form of a white solid identified by its IR, NMR and mass spectra. The overall yield of all 2 stages is 64%.

Exemple 2 - Préparation d'un cordeau détonant à l'oxynitrotriazoleEXAMPLE 2 Preparation of an Oxynitrotriazole Detonating Cord

On prépare, selon la technique classique de la fabrication des cordeaux détonants par étirage, un cordeau détonant sous gaine de cuivre chargé en oxynitrotriazole. Après étirage ses caractéristiques sont les suivantes :

  • - diamètre extérieur : 4 mm,
  • - densité de chargement : 1,69
A detonating cord under a copper sheath loaded with oxynitrotriazole is prepared according to the conventional technique of manufacturing detonating cords by drawing. After stretching its characteristics are as follows:
  • - outside diameter: 4 mm,
  • - loading density: 1.69

La vitesse de détonation d'un tel cordeau à l'oxynitrotriazole est de 7 400 m/s.The detonation speed of such an oxynitrotriazole cord is 7,400 m / s.

Exemple 3 - Préparation d'un deuxième cordeau détonant à l'oxynitrotriazoleEXAMPLE 3 Preparation of a Second Oxynitrotriazole Detonating Cord

La même technique que celle décrite pour l'exemple 2 est utilisée ses caractéristiques sont les suivantes :

  • - diamètre extérieur : 4 mm,
  • - densité de chargement : 1,71.
The same technique as that described for example 2 is used, its characteristics are the following:
  • - outside diameter: 4 mm,
  • - loading density: 1.71.

La vitesse de détonation de ce cordeau est de 7 770 m/s.The detonation speed of this cord is 7,770 m / s.

Exemple 4 - Composition explosive à liant plastique mise en oeuvre par compressionExample 4 Explosive composition with plastic binder used by compression

Cette composition est constituée de 7% en poids du liant fluoré vendu sous le nom commercial "Kel F 800" par la Société 3M et de 93% en poids de charges. Les charges sont l'oxynitrotriazole et l'octogène dans les proportions relatives en poids 50/50. Pour réaliser cette composition on introduit le liant en solution dans l'acétate d'éthyle dans un malaxeur avec les charges solides. Après malaxage sous pression réduite, ce qui permet d'éliminer le solvant, les granulés ainsi obtenus sont séchés sous vide puis comprimés à 110° C sous une pression de 1,5 10 8 Pa.This composition consists of 7% by weight of the fluorinated binder sold under the trade name "Kel F 800" by the company 3M and 93 % by weight of fillers. The charges are oxynitrotriazole and octogen in the relative proportions by weight 50/50. To make this composition, the binder is introduced in solution in ethyl acetate in a mixer with the solid fillers. After mixing under reduced pressure, which makes it possible to remove the solvent, the granules thus obtained are dried under vacuum and then compressed at 110 ° C. under a pressure of 1.5 × 10 8 Pa .

Les caractéristiques explosives de cette composition sont regroupées dans le tableau 2, comparativement à celles de 2 compositions connues contenant 7% en poids du même liant KelF 800 et 93% en poids de charges ; pour l'une d'elles ces charges sont le TATB et l'octogène dans les proportions relatives en poids 60/40 respectivement et pour l'autre l'octogène uniquement. On constate que la composition à l'oxynitrotriazole est moins sensible au choc et à la friction que celle au TATB alors que la vitesse de détonation est supérieure et que l'amorçabilité par onde de détonation demeure tout à fait satisfaisante.The explosive characteristics of this composition are grouped in Table 2, compared with those of 2 known compositions containing 7% by weight of the same binder KelF 800 and 93% by weight of fillers; for one of them, these charges are TATB and octogen in the relative proportions by weight 60/40 respectively and for the other octogen only. It can be seen that the composition with oxynitrotriazole is less sensitive to shock and friction than that with TATB while the detonation speed is higher and that the initiation by detonation wave remains entirely satisfactory.

Comparativement à la composition uniquement chargée à l'octogène, celle contenant l'oxynitrotriazole est très nettement moins sensible au choc et à la friction alors que la vitesse de détonation n'est que peu abaissée.Compared to the composition charged only with octogen, that containing oxynitrotriazole is very much less sensitive to shock and friction while the detonation speed is only slightly lowered.

La sensibilité à l'impact et la sensibilité à la friction sont déterminées selon les méthodes précitées. L'amorçabilité par onde de détonation est déterminée à l'aide d'un dispositif constitué par :

  • 1 initiateur : brin de 50 mm de cordeau à l'hexogène sous plomb de 0 5 mm, charge normale. Ce cordeau est amorcé coaxia. lament par un détonateur n° 8 du commerce.
  • 1 barrière : constituée d'un empilement de disques d'acétate de cellulose de 0,19 mm d'épaisseur
  • 1 éprouvette : cylindre φ 5 mm, h = 15 mm, obtenu par compression de la composition à tester.
  • 1 cible : constituée par l'aluminium AU4G de 3 mm d'épaisseur.
The sensitivity to impact and the sensitivity to friction are determined according to the aforementioned methods. Detonation wave initiation is determined using a device consisting of:
  • 1 initiator: 50 mm strand of leaded lead with 0 5 mm lead, normal charge. This cord is primed coaxia. lament by a commercial detonator n ° 8.
  • 1 barrier: consisting of a stack of cellulose acetate discs 0.19 mm thick
  • 1 test piece: cylinder φ 5 mm, h = 15 mm, obtained by compression of the composition to be tested.
  • 1 target: made of 3 mm thick AU4G aluminum.

Tous les éléments sont montés à l'intérieur d'un tube plastique de 5 mm de diamètre intérieur.All the elements are mounted inside a plastic tube 5 mm inside diameter.

On détermine alors par la méthode connue de Bruceton l'épaisseur de barrière qui permet 50% d'amorçages positifs sur 30 essais.

Figure imgb0006
Exemples 5 à 11 - Autres compositions explosives à liant plastiqueThe barrier thickness is then determined by the known Bruceton method, which allows 50% positive priming over 30 tests.
Figure imgb0006
 Examples 5 to 11 - Other explosive compositions with a plastic binder

mises en oeuvre par compressionimplemented by compression

Dans l'exemple 5, on réalise la même composition qu'à l'exemple 4, mais la charge est uniquement constituée d'oxynitrotriazole.In Example 5, the same composition is made as in Example 4, but the filler consists only of oxynitrotriazole.

Dans les exemples 6 et 7 le liant est un liant polyuréthanne, vendu sous le nom commercial ESTANE par la Société GOODRICH.In Examples 6 and 7, the binder is a polyurethane binder, sold under the trade name ESTANE by the company GOODRICH.

Dans les exemples 8 et 9 le liant est un liant polyamide (nylon).In Examples 8 and 9 the binder is a polyamide (nylon) binder.

Dans les exemples 10 et 11 le liant est un liant polyacétate de vinyle, vendu sous le nom commercial RHODO HV2 par la Société RHONE-POULENC.In Examples 10 and 11 the binder is a polyvinyl acetate binder, sold under the trade name RHODO HV2 by the company RHONE-POULENC.

Les compositions des exemples 5 à 11 contiennent comme charges un mélange d'octogène et d'oxynitrotriazole ; elles ont été réalisées selon le même procédé que celui de l'exemple 4.The compositions of Examples 5 to 11 contain as fillers a mixture of octogen and oxynitrotriazole; they were carried out according to the same method as that of Example 4.

Les caractéristiques explosives de la composition de l'exemple 5 sont regroupées dans le tableau 3 comparativement à celles de 2 compositions connues, l'une chargée à l'octogène, l'autre au TATB.The explosive characteristics of the composition of Example 5 are grouped in Table 3 compared with those of 2 known compositions, one charged with octogen, the other with TATB.

On constate que les compositions à l'oxynitrotriazole d'une part et au TATB d'autre part sont très peu sensibles au choc, à la friction et à l'onde de choc comparativement à celle de l'octogène.

Figure imgb0007
Le pourcentage pondéral en liant, les proportions relatives pondérales des charges et les caractéristiques explosives des compositions des exemples 6 à 11 sont regroupées dans le tableau 4.It is found that the compositions with oxynitrotriazole on the one hand and with TATB on the other hand are very little sensitive to shock, friction and shock wave compared to that of octogen.
Figure imgb0007
 The weight percentage by binder, the relative weight proportions of the charges and the explosive characteristics of the compositions of Examples 6 to 11 are grouped in Table 4.

On constate que toutes ces compositions ont une vitesse de détonation supérieure à 8 000 m/s alors que leur sensibilité est relativement faible.

Figure imgb0008
Exemples 12 et 13 - Compositions explosives à liant plastique mises enIt is found that all of these compositions have a detonation speed greater than 8000 m / s while their sensitivity is relatively low.
Figure imgb0008
 Examples 12 and 13 - Explosive compositions with plastic binder

oeuvre par couléework by casting

Ces compositions sont constituées de 19,4 % en poids d'un liant polyuréthanne obtenu par réaction du polyester hydroxylé vendu sous le nom commercial T1271 par la Société ISEL avec l'isophorore diisocyanate (IPDI) et de 80,6 % en poids de charges. Les charges sont l'oxynitrotriazole et l'octogène dans les proportions relatives en poids 44/56 respectivement pour l'exemple 12 et 58/42 respectivement pour l'exemple 13. Pour réaliser ces compositions, on introduit successivement, avec malaxage intermédiaire sous pression réduite, le polyester hydroxylé, les charges et l'isocyanate. La pâte obtenue est coulée dans des moules puis ensuite polymérisée par cuisson à 40° C pendant 8 jours.These compositions consist of 19.4% by weight of a polyurethane binder obtained by reaction of the hydroxylated polyester sold under the trade name T1271 by the company ISEL with isophorore diisocyanate (IPDI) and 80.6% by weight of fillers. . The fillers are oxynitrotriazole and octogen in the relative proportions by weight 44/56 respectively for Example 12 and 58/42 respectively for Example 13. To make these compositions, successively are introduced, with intermediate kneading under pressure reduced, hydroxylated polyester, fillers and isocyanate. The paste obtained is poured into molds and then polymerized by baking at 40 ° C for 8 days.

Les caractéristiques explosives de ces compositions sont regroupées dans le tableau 5, comparativement à celles de 2 compositions connues contenant 19,4 % en poids du même liant et 80,6 % en poids de charges. Pour l'une d'elles les charges sont le TATB et l'octogène dans les proportions relatives en poids 44/56 respectivement et pour l'autre l'octogène uniquement.The explosive characteristics of these compositions are grouped in Table 5, compared with those of 2 known compositions containing 19.4% by weight of the same binder and 80.6% by weight of fillers. For one of them, the charges are TATB and octogen in the relative proportions by weight 44/56 respectively and for the other octogen only.

Les propriétés mécaniques des compositions sont voisines. La vitesse de détonation des compositions contenant d'une part le TATB et d'autre part l'oxynitrotriazole soit voisines et légèrement inférieures à celle de la composition uniquement chargée en octogène.The mechanical properties of the compositions are similar. The detonation speed of the compositions containing on the one hand the TATB and on the other hand the oxynitrotriazole are close to and slightly lower than that of the composition solely charged with octogen.

La sensibilité à l'onde de choc (IAD) est abaissée par la substitution d'une partie de l'octogène par le TATB ou par l'oxynitrotriazole. De façon inattendue la baisse est toutefois nettement plus importante avec l'oxynitrotriazole qu'avec le TATB.The shock wave sensitivity (IAD) is lowered by the substitution of part of the octogen by TATB or by oxynitrotriazole. Unexpectedly, however, the drop is significantly greater with oxynitrotriazole than with TATB.

De même, l'amorçabilité (sensibilité au détonateur BRISKA, éventuellement avec relais plastic) est abaissée par la substitution d'une partie de l'octogène par le TATB ou par l'oxynitrotriazole.Similarly, the initiability (sensitivity to the BRISKA detonator, possibly with plastic relay) is lowered by the substitution of part of the octogen by TATB or by oxynitrotriazole.

Ces résultats montrent que l'oxynitrotriazole peut se substituer au TATB dans toutes ses applications comme explosif secondaire.

Figure imgb0009
These results show that oxynitrotriazole can replace TATB in all its applications as a secondary explosive.
Figure imgb0009

Exemple 14 - Poudre triple baseEXAMPLE 14 Triple Base Powder

On a réalisé, selon un procédé à solvants, la poudre triple base de composition suivante :

  • nitrocellulose : 28 %
  • nitroglycérine : 30 %
  • oxynitrotriazole : 40 %
  • 2-nitrodiphénylamine (stabilisant) : 2 %
The triple base powder with the following composition was produced according to a solvent process:
  • nitrocellulose: 28%
  • nitroglycerin: 30%
  • oxynitrotriazole: 40%
  • 2-nitrodiphenylamine (stabilizer): 2%

Le couple de solvant utilisé est l'acétone-éthanol dans le rapport massique 50/50 et le taux d'arrosage est de 70 % par rapport à la nitrocellulose sèche.The solvent couple used is acetone-ethanol in the 50/50 mass ratio and the watering rate is 70% compared to dry nitrocellulose.

Après malaxage 2h à 20° C la pâte est extrudée à travers une filière tubulaire (Diamètre extérieur D = 3 mm et diamètre de la broche d = 0,6 mm) puis la poudre est essorée 24h à la température ambiante puis séchée 24h à 50° C.After kneading for 2 hours at 20 ° C. the paste is extruded through a tubular die (outside diameter D = 3 mm and diameter of the spindle d = 0.6 mm) then the powder is wrung 24 hours at room temperature and then dried 24 hours at 50 ° C.

La poudre triple base monotubulaire obtenue ne montre pas de sensibilité particulière. Elle présente une sensibilité à la friction de 309 N, un amorçage par une étincelle électrique supérieure à 726 mJ et un amorçage aux décharges capacitives en milieu confiné supérieur à 15,6 J.The triple base monotubular powder obtained does not show any particular sensitivity. It has a sensitivity to friction of 309 N, ignition by an electric spark greater than 726 mJ and ignition by capacitive discharges in a confined environment greater than 15.6 J.

Ses caractéristiques physico-chimiques sont les suivantes :

  • eau : 0,047 %
  • éthanol : < 0,05 %
  • acétone : < 0,05 %
  • masse volumique réelle (pycnomètre à gaz) : 1,640 g/cm3
  • (valeur théorique 1,718 g/cm3)
Its physico-chemical characteristics are as follows:
  • water: 0.047%
  • ethanol: <0.05%
  • acetone: <0.05%
  • actual density (gas pycnometer): 1,640 g / cm 3
  • (theoretical value 1.718 g / cm 3 )

Les dimensions de la poudre après finition sont les suivantes : longueur (L) : 3,87 mm ; Diamètre externe (D) : 3,31 mm ; Diamètre du trou (d) : 0,56 mm ; Epaisseur de poudre (Web) : 1,38 mm.The dimensions of the powder after finishing are as follows: length (L): 3.87 mm; External diameter (D): 3.31 mm; Hole diameter (d): 0.56 mm; Powder thickness (Web): 1.38 mm.

Des tirs en bombe manométrique de 200 cm3 à plusieurs densités de chargement (0,12 ; 0,15 ; 0,18 ; 0,20 et 0,23 g/cm3) ont permis de déterminer la courbe de vitesse de combustion. Celle-ci est bien régulière. On relève une vitesse de 110 mm/s à 100 MPa.Firing in a 200 cm 3 gauge bomb at several loading densities (0.12; 0.15; 0.18; 0.20 and 0.23 g / cm 3 ) made it possible to determine the combustion speed curve. It is very regular. There is a speed of 110 mm / s at 100 MPa.

La température de flamme est faible (3600 K) comparativement à celle d'une poudre double base nitrocellulose nitroglycérine 60/40 (3900 K environ) alors que la force volumique est voisine. Elle est toutefois supérieure à celle d'une poudre triple base à la nitroguanidine (3000 K environ). La force théorique (1,15 MJ/kg) est par contre supérieure à celle d'une poudre triple base à la nitroguanidine (1,08 MJ/kg) mais légèrement inférieure à celle d'une double base (1,19 MJ/kg).The flame temperature is low (3600 K) compared to that of a double base nitrocellulose nitroglycerine 60/40 powder (about 3900 K) while the density is close. It is, however, superior to that of a triple base powder with nitroguanidine (around 3000 K). The theoretical strength (1.15 MJ / kg) is on the other hand greater than that of a triple base powder with nitroguanidine (1.08 MJ / kg) but slightly less than that of a double base (1.19 MJ / kg).

Exemple 15 - Poudre à liant inerte pour armesEXAMPLE 15 Inert Binder Powder for Weapons

La poudre réalisée se présente sous forme de grains cylindriques comportant 7 canaux parallèles à l'axe des grains. Elle est utilisée pour les munitions de gros calibres.The powder produced is in the form of cylindrical grains having 7 channels parallel to the axis of the grains. It is used for large caliber ammunition.

Sa composition centésimale en poids est la suivante :

Figure imgb0010
Its percentage composition by weight is as follows:
Figure imgb0010

Pour la réaliser, on homogénéise tout d'abord dans un malaxeur, à 60° C sous pression réduite, le mélange des divers ingrédients de la composition, à l'exception de l'isocyanate. On ajoute alors une partie de l'isocyanate de façon à ce que le rapport NCO/OH soit de 0,72. Après homogénéisation, on préréticule la pâte à 60° C pendant 5 jours, puis on l'introduit dans un malaxeur extrudeur. On ajoute alors le reste de l'isocyanate puis on extrude la pâte au travers d'une filière présentant la géométrie finale recherchée de la poudre.To achieve this, the mixture of the various ingredients of the composition, except for the isocyanate, is firstly homogenized in a kneader, at 60 ° C. under reduced pressure. Part of the isocyanate is then added so that the NCO / OH ratio is 0.72. After homogenization, the dough is pre-crosslinked at 60 ° C for 5 days, then it is introduced into an extruder mixer. The remainder of the isocyanate is then added and the paste is extruded through a die having the desired final geometry of the powder.

Les brins obtenus sont ensuite chauffés à 60° C pendant 2 jours, puis découpés en grains.The strands obtained are then heated at 60 ° C for 2 days, then cut into grains.

Les dimensions des grains obtenus sont les suivantes :

  • L : 8,1 mm D : 5,4 mm d : 0,6 mm Web : 0,9 mm
  • Sa masse volumique mesurée est de 1,52 g/cm3.
The dimensions of the grains obtained are as follows:
  • L: 8.1 mm D: 5.4 mm d: 0.6 mm Web: 0.9 mm
  • Its density measured is 1.52 g / cm 3 .

Des tirs en bombe manométrique ont permis de mesurer une vitesse de combustion de 40 mm/s à 100 MPa et une force de 0,97 MJ/kg.Manometric bombs were used to measure a combustion speed of 40 mm / s at 100 MPa and a force of 0.97 MJ / kg.

La température de flamme est de 2211 K.The flame temperature is 2211 K.

Comparativement à la même poudre constituée du même liant, à la même teneur, mais chargée uniquement à l'hexogène (au lieu d'un mélange hexogène-oxynitrotriazole) la poudre contenant l'oxynitrotriazole selon l'invention possède une température de flamme plus faible (2211 K au lieu de 2430 K) et une concentration de gaz réducteurs tels que H2 et CO plus faible.Compared to the same powder consisting of the same binder, at the same content, but loaded only with hexogen (instead of a hexogen-oxynitrotriazole mixture), the powder containing the oxynitrotriazole according to the invention has a lower flame temperature. (2211 K instead of 2430 K) and a lower concentration of reducing gases such as H 2 and CO.

Exemple 16 - Propergol compositeEXAMPLE 16 Composite Propellant

On a réalisé un propergol composite générateur de gaz constitué de 81 % en poids d'oxynitrotriazole et de 19 % en poids d'un liant polyuréthanne. Les constituants de base de ce liant sont le polybutadiène hydroxylé R45M et le méthylènedicyclohexyldiisocyanate. Ce liant contient également un plastifiant (azélate de dioctyle), un antioxydant (ionol) et de la lécithine. Ce propergol composite a été réalisé selon la méthode classique dite "globale" ou de "coulée" en utilisant un rapport NCO/OH de 1.A gas-generating composite propellant consisting of 81% by weight of oxynitrotriazole and 19% by weight of a polyurethane binder was produced. The basic constituents of this binder are hydroxylated polybutadiene R45M and methylenedicyclohexyldiisocyanate. This binder also contains a plasticizer (dioctyl azelate), an antioxidant (ionol) and lecithin. This composite propellant was produced according to the conventional so-called "global" or "casting" method using an NCO / OH ratio of 1.

Sa masse volumique mesurée est de 1,59 g/cm3 et ses propriétés mécaniques sont satisfaisantes. La température de flamme est 1365 K. On a réalisé la combustion au Strand-Burner de ce propergol. La vitesse de combustion (Vc) est de 1,9 mm/s à 7 MPa et les coefficients a et n de la loi Vc : aPn sont a = 0,67 et n = 0,53.Its measured density is 1.59 g / cm 3 and its mechanical properties are satisfactory. The flame temperature is 1365 K. The propellant was burnt with a Strand-Burner. The combustion speed (Vc) is 1.9 mm / s at 7 MPa and the coefficients a and n of the law Vc: aP n are a = 0.67 and n = 0.53.

Claims (21)

1. Utilisation du 5-oxo 3-nitro 1,2,4-triazole comme explosif secondaire.1. Use of 5-oxo 3-nitro 1,2,4-triazole as a secondary explosive. 2. Composition pyrotechnique caractérisée en ce qu'elle contient du 5-oxo 3-nitro 1,2,4-triazole.2. Pyrotechnic composition characterized in that it contains 5-oxo 3-nitro 1,2,4-triazole. 3. Composition pyrotechnique selon la revendication 2 caractérisée en ce qu'il s'agit d'une composition explosive.3. Pyrotechnic composition according to claim 2 characterized in that it is an explosive composition. 4. Composition pyrotechnique selon la revendication 3 caractérisée en ce qu'il s'agit d'une composition explosive à liant plastique mise en oeuvre par compression.4. Pyrotechnic composition according to claim 3 characterized in that it is an explosive composition with plastic binder implemented by compression. 5. Composition pyrotechnique selon la revendication 3 caractérisée en ce qu'il s'agit d'une composition explosive composite à liant plastique mise en oeuvre par coulée.5. Pyrotechnic composition according to claim 3 characterized in that it is a composite explosive composition with plastic binder used by casting. 6. Composition pyrotechnique selon l'une quelconque des revendications 3 à 5 caractérisée en ce qu'elle ne contient pas d'autre explosif secondaire que le 5-oxo 3-nitro 1,2,4-triazole.6. Pyrotechnic composition according to any one of claims 3 to 5 characterized in that it does not contain any secondary explosive other than 5-oxo 3-nitro 1,2,4-triazole. 7. Composition pyrotechnique selon l'une quelconque des revendications 3 à 5 caractérisée en ce qu'elle contient au moins un autre explosif secondaire que le 5-oxo 3-nitro 1,2,4-triazole.7. Pyrotechnic composition according to any one of claims 3 to 5 characterized in that it contains at least one other secondary explosive than 5-oxo 3-nitro 1,2,4-triazole. 8. Composition pyrotechnique selon l'une quelconque des revendications 4 et 5 caractérisée en ce qu'elle contient au moins un explosif secondaire choisi dans le groupe formé par l'octogène et l'hexogène.8. Pyrotechnic composition according to any one of claims 4 and 5 characterized in that it contains at least one secondary explosive selected from the group formed by octogen and hexogen. 9. Composition pyrotechnique selon la revendication 4 caractérisée en ce que le liant plastique est choisi dans le groupe constitué par les liants fluorés, les liants polyuréthannes et les liants polyesters.9. Pyrotechnic composition according to claim 4 characterized in that the plastic binder is chosen from the group consisting of fluorinated binders, polyurethane binders and polyester binders. 10. Composition pyrotechnique selon la revendication 5 caractérisée en ce que le liant est un liant polyuréthanne et en ce que la teneur pondérale du liant dans la composition explosive est comprise entre 12 et 20 %.10. Pyrotechnic composition according to claim 5 characterized in that the binder is a polyurethane binder and in that the weight content of the binder in the explosive composition is between 12 and 20%. 11. Composition pyrotechnique selon la revendication 3 caractérisée en ce qu'il s'agit d'une composition à base de tolite mise en oeuvre à partir de tolite fondue.11. Pyrotechnic composition according to claim 3 characterized in that it is a tolite-based composition used from molten tolite. 12. Composition pyrotechnique selon la revendication 11 caractérisée en ce que la teneur pondérale en 5-oxo 3-nitro 1,2,4-triazole dans la composition est comprise entre 50 et 90 %.12. Pyrotechnic composition according to claim 11 characterized in that the weight content of 5-oxo 3-nitro 1,2,4-triazole in the composition is between 50 and 90%. 13. Composition pyrotechnique selon la revendication 2 caractérisée en ce qu'il s'agit d'une poudre pour armes.13. Pyrotechnic composition according to claim 2 characterized in that it is a powder for weapons. 14. Composition pyrotechnique selon la revendication 13 caractérisée en ce qu'il s'agit d'une poudre triple base dont les 3 bases sont la nitrocellulose, la nitroglycérine et le 5-oxo 3-nitro 1,2,4-triazole.14. Pyrotechnic composition according to claim 13 characterized in that it is a triple base powder whose 3 bases are nitrocellulose, nitroglycerin and 5-oxo 3-nitro 1,2,4-triazole. 15. Composition pyrotechnique selon la revendication 13 caractérisée en ce qu'il s'agit d'une poudre composite à liant inerte.15. Pyrotechnic composition according to claim 13 characterized in that it is a composite powder with inert binder. 16. Composition pyrotechnique selon la revendication 15 caractérisée en ce qu'elle contient au moins un explosif secondaire choisi dans le groupe constitué par l'hexogène, l'octogène et la pentrite.16. Pyrotechnic composition according to claim 15 characterized in that it contains at least one secondary explosive selected from the group consisting of hexogen, octogen and pentrite. 17. Composition pyrotechnique selon l'une quelconque des revendications 15 et 16 caractérisée en ce que le liant inerte est un liant polyuréthanne.17. Pyrotechnic composition according to any one of claims 15 and 16 characterized in that the inert binder is a polyurethane binder. 18. Composition pyrotechnique selon l'une quelconque des revendications 15 à 17 caractérisée en ce que le taux de liant est de l'ordre de 20 %.18. Pyrotechnic composition according to any one of claims 15 to 17 characterized in that the binder content is of the order of 20%. 19. Composition pyrotechnique selon la revendication 2 caractérisée en ce qu'il s'agit d'un propergol composite.19. Pyrotechnic composition according to claim 2 characterized in that it is a composite propellant. 20. Composition pyrotechnique selon la revendication 19 caractérisée en ce qu'elle contient environ 20 % en poids d'un liant polyuréthanne et environ 80 % en poids de 5-oxo 3-nitro 1,2,4-triazole.20. Pyrotechnic composition according to claim 19 characterized in that it contains approximately 20% by weight of a polyurethane binder and approximately 80% by weight of 5-oxo 3-nitro 1,2,4-triazole. 21. Composition pyrotechnique selon la revendication 19 caractérisée en ce qu'elle contient un liant polyuréthanne et au moins un autre explosif secondaire que le 5-oxo 3-nitro 1,2,4-triazole choisi dans le groupe formé par l'hexogène et l'octogène.21. Pyrotechnic composition according to claim 19 characterized in that it contains a polyurethane binder and at least one other secondary explosive than 5-oxo 3-nitro 1,2,4-triazole chosen from the group formed by hexogen and octogen.
EP86401282A 1985-06-28 1986-06-13 Use of 5-oxo-3-nitro-1,2,4-triazole as a secondary explosive and pyrotechnical compositions comprising 5-oxo-3-nitro-1,2,4-triazole Expired EP0210881B1 (en)

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FR8509885A FR2584066B1 (en) 1985-06-28 1985-06-28 USE OF 5-OXO 3-NITRO, 1,2,4-TRIAZOLE AS AN EXPLOSIVE SUBSTANCE AND PYROTECHNIC COMPOSITIONS CONTAINING 5-OXO 3-NITRO 1,2,4-TRIAZOLE.

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WO2011086246A1 (en) 2009-12-23 2011-07-21 Nexter Munitions Fusible/castable explosive composition having low vulnerability
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US5112983A (en) * 1987-09-28 1992-05-12 Olin Corporation Process for producing 1,2,4-triazol-5-one using organic sulfonic acids and polymers thereof as a catalyst
DE3917228A1 (en) * 1988-05-27 1989-12-07 Olin Corp METHOD FOR PRODUCING 3-NITRO-1,2,4-TRIAZOL-5-ON
US4927940A (en) * 1989-05-01 1990-05-22 Olin Corporation Process for low chloride 1,2,4-triazol-5-one
EP0430463A3 (en) * 1989-11-20 1991-10-23 Morton International, Inc. Gas generating compositions containing nitrotriazalone
US5039816A (en) * 1990-08-27 1991-08-13 Olin Corporation Process for the production of 1,2,4-triazol-5-one
EP0546041A4 (en) * 1990-08-27 1993-07-07 Olin Corporation Process for the production of 1,2,4-triazol-5-one
WO1994006779A1 (en) * 1992-09-21 1994-03-31 Dynamit Nobel Aktiengesellschaft Nitrotriazolone for detonation purposes
FR2738562A1 (en) * 1995-09-08 1997-03-14 Poudres & Explosifs Ste Nale Melt-flow explosives compositions with low sensitivity
WO1999035108A1 (en) * 1998-01-05 1999-07-15 Dynamit Nobel Gmbh Explosivstoff- Und Systemtechnik Propellant explosive
FR2801883A1 (en) * 1999-12-06 2001-06-08 Giat Ind Sa Low-sensitivity compressible explosive composition for use in medium caliber ammunition, comprising oxynitrotriazole, hexogen or octogen, aluminum powder and optionally graphite powder
WO2009039257A1 (en) * 2007-09-19 2009-03-26 Albemarle Corporation Methods for production of 1,2,4-triazol-3-one
US8178692B2 (en) 2007-09-19 2012-05-15 Albemarle Corporation Methods for production of 1,2,4-triazol-3-one
US8178691B2 (en) 2007-09-19 2012-05-15 Albemarle Corporation Methods for production of 1,2,4-triazol-3-one
WO2011086246A1 (en) 2009-12-23 2011-07-21 Nexter Munitions Fusible/castable explosive composition having low vulnerability
WO2014167226A1 (en) 2013-04-08 2014-10-16 Herakles Method for obtaining solutions of ota in a concentrated sulphuric acid medium; said solutions; and method for preparing onta
US9676733B2 (en) 2013-04-08 2017-06-13 Herakles Method for obtaining solutions of OTA in a concentrated sulfuric acid medium; said solutions; and method for preparing ONTA

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DE3666582D1 (en) 1989-11-30
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CA1304228C (en) 1992-06-30
US5034072A (en) 1991-07-23
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FR2584066B1 (en) 1987-08-07

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