EP3071536B1 - Composite pyrotechnical product with crosslinked binder and method for preparing same - Google Patents

Composite pyrotechnical product with crosslinked binder and method for preparing same Download PDF

Info

Publication number
EP3071536B1
EP3071536B1 EP14814912.3A EP14814912A EP3071536B1 EP 3071536 B1 EP3071536 B1 EP 3071536B1 EP 14814912 A EP14814912 A EP 14814912A EP 3071536 B1 EP3071536 B1 EP 3071536B1
Authority
EP
European Patent Office
Prior art keywords
charges
crosslinking
mol
gum
polyurethane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP14814912.3A
Other languages
German (de)
French (fr)
Other versions
EP3071536A1 (en
Inventor
Nancy Desgardin
Mathieu W. Werschine
Claire J. Franson
Philippe Ragon
Jean-Louis Paulin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eurenco SA
ArianeGroup SAS
Original Assignee
Eurenco SA
Eurenco France SA
Herakles SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eurenco SA, Eurenco France SA, Herakles SA filed Critical Eurenco SA
Priority to PL14814912T priority Critical patent/PL3071536T3/en
Publication of EP3071536A1 publication Critical patent/EP3071536A1/en
Application granted granted Critical
Publication of EP3071536B1 publication Critical patent/EP3071536B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
    • C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
    • C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
    • C06B45/105—The resin being a polymer bearing energetic groups or containing a soluble organic explosive
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0008—Compounding the ingredient
    • C06B21/0025—Compounding the ingredient the ingredient being a polymer bonded explosive or thermic component

Definitions

  • the present invention relates to composite pyrotechnic products, particularly suitable as propellant powders for tube weapons (more particularly for tank artillery). These are composite pyrotechnic products, which contain a high level of energy charges in an energy crosslinked binder. These products are particularly interesting, especially in terms of strength (of energy power), vulnerability (see below a reminder on this concept, familiar to the skilled person), and scope of application as to the nature of loads that they can contain. They can opportunely be optimized in terms of erosivity.
  • the present invention also relates to a process for preparing said composite pyrotechnic products. Said method is of a particularly easy implementation. It does not require a solvent or precipitation to carry out a shaping while the crosslinking begins, nor pre-crosslinking step.
  • Known propellant powders known “homogeneous” consisting of one or more gelatinized energy bases having a homogeneous appearance (hence their name).
  • homogeneous propellant powders consisting of "smoke-free" powders based on nitrocellulose alone or based on a nitrocellulose-nitroglycerine mixture.
  • organic (powdery) energy charges In order to improve the energy performance of these "homogeneous" powders, it has been sought to incorporate organic (powdery) energy charges. These charged powders no longer have a homogeneous appearance, but a heterogeneous appearance in which we distinguish on the one hand, the energy binder and on the other hand, the charges.
  • Such charged powders are said “Composite” or “heterogeneous”. Such charged powders are for example described in the French patent application FR 2,488,246 .
  • Vulnerability is defined as the property that powders can be able to ignite and deflag under the effect of a physical, random, undesired phenomenon, such as the impact of a projectile. Vulnerability is a major defect for powders intended to be loaded on board battle tanks. The development of modern combat gear has therefore led the skilled person to look for propellant powders that are not very vulnerable.
  • inert binder composite powders consisting mainly of organic energy charges in a synthetic resin.
  • Such powders are much less vulnerable than homogeneous powders or composites with energy binders (nitrocellulose).
  • energy binders nitrocellulose.
  • these powders must, in order to deliver the necessary energy during firing, contain very high levels of charges, often close to 80% of the total mass of the powder.
  • the inert binder composite powders thus have the characteristic of containing very little binder with respect to their powdery filler.
  • the precursor mixtures of these powders must, however, be able to be worked (in particular being able to be calendered or spun through a die of relatively small diameter, most often including pins intended to create the channels present in the final strand of powder), and the powders must keep their geometric shape in time. It is particularly with reference to obtaining these composite propellant powders with inert binder for tube weapons that the skilled person has encountered and still faces serious difficulties.
  • Inert binders of synthetic origin which can be used in the preparation of composite pyrotechnic products and present in their composition, exist as thermoplastic binders and as heat-curable binders (obtained from oligomers).
  • thermoplastic binders allow, in theory, temperature, a mechanical work of the product to give it the desired geometry. It should, however, of course, that the working temperature (to which the binder is deformable) is compatible with the stability of the present charges and, with reference to this unavoidable requirement, it is often necessary to involve a solvent. The intervention of such a solvent increases the implementation of the process.
  • EP 0 036 481 discloses a method of manufacturing composite explosives with thermoplastic binder.
  • the patent application IN 498 / DEL / 2001 discloses a method of preparing propellant containing hexogen (RDX) fillers in a thermoplastic binder.
  • RDX hexogen
  • thermosetting binders obtained from oligomers
  • polyurethane binders crosslinkable
  • the dosages of the crosslinking agent (diisocyanate) for carrying out the pre-crosslinking are delicate. They require great precision.
  • the field of application of said technique is limited, in view of the nature of the intervening crosslinking agent (of isocyanate type, to react with hydroxyl functions), as to the nature of the energy charges present, in the extent where certain charges energy (having intrinsic acidity) are likely to react, in a parasitic reaction, with said crosslinking agent (isocyanate type) present.
  • the presence of such fillers (EDNA, nitropyrazoles, for example) is therefore problematic for managing the steps of pre-crosslinking and complementary crosslinking.
  • the inventors propose new composite pyrotechnic products, particularly suitable as propellant powders for tube weapons, containing a high level of charges in a crosslinked energetic binder.
  • Said new composite pyrotechnic products are optimized in terms of strength (they contain a high energy charge rate in an energy binder), vulnerability (they do not contain nitrocellulose and may advantageously contain energy charges that are not very vulnerable), process obtaining (said method is easy to implement: without solvent, without precipitation for the implementation of a shaping while the crosslinking begins, without pre-crosslinking) and they can also be optimized in terms of erosivity ( they can advantageously contain EDNA charges as a total or partial substitution of RDX charges).
  • the composite pyrotechnic products of the invention therefore contain a high level of organic energy charges: from 78 to 90% by weight, advantageously from 80 to 86% by weight.
  • RDX hexogen
  • HMX octogen
  • NGU nitroguanidine
  • EDNA ethylene dinitramine
  • GUDN dinitramide N-guanylurea
  • 1,1-diamino-2,2-dinitroethylene FOX 7 (DADE)
  • TAGZT triaminoguanidinium
  • DHDZT dihydrazinium 5,5'-azotetrazolate
  • HBT bis (2,2-dinitropropyl) nitramine
  • BDNPN 2,2-dinitropropyl) nitramine
  • organic energetic charges of EDNA particularly preferably, there is a mixture of EDNA charges and RDX charges. It is by no means excluded to find only RDX loads or EDNA loads, but as noted above, mixes of EDNA loads and RDX loads can achieve an optimum in reference to the strength tradeoff. / erosivity. It is understood that the more these mixtures contain RDX, the more they are energetic but the more they are erosive.
  • the energy charges are in the form of solid grains, distributed homogeneously within the crosslinked binder. These solid grains suitably have, in a known manner per se, several particle size distributions.
  • the binder It is present in a proportion of 10 to 22% by weight; these 10 to 22% by weight including 1 to 5% of gum.
  • thermoset binder crosslinked in the presence of a gum, obtained from a thermosetting polymer (crosslinkable) in the presence of a gum. It is such a binder, energetic, obtained from such a polymer, energetic.
  • one polymer must read “at least one polymer” throughout the present text. Indeed, it is not excluded from the scope of the invention that a mixture of at least two polymers (each of the type indicated and having different molecular weights and / or branching ratios) is used.
  • the energy polymer in question is a glycidyl polyazide (PAG).
  • Mn number-average molecular weight
  • Said polymer is a polyazide, hence 1) its energetic properties and 2) its ability to be crosslinked with crosslinking agents other than isocyanates.
  • crosslinking only involves 8 to 12% of its azide functions (such a low level of crosslinking, used on the polymer having the above molecular weight, makes it possible to obtain the final product with suitable mechanical properties) .
  • Said crosslinked polymer thus retains its energetic properties.
  • the binder of the composite pyrotechnic products of the invention is therefore, as indicated above, an energy binder.
  • the force of said composite pyrotechnic products of the invention is better understood (containing a high level of energetic charges in an energy (crosslinked) binder).
  • the crosslinked binder of the invention is thus obtained by crosslinking a pre-polymer, as specified above, with at least one crosslinking agent containing alkyne functions, ie via triazole ball joints of formula:
  • the at least one crosslinking agent used is a compound containing at least two propargyl functions in its chemical formula ("a polypropargyl"), it generally consists of a di- and / or tri-propargyl.
  • a polypropargyl generally consists of dipropargyl succinate (DPS), dipropargyl maleate (DPM), tripropargyl tricarballylate (TCATP), benzene tripropargyl ester (BETP), and a dipropargyl poly (ethylene glycol) (PEG). having a number average molecular weight of between 200 and 1500 g / mol.
  • DPS dipropargyl succinate
  • DPM dipropargyl maleate
  • TCATP tripropargyl tricarballylate
  • BETP benzene tripropargyl ester
  • PEG dipropargyl poly (ethylene glycol)
  • PEG dipropargyl poly (ethylene glycol)
  • Such a rubber is perfectly suitable for the purposes of the invention, insofar as it allows shaping of the mixture to be crosslinked at a temperature below 100 ° C. (which is entirely compatible with the present charges), and this, without any use of solvent, without precipitation (for the implementation of said shaping while the crosslinking begins) and without any pre-crosslinking.
  • Said gum is miscible with the polymer (PAG) (the gum / polymer mixture is "stable", no exudation phenomenon is observed). It performs its (beneficial) action by being present in small quantities (it represents at most 5% of the total mass of the product): its presence is not too detrimental in reference to the strength of said products.
  • Said gum generally consists of a polyurethane-polyester gum or a polyurethane-polyether, but mixtures of at least two gums (at least two polyurethane-polyester gums, at least two polyurethane-polyether gums or at least one polyurethane-polyester gum and at least one polyurethane-polyether gum, such gum mixtures (gums within the meaning of the invention) constituting a gum within the meaning of the invention) having the required properties (mentioned above) may be used.
  • Said gum advantageously consists of a polyurethane-polyester gum.
  • This gum therefore intervenes upstream of the crosslinking process, upstream of the forming step, as a manufacturing aid. It is this which makes it possible to confer, without danger, on the polymer charged, due to its properties (sufficient molecular mass and adequate viscosity), the mechanical and cohesion required. It is this which allows the easy preparation, without solvent, without precipitation (for the implementation of a shaping while the crosslinking begins) and without pre-crosslinking, composite pyrotechnic products of the invention. It acts at suitable temperatures (below 100 ° C) as a thickener and cohesive agent of said charged polymer. Said gum, auxiliary manufacturing, intervening upstream of any crosslinking, makes it possible, easy, the manufacture of composite pyrotechnic products of the invention. In the end, it is entangled in the cross-linked polymer network (PAG).
  • a composite pyrotechnic product so the composition contains a polymeric gum is described in the patent US3026672 .
  • the crosslinked binder is therefore the product resulting from the reaction, between the polymer (PAG) and the at least one crosslinking agent, used in the presence of the compound and that it therefore contains , in addition to said crosslinked polymer via triazole patches, said gum.
  • composition of the composite pyrotechnic products of the invention is therefore essentially composed of energy charges and crosslinked binder (containing said gum). It may consist of 100% by mass of said energy charges and said crosslinked binder (containing said gum). It is generally at least 95% by weight, more generally at least 98% by weight. It can not be excluded that it contains in addition at least one other additive; said gum, present in small quantities, which can rightly be considered as an additive: it is not an essential constituent of the binder, it is a manufacturing aid whose intervention allows a simple obtaining of the desired product (according to the method described further in the present text). Such at least one other additive, when present, is generally at a level of 0.1 to 5% by weight, more generally at 0.1 to 2% by weight. It may especially be at least one other additive, chosen from the agents of implementation (candelilla wax and / or paraffin), the plasticizers (energetic or not) and the stabilizers.
  • the composite pyrotechnic products of the invention are perfectly suitable as propellant powder for tube weapons. Said composite pyrotechnic products of the invention therefore advantageously consist of such powders.
  • the composite pyrotechnic products of the invention, as described above, are also suitable, in particular, as tactical propellant, explosive composition and gas generator.
  • Said method therefore comprises the provision of the constituent (essential) ingredients of the desired composite pyrotechnic products: the fillers + the elements from which the crosslinked binder is obtained, i.e. the polymer, the at least one crosslinking agent and the gum. It has been indicated that the fillers represent between 78 and 90% of the mass of the desired product while the crosslinked binder represents between 10 and 22%, said 10 to 22% including the 1 to 5% of said gum (the complement of said 1 to 5% corresponding to the product of the reaction of the polymer and the at least one crosslinking agent).
  • Said at least one crosslinking agent intervenes in the appropriate amount to cross-link the 8 to 12% of the azide functions of the polymer; it generally occurs at less than 5% by weight (more generally between 0.5% and 4%) of the reaction mixture. It is recalled here incidentally that additives, other than said gum, are likely to occur.
  • a pasty mixture is thus produced, the precursor of the final product. (crosslinked) targeted.
  • a pasty mixture is advantageously made by twin-screw (extrusion) or twin-cylinder, depending on the quantities to be used. It is generally carried out at a temperature between 15 ° C and 45 ° C. It can therefore be performed at room temperature or at a temperature above room temperature. In any case, the intervention of the rubber provides said pasty mixture, which can be manipulated and shaped.
  • At least one element is prepared in the third step of the process of the invention (generally n elements are prepared) to a desired shape (directly that desired for the final product (s). (final) or an "intermediate” form from which is obtained after crosslinking (and generally cutting), said (s) product (s) final (s) to the desired shape).
  • Said third step is therefore analyzed as a step of shaping the dough.
  • This formatting can include spinning or calendering. At the end of such spinning (used in a press pot, having an outlet orifice of greater or lesser diameter), a spun product is obtained. This spun product is generally heat treated for crosslinking and then cut into strands (at the desired length).
  • Such strands suitable as propellant powders for tube weapons, generally have a length of 2 to 20 mm, for a diameter of 1 to 20 mm (more generally for a diameter of 2 to 15 mm). However, it is not excluded to cut the spun product (thus non-crosslinked strands) and crosslink said strands.
  • the calendered product in the form of a plate (such a plate generally has a thickness of 10 to 20 mm), can be directly cut into platelets or heat treated for crosslinking and then cut into platelets.
  • the pasty mixture, shaped to the desired shape for the final product or an intermediate form, is then heat-treated.
  • the heat treatment must make it possible to ensure the expected result (the crosslinking of the polymer) at a non-excessive temperature (compatible with the presence of energy charges at a high rate). Generally, said temperature is above 45 ° C and remains below 80 ° C.
  • the crosslinking is carried out at 55 ° C. (+/- 5 ° C.).
  • Said at least one thermally treated element corresponds to the at least one product of the invention sought or enables it to be obtained, generally by cutting.
  • EDNA ethylene dinitramine
  • the medium was stirred for 30 minutes at room temperature.
  • the mixture was poured on a bath of cold water at about 5 ° C. with stirring.
  • the solid was then separated from the mother liquors by filtration, and washed several times with distilled water to neutral pH and then filtered off. It was then taken up, wet, for the synthesis of EDNA.
  • the decarboxylation step was carried out by adding DNEU to an aqueous solution buffered with hot sodium acetate. Gaseous evolution (of CO 2 ) was observed, which required a fractional introduction of the powder.
  • the reaction medium was then cooled so that the EDNA precipitated.
  • the suspension was then filtered and dried. A yield of 85% was obtained.
  • Crosslinking agent propargyl polyethylene glycol with a molecular weight of 1,000 g / mol (dipropargyl PEG 1000)
  • PEG-1000 50 g was first introduced; it was then heated to a temperature of 45-50 ° C to be stirred. Then 40% by weight sodium hydroxide (6 g) was added and then propargyl bromide, in 80% by weight solution in toluene (13.36 ml, 0.12 mol), with stirring, dropwise at room temperature. drop. The medium was brought to 65 ° C. over a period of 36 hours. At the end of the reaction, 150 ml of dichloromethane were added to the medium, brought to room temperature. The resulting medium was then washed with water until a pH equal to 7 of the washings. The organic solution was then dried and the solvent evaporated.
  • the recovered product (35 g) was in the form of a wax.
  • Step b of the process of the invention the pasty mixtures were obtained by twin-cylinder, in a known manner per se.
  • the gum was first introduced between the rolls of the bi-roll (rolling mill), brought to a temperature of 38 ° C. It has been softened. Then, a mixture + PAG charges (previously made in a container) was added. To the resulting mixture, the candelilla wax (processing agent) and then the crosslinking agent (in a ratio -C ⁇ CH / -N 3 equal to 10) were then successively added.
  • Step c of the process of the invention the pasty mixtures obtained were introduced into a press pot heated to 38 ° C to perform a spinning at a pressure of between 180 and 220 bar.
  • Step d of the process of the invention the heat treatment of the spun product was carried out at 50 ° C for 5 days. After cutting (crosslinked spun product), strands of powder (diameter: 10 mm, length: 11 mm) were obtained.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Molecular Biology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

La présente invention concerne des produits pyrotechniques composites, convenant notamment comme poudres propulsives pour armes à tube (plus particulièrement pour l'artillerie de chars). Il s'agit de produits pyrotechniques composites, renfermant un fort taux de charges énergétiques dans un liant réticulé énergétique. Lesdits produits sont particulièrement intéressants, notamment en termes de force (de pouvoir énergétique), de vulnérabilité (voir ci-après un rappel sur cette notion, familière à l'homme du métier), et de champ d'application quant à la nature des charges qu'ils peuvent renfermer. Ils peuvent opportunément être optimisés en terme d'érosivité.The present invention relates to composite pyrotechnic products, particularly suitable as propellant powders for tube weapons (more particularly for tank artillery). These are composite pyrotechnic products, which contain a high level of energy charges in an energy crosslinked binder. These products are particularly interesting, especially in terms of strength (of energy power), vulnerability (see below a reminder on this concept, familiar to the skilled person), and scope of application as to the nature of loads that they can contain. They can opportunely be optimized in terms of erosivity.

La présente invention a également pour objet un procédé de préparation desdits produits pyrotechniques composites. Ledit procédé est d'une mise en oeuvre particulièrement aisée. Il ne requiert ni solvant, ni précipitation pour la mise en oeuvre d'une mise en forme alors que la réticulation commence, ni étape de pré-réticulation.The present invention also relates to a process for preparing said composite pyrotechnic products. Said method is of a particularly easy implementation. It does not require a solvent or precipitation to carry out a shaping while the crosslinking begins, nor pre-crosslinking step.

On connait les poudres propulsives dites « homogènes » constituées par une ou plusieurs bases énergétiques gélatinisées présentant un aspect homogène (d'où leur nom). Parmi les poudres propulsives homogènes les plus connues, on peut citer les poudres "sans fumées" à base de nitrocellulose seule ou à base d'un mélange nitrocellulose-nitroglycérine. En vue d'améliorer les performances énergétiques de ces poudres « homogènes », on a cherché à y incorporer des charges énergétiques organiques (pulvérulentes). Ces poudres chargées ne présentent plus un aspect homogène, mais un aspect hétérogène dans lequel on distingue d'une part, le liant énergétique et d'autre part, les charges. De telles poudres chargées sont dites « composites » ou « hétérogènes ». De telles poudres chargées sont par exemple décrites dans la demande de brevet français FR 2 488 246 .Known propellant powders known "homogeneous" consisting of one or more gelatinized energy bases having a homogeneous appearance (hence their name). Among the most well-known homogeneous propellant powders, mention may be made of "smoke-free" powders based on nitrocellulose alone or based on a nitrocellulose-nitroglycerine mixture. In order to improve the energy performance of these "homogeneous" powders, it has been sought to incorporate organic (powdery) energy charges. These charged powders no longer have a homogeneous appearance, but a heterogeneous appearance in which we distinguish on the one hand, the energy binder and on the other hand, the charges. Such charged powders are said "Composite" or "heterogeneous". Such charged powders are for example described in the French patent application FR 2,488,246 .

L'emploi du liant énergétique nitrocellulose présente cependant l'inconvénient de rendre ces poudres vulnérables. On entend par vulnérabilité la propriété que présentent des poudres de pouvoir s'allumer et déflagrer sous l'effet d'un phénomène physique, aléatoire, non désiré, comme par exemple l'impact d'un projectile. La vulnérabilité est un défaut majeur pour les poudres destinées à être embarquées à bord des chars de combat. Le développement des engins modernes de combat a donc amené l'homme du métier à rechercher des poudres propulsives peu vulnérables.However, the use of nitrocellulose energy binder has the disadvantage of making these powders vulnerable. Vulnerability is defined as the property that powders can be able to ignite and deflag under the effect of a physical, random, undesired phenomenon, such as the impact of a projectile. Vulnerability is a major defect for powders intended to be loaded on board battle tanks. The development of modern combat gear has therefore led the skilled person to look for propellant powders that are not very vulnerable.

Dans cet esprit, il a été proposé des poudres composites à liant inerte (constituées principalement de charges énergétiques organiques dans une résine synthétique). De telles poudres sont nettement moins vulnérables que les poudres homogènes ou composites à liant énergétique (nitrocellulose). Mais, du fait qu'elles contiennent un liant inerte, ces poudres doivent, pour délivrer lors de la mise à feu l'énergie nécessaire, renfermer des taux de charges très élevés, souvent voisins de 80 % de la masse totale de la poudre. Les poudres composites à liant inerte présentent ainsi la caractéristique de contenir très peu de liant par rapport à leur charge pulvérulente. Les mélanges précurseurs de ces poudres doivent toutefois pouvoir être travaillés (notamment pouvoir être calandrés ou filés à travers une filière de diamètre relativement petit, comportant le plus souvent des broches destinées à créer les canaux présents dans le brin de poudre final), et les poudres doivent conserver leur forme géométrique dans le temps. C'est particulièrement en référence à l'obtention de ces poudres propulsives composites à liant inerte pour armes à tube que l'homme de métier a rencontré et rencontre encore de sérieuses difficultés.In this spirit, it has been proposed inert binder composite powders (consisting mainly of organic energy charges in a synthetic resin). Such powders are much less vulnerable than homogeneous powders or composites with energy binders (nitrocellulose). However, because they contain an inert binder, these powders must, in order to deliver the necessary energy during firing, contain very high levels of charges, often close to 80% of the total mass of the powder. The inert binder composite powders thus have the characteristic of containing very little binder with respect to their powdery filler. The precursor mixtures of these powders must, however, be able to be worked (in particular being able to be calendered or spun through a die of relatively small diameter, most often including pins intended to create the channels present in the final strand of powder), and the powders must keep their geometric shape in time. It is particularly with reference to obtaining these composite propellant powders with inert binder for tube weapons that the skilled person has encountered and still faces serious difficulties.

Les liants inertes, d'origine synthétique, utilisables dans la préparation des produits pyrotechniques composites et présents dans leur composition, existent en tant que liants thermoplastiques et en tant que liants thermodurcissables (obtenus à partir d'oligomères).Inert binders of synthetic origin, which can be used in the preparation of composite pyrotechnic products and present in their composition, exist as thermoplastic binders and as heat-curable binders (obtained from oligomers).

C'est tout d'abord vers l'emploi de liants inertes thermoplastiques que s'est orienté l'homme du métier. En effet, de tels liants thermoplastiques permettent, en théorie, en température, un travail mécanique du produit pour lui conférer la géométrie voulue. Il convient toutefois, bien évidemment, que la température de travail (à laquelle le liant est déformable) soit compatible avec la stabilité des charges présentes et, en référence à cette exigence incontournable, il est souvent nécessaire de faire intervenir un solvant. L'intervention d'un tel solvant alourdit la mise en oeuvre du procédé. La demande de brevet EP 0 036 481 décrit un procédé de fabrication d'explosifs composites à liant thermoplastique. La demande de brevet IN 498/DEL/2001 décrit un procédé de préparation de propergol renfermant des charges d'hexogène (RDX) dans un liant thermoplastique. Les produits composites à liant thermoplastique ne donnent pas, en général, entière satisfaction, dans la mesure où leurs propriétés mécaniques sont trop sensibles aux variations thermiques.It is first of all towards the use of inert thermoplastic binders that the person skilled in the art has turned. Indeed, such thermoplastic binders allow, in theory, temperature, a mechanical work of the product to give it the desired geometry. It should, however, of course, that the working temperature (to which the binder is deformable) is compatible with the stability of the present charges and, with reference to this unavoidable requirement, it is often necessary to involve a solvent. The intervention of such a solvent increases the implementation of the process. The patent application EP 0 036 481 discloses a method of manufacturing composite explosives with thermoplastic binder. The patent application IN 498 / DEL / 2001 discloses a method of preparing propellant containing hexogen (RDX) fillers in a thermoplastic binder. Thermoplastic-bonded composite products do not, in general, give complete satisfaction, inasmuch as their mechanical properties are too sensitive to thermal variations.

L'homme du métier s'est alors orienté vers l'emploi de liants inertes thermodurcissables (obtenus à partir d'oligomères), comme les liants polyuréthannes (réticulables), permettant, après réticulation, de constituer un réseau tridimensionnel (dans lequel on trouve enrobées les charges), i.e. de figer définitivement la géométrie du grain de poudre (obtenu finalement). La fabrication à l'échelle industrielle de poudres (produits pyrotechniques composites en général) à liant inerte réticulé (essentiellement constituées donc d'un fort taux de charges dans une quantité minimale de liant) reste très difficile du fait d'une part des tenue mécanique et cohésion minimales requises du produit avant réticulation (pour sa mise en forme) et d'autre part de la durée de "vie de pot" limitée des résines thermodurcissables (on entend par "vie de pot" la période de démarrage de réticulation de la résine durant laquelle cette dernière peut être travaillée comme une matière plastique). De plus, bien évidement, la température de réticulation doit être compatible avec la stabilité des charges et l'agent de réticulation utilisé doit lui aussi être compatible avec lesdites charges.Those skilled in the art then turned to the use of inert thermosetting binders (obtained from oligomers), such as polyurethane binders (crosslinkable), allowing, after crosslinking, to form a three-dimensional network (in which one finds coated charges), ie to definitively freeze the geometry of the grain of powder (finally obtained). The manufacture on an industrial scale of powders (composite pyrotechnic products in general) with inert crosslinked binder (essentially thus consisting of a high level of charges in a minimal amount of binder) remains very difficult because of the one hand holding minimum mechanical and cohesion required of the product before crosslinking (for its shaping) and secondly the duration of "pot life" limited thermosetting resins ("pot life" means the starting period of crosslinking of the resin during which the latter can be worked as a plastic). In addition, of course, the crosslinking temperature must be compatible with the stability of the charges and the crosslinking agent used must also be compatible with said charges.

Confronté à ces difficultés, dans le cadre de l'emploi de liants thermodurcissables :

  • l'homme du métier a proposé de travailler en présence de solvants. Un procédé avec solvant a notamment été décrit dans la demande de brevet français FR 2 268 770 . De tels procédés sont cependant d'une mise en oeuvre complexe et coûteuse, qui ne donne pas satisfaction à l'échelle industrielle ;
  • pour opérer sans solvant, avec des liants thermodurcissables, ledit homme du métier a eu largement recours à la technique dite "de coulée" ou encore "globale", qui consiste à mélanger simultanément dans un malaxeur les constituants élémentaires liquides de la résine et les charges énergétiques et à couler, avant polymérisation, le mélange ainsi obtenu dans un moule pour y conduire la polymérisation proprement dite. Cette technique qui a été largement décrite, par exemple dans les demandes de brevet français FR 2 109 102 , FR 2 196 998 , FR 2 478 623 et FR 2 491 455 , peut convenir à la fabrication de propergols solides composites pour moteurs de fusées ou de roquettes, ou encore à la fabrication d'explosifs composites pour les têtes d'engins, qui sont le plus souvent utilisés sous forme de produits de gros diamètre, mais se révèle totalement inadaptée à la fabrication industrielle de poudres composites de gros, moyens et petits calibres et plus généralement à celle de certains produits pyrotechniques composites ;
  • pour fabriquer sans solvant des produits pyrotechniques composites à liant inerte thermodurcissable, notamment de petits diamètres, ledit homme du métier ne dispose en fait, à l'heure actuelle, que des deux techniques ci-après :
    1. a) la première qui consiste à mélanger dans un malaxeur les constituants de la résine avec les charges énergétiques, à amorcer la réticulation de la résine et, en cours de réticulation, à effectuer, en un laps de temps très court, la mise en forme du produit, comme décrit par exemple dans les demandes de brevet français FR 1 409 203 et FR 2 159 826 . Cette technique nécessite un réglage pointu de la cinétique de réticulation pour permettre de travailler la pâte et de ce fait, elle est difficilement gérable à l'échelle industrielle ;
    2. b) la seconde, beaucoup plus performante, y compris à l'échelle industrielle, décrite dans la demande de brevet EP 0 194 180 . Les produits pyrotechniques composites obtenus par cette seconde technique sont constitués principalement, d'une part, par un liant polymère (par exemple polyuréthanne) obtenu par réaction d'un prépolymère (polymère) polyhydroxylé (présentant une masse moléculaire moyenne en nombre comprise entre 2000 et 5000 et une fonctionnalité moyenne en groupes hydroxyles (OH supérieure à 2 et inférieure à 3) (PBHT, polyéther, polyester, par exemple) avec un agent de réticulation (diisocyanate), et d'autre part, par une charge énergétique, préférentiellement d'octogène (HMX) ou d'hexogène (RDX), à un taux d'environ 80 % en masse. Ladite seconde technique consiste :
      • + dans une première étape, à mélanger ledit prépolymère polyhydroxylé avec ladite charge énergétique et avec une quantité de diisocyanate comprise entre 50 % et 90 % en masse de la quantité stoechiométrique nécessaire à la polymérisation (réaction) complète de tous les groupes hydroxyles (OH) dudit prépolymère et à effectuer la réaction de condensation des groupes isocyanates (NCO) sur les groupes hydroxyles (OH) de manière à obtenir une pâte partiellement polymérisée (réticulée) ; + dans une seconde étape, à mélanger à ladite pâte partiellement polymérisée (réticulée) ainsi obtenue le complément de diisocyanate nécessaire pour atteindre ladite quantité stoechiométrique nécessaire à la polymérisation (réticulation) complète et à extruder le mélange pâteux ainsi obtenu ; puis,
      • + dans une troisième étape, à achever par cuisson à chaud la réaction de condensation des groupes isocyanates (NCO) ajoutés au cours de la deuxième étape sur les groupes hydroxyles (OH) encore libres.
La technique en cause comprend donc deux étapes de polymérisation ou réticulation, plus précisément une première étape de pré-réticulation (ou première phase de réticulation) avec une quantité d'isocyanate permettant l'obtention d'une pâte partiellement polymérisée (réticulée), présentant tenue mécanique et cohésion adéquates pour la mise en oeuvre de la suite du procédé (notamment de l'extrusion) et une seconde étape de réticulation conduisant au produit final avec liant réticulé souhaité. En cela, ladite technique surmonte les deux types de difficultés énoncées ci-dessus (difficulté due au manque de tenue mécanique et cohésion du produit à extruder et problème de la « vie de pot »).Faced with these difficulties, in the context of the use of thermosetting binders:
  • the skilled person has proposed to work in the presence of solvents. A process with a solvent has in particular been described in the French patent application FR 2,268,770 . Such methods are, however, of a complex and expensive implementation, which does not give satisfaction on an industrial scale;
  • to operate without solvent, with thermosetting binders, said person skilled in the art has made extensive use of the so-called "casting" or "global" technique, which consists in simultaneously mixing in a kneader the liquid elemental constituents of the resin and the fillers energy and cast, before polymerization, the mixture thus obtained in a mold to conduct the actual polymerization. This technique has been widely described, for example in French patent applications FR 2 109 102 , FR 2 196 998 , FR 2,478,623 and FR 2,491,455 , may be suitable for the manufacture of composite solid propellants for rocket or rocket engines, or for the manufacture of composite explosives for gear heads, which are most often used in the form of large diameter products, but totally unsuited to the industrial manufacture of composite powders large, medium and small calibres and more generally to that of certain composite pyrotechnic products;
  • to manufacture solvent-free composite pyrotechnic products with a thermosetting inert binder, in particular of small diameters, said person skilled in the art currently only has the following two techniques:
    1. a) the first which consists in mixing in a kneader the constituents of the resin with the energetic charges, to initiate the crosslinking of the resin and, during crosslinking, to perform, in a very short time, the shaping of the product, as described for example in the French patent applications FR 1 409 203 and FR 2 159 826 . This technique requires a sharp adjustment of the kinetics of crosslinking to enable the dough to work and because of this, it is difficult to manage on an industrial scale;
    2. b) the second, much more efficient, including on an industrial scale, described in the patent application EP 0 194 180 . The composite pyrotechnic products obtained by this second technique mainly consist, on the one hand, of a polymeric binder (for example polyurethane) obtained by reaction of a polyhydroxylated prepolymer (having a number-average molecular weight of between 2000 and 5000 and an average functionality in hydroxyl groups (OH greater than 2 and less than 3) (PBHT, polyether, polyester, for example) with a crosslinking agent (diisocyanate), and on the other hand, by an energy charge, preferably d octogen (HMX) or hexogen (RDX) at a level of about 80% by weight, said second technique consisting of:
      • in a first step, mixing said polyhydroxy prepolymer with said energetic charge and with a quantity of diisocyanate of between 50% and 90% by mass of the stoichiometric amount necessary for the complete polymerization (reaction) of all the hydroxyl groups (OH) of said prepolymer and for carrying out the condensation reaction of the isocyanate groups (NCO) on the hydroxyl groups (OH) so as to obtain a partially polymerized (crosslinked) paste; + in a second step, mixing with said partially polymerized (crosslinked) pulp thus obtained the complement of diisocyanate necessary to reach said stoichiometric amount necessary for complete polymerization (crosslinking) and extruding the pasty mixture thus obtained; then,
      • + in a third step, to complete by hot cooking the condensation reaction of the isocyanate groups (NCO) added during the second step on hydroxyl groups (OH) still free.
The technique in question thus comprises two polymerization or crosslinking steps, more specifically a first pre-crosslinking step (or first crosslinking step) with an amount of isocyanate allowing a partially polymerized (crosslinked) paste to be obtained, exhibiting adequate mechanical strength and cohesion for carrying out the rest of the process (in particular extrusion) and a second crosslinking step leading to the final product with the desired crosslinked binder. In this, said technique overcomes the two types of difficulties mentioned above (difficulty due to lack of mechanical strength and cohesion of the product to extrude and "pot life" problem).

En référence à cette seconde technique, on doit toutefois noter que les dosages de l'agent de réticulation (diisocyanate) pour la mise en oeuvre de la pré-réticulation sont délicats. Ils nécessitent une grande précision. Par ailleurs, le champ d'application de ladite technique est limité, au vu de la nature de l'agent de réticulation intervenant (de type isocyanate, pour réagir avec des fonctions hydroxyles), quant à la nature des charges énergétiques présentes, dans la mesure où certaines charges énergétiques (possédant une acidité intrinsèque) sont susceptibles de réagir, selon une réaction parasite, avec ledit agent de réticulation (de type isocyanate) présent. La présence de telles charges (EDNA, nitropyrazoles, par exemple) pose donc problème pour gérer les étapes de pré-réticulation et réticulation complémentaire. Or, cette présence est loin d'être anecdotique, dans le cadre de la présente invention, celui des produits pyrotechniques composites, notamment des poudres propulsives pour armes à tube. En effet, dans ce cadre, on vise à utiliser de fort taux de charges énergétiques (voir ci-dessus), notamment de fort taux de charges de type RDX. Or, l'homme du métier connait l'impact négatif d'un fort taux de telles charges sur l'érosivité de la poudre le contenant. Le remplacement d'au moins une partie du RDX par d'autres charges énergétiques (telles que l'EDNA), moins érosives, est donc souhaitable. Il serait donc vivement opportun de disposer d'un nouveau type de liant réticulable, réticulable avec des agents de réticulation qui ne soient pas des isocyanates.With reference to this second technique, it should however be noted that the dosages of the crosslinking agent (diisocyanate) for carrying out the pre-crosslinking are delicate. They require great precision. Moreover, the field of application of said technique is limited, in view of the nature of the intervening crosslinking agent (of isocyanate type, to react with hydroxyl functions), as to the nature of the energy charges present, in the extent where certain charges energy (having intrinsic acidity) are likely to react, in a parasitic reaction, with said crosslinking agent (isocyanate type) present. The presence of such fillers (EDNA, nitropyrazoles, for example) is therefore problematic for managing the steps of pre-crosslinking and complementary crosslinking. However, this presence is far from being anecdotal, in the context of the present invention, that of composite pyrotechnic products, in particular propellant powders for tube weapons. Indeed, in this context, we aim to use high energy charge rates (see above), including high RDX type charge rates. However, the skilled person knows the negative impact of a high rate of such charges on the erosivity of the powder containing it. Replacing at least some of the RDX with other, less erosive, energetic loads (such as EDNA) is therefore desirable. It would therefore be highly desirable to have a new type of crosslinkable binder crosslinkable with crosslinking agents which are not isocyanates.

Dans un tel contexte, les inventeurs proposent de nouveaux produits pyrotechniques composites, convenant notamment comme poudres propulsives pour armes à tube, renfermant un fort taux de charges dans un liant réticulé énergétique. Lesdits nouveaux produits pyrotechniques composites sont optimisés en termes de force (ils renferment un fort taux de charges énergétiques dans un liant énergétique), de vulnérabilité (ils ne renferment pas de nitrocellulose et peuvent avantageusement renfermer des charges énergétiques peu vulnérables), de procédé d'obtention (ledit procédé est aisé à mettre en oeuvre : sans solvant, sans précipitation pour la mise en oeuvre d'une mise en forme alors que la réticulation commence, sans pré-réticulation) et ils peuvent aussi être optimisés en terme d'érosivité (ils peuvent avantageusement renfermer des charges d'EDNA en substitution totale ou partielle de charges de RDX).In such a context, the inventors propose new composite pyrotechnic products, particularly suitable as propellant powders for tube weapons, containing a high level of charges in a crosslinked energetic binder. Said new composite pyrotechnic products are optimized in terms of strength (they contain a high energy charge rate in an energy binder), vulnerability (they do not contain nitrocellulose and may advantageously contain energy charges that are not very vulnerable), process obtaining (said method is easy to implement: without solvent, without precipitation for the implementation of a shaping while the crosslinking begins, without pre-crosslinking) and they can also be optimized in terms of erosivity ( they can advantageously contain EDNA charges as a total or partial substitution of RDX charges).

Selon son premier objet, la présente invention concerne donc de nouveaux produits pyrotechniques composites. Ils sont du type à liant réticulé renfermant des charges énergétiques organiques (voir ci-dessus). De façon caractéristique, leurs compositions, exprimées en pourcentages massiques, renferment :

  • de 78 à 90 %, avantageusement de 80 à 86 %, de charges énergétiques organiques, et
  • de 10 à 22 % d'un liant réticulé énergétique obtenu par réticulation, via seulement 8 à 12 % de ses fonctions azoture, d'un polyazoture de glycidyle (PAG) ayant une masse moléculaire moyenne en nombre (Mn) comprise entre 700 et 3 000 g/mol, avec au moins un agent de réticulation renfermant au moins deux fonctions propargyle dans sa formule chimique, en présence d'une gomme polymérique, choisie parmi les gommes polyuréthanne-polyester, les gommes polyuréthanne-polyéther et leurs mélanges, dont la masse moléculaire moyenne en nombre est supérieure à 20 000 g/mol et dont la viscosité Mooney est comprise entre 20 et 70 ML (5 + 4) à 100°C ; ladite gomme polymérique représentant de 1 à 5 % en masse de la composition dudit produit pyrotechnique.
According to its first object, the present invention thus relates to new composite pyrotechnic products. They are of the crosslinked binder type containing organic energy charges (see above). Characteristically, their compositions, expressed in percentages by weight, contain:
  • from 78 to 90%, advantageously from 80 to 86%, of organic energy charges, and
  • from 10 to 22% of a crosslinked energetic binder obtained by crosslinking, via only 8 to 12% of its azide functions, of a glycidyl polyazide (PAG) having a number-average molecular weight (Mn) of between 700 and 3; 000 g / mol, with at least one crosslinking agent containing at least two propargyl functions in its chemical formula, in the presence of a polymeric gum, chosen from polyurethane-polyester gums, polyurethane-polyether gums and mixtures thereof, the composition of which number average molecular weight is greater than 20,000 g / mol and the Mooney viscosity is between 20 and 70 ML (5 + 4) at 100 ° C; said polymeric gum representing from 1 to 5% by weight of the composition of said pyrotechnic product.

Les produits pyrotechniques composites de l'invention renferment donc un fort taux de charges énergétiques organiques : de 78 à 90 % en masse, avantageusement de 80 à 86 % en masse.The composite pyrotechnic products of the invention therefore contain a high level of organic energy charges: from 78 to 90% by weight, advantageously from 80 to 86% by weight.

Les charges en cause (charges organiques ; les charges minérales ayant été écartées dans la mesure où elles génèrent des particules solides) ne sont pas per se originales. Il s'agit de charges énergétiques organiques connues per se et, pour la plupart, déjà conditionnées selon l'art antérieur dans un liant polymérique organique conventionnel (tel le PBHT), notamment réticulé. Il s'agit avantageusement de charges d'hexogène (RDX), d'octogène (HMX), de nitroguanidine (NGU), d'éthylène dinitramine (EDNA), de dinitramide de N-guanylurée (FOX 12 (GUDN)), de 1,1-diamino-2, 2-dinitro éthylène (FOX 7 (DADE)), de 5,5'-azotétrazolate de bis(triaminoguanidinium) (TAGZT), de 5,5'-azotétrazolate de dihydrazinium (DHDZT), de 5,5'-bis(tétrazolyl)hydrazine (HBT), de bis(2,2-dinitropropyl) nitramine (BDNPN), d'un nitropyrazole ou d'un mélange de ces charges énergétiques.Loads in question (organic fillers, mineral fillers have been avoided in so far as they generate solid particles) are not per se original. These are organic energy charges known per se and, for the most part, already conditioned according to the prior art in an organic polymeric binder. conventional (such as PBHT), in particular crosslinked. It is advantageously charges of hexogen (RDX), octogen (HMX), nitroguanidine (NGU), ethylene dinitramine (EDNA), dinitramide N-guanylurea (FOX 12 (GUDN)), 1,1-diamino-2,2-dinitroethylene (FOX 7 (DADE)), bis (triaminoguanidinium) 5,5'-azotetrazolate (TAGZT), dihydrazinium 5,5'-azotetrazolate (DHDZT), 5,5'-bis (tetrazolyl) hydrazine (HBT), bis (2,2-dinitropropyl) nitramine (BDNPN), a nitropyrazole or a mixture of these energetic charges.

Au sein des produits pyrotechniques composites de l'invention, on trouve donc un type de charges énergétiques, avantageusement choisi parmi la liste ci-dessus, ou un mélange d'au moins deux types de charges énergétiques, avantageusement choisis parmi la liste ci-dessus. De façon préféré, on y trouve des charges énergétiques organiques d'EDNA. De façon particulièrement préférée, on y trouve un mélange de charges d'EDNA et de charges de RDX. Il est nullement exclu de ne trouver que des charges de RDX ou que des charges d'EDNA, mais comme indiqué ci-dessus, des mélanges de charges d'EDNA et de charges de RDX permettent d'atteindre un optimum en référence au compromis force/érosivité. On a compris que plus lesdits mélanges renferment de RDX, plus ils sont énergétiques mais plus ils sont érosifs.Within the composite pyrotechnic products of the invention, there is therefore a type of energy charges, advantageously chosen from the list above, or a mixture of at least two types of energetic charges, advantageously chosen from the list above. . In a preferred manner, there are organic energetic charges of EDNA. Particularly preferably, there is a mixture of EDNA charges and RDX charges. It is by no means excluded to find only RDX loads or EDNA loads, but as noted above, mixes of EDNA loads and RDX loads can achieve an optimum in reference to the strength tradeoff. / erosivity. It is understood that the more these mixtures contain RDX, the more they are energetic but the more they are erosive.

Les charges énergétiques se présentent sous la forme de grains solides, répartis de façon homogène au sein du liant réticulé. Ces grains solides présentent opportunément, de façon connue per se, plusieurs distributions granulométriques.The energy charges are in the form of solid grains, distributed homogeneously within the crosslinked binder. These solid grains suitably have, in a known manner per se, several particle size distributions.

On en vient maintenant à l'« élément clé » de la composition des produits pyrotechniques composites de l'invention : le liant. Celui-ci est présent à raison de 10 à 22 % en masse ; ces 10 à 22 % en masse incluant les 1 à 5 % de gomme.It now comes to the "key element" of the composition of the composite pyrotechnic products of the invention: the binder. It is present in a proportion of 10 to 22% by weight; these 10 to 22% by weight including 1 to 5% of gum.

Il s'agit d'un liant thermodurci (réticulé) en présence d'une gomme, obtenu à partir d'un polymère thermodurcissable (réticulable) mis en présence d'une gomme. Il s'agit d'un tel liant, énergétique, obtenu à partir d'un tel polymère, énergétique.It is a thermoset binder (crosslinked) in the presence of a gum, obtained from a thermosetting polymer (crosslinkable) in the presence of a gum. It is such a binder, energetic, obtained from such a polymer, energetic.

Notons incidemment ici que le « un polymère » doit se lire « au moins un polymère » dans tout le présent texte. En effet, il n'est nullement exclu du cadre de l'invention qu'un mélange d'au moins deux polymères (chacun du type indiqué et présentant des masses moléculaires et/ou des taux de ramification différents) soit utilisé.Incidentally note here that the "one polymer" must read "at least one polymer" throughout the present text. Indeed, it is not excluded from the scope of the invention that a mixture of at least two polymers (each of the type indicated and having different molecular weights and / or branching ratios) is used.

Le polymère énergétique en cause est un polyazoture de glycidyle (PAG).The energy polymer in question is a glycidyl polyazide (PAG).

Il présente une masse moléculaire adéquate, masse moléculaire moyenne en nombre (Mn) comprise entre 700 et 3 000 g/mol, avantageusement entre 1 700 et 2 300 g/mol, en référence à la consistance de son mélange, avec essentiellement les charges et la gomme (et aux propriétés mécaniques recherchées du produit final, qui doivent être obtenues avec un faible taux de réticulation (voir ci-après)). Il ne doit en effet pas être trop liquide, de sorte qu'une quantité raisonnable de gomme suffit à l'épaississement dudit mélange, qui autorise sa mise en forme (tenue mécanique et cohésion minimales) avant toute réticulation.It has a suitable molecular weight, number-average molecular weight (Mn) of between 700 and 3000 g / mol, advantageously between 1700 and 2300 g / mol, with reference to the consistency of its mixture, with essentially the fillers and the gum (and the desired mechanical properties of the final product, which must be obtained with a low degree of crosslinking (see below)). It must not be too liquid, so that a reasonable amount of rubber is sufficient for the thickening of said mixture, which allows its shaping (minimum mechanical strength and cohesion) before crosslinking.

Ledit polymère est un polyazoture, d'où 1) ses propriétés énergétiques et 2) sa capacité à être réticulé avec des agents de réticulation autres que les isocyanates.Said polymer is a polyazide, hence 1) its energetic properties and 2) its ability to be crosslinked with crosslinking agents other than isocyanates.

Sa réticulation ne met en jeu que 8 à 12 % de ses fonctions azoture (un tel faible taux de réticulation, mis en oeuvre sur le polymère présentant la masse moléculaire ci-dessus, permet l'obtention du produit final avec des propriétés mécaniques convenables). Ledit polymère réticulé conserve donc ses propriétés énergétiques. Le liant des produits pyrotechniques composites de l'invention est donc, comme indiqué ci-dessus, un liant énergétique. On comprend mieux la force desdits produits pyrotechniques composites de l'invention (renfermant un fort taux de charges énergétiques dans un liant (réticulé) énergétique).Its crosslinking only involves 8 to 12% of its azide functions (such a low level of crosslinking, used on the polymer having the above molecular weight, makes it possible to obtain the final product with suitable mechanical properties) . Said crosslinked polymer thus retains its energetic properties. The binder of the composite pyrotechnic products of the invention is therefore, as indicated above, an energy binder. The force of said composite pyrotechnic products of the invention is better understood (containing a high level of energetic charges in an energy (crosslinked) binder).

Pour ce qui concerne la nature du polymère énergétique et sa réticulation avec des agents de réticulation, autres que des isocyanates (une telle réticulation avec des isocyanates étant possible via des fonctions hydroxytéléchéliques lorsque ledit polymère (PAG) est hydroxytéléchélique) (voir le problème technique de l'utilisation des charges à acidité intrinsèque développé ci-dessus), il est du mérite des inventeurs d'avoir fait appel au concept de la « Click chemistry », plus précisément à son application dans la réaction de cycloaddition de Huisgen (cycloaddition -1,3 dipolaire) entre un azoture et un alcyne ; ladite réaction donnant un triazole. Ledit concept et son application mentionnée ci-dessus ont été décrits dans de nombreuses publications, notamment par Rostovtsev, Vsevolod V. ; Green, Luke G. ; Fokin Valery V. et Sharpless K. Barry en 2002 dans Angewandte Chemie International Edition 41 (14), pages 2596-2599 (publication intitulée : « A stepwise Huisgen Cycloaddition Process : Copper(I)-Catalyzed Regloselective « Ligation » of Azides and Terminal Alkynes») et dans le brevet US6872266 . Le liant réticulé de l'invention est donc obtenu par réticulation d'un pré-polymère, tel que précisé ci-dessus, avec au moins un agent de réticulation renfermant des fonctions alcynes, i.e. via des rotules triazoles de formule :

Figure imgb0001
With regard to the nature of the energy polymer and its crosslinking with crosslinking agents, other than isocyanates (such crosslinking with isocyanates being possible via hydroxytelechelic functions when said polymer (PAG) is hydroxytelechelic) (see the technical problem of the use of intrinsic acid charges developed above), it is the merit of the inventors to have resorted to the concept of "Click chemistry", specifically to its application in the Huisgen cycloaddition reaction (cycloaddition -1 , 3 dipolar) between an azide and an alkyne; said reaction giving a triazole. Said concept and its application mentioned above have been described in numerous publications, in particular by Rostovtsev, Vsevolod V.; Green, Luke G.; Fokin Valery V. and Sharpless K. Barry in 2002 in Angewandte Chemie International Edition 41 (14), pages 2596-2599 (Publication titled: "A stepwise Huisgen Cycloaddition Process: Copper (I) -Catalyzed Regloselective" Ligation "of Azides and Terminal Alkynes") and in the patent US6872266 . The crosslinked binder of the invention is thus obtained by crosslinking a pre-polymer, as specified above, with at least one crosslinking agent containing alkyne functions, ie via triazole ball joints of formula:
Figure imgb0001

Plus précisément, le au moins un agent de réticulation utilisé est un composé renfermant au moins deux fonctions propargyle dans sa formule chimique (« un polypropargyle »), il consiste généralement en un di- et/ou tri-propargyle. Avantageusement, il consiste en le succinate de dipropargyle (DPS), le maléate de dipropargyle (DPM), le tricarballylate de tripropargyle (TCATP), le benzène ester de tripropargyle (BETP), et un poly(éthylène glycol) (PEG) de dipropargyle de masse moléculaire moyenne en nombre comprise entre 200 et 1500 g/mol. Très avantageusement, il consiste en le succinate de dipropargyle (DPS).More specifically, the at least one crosslinking agent used is a compound containing at least two propargyl functions in its chemical formula ("a polypropargyl"), it generally consists of a di- and / or tri-propargyl. Advantageously, it consists of dipropargyl succinate (DPS), dipropargyl maleate (DPM), tripropargyl tricarballylate (TCATP), benzene tripropargyl ester (BETP), and a dipropargyl poly (ethylene glycol) (PEG). having a number average molecular weight of between 200 and 1500 g / mol. Very advantageously, it consists of dipropargyl succinate (DPS).

Notons ici que la compatibilité des charges énergétiques organiques avec les agents de réticulation du type indiqué a été vérifiée (leur mise en présence, « à haute température » (70°C), n'induit pas de dégagement gazeux significatif).It should be noted here that the compatibility of the organic energy charges with the crosslinking agents of the type indicated has been verified (their bringing into contact "at high temperature" (70 ° C.) does not induce significant gas evolution).

La composition des produits pyrotechniques composites de l'invention renferme également une gomme polymérique (« caoutchouc cru ») du type précisé. Ladite gomme :

  • est choisie parmi les gommes polyuréthanne-polyester (i.e. de nature polyuréthanne à segments souples de type polyester), les gommes polyuréthanne-polyéther (i.e. de nature polyuréthanne à segments souples de type polyéther) et leurs mélanges,
  • elle présente une masse moléculaire moyenne en nombre supérieure à 20 000 g/mol (avantageusement supérieure à 50 000 g/mol, très avantageusement supérieure à 75 000 g/mol), et
  • elle présente une viscosité Mooney comprise entre 20 et 70 ML (5 + 4) à 100°C. Ce paramètre est très utilisé dans l'industrie du caoutchouc. « x ML (5 + 4) à 100°C » se lit « x M égal à la viscosité en unités (ou points) Mooney ; L ou S (ici L) correspondant à la taille du rotor, 5 indiquant le temps de préchauffage du produit et 4, le temps en minutes après le démarrage du moteur auquel lecture est prise, 100°C étant la température de la mesure ». La valeur « x » est généralement donnée à « +/- y » ; c'est la valeur « x » qui doit, selon l'invention, être dans la plage 20-70 (valeurs d'extrémités comprises).
The composition of the composite pyrotechnic products of the invention also contains a polymeric gum ("raw rubber") of the type specified. Said eraser:
  • is chosen from polyurethane-polyester gums (ie of polyurethane type with flexible segments of the polyester type), polyurethane-polyether gums (ie polyurethane-type polyurethane-type gums) and mixtures thereof,
  • it has a number average molecular weight greater than 20,000 g / mol (advantageously greater than 50,000 g / mol, very advantageously greater than 75,000 g / mol), and
  • it has a Mooney viscosity of between 20 and 70 ML (5 + 4) at 100 ° C. This parameter is widely used in the rubber industry. "X ML (5 + 4) at 100 ° C" reads "x M equal to the viscosity in units (or points) Mooney; L or S (here L) corresponding to the size of the rotor, 5 indicating the preheating time of the product and 4, the time in minutes after starting the engine to which reading is taken, 100 ° C. being the temperature of the measurement ". The value "x" is usually given to "+/- y"; it is the value "x" which, according to the invention, must be in the range 20-70 (including end values).

Une telle gomme convient parfaitement aux fins de l'invention, dans la mesure où elle permet une mise en forme du mélange à réticuler à une température inférieure à 100°C (tout à fait compatible avec les charges présentes), et ce, sans utilisation de solvant, sans précipitation (pour la mise en oeuvre de ladite mise en forme alors que la réticulation commence) et sans une quelconque pré-réticulation. Ladite gomme est miscible avec le polymère (PAG) (le mélange gomme/polymère est « stable », on n'observe pas de phénomène d'exsudation). Elle exerce son action (bénéfique) en étant présente en faible quantité (elle ne représente qu'au maximum 5 % de la masse totale du produit) : sa présence n'est donc pas trop préjudiciable en référence à la force desdits produits.Such a rubber is perfectly suitable for the purposes of the invention, insofar as it allows shaping of the mixture to be crosslinked at a temperature below 100 ° C. (which is entirely compatible with the present charges), and this, without any use of solvent, without precipitation (for the implementation of said shaping while the crosslinking begins) and without any pre-crosslinking. Said gum is miscible with the polymer (PAG) (the gum / polymer mixture is "stable", no exudation phenomenon is observed). It performs its (beneficial) action by being present in small quantities (it represents at most 5% of the total mass of the product): its presence is not too detrimental in reference to the strength of said products.

Il est du mérite des inventeurs d'avoir identifié (sélectionné) ce type de gomme, convenant parfaitement aux fins de l'invention.It is the merit of the inventors to have identified (selected) this type of rubber, perfectly suitable for the purposes of the invention.

Ladite gomme consiste généralement en une gomme polyuréthanne-polyester ou une polyuréthanne-polyéther, mais des mélanges d'au moins deux gommes (au moins deux gommes polyuréthanne-polyester, au moins deux gommes polyuréthanne-polyéther ou au moins une gomme polyuréthanne-polyester et au moins une gomme polyuréthanne-polyéther ; de tels mélanges de gommes (gommes au sens de l'invention) constituant une gomme au sens de l'invention) présentant les propriétés requises (rappelées ci-dessus) peuvent être utilisés. Ladite gomme consiste avantageusement en une gomme polyuréthanne-polyester.Said gum generally consists of a polyurethane-polyester gum or a polyurethane-polyether, but mixtures of at least two gums (at least two polyurethane-polyester gums, at least two polyurethane-polyether gums or at least one polyurethane-polyester gum and at least one polyurethane-polyether gum, such gum mixtures (gums within the meaning of the invention) constituting a gum within the meaning of the invention) having the required properties (mentioned above) may be used. Said gum advantageously consists of a polyurethane-polyester gum.

Cette gomme intervient donc en amont du procédé de réticulation, en amont de l'étape de mise en forme, comme auxiliaire de fabrication. C'est elle qui permet de conférer, sans danger, au polymère chargé, de par ses propriétés (masse moléculaire suffisante et viscosité adéquate), les tenues mécanique et cohésion requises. C'est elle qui permet la préparation aisée, sans solvant, sans précipitation (pour la mise en oeuvre d'une mise en forme alors que la réticulation commence) et sans pré-réticulation, des produits pyrotechniques composites de l'invention. Elle agit, à des températures adéquates (inférieures à 100°C), comme épaississant et agent de cohésion dudit polymère chargé. Ladite gomme, auxiliaire de fabrication, en intervenant en amont de toute réticulation, rend donc possible, aisée, la fabrication des produits pyrotechniques composites de l'invention. Elle se retrouve, au final, enchevêtrée dans le réseau du polymère (PAG) réticulé. Un produit pyrotechnique composite donc la composition renferme une gomme polymérique est décrit dans le brevet US3026672 .This gum therefore intervenes upstream of the crosslinking process, upstream of the forming step, as a manufacturing aid. It is this which makes it possible to confer, without danger, on the polymer charged, due to its properties (sufficient molecular mass and adequate viscosity), the mechanical and cohesion required. It is this which allows the easy preparation, without solvent, without precipitation (for the implementation of a shaping while the crosslinking begins) and without pre-crosslinking, composite pyrotechnic products of the invention. It acts at suitable temperatures (below 100 ° C) as a thickener and cohesive agent of said charged polymer. Said gum, auxiliary manufacturing, intervening upstream of any crosslinking, makes it possible, easy, the manufacture of composite pyrotechnic products of the invention. In the end, it is entangled in the cross-linked polymer network (PAG). A composite pyrotechnic product so the composition contains a polymeric gum is described in the patent US3026672 .

On note, à toutes fins utiles, que le liant réticulé est donc le produit résultant de la réaction, entre le polymère (PAG) et le au moins un agent de réticulation, mise en oeuvre en présence de la gomme et qu'il renferme donc, outre ledit polymère réticulé via des rotules triazole, ladite gomme.It is noted, for all intents and purposes, that the crosslinked binder is therefore the product resulting from the reaction, between the polymer (PAG) and the at least one crosslinking agent, used in the presence of the compound and that it therefore contains , in addition to said crosslinked polymer via triazole patches, said gum.

La composition des produits pyrotechniques composites de l'invention est donc essentiellement constituée des charges énergétiques et du liant réticulé (renfermant ladite gomme). Elle peut être constituée à 100 % en masse desdites charges énergétiques et dudit liant réticulé (renfermant ladite gomme). Elle l'est généralement à au moins 95 % en masse, plus généralement à au moins 98 % en masse. Il ne saurait en effet être exclu qu'elle renferme en sus au moins un autre additif ; ladite gomme, présente en faible quantité, pouvant, à juste titre, être considérée comme un additif : il ne s'agit pas d'un constituant essentiel du liant, il s'agit d'un auxiliaire de fabrication dont l'intervention permet une obtention simple du produit recherché (selon le procédé décrit plus avant dans le présent texte). Un tel au moins un autre additif, lorsqu'il est présent, l'est généralement à raison de 0,1 à 5 % en masse, plus généralement à raison de 0,1 à 2 % en masse. Il peut notamment s'agir d'au moins un autre additif, choisi parmi les agents de mise en oeuvre (cire de candellila et/ou paraffine), les plastifiants (énergétiques ou non) et les stabilisants.The composition of the composite pyrotechnic products of the invention is therefore essentially composed of energy charges and crosslinked binder (containing said gum). It may consist of 100% by mass of said energy charges and said crosslinked binder (containing said gum). It is generally at least 95% by weight, more generally at least 98% by weight. It can not be excluded that it contains in addition at least one other additive; said gum, present in small quantities, which can rightly be considered as an additive: it is not an essential constituent of the binder, it is a manufacturing aid whose intervention allows a simple obtaining of the desired product (according to the method described further in the present text). Such at least one other additive, when present, is generally at a level of 0.1 to 5% by weight, more generally at 0.1 to 2% by weight. It may especially be at least one other additive, chosen from the agents of implementation (candelilla wax and / or paraffin), the plasticizers (energetic or not) and the stabilizers.

Les produits pyrotechniques composites de l'invention, tels que décrits ci-dessus, conviennent parfaitement comme poudre propulsive pour armes à tube. Lesdits produits pyrotechniques composites de l'invention consistent donc avantageusement en de telles poudres. Les produits pyrotechniques composites de l'invention, tels que décrits ci-dessus, conviennent également, notamment, comme propergol tactique, composition explosive et générateur de gaz.The composite pyrotechnic products of the invention, as described above, are perfectly suitable as propellant powder for tube weapons. Said composite pyrotechnic products of the invention therefore advantageously consist of such powders. The composite pyrotechnic products of the invention, as described above, are also suitable, in particular, as tactical propellant, explosive composition and gas generator.

Le grand intérêt des produits de l'invention ressort à l'évidence des propos ci-dessus. Les produits sont intéressants per se (en termes de force, de vulnérabilité, de large champ d'application en référence à la nature des charges) et dans la mesure où ils peuvent être obtenus par un procédé simple à mettre en oeuvre (beaucoup plus simple à mettre en oeuvre que les procédés de l'art antérieur).The great interest of the products of the invention is evident from the above remarks. The products are interesting per se (in terms of strength, vulnerability, wide field of application with reference to the nature of the loads) and to the extent that they can be obtained by a simple process to implement (much simpler to implement that the methods of the prior art).

Ledit procédé constitue le deuxième objet de la présente invention. Il comprend :

  1. a) la mise à disposition des ingrédients ci-après :
    • des charges énergétiques organiques,
    • un polyazoture de glycidyle (PAG) ayant une masse moléculaire en nombre (Mn) comprise entre 700 et 3 000 g/mol,
    • au moins un agent de réticulation dudit polyazoture, renfermant au moins deux fonctions propargyle dans sa formule chimique, et
    • une gomme polymérique, choisie parmi les gommes polyuréthanne-polyester, les gommes polyuréthanne-polyéther et leurs mélanges, dont la masse moléculaire en nombre est supérieure à 20 000 g/mol et dont la viscosité Mooney est comprise entre 20 et 60 ML (5 + 4) à 100°C ;
  2. b) l'obtention d'un mélange pâteux à partir desdits ingrédients ; les charges énergétiques organiques, polyazoture de glycidyle, gomme polymérique étant utilisés en des proportions adéquates en référence à la composition souhaitée du produit final, et ledit au moins un agent de réticulation en la quantité nécessaire à la réticulation de 8 à 12 % des fonctions azoture dudit polyazoture de glycidyle ;
  3. c) l'obtention, à partir dudit mélange pâteux, d'au moins un élément à une forme souhaitée ;
  4. d) le traitement thermique dudit au moins un élément pour la réticulation dudit polyazoture de glycidyle.
Said method constitutes the second object of the present invention. He understands :
  1. (a) the provision of the following ingredients:
    • organic energy charges,
    • a glycidyl polyazide (PAG) having a number-average molecular weight (Mn) of between 700 and 3,000 g / mol,
    • at least one crosslinking agent of said polyazide, containing at least two propargyl functions in its chemical formula, and
    • a polymeric gum chosen from polyurethane-polyester gums, polyurethane-polyether gums and mixtures thereof, the number-average molecular mass of which is greater than 20,000 g / mol and the Mooney viscosity of which is between 20 and 60 ML (5 + 4) at 100 ° C;
  2. b) obtaining a pasty mixture from said ingredients; the organic energy charges, glycidyl polyazide, polymeric gum being used in adequate proportions with reference to the desired composition of the final product, and said at least one crosslinking agent in the amount necessary for the crosslinking of 8 to 12% of the azide functions said glycidyl polyazide;
  3. c) obtaining, from said pasty mixture, at least one element to a desired shape;
  4. d) heat treating said at least one element for crosslinking said glycidyl polyazide.

Ledit procédé comprend donc la mise à disposition des ingrédients constitutifs (essentiels) des produits pyrotechniques composites recherchés : les charges + les éléments à partir desquels le liant réticulé est obtenu, i.e. le polymère, le au moins un agent de réticulation et la gomme. On a indiqué que les charges représentent entre 78 et 90 % de la masse du produit recherché tandis que le liant réticulé représente entre 10 et 22 %, lesdits 10 à 22 % englobant les 1 à 5 % de ladite gomme (le complément desdits 1 à 5 % correspondant au produit de la réaction du polymère et du au moins un agent de réticulation). Ledit au moins un agent de réticulation intervient en la quantité adéquate pour réticuler les 8 à 12 % des fonctions azoture du polymère ; il intervient généralement à moins de 5 % en masse (plus généralement entre 0,5 % et 4 %) du mélange réactionnel. On rappelle incidemment ici que des additifs, autres que ladite gomme, sont susceptibles d'intervenir.Said method therefore comprises the provision of the constituent (essential) ingredients of the desired composite pyrotechnic products: the fillers + the elements from which the crosslinked binder is obtained, i.e. the polymer, the at least one crosslinking agent and the gum. It has been indicated that the fillers represent between 78 and 90% of the mass of the desired product while the crosslinked binder represents between 10 and 22%, said 10 to 22% including the 1 to 5% of said gum (the complement of said 1 to 5% corresponding to the product of the reaction of the polymer and the at least one crosslinking agent). Said at least one crosslinking agent intervenes in the appropriate amount to cross-link the 8 to 12% of the azide functions of the polymer; it generally occurs at less than 5% by weight (more generally between 0.5% and 4%) of the reaction mixture. It is recalled here incidentally that additives, other than said gum, are likely to occur.

En référence à chacun des ingrédients utilisés pour la mise en oeuvre du procédé, on peut se référer à la première partie du texte relative au produit.With reference to each of the ingredients used for the implementation of the process, reference can be made to the first part of the text relating to the product.

Dans un premier temps, à partir des ingrédients identifiés ci-dessus, on réalise donc un mélange pâteux, précurseur du produit final (réticulé) visé. Un tel mélange pâteux est avantageusement réalisé à la bi-vis (par extrusion) ou au bi-cylindre, suivant les quantités à mettre en oeuvre. Il est généralement réalisé à une température comprise entre 15°C et 45°C. Il peut donc être réalisé à la température ambiante ou à une température supérieure à la température ambiante. En tout état de cause, l'intervention de la gomme permet l'obtention dudit mélange pâteux, pouvant être manipulé et mis en forme.In a first step, from the ingredients identified above, a pasty mixture is thus produced, the precursor of the final product. (crosslinked) targeted. Such a pasty mixture is advantageously made by twin-screw (extrusion) or twin-cylinder, depending on the quantities to be used. It is generally carried out at a temperature between 15 ° C and 45 ° C. It can therefore be performed at room temperature or at a temperature above room temperature. In any case, the intervention of the rubber provides said pasty mixture, which can be manipulated and shaped.

A partir dudit mélange pâteux, on prépare, dans la troisième étape du procédé de l'invention, au moins un élément (on prépare ainsi généralement n éléments) à une forme souhaitée (directement celle souhaitée pour le(s) produit(s) final(finaux) ou une forme « intermédiaire » à partir de laquelle on obtient, après réticulation (et généralement découpage), le(s)dit(s) produit(s) final(aux) à la forme souhaitée). Ladite troisième étape s'analyse donc comme une étape de mise en forme de la pâte. Cette mise en forme peut notamment comprendre un filage ou un calandrage. A l'issue d'un tel filage (mis en oeuvre dans un pot de presse, présentant un orifice de sortie de diamètre plus ou moins conséquent), on obtient un produit filé. Ce produit filé est généralement traité thermiquement pour réticulation puis découpé en brins (à la longueur souhaitée). De tels brins, convenant comme poudres propulsives pour armes à tube, présentent, généralement, une longueur de 2 à 20 mm, pour un diamètre de 1 à 20 mm (plus généralement pour un diamètre de 2 à 15 mm). Il n'est toutefois pas exclu de découper le produit filé (en brins donc non réticulés) puis de réticuler lesdits brins. A l'issue d'un tel calandrage, le produit calandré, sous la forme d'une plaque (une telle plaque présente généralement une épaisseur de 10 à 20 mm), peut être directement découpé en plaquettes ou traité thermiquement pour réticulation puis découpé en plaquettes.From said pasty mixture, at least one element is prepared in the third step of the process of the invention (generally n elements are prepared) to a desired shape (directly that desired for the final product (s). (final) or an "intermediate" form from which is obtained after crosslinking (and generally cutting), said (s) product (s) final (s) to the desired shape). Said third step is therefore analyzed as a step of shaping the dough. This formatting can include spinning or calendering. At the end of such spinning (used in a press pot, having an outlet orifice of greater or lesser diameter), a spun product is obtained. This spun product is generally heat treated for crosslinking and then cut into strands (at the desired length). Such strands, suitable as propellant powders for tube weapons, generally have a length of 2 to 20 mm, for a diameter of 1 to 20 mm (more generally for a diameter of 2 to 15 mm). However, it is not excluded to cut the spun product (thus non-crosslinked strands) and crosslink said strands. At the end of such calendering, the calendered product, in the form of a plate (such a plate generally has a thickness of 10 to 20 mm), can be directly cut into platelets or heat treated for crosslinking and then cut into platelets.

Selon des variantes de mise en oeuvre du procédé de l'invention, les étapes b et c dudit procédé peuvent comprendre :

  • malaxage à la bi-vis (ou extrusion) et filage,
  • malaxage au bi-cylindre et filage, ou
  • malaxage (à la bi-vis ou au bi-cylindre) et calandrage.
According to alternative embodiments of the method of the invention, steps b and c of said method may comprise:
  • mixing with twin-screw (or extrusion) and spinning,
  • twin-roll milling and spinning, or
  • mixing (twin-screw or twin cylinder) and calendering.

Le mélange pâteux, mis en forme à la forme désirée pour le produit final ou à une forme intermédiaire, est alors traité thermiquement. Le traitement thermique doit permettre d'assurer le résultat escompté (la réticulation du polymère) à une température non excessive (compatible avec la présence des charges énergétiques à un taux élevé). Généralement, ladite température est supérieure à 45°C et reste inférieure à 80°C. Avantageusement, la réticulation est mise en oeuvre à 55°C (+/- 5°C). Ledit au moins un élément traité thermiquement correspond au au moins un produit de l'invention recherché ou permet l'obtention de celui-ci, généralement par découpage.The pasty mixture, shaped to the desired shape for the final product or an intermediate form, is then heat-treated. The heat treatment must make it possible to ensure the expected result (the crosslinking of the polymer) at a non-excessive temperature (compatible with the presence of energy charges at a high rate). Generally, said temperature is above 45 ° C and remains below 80 ° C. Advantageously, the crosslinking is carried out at 55 ° C. (+/- 5 ° C.). Said at least one thermally treated element corresponds to the at least one product of the invention sought or enables it to be obtained, generally by cutting.

On se propose maintenant d'illustrer l'invention, de façon nullement limitative, sous ces aspects de produit et de procédé, par les exemples ci-après.It is now proposed to illustrate the invention, in no way limiting, in these aspects of product and process, by the examples below.

1) Matières premières utilisées1) Raw materials used a) Commercialesa) Commercial

  • Charges : RDX (0-100 CH ; D50 = 35 µm (D50 = diamètre pour lequel le pourcentage volumique cumulé est de 50 %)), commercialisées par la société Eurenco.Charges: RDX (0-100 CH, D 50 = 35 μm (D 50 = diameter for which the cumulative volume percentage is 50%)), sold by the company Eurenco.
  • Liant : PAG, commercialisé par la société Eurenco (Mn (masse moléculaire moyenne en nombre) : 1900).Binder: PAG, marketed by Eurenco (Mn (number average molecular weight): 1900).
  • Gomme : UREPAN® 643 G, commercialisée par la société RheinChemie, (produit de polyaddition du diphényl-méthane diisocyanate et d'un polyester). Elle présente les caractéristiques ci-après :
    • Masse moléculaire moyenne en nombre : 80 000 g/mol
    • Viscosité Mooney : 40 (+/-10) ML (5 + 4) à 100°C.
    Gum: UREPAN ® 643 G, sold by RheinChemie, (polyaddition product of diphenylmethane diisocyanate and a polyester). It has the following characteristics:
    • Number average molecular weight: 80,000 g / mol
    • Mooney viscosity: 40 (+/- 10) ML (5 + 4) at 100 ° C.
  • Agent de réticulation : succinate de dipropargyle, commercialisé par la société ARIAC.Crosslinking agent: dipropargyl succinate, marketed by ARIAC.
b) Préparéesb) Prepared • Charges : EDNA• Expenses: EDNA

La synthèse de l'éthylène dinitramine (EDNA) a été réalisée en deux temps via l'isolement d'un intermédiaire : la dinitroéthylène urée (DNEU), humide, qui a ensuite été transformée en EDNA.The synthesis of ethylene dinitramine (EDNA) was carried out in two stages via the isolation of an intermediate: the wet dinitroethylene urea (DNEU), which was then converted to EDNA.

Dans un réacteur double enveloppe de 50 cm3, on a introduit de l'acide nitrique concentré. Le bain nitrant a ensuite été refroidi à une température réactionnelle de 0°C. Dès que ledit bain a atteint 0°C, on a commencé l'introduction d'imidazolidone. On a introduit lentement ce réactif pour ne pas dépasser 20°C. La DNEU a précipité, dès que sa concentration dans le milieu a été supérieure à 23 % en masse. On a poursuivi l'introduction d'imidazolidone dans le milieu hétérogène (bain nitrant + DNEU solide).In a 50 cm 3 jacketed reactor, concentrated nitric acid was introduced. The nitrating bath was then cooled to a reaction temperature of 0 ° C. As soon as said bath reached 0 ° C, the introduction of imidazolidone was started. This reagent was slowly introduced so as not to exceed 20 ° C. DNEU precipitated as soon as its concentration in the medium was greater than 23% by mass. The introduction of imidazolidone into the heterogeneous medium (nitrating bath + solid DNEU) was continued.

Après la fin de l'introduction de l'imidazolidone, le milieu a été laissé sous agitation pendant 30 minutes à température ambiante.After the end of the introduction of the imidazolidone, the medium was stirred for 30 minutes at room temperature.

En fin de réaction, le mélange a été coulé sur un bain d'eau froide à environ 5°C sous agitation. Le solide a alors été séparé des eaux mères par filtration, et lavé plusieurs fois à l'eau distillée jusqu'à pH neutre puis essoré. Il a ensuite été repris, humide, pour la synthèse de l'EDNA.At the end of the reaction, the mixture was poured on a bath of cold water at about 5 ° C. with stirring. The solid was then separated from the mother liquors by filtration, and washed several times with distilled water to neutral pH and then filtered off. It was then taken up, wet, for the synthesis of EDNA.

L'étape de décarboxylation a été réalisée par addition de la DNEU sur une solution aqueuse tamponnée par de l'acétate de sodium à chaud. Un dégagement gazeux (de CO2) a été observé, ce qui a nécessité une introduction fractionnée de la poudre.The decarboxylation step was carried out by adding DNEU to an aqueous solution buffered with hot sodium acetate. Gaseous evolution (of CO 2 ) was observed, which required a fractional introduction of the powder.

Une fois l'introduction de ladite poudre de DNEU terminée, un palier à 95°C est réalisé pour terminer la formation de l'EDNA.Once the introduction of said DNEU powder is complete, a 95 ° C plateau is performed to complete the formation of the EDNA.

Le milieu réactionnel a ensuite été refroidi pour que l'EDNA précipite. La suspension a alors été filtrée puis séchée. Un rendement de 85 % a été obtenu.The reaction medium was then cooled so that the EDNA precipitated. The suspension was then filtered and dried. A yield of 85% was obtained.

L'obtention d'EDNA a été confirmée par infra-rouge.
IR : 2936 cm-1 CH aliphatique, 1593 cm-1 NO2, 1448 cm-1 N=N, 1360 cm-1 C-H.The obtaining of EDNA has been confirmed by infra-red.
IR: 2936 cm -1 Aliphatic CH, 1593 cm -1 NO 2 , 1448 cm -1 N = N, 1360 cm -1 CH.

Les cristaux d'EDNA obtenus sont de gros cristaux (ils présentent un D50 supérieur ou égal à 100 µm (D50 = diamètre pour lequel le pourcentage volumique cumulé est de 50 %)). Pour leur utilisation, ils sont broyés dans un broyeur de type SWECO®. A l'issue dudit broyage, ils présente un D50 de 30 µm.The EDNA crystals obtained are large crystals (they have a D 50 greater than or equal to 100 μm (D 50 = diameter for which the cumulative volume percentage is 50%)). For their use, they are ground in a SWECO ® mill. At the end of said grinding, they have a D 50 of 30 μm.

. Agent de réticulation : polyéthylène glycol de propargyle de masse moléculaire en nombre 1 000 g/mol (PEG 1000 de dipropargyle). Crosslinking agent: propargyl polyethylene glycol with a molecular weight of 1,000 g / mol (dipropargyl PEG 1000)

La synthèse a été mise en oeuvre conformément à l'enseignement de David Fournier, Richard Hoogenbooma et Ulrich S. Schubert dans Chem. Soc. Rev., 2007, 36, 1369-1380 («A straightforward approach to novel macromolecular architectures»).The synthesis was implemented in accordance with the teaching of David Fournier, Richard Hoogenbooma and Ulrich S. Schubert in Chem. Soc. Rev., 2007, 36, 1369-1380 ("A straightforward approach to novel macromolecular architectures").

Dans un tricol de 100 mL, on a tout d'abord introduit du PEG-1000 (50 g) ; celui-ci a alors été chauffé à une température de 45-50°C pour pouvoir être agité. Ensuite de la soude à 40 % en masse (6 g) a été ajoutée puis du bromure de propargyle, en solution à 80 % en masse dans du toluène (13,36 ml, 0,12 mole), sous agitation, au goutte à goutte. Le milieu a été porté à 65°C sur une période de 36 h. En fin de réaction, sur le milieu, amené à température ambiante, ont été ajoutés 150 ml de dichlorométhane. Le milieu résultant a alors été lavé à l'eau jusqu'à l'obtention d'un pH égal à 7 des eaux de lavage. La solution organique a ensuite été séchée puis le solvant évaporé.In a three-necked 100 mL, PEG-1000 (50 g) was first introduced; it was then heated to a temperature of 45-50 ° C to be stirred. Then 40% by weight sodium hydroxide (6 g) was added and then propargyl bromide, in 80% by weight solution in toluene (13.36 ml, 0.12 mol), with stirring, dropwise at room temperature. drop. The medium was brought to 65 ° C. over a period of 36 hours. At the end of the reaction, 150 ml of dichloromethane were added to the medium, brought to room temperature. The resulting medium was then washed with water until a pH equal to 7 of the washings. The organic solution was then dried and the solvent evaporated.

Le produit récupéré (35 g) se présentait sous la forme d'une cire.The recovered product (35 g) was in the form of a wax.

Son identité a été confirmée par RMN 1H.
RMN 1H : 3,4 ppm (multiplet) C-H propargyl ; 3,45 ppm (singulet) C-H2 PEG ; 4,18 ppm (doublet) C-H2 propargylHis identity was confirmed by 1 H NMR
1 H NMR: 3.4 ppm (multiplet) propargyl CH; 3.45 ppm (singlet) CH 2 PEG; 4.18 ppm (doublet) CH 2 propargyl

2) Procédé de préparation de produits pyrotechniques composites de l'invention2) Process for the preparation of composite pyrotechnic products of the invention

Des produits pyrotechniques composites de l'invention de deux types (exemple 1 et exemple 2) ont été préparés et testés. Leur composition massique et leur force (mesurées) sont respectivement données dans les tableaux 1 et 2 ci-après. En dessous de chacun desdits tableaux 1 et 2, on a précisé d'autres caractéristiques desdits produits.Composite pyrotechnic products of the invention of two types (Example 1 and Example 2) were prepared and tested. Their mass composition and their force (measured) are respectively given in Tables 1 and 2 below. Below each of said tables 1 and 2 are specified other characteristics of said products.

Ces produits pyrotechniques composites de l'invention ont été obtenus à partir des matières premières identifiées ci-dessus.These composite pyrotechnic products of the invention were obtained from the raw materials identified above.

Etape b du procédé de l'invention : les mélanges pâteux ont été obtenus au bi-cylindre, de façon connue per se. La gomme a tout d'abord été introduite entre les rouleaux du bi-cylindre (laminoir), portés à une température de 38°C. Elle a ainsi été ramollie. Ensuite, un mélange charges + PAG (préalablement réalisé dans un récipient) a été ajouté. Au mélange résultant, on a alors successivement additionné la cire de candelilla (agent de mise en oeuvre) puis l'agent de réticulation (en un rapport -C≡CH/-N3 égal à 10).Step b of the process of the invention: the pasty mixtures were obtained by twin-cylinder, in a known manner per se. The gum was first introduced between the rolls of the bi-roll (rolling mill), brought to a temperature of 38 ° C. It has been softened. Then, a mixture + PAG charges (previously made in a container) was added. To the resulting mixture, the candelilla wax (processing agent) and then the crosslinking agent (in a ratio -C≡CH / -N 3 equal to 10) were then successively added.

Etape c du procédé de l'invention : les mélanges pâteux obtenus ont été introduits dans un pot de presse chauffé à 38°C pour réaliser un filage sous une pression comprise entre 180 et 220 bars.Step c of the process of the invention: the pasty mixtures obtained were introduced into a press pot heated to 38 ° C to perform a spinning at a pressure of between 180 and 220 bar.

Etape d du procédé de l'invention : le traitement thermique du produit filé a été mis en oeuvre à 50°C pendant 5 jours. Après découpe (du produit filé réticulé), on a obtenu des brins de poudre (diamètre : 10 mm, longueur : 11 mm).Step d of the process of the invention: the heat treatment of the spun product was carried out at 50 ° C for 5 days. After cutting (crosslinked spun product), strands of powder (diameter: 10 mm, length: 11 mm) were obtained.

Exemple 1Example 1

Tableau 1Table 1 % massique% mass LiantBinder UREPAN® 643 GUREPAN ® 643 G 2,802.80 15,515.5 PAGPAG 8,698.69 PEG 1000 de dipropargylePEG 1000 of dipropargyl 3,713.71 Cire de candelillaCandelilla wax 0,30.3 ChargeCharge RDX (0-100CH)RDX (0-100CH) 31,531.5 84,584.5 EDNAEDNA 5353 100100 F mesurée (MJ/kg)F measured (MJ / kg) 1,21.2

Des caractéristiques du produit obtenu (après mélange au bi-cylindre, filage et réticulation) sont indiquées ci-après.

  • Masse volumique : 1,619 g/cm3.
  • Propriétés mécaniques à 20°C en compression (10 mm/min) : Sm (contrainte maximum à la rupture) : 1,49 MPa
  • E (module d'élasticité) : 73,6 MPa
  • Em (écrasement maximum avant rupture) : 4 %.
Characteristics of the product obtained (after twin-cylinder mixing, spinning and crosslinking) are given below.
  • Density: 1.619 g / cm 3 .
  • Mechanical properties at 20 ° C in compression (10 mm / min): Sm (maximum stress at break): 1.49 MPa
  • E (modulus of elasticity): 73.6 MPa
  • Em (maximum crush before breaking): 4%.

Exemple 2Example 2

Tableau 2Table 2 % massique% mass LiantBinder UREPAN® 643 GUREPAN ® 643 G 3,433.43 15,315.3 PAGPAG 10,5510.55 Succinate de dipropargyleDipropargyl succinate 1,021.02 Cire de candelillaCandelilla wax 0,30.3 ChargeCharge RDX (0-100CH)RDX (0-100CH) 31,231.2 84,784.7 EDNAEDNA 53,553.5 100100 F mesurée (MJ/kg)F measured (MJ / kg) 1,21.2

Des caractéristiques du produit obtenu (après mélange au bi-cylindre, filage et réticulation) sont indiquées ci-après.

  • Masse volumique : 1,635 g/cm3.
  • Propriétés mécaniques à 20°C en compression (10 mm/min) : Sm (contrainte maximum à la rupture) : 11,8 MPa
  • E (module d'élasticité) : 184 MPa
  • Em (écrasement maximum avant rupture) : 13,6 %
Characteristics of the product obtained (after twin-cylinder mixing, spinning and crosslinking) are given below.
  • Density: 1.635 g / cm 3 .
  • Mechanical properties at 20 ° C in compression (10 mm / min): Sm (maximum stress at break): 11.8 MPa
  • E (modulus of elasticity): 184 MPa
  • Em (maximum crush before rupture): 13.6%

Claims (14)

  1. A composite pyrotechnic product containing organic energetic charges in a crosslinked binder, characterized in that its composition, expressed as weight percentages, contains:
    - from 78% to 90%, advantageously from 80% to 86%, of organic energetic charges, and
    - from 10% to 22% of an energetic crosslinked binder obtained by crosslinking, via only 8% to 12% of its azide functions, a polyglycidyl azide with a number-average molecular weight of between 700 and 3000 g/mol, with at least one crosslinking agent containing at least two propargyl functions in its chemical formula, in the presence of a polymeric gum, chosen from polyurethane-polyester gums, polyurethane-polyether gums and mixtures thereof, the number-average molecular weight of which is greater than 20 000 g/mol and the Mooney viscosity of which is between 20 and 70 ML (5 + 4) at 100°C; said at least one polymeric gum representing from 1% to 5% by weight of the composition of said pyrotechnic product.
  2. The composite pyrotechnic product according to claim 1, characterized in that said organic energetic charges consist of hexogen, octogen, nitroguanidine, ethylene dinitramine, N-guanylurea dinitramide, 1,1-diamino-2,2-dinitroethylene, bis(triaminoguanidinium) 5,5'-azotetrazolate, dihydrazinium 5,5'-azotetrazolate, 5,5'-bis(tetrazolyl)hydrazine, bis(2,2-dinitropropyl)nitramine, a nitropyrazole, or a mixture of such charges.
  3. The composite pyrotechnic product according to claim 1 or 2, characterized in that said organic energetic charges contain ethylene dinitramine charges, advantageously hexogen charges and ethylene dinitramine charges.
  4. The composite pyrotechnic product according to any one of claims 1 to 3, characterized in that said polyglycidyl azide has a number-average molecular weight of between 1700 and 2300 g/mol.
  5. The composite pyrotechnic product according to any one of claims 1 to 4, characterized in that said at least one crosslinking agent is chosen from dipropargyl succinate, dipropargyl maleate, tripropargyl tricarballylate, the benzyl ester of tripropargyl, and a dipropargyl polyethylene glycol with a number-average molecular weight of between 200 and 1500 g/mol.
  6. The composite pyrotechnic product according to any one of claims 1 to 5, characterized in that said polymeric gum has a number-average molecular weight of greater than 50 000 g/mol, advantageously greater than 75 000 g/mol.
  7. The composite pyrotechnic product according to any one of claims 1 to 6, characterized in that said polymeric gum is a polyurethane-polyester gum or a polyurethane-polyether gum, advantageously a polyurethane-polyester gum.
  8. The composite pyrotechnic product according to any one of claims 1 to 7, characterized in that its composition also contains from 0.1% to 5% by weight of at least one additive, chosen especially from formulation agents and plasticizers.
  9. The composite pyrotechnic product according to any one of claims 1 to 8, characterized in that it consists of a propellant powder for barrel weapons.
  10. A process for preparing at least one composite pyrotechnic product according to any one of claims 1 to 9, characterized in that it comprises:
    a) the provision of the ingredients below:
    - organic energetic charges,
    - a polyglycidyl azide (PGA) with a number-average molecular weight of between 700 and 3000 g/mol,
    - at least one agent for crosslinking said polyazide, containing at least two propargyl functions in its chemical formula, and
    - a polymeric gum, chosen from polyurethane-polyester gums, polyurethane-polyether gums and mixtures thereof, the number-average molecular weight of which is greater than 20 000 g/mol and the Mooney viscosity of which is between 20 and 70 ML (5 + 4) at 100°C;
    b) the production of a pasty mixture from said ingredients; the organic energetic charges, polyglycidyl azide and polymeric gum being used in suitable proportions relative to the desired composition of the final product, and said at least one crosslinking agent in the amount required for crosslinking from 8% to 12% of the azide functions of said polyglycidyl azide;
    c) the production, from said pasty mixture, of at least one element in a desired form;
    d) heat treatment of said at least one element for crosslinking of said polyglycidyl azide.
  11. The process according to claim 10, characterized in that said pasty mixture is prepared with a twin-screw extruder or a two-roll mill.
  12. The process according to claim 10 or 11, characterized in that said pasty mixture is prepared at a temperature of between 15°C and 45°C.
  13. The process as claimed according to any one of claims 10 to 12, characterized in that said at least one element is obtained by spinning or calendering.
  14. The process according to any one of claims 10 to 13, characterized in that said heat treatment is performed at a temperature above 45°C and below 80°C.
EP14814912.3A 2013-11-22 2014-11-21 Composite pyrotechnical product with crosslinked binder and method for preparing same Active EP3071536B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL14814912T PL3071536T3 (en) 2013-11-22 2014-11-21 Composite pyrotechnical product with crosslinked binder and method for preparing same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1302708A FR3013706B1 (en) 2013-11-22 2013-11-22 COMPOSITE PYROTECHNIC PRODUCT WITH RETICULATED BINDER AND PROCESS FOR PREPARING THE SAME
PCT/FR2014/000251 WO2015075328A1 (en) 2013-11-22 2014-11-21 Composite pyrotechnical product with crosslinked binder and method for preparing same

Publications (2)

Publication Number Publication Date
EP3071536A1 EP3071536A1 (en) 2016-09-28
EP3071536B1 true EP3071536B1 (en) 2017-09-20

Family

ID=50473356

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14814912.3A Active EP3071536B1 (en) 2013-11-22 2014-11-21 Composite pyrotechnical product with crosslinked binder and method for preparing same

Country Status (6)

Country Link
US (1) US20160289134A1 (en)
EP (1) EP3071536B1 (en)
CA (1) CA2930488A1 (en)
FR (1) FR3013706B1 (en)
PL (1) PL3071536T3 (en)
WO (1) WO2015075328A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115180994B (en) * 2022-07-12 2023-06-09 西安近代化学研究所 Photo-thermal dual-curing allyl type energetic adhesive and preparation method thereof

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3151010A (en) * 1955-02-11 1964-09-29 Phillips Petroleum Co Method of preparing a solid composite propellant
US3026672A (en) * 1959-06-29 1962-03-27 Phillips Petroleum Co Composite propellant containing burning rate depressant and method of use
FR1409203A (en) 1961-01-10 1965-08-27 Aerojet General Co Polyurethane-based propellants
US3577289A (en) * 1968-02-12 1971-05-04 Jacque C Morrell Composite high energy solid rocket propellants and process for same
GB1316692A (en) 1970-05-04 1973-05-09 North American Rockwell Monomers polymerisable to form binders for explosive and propellant compositions and polymers and compositions formed therefrom
FR2109102A5 (en) 1970-10-01 1972-05-26 France Etat Resin bound explosive - contg rounded particles of explosive
FR2159826A5 (en) 1971-11-12 1973-06-22 Voith Gmbh Extruding thermosetting resins - eg polyesters with fibrous fillers to give stable profiles
FR2268770A1 (en) 1974-04-24 1975-11-21 Commissariat Energie Atomique Resin coated explosive compsn - prepd by liquid phase prodn of granules which are then compressed and crosslinked by heating
FR2319602A1 (en) * 1975-07-30 1977-02-25 Poudres & Explosifs Ste Nale NEW COMPOSITE EXPLOSIVE THERMOSTABLE MOLD AND MANUFACTURING PROCESS
DE3010052C2 (en) 1980-03-15 1982-09-09 Friedrich-Ulf 8899 Rettenbach Deisenroth Process for the production of plastic-bound explosives
JPS56160395A (en) 1980-03-20 1981-12-10 Hercules Inc Crosslinked propellant
US4381958A (en) 1980-08-07 1983-05-03 Hercules Incorporated Triaminoguanidine nitrate-containing propellants
JPS609996B2 (en) 1980-10-07 1985-03-14 日本油脂株式会社 Nitramine Composite Propellant Composition
US4335231A (en) * 1981-04-03 1982-06-15 Uniroyal, Inc. Sulfur curable millable polyurethane gum
FR2577919B1 (en) 1985-02-27 1987-02-20 Poudres & Explosifs Ste Nale PROCESS FOR THE MANUFACTURE WITHOUT SOLVENT OF COMPOSITE PYROTECHNIC PRODUCTS WITH THERMOSETTING BINDER AND PRODUCTS THUS OBTAINED, IN PARTICULAR COMPOSITE PROPULSIVE POWDERS
US4919737A (en) * 1988-08-05 1990-04-24 Morton Thiokol Inc. Thermoplastic elastomer-based low vulnerability ammunition gun propellants
US6103029A (en) * 1997-06-23 2000-08-15 The United States Of America As Represented By The Secretary Of The Navy Triazole cross-linked polymers
AU3690800A (en) * 1998-11-12 2000-06-26 Cordant Technologies, Inc. Synthesis of energetic thermoplastic elastomers containing oligomeric urethane linkages
US20050267245A1 (en) * 2003-03-18 2005-12-01 Sandusky Donald A Alloy blends of polyurethane and rubber
US6872266B1 (en) * 2003-05-30 2005-03-29 The United States Of America As Represented By The Secretary Of The Navy Triazole crosslinked polymers in recyclable energetic compositions and method of preparing the same
WO2006025615A1 (en) * 2004-09-03 2006-03-09 Kuraray Co., Ltd. Multilayered pellet comprising ethylene/vinyl alcohol copolymer resin compositions
US8501390B2 (en) * 2006-06-27 2013-08-06 Xiper Innovations, Inc. Laser engravable flexographic printing articles based on millable polyurethanes, and method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
WO2015075328A1 (en) 2015-05-28
EP3071536A1 (en) 2016-09-28
FR3013706A1 (en) 2015-05-29
US20160289134A1 (en) 2016-10-06
CA2930488A1 (en) 2015-05-28
FR3013706B1 (en) 2015-12-25
PL3071536T3 (en) 2018-02-28

Similar Documents

Publication Publication Date Title
EP0194180B1 (en) Process for the solventless production of pyrotechnical products having a thermosetting binder
EP0210881B1 (en) 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
EP1790626B1 (en) Semicontiunuous process for making an explosive composite charge having a polyurethane matrix by using two components
EP2516356B1 (en) Malleable solid explosive and method for obtaining it
CA2418319C (en) Semi-continuous bicomposite process for obtaining a composite explosive charge with a polyurethane matrix
EP0125166A1 (en) Cold-mouldable explosive composition and process for its preparation
EP3212593B1 (en) Composite pyrotechnic product with adn and rdx charges in a gpa binder and preparation of same
EP3071536B1 (en) Composite pyrotechnical product with crosslinked binder and method for preparing same
EP3071537B1 (en) Composite pyrotechnical product with non-crosslinked binder and method for preparing same
EP3212594B1 (en) Efficient composite pyrotechnic product with no lead in the composition thereof and preparation of same
EP0218511B1 (en) Binder-charge bonding agent and propellant composition containing it
FR2510987A1 (en) FLOWABLE PYROTECHNIC COMPOSITION OF THE SMOKE TYPE WITH COLORED FLAME OR NOT COMPRISING A CHLORINE BINDER
EP3656753B1 (en) Method for preparing composite pyrotechnical products
EP1364931B1 (en) Gun propellant powders of high power and reduced erosive action
EP3753916B1 (en) Composite pyrotechnical product
EP0124398B1 (en) Compressed propellant charge for munition and process for its manufacture
FR2915196A1 (en) NEW AZIDOALKYLFORMALS. SYNTHESIS METHOD USE AS A PLASTICIZER IN PYROTECHNIC SOLID COMPOSITIONS AND NEW PYROTECHNIC SOLID COMPOSITIONS.
FR3028853A1 (en) DETONATING CUTTING ROPES AND THEIR PREPARATION
FR2501194A1 (en) Solid explosive desensitised with phlegmatising agent - contg. functional gps. which are reactive to binder ingredients

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20160512

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

RIN1 Information on inventor provided before grant (corrected)

Inventor name: WERSCHINE, MATHIEU W.

Inventor name: FRANSON, CLAIRE J.

Inventor name: PAULIN, JEAN-LOUIS

Inventor name: DESGARDIN, NANCY

Inventor name: RAGON, PHILIPPE

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

INTG Intention to grant announced

Effective date: 20170329

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20170504

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 929979

Country of ref document: AT

Kind code of ref document: T

Effective date: 20171015

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: FRENCH

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: BOVARD AG PATENT- UND MARKENANWAELTE, CH

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602014014914

Country of ref document: DE

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 4

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20170920

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170920

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170920

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171220

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170920

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 929979

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170920

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171221

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170920

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171220

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170920

REG Reference to a national code

Ref country code: CH

Ref legal event code: PUEA

Owner name: EURENCO, FR

Free format text: FORMER OWNER: HERAKLES, FR

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170920

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: SAFRAN CERAMICS

Owner name: EURENCO

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: EURENCO

Owner name: ARIANEGROUP SAS

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170920

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170920

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170920

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170920

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180120

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170920

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170920

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602014014914

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170920

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170920

26N No opposition filed

Effective date: 20180621

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171121

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20171130

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170920

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171121

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170920

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171130

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20181116

Year of fee payment: 9

Ref country code: PL

Payment date: 20181030

Year of fee payment: 5

Ref country code: FI

Payment date: 20181018

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20141121

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170920

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170920

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170920

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170920

REG Reference to a national code

Ref country code: FI

Ref legal event code: MAE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191121

Ref country code: FI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191121

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170920

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191121

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191121

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 602014014914

Country of ref document: DE

Representative=s name: CBDL PATENTANWAELTE GBR, DE

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20231120

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20231120

Year of fee payment: 10

Ref country code: DE

Payment date: 20231107

Year of fee payment: 10

Ref country code: CH

Payment date: 20231201

Year of fee payment: 10