EP3071536B1 - Zusammengesetztes pyrotechnisches produkt mit einem vernetzten bindemittel und verfahren zur herstellung davon - Google Patents

Zusammengesetztes pyrotechnisches produkt mit einem vernetzten bindemittel und verfahren zur herstellung davon Download PDF

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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
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Prior art keywords
charges
crosslinking
mol
gum
polyurethane
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English (en)
French (fr)
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EP3071536A1 (de
Inventor
Nancy Desgardin
Mathieu W. Werschine
Claire J. Franson
Philippe Ragon
Jean-Louis Paulin
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Eurenco SA
ArianeGroup SAS
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Eurenco SA
Eurenco France SA
Herakles SA
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Priority to PL14814912T priority Critical patent/PL3071536T3/pl
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    • 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.

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Claims (14)

  1. Zusammengesetztes pyrotechnisches Produkt, umfassend organische energetische Ladungen in einem vernetzten Bindemittel, dadurch gekennzeichnet, dass dessen Zusammensetzung, ausgedrückt in Masseprozent, umfasst:
    - von 78 bis 90 %, vorteilhaft von 80 bis 86 %, organische energetische Ladungen, und
    - von 10 bis 22 % eines energetischen vernetzten Bindemittels, das erhalten wird durch Vernetzung, über nur 8 bis 12 % seiner Azid-Funktionen, eines Glycidylpolyazids mit einer zahlenmittleren Molmasse zwischen 700 und 3.000 g/mol mit mindestens einem Vernetzungsmittel, umfassend mindestens zwei Propargyl-Funktionen in seiner chemischen Formel, in Anwesenheit eines Polymergummis, ausgewählt aus den Polyurethan-Polyester-Gummis, Polyurethan-Polyether-Gummis und ihren Mischungen, deren zahlenmittlere Molmasse größer ist als 20.000 g/mol und deren Mooney-Viskosität zwischen 20 und 70 ML (5 + 4) bei 100°C beträgt; wobei der mindestens eine Polymergummi 1 bis 5 Masse-% der Zusammensetzung des pyrotechnischen Produkts ausmacht.
  2. Zusammengesetztes pyrotechnisches Produkt nach Anspruch 1, dadurch gekennzeichnet, dass die organischen energetischen Ladungen aus Ladungen von Hexogen, Octogen, Nitroguanidin, Ethylendinitramin, N-Guanylharnstoffdinitramid, 1,1-Diamino-2,2-dinitroethylen, Bis(triaminoguanidinium)-5,5'-azotetrazolat, Dihydrazinium-5,5'-azotetrazolat, 5,5'-Bis(tetrazolyl)hydrazin, Bis(2,2-dinitropropyl)nitramin, einem Nitropyrazol oder aus einer Mischung derartiger Ladungen bestehen.
  3. Zusammengesetztes pyrotechnisches Produkt nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die organischen energetischen Ladungen Ladungen von Ethylendinitramin, vorteilhaft Ladungen von Hexogen und Ladungen von Ethylendinitramin, umfassen.
  4. Zusammengesetztes pyrotechnisches Produkt nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das Glycidylpolyazid eine zahlenmittlere Molmasse zwischen 1.700 und 2.300 g/mol aufweist.
  5. Zusammengesetztes pyrotechnisches Produkt nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das mindestens eine Vernetzungsmittel ausgewählt ist aus Dipropargylsuccinat, Dipropargylmaleat, Tripropargyltricarballylat, Tripropargylbenzylester und einem Diporpargylpolyethylenglykol mit einer zahlenmittleren Molmasse zwischen 200 und 1.500 g/mol.
  6. Zusammengesetztes pyrotechnisches Produkt nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass der Polymergummi eine zahlenmittlere Molmasse von mehr als 50.000 g/mol, vorteilhaft von mehr als 75.000 g/mol, aufweist.
  7. Zusammengesetztes pyrotechnisches Produkt nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass der Polymergummi ein Polyurethan-Polyester-Gummi oder ein Polyurethan-Polyether-Gummi, vorteilhaft ein Polyurethan-Polyester-Gummi, ist.
  8. Zusammengesetztes pyrotechnisches Produkt nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass dessen Zusammensetzung außerdem von 0,1 bis 5 Masse-% mindestens eines Additivs, insbesondere ausgewählt aus Hilfsmitteln und Weichmachern, umfasst.
  9. Zusammengesetztes pyrotechnisches Produkt nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass dieses aus einem Zündpulver für Rohrwaffen besteht.
  10. Verfahren zur Herstellung mindestens eines zusammengesetzten pyrotechnischen Produkts nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass dieses umfasst:
    a) Bereitstellen der nachstehenden Bestandteile:
    - organischer energetischer Ladungen,
    - eines Glycidylpolyazids (PAG) mit einer zahlenmittleren Molmasse zwischen 700 und 3.000 g/mol,
    - mindestens eines Vernetzungsmittels des Polyazids, umfassend mindestens zwei Propargyl-Funktionen in seiner chemischen Formel, und
    - eines Polymergummis, ausgewählt aus Polyurethan-Polyester-Gummis, Polyurethan-Polyether-Gummis und ihren Mischungen, deren zahlenmittlere Molmasse größer ist als 20.000 g/mol und deren Mooney-Viskosität zwischen 20 und 70 ML (5 + 4) bei 100°C beträgt;
    b) Erhalten einer pastenartigen Masse aus den Bestandteilen; wobei die organischen energetischen Ladungen, das Glycidylpolyazid, der Polymergummi in adäquaten Anteilen unter Bezugnahme auf die gewünschte Zusammensetzung des Endprodukts verwendet werden, und das mindestens eine Vernetzungsmittel in der Menge, die für die Vernetzung von 8 bis 12 % der Azid-Funktionen des Glycidylpolyazids notwendig ist;
    c) Erhalten, aus der pastenartigen Mischung, mindestens eines Elements in einer gewünschten Form;
    d) thermisches Behandeln des mindestens einen Elements zur Vernetzung des Glycidylpolyazids.
  11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, dass die pastenartige Mischung mit einer Doppelschnecke oder einem Doppelzylinder hergestellt wird.
  12. Verfahren nach Anspruch 10 oder 11, dadurch gekennzeichnet, dass die pastenartige Mischung bei einer Temperatur zwischen 15°C und 45°C hergestellt wird.
  13. Verfahren nach einem der Ansprüche 10 bis 12, dadurch gekennzeichnet, dass das mindestens eine Element über ein Spinnen oder Kalandern erhalten wird.
  14. Verfahren nach einem der Ansprüche 10 bis 13, dadurch gekennzeichnet, dass die thermische Behandlung bei einer Temperatur von mehr als 45°C und weniger als 80°C durchgeführt wird.
EP14814912.3A 2013-11-22 2014-11-21 Zusammengesetztes pyrotechnisches produkt mit einem vernetzten bindemittel und verfahren zur herstellung davon Active EP3071536B1 (de)

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FR1302708A FR3013706B1 (fr) 2013-11-22 2013-11-22 Produit pyrotechnique composite a liant reticule et son procede de preparation
PCT/FR2014/000251 WO2015075328A1 (fr) 2013-11-22 2014-11-21 Produit pyrotechnique composite a liant réticule et son procédé de préparation

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EP3071536B1 true EP3071536B1 (de) 2017-09-20

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US (1) US20160289134A1 (de)
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CA (1) CA2930488A1 (de)
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WO (1) WO2015075328A1 (de)

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CN115180994B (zh) * 2022-07-12 2023-06-09 西安近代化学研究所 一种光-热双固化烯丙基型含能粘合剂及制备方法

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FR3013706B1 (fr) 2015-12-25
CA2930488A1 (fr) 2015-05-28
EP3071536A1 (de) 2016-09-28
WO2015075328A1 (fr) 2015-05-28
US20160289134A1 (en) 2016-10-06
PL3071536T3 (pl) 2018-02-28
FR3013706A1 (fr) 2015-05-29

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