EP2516356B1 - Verformbarer explosiver feststoff und verfahren zu seiner herstellung - Google Patents

Verformbarer explosiver feststoff und verfahren zu seiner herstellung Download PDF

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Publication number
EP2516356B1
EP2516356B1 EP10810850.7A EP10810850A EP2516356B1 EP 2516356 B1 EP2516356 B1 EP 2516356B1 EP 10810850 A EP10810850 A EP 10810850A EP 2516356 B1 EP2516356 B1 EP 2516356B1
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Prior art keywords
explosive
weight
malleable solid
polyols
malleable
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EP10810850.7A
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English (en)
French (fr)
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EP2516356A1 (de
Inventor
Bernard Mahe
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Eurenco SA
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Eurenco SA
Eurenco France SA
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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

Definitions

  • the present invention relates to a new malleable solid explosive, which constitutes an alternative, or even an improvement, to the plastic explosives known to date (see below). It also relates to a process for obtaining said new malleable solid explosive.
  • the technical field of the invention is that of (blocks of) malleable (pasty) solid explosives, commonly called plastic explosives, initiated by a detonator, for military and civil use. They are generally used in the form of breads weighing a few hundred grams. The malleability of these loaves of explosives makes it possible to perfectly adapt their shapes to the contours of the objects or structures to be destroyed.
  • the first known plastic explosive called "gelignite” was invented by Alfred Nobel in 1875. It consisted of nitrocellulose dissolved in nitroglycerin and mixed with wood pulp and saltpeter.
  • the patent US 3,113,894 describes a heterogeneous propellant composition comprising inorganic oxidant particles dispersed in a liquid fuel matrix consisting essentially of a liquid synthetic organic polymer.
  • the patent DE 198 21 150 describes a malleable explosive charge containing from 70 to 95% by mass of a solid explosive charge and optionally a plasticizer preferably chosen from a non-crosslinked silicone, a polyethylene glycol, a polyisobutylene, a polyol or a wax.
  • plastic explosives contain an explosive charge (hexogen (RDX) and / or pentrite, for example), a polymeric binder rubber (most often synthetic such as butadiene-styrene gum or polyisobutylene ), a plasticizer (such as bis (2-ethylhexyl) adipate or sebacate, di-n-octyl phthalate, tri-n-butyl citrate), and additives (such as dyes, antioxidants and detection).
  • RDX hexogen
  • pentrite a polymeric binder rubber
  • plasticizer such as bis (2-ethylhexyl) adipate or sebacate, di-n-octyl phthalate, tri-n-butyl citrate
  • additives such as dyes, antioxidants and detection.
  • the plasticizer (generally present at mass rates of 2 to 5%) has the role of conferring on plastic explosives their malleability and a better mechanical resistance not requiring their conditioning in a structure (see the teaching of the prior art recalled here above, relating to malleable explosives without plasticizer).
  • the best known plastic explosives with this type of formulation are C-4 plastic and Semtex®, which are familiar to those skilled in the art. These plastic explosives therefore contain, in their composition, with reference to their plastic nature, a polymeric rubber binder (solid) associated with a plasticizer. These two inert components do not participate in the desired explosive effect.
  • the controlled dosage of the binder (polymer) and of the plasticizer generally introduced at a low rate (a few percent) within the energy charge of the plastic explosive, complicates the process for manufacturing the plastic explosive.
  • the inventor sought a new type of "plastic” explosive, more precisely a new malleable solid explosive, more interesting in terms of composition (without plasticizer), of performance (with “less diluted” energy charge) and manufacturing process (simpler).
  • the present invention therefore relates to an original malleable solid explosive, which constitutes an alternative, or even an improvement, to the plastic explosives known to date (see above).
  • Said explosive is solid in that it does not flow by gravity (at room temperature and above: in fact, up to the temperature where the explosive charge it contains is no longer stable).
  • Said explosive is malleable in that it can be shaped by hand (manually) at temperatures from -40 ° C to + 70 ° C.
  • the malleable solid explosive of the invention is characterized in that it is in the form of a (solid) block consisting, for at least 98% of its mass, of a powdery explosive charge consisting of octogen (HMX), hexogen (RDX), pentaerythritis tetranitrate (pentrite or PETN), hexanitrohexaazaisowurtzitane (CL20), triaminotrinitrobenzene (TATB), 5-nitro-2,2,4 -triazole-3-one (ONTA), hexanitrostilbene (HNS), 1,1-diamino-2,2-dinitroethene (DADNE or Fox-7) or one of their mixtures and of a liquid chosen from polyol polymers from the group of polyisobutylenes polyols, polybutadienes polyols, polyether polyols, polyester polyols and polysiloxane polyols, the number average molecular weight of which is between 500
  • the malleable solid explosive of the invention is therefore in the form of a block, ie in the form of a compact mass. It is in fact a block, obtained by molding or by cutting a paste (see its process of obtaining described below).
  • the malleable solid explosive of the invention can thus be obtained by molding a pasty component A according to the patent application EP-A-1 333 015 .
  • the presently claimed invention offers an original outlet for this component A, proposes a completely original use for it (in the context of the invention, said component is not crosslinked but used "as is"", after a simple formatting). Note however that the scope of the invention is in no way limited to said components A according to the patent application EP-A-1 333 015 .
  • the powder explosive charge (whose particle size (s), not original (s) per se, is (are), conventionally, generally between 2 and 500 ⁇ m) of the block contains one or more explosives (mixed).
  • the said explosive (s) present (s) is (are) advantageously at different particle sizes (particle size sections). It is thus possible to have high charge rates.
  • the powder explosive charge of the block represents at least 85% by mass of the total mass of the block.
  • the liquid present also consists of a liquid (chosen from the polyol polymers specified above) or a mixture of liquids (chosen from the polyol polymers specified above). It may or may not be a solvent for the powder explosive charge. Assuming that said liquid is a solvent for said filler, it is understood that said filler is present at concentrations beyond the saturation concentration, insofar as a solid block is involved.
  • the block of solid malleable explosive is essentially (for at least 98% of its mass) made up of said charge and of said liquid. In addition to said charge and said liquid, it is only likely to contain additives (see below). It can quite entirely (100%) consist of said charge and said liquid. No plasticizer is present in its composition.
  • the mass ratio (S / L) is a priori high.
  • the powder explosive charge of the block advantageously represents at least 85% by mass of the total mass of the block.
  • a liquid of dynamic viscosity between 0.1 and 1 Pa.s is advantageously combined in the temperature range: - 40 ° C and + 70 ° C and an explosive charge with a particle size between 1 and 150 ⁇ m.
  • a solid explosive charge is chosen having several particle size sections between 1 and 150 ⁇ m.
  • the explosive charge of the solid explosive blocks of the invention is not per se original. It consists, as indicated above, of octogen (HMX), hexogen (RDX), pentaerythritis tetranitrate (pentrite or PETN), hexanitrohexaazaisowurtzitane (CL20), triaminotrinitrobenzene, TATB), 5-nitro-2,2,4-triazole-3-one (ONTA), hexanitrostilbene (HNS), 1,1-diamino-2,2-dinitroethene (DADNE or Fox-7) or one of their mixtures. It is advantageously chosen from octogen, hexogen, penthrite and CL20. Hexogen is the preferred (energetic) explosive charge of the blocks of the invention.
  • the liquid is therefore chosen from the following polyol polymers: polyisobutylene polyols, polybutadiene polyols, polyether polyols, polyester polyols and polysiloxane polyols, the molecular mass of which number average is between 500 and 10,000, and mixtures thereof.
  • Said liquid is advantageously chosen from said polybutadien polyols and their mixtures.
  • Said liquid very advantageously consists of a hydroxytelechelic polybutadiene of this type. In fact, they are perfectly suitable, as liquid for the malleable solid explosives of the invention, the hydroxytelechelic polybutadienes usually used in the crosslinked state as a binder of solid propellants for self-propulsion.
  • this type of polymer see in particular the teaching of the application EP-A-1 333 015 ).
  • said charge and said liquid constitute from 98% to 100% (by mass) of the malleable solid explosive of the invention, of the malleable solid explosive blocks of the invention.
  • Said explosive blocks are in fact capable of containing additives, in particular antioxidants, anti-aging agents, chemical detection markers, for at most 2% of their total mass.
  • the blocks of the invention generally have a mass of between 100 g and 5 kg.
  • Said blocks of malleable solid explosive can be considered as loaves (in the sense of the loaves of plastic explosives of the prior art).
  • the blocks of the invention have rheological qualities and performances superior to those of blocks of malleable explosives incorporating a plasticizer. They can be stored and used in large mass breads (for example several kilograms) without any precaution with reference to their mechanical strength, unlike the malleable explosives of the prior art without plasticizer.
  • Mixing powdery explosive charge + polyol polymer liquid, to obtain the paste can be carried out at room temperature or hot.
  • the mixing temperature is obviously compatible with safety standards, given the exact nature of the explosive charge. In this spirit, it is generally less than 80 ° C.
  • the process for obtaining the original explosive of the invention can be carried out continuously or discontinuously.
  • the constituents of the blocks of the invention are hot mixed (typically 60 ° C.) in a mixer; the mixture obtained (whose mass can for example vary from 100 kg to 5 tonnes) is then discharged from the mixer to be introduced into a funnel terminated by a worm; said mixture is driven by the worm to be placed in molds (the volume of which can be variable, typically between 100 and 700 cm 3 depending on the intended applications, generally 350 cm 3 ); said mixture contained in each mold is then removed from the mold in order to obtain a block of malleable explosive.
  • the constituents of the blocks of the invention are hot mixed (typically 60 ° C.) in a mixer; the mixture obtained (whose mass can for example vary from 100 kg to 5 tonnes) is then discharged from the mixer to be introduced into a funnel terminated by a worm; said mixture is driven by the worm to be placed in molds (the volume of which can be variable, typically between 100 and 700 cm 3 depending on the intended applications, generally 350 cm 3 ); said mixture contained in each mold is then removed from the mold in
  • the mixture is obtained by continuous hot mixing and then directly extruded in molds (the volume of which can be variable, typically between 100 and 700 cm 3 depending on the intended applications, generally 350 cm 3 ).
  • the mixture is obtained by continuous hot mixing and then directly extruded, the extruded rod being chopped so as to directly obtain blocks of determined mass.
  • the density of the explosive block obtained can vary depending on the amount of air trapped in the explosive charge during the obtaining process. Said density is advantageously between 1300 and 1700 kg / m 3 .
  • Table 1 below presents the composition of said malleable solid explosive according to the invention.
  • the liquid is a hydroxytelechelic polybutadiene (PBHT). It is the PBHT R45HTLO marketed by the company Sartomer (Mn ⁇ 3000). It intervenes at around 10% by mass.
  • PBHT hydroxytelechelic polybutadiene
  • the mass composition of the malleable solid explosive block also contains additives (an antioxidant, an anti-aging agent and a chemical marker), for less than 2 percent of its total mass.
  • Table 1 Composition of the malleable solid explosive block Constituents mass percentage (%) Granulometry Liquid Hydroxytelechelic polybutadiene 10.4 / Explosive charge
  • Antioxidant agent 2,2-methylene bis (4-methyl-6-tertio butyl) phenol 0.4% / Chemical marker 2,3-dimethyl-2,3-dinitrobutane 1 / Anti-hardening agent in aging soy lecithin 0.2 /
  • the constituents of the malleable solid explosive block of the invention are kneaded hot (60 ° C +/- 10 ° C), each kneading operation uses approximately 200 kg of material.
  • the dough obtained is then discharged and introduced into a funnel fitted with an endless screw for filling molds.
  • the volume of the molds is approximately 50 cm 3 .
  • the solid block of malleable explosive generated in each mold is then removed from the mold to obtain a strip of malleable explosive of approximately 0.5 kg.
  • the density of the explosive bars obtained by this process can vary depending on the amount of air trapped in the dough during the process. Said density is between 1480 and 1520 kg / m 3 .

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)

Claims (12)

  1. Formbarer, fester Sprengstoff, dadurch gekennzeichnet, dass er in der Form eines Blocks vorliegt, der zu zumindest 98 % seiner Masse aus:
    einer pulverförmigen Sprengladung, bestehend aus Oktogen (HMX), Hexogen (RDX), Pentaerythrityltetranitrat (Pentrit oder PEFN), Hexanitrohexaazaisowurtzitan (CL20), Triaminotrinitrobenzol (TATB), 5-Nitro-2,2,4-triazol-3-on (ONTA), Hexanitrostilben (HNS), 1,1-Diamino-2,2-dinitroethen (DADNE oder Fox-7) oder aus einer der Mischungen davon, und
    einer Flüssigkeit gebildet wird, die aus den Polyol-Polymeren der Gruppe der Polyisobutylenpolyole, Polybutadienpolyole, Polyetherpolyole, Polyesterpolyole und Polysiloxanpolyole, deren zahlenmittleres Molekulargewicht zwischen 500 und 10.000 liegt, und Mischungen davon ausgewählt ist.
  2. Formbarer, fester Sprengstoff nach Anspruch 1, dadurch gekennzeichnet, dass die pulverförmige Sprengladung zumindest 85 Massen-% der Gesamtmasse des Blocks ausmacht.
  3. Formbarer, fester Sprengstoff nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Sprengladung aus Oktogen (HMX), Hexogen (RDX), Pentaerythrityltetranitrat (Pentrit oder PEFN) und Hexanitrohexaazaisowurtzitan (CL20) ausgewählt ist.
  4. Formbarer, fester Sprengstoff nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Flüssigkeit aus den Polybutadienpolyolen und Mischungen davon ausgewählt ist.
  5. Formbarer, fester Sprengstoff nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Flüssigkeit aus einem hydroxyl-terminierten Polybutadien besteht.
  6. Formbarer, fester Sprengstoff nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass der Block bis zu 2 Massen-% zumindest eines Additivs umfasst.
  7. Formbarer, fester Sprengstoff nach Anspruch 6, dadurch gekennzeichnet, dass das zumindest eine Additiv ausgewählt ist aus: Antioxidantien, Mitteln, welche die alterungsbedingte Härtung verhindern, chemischen Nachweismarkern.
  8. Formbarer, fester Sprengstoff nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass der Block umfasst:
    - 0 bis 2 Massen-% zumindest eines Additivs, und
    - für zumindest 98 % seiner Masse:
    + 85 bis 95 Massen-%, vorzugsweise 87 bis 90 Massen-%, der Sprengladung,
    + 3 bis 13 Massen-%, vorzugsweise 8 bis 12 Massen-%, der Flüssigkeit.
  9. Formbarer, fester Sprengstoff nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass der Block oder Kuchen eine Masse zwischen 100 g und 5 kg aufweist.
  10. Verfahren zum Erhalt eines formbaren, festen Sprengstoffs nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass es umfasst:
    - Erhalten einer Paste durch Kneten einer Mischung, die zu zumindest 98 % ihrer Masse aus einer pulverförmigen Sprengladung, bestehend aus Oktogen (HMX), Hexogen (RDX), Pentaerythrityltetranitrat (Pentrit oder PEFN), Hexanitrohexaazaisowurtzitan (CL20), Triaminotrinitrobenzol (TATB), 5-Nitro-2,2,4-triazol-3-on (ONTA), Hexanitrostilben (HNS), 1,1-Diamino-2,2-dinitroethen (DADNE oder Fox-7) oder einer der Mischungen davon, und einer Flüssigkeit gebildet wird, die aus den Polyol-Polymeren der Gruppe der Polyisobutylenpolyole, Polybutadienpolyole, Polyetherpolyole, Polyesterpolyole und Polysiloxanpolyole, deren zahlen Molekulargewicht zwischen 500 und 10.000 liegt, und Mischungen davon ausgewählt ist,
    - Formen der Paste in einer oder mehreren Formen und Entformen der geformten Paste, um einen oder mehrere Blöcke des formbaren, festen Sprengstoffs zu erhalten, oder Schneiden der extrudierten Paste, um Blöcke des formbaren, festen Sprengstoffs zu erhalten.
  11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, dass das Kneten bei Umgebungstemperatur oder warm, bei einer Temperatur kleiner oder gleich 80 °C, erfolgt.
  12. Verfahren nach Anspruch 10 oder 11, dadurch gekennzeichnet, dass es kontinuierlich oder in Chargen erfolgt.
EP10810850.7A 2009-12-21 2010-12-20 Verformbarer explosiver feststoff und verfahren zu seiner herstellung Active EP2516356B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0959290A FR2954309B1 (fr) 2009-12-21 2009-12-21 Explosif solide malleable et son obtention
PCT/FR2010/052827 WO2011083249A1 (fr) 2009-12-21 2010-12-20 Explosif solide malleable et son obtention

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Publication Number Publication Date
EP2516356A1 EP2516356A1 (de) 2012-10-31
EP2516356B1 true EP2516356B1 (de) 2020-03-11

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US (1) US20120305148A1 (de)
EP (1) EP2516356B1 (de)
JP (1) JP2013514962A (de)
KR (1) KR20120108014A (de)
CN (1) CN102666438B (de)
AU (1) AU2010340832B2 (de)
BR (1) BR112012015076A2 (de)
CA (1) CA2784311C (de)
ES (1) ES2796830T3 (de)
FR (1) FR2954309B1 (de)
IL (1) IL220431A (de)
RU (1) RU2541079C2 (de)
SG (1) SG181832A1 (de)
WO (1) WO2011083249A1 (de)

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FR3028852B1 (fr) * 2014-11-21 2017-01-06 Herakles Produits explosifs composites de faible epaisseur et leur preparation
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US20120305148A1 (en) 2012-12-06
FR2954309A1 (fr) 2011-06-24
JP2013514962A (ja) 2013-05-02
CA2784311A1 (fr) 2011-07-14
KR20120108014A (ko) 2012-10-04
SG181832A1 (en) 2012-07-30
EP2516356A1 (de) 2012-10-31
CA2784311C (fr) 2018-03-13
CN102666438A (zh) 2012-09-12
BR112012015076A2 (pt) 2017-03-07
AU2010340832A1 (en) 2012-07-12
RU2541079C2 (ru) 2015-02-10
RU2012129733A (ru) 2014-02-10
CN102666438B (zh) 2014-10-08
AU2010340832B2 (en) 2015-04-09
ES2796830T3 (es) 2020-11-30
WO2011083249A1 (fr) 2011-07-14
IL220431A (en) 2017-04-30
FR2954309B1 (fr) 2012-03-23

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