EP2872464B1 - Insensitive explosive active substance - Google Patents

Insensitive explosive active substance Download PDF

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Publication number
EP2872464B1
EP2872464B1 EP13732834.0A EP13732834A EP2872464B1 EP 2872464 B1 EP2872464 B1 EP 2872464B1 EP 13732834 A EP13732834 A EP 13732834A EP 2872464 B1 EP2872464 B1 EP 2872464B1
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EP
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Prior art keywords
explosive
active material
insensitive
chloroparaffin
explosive active
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EP13732834.0A
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German (de)
French (fr)
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EP2872464A1 (en
Inventor
Arno Hahma
Johann Licha
Oliver PHAM-SCHÖNWETTER
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Diehl Defence GmbH and Co KG
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Diehl Defence GmbH and Co KG
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0033—Shaping the mixture
    • C06B21/0041—Shaping the mixture by compression
    • 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
    • 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
    • C06B45/18—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component
    • C06B45/20—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component the component base containing an organic explosive or an organic thermic component
    • C06B45/22—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component the component base containing an organic explosive or an organic thermic component the coating containing an organic compound

Definitions

  • the invention relates to an insensitive explosive active material which requires no plasticizer and can nevertheless be realized with a high density.
  • a reduction in the density of an explosive active mass reduces its performance as it detonates. It is therefore always trying to produce explosive active materials with the highest possible density.
  • Known insensitive explosive compositions contain either more than 8% by weight of binder and thus have a relatively low density or contain a binder with a plasticizer, such as explosive DXP-1340, which consists of octogen, acrylate rubber and dioctyl adipate as plasticizer and which is currently the most powerful Insensitive explosives active substance is.
  • the plasticizer migrates over time in the explosive active mass and out of the explosive active mass. Due to the migration of the plasticizer, the sensitivity can locally increase so that the explosive active material loses its insensitivity. Furthermore, the migration of the plasticizer changes the mechanical properties of the explosive active material. The shelf life of the explosive active mass is limited by the migration of the plasticizer.
  • the object of the present invention is to provide an insensitive explosive active material which does not have the above disadvantages. It should in particular have a high density coupled with long shelf life and good compatibility with plastics. Another object is to provide an insensitive explosive active mass that can be provided with at least the same performance as DXP-1340.
  • an insensitive explosive active composition comprising an explosive and a mixture of a chlorinated paraffin and polyvinyl chloride (PVC) is provided as a binder.
  • PVC polyvinyl chloride
  • chloroparaffins combine a large number of advantageous properties and are thus ideally suited as binders for an insensitive explosive active material.
  • Chloroparaffins are fire-retardant, whereby the unwanted ignition of the explosive active material according to the invention is inhibited by heat.
  • chloroparaffins have sufficient mechanical strength to act as a binder and adhere well to most materials.
  • a plasticizer is not required. In contrast to the usual plasticizers, chloroparaffins are not readily volatile and not highly liquid, so that migration is ruled out.
  • chloroparaffins make it possible to realize an insensitive explosive active material with very high performance, because chloroparaffins have a relatively high density.
  • the performance is a function of the density and is the higher, the higher the density of an explosive active mass.
  • compacts produced from the explosive active composition according to the invention have a higher mechanical strength than compacts from DXP-1340.
  • the invention enables the provision of an insensitive explosive active material without plasticizer and without the power loss usually associated with an increased content of binder. In particular, it also enables the production of an explosive active mass with a higher density and performance than DXP-1340.
  • Producing the explosive active material according to the invention by mixing the explosive with a chloroparaffin is considerably easier than producing a Explosive material with polymeric binders, because chloroparaffins are readily soluble in hydrocarbons and ethers, while the usual explosives are completely insoluble therein. This allows a simple coating of explosive particles with chloroparaffin by slurrying the explosive in a chlorinated paraffin solution and during mixing, the solvent is removed under reduced pressure.
  • Chlorine paraffin dissolves immediately in the mentioned solvents.
  • polymeric binders it is necessary to first prepare a solution of the polymeric binder in a solvent. This process is usually time consuming. Further time can be saved when removing the solvent.
  • chloroparaffin the solvent can be removed very quickly, without the coating of the explosive particles becoming uneven and therefore the insensitivity of the resulting explosive active material can no longer be guaranteed.
  • the insensitive explosive active material in one embodiment, no plasticizer is contained therein.
  • the explosive active material is permanently compatible with almost all plastics. Because no plasticizer can migrate out of the explosive active mass, its composition does not change over time. He thus has a very long shelf life.
  • the explosive active substance according to the invention contains no further binder.
  • chloroparaffin With chloroparaffin, it is possible to provide an insensitive explosive active material with only 5 wt .-% binder, without the explosives active mass thereby significantly loses power over the explosive itself. This is because chloroparaffins have a high density and thus the entire explosive active mass is denser than, for example, with an acrylate-based binder such. HyTemp® from Zeon Europe GmbH, Germany, with a plasticizer such as dioctyl adipate (DOA). The power, ie the detonation pressure, is dependent on the density of the explosive active substance in the third power. As a result, increasing the density of a chloroparaffin to compensate for the loss of power in the explosives active composition of the invention by replacing otherwise occupied by the explosive volume by the binder.
  • DOA dioctyl adipate
  • the chloroparaffin may have a chain length of at least 14 and at most 17 C atoms.
  • Such chloroparaffin is commonly referred to as medium molecular weight chlorinated paraffin and sold as such.
  • the chloroparaffin is incompletely chlorinated. It may have a degree of chlorination in the range of from 45% to 65%, especially from 48% to 62%, especially from 48 to 58%.
  • the chlorinated paraffin is contained therein with a content of at most 8% by weight, in particular at most 6% by weight, in particular at most 5% by weight.
  • the proportion of PVC in the binder is in the range of 5 wt .-% to 50 wt .-%, in particular 15 wt .-% to 35 wt .-%, in particular 20 wt .-% to 30 wt .-%.
  • the explosive may be a crystalline explosive. With crystalline explosives the problem of the sensitivity and thus an unwanted ignition is particularly large. There is therefore a great need for the insensitization of these explosives.
  • the crystalline explosives in the explosive crystals should not have any cavities, since a collapse of these cavities under pressure also always entails the risk of an unwanted ignition.
  • the explosive may be octogen, hexogen, nitropenta (PETN), triaminotrinitrobenzene (TATB), diaminodinitroethylene (FOX-7) or hexanitrohexaazaisowurtzitane (HNIW, CL-20).
  • Examples 2 to 8 and 10 are not insensitive explosive compositions according to the invention, while Example 1 is the known explosive DXP-1340.
  • TMD means "theoretical maximum density” in the unit kg / m 3 .
  • Chlorine paraffin was in the above examples in each case by the company Leuna-Tenside GmbH, 06237 Leuna, Germany.
  • Polyvinyl chloride was purchased from Solvay SA, Belgium and Oktogen from Nexplo Bofors AB, Karlskoga, Sweden.
  • sieved 630 ⁇ m means that the maximum size of the particles contained therein is 630 ⁇ m.
  • CP is the abbreviation for chlorinated paraffin.
  • Examples 2 to 10 All mixtures of Examples 2 to 10 were mixed in a 1 kilogram batch.
  • the explosive octogen and the chloroparaffin were weighed into a mixer. Subsequently, about 800 ml of solvent were added.
  • Suitable solvents are any solvent in which the binder can be dissolved homogeneously, but the explosive is not or at most slightly soluble.
  • n-hexane was used as the solvent.
  • Other solvents suitable for this purpose are, for example, dichloromethane or dichloroethane.
  • tetrahydrofuran was used as the solvent.
  • the gap test is a standard test for determining the insensitivity of explosive compounds or explosives.
  • the height of a standardized water column is measured, which is sufficient to transmit a shock wave generated by detonation of a standard explosive charge in the water column on the explosive active mass to be examined, so that they still reliably detonated, and reliably no longer detonated.
  • the values are given in mm of the water column.
  • the first value under "Gap [mm]” in each case denotes the value at which the explosive active substance to be investigated reliably detonates ("GO") and a second value, the value at which the explosive active substance to be investigated no longer detonates ("NO GO "). The lower these values are, the more insensitive the explosive active mass is.
  • the results of the gap test are shown in the table below.
  • Tg glass transition temperature
  • n. G means "not measured”.
  • the glass transition temperature was measured by differential scanning calorimetry (DSC).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Molecular Biology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Description

Die Erfindung betrifft eine insensitive Sprengstoffwirkmasse, welche keinen Weichmacher benötigt und dennoch mit einer hohen Dichte realisiert werden kann. Eine Reduktion der Dichte einer Sprengstoffwirkmasse verringert deren Leistung bei deren Detonation. Man versucht daher stets Sprengstoffwirkmassen mit möglichst hoher Dichte herzustellen.The invention relates to an insensitive explosive active material which requires no plasticizer and can nevertheless be realized with a high density. A reduction in the density of an explosive active mass reduces its performance as it detonates. It is therefore always trying to produce explosive active materials with the highest possible density.

Bekannte insensitive Sprengstoffwirkmassen enthalten entweder über 8 Gew.-% Bindemittel und weisen dadurch eine verhältnismäßig geringe Dichte auf oder sie enthalten ein Bindemittel mit einem Weichmacher, wie die Sprengstoffwirkmasse DXP-1340, die aus Oktogen, Acrylatgummi und Dioctyladipat als Weichmacher besteht und die derzeit leistungsstärkste insensitive Sprengstoffwirkmasse ist. Der Weichmacher migriert im Laufe der Zeit in der Sprengstoffwirkmasse und aus der Sprengstoffwirkmasse heraus. Durch die Migration des Weichmachers kann die Empfindlichkeit lokal so steigen, dass die Sprengstoffwirkmasse ihre Insensitivität verliert. Weiterhin verändern sich durch die Migration des Weichmachers die mechanischen Eigenschaften der Sprengstoffwirkmasse. Die Lagerfähigkeit der Sprengstoffwirkmasse wird durch die Migration des Weichmachers begrenzt. Eine Sprengstoffladung, die einen Sprengstoff und eine Mischung aus einem chlorierten Paraffinwachs und einem flüssigen chlorierten Öl umfasst, ist aus US-Patent 8,216,404 B1 bekannt. Weiterhin zerstört der Weichmacher bei Kontakt nahezu alle bekannten Kunststoffe oder bringt sie zum Quellen. Daher muss eine Weichmacher enthaltende Sprengstoffwirkmasse immer von allen Kunststoffteilen mittels einer metallischen Diffusionssperre isoliert werden. Dies ist verhältnismäßig aufwendig. Darüber hinaus birgt die Beschädigung dieser Diffusionssperre oder ein fehlerhafter oder versehentlich nicht erfolgter Einbau der Diffusionssperre große Risiken in sich.Known insensitive explosive compositions contain either more than 8% by weight of binder and thus have a relatively low density or contain a binder with a plasticizer, such as explosive DXP-1340, which consists of octogen, acrylate rubber and dioctyl adipate as plasticizer and which is currently the most powerful Insensitive explosives active substance is. The plasticizer migrates over time in the explosive active mass and out of the explosive active mass. Due to the migration of the plasticizer, the sensitivity can locally increase so that the explosive active material loses its insensitivity. Furthermore, the migration of the plasticizer changes the mechanical properties of the explosive active material. The shelf life of the explosive active mass is limited by the migration of the plasticizer. An explosive charge comprising an explosive and a mixture of a chlorinated paraffin wax and a liquid chlorinated oil is out U.S. Patent 8,216,404 B1 known. Furthermore, the plasticizer destroys almost all known plastics or causes them to swell on contact. Therefore, a plasticizer-containing explosives active mass must always be isolated from all plastic parts by means of a metallic diffusion barrier. This is relatively expensive. In addition, the damage to this diffusion barrier or a faulty or accidentally failed installation of the diffusion barrier entails great risks.

Aufgabe der vorliegenden Erfindung ist es, eine insensitive Sprengstoffwirkmasse bereitzustellen, welche die obigen Nachteile nicht aufweist. Sie soll insbesondere eine hohe Dichte bei gleichzeitig langer Lagerfähigkeit und guter Verträglichkeit mit Kunststoffen aufweisen. Eine weitere Aufgabe besteht darin, eine insensitive Sprengstoffwirkmasse bereitzustellen, die mit mindestens der gleichen Leistungsstärke wie DXP-1340 bereitgestellt werden kann.The object of the present invention is to provide an insensitive explosive active material which does not have the above disadvantages. It should in particular have a high density coupled with long shelf life and good compatibility with plastics. Another object is to provide an insensitive explosive active mass that can be provided with at least the same performance as DXP-1340.

Die Aufgabe wird durch die Merkmale des Anspruchs 1 gelöst. Zweckmäßige Ausgestaltungen ergeben sich aus den Merkmalen der Ansprüche 2 bis 8. Erfindungsgemäß ist eine insensitive Sprengstoffwirkmasse umfassend einen Sprengstoff und eine Mischung aus einem Chlorparaffin und Polyvinylchlorid (PVC) als Bindemittel vorgesehen.The object is solved by the features of claim 1. Expedient embodiments result from the features of claims 2 to 8. According to the invention, an insensitive explosive active composition comprising an explosive and a mixture of a chlorinated paraffin and polyvinyl chloride (PVC) is provided as a binder.

Die Erfinder der vorliegenden Erfindung haben erkannt, dass Chlorparaffine eine große Zahl vorteilhafter Eigenschaften vereinen und damit ideal als Bindemittel für eine insensitive Sprengstoffwirkmasse geeignet sind. Chlorparaffine sind brandhemmend, wodurch die ungewollte Zündung der erfindungsgemäßen Sprengstoffwirkmasse durch Hitze gehemmt wird. Darüber hinaus weisen Chlorparaffine eine ausreichende mechanische Festigkeit auf, um als Bindemittel zu fungieren und haften hervorragend an den meisten Materialien. Wenn Chlorparaffine als Bindemittel eingesetzt werden, ist der Einsatz eines Weichmachers nicht erforderlich. Im Gegensatz zu den üblichen Weichmachern sind Chlorparaffine nicht leicht flüchtig und nicht dünnflüssig, so dass eine Migration ausgeschlossen ist. Weiterhin ermöglichen es Chlorparaffine, eine insensitive Sprengstoffwirkmasse mit sehr hoher Leistungsstärke zu realisieren, weil Chlorparaffine eine relativ hohe Dichte aufweisen. Die Leistung ist eine Funktion der Dichte und ist umso höher, je höher die Dichte einer Sprengstoffwirkmasse ist. Weiterhin hat es sich gezeigt, dass aus der erfindungsgemäßen Sprengstoffwirkmasse hergestellte Presslinge eine höhere mechanische Festigkeit als Presslinge aus DXP-1340 aufweisen. Die Erfindung ermöglicht die Bereitstellung einer insensitiven Sprengstoffwirkmasse ohne Weichmacher und ohne den üblicherweise mit einem erhöhten Anteil an Bindemittel einhergehenden Leistungsverlust. Insbesondere ermöglicht sie auch die Herstellung einer Sprengstoffwirkmasse mit einer höheren Dichte und Leistungsstärke als DXP-1340.The inventors of the present invention have recognized that chloroparaffins combine a large number of advantageous properties and are thus ideally suited as binders for an insensitive explosive active material. Chloroparaffins are fire-retardant, whereby the unwanted ignition of the explosive active material according to the invention is inhibited by heat. In addition, chloroparaffins have sufficient mechanical strength to act as a binder and adhere well to most materials. When chloroparaffins are used as binders, the use of a plasticizer is not required. In contrast to the usual plasticizers, chloroparaffins are not readily volatile and not highly liquid, so that migration is ruled out. Furthermore, chloroparaffins make it possible to realize an insensitive explosive active material with very high performance, because chloroparaffins have a relatively high density. The performance is a function of the density and is the higher, the higher the density of an explosive active mass. Furthermore, it has been shown that compacts produced from the explosive active composition according to the invention have a higher mechanical strength than compacts from DXP-1340. The invention enables the provision of an insensitive explosive active material without plasticizer and without the power loss usually associated with an increased content of binder. In particular, it also enables the production of an explosive active mass with a higher density and performance than DXP-1340.

Das Herstellen der erfindungsgemäßen Sprengstoffwirkmasse durch Mischen des Sprengstoffs mit einem Chlorparaffin ist erheblich einfacher als das Herstellen einer Sprengstoffwirkmasse mit polymeren Bindemitteln, weil Chlorparaffine in Kohlenwasserstoffen und Ether leicht löslich sind, während die üblichen Sprengstoffe darin völlig unlöslich sind. Dies ermöglicht eine einfache Beschichtung von Sprengstoffpartikeln mit Chlorparaffin, indem der Sprengstoff in eine Chlorparaffinlösung eingeschlämmt wird und während des Mischens das Lösungsmittel unter reduziertem Druck abgezogen wird.Producing the explosive active material according to the invention by mixing the explosive with a chloroparaffin is considerably easier than producing a Explosive material with polymeric binders, because chloroparaffins are readily soluble in hydrocarbons and ethers, while the usual explosives are completely insoluble therein. This allows a simple coating of explosive particles with chloroparaffin by slurrying the explosive in a chlorinated paraffin solution and during mixing, the solvent is removed under reduced pressure.

Chlorparaffin löst sich sofort in den genannten Lösungsmitteln. Bei polymeren Bindemitteln ist es dagegen erforderlich, zunächst eine Lösung des polymeren Bindemittels in einem Lösungsmittel herzustellen. Dieser Vorgang ist üblicherweise zeitaufwendig. Weitere Zeit kann beim Abziehen des Lösungsmittels eingespart werden. Im Gegensatz zu polymeren Bindemitteln kann bei Chlorparaffin das Lösungsmittel sehr schnell abgezogen werden, ohne dass dadurch die Beschichtung der Sprengstoffpartikel ungleichmäßig wird und deshalb die Insensitivität der resultierenden Sprengstoffwirkmasse nicht mehr gewährleistet werden kann.Chlorine paraffin dissolves immediately in the mentioned solvents. For polymeric binders, however, it is necessary to first prepare a solution of the polymeric binder in a solvent. This process is usually time consuming. Further time can be saved when removing the solvent. In contrast to polymeric binders, with chloroparaffin the solvent can be removed very quickly, without the coating of the explosive particles becoming uneven and therefore the insensitivity of the resulting explosive active material can no longer be guaranteed.

Bei einer Ausgestaltung der erfindungsgemäßen insensitiven Sprengstoffwirkmasse ist darin kein Weichmacher enthalten. Dadurch ist die Sprengstoffwirkmasse mit nahezu allen Kunststoffen dauerhaft verträglich. Weil dadurch kein Weichmacher aus der Sprengstoffwirkmasse herausmigrieren kann, ändert sich dessen Zusammensetzung mit der Zeit nicht. Er weist dadurch eine sehr lange Lagerfähigkeit auf. Die erfindungsgemäße Sprengstoffwirkmasse enthält neben der Mischung aus Chlorparaffin und PVC kein weiteres Bindemittel.In one embodiment of the insensitive explosive active material according to the invention, no plasticizer is contained therein. As a result, the explosive active material is permanently compatible with almost all plastics. Because no plasticizer can migrate out of the explosive active mass, its composition does not change over time. He thus has a very long shelf life. In addition to the mixture of chlorinated paraffin and PVC, the explosive active substance according to the invention contains no further binder.

Mit Chlorparaffin ist es möglich, eine insensitive Sprengstoffwirkmasse mit nur 5 Gew.-% Bindemittel bereitzustellen, ohne dass die Sprengstoffwirkmasse dadurch gegenüber dem Sprengstoff selbst wesentlich an Leistung verliert. Das liegt daran, dass Chlorparaffine eine hohe Dichte haben und somit die gesamte Sprengstoffwirkmasse dichter wird als beispielsweise mit einem Bindemittel auf Acrylatbasis, wie z. B. HyTemp® der Fa. Zeon Europe GmbH, Deutschland, mit einem Weichmacher wie Dioctyladipat (DOA). Die Leistung, d. h. der Detonationsdruck, ist in der dritten Potenz von der Dichte der Sprengstoffwirkmasse abhängig. Dadurch reicht die Erhöhung der Dichte durch ein Chlorparaffin aus, um bei der erfindungsgemäßen Sprengstoffwirkmasse einen Leistungsverlust durch ein Ersetzen von ansonsten vom Sprengstoff eingenommenen Volumen durch das Bindemittel zu kompensieren.With chloroparaffin, it is possible to provide an insensitive explosive active material with only 5 wt .-% binder, without the explosives active mass thereby significantly loses power over the explosive itself. This is because chloroparaffins have a high density and thus the entire explosive active mass is denser than, for example, with an acrylate-based binder such. HyTemp® from Zeon Europe GmbH, Germany, with a plasticizer such as dioctyl adipate (DOA). The power, ie the detonation pressure, is dependent on the density of the explosive active substance in the third power. As a result, increasing the density of a chloroparaffin to compensate for the loss of power in the explosives active composition of the invention by replacing otherwise occupied by the explosive volume by the binder.

Das Chlorparaffin kann eine Kettenlänge von mindestens 14 und höchstens 17 C-Atomen aufweisen. Derartiges Chlorparaffin wird üblicherweise als Chlorparaffin mit mittlerem Molekulargewicht bezeichnet und als solches verkauft.The chloroparaffin may have a chain length of at least 14 and at most 17 C atoms. Such chloroparaffin is commonly referred to as medium molecular weight chlorinated paraffin and sold as such.

Bei einer Ausgestaltung der erfindungsgemäßen insensitiven Sprengstoffwirkmasse ist das Chlorparaffin unvollständig chloriert. Es kann einen Chlorierungsgrad im Bereich von 45 % bis 65 %, insbesondere von 48 % bis 62 %, insbesondere von 48 bis 58 %, aufweisen.In one embodiment of the insensitive explosive active material according to the invention, the chloroparaffin is incompletely chlorinated. It may have a degree of chlorination in the range of from 45% to 65%, especially from 48% to 62%, especially from 48 to 58%.

Bei einer weiteren Ausgestaltung der erfindungsgemäßen Sprengstoffwirkmasse ist das Chlorparaffin darin mit einem Anteil von höchstens 8 Gew.-%, insbesondere höchstens 6 Gew.-%, insbesondere höchstens 5 Gew.-%, enthalten. Der Anteil des PVCs in dem Bindemittel liegt im Bereich von 5 Gew.-% bis 50 Gew.-%, insbesondere 15 Gew.-% bis 35 Gew.-%, insbesondere 20 Gew.-% bis 30 Gew.-%. Bei dem Sprengstoff kann es sich um einen kristallinen Sprengstoff handeln. Bei kristallinen Sprengstoffen ist das Problem der Empfindlichkeit und damit einer ungewollten Zündung besonders groß. Es besteht daher ein großer Bedarf an der Insensitivierung dieser Sprengstoffe. Für die erfindungsgemäße insensitive Sprengstoffwirkmasse sollten die kristallinen Sprengstoffe in den Sprengstoffkristallen keine Hohlräume aufweisen, da bei einem Kollabieren dieser Hohlräume unter Druck stets auch die Gefahr einer ungewollten Zündung besteht.In a further embodiment of the explosive active material according to the invention, the chlorinated paraffin is contained therein with a content of at most 8% by weight, in particular at most 6% by weight, in particular at most 5% by weight. The proportion of PVC in the binder is in the range of 5 wt .-% to 50 wt .-%, in particular 15 wt .-% to 35 wt .-%, in particular 20 wt .-% to 30 wt .-%. The explosive may be a crystalline explosive. With crystalline explosives the problem of the sensitivity and thus an unwanted ignition is particularly large. There is therefore a great need for the insensitization of these explosives. For the insensitive explosive active material according to the invention, the crystalline explosives in the explosive crystals should not have any cavities, since a collapse of these cavities under pressure also always entails the risk of an unwanted ignition.

Bei dem Sprengstoff kann es sich um Oktogen, Hexogen, Nitropenta (PETN), Triaminotrinitrobenzol (TATB), Diaminodinitroethylen (FOX-7) oder Hexanitrohexaazaisowurtzitan (HNIW, CL-20) handeln.The explosive may be octogen, hexogen, nitropenta (PETN), triaminotrinitrobenzene (TATB), diaminodinitroethylene (FOX-7) or hexanitrohexaazaisowurtzitane (HNIW, CL-20).

Nachfolgend wird die Erfindung anhand von Ausführungsbeispielen näher erläutert.The invention will be explained in more detail by means of exemplary embodiments.

Die Beispiele 2 bis 8 und 10 stellen dabei nicht erfindungsgemäße insensitive Sprengstoffwirkmassen dar, während es sich bei Beispiel 1 um die bekannte Sprengstoffwirkmasse DXP-1340 handelt.Examples 2 to 8 and 10 are not insensitive explosive compositions according to the invention, while Example 1 is the known explosive DXP-1340.

Beispiel 1:Example 1:

Pressbare herkömmliche Sprengstoffwirkmasse DXP-1340 mit Weichmacher: Stoff Typ Gewichtsprozent Sonstiges Acrylatgummi Hytemp 4454 1,0 TMD=1833 Dioctyladipat Weichmacher 3,0 Oktogen NSO 137 gesiebt 630 µm 67,2 Oktogen NSO 152 28,8 Pressable conventional explosive DXP-1340 with plasticizer: material Type weight miscellaneous acrylate rubber Hytemp 4454 1.0 TMD = 1833 dioctyl softener 3.0 Oktogen NSO 137 sieved 630 μm 67.2 Oktogen NSO 152 28.8

Beispiel 2:Example 2:

Pressbare Sprengstoffwirkmasse ohne Weichmacher: Stoff Typ Gewichtsprozent Sonstiges Chlorparaffin Leuna Tenside CP 135 4,0 TMD=1884 Oktogen NSO 137 gesiebt 630 µm 67,2 Oktogen NSO 152 28,8 Pressable explosives active substance without plasticizer: material Type weight miscellaneous chlorinated paraffin Leuna surfactants CP 135 4.0 TMD = 1884 Oktogen NSO 137 sieved 630 μm 67.2 Oktogen NSO 152 28.8

Beispiel 3:Example 3:

Pressbare Sprengstoffwirkmasse ohne Weichmacher: Stoff Typ Gewichtsprozent Sonstiges Chlorparaffin Hordaflex LC 70 4,0 TMD=1880 Oktogen NSO 137 gesiebt 630 µm 67,2 Oktogen NSO 152 28,8 Pressable explosives active substance without plasticizer: material Type weight miscellaneous chlorinated paraffin Hordaflex LC 70 4.0 TMD = 1880 Oktogen NSO 137 sieved 630 μm 67.2 Oktogen NSO 152 28.8

Beispiel 4:Example 4:

Pressbare Sprengstoffwirkmasse ohne Weichmacher: Stoff Typ Gewichtsprozent Sonstiges Chlorparaffin Leuna Tenside CP 140 4,0 TMD=1883 Oktogen NSO 137 gesiebt 630 µm 67,2 Oktogen NSO 152 28,8 Pressable explosives active substance without plasticizer: material Type weight miscellaneous chlorinated paraffin Leuna surfactants CP 140 4.0 TMD = 1883 Oktogen NSO 137 sieved 630 μm 67.2 Oktogen NSO 152 28.8

Beispiel 5:Example 5:

Pressbare Sprengstoffwirkmasse ohne Weichmacher: Stoff Typ Gewichtsprozent Sonstiges Chlorparaffin Leuna Tenside CP 52 flüssig 4,0 TMD=1871 Oktogen NSO 137 gesiebt 630 µm 67,2 Oktogen NSO 152 28,8 Pressable explosives active substance without plasticizer: material Type weight miscellaneous chlorinated paraffin Leuna surfactants CP 52 liquid 4.0 TMD = 1871 Oktogen NSO 137 sieved 630 μm 67.2 Oktogen NSO 152 28.8

Beispiel 6:Example 6:

Pressbare Sprengstoffwirkmasse ohne Weichmacher: Stoff Typ Gewichtsprozent Sonstiges Chlorparaffin Leuna Tenside CP 135 6,0 TMD=1871 Oktogen NSO 137 gesiebt 630 µm 66,2 Oktogen NSO 152 27,8 Pressable explosives active substance without plasticizer: material Type weight miscellaneous chlorinated paraffin Leuna surfactants CP 135 6.0 TMD = 1871 Oktogen NSO 137 sieved 630 μm 66.2 Oktogen NSO 152 27.8

Beispiel 7:Example 7:

Pressbare Sprengstoffwirkmasse ohne Weichmacher: Stoff Typ Gewichtsprozent Sonstiges Chlorparaffin Leuna Tenside CP 52 flüssig 6,0 TMD=1852 Oktogen NSO 137 gesiebt 630 µm 66,2 Oktogen NSO 152 27,8 Pressable explosives active substance without plasticizer: material Type weight miscellaneous chlorinated paraffin Leuna surfactants CP 52 liquid 6.0 TMD = 1852 Oktogen NSO 137 sieved 630 μm 66.2 Oktogen NSO 152 27.8

Beispiel 8:Example 8:

Pressbare Sprengstoffwirkmasse ohne Weichmacher: Stoff Typ Gewichtsprozent Sonstiges Chlorparaffin Leuna Tenside CP 52 flüssig 5,0 TMD=1862 Oktogen NSO 137 gesiebt 630 µm 66,7 Oktogen NSO 152 28,3 Pressable explosives active substance without plasticizer: material Type weight miscellaneous chlorinated paraffin Leuna surfactants CP 52 liquid 5.0 TMD = 1862 Oktogen NSO 137 sieved 630 μm 66.7 Oktogen NSO 152 28.3

Beispiel 9:Example 9:

Erfindungsgemäße pressbare Sprengstoffwirkmasse ohne Weichmacher: Stoff Typ Gewichtsprozent Sonstiges Chlorparaffin Leuna Tenside CP 52 flüssig 4,5 TMD=1857 Polyvinylchlorid Solvin 266 SF 1,5 Oktogen NSO 137 gesiebt 630 µm 66,2 Oktogen NSO 152 27,8 Pressable explosives active substance without plasticizer according to the invention: material Type weight miscellaneous chlorinated paraffin Leuna surfactants CP 52 liquid 4.5 TMD = 1857 polyvinylchloride Solvin 266 SF 1.5 Oktogen NSO 137 sieved 630 μm 66.2 Oktogen NSO 152 27.8

Beispiel 10:Example 10:

Pressbare Sprengstoffwirkmasse ohne Weichmacher: Stoff Typ Gewichtsprozent Sonstiges Chlorparaffin Leuna Tenside CP 52 flüssig 7,0 TMD=1843 Oktogen NSO 137 gesiebt 630 µm 65,7 Oktogen NSO 152 27,3 Pressable explosives active substance without plasticizer: material Type weight miscellaneous chlorinated paraffin Leuna surfactants CP 52 liquid 7.0 TMD = 1843 Oktogen NSO 137 sieved 630 μm 65.7 Oktogen NSO 152 27.3

TMD bedeutet dabei "theoretische maximale Dichte" in der Einheit kg/m3. Chlorparaffin wurde bei den obigen Beispielen jeweils von der Firma Leuna-Tenside GmbH, 06237 Leuna, Deutschland bezogen. Polyvinylchlorid wurde von Solvay SA, Belgien und Oktogen von Nexplo Bofors AB, Karlskoga, Schweden, bezogen. Bei Oktogen bedeutet "gesiebt 630 µm", dass die maximale Größe der darin enthaltenen Partikel 630 µm beträgt. "CP" ist jeweils die Abkürzung für Chlorparaffin.TMD means "theoretical maximum density" in the unit kg / m 3 . Chlorine paraffin was in the above examples in each case by the company Leuna-Tenside GmbH, 06237 Leuna, Germany. Polyvinyl chloride was purchased from Solvay SA, Belgium and Oktogen from Nexplo Bofors AB, Karlskoga, Sweden. For octogen, "sieved 630 μm" means that the maximum size of the particles contained therein is 630 μm. "CP" is the abbreviation for chlorinated paraffin.

Alle Mischungen der Beispiele 2 bis 10 wurden in einem 1 Kilogramm Ansatz gemischt. Der Sprengstoff Oktogen und das Chlorparaffin wurden in einen Mischer eingewogen. Anschließend wurden circa 800 ml Lösungsmittel zugegeben. Als Lösungsmittel ist jedes Lösungsmittel geeignet, in welchem sich das Bindemittel homogen auflösen lässt, der Sprengstoff aber nicht oder allenfalls geringfügig löslich ist. Im Falle der nur Chlorparaffin als Bindemittel enthaltenden Beispiele wurde n-Hexan als Lösungsmittel eingesetzt. Weitere dafür geeignete Lösungsmittel sind beispielsweise Dichlormethan oder Dichlorethan. Im Falle einer Mischung aus Chlorparaffin und PVC als Bindemittel wurde Tetrahydrofuran als Lösungsmittel eingesetzt.All mixtures of Examples 2 to 10 were mixed in a 1 kilogram batch. The explosive octogen and the chloroparaffin were weighed into a mixer. Subsequently, about 800 ml of solvent were added. Suitable solvents are any solvent in which the binder can be dissolved homogeneously, but the explosive is not or at most slightly soluble. In the case of examples containing only chloroparaffin as a binder, n-hexane was used as the solvent. Other solvents suitable for this purpose are, for example, dichloromethane or dichloroethane. In the case of a mixture of chlorinated paraffin and PVC as a binder, tetrahydrofuran was used as the solvent.

Nach 5 Minuten Mischen wurde ein Vakuum angelegt und eine Temperatur von 70°C eingestellt bis das Lösungsmittel verdunstet war. Danach wurde die Sprengstoffwirkmasse aus dem Mischer entleert. Sie lag als leicht klebriges, weißes Pulver vor. 24 g der jeweiligen Sprengstoffwirkmasse wurden jeweils in einem Presswerkzeug zu Tabletten von 21 mm Durchmesser gepresst. Die Presslinge wurden gewogen und vermessen. Aus den erhaltenden Werten wurde die Dichte der Presslinge ermittelt. Anschließend wurden die Presslinge im sogenannten Gap-Test eingesetzt. Bei dem Gap-Test handelt es sich um einen Standardtest für die Ermittlung der Insensitivität von Sprengstoffwirkmassen oder Sprengstoffen. Dabei wird die Höhe einer standardisierten Wassersäule gemessen, die ausreicht um eine durch Detonation einer Standardsprengladung erzeugte Stoßwelle in der Wassersäule auf die zu untersuchenden Sprengstoffwirkmasse zu übertragen, so dass diese noch zuverlässig detoniert, bzw. zuverlässig nicht mehr detoniert. Die Werte sind dabei jeweils in mm der Wassersäule angegeben. Der erste Wert unter "Gap [mm]" bezeichnet dabei jeweils den Wert, bei dem die zu untersuchende Sprengstoffwirkmasse zuverlässig detoniert ("GO") und ein zweiter Wert, den Wert, bei dem die zu untersuchende Sprengstoffwirkmasse nicht mehr detoniert ("NO GO"). Je niedriger diese Werte sind, desto insensitiver ist die Sprengstoffwirkmasse. Die Ergebnisse des Gap-Tests sind in der nachfolgenden Tabelle aufgeführt. Tabelle 1 Stoff TMD [kg/m3] Dichte [kg/m3] % TMD Gap[mm] Ergebnis Tg/°C Beispiel 1 1833 1810 98,7 12/13 GO/NO GO -60 Beispiel 2 1884 1841 97,7 16/17 GO/NO GO n. g. Beispiel 3 1880 1830 97,3 18/19 GO/NO GO n. g. Beispiel 4 1883 1832 97,3 19 GO n. g. Beispiel 5 1871 1827 97,6 16/17 GO/NO GO -48 Beispiel 6 1871 1835 98,1 16/17 GO/NO GO n. g. Beispiel 7 1852 1814 97,9 13/14 GO/NO GO -48 Beispiel 8 1862 1818 97,6 15/16 GO/NO GO -48 Beispiel 9 1857 1801 97,0 16 GO -48 Beispiel 10 1843 1810 98,2 12/14 GO/NO GO -48 After mixing for 5 minutes, a vacuum was applied and a temperature of 70 ° C was set until the solvent had evaporated. After that, the Explosive material from the mixer emptied. It was a slightly sticky, white powder. 24 g of each explosives active material were pressed in each case in a pressing tool into tablets of 21 mm diameter. The pellets were weighed and measured. From the obtained values, the density of the pellets was determined. Subsequently, the compacts were used in the so-called gap test. The gap test is a standard test for determining the insensitivity of explosive compounds or explosives. In this case, the height of a standardized water column is measured, which is sufficient to transmit a shock wave generated by detonation of a standard explosive charge in the water column on the explosive active mass to be examined, so that they still reliably detonated, and reliably no longer detonated. The values are given in mm of the water column. The first value under "Gap [mm]" in each case denotes the value at which the explosive active substance to be investigated reliably detonates ("GO") and a second value, the value at which the explosive active substance to be investigated no longer detonates ("NO GO "). The lower these values are, the more insensitive the explosive active mass is. The results of the gap test are shown in the table below. Table 1 material TMD [kg / m 3 ] Density [kg / m 3 ] % TMD Gap [mm] Result Tg / ° C example 1 1833 1810 98.7 12/13 GO / NO GO -60 Example 2 1884 1841 97.7 16/17 GO / NO GO ng Example 3 1880 1830 97.3 18/19 GO / NO GO ng Example 4 1883 1832 97.3 19 GO ng Example 5 1871 1827 97.6 16/17 GO / NO GO -48 Example 6 1871 1835 98.1 16/17 GO / NO GO ng Example 7 1852 1814 97.9 13/14 GO / NO GO -48 Example 8 1862 1818 97.6 15/16 GO / NO GO -48 Example 9 1857 1801 97.0 16 GO -48 Example 10 1843 1810 98.2 12/14 GO / NO GO -48

Tg bedeutet dabei "Glasübergangstemperatur", "n. g." bedeutet "nicht gemessen". Die Glasübergangstemperatur wurde mittels dynamischer Differenz-Kalorimetrie (DSC) gemessen.Tg means "glass transition temperature", "n. G." means "not measured". The glass transition temperature was measured by differential scanning calorimetry (DSC).

Die für die obigen Beispiele 1 bis 10 berechneten Detonationsgeschwindigkeiten (D[m/s]) und die Detonationsdrücke (p[GPa]) bei den tatsächlich ermittelten und aus der obigen Tabelle ersichtlichen Dichten sind aus der nachfolgenden Tabelle ersichtlich. Tabelle 2 Stoff D [m/s] p [GPa] Beispiel 1 8950 33,0 Beispiel 2 8960 34,1 Beispiel 3 8920 33,6 Beispiel 4 8930 33,7 Beispiel 5 8930 33,6 Beispiel 6 8850 33,7 Beispiel 7 8810 32,8 Beispiel 8 8860 33,1 Beispiel 9 8750 32,2 Beispiel 10 8760 32,6 The detonation velocities (D [m / s]) and the detonation pressures (p [GPa]) calculated for the above examples 1 to 10 at the densities actually determined and apparent from the above table are shown in the table below. Table 2 material D [m / s] p [GPa] example 1 8950 33.0 Example 2 8960 34.1 Example 3 8920 33.6 Example 4 8930 33.7 Example 5 8930 33.6 Example 6 8850 33.7 Example 7 8810 32.8 Example 8 8860 33.1 Example 9 8750 32.2 Example 10 8760 32.6

Claims (8)

  1. Insensitive explosive active material comprising an explosive and a mixture of a chloroparaffin and polyvinylchloride (PVC) as a binder, wherein no further binder is present in the explosive active material in addition to the mixture of chloroparaffin and PVC, wherein the chloroparaffin is present in the explosive active material in a proportion of not more than 8% by weight, wherein the PVC is present in the binder in a proportion in the range from 5% by weight to 50% by weight.
  2. Insensitive explosive active material according to Claim 1, wherein no plasticizer is present therein.
  3. Insensitive explosive active material according to either of the preceding claims, wherein the chloroparaffin has a chain length of not less than 14 and not more than 17 carbon atoms.
  4. Insensitive explosive active material according to any of the preceding claims, wherein the chloroparaffin is incompletely chlorinated.
  5. Insensitive explosive active material according to Claim 4, wherein the chloroparaffin has a degree of chlorination in the range from 45% to 65%, in particular from 48% to 62%, in particular from 48% to 58%.
  6. Insensitive explosive active material according to any of the preceding claims, wherein the chloroparaffin is present therein in a proportion of not more than 6% by weight, in particular not more than 5% by weight.
  7. Insensitive explosive active material according to any of the preceding claims, wherein the explosive is a crystalline explosive.
  8. Insensitive explosive active material according to any of the preceding claims, wherein the explosive is octogen, hexogen, nitropenta (PETN), triaminotrinitrobenzene (TATB), diaminodinitroethylene (FOX-7) or hexa-nitroisowurtzitane (CL-20).
EP13732834.0A 2012-07-13 2013-06-28 Insensitive explosive active substance Not-in-force EP2872464B1 (en)

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NL126297C (en) * 1961-06-26 1900-01-01
DE1209926B (en) * 1964-08-31 1966-01-27 Buck K G Chemische Und Tech Smoke agent
US3290190A (en) * 1965-07-06 1966-12-06 Atlantic Res Corp Plastisol propellant process with improved dispersion stability
ES381787A1 (en) * 1969-08-29 1972-11-16 Knapsack Ag Procedure for the production of scraper surfaces stable against the water, for matches. (Machine-translation by Google Translate, not legally binding)
DE2451701C3 (en) * 1974-10-31 1978-03-09 Pyrotechnische Fabrik F. Feistel Kg, 6719 Goellheim Smoke or mist composition and process for its manufacture
CH643804A5 (en) * 1980-07-24 1984-06-29 Oerlikon Buehrle Ag Explosive and process for its manufacture
FR2545478B1 (en) * 1983-05-03 1985-07-05 Commissariat Energie Atomique COLD-MOLDABLE EXPLOSIVE COMPOSITION AND PROCESS FOR PREPARING THE SAME
US4981534B1 (en) * 1990-03-07 1997-02-04 Atlantic Res Corp Occupant restraint system and composition useful therein
US5540794A (en) * 1992-05-11 1996-07-30 Thiokol Corporation Energetic binder and thermoplastic elastomer-based low vulnerability ammunition gun propellants with improved mechanical properties
CA2107256A1 (en) * 1993-03-12 1994-09-13 Joseph E. Flanagan High-density insensitive explosives
WO2002048641A1 (en) * 2000-12-13 2002-06-20 The Secretary Of State For Defence Infra-red emitting decoy flare
US7955452B1 (en) * 2009-03-10 2011-06-07 The United States Of America As Represented By The Secretary Of The Army Process for crystalline explosives containing halogenated wax binders

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