Classifications

• • C—CHEMISTRY; METALLURGY
  • C06—EXPLOSIVES; MATCHES
  • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
  • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
  • C06B23/005—Desensitisers, phlegmatisers
• • 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
• • 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 composition
• an insensitive explosive active composition comprising an explosive and a phlegmatizer.
• 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.
• 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, damaging this diffusion barrier or incorrect or accidentally failed installation of the diffusion barrier poses a great security risk.
• Binders and plasticizers are generally inert substances which reduce the performance of an explosive active mass when it is detonated, for example by a reduction in density. You always try explosive effects with the highest possible Density and thus high performance produce. So far, it has not been possible to provide an energetic binder or an energetic plasticizer and thus make an explosive active material insensitive without adversely affecting other important properties or the energy density.
• GAP glycidyl azide polymer
• GAP glycidyl azide polymer
• the glass transition temperature is in the range of -30 ° C. This is generally considered insufficient for military purposes.
• GAP as an energetic binder, reduces the density and thus the performance of an insensitive explosive active material bound thereto to such an extent that the GAP has no advantage over an inert higher density binder. Even with other energetic binders and / or plasticizers, it has not been possible to provide an explosive active material whose energy density exceeds that of explosive active compounds with an inert binder and plasticizer, such as DXP-1340.
• the object of the present invention is to provide an insensitive explosive active material which does not have the above disadvantages.
• the explosives active material should have a long shelf life and good compatibility with many common plastics.
• Common plastics are z.
• polyesters polyamides, polyolefins, polytetrafluoroethylene (Teflon®), polyacrylate, polycarbonates, nitrile-butadiene rubber, chloroprene rubber (Neoprene®) and fluororubber (Viton®).
• the explosive active mass should be able to provide a high power at its detonation.
• an insensitive explosive active mass which comprises an explosive and a phlegmatizer.
• the phlegmatizer comprises at least one ionic liquid.
• An ionic liquid (liquid salt) is a liquid which consists exclusively of ions and, in contrast to a molten salt, is liquid even at a temperature below 100 ° C., without the salt being dissolved in a solvent such as water.
• an ionic liquid is an organic salt, its ions hinder the formation of a stable crystal lattice through charge delocalization and steric effects.
• Ionic liquids have proven to be extremely insensitive. At the same time they have a relatively high density.
• the ionic liquid can simultaneously serve as a phlegmatizer and plasticizer in the explosive active material according to the invention, but without the usual disadvantages of the plasticizer previously used in insensitive explosive compositions. It has been shown that the ionic liquid does not migrate in the insensitive explosive active material. The disadvantage of the limited shelf life due to the migration of the plasticizer associated with conventional insensitive explosive compositions with the plasticizer is eliminated in the case of the explosive active material according to the invention.
• a binder is not absolutely necessary in the explosives active composition according to the invention, since ionic liquids can simultaneously bind the explosive as phlegmatizers. With an ionic liquid, an insensitive explosive active mass can be realized with a higher power than known explosive active compounds. This is due, first, to the relatively high density of the ionic liquid and, secondly, to the fact that a binder which generally has a relatively low density can be dispensed with or, if a binder is used, only a very small amount in the simultaneous presence of the ionic liquid Binder is needed.
• the ionic liquid may be an energetic liquid.
• An energetic fluid is one that releases energy itself during the reaction of the explosive.
• the explosive active composition according to the invention knead relatively well by the ionic liquid and can be mixed easily and quickly. Furthermore, it can be pressed well and the resulting compacts have a relatively high mechanical strength.
• a significant advantage is that the explosive active material according to the invention can be tolerated indefinitely with nonpolar plastics, since ionic liquids do not attack these plastics.
• the disadvantage of the incompatibility of the plasticizer associated with customary insensitive explosive actives with the plasticizer with most plastics is eliminated by the use of ionic liquid as a phlegmatizer.
• Another advantage is the electrical conductivity of the ionic liquid. As a result of the ionic liquid, the explosive active mass automatically becomes conductive and any electrical charges that may occur can flow away. As a result, the risk of accidental ignition of the explosive active material according to the invention by an electrostatic discharge is drastically reduced.
• the ionic liquid is water-insoluble and non-hygroscopic. This prevents the composition and the properties of the explosive active composition according to the invention from changing due to moisture absorbed from the air.
• the ionic liquid may have a density of at least 1100 kg / m 3 .
• the explosive active material according to the invention can be provided with a high density and thus also a high explosive power.
• the ionic liquid may comprise a perchlorate, nitrate, acetate, dicyanamide, hexafluorophosphate or tetrafluoroborate ion as an anion.
• the anion containing in the ionic liquid the reaction behavior of the explosive active material according to the invention can be varied during heating.
• the anion may be oxidizing, as the z. B. perchlorate or nitrate is the case.
• an inert anion for example acetate, dicyanamide, hexafluorophosphate or tetrafluoroborate.
• the decomposition of the ionic liquid is endothermic at least at the beginning of heating. Furthermore, the choice of anion has an influence on the decomposition temperature. Of the above anions, acetate decomposes at the lowest temperature and tetrafluoroborate at the highest temperature. By providing a mixture of these anions in the ionic liquid or a mixture of ionic liquids, the temperature-dependent behavior of the liquid or of the mixture can be influenced. These capabilities can be used to adjust the sensitivity and thermal behavior of the explosive active mass. If the ionic liquid at least initially decomposes endothermically at a lower temperature than the explosive, the sensitivity of the explosive active material according to the invention is considerably reduced.
• the ionic liquid can be 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM-BF 4 ), 1-butyl-3-methylimidazolium dicyanamide (BMIM-C 2 N 2 ), n-butylmethylimidazolium perchlorate (BMIM-ClO 4 ), an alkylmethylimidazole, in particular Dimethylimidazole or ethylmethylimidazole, a tetrazolate or a triazolate.
• BMIM-BF 4 1-butyl-3-methylimidazolium tetrafluoroborate
• BMIM-C 2 N 2 1-butyl-3-methylimidazolium dicyanamide
• BMIM-ClO 4 n-butylmethylimidazolium perchlorate
• an alkylmethylimidazole in particular Dimethylimidazole or ethylmethylimidazole, a tetrazolate or a triazo
• the ionic liquid is contained therein with a proportion based on the total weight of the active material in the range of 3 wt .-% to 7 wt .-%, in particular 4 wt .-% to 6 wt .-%.
• the total density of the explosive active material according to the invention is not significantly affected.
• the said proportion is completely sufficient for adequate phlegmatization.
• the explosive active material according to the invention can furthermore comprise a, in particular energetic, binder. If both the binder and the ionic liquid are energetic, an insensitive yet very powerful full energetic, d. H. no inert constituent explosives active mass are provided.
• the binder may comprise a polar polymer or polar macromolecule or a polymer or macromolecule which is soluble in or swollen by the ionic liquid.
• the polymer may comprise polyacrylonitrile, polyvinyl nitrate, polyvinylpyrrolidone (PVP) or nitrocellulose. Relatively little ionic liquid is needed to turn the polymers mentioned by dissolving them into a viscous and sticky mass. As a result, the amount of the usually relatively expensive ionic liquid required for the phlegmatization can be reduced.
• the explosive particles can be coated with the ionic liquid and optionally the binder by slurrying the explosive particles into the solution of the ionic liquid and optionally additionally contained binder and, during mixing, withdrawing the solvent under reduced pressure. It has been shown that it does not matter how fast that Solvent is removed. The ionic liquid and optionally the binder settle on the explosive particles and coat / coat them evenly.
• an energetic binder which decomposes with gas evolution at a lower temperature or decomposes as the explosive
• the safety of a explosives active material containing fire or heat-exposed active body can be increased.
• the evolution of gas at low temperature causes the sheath of the active body to rupture, causing the explosive to ignite in the event of an abrupt increase in pressure Detonation of the explosive is thus unlikely and, ideally, when the explosive only burns out, does not take place
• a low-temperature decomposing binder is, for example, nitrocellulose, which begins to decompose at about 120 ° C in the range between about 160 ° C and 180 ° C decomposes strongly and completely with evolution of gas.
• a explosive which decomposes at a significantly higher temperature is, for example, octogen, the decomposition of which takes place at about 280 ° C.
• the binder in the explosive active material in a proportion in the range of 1 wt .-% to 2.5 wt .-%, in particular 1.5 wt .-% to 2 wt .-%, contained.
• the explosive may be a crystalline explosive.
• the explosive can z. Octogen, hexogen, nitropenta (PETN), triaminotrinitrobenzene (TATB), diaminodinitroethylene (FOX-7) or hexanitroisowurtzitane (CL-20).
• Example 1 represents an insensitive explosive according to the prior art
• Examples 4 and 5 are explosive compositions of the invention
• Examples 2 and 3 are other novel insensitive explosive compositions.
• BMIM-ClO 4 200 g of the ionic liquid BMIM-ClO 4 used in Example 5 were synthesized as follows: 150 g of BMIM-Cl were dissolved in about 600 ml of dry methanol at 25 ° C. in a 2 liter one-necked flask. A stoichiometric amount of dry sodium perchlorate was also separately dissolved in 600 ml of dry methanol in a 2 liter one-necked flask. Then all the perchlorate solution was added all at once to the BMIM chloride solution. The bottle containing the perchlorate solution was washed 3 times with 50 ml of dry methanol and the methanol was added to the BMIM chloride solution. The resulting solution became cloudy and yellow after several minutes as the resulting sodium chloride began to precipitate.
• the one-necked flask was then connected to a rotary evaporator and the methanol distilled off under about 500 mbar pressure, the water bath was heated to 90 ° C in the evaporator.
• the warm crude BMIM-ClO 4 from the flask was again filtered through the frit into a 250 ml separatory funnel, because even more common salt had precipitated upon evaporation of the methanol.
• the final BMIM-ClO 4 (a yellowish, viscous oil) was filled from the separating funnel into a laboratory flask and weighed. The yield was almost quantitative.
• the BMIM-ClO 4 has proven to be a very good binder and phlegmatizer for energetic active compounds. From this it is possible to produce very insensitive explosive active compounds with a small or large proportion of polymeric binder and high density and performance.
• the ratio of BMIM-ClO 4 to polymeric binder, the hardness and mechanical strength of the active material can be adjusted within wide limits.
• the polyvinylpyrrolidone was dissolved in ethanol and the nitrocellulose in ethanol-ethyl acetate (2: 1). Subsequently, the ionic liquid was metered into this solution. The mixture was then stirred for a further 1 minute to homogenize the solution. For 1 kg of explosive, about 400 ml of solvent were needed.
• the explosive dried over night at 50 ° C. and the binder solution were thoroughly mixed. After mixing for 5 minutes, a vacuum was applied and a temperature of 70 ° C was set until the solvent had evaporated. Thereafter, the explosive active mass was discharged from the mixer. It was a slightly sticky, colorless powder.
• 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 results of the gap test are shown in the table below.

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• 2012
  • 2012-08-17 DE DE102012016478.5A patent/DE102012016478A1/de not_active Withdrawn
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