EP2698359B1 - Low sensitivity explosive agent mass with a retarding agent - Google Patents
Low sensitivity explosive agent mass with a retarding agent Download PDFInfo
- Publication number
- EP2698359B1 EP2698359B1 EP13004005.8A EP13004005A EP2698359B1 EP 2698359 B1 EP2698359 B1 EP 2698359B1 EP 13004005 A EP13004005 A EP 13004005A EP 2698359 B1 EP2698359 B1 EP 2698359B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- explosive
- ionic liquid
- insensitive
- composition according
- explosive composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002360 explosive Substances 0.000 title claims description 110
- 230000035945 sensitivity Effects 0.000 title description 4
- 239000003340 retarding agent Substances 0.000 title 1
- 239000002608 ionic liquid Substances 0.000 claims description 48
- 239000011230 binding agent Substances 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 32
- -1 dicyanamide Chemical compound 0.000 claims description 14
- UZGLIIJVICEWHF-UHFFFAOYSA-N octogen Chemical group [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UZGLIIJVICEWHF-UHFFFAOYSA-N 0.000 claims description 14
- 150000001450 anions Chemical class 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229920002521 macromolecule Polymers 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 239000000020 Nitrocellulose Substances 0.000 claims description 5
- 229920001220 nitrocellulos Polymers 0.000 claims description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 5
- MKWKGRNINWTHMC-UHFFFAOYSA-N 4,5,6-trinitrobenzene-1,2,3-triamine Chemical compound NC1=C(N)C([N+]([O-])=O)=C([N+]([O-])=O)C([N+]([O-])=O)=C1N MKWKGRNINWTHMC-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 239000000028 HMX Substances 0.000 claims description 4
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 claims description 4
- 229920006112 polar polymer Polymers 0.000 claims description 4
- ICIVTHOGIQHZRY-UHFFFAOYSA-N 1-butyl-3-methylimidazol-3-ium;cyanoiminomethylideneazanide Chemical compound [N-]=C=NC#N.CCCCN1C=C[N+](C)=C1 ICIVTHOGIQHZRY-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 claims description 2
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 2
- RIAHASMJDOMQER-UHFFFAOYSA-N 5-ethyl-2-methyl-1h-imidazole Chemical compound CCC1=CN=C(C)N1 RIAHASMJDOMQER-UHFFFAOYSA-N 0.000 claims description 2
- QVYSQTANFYDRPQ-UHFFFAOYSA-N NC(=C([N+](=O)[O-])N)[N+](=O)[O-] Chemical group NC(=C([N+](=O)[O-])N)[N+](=O)[O-] QVYSQTANFYDRPQ-UHFFFAOYSA-N 0.000 claims description 2
- XEVWREPHXINOTM-UHFFFAOYSA-N [O-][Cl](=O)(=O)=O.CCCCc1[nH]cc[n+]1C Chemical compound [O-][Cl](=O)(=O)=O.CCCCc1[nH]cc[n+]1C XEVWREPHXINOTM-UHFFFAOYSA-N 0.000 claims description 2
- FUHQFAMVYDIUKL-UHFFFAOYSA-N fox-7 Chemical compound NC(N)=C([N+]([O-])=O)[N+]([O-])=O FUHQFAMVYDIUKL-UHFFFAOYSA-N 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920001004 polyvinyl nitrate Polymers 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims 1
- 239000011149 active material Substances 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 239000004014 plasticizer Substances 0.000 description 22
- 235000002639 sodium chloride Nutrition 0.000 description 8
- 229910020366 ClO 4 Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000013543 active substance Substances 0.000 description 5
- 238000005474 detonation Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- LJQKCYFTNDAAPC-UHFFFAOYSA-N ethanol;ethyl acetate Chemical compound CCO.CCOC(C)=O LJQKCYFTNDAAPC-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- JSOGDEOQBIUNTR-UHFFFAOYSA-N 2-(azidomethyl)oxirane Chemical compound [N-]=[N+]=NCC1CO1 JSOGDEOQBIUNTR-UHFFFAOYSA-N 0.000 description 1
- 235000009917 Crataegus X brevipes Nutrition 0.000 description 1
- 235000013204 Crataegus X haemacarpa Nutrition 0.000 description 1
- 235000009685 Crataegus X maligna Nutrition 0.000 description 1
- 235000009444 Crataegus X rubrocarnea Nutrition 0.000 description 1
- 235000009486 Crataegus bullatus Nutrition 0.000 description 1
- 235000017181 Crataegus chrysocarpa Nutrition 0.000 description 1
- 235000009682 Crataegus limnophila Nutrition 0.000 description 1
- 235000004423 Crataegus monogyna Nutrition 0.000 description 1
- 240000000171 Crataegus monogyna Species 0.000 description 1
- 235000002313 Crataegus paludosa Nutrition 0.000 description 1
- 235000009840 Crataegus x incaedua Nutrition 0.000 description 1
- 229920002449 FKM Polymers 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920006362 TeflonĀ® Polymers 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- PSLIMVZEAPALCD-UHFFFAOYSA-N ethanol;ethoxyethane Chemical compound CCO.CCOCC PSLIMVZEAPALCD-UHFFFAOYSA-N 0.000 description 1
- XTLNYNMNUCLWEZ-UHFFFAOYSA-N ethanol;propan-2-one Chemical compound CCO.CC(C)=O XTLNYNMNUCLWEZ-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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.
- Such an item is from the US 2012/024437 A1 known.
- 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. Attempts are always made to produce explosive active compounds with the highest possible density and thus high performance. 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 Ā° 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 yet 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 (TeflonĀ®), polyacrylate, polycarbonates, nitrile-butadiene rubber, chloroprene rubber (NeopreneĀ®) and fluororubber (VitonĀ®).
- 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
- the explosive active material further comprises a binder, wherein the binder comprises a polar polymer or polar macromolecule or a polymer or macromolecule which is soluble in or can be swollen in the ionic liquid.
- An ionic liquid (liquid salt) is a liquid which consists exclusively of ions and, unlike a molten salt, is liquid even at a temperature below 100 Ā° C., without the salt being dissolved in a solvent such as water.
- an ionic liquid is an organic salt whose 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 necessarily required per se in the explosive active substance, since ionic liquids can simultaneously bind the explosive as phlegmatizer. 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 incompatibility of the plasticizer with most plastics associated with conventional insensitive explosive compositions with the plasticizer is eliminated by the use of the 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 alkyl-methylimidazole, especially 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 alkyl-methylimidazole especially dimethylimidazole or ethylmethylimidazole, a tetrazolate or a triazo
- the ionic liquid is contained therein with a relative to the total weight of the active material content 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 furthermore comprises 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 explosive active mass is provided.
- the binder according to the invention comprises 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 in the solution of the ionic liquid and optionally additionally contained binder and during mixing, the solvent is removed 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 shell of the body to rupture, and the ignition of the explosive then fails to produce the sudden increase in pressure
- a low-temperature decomposing binder is, for example, nitrocellulose, which begins to decompose at about 120 Ā° C in the range between about 160 Ā° C and 180 Ā° 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 Ā° 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-CI were dissolved in about 600 ml of dry methanol at 25 Ā° 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 Ā° 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 which had been dried overnight at 50 Ā° C., and the binder solution were thoroughly mixed. After mixing for 5 minutes, a vacuum was applied and a temperature of 70 Ā° 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 āGap [mm]ā 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.
- Tg glass transition temperature
- n. G means "not measuredā.
- 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)
- Air Bags (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Medicinal Preparation (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Description
Die Erfindung betrifft eine insensitive Sprengstoffwirkmasse, umfassend einen Sprengstoff und ein Phlegmatisierungsmittel. Eine solcher Gegenstand ist aus der
Bekannte insensitive Sprengstoffwirkmassen enthalten entweder Ć¼ber 8 Gew.-% Bindemittel und weisen dadurch eine verhƤltnismƤĆig 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 leistungsstƤrkste 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 InsensitivitƤt verliert. Weiterhin verƤndern sich durch die Migration des Weichmachers die mechanischen Eigenschaften der Sprengstoffwirkmasse. Die LagerfƤhigkeit der Sprengstoffwirkmasse wird durch die Migration des Weichmachers begrenzt.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.
Weiterhin zerstƶrt 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 verhƤltnismƤĆig aufwendig. DarĆ¼ber hinaus birgt eine BeschƤdigung dieser Diffusionssperre oder ein fehlerhafter oder versehentlich nicht erfolgter Einbau der Diffusionssperre ein groĆes Sicherheitsrisiko in sich.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, damaging this diffusion barrier or incorrect or accidentally failed installation of the diffusion barrier poses a great security risk.
Bindemittel und Weichmacher sind im Allgemeinen inerte Stoffe, die die Leistung einer Sprengstoffwirkmasse bei deren Detonation, beispielsweise durch eine Reduktion der Dichte, herabsetzen. Man versucht stets Sprengstoffwirkmassen mit mƶglichst hoher Dichte und damit hoher Leistung herzustellen. Bisher ist es nicht gelungen, ein energetisches Bindemittel bzw. einen energetischen Weichmacher bereitzustellen und damit eine Sprengstoffwirkmasse insensitiv zu gestalten, ohne andere wichtige Eigenschaften oder die Energiedichte negativ zu beeinflussen. Beispielsweise wird Glycidylazidpolymer (GAP) als Bindemittel fĆ¼r Sprengstoffwirkmassen verwendet. Um die Sprengstoffwirkmassen insensitiv zu machen, sind dazu jedoch mehr als 10% GAP und Weichmacher erforderlich. Die GlasĆ¼bergangstemperatur liegt dabei im Bereich von -30Ā°C. Dies wird fĆ¼r militƤrische Zwecke im Allgemeinen fĆ¼r unzureichend erachtet. GewĆ¼nscht wird hƤufig eine GlasĆ¼bergangstemperatur von -54Ā°C oder darunter. Durch GAP als energetischem Bindemittel wird die Dichte und dadurch die Leistung einer damit gebundenen insensitiven Sprengstoffwirkmasse soweit reduziert, dass das GAP gegenĆ¼ber einem inerten Bindemittel hƶherer Dichte keinen Vorteil aufweist. Auch mit anderen energetischen Bindemitteln und/oder Weichmachern ist es bisher nicht gelungen, eine Sprengstoffwirkmasse bereitzustellen, deren Energiedichte diejenige von Sprengstoffwirkmassen mit einem inerten Bindemittel und Weichmacher, wie DXP-1340, Ć¼bersteigt.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. Attempts are always made to produce explosive active compounds with the highest possible density and thus high performance. 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. For example, glycidyl azide polymer (GAP) is used as a binder for explosive actives. Around However, to render the explosive compositions insensitive, more than 10% of GAP and plasticizer are required. The glass transition temperature is in the range of -30 Ā° C. This is generally considered insufficient for military purposes. Often, a glass transition temperature of -54 Ā° C or below is desired. 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 yet 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.
Aufgabe der vorliegenden Erfindung ist es, eine insensitive Sprengstoffwirkmasse bereitzustellen, die die obigen Nachteile nicht aufweist. Insbesondere soll die Sprengstoffwirkmasse eine lange LagerfƤhigkeit und gute VertrƤglichkeit mit vielen gebrƤuchlichen Kunststoffen aufweisen. GebrƤuchliche Kunststoffe sind z. B. Polyester, Polyamide, Polyolefine, Polytetrafluorethylen (TeflonĀ®), Polyacrylat, Polycarbonate, Nitril-Butadien-Kautschuk, Chloropren-Kautschuk (NeoprenĀ®) und Fluorkautschuk (VitonĀ®). Weiterhin soll die Sprengstoffwirkmasse bei ihrer Detonation eine hohe Leistung bereitstellen kƶnnen.The object of the present invention is to provide an insensitive explosive active material which does not have the above disadvantages. In particular, the explosives active material should have a long shelf life and good compatibility with many common plastics. Common plastics are z. As polyesters, polyamides, polyolefins, polytetrafluoroethylene (TeflonĀ®), polyacrylate, polycarbonates, nitrile-butadiene rubber, chloroprene rubber (NeopreneĀ®) and fluororubber (VitonĀ®). Furthermore, the explosive active mass should be able to provide a high power at its detonation.
Die Aufgabe wird durch die Merkmale des Anspruchs 1 gelƶst. ZweckmƤĆige Ausgestaltungen ergeben sich aus den Merkmalen der AnsprĆ¼che 2 bis 12.The object is solved by the features of claim 1. Advantageous embodiments emerge from the features of claims 2 to 12.
ErfindungsgemĆ¤Ć ist eine insensitive Sprengstoffwirkmasse vorgesehen, die einen Sprengstoff und ein Phlegmatisierungsmittel umfasst. Dabei umfasst das Phlegmatisierungsmittel mindestens eine ionische FlĆ¼ssigkeit, wobei die Sprengstoffwirkmasse weiterhin ein Bindemittel umfasst, wobei das Bindemittel ein polares Polymer oder polares MakromolekĆ¼l oder ein Polymer oder MakromolekĆ¼l, das in der ionischen FlĆ¼ssigkeit lƶslich ist oder davon gequollen werden kann, umfasst. Eine ionische FlĆ¼ssigkeit (FlĆ¼ssigsalz) ist eine FlĆ¼ssigkeit, die ausschlieĆlich aus Ionen bestehen und im Gegensatz zu einer Salzschmelze bereits bei einer Temperatur unter 100Ā°C flĆ¼ssig ist, ohne dass das Salz dabei in einem Lƶsungsmittel, wie Wasser, gelƶst ist. Im Allgemeinen handelt es sich bei einer ionischen FlĆ¼ssigkeit um ein organisches Salz, dessen Ionen durch Ladungsdelokalisierung und sterische Effekte die Bildung eines stabilen Kristallgitters behindern.According to the invention, an insensitive explosive active mass is provided which comprises an explosive and a phlegmatizer. In this case, the phlegmatizer comprises at least one ionic liquid, wherein the explosive active material further comprises a binder, wherein the binder comprises a polar polymer or polar macromolecule or a polymer or macromolecule which is soluble in or can be swollen in the ionic liquid. An ionic liquid (liquid salt) is a liquid which consists exclusively of ions and, unlike a molten salt, is liquid even at a temperature below 100 Ā° C., without the salt being dissolved in a solvent such as water. In general, an ionic liquid is an organic salt whose ions hinder the formation of a stable crystal lattice through charge delocalization and steric effects.
Ionische FlĆ¼ssigkeiten haben sich als extrem insensitiv erwiesen. Gleichzeitig weisen sie eine verhƤltnismƤĆig hohe Dichte auf. Die ionische FlĆ¼ssigkeit kann in der erfindungsgemƤĆen Sprengstoffwirkmasse gleichzeitig als Phlegmatisierungsmittel und Weichmacher, jedoch ohne Ć¼bliche Nachteile der bisher bei insensitiven Sprengstoffwirkmassen verwendeten Weichmacher, dienen. Es hat sich nƤmlich gezeigt, dass die ionische FlĆ¼ssigkeit in der insensitiven Sprengstoffwirkmasse nicht migriert. Der bei Ć¼blichen insensitiven Sprengstoffwirkmassen mit dem Weichmacher einhergehende Nachteil der begrenzten LagerfƤhigkeit wegen der Migration des Weichmachers entfƤllt bei der erfindungsgemƤĆen Sprengstoffwirkmasse.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.
Ein Bindemittel ist in der Sprengstoffwirkmasse an sich nicht unbedingt erforderlich, da ionische FlĆ¼ssigkeiten als Phlegmatisierungsmittel gleichzeitig auch den Sprengstoff binden kƶnnen. Mit einer ionischen FlĆ¼ssigkeit kann eine insensitive Sprengstoffwirkmasse mit einer hƶheren Leistung als bekannte Sprengstoffwirkmassen realisiert werden. Dies liegt zum einen an der verhƤltnismƤĆig hohen Dichte der ionischen FlĆ¼ssigkeit und zum anderen daran, dass ein im Allgemeinen eine verhƤltnismƤĆig geringe Dichte aufweisendes Bindemittel entfallen kann oder, sofern doch ein Bindemittel eingesetzt wird, beim gleichzeitigen Vorhandensein der ionischen FlĆ¼ssigkeit nur eine sehr geringe Menge des Bindemittels benƶtigt wird.A binder is not necessarily required per se in the explosive active substance, since ionic liquids can simultaneously bind the explosive as phlegmatizer. 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.
Weiterhin kann es sich bei der ionischen FlĆ¼ssigkeit um eine energetische FlĆ¼ssigkeit handeln. Eine energetische FlĆ¼ssigkeit ist eine solche, die bei der Reaktion des Sprengstoffs selbst Energie freisetzt.Furthermore, the ionic liquid may be an energetic liquid. An energetic fluid is one that releases energy itself during the reaction of the explosive.
Weiterhin hat sich gezeigt, dass sich die erfindungsgemƤĆe Sprengstoffwirkmasse durch die ionische FlĆ¼ssigkeit verhƤltnismƤĆig gut kneten und einfach und schnell mischen lƤsst. Weiterhin lƤsst sie sich gut pressen und die daraus resultieren Presslinge weisen eine verhƤltnismƤĆig hohe mechanische Festigkeit auf.Furthermore, it has been found that 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.
Ein wesentlicher Vorteil ist, dass sich die erfindungsgemƤĆe Sprengstoffwirkmasse unbegrenzt mit unpolaren Kunststoffen vertrƤgt, da ionische FlĆ¼ssigkeiten diese Kunststoffe nicht angreifen. Der bei Ć¼blichen insensitiven Sprengstoffwirkmassen mit dem Weichmacher einhergehende Nachteil der UnvertrƤglichkeit des Weichmachers mit den meisten Kunststoffen entfƤllt durch den Einsatz der ionischen FlĆ¼ssigkeit als Phlegmatisierungsmittel.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 incompatibility of the plasticizer with most plastics associated with conventional insensitive explosive compositions with the plasticizer is eliminated by the use of the ionic liquid as a phlegmatizer.
Ein weiterer Vorteil besteht in der elektrischen LeitfƤhigkeit der ionischen FlĆ¼ssigkeit. Durch die ionische FlĆ¼ssigkeit wird die Sprengstoffwirkmasse automatisch leitfƤhig und gegebenenfalls auftretende elektrische Ladungen kƶnnen abflieĆen. Dadurch wird das Risiko einer ungewollten ZĆ¼ndung der erfindungsgemƤĆen Sprengstoffwirkmasse durch eine elektrostatische Entladung drastisch verringert.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.
Bei einem AusfĆ¼hrungsbeispiel ist die ionische FlĆ¼ssigkeit wasserunlƶslich und nicht hygroskopisch. Dadurch wird verhindert, dass sich die Zusammensetzung und die Eigenschaften der erfindungsgemƤĆen Sprengstoffwirkmasse durch aus der Luft aufgenommene Feuchtigkeit verƤndern.In one embodiment, 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.
Die ionische FlĆ¼ssigkeit kann eine Dichte von mindestens 1100 kg/m3 aufweisen. Dadurch kann die erfindungsgemƤĆe Sprengstoffwirkmasse mit einer hohen Dichte und damit auch einer hohen Sprengleistung bereitgestellt werden.The ionic liquid may have a density of at least 1100 kg / m 3 . As a result, the explosive active material according to the invention can be provided with a high density and thus also a high explosive power.
Die ionische FlĆ¼ssigkeit kann ein Perchlorat-, Nitrat-, Acetat-, Dicyanamid-, Hexafluorophosphat- oder Tetrafluoroborat-Ion als Anion umfassen. Durch die Wahl des in der ionischen FlĆ¼ssigkeit enthaltenden Anions kann das Reaktionsverhalten der erfindungsgemƤĆen Sprengstoffwirkmasse beim Erhitzen variiert werden. Z. B. kann das Anion oxidierend sein, wie das z. B. bei Perchlorat oder Nitrat der Fall ist. Dadurch wird der durch Erhitzen bedingte Zerfall der ionischen FlĆ¼ssigkeit exotherm. Es kann aber auch ein inertes Anion, wie beispielsweise Acetat, Dicyanamid, Hexafluorophosphat oder Tetrafluoroborat gewƤhlt werden. Dann ist der Zerfall der ionischen FlĆ¼ssigkeit zumindest am Beginn einer ErwƤrmung endotherm. Weiterhin hat die Wahl des Anions einen Einfluss auf die Zerfallstemperatur. Von den oben genannten Anionen zerfƤllt Acetat bei der niedrigsten und Tetrafluoroborat bei der hƶchsten Temperatur. Durch das Vorsehen eines Gemischs dieser Anionen in der ionischen FlĆ¼ssigkeit bzw. einem Gemisch der ionischen FlĆ¼ssigkeiten kann das temperaturabhƤngige Verhalten der FlĆ¼ssigkeit bzw. des Gemischs beeinflusst werden. Durch diese Mƶglichkeiten kann die Empfindlichkeit und das thermische Verhalten der Sprengstoffwirkmasse eingestellt werden. Wenn sich die ionische FlĆ¼ssigkeit bei einer niedrigeren Temperatur als der Sprengstoff zumindest anfƤnglich endotherm zersetzt wird die Empfindlichkeit der erfindungsgemƤĆen Sprengstoffwirkmasse erheblich reduziert.The ionic liquid may comprise a perchlorate, nitrate, acetate, dicyanamide, hexafluorophosphate or tetrafluoroborate ion as an anion. By choosing the anion containing in the ionic liquid, the reaction behavior of the explosive active material according to the invention can be varied during heating. For example, the anion may be oxidizing, as the z. B. perchlorate or nitrate is the case. As a result, the heating of the disintegration of the ionic liquid is exothermic. However, it is also possible to choose an inert anion, for example acetate, dicyanamide, hexafluorophosphate or tetrafluoroborate. Then, 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.
Die ionische FlĆ¼ssigkeit kann 1-Butyl-3-methylimidazoliumtetrafluoroborat (BMIM-BF4), 1-Butyl-3-methylimidazoliumdicyanamid (BMIM-C2N2), n-Butylmethylimidazoliumperchlorat (BMIM-ClO4), ein Alkyl-Methylimidazol, insbesondere Dimethylimidazol oder Ethylmethylimidazol, ein Tetrazolat oder ein Triazolat umfassen.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 alkyl-methylimidazole, especially dimethylimidazole or ethylmethylimidazole, a tetrazolate or a triazolate.
Bei einer Ausgestaltung der erfindungsgemƤĆen Sprengstoffwirkmasse ist die ionische FlĆ¼ssigkeit darin mit einem auf das Gesamtgewicht der Wirkmasse bezogenen Anteil im Bereich von 3 Gew.-% bis 7 Gew.-%, insbesondere 4 Gew.-% bis 6 Gew.-%, enthalten. Dadurch wird selbst bei ionischen FlĆ¼ssigkeiten mit einer Dichte von weniger als 1100 kg/m3 die Gesamtdichte der erfindungsgemƤĆen Sprengstoffwirkmasse nicht wesentlich beeinflusst. Der genannte Anteil reicht jedoch fĆ¼r eine ausreichende Phlegmatisierung vollkommen aus.In one embodiment of the explosive active material according to the invention, the ionic liquid is contained therein with a relative to the total weight of the active material content in the range of 3 wt .-% to 7 wt .-%, in particular 4 wt .-% to 6 wt .-%. As a result, even with ionic liquids having a density of less than 1100 kg / m 3, the total density of the explosive active material according to the invention is not significantly affected. However, the said proportion is completely sufficient for adequate phlegmatization.
Die erfindungsgemƤĆe Sprengstoffwirkmasse umfasst weiterhin ein, insbesondere energetisches, Bindemittel. Wenn sowohl das Bindemittel als auch die ionische FlĆ¼ssigkeit energetisch sind, kann eine insensitive und dennoch sehr leistungsstarke vollenergetische, d. h. keine inerten Bestandteile aufweisende, Sprengstoffwirkmasse bereitgestellt werden. Das Bindemittel umfasst erfindungsgemĆ¤Ć ein polares Polymer oder polares MakromolekĆ¼l oder ein Polymer oder MakromolekĆ¼l, das in der ionischen FlĆ¼ssigkeit lƶslich ist oder davon gequollen werden kann. Beispielsweise kann das Polymer Polyacrylnitril, Polyvinylnitrat, Polyvinylpyrrolidon (PVP) oder Nitrocellulose umfassen. Es wird verhƤltnismƤĆig wenig ionische FlĆ¼ssigkeit benƶtigt, um die genannten Polymere durch Lƶsen in eine zƤhflĆ¼ssige und klebrige Masse zu verwandeln. Dadurch kann die fĆ¼r die Phlegmatisierung erforderliche Menge der meist verhƤltnismƤĆig teuren ionischen FlĆ¼ssigkeit verringert werden.The explosive active material according to the invention furthermore comprises 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 explosive active mass is provided. The binder according to the invention comprises a polar polymer or polar macromolecule or a polymer or macromolecule which is soluble in or swollen by the ionic liquid. For example, 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.
Weiterhin hat es sich gezeigt, dass das Mischen mit dem Sprengstoff erheblich einfacher ist als mit herkƶmmlichen polymeren Bindemitteln, da sich FlĆ¼ssigsalze und gegebenenfalls polare Polymere oder MakromolekĆ¼le als Bindemittel in Ethanol, Ethanol-Ethylether (2:1), Ethanol-Aceton (2:1) oder Ethanol-Ethylacetat (2:1) schnell und in allen MischungsverhƤltnissen lƶsen lassen. Somit kƶnnen die Sprengstoffpartikel mit der ionischen FlĆ¼ssigkeit und gegebenenfalls dem Bindemittel beschichtet werden, indem die Sprengstoffpartikel in die Lƶsung der ionischen FlĆ¼ssigkeit und gegebenenfalls zusƤtzlich enthaltenem Bindemittel eingeschlƤmmt werden und wƤhrend des Mischens das Lƶsungsmittel unter reduziertem Druck abgezogen wird. Dabei hat es sich gezeigt, dass es keine Rolle spielt, wie schnell das Lƶsungsmittel abgezogen wird. Die ionische FlĆ¼ssigkeit und gegebenenfalls das Bindemittel setzt/setzen sich auf den Sprengstoffpartikeln ab und beschichtet/beschichten sie gleichmƤĆig. Dies begĆ¼nstigt sehr die Unempfindlichkeit der resultierenden Sprengstoffwirkmasse, da jedes Sprengstoffpartikel vollstƤndig eingebettet wird. Bei bekannten Bindemitteln muss das Lƶsungsmittel dagegen langsam aus einem Gemisch mit Sprengstoffpartikeln entfernt werden, um eine gleichmƤĆige Beschichtung der Sprengstoffpartikel und damit die InsensitivitƤt des Produktes zu gewƤhrleisten.It has also been found that blending with the explosive is considerably easier than with conventional polymeric binders, since liquid salts and optionally polar polymers or macromolecules are used as binders in ethanol, ethanol-ethyl ether (2: 1), ethanol-acetone (2: 1). 1) or ethanol-ethyl acetate (2: 1) quickly and in all proportions. Thus, the explosive particles can be coated with the ionic liquid and optionally the binder by slurrying the explosive particles in the solution of the ionic liquid and optionally additionally contained binder and during mixing, the solvent is removed 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. This greatly favors the insensitivity of the resulting explosive active mass, as each explosive particle is completely embedded. With known binders, however, the solvent must be slowly removed from a mixture with explosive particles in order to ensure a uniform coating of the explosive particles and thus the insensitivity of the product.
Weiterhin kann durch ein energetisches Bindemittel, welches unter Gasentwicklung bei einer niedrigeren Temperatur zerfƤllt bzw. sich zersetzt als der Sprengstoff, die Sicherheit eines die Sprengstoffwirkmasse enthaltenden Brand oder Hitze ausgesetzten Wirkkƶrpers erhƶht werden. Bei diesen im sogenannten "fast cook off"- oder "slow cook off'-Test simulierten ZustƤnden bewirkt die Gasentwicklung bei niedriger Temperatur ein Aufbrechen der HĆ¼lle des Wirkkƶrpers. Bei einer dann erfolgenden ZĆ¼ndung des Sprengstoffs kann es nicht mehr zu dem ansonsten stattfindenden plƶtzlichen Druckanstieg kommen. Eine Detonation des Sprengstoffs ist dadurch unwahrscheinlich und findet im Idealfall, wenn der Sprengstoff nur abbrennt, nicht statt. Ein solches sich bei niedriger Temperatur zersetzendes Bindemittel ist z. B. Nitrocellulose, das sich bei etwa 120Ā°C zu zersetzen beginnt und sich im Bereich zwischen etwa 160Ā°C und 180Ā°C stark und vollstƤndig unter Gasentwicklung zersetzt. Ein bei deutlich hƶherer Temperatur sich zersetzender Sprengstoff ist z. B. Oktogen, dessen Zersetzung bei etwa 280Ā°C erfolgt.Furthermore, by 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. In these conditions, simulated in the so-called "almost cook off" or "slow cook off" test, the evolution of gas at low temperature causes the shell of the body to rupture, and the ignition of the explosive then fails to produce the sudden increase in pressure Detonation of the explosive is thus unlikely and, ideally, when the explosive only burns out, does not take place, such a low-temperature decomposing binder is, for example, nitrocellulose, which begins to decompose at about 120 Ā° C in the range between about 160 Ā° C and 180 Ā° 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 Ā° C.
Bei einer Ausgestaltung ist das Bindemittel in der Sprengstoffwirkmasse mit einem Anteil im Bereich von 1 Gew.-% bis 2,5 Gew.-%, insbesondere 1,5 Gew.-% bis 2 Gew.-%, enthalten. Durch die Wahl dieser geringen, jedoch ausreichenden Menge des im Allgemeinen eine verhƤltnismƤĆig geringe Dichte aufweisenden Bindemittels wird eine ins Gewicht fallende Verringerung der Dichte der erfindungsgemƤĆen Sprengstoffwirkmasse vermieden.In one embodiment, 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. By choosing this small but sufficient amount of the generally relatively low density binder, a significant reduction in the density of the explosive active material of the present invention is avoided.
Bei dem Sprengstoff kann es sich um einen kristallinen Sprengstoff handeln. Der Sprengstoff kann z. B. Oktogen, Hexogen, Nitropenta (PETN), Triaminotrinitrobenzol (TATB), Diaminodinitroethylen (FOX-7) oder Hexanitroisowurtzitan (CL-20) sein.The explosive may be a crystalline explosive. The explosive can z. Octogen, hexogen, nitropenta (PETN), triaminotrinitrobenzene (TATB), diaminodinitroethylene (FOX-7) or hexanitroisowurtzitane (CL-20).
Nachfolgend wird die Erfindung anhand von AusfĆ¼hrungsbeispielen nƤher erlƤutert. Beispiel 1 stellt einen insensitiven Sprengstoff nach dem Stand der Technik dar, wƤhrend es sich bei den Beispielen 4 und 5 um erfindungsgemƤĆe Sprengstoffwirkmassen und bei den Beispielen 2 und 3 um andere neue insensitive Sprengstoffwirkmassen handelt.The invention will be explained in more detail by means of exemplary embodiments. Example 1 represents an insensitive explosive according to the prior art, while Examples 4 and 5 are explosive compositions of the invention and Examples 2 and 3 are other novel insensitive explosive compositions.
200 g der in Beispiel 5 verwendeten ionischen FlĆ¼ssigkeit BMIM-ClO4 wurden wie folgt synthetisiert:
150 g BMIM-CI wurden in ca. 600 ml trockenem Methanol bei 25Ā°C in einem 2 Liter Einhalskolben aufgelƶst. Eine stƶchiometrische Menge trockenes Natriumperchlorat wurde ebenfalls in 600 ml trockenem Methanol in einem 2 Liter Einhalskolben getrennt aufgelƶst. Dann wurde die gesamte Perchloratlƶsung auf einmal in die BMIM-Chloridlƶsung gegeben. Die Flasche, in der die Perchloratlƶsung war, wurde noch 3 x mit 50 ml trockenem Methanol gewaschen und das Methanol auch noch zu der BMIM-Chloridlƶsung gegeben. Die resultierende Lƶsung wurde nach einigen Minuten trĆ¼b und gelb, als das entstandene Natriumchlorid begann auszufallen.200 g of the ionic liquid BMIM-ClO 4 used in Example 5 were synthesized as follows:
150 g of BMIM-CI were dissolved in about 600 ml of dry methanol at 25 Ā° 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.
Die gesamte Lƶsung wurde anschlieĆend eine Stunde unter RĆ¼ckfluss gekocht. Die heiĆe Lƶsung wurde danach mittels einer Fritte in einen 2 Liter Einhalskolben filtriert und der Niederschlag noch 3 x mit 50 ml trockenem Methanol gewaschen. Der praktisch ausschlieĆlich aus Kochsalz bestehende Filterkuchen wurde entsorgt.The entire solution was then refluxed for one hour. The hot solution was then filtered by means of a frit in a 2 liter one-necked flask and the precipitate was washed 3 times with 50 ml of dry methanol. The practically exclusively made of common salt filter cake was disposed of.
Der Einhalskolben wurde anschlieĆend an einen Rotationsverdampfer angeschlossen und das Methanol unter ca. 500 mbar Druck abdestilliert, wobei das Wasserbad im Verdampfer auf 90Ā°C erhitzt wurde. Als das Methanol abdestilliert war, wurde das warme rohe BMIM-ClO4 aus dem Kolben nochmals durch die Fritte in einen 250 ml Scheidetrichter filtriert, weil beim Verdampfen des Methanols noch weiteres Kochsalz ausgefallen ist.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 Ā° C in the evaporator. When the methanol was distilled off, 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.
Das fertige BMIM-ClO4 (ein gelbliches, zƤhflĆ¼ssiges Ćl) wurde aus dem Scheidetrichter in eine Laborflasche gefĆ¼llt und gewogen. Die Ausbeute war nahezu quantitativ.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.
Das BMIM-ClO4 hat sich als sehr gutes Bindemittel und Phlegmatisierungsmittel fĆ¼r energetische Wirkmassen erwiesen. Daraus kƶnnen sehr insensitive Sprengstoffwirkmassen mit kleinem oder groĆem Anteil an polymerem Bindemittel und hoher Dichte und Leistung hergestellt werden. Durch das VerhƤltnis von BMIM-ClO4 zu polymerem Bindemittel kann die HƤrte und mechanische Festigkeit der Wirkmasse in weiten Grenzen eingestellt werden.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.
Zur Herstellung der Sprengstoffwirkmassen gemĆ¤Ć der nachfolgenden Beispiele 4 und 5 wurde das Polyvinylpyrrolidon in Ethanol und die Nitrocellulose in Ethanol-Ethylacetat (2:1) aufgelƶst. AnschlieĆend wurde die ionische FlĆ¼ssigkeit in diese Lƶsung eindosiert. Danach wurde noch 1 Minute weitergerĆ¼hrt, um die Lƶsung zu homogenisieren. FĆ¼r 1 kg Sprengstoff wurden etwa 400 ml Lƶsungsmittel benƶtigt.To prepare the explosive compositions of Examples 4 and 5 below, 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.
Zur Herstellung der erfindungsgemƤĆen Sprengstoffwirkmassen wurden der jeweils Ć¼ber Nacht bei 50Ā°C getrocknete Sprengstoff und die Bindemittellƶsung grĆ¼ndlich gemischt. Nach 5 Minuten Mischen wurde ein Vakuum angelegt und eine Temperatur von 70Ā°C eingestellt bis das Lƶsungsmittel verdunstet war. Danach wurde die Sprengstoffwirkmasse aus dem Mischer entleert. Sie lag als leicht klebriges, farbloses Pulver vor.To prepare the explosive compositions of the invention, the explosive, which had been dried overnight at 50 Ā° C., and the binder solution were thoroughly mixed. After mixing for 5 minutes, a vacuum was applied and a temperature of 70 Ā° 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.
Pressbare herkƶmmliche insensitive Sprengstoffwirkmasse DXP-1340 mit Weichmacher:
Pressbare insensitive Sprengstoffwirkmasse ohne Weichmacher:
Pressbare insensitive Sprengstoffwirkmasse ohne Weichmacher:
ErfindungsgemƤĆe pressbare insensitive Sprengstoffwirkmasse mit ionischer FlĆ¼ssigkeit als Phlegmatisierungsmittel:
ErfindungsgemƤĆe pressbare vollenergetische insensitive Sprengstoffwirkmasse mit ionischer FlĆ¼ssigkeit als Phlegmatisierungsmittel:
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. AnschlieĆend wurden die Presslinge im sogenannten Gap-Test eingesetzt. Bei dem Gap-Test handelt es sich um einen Standardtest fĆ¼r die Ermittlung der InsensitivitƤt von Sprengstoffwirkmassen oder Sprengstoffen. Dabei wird die Hƶhe einer standardisierten WassersƤule gemessen, die ausreicht um eine durch Detonation einer Standardsprengladung erzeugte StoĆwelle in der WassersƤule auf die zu untersuchenden Sprengstoffwirkmasse zu Ć¼bertragen, so dass diese noch zuverlƤssig detoniert, bzw. zuverlƤssig nicht mehr detoniert. Die Werte sind dabei jeweils in mm der WassersƤule angegeben. Der erste Wert unter "Gap [mm]" bezeichnet dabei jeweils den Wert, bei dem die zu untersuchende Sprengstoffwirkmasse zuverlƤssig 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 aufgefĆ¼hrt.
Tg bedeutet dabei "GlasĆ¼bergangstemperatur", "n. g." bedeutet "nicht gemessen". Die GlasĆ¼bergangstemperatur 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 fĆ¼r die obigen Beispiele 1 bis 5 berechneten Detonationsgeschwindigkeiten (D[m/s]) und die DetonationsdrĆ¼cke (p[GPa]) bei den tatsƤchlich ermittelten und aus der obigen Tabelle ersichtlichen Dichten sind aus der nachfolgenden Tabelle ersichtlich.
Claims (12)
- Insensitive active explosive composition comprising an explosive and a stabilizer, wherein the stabilizer comprises at least one ionic liquid, wherein the active explosive composition further comprises a binder, wherein the binder comprises a polar polymer or polar macromolecule or a polymer or macromolecule which is soluble in the ionic liquid or can be swelled thereby.
- Insensitive active explosive composition according to Claim 1, wherein the ionic liquid is water-insoluble and not hygroscopic.
- Insensitive active explosive composition according to either of the preceding claims, wherein the ionic liquid is a high-energy liquid.
- Insensitive active explosive composition according to any of the preceding claims, wherein the ionic liquid has a density of at least 1100 kg/m3.
- Insensitive active explosive composition according to any of the preceding claims, wherein the ionic liquid comprises a perchlorate, nitrate, acetate, dicyanamide, hexafluorophosphate or tetrafluoroborate ion as anion.
- Insensitive active explosive composition according to any of the preceding claims, wherein the ionic liquid comprises 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM-BF4), 1-butyl-3-methylimidazolium dicyanamide (BMIM-C2N2), n-butylmethyl-imidazolium perchlorate (BMIM-ClO4), an alkyl methylimidazole, in particular dimethylimidazole or ethylmethylimidazole, a tetrazolate or a triazolate.
- Insensitive active explosive composition according to any of the preceding claims, wherein the ionic liquid is present therein in a proportion based on the total weight of the active composition in the range from 3% by weight to 7% by weight, in particular from 4% by weight to 6% by weight.
- Insensitive active explosive composition according to any of the preceding claims, wherein the binder is a high-energy binder.
- Insensitive active explosive composition according to any of the preceding claims, wherein the polymer comprises polyacrylonitrile, polyvinyl nitrate, polyvinylpyrrolidone (PVP) or nitrocellulose.
- Insensitive active explosive composition according to any of the preceding claims, wherein the binder is present therein in a proportion in the range from 1% by weight to 2.5% by weight, in particular from 1.5% by weight to 2% by weight.
- Insensitive active explosive composition according to any of the preceding claims, wherein the explosive is a crystalline explosive.
- Insensitive active explosive composition according to any of the preceding claims, wherein the explosive is octogen, hexogen, nitropenta (PETN), triaminotrinitrobenzene (TATB), diaminodinitroethylene (FOX-7) or hexanitroisowurtzitane (CL-20).
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CN107793280B (en) * | 2017-11-23 | 2021-01-29 | ęå„ | Composite type insensitive agent for firework powder |
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US3147162A (en) * | 1955-10-21 | 1964-09-01 | Jr James T Paul | Organic explosive compositions suitable for weapon casings |
DE3934368C1 (en) * | 1989-10-14 | 1990-11-15 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung Ev, 8000 Muenchen, De | |
US8025010B1 (en) * | 1990-09-18 | 2011-09-27 | Alliant Techsystems Inc. | Method for reducing charge retention properties of solid propellants |
JP2005532440A (en) * | 2002-07-05 | 2005-10-27 | ćć°ćµ ć¢ćÆććØć³ć²ć¼ć«ć·ć£ćć | Polymer composition comprising polymer and ionic liquid |
US7771549B1 (en) * | 2002-10-07 | 2010-08-10 | United States Of America As Represented By The Secretary Of The Air Force | Energetic ionic liquids |
US8012277B2 (en) * | 2007-04-13 | 2011-09-06 | Alliant Techsystems Inc. | Ionic liquid and a method of synthesizing an ionic liquid |
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