EP4296253A1 - Plastic explosive composition - Google Patents
Plastic explosive composition Download PDFInfo
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- EP4296253A1 EP4296253A1 EP23181199.3A EP23181199A EP4296253A1 EP 4296253 A1 EP4296253 A1 EP 4296253A1 EP 23181199 A EP23181199 A EP 23181199A EP 4296253 A1 EP4296253 A1 EP 4296253A1
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- EP
- European Patent Office
- Prior art keywords
- explosive
- composition according
- explosive composition
- nitroguanidine
- weight
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- 239000002360 explosive Substances 0.000 title claims abstract description 56
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- 239000004033 plastic Substances 0.000 title claims abstract description 12
- 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 abstract description 25
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- OCKWAZCWKSMKNC-UHFFFAOYSA-N [3-octadecanoyloxy-2,2-bis(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC OCKWAZCWKSMKNC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000026 Pentaerythritol tetranitrate Substances 0.000 claims abstract description 10
- 229960004321 pentaerithrityl tetranitrate Drugs 0.000 claims abstract description 10
- 229920002545 silicone oil Polymers 0.000 claims abstract description 9
- 239000003550 marker Substances 0.000 claims abstract description 5
- 239000004014 plasticizer Substances 0.000 claims abstract description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 11
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 11
- -1 polydimethylsiloxane Polymers 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- DWCLXOREGBLXTD-UHFFFAOYSA-N dmdnb Chemical compound [O-][N+](=O)C(C)(C)C(C)(C)[N+]([O-])=O DWCLXOREGBLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 235000013539 calcium stearate Nutrition 0.000 claims description 4
- 239000008116 calcium stearate Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- 229940114069 12-hydroxystearate Drugs 0.000 claims 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 231100000252 nontoxic Toxicity 0.000 description 10
- 230000003000 nontoxic effect Effects 0.000 description 10
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- YWSPWKXREVSQCA-UHFFFAOYSA-N 4,5-dimethoxy-2-nitrobenzaldehyde Chemical compound COC1=CC(C=O)=C([N+]([O-])=O)C=C1OC YWSPWKXREVSQCA-UHFFFAOYSA-N 0.000 description 4
- 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 description 3
- 235000019359 magnesium stearate Nutrition 0.000 description 3
- 239000012170 montan wax Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- UZGLIIJVICEWHF-UHFFFAOYSA-N octogen Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UZGLIIJVICEWHF-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- UQXKXGWGFRWILX-UHFFFAOYSA-N ethylene glycol dinitrate Chemical compound O=N(=O)OCCON(=O)=O UQXKXGWGFRWILX-UHFFFAOYSA-N 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PGHBYDVOOPRPQW-UHFFFAOYSA-N 1,3-dinitrooxypropan-2-yl nitrate Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O.[O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O PGHBYDVOOPRPQW-UHFFFAOYSA-N 0.000 description 1
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 1
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 description 1
- 241000282472 Canis lupus familiaris Species 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 230000007059 acute toxicity Effects 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- C06B21/005—By a process involving melting at least part of the ingredients
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
- C06B25/32—Compositions containing a nitrated organic compound the compound being nitrated pentaerythritol
-
- 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
Definitions
- the present invention relates to new plastic explosive compositions which include pentaerythritol tetranitrate as a highly explosive explosive.
- plastic explosives are based on synthetic rubber, e.g. styrene-butadiene rubber, which becomes brittle or hard over time, affecting the performance and initiation ability of the explosive. They also usually contain, for example as (further) plasticizing or phlegmatizing agents, various chemical compounds that are toxic and harmful to the environment, so that even when disposed of by burning, highly toxic (e.g. aromatic) compounds are sometimes released in addition to soot particles and tar slag.
- synthetic rubber e.g. styrene-butadiene rubber
- plasticizing or phlegmatizing agents various chemical compounds that are toxic and harmful to the environment, so that even when disposed of by burning, highly toxic (e.g. aromatic) compounds are sometimes released in addition to soot particles and tar slag.
- pentaerythritol tetranitrate nitrogenpenta, pentaerythrityl tetranitrate, pentrite, PETN
- Nitropenta as the only highly explosive explosive, which is why it is used in a mixture with other, less sensitive explosives.
- Hexahydro-1,3,5-trinitro-1,3,5-triazine Hexogen, RDX
- cyclotetramethylenetetranitramine Oktogen, HMX
- 2,4,6-trinitrotoluene TNT
- glycerol trinitrate nitrogen glycol
- Glycol dinitrate nitrogenglycol
- the invention achieves this aim by providing a plastic explosive composition which comprises pentaerythritol tetranitrate as a highly explosive explosive, at least one insensitive explosive, silicone oil as a plasticizer, at least one phlegmatizing agent and a marker, the composition according to the invention being characterized in that it comprises a combination of a ) Nitroguanidine as an insensitive explosive and b) pentaerythritol tetrastearate as a phlegmatizing agent.
- Nitroguanidine has been known as an explosive for a long time - a very insensitive one that only detonates after initiation with ignition amplifiers - and is therefore used as a component of propellant powders and security explosives.
- Nitropenta i.e. pentaerythritol tetranitrate
- Both chemical compounds are of course - just like Nitropenta - classified as non-toxic, so that a combination according to the invention of these three compounds and any non-toxic silicone oil as a plasticizer represents for the first time a completely non-toxic plastic explosive composition based on Nitropenta.
- plastic explosive according to the invention is to be disposed of, for example by burning, only carbon dioxide, nitrogen oxides and water vapor are released, and only fine sand remains as a residue, which enables a completely non-toxic disposal chain.
- nitroguanidine as a further explosive to a plastic explosive composition, which already includes nitropenta as a highly explosive explosive, silicone oil as a plasticizer and pentaerythritol tetrastearate as a phlegmatizing agent, the friction sensitivity of the composition can even be reduced, although the addition of nitroguanidine increases the total amount of explosives. From the fact that this effect can be observed with the addition of just a few percent by weight of nitroguanidine, it clearly follows that nitroguanidine and pentaerythritol tetrastearate show a synergistic effect, as demonstrated by the later exemplary embodiments.
- the explosive composition preferably comprises a completely non-toxic polydimethylsiloxane (PDMS) as a silicone oil, more preferably polydimethylsiloxane with a kinematic viscosity of 1,000 to 30,000 mm 2 /s in order to be able to achieve the required plasticizing effect - depending on the respective grain sizes of the other components .
- PDMS polydimethylsiloxane
- this silicone oil makes the composition Not only completely water-resistant, but also plastically deformable at both low and elevated temperatures, for example from -30 °C to 65 °C, and therefore easy to handle and process - worldwide.
- the nitropenta has a grain size of 30 to 300 ⁇ m and/or the nitroguanidine has a grain size ⁇ 10 ⁇ m in order to achieve the desired impact and friction sensitivity values of the composition.
- composition according to the invention preferably comprises a further phlegmatizing agent, more preferably a fatty acid, such as stearic acid or 12-hydroxystearic acid, or a salt thereof, such as a zinc, calcium, magnesium or aluminum salt, particularly preferably calcium and/or Magnesium stearate, all of which can also act as crosslinkers for the silicone oil.
- a marker according to the Montreal Convention is generally included, which in preferred embodiments of the invention is 2,3-dimethyldinitrobutane (DMNB), which can be easily detected by explosive detection dogs and which also represents a non-toxic chemical compound.
- DMNB 2,3-dimethyldinitrobutane
- the composition according to the invention comprises the following components in the following amounts: Pentaerythritol tetranitrate (Nitropenta) 70-85 Polydimethylsiloxane (PDMS) 8-15 Nitroguanidine 1-10 Pentaerythritol tetrastearate 0.1-5 Calcium or magnesium stearate 0.1-3 2,3-Dimethyldinitrobutane (DMNB) 0.1-1.5 and more preferably in the following amounts: Pentaerythritol tetranitrate (Nitropenta) 75-80 Polydimethylsiloxane (PDMS) 12-15 Nitroguanidine 3-7 Pentaerythritol tetrastearate 1-2 Calcium or magnesium stearate 0.5-1.5 2,3-Dimethyldinitrobutane (DMNB) 0.5-1 each in% by weight, which together make up 100% by weight.
- Pentaerythritol tetranitrate Natropenta
- PDMS Polyd
- the invention also provides a method for producing an explosive composition according to the first aspect, characterized in that the individual components are mixed together in a masticator at an elevated temperature and during cooling and/or after cooling be brought into a specific shape, the mixing of the components preferably taking place at a temperature of 65-78 ° C, more preferably at about 70 ° C.
- All examples and comparative examples contained 82.5 parts by weight of nitropenta (various grain sizes from 10 to 200 ⁇ m), 13 parts by weight of PDMS with an average kinematic viscosity of 15,000 mm 2 /s, 1.5 parts by weight of zinc stearate and 1.5 parts by weight of DMNB as well as 1.
- Phlegmatizing agents selected from pentaerythritol tetrastearate (Examples 1 to 3 and Comparative Example 1) and montan wax (Comparative Example 2) (100 parts by weight in total) are used. The addition took place in the following order: PDMS - zinc stearate - phlegmatizing agent - DMNB - Nitropenta.
- Example 1 in addition to the above 100 parts by weight of the compositions, an additional 2 parts by weight in Example 1, 6 parts by weight in Example 2 and 10 parts by weight in Example 3 of nitroguanidine (grain size ⁇ 10 ⁇ m) were added as an insensitive explosive.
- the resulting masses were allowed to cool to 40 °C and shaped into a predefined cuboid shape. After cooling to room temperature, they were all subjected to a friction sensitivity test in accordance with Directive 2014/28/EU.
- a friction sensitivity test in accordance with Directive 2014/28/EU.
- the compositions between two porcelain bodies were loaded with a defined friction force, which results from the product of the friction path and the weight setting on the testing device and is given in the unit Newton (N). Table 1 below lists the friction sensitivity values achieved.
- plastic explosive compositions of the examples according to the invention which contain a combination of pentaerythritol tetrastearate as a phlegmatizing agent and nitroguanidine as an insensitive explosive, were clearly superior to the comparative examples in terms of sensitivity to friction.
- an increase in the friction sensitivity value of 25% was achieved by switching from montan wax as a phlegmatizing agent to pentaerythritol tetrastearate in the comparative examples, this could be improved by a further 20% by adding only 2% by weight of nitroguanidine in Example 1.
- Example 2 By adding 6% by weight of nitroguanidine in Example 2 or 10% by weight in Example 3, improvements in the value of 65% in Example 2 and even 100% in Example 3 were achieved compared to Comparative Example 1. This clearly indicates a synergistic effect of nitroguanidine and pentaerythritol tetrastearate in the compositions according to the invention.
- nitroguanidine as an insensitive explosive and pentaerythritol tetrastearate as a phlegmatizing agent, not only can a completely non-toxic plastic explosive based on nitropenta be produced, but at the same time its sensitivity to friction can also be significantly increased, which offers enormous advantages over the prior art.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Molecular Biology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Die Erfindung betrifft eine plastische Sprengstoff-Zusammensetzung, die Pentaerythrittetranitrat als hochbrisanten Explosivstoff, zumindest einen unempfindlichen Explosivstoff, Silikonöl als Plastifizierungsmittel, zumindest ein Phlegmatisierungsmittel und einen Markierungsstoff umfasst und dadurch gekennzeichnet ist, dass sie eine Kombination aus a) Nitroguanidin als unempfindlichen Explosivstoff und b) Pentaerythrittetrastearat als Phlegmatisierungsmittel umfasst.The invention relates to a plastic explosive composition which comprises pentaerythritol tetranitrate as a highly explosive explosive, at least one insensitive explosive, silicone oil as a plasticizer, at least one phlegmatizing agent and a marker and is characterized in that it comprises a combination of a) nitroguanidine as an insensitive explosive and b) Pentaerythritol tetrastearate is included as a phlegmatizing agent.
Description
Die vorliegende Erfindung betrifft neue plastische Sprengstoff-Zusammensetzungen, die Pentaerythrittetranitrat als hochbrisanten Explosivstoff umfassen.The present invention relates to new plastic explosive compositions which include pentaerythritol tetranitrate as a highly explosive explosive.
Derzeit erhältliche plastische Sprengstoffe sind mehrheitlich auf Basis von synthetischem Gummi, z.B. aus Styrol-Butadien-Kautschuk, aufgebaut, der mit der Zeit spröde oder hart wird, was sich die Leistung und die Initiierfähigkeit des Sprengstoffs beeinträchtigt. Sie enthalten zudem üblicherweise, z.B. als (weitere) Plastifizierungs- oder Phlegmatisierungsmittel, diverse chemische Verbindungen, die giftig und umweltbelastend sind, so dass selbst bei der Entsorgung durch Verbrennen neben Rußpartikeln und Teerschlacke mitunter hochgiftige (z.B. aromatische) Verbindungen frei werden.The majority of currently available plastic explosives are based on synthetic rubber, e.g. styrene-butadiene rubber, which becomes brittle or hard over time, affecting the performance and initiation ability of the explosive. They also usually contain, for example as (further) plasticizing or phlegmatizing agents, various chemical compounds that are toxic and harmful to the environment, so that even when disposed of by burning, highly toxic (e.g. aromatic) compounds are sometimes released in addition to soot particles and tar slag.
Weiters stellt unter all den in solchen plastischen Sprengstoffen enthaltenen hochbrisanten Explosivstoffen Pentaerythrittetranitrat (Nitropenta, Pentaerythrityltetranitrat, Pentrit, PETN) der nachstehenden Formel den einzigen ungiftigen Vertreter dar:
Allerdings war es bislang nicht möglich, bei Verwendung von Nitropenta als einzigem hochbrisantem Explosivstoff die strengen Auflagen der Prüfungen gemäß der Richtlinie 2014/28/EU in Bezug auf Schlagempfindlichkeit und Reibempfindlichkeit zu erfüllen, weswegen es im Gemisch mit anderen, weniger empfindlichen Explosivstoffen eingesetzt wird, z.B. in Kombination mit Hexahydro-1,3,5-trinitro-1,3,5-triazin (Hexogen, RDX), Cyclotetramethylentetranitramin (Oktogen, HMX), 2,4,6-Trinitrotoluol (TNT), Glycerintrinitrat (Nitroglycerin) oder Glykoldinitrat (Nitroglykol):
Diese sind jedoch allesamt durch eine "akute Toxizität" gekennzeichnet, so dass es bislang als unmöglich galt, eine im Wesentlichen ungiftige - aber nichtsdestotrotz hochexplosive - Sprengstoff-Zusammensetzung mit Nitropenta als hochbrisantem Explosivstoff herzustellen, was daher das Ziel der vorliegenden Erfindung darstellt.However, these are all characterized by "acute toxicity", so that it was previously considered impossible to produce an essentially non-toxic - but nevertheless highly explosive - explosive composition with nitropenta as a highly explosive explosive, which is therefore the aim of the present invention.
Dieses Ziel erreicht die Erfindung durch Bereitstellung einer plastischen Sprengstoff-Zusammensetzung, die Pentaerythrittetranitrat als hochbrisanten Explosivstoff, zumindest einen unempfindlichen Explosivstoff, Silikonöl als Plastifizierungsmittel, zumindest ein Phlegmatisierungsmittel und einen Markierungsstoff umfasst, wobei die erfindungsgemäße Zusammensetzung dadurch gekennzeichnet ist, dass sie eine Kombination aus a) Nitroguanidin als unempfindlichem Explosivstoff und b) Pentaerythrittetrastearat als Phlegmatisierungsmittel umfasst.
Zwar ist Nitroguanidin seit langer Zeit als Explosivstoff bekannt - und zwar als sehr unempfindlicher, der nur nach Initiierung mit Zündverstärkern detoniert - und wird daher als Komponente von Treibladungspulvern und Sicherheits-Sprengstoffen eingesetzt. Allerdings sind Kombinationen davon mit Nitropenta, also Pentaerythrittetranitrat, ebenso unbekannt wie solche mit Pentaerythrittetrastearat als Phlegmatisierungsmittel dafür. Beide chemische Verbindungen sind freilich - genau wie Nitropenta - als ungiftig einzustufen, so dass eine erfindungsgemäße Kombination aus diesen drei Verbindungen und einem beliebigen ungiftigen Silikonöl als Plastifizierungsmittel erstmals eine gänzlich ungiftige plastische Sprengstoff-Zusammensetzung auf Basis von Nitropenta darstellt.Nitroguanidine has been known as an explosive for a long time - a very insensitive one that only detonates after initiation with ignition amplifiers - and is therefore used as a component of propellant powders and security explosives. However, combinations of this with Nitropenta, i.e. pentaerythritol tetranitrate, are just as unknown as those with pentaerythritol tetrastearate as a phlegmatizing agent. Both chemical compounds are of course - just like Nitropenta - classified as non-toxic, so that a combination according to the invention of these three compounds and any non-toxic silicone oil as a plasticizer represents for the first time a completely non-toxic plastic explosive composition based on Nitropenta.
Soll der erfindungsgemäße plastische Sprengstoff beispielsweise durch Verbrennen entsorgt werden, so werden dabei nur Kohlendioxid, Stickstoffoxide und Wasserdampf freigesetzt, und als Rückstand bleibt lediglich ein feiner Sand zurück, was eine gänzlich nichttoxische Entsorgungskette ermöglicht.If the plastic explosive according to the invention is to be disposed of, for example by burning, only carbon dioxide, nitrogen oxides and water vapor are released, and only fine sand remains as a residue, which enables a completely non-toxic disposal chain.
Darüber hinaus hat der Erfinder jedoch überraschenderweise festgestellt, dass durch die Zugabe von Nitroguanidin als weiterem Explosivstoff zu einer plastischen Sprengstoff-Zusammensetzung, die bereits Nitropenta als hochbrisanten Explosivstoff, Silikonöl als Plastifizierungsmittel und Pentaerythrittetrastearat als Phlegmatisierungsmittel umfasst, die Reibempfindlichkeit der Zusammensetzung sogar verringert werden kann, obwohl durch die Nitroguanidin-Zugabe die Gesamtmenge an Explosivstoffen erhöht wird. Aus der Tatsache, dass dieser Effekt bereits bei Zugabe von wenigen Gewichtsprozenten Nitroguanidin zu beobachten ist, folgt eindeutig, dass Nitroguanidin und Pentaerythrittetrastearat eine synergistische Wirkung zeigen, wie dies durch die späteren Ausführungsbeispiele belegt wird.In addition, however, the inventor has surprisingly found that by adding nitroguanidine as a further explosive to a plastic explosive composition, which already includes nitropenta as a highly explosive explosive, silicone oil as a plasticizer and pentaerythritol tetrastearate as a phlegmatizing agent, the friction sensitivity of the composition can even be reduced, although the addition of nitroguanidine increases the total amount of explosives. From the fact that this effect can be observed with the addition of just a few percent by weight of nitroguanidine, it clearly follows that nitroguanidine and pentaerythritol tetrastearate show a synergistic effect, as demonstrated by the later exemplary embodiments.
Vorzugsweise umfasst die Sprengstoff-Zusammensetzung als Silikonöl ein völlig ungiftiges Polydimethylsiloxan (PDMS), noch bevorzugter Polydimethylsiloxan mit einer kinematischen Viskosität von 1.000 bis 30.000 mm2/s, um - in Abhängigkeit von den jeweiligen Korngrößen der sonstigen Komponenten - die erforderliche Plastifizierungswirkung erzielen zu können. Darüber hinaus macht dieses Silikonöl die Zusammensetzung nicht nur völlig wasserbeständig, sondern darüber hinaus sowohl bei tiefen als auch bei erhöhten Temperaturen, z.B. von -30 °C bis 65 °C, plastisch verformbar und daher problemlos handhab- und verarbeitbar - und das weltweit.The explosive composition preferably comprises a completely non-toxic polydimethylsiloxane (PDMS) as a silicone oil, more preferably polydimethylsiloxane with a kinematic viscosity of 1,000 to 30,000 mm 2 /s in order to be able to achieve the required plasticizing effect - depending on the respective grain sizes of the other components . In addition, this silicone oil makes the composition Not only completely water-resistant, but also plastically deformable at both low and elevated temperatures, for example from -30 °C to 65 °C, and therefore easy to handle and process - worldwide.
In bevorzugten Ausführungsformen der Erfindung weist das Nitropenta eine Korngröße von 30 bis 300 µm und/oder weist das Nitroguanidin eine Korngröße < 10 µm auf, um die gewünschten Schlag- und Reibempfindlichkeitswerte der Zusammensetzung zu erzielen.In preferred embodiments of the invention, the nitropenta has a grain size of 30 to 300 μm and/or the nitroguanidine has a grain size <10 μm in order to achieve the desired impact and friction sensitivity values of the composition.
Weitere Komponenten der erfindungsgemäßen Zusammensetzung sind nicht speziell eingeschränkt, solange es sich um im Wesentlichen ungiftige chemische Verbindungen handelt. Beispielsweise umfasst die erfindungsgemäße Zusammensetzung vorzugsweise noch ein weiteres Phlegmatisierungsmittel, noch bevorzugter eine Fettsäure, wie z.B. Stearinsäure oder 12-Hydroxystearinsäure, oder ein Salz davon, wie z.B. ein Zink-, Calcium-, Magnesium- oder Aluminiumsalz, besonders bevorzugt Calcium-und/oder Magnesiumstearat, die allesamt gleichzeitig als Vernetzer für das Silikonöl fungieren können. Weiters ist in der Regel ein Markierungsstoff gemäß dem Montrealer Übereinkommen enthalten, was in bevorzugten Ausführungsformen der Erfindung 2,3-Dimethyldinitrobutan (DMNB) ist, das mittels Sprengstoffspürhunden gut detektierbar ist und das ebenfalls eine ungiftige chemische Verbindung darstellt.Further components of the composition according to the invention are not specifically limited as long as they are essentially non-toxic chemical compounds. For example, the composition according to the invention preferably comprises a further phlegmatizing agent, more preferably a fatty acid, such as stearic acid or 12-hydroxystearic acid, or a salt thereof, such as a zinc, calcium, magnesium or aluminum salt, particularly preferably calcium and/or Magnesium stearate, all of which can also act as crosslinkers for the silicone oil. Furthermore, a marker according to the Montreal Convention is generally included, which in preferred embodiments of the invention is 2,3-dimethyldinitrobutane (DMNB), which can be easily detected by explosive detection dogs and which also represents a non-toxic chemical compound.
In bevorzugten Ausführungsformen umfasst die erfindungsgemäße Zusammensetzung die folgenden Komponenten in den nachstehenden Mengen:
In einem zweiten Aspekt stellt die Erfindung auch ein Verfahren zur Herstellung einer Sprengstoff-Zusammensetzung gemäß dem ersten Aspekt bereit, das dadurch gekennzeichnet ist, dass die einzelnen Komponenten in einem Mastikator bei einer erhöhten Temperatur miteinander vermischt und während des Abkühlens und/oder nach dem Abkühlen in einer bestimmte Form gebracht werden, wobei das Vermischen der Komponenten vorzugsweise bei einer Temperatur von 65-78 °C, noch bevorzugter bei etwa 70 °C erfolgt.In a second aspect, the invention also provides a method for producing an explosive composition according to the first aspect, characterized in that the individual components are mixed together in a masticator at an elevated temperature and during cooling and/or after cooling be brought into a specific shape, the mixing of the components preferably taking place at a temperature of 65-78 ° C, more preferably at about 70 ° C.
Die vorliegende Erfindung wird nachstehend anhand von konkreten Beispielen näher beschrieben, die jedoch lediglich zur Illustration und als Beleg für die Wirksamkeit der erfindungsgemäßen Sprengstoff-Zusammensetzungen dienen und nicht als Einschränkung zu verstehen sind.The present invention is described in more detail below using concrete examples, which, however, serve only as illustration and as evidence of the effectiveness of the explosive compositions according to the invention and are not to be understood as a limitation.
Die nachstehenden Komponenten wurden zunächst bei 60 °C in einem Trockenschrank getrocknet und danach einem auf 70 °C vorgeheizten Mastikator der Fa. Werner und Pfleiderer, Modell UK 80-K-2, zugesetzt und jeweils 20 min lang zu einer homogenen Masse verknetet. In allen Beispielen und Vergleichsbeispielen kamen 82,5 Gewichtsteile Nitropenta (verschiedene Korngrößen von 10 bis 200 µm), 13 Gewichtsteile PDMS mit einer kinematischen Viskosität von durchschnittlich 15.000 mm2/s, 1,5 Gewichtsteile Zinkstearat und 1,5 Gewichtsteile DMNB sowie 1,5 Gewichtsteile Phlegmatisierungsmittel, ausgewählt aus Pentaerythrittetrastearat (Beispiele 1 bis 3 und Vergleichsbeispiel 1) und Montanwachs (Vergleichsbeispiel 2) (insgesamt 100 Gewichtsteile), zum Einsatz. Die Zugabe erfolgte dabei in der folgenden Reihenfolge: PDMS - Zinkstearat - Phlegmatisierungsmittel - DMNB - Nitropenta.The following components were first dried at 60 ° C in a drying cabinet and then added to a masticator from Werner and Pfleiderer, model UK 80-K-2, preheated to 70 ° C and kneaded for 20 minutes each to form a homogeneous mass. All examples and comparative examples contained 82.5 parts by weight of nitropenta (various grain sizes from 10 to 200 μm), 13 parts by weight of PDMS with an average kinematic viscosity of 15,000 mm 2 /s, 1.5 parts by weight of zinc stearate and 1.5 parts by weight of DMNB as well as 1. 5 parts by weight Phlegmatizing agents selected from pentaerythritol tetrastearate (Examples 1 to 3 and Comparative Example 1) and montan wax (Comparative Example 2) (100 parts by weight in total) are used. The addition took place in the following order: PDMS - zinc stearate - phlegmatizing agent - DMNB - Nitropenta.
Schließlich wurden in den erfindungsgemäßen Beispielen zu den obigen 100 Gewichtsteilen der Zusammensetzungen noch zusätzliche 2 Gewichtsteile in Beispiel 1, 6 Gewichtsteile in Beispiel 2 bzw. 10 Gewichtsteile in Beispiel 3 an Nitroguanidin (Korngröße < 10 µm) als unempfindlicher Explosivstoff zugesetzt.Finally, in the examples according to the invention, in addition to the above 100 parts by weight of the compositions, an additional 2 parts by weight in Example 1, 6 parts by weight in Example 2 and 10 parts by weight in Example 3 of nitroguanidine (grain size <10 μm) were added as an insensitive explosive.
Die so erhaltenen Massen wurden auf 40 °C abkühlen gelassen und in eine vordefinierte Quaderform gebracht. Nach dem Abkühlen auf Raumtemperatur wurden sie allesamt einem Reibempfindlichkeitstest gemäß der Richtlinie 2014/28/EU unterzogen. Dazu wurden die Zusammensetzungen zwischen zwei Porzellankörpern mit einer definierten Reibkraft belastet, die sich aus dem Produkt von Reibweg und Gewichtseinstellung am Prüfgerät ergibt und in der Einheit Newton (N) angegeben wird. In der nachstehenden Tabelle 1 sind die dabei erzielten Reibempfindlichkeitswerte aufgelistet.
Aus diesen Werten geht klar hervor, dass die plastischen Sprengstoff-Zusammensetzungen der erfindungsgemäßen Beispiele, die eine Kombination aus Pentaerythrittetrastearat als Phlegmatisierungsmittel und Nitroguanidin als unempfindlichem Explosivstoff umfassten, den Vergleichsbeispielen in Bezug auf die Reibempfindlichkeit deutlich überlegen waren. Obwohl schon durch den Wechsel von Montanwachs als Phlegmatisierungsmittel zu Pentaerythrittetrastearat in den Vergleichsbeispielen eine Erhöhung des Reibempfindlichkeitswerts um 25 % erzielt wurde, konnte dieser durch Zusatz von nur 2 Gew.-% Nitroguanidin in Beispiel 1 noch einmal um 20 % verbessert werden. Durch Zusatz von 6 Gew.-% Nitroguanidin in Beispiel 2 bzw. 10 Gew.-% in Beispiel 3 wurden gegenüber Vergleichsbeispiel 1 sogar Verbesserungen des Werts um 65 % in Beispiel 2 und sogar um 100 % in Beispiel 3 erzielt. Dies deutet klar auf eine synergistische Wirkung von Nitroguanidin und Pentaerythrittetrastearat in den erfindungsgemäßen Zusammensetzungen hin.From these values it is clear that the plastic explosive compositions of the examples according to the invention, which contain a combination of pentaerythritol tetrastearate as a phlegmatizing agent and nitroguanidine as an insensitive explosive, were clearly superior to the comparative examples in terms of sensitivity to friction. Although an increase in the friction sensitivity value of 25% was achieved by switching from montan wax as a phlegmatizing agent to pentaerythritol tetrastearate in the comparative examples, this could be improved by a further 20% by adding only 2% by weight of nitroguanidine in Example 1. By adding 6% by weight of nitroguanidine in Example 2 or 10% by weight in Example 3, improvements in the value of 65% in Example 2 and even 100% in Example 3 were achieved compared to Comparative Example 1. This clearly indicates a synergistic effect of nitroguanidine and pentaerythritol tetrastearate in the compositions according to the invention.
Somit kann unter Verwendung einer Kombination aus Nitroguanidin als unempfindlichem Explosivstoff und Pentaerythrittetrastearat als Phlegmatisierungsmittel nicht nur ein völlig ungiftiger plastischer Sprengstoff auf Basis von Nitropenta hergestellt, sondern gleichzeitig auch dessen Reibempfindlichkeit deutlich erhöht werden, was gegenüber dem Stand der Technik enorme Vorteile bietet.Thus, using a combination of nitroguanidine as an insensitive explosive and pentaerythritol tetrastearate as a phlegmatizing agent, not only can a completely non-toxic plastic explosive based on nitropenta be produced, but at the same time its sensitivity to friction can also be significantly increased, which offers enormous advantages over the prior art.
Claims (9)
die Zusammensetzung eine Kombination aus
the composition is a combination
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| ATA129/2022A AT525440B1 (en) | 2022-06-23 | 2022-06-23 | Plastic explosive composition |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5034073A (en) * | 1990-10-09 | 1991-07-23 | Aerojet General Corporation | Insensitive high explosive |
| EP1342704A2 (en) * | 2002-03-09 | 2003-09-10 | TDW Gesellschaft für verteidigungstechnische Wirksysteme mbH | Cast plastic-bonded explosive |
| EP1478608B1 (en) * | 2002-01-31 | 2010-09-29 | MAXAM Deutschland GmbH | Plastic explosive composition, especially for a small-calibre priming for tunnel construction, a method for the production thereof, and a booster for using the same |
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| US4047990A (en) * | 1967-08-01 | 1977-09-13 | The United States Of America As Represented By The Secretary Of The Navy | Plastic bonded explosive composition |
| DE2027709C3 (en) * | 1970-06-05 | 1978-10-19 | Dynamit Nobel Ag, 5210 Troisdorf | Plastic, easily deformable explosive mass by hand |
| GB1355234A (en) * | 1971-10-04 | 1974-06-05 | Ici Ltd | Pnetaerythritol tetranitrate |
| DE3627520C1 (en) * | 1986-08-13 | 1989-05-03 | Messerschmitt Boelkow Blohm | Process for producing plastic-bonded explosives containing nitro groups |
| SE460901B (en) * | 1987-06-04 | 1989-12-04 | Exploweld Ab | WATER RESISTANT ELASTIC EXPLOSIVE MATERIAL |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5034073A (en) * | 1990-10-09 | 1991-07-23 | Aerojet General Corporation | Insensitive high explosive |
| EP1478608B1 (en) * | 2002-01-31 | 2010-09-29 | MAXAM Deutschland GmbH | Plastic explosive composition, especially for a small-calibre priming for tunnel construction, a method for the production thereof, and a booster for using the same |
| EP1342704A2 (en) * | 2002-03-09 | 2003-09-10 | TDW Gesellschaft für verteidigungstechnische Wirksysteme mbH | Cast plastic-bonded explosive |
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