EP3872054A1 - Liant pour un explosif - Google Patents

Liant pour un explosif Download PDF

Info

Publication number: EP3872054A1
Authority: EP; European Patent Office
Prior art keywords: ionic liquid; polymer; molecules; explosive; binder according
Prior art date: 2020-02-25
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.): Granted

Application number

EP21158071.7A

Other languages

German (de)

English (en)

Other versions

EP3872054B1 (fr

Inventor

Arno Hahma

Oliver PHAM-SCHÖNWETTER

Philipp Schwegler

Esme Roth

Björn DONNER

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Diehl Defence GmbH and Co KG

Original Assignee

Diehl Defence GmbH and Co KG

Priority date (The priority date 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 date listed.)

2020-02-25

Filing date

2021-02-19

Publication date

2021-09-01

2021-02-19 Application filed by Diehl Defence GmbH and Co KG filed Critical Diehl Defence GmbH and Co KG

2021-09-01 Publication of EP3872054A1 publication Critical patent/EP3872054A1/fr

2024-06-12 Application granted granted Critical

2024-06-12 Publication of EP3872054B1 publication Critical patent/EP3872054B1/fr

Status Active legal-status Critical Current

2041-02-19 Anticipated expiration legal-status Critical

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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
- C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
- C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
- C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/006—Stabilisers (e.g. thermal stabilisers)

Definitions

the invention relates to a binder for an explosive, comprising at least one ionic liquid and a polymer. More than one ionic liquid can be present in a mixture of ionic liquids.
compositions comprising a polar polymer and an ionic liquid or a mixture of ionic liquids as a means for phlegmatizing and binding a pyrotechnic active mass.
the composition is a viscoelastic material formed by dissolving the polymer in the ionic liquid or the mixture of ionic liquids, the polymer comprising polyacrylonitrile, polyvinyl nitrate, polyvinylpyrrolidone (PVP) or nitrocellulose.
an insensitive explosive substance comprising an explosive and a phlegmatizer
the phlegmatizer comprising at least one ionic liquid
the explosive substance further comprising a binder.
the binder comprises a polar polymer or polar macromolecule or a polymer or macromolecule which is soluble in the ionic liquid or can be swollen by it.
the well-known pourable and curing high-performance active compound DLE-C038 is hexanitroisowurtzitane (CL-20) in the form of particles of different sizes, which are mixed with a binder consisting of hydroxyl-terminated polybutadiene (HTPB), which is cured using an isocyanate as a hardener became.
CL-20 hexanitroisowurtzitane
HTPB hydroxyl-terminated polybutadiene
the object of the present invention is to provide an alternative binding agent for an explosive which, when binding an explosive, results in the formation of an insensitive explosive substance. Furthermore, a method for producing such a binder is to be specified.
a binder for an explosive which comprises at least one ionic liquid and a polymer.
the polymer is formed from monomers or molecules of a further polymer which are crosslinked to form an elastic network by means of a crosslinking agent.
the crosslinking agent has at least two functional groups per molecule which react with the monomers or molecules of the further polymer each having at least two functional groups per molecule in order to bring about the crosslinking.
a network is understood to mean a polymer extending two-dimensionally or three-dimensionally, i. H. the crosslinked polymer is by no means merely linear.
a small proportion, for example 1%, of the molecules of the crosslinking agent or of the monomers or of the molecules of the further polymer has at least three functional groups.
the functional groups of the monomers or the molecules of the further polymer can be, for example, OH groups and the functional groups of the molecules of the crosslinking agent can be isocyanate groups.
the ionic liquid is embedded in the network.
the monomers or molecules of the further polymer are preferably polar so that they are soluble in the ionic liquid, which is always polar, or can be swollen or gelled by the ionic liquid.
an ionic liquid is already liquid at a temperature below 100 ° C without the salt being dissolved in a solvent such as water.
an ionic liquid is an organic salt, the ions of which prevent the formation of a stable crystal through charge delocalization and steric effects.
the inventors have found that the viscoelastic properties of the EP 2 698 359 B1 known insensitive explosive active mass and from the use according to the EP 2 698 361 B1 resulting pyrotechnic active mass change strongly depending on the temperature. When it is hot, the viscosity of the active compound is greatly reduced, while when it is cold it rises sharply, thereby hardening the active compound. This hardening increases the sensitivity to mechanical stress, so that when it is cold, mechanical stress, such as a blow, can lead to an undesired conversion or detonation of the active material.
the inventors have recognized that the advantageous properties of the known active composition containing a polymer and an ionic liquid can be maintained over a wide temperature range and at the same time the temperature dependence of the viscoelastic properties can be reduced if the polymer forms a two-dimensional or three-dimensional network in which the ionic liquid is incorporated.
crosslinking the monomers or the molecules of the further polymer migration of the ionic liquid within the binder is avoided or at least greatly reduced and the temperature dependence of the mechanical properties of the binder is greatly reduced.
Such a binder can be produced by the method according to the invention, in which the monomers or the molecules of the further polymer, the ionic liquid and the crosslinking agent and optionally the explosive for crosslinking the monomers or molecules of the further polymer are mixed with one another in a crosslinking reaction and the resultant Mixture is incubated. Incubation allows crosslinking to occur. The incubation usually takes place until the crosslinking reaction is complete. The crosslinking can be accelerated by adding heat. During the incubation, the binding agent can be brought into shape with any explosives it may contain, for example by pouring it into an appropriate ammunition casing or introducing it in some other way.
the monomers or molecules of the further polymer can be dissolved or swollen in the ionic liquid, in particular before mixing with the explosive and / or with the crosslinking agent or also during this.
the crosslinking agent can then before, during or after dissolving with the ionic Liquid can be mixed.
the mixture can be heated to accelerate the crosslinking reaction.
a catalyst which catalyzes the crosslinking reaction in particular iron acetylacetonate to activate isocyanate groups in the crosslinking agent, can be mixed with the monomers or molecules of the further polymer, the ionic liquid and the crosslinking agent and optionally the explosive to accelerate the crosslinking reaction.
the catalyst can be added before, during or after the mixing of individual components mentioned or of a resulting mixture.
it can also be dissolved in the ionic liquid before the monomers or molecules of the further polymer are brought into contact with the ionic liquid.
the monomers and the molecules of the further polymer and / or the ionic liquid can be selected such that the decomposition temperature of the crosslinked polymer or the ionic liquid is lower than the decomposition temperature of the explosive.
the safety of an explosive active compound containing the binder according to the invention is significantly increased if the container with the explosive active compound is slowly heated, as is done, for example, in the event of a fire or simulated in the so-called cook-off test.
the reason for this is that the container is broken open before the explosive can react due to an early decomposition of the polymer or the ionic liquid due to an increase in temperature and the resulting pressure inside the container.
a detonation of a warhead or a projectile in the event of a fire can thereby be prevented or the detonation effect of the explosive substance contained therein can at least be greatly reduced.
the further polymer can comprise or consist of a linear, ie unbranched, polymer or an energetic polymer.
the energetic polymer can be a linear polymer.
An energetic polymer is understood to mean a polymer which, after ignition or ignition, releases energy, in particular at least 1 kJ / g, by reaction without external oxidizing agents, such as atmospheric oxygen. Such polymers usually carry energetic groups such as azido groups, nitro groups, nitramine groups or nitrate groups.
Energetic polymers which are well suited for the binder according to the invention are, for example, nitrocellulose (NC) or polyvinyl nitrate (PVN).
NC and PVN are usually always incompletely nitrided, ie not all in the underlying Base molecule cellulose or polyvinyl alcohol containing OH groups have been esterified during the nitration of the base molecule.
NC and PVN are available commercially with different N contents. For example, an NC with an N content of 12% has proven to be well suited for the binder according to the invention.
NC and commercially available PVN there are always molecules with at least two or three free OH groups that are available for a crosslinking reaction with the crosslinking agent. The presence of molecules with only one or no free OH group is harmless because these molecules cannot be crosslinked to form a network and thus even act as plasticizers in the binder according to the invention, which reduces the sensitivity of an explosive bound therewith.
the binder can comprise at most 50% by weight of a non-energetic polymer.
the non-energetic polymer can be an epoxy resin, a polyester, polytetrahydrofuran, polyethylene glycol or polypropylene glycol. A proportion of more than 50% by weight of a non-energetic polymer leads to a relatively strong reduction in the performance of an active explosive composition containing the binder according to the invention.
the crosslinking agent can be an, in particular aliphatic, diisocyanate, triisocyanate, polyisocyanate or a mixture of at least two of these isocyanates, an, in particular di-, tri- or polyfunctional, epoxide, in particular a bisphenol-A-based epoxide, or a, in particular di -, tri- or polyfunctional, include or consist of acid anhydride.
the diisocyanate can be hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPI), tolylene diisocyanate (TDI) or methylenediphenyl diisocyanate (MDI).
the triisocyanate can be, for example, hexamethylene triisocyanate, hexamethylene diamine biuret or a biuret triisocyanate.
a suitable mixture of hexamethylene diisocyanate and hexamethylene diamine biuret is sold by Covestro AG under the trade name "Desmodur® N100".
this mixture should be used in the binder according to the invention in order to avoid a relatively strong crosslinking and thus a relatively high hardness of the binder.
molecules of the crosslinking agent each have at least three functional ones that are each suitable for forming a bond with one of the monomers or the molecules of the further polymer Groups, in particular isocyanate groups, on.
the monomers or molecules of the further polymer can each have at least three functional groups, in particular OH groups, each suitable for forming a bond with a molecule of the crosslinking agent. It has proven to be advantageous if at least 1% of the molecules of the crosslinking agent or the monomers or molecules of the further polymer or 1% of the total molecules of the crosslinking agent and the monomers or molecules of the further polymer have at least three functional groups. As a result, good immobilization of the ionic liquid can be ensured by forming an at least two-dimensional network.
the ionic liquid is insoluble in water and, in particular, insoluble in water and not hygroscopic. This can prevent the composition and the properties of the binder according to the invention from changing due to water absorbed, in particular from the air.
the ionic liquid can contain a perchlorate, nitrate, acetate, dicyanamide, hexafluorophosphate or tetrafluoroborate ion as the anion.
the ionic liquid can contain an alkylimidazolium ion, an alkyl-alkylimidazolium ion, an alkyl-methylimidazolium ion, in particular a dimethylimidazolium ion or ethylmethylimidazolium ion, a tetrazolium ion or a triazolium ion.
the ionic liquid can be, for example, an alkyl imidazolium perchlorate, an alkyl alkyl imidazolium perchlorate, an alkyl imidazolium tetrafluoroborate, an alkyl alkyl imidazolium tetrafluoroborate, alkyl imidazolium dicyanamide or an alkyl alkyl imidazolium dicyanamide.
Suitable ionic liquids are, for example, 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM-BF 4 ), 1-butyl-3-methylimidazolium dicyanamide (BMIM-C 2 N 2 ) or n-butylmethylimidazolium perchlorate (BMIM-ClO 4 ).
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 energetic ionic liquid is one that releases energy, in particular at least 1 kJ / g, after ignition or ignition without the need for an additional oxidizing agent, such as, for example, atmospheric oxygen. In this way it is possible to provide a binding agent which releases at least 1 MJ / kg of energy when an explosive bound therewith is reacted.
the ionic liquid is one whose density is at least 1000 kg / m 3 , in particular at least 1100 kg / m 3 .
the binder can be contained in an explosive active compound comprising an explosive, in particular a crystalline explosive.
the explosive can be octogen, hexogen, nitropenta (PETN), triaminotrinitrobenzene (TATB), diaminodinitroethylene (FOX-7), hexanitroisowurtzitane (CL-20) or dihydroxyl-ammonium-5,5'-bistetrazole-1,1 '-diolate (TKX-50).
the reagents for the preparation of active explosives containing binders are given in the tables below. 1 kg of each of the explosive active masses was produced.
the NC was first dissolved in a mixture of acetone and ethyl acetate in a ratio of 1: 1.
the respective ionic liquid, the respective isocyanate and the iron acetylacetonate serving as a catalyst were then each added to this solution and then stirred for a few minutes using a magnetic stirrer in order to obtain a homogeneous mixture. Approx. 400 ml of the acetone-ethyl acetate mixture were used in each case.
ethanol, ethanol and ethyl ether in a ratio of 2: 1 ethanol, ethanol and acetone in a ratio of 2: 1 or ethanol-ethyl acetate in a ratio of 2: 1 or any other solvent or solvent mixture that both the to crosslinking monomers or molecules of the further polymer dissolves and is also miscible with the ionic liquid, can be used.
the dried explosive is slurried into the resulting solution, and the resulting mixture is poured into a mixer and mixed therein. After 5 minutes, the mixture is heated to about 70 ° C. and the pressure is gradually reduced to below 2 mbar in order to completely draw off the acetone-ethyl acetate mixture. As a result, the explosive crystals are coated with the binder. After the solvent had been removed, the mixing and heating of the mixer were ended and the pressure in the mixer was adjusted to atmospheric pressure again. After opening the mixer, a slightly sticky, colorless, powdery mass that was easy to dose was found in it. This was removed and in each case 24 g of it was pressed into a tablet in a pressing tool having a diameter of 21 mm. Tablets produced in this way were used in a gap test.
the gap test is a standard test for determining the insensitivity of explosive substances or explosives.
the height of a standardized water column referred to as a "gap” or “gap” is measured which is sufficient to transfer a shock wave generated by detonation of a standard explosive charge in the water column to the explosive substance to be examined, so that it still detonates reliably or reliably no longer detonated.
the Values are given in mm of the water column.
the first value under "Gap [mm]" denotes the value at which the explosive substance to be investigated still reliably detonates ("GO") and the second value the value at which the explosive substance to be investigated is no longer reliable detonated ("NO GO"). The lower these values are, the more insensitive the explosive substance is.
“TMD” denotes the theoretical maximum density of the respective explosive active mass, given in kg / m 3.
the loss modulus G ′′ corresponds to the proportion of energy lost which is converted into heat by internal friction in the binder.
the binder samples with crosslinking agent were each measured at the highest temperature shown until the storage modulus G 'no longer increased. This was shown The temperature was then slowly reduced over the temperature range indicated in each case in the figures.
Fig. 1 shows the result of the rheometric measurement of the binder from Example 2.
This binder contains nitrocellulose and an ionic liquid, but no crosslinking agent.
the course of the curves in Fig. 1 shows that the storage modulus G 'changes in the temperature range from +80 ° C to -60 ° C from 5 Pa to 500 kPa, ie over 5 orders of magnitude.
Fig. 2 shows the result of the corresponding rheometric measurement for the binder composition according to the invention contained in Example 3, which contains the crosslinking agent hexamethylene diisocyanate and the catalyst iron acetylacetonate which catalyzes the crosslinking.
the figure shows that the storage modulus G 'here in the range from +80 ° C. to -60 ° C. changes significantly less than in the case of the binder from example 2.
Fig. 3 shows the results of the measurements of the binder compositions from Example 1 ("Hytemp / DOA 25/75”), Example 2 ("NC / BMIM-ClO 4 25/75") and Example 3 ("NC / BMIM-ClO 4 / HDMI 90 /10/0.055 ").
Fig. 3 clearly shows the effect of the networking.
the binder from Example 1, which is used as a reference, is also crosslinked. However, this binder is not energetic and therefore results in a reduced
Table 1 material TMD / (kg / m 3 ) Density / (kg / m 3 ) % TMD Gap / mm Result Tg / ° C Insensitive? % Plasticizer example 1 1833 1810 98.7 12/13 GO / NO GO -55 Yes DOA
Example 2 1853 1840 99.3 12/13 GO / NO GO ⁇ -60 Yes BMIM-ClO 4
Example 3 1849 1820 98.5 12/13 GO / NO GO ⁇ -60 Yes BMIM-ClO 4
the limit value of the gap for an insensitive explosive is 15 mm. If the gap is equal to or smaller than 15 mm and the explosive does not detonate repeatedly, it is classified as insensitive. In all of the examples in the above table, no detonation took place at a gap of 13 mm, so that the tested explosive substances can all be classified as insensitive.
"Tg” means "glass transition temperature” in the table above. The glass transition temperature was measured by means of dynamic difference calorimetry (DSC). For military purposes, the glass transition temperature should be below -54 ° C. This is easily achieved for the active composition according to the invention according to Example 3.
Table 2 below shows the performance data calculated and measured for Examples 1 to 3 at the densities actually achieved in accordance with Table 1 above. The measured values are given in brackets. Table 2: material D / (m / s) p / GPa example 1 8850 (8615) 33.0 Example 2 8860 (8630) 34.5 Example 3 8770 33.5

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EP21158071.7A 2020-02-25 2021-02-19 Liant pour un explosif Active EP3872054B1 (fr)

Applications Claiming Priority (1)

Application Number	Priority Date	Filing Date	Title
DE102020001204.3A DE102020001204A1 (de)	2020-02-25	2020-02-25	Bindemittel für einen Sprengstoff

Publications (2)

Publication Number	Publication Date
EP3872054A1 true EP3872054A1 (fr)	2021-09-01
EP3872054B1 EP3872054B1 (fr)	2024-06-12

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ID=74672112

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP21158071.7A Active EP3872054B1 (fr)	2020-02-25	2021-02-19	Liant pour un explosif

Country Status (5)

Country	Link
EP (1)	EP3872054B1 (fr)
DE (1)	DE102020001204A1 (fr)
HU (1)	HUE067922T2 (fr)
PL (1)	PL3872054T3 (fr)
ZA (1)	ZA202101163B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
CN115231983A (zh) *	2022-07-15	2022-10-25	西安近代化学研究所	一种含荧光分子笼的六亚甲基二异氰酸胺酯粘合剂、制备方法及应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
CN115368376B (zh) *	2022-08-10	2023-07-18	西安近代化学研究所	一种双功能1,4-环己烷二异氰酸酯粘合剂、制备方法及应用

Citations (4)

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Publication number	Priority date	Publication date	Assignee	Title
US20060011276A1 (en) *	2002-04-24	2006-01-19	Charles Grix	Electrically controlled solid propellant
EP2698361B1 (fr)	2012-08-17	2017-03-29	Diehl BGT Defence GmbH & Co.KG	Utilisation d'une composition comprenant un polymère et un liquide ionique
CN105542222B (zh) *	2015-12-30	2018-07-27	江阴市长泾花园毛纺织有限公司	一种聚乳酸凝胶增韧海绵的制备方法
EP2698359B1 (fr)	2012-08-17	2019-11-27	Diehl Defence GmbH & Co. KG	Masse active d'explosif insensible dotée d'un agent flegmatisant

2020
- 2020-02-25 DE DE102020001204.3A patent/DE102020001204A1/de active Pending
2021
- 2021-02-19 EP EP21158071.7A patent/EP3872054B1/fr active Active
- 2021-02-19 HU HUE21158071A patent/HUE067922T2/hu unknown
- 2021-02-19 PL PL21158071.7T patent/PL3872054T3/pl unknown
- 2021-02-22 ZA ZA2021/01163A patent/ZA202101163B/en unknown

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Publication number	Priority date	Publication date	Assignee	Title
US20060011276A1 (en) *	2002-04-24	2006-01-19	Charles Grix	Electrically controlled solid propellant
EP2698361B1 (fr)	2012-08-17	2017-03-29	Diehl BGT Defence GmbH & Co.KG	Utilisation d'une composition comprenant un polymère et un liquide ionique
EP2698359B1 (fr)	2012-08-17	2019-11-27	Diehl Defence GmbH & Co. KG	Masse active d'explosif insensible dotée d'un agent flegmatisant
CN105542222B (zh) *	2015-12-30	2018-07-27	江阴市长泾花园毛纺织有限公司	一种聚乳酸凝胶增韧海绵的制备方法

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Title
JIAN-YING WANG ET AL: "Properties of-butylpyridinium nitrate ionic liquid and its binary mixtures with water", THE JOURNAL OF CHEMICAL THERMODYNAMICS, ACADEMIC PRESS LONDON, GB, vol. 45, no. 1, 8 September 2011 (2011-09-08), pages 43 - 47, XP028328650, ISSN: 0021-9614, [retrieved on 20110916], DOI: 10.1016/J.JCT.2011.09.003 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
CN115231983A (zh) *	2022-07-15	2022-10-25	西安近代化学研究所	一种含荧光分子笼的六亚甲基二异氰酸胺酯粘合剂、制备方法及应用
CN115231983B (zh) *	2022-07-15	2023-06-09	西安近代化学研究所	一种含荧光分子笼的六亚甲基二异氰酸胺酯粘合剂、制备方法及应用

Also Published As

Publication number	Publication date
DE102020001204A1 (de)	2021-08-26
PL3872054T3 (pl)	2024-10-28
HUE067922T2 (hu)	2024-11-28
ZA202101163B (en)	2022-07-27
EP3872054B1 (fr)	2024-06-12

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