GB2394222A - A polynitramine and method for producing it - Google Patents
A polynitramine and method for producing it Download PDFInfo
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- GB2394222A GB2394222A GB9513427A GB9513427A GB2394222A GB 2394222 A GB2394222 A GB 2394222A GB 9513427 A GB9513427 A GB 9513427A GB 9513427 A GB9513427 A GB 9513427A GB 2394222 A GB2394222 A GB 2394222A
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- GB
- United Kingdom
- Prior art keywords
- dodecane
- hexaazatetracyclo
- hexanitro
- temperature
- nitrozation
- 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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- 238000004519 manufacturing process Methods 0.000 title description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 239000002360 explosive Substances 0.000 claims abstract description 22
- 238000006396 nitration reaction Methods 0.000 claims abstract description 15
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 22
- WFPZPJSADLPSON-UHFFFAOYSA-N dinitrogen tetraoxide Chemical compound [O-][N+](=O)[N+]([O-])=O WFPZPJSADLPSON-UHFFFAOYSA-N 0.000 claims description 18
- 239000011541 reaction mixture Substances 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000004449 solid propellant Substances 0.000 claims description 6
- 235000011149 sulphuric acid Nutrition 0.000 claims description 6
- 239000001117 sulphuric acid Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- NXJCBFBQEVOTOW-UHFFFAOYSA-L palladium(2+);dihydroxide Chemical compound O[Pd]O NXJCBFBQEVOTOW-UHFFFAOYSA-L 0.000 claims description 4
- 238000006699 reductive acetylation reaction Methods 0.000 claims description 4
- 239000003721 gunpowder Substances 0.000 claims 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 abstract description 23
- 239000000028 HMX Substances 0.000 abstract description 22
- 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 abstract description 19
- NDYLCHGXSQOGMS-UHFFFAOYSA-N CL-20 Chemical compound [O-][N+](=O)N1C2N([N+]([O-])=O)C3N([N+](=O)[O-])C2N([N+]([O-])=O)C2N([N+]([O-])=O)C3N([N+]([O-])=O)C21 NDYLCHGXSQOGMS-UHFFFAOYSA-N 0.000 abstract description 17
- NINQAYBICGTGQD-UHFFFAOYSA-N 1-(6,8,12-triacetyl-4,10-dibenzyl-2,4,6,8,10,12-hexazatetracyclo[5.5.0.03,11.05,9]dodecan-2-yl)ethanone Chemical compound CC(=O)N1C2C(N3CC=4C=CC=CC=4)N(C(=O)C)C1C(N1C(C)=O)N(C(C)=O)C3C1N2CC1=CC=CC=C1 NINQAYBICGTGQD-UHFFFAOYSA-N 0.000 description 11
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 238000005474 detonation Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- IUKZSMGVHPBEHK-UHFFFAOYSA-N hexabenzilisovyurtsitan Chemical compound C=1C=CC=CC=1CN(C1C(N(CC=2C=CC=CC=2)C(N2CC=3C=CC=CC=3)C3N1CC=1C=CC=CC=1)N1CC=4C=CC=CC=4)C1C2N3CC1=CC=CC=C1 IUKZSMGVHPBEHK-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- -1 nitrosonium fluoroborate Chemical compound 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KEJOCWOXCDWNID-UHFFFAOYSA-N Nitrilooxonium Chemical class [O+]#N KEJOCWOXCDWNID-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- SPWVRYZQLGQKGK-UHFFFAOYSA-N dichloromethane;hexane Chemical compound ClCCl.CCCCCC SPWVRYZQLGQKGK-UHFFFAOYSA-N 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- OMBRFUXPXNIUCZ-UHFFFAOYSA-N dioxidonitrogen(1+) Chemical class O=[N+]=O OMBRFUXPXNIUCZ-UHFFFAOYSA-N 0.000 description 1
- 238000010892 electric spark Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- 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
- C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
A new polynitramine, 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazatetracyclo (5.5.0.0<5,9>.0<3,11>) dodecane (also called hexanitro hexaazaisowurtzitane) is made by nitrozation of 4,10-dibenzyl-2,6,8,12-tetraacetyl-2,4,6,8,10,12-hexaazatetracyclo (5.5.0.0<5,9>.0<3,11>) dodecane followed by a nitration of the product. This polynitramine is an explosive with a higher performance than hexogen or octogen, and it can be used as an explosive or oxidizing charge in pyrotechnic compositions.
Description
( A NEW POLYNITRAMINE, ITS PRODUCTION,
AND PYROTECHNIC COMPOSITIONS CONTAINING IT
This invention relates to a new polynitramine, to a process for its production, and to pyrotechnic compositions containing it.
As is well known, explosive substances and pyrotechnic compositions such as explosive compositions, gun powders and solid propellants, are very often used not only in the armament industries but also in non-military fields
such as space technology, mining and quarry extraction, public works, etc. There are many explosive substances known for use either as explosive charges in explosive compositions or as oxidizing charges in gun powders and in solid propellants.
In the explosives art, it is well known that for some applications, military ones in particular, it is necessary to use pulverulent explosive substances (ie.
substances which are solid at room temperature) with a high detonation pressure, i.e. with a high density and detonation velocity. The secondary explosives that meet these requirements and are currently in use, are mainly cyclotetramethylene tetranitramine, also called octogen or HMX, and cyclotrimethylene trinitramine, also called hexogen or RDX.
There is generally a need to find new explosives that are both solid at room temperature and thermally stable, and in addition more powerful and energetic than RDX or HMX. However, for obvious security reasons, any such new
( - 2 explosives must not be any more sensitive to external shock. U.S. patent specification no. 4,503,229 describes
1,4,5,8-tetranitro-1,4,5,8-tetraazadifurazano-(3,4-c)(3,4-h) decalin as an energetic explosive. However, this is thermally very unstable, even at room temperature.
We have now discovered a new polynitramine, namely 2,4,6,8,10,12hexanitro-2,4,6,8,10,-12-hexaazatetracyclo (5.5.o.o59.o31l) dodecane, which is an explosive solid at room temperature and thermally stable. Its density and its detonation velocity are superior to those of HMX and RDX and its sensitivity to external shock is close to those of HMX and RDX.
Nielsen et al., J. Org. Chem., 1990,55,1459-1466, describe the synthesis of 2,4,6,8,10,12-hexabenzyl-
2,4,6,8,10,12-hexaazatetracyclo (5.5.o.o.59.031l) dodecane, also called hexabenzyl hexaazaisowurtzitane. No use of this material is described. At a congress organized by the American Defense Preparedness Association, on October 27-29, 1986, at Queen Mary Hotel, Long Beach (California, U.S.A.), the same author, Arnold T. Nielsen disclosed the synthesis of 4,10dibenzyl-2,6,8,12-tetraacetyl-
2,4,6,8,10,12-hexaazatetracyclo (5.5.o.o59.031l) dodecane, also called tetraacetyldibenzyl hexaazaisowurtzitane, by reductive acetylation of hexabenzyl hexaazaisowurtzitane at 60 C, for 6 hours, in acetic anhydride medium, in the presence of hydrogen and Pd/C as catalyst. The yield is low (25%). However, he also pointed out that whilst he had tried numerous ways of nitrating tetraacetyl dibenzyl hexaazaisowurtzitane in order to try to obtain 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazatetracyclo (5. 5.0.059.031l)dodecane, also called hexanitro hexaazaisowurtzitane, he never succeeded.
In spite of this, we have now found a way of making hexanitro hexaazaisowurtzitane and we have unexpectedly found that this composition, which is solid at
( - 3 room temperature and thermally stable, has a density and a detonation velocity far exceeding those of HMX and RDX, whereas its sensitivity to external shock is close to those of RDX and HMX.
In one aspect, therefore, the present invention provides a new polynitramine, 2,4,6,8,10,12-hexanitro-
2,4,6,8,10,12-hexaazatetracyclo (5.5.o.o59.031l) dodecane, which is herein referred to also as hexanitro hexaazaisowurtzitane. The invention also provides a process for making hexanitro hexaazaisowurtzitane, which comprises nitrozation of 4,10-dibenzyl-2,6,8,12-tetraacetyl-2,4,6,8,10,12-
hexaazatetracyclo (5.5.o.o59.o31l) dodecane (tetraacetyl dibenzyl hexaazaisowurtzitane) as a first step, using any nitrozation agent, and then, (as a second step) nitration of the product obtained from the first step, by any nitration agent. The nitrozation and nitration agents are well-known to those skilled in the art. For example, as nitrozation agents, there may be used dinitrogen tetroxide or nitrosonium salts, and as nitration agents, there may be used nitric acid, N2Os, sulfonitric or acetonitric mixtures or nitronium salts.
Preferably, the first step comprises reacting tetraacetyl dibenzyl hexaazaisowurtzitane with dinitrogen tetroxide. In this case, the dinitrogen tetroxide nitrozation agent can also act as a solvent.
Preferably, the nitrozation and/or the nitration reactions are carried out in an organic solvent, most preferably using a chlorinated solvent such as chloroform, 1,2-dichloroethane, or methylene dichloride, which is the most preferred.
It is very much preferred to carry out the nitrozation reaction in the presence of concentrated sulphuric acid, especially when dinitrogen tetroxide is the nitrozation agent.
( - 4 Another preferred way consists in performing the nitration using concentrated nitric acid. In this procedure, it is only necessary to add concentrated nitric acid to the reaction medium after the first step.
Preferably, the nitrozation temperature should be between 10 C and 35 C, e.g. room temperature for instance, and the nitration temperature should be between 45 C and 75.C. The nitrozation and the nitration agents should preferably be used in stoichiometric excess in relation to the tetraacetyl dibenzyl hexaazaisowurtzitane.
The tetraacetyl dibenzyl hexaazaisowurtzitane starting material can, for example, be made by reductive acetylation of hexabenzyl hexaazaisowurtaitane at 60 C, for 6 hours, in the presence of Pd/C as catalyst, in acetic medium (acetic anhydride preferably) and in the presence of hydrogen. Unexpectedly, the yield is much higher when using palladium hydroxide as catalyst than when using Pd. and when progressively raising the temperature of the reaction mixture during the reaction, starting, for example, from a temperature of O to +20 C up to a temperature of 45 C to 75.C, rather than conducting the reaction at a constant temperature level. Thus, yields of above 50% can be obtained by this new process.
The invention also relates to pyrotechnic compositions which contain hexanitro hexaazaisowurtzitane.
Pyrotechnic compositions are compositions which can partially or totally burn, deflagrate or detonate. In the pyrotechnic compositions of the invention, hexanitro hexaazaisowurtzitane is used partially or totally in place of the pulverulent explosive substances commonly used as explosive and/or oxidizing charges in these compositions, e.g. RDX and/or HMX in particular.
Preferred examples of pyrotechnic compositions of the invention include plastic-bonded explosives, especially those performed by casting and then polymerization, and
( 5 - solid propellants and gun powders. These sorts of explosives, propellants and powders containing conventionally RDX and/or HMX as charges, are well known to persons skilled in the art.
According to the present invention, the new pyrotechnic compositions can be obtained in a way similar to known processes applied to compositions with RDX and/or HMX, by replacing all or part of RDX and/or HMX by hexanitro hexaazaisowurtzitane. In accordance with the present invention, the hexanitro hexaazaisowurtzitane can be used as an explosive substance, alone or mixed in an explosive composition, or it can be used as an oxidizing charge in a solid propellant or in a gun powder. This provides an increase in the burning rate of the propellant or of the powder compared to the conventional use of HMX and/or RDX.
In order that the invention may be more fully understood, the following Examples are given by way of illustration only.
Example 1: Synthesis of tetraacetyl dibenzyl hexaazaisowurtzitane. Acetic anhydride (120ml) and recrystallized hexabenzyl hexaazaisowurtzitane (9. 45g (1.33 x 10-2 mol)) are mixed in a 250ml double-walled reactor. The mixture is cooled to 10 C and then 6.7 g of palladium hydroxide on coal are added (with 50% humidity; Ed rate in dry substance: 20%). Hydrogen is introduced into the mixture by means of a diffuser, whilst the temperature of the reaction mixture is progressively raised from 10 C to 20 C in 2 hours, from 20 C to 40 C in 2 hours and from 40 C to 59 C in 2 hours.
The hydrogen supply is then stopped, and the equipment is vented with nitrogen. The reaction mixture is filtered whilst warm. After concentration under reduced pressure (lmm Hg at 50 C), the residual matter is washed with a mixture of hexanedichloromethane in a 50/50 volume
( - 6 ratio. There is obtained 3.87g of tetraacetyl dibenzyl hexaazaisowurtzitane, i.e. a 56% yield.
The compound was identified by elemental analysis, mass spectrometry, infra red (in KBr) and NMR of the proton at 200 MHz.
Its melting point is above 300 C.
Example 2: Synthesis of hexanitro hexaazaisowurtzitane.
50ml of CH2C12 are poured into a lOOml three-
necked bottle fitted with a cooler, a thermometer and a plunger tube. The temperature is brought down to -5 C. 14g of dinitrogen tetroxide are bubbled through, and then 9 drops of sulphuric acid at 95-97% and 1.15g of tetracyl dibenzyl hexaazaisowurtzitane, (obtained in accordance with Example 1) are successively added.
After stirring for 71 hours at room temperature, the mixture is degassed, concentrated at 40 C and then cooled down to 0 C.
Then, over about 1 hour, 16.17g of nitric oleum at 28% are added while maintaining the temperature between -1 C and 3 C. The mixture is then warmed up to 50-52 C for 7 days, after which it is poured into 200ml of freezing water.
After filtering, there is obtained a white solid which is rinsed with water and dried in a vacuum desiccator. This solid is hexanitro hexaazaisowurtzitane and was identified by NMR of the proton at 200 MHz in DMSO, by NMR of carbon in the same conditions, by IR, by elemental analysis and by X-
ray crystallography. Its melting temperature is about 170 C. Its purity, determined by high pressure liquid chromatography, is about 95%. The yield is 51%.
By differential thermal analysis (DTA), initiation of decomposition can be detected at about 220 C. The heat of formation Hf is about 230 cal/g.
( Example 3: Synthesis of hexanitro hexaazaisowurtzitane.
50ml of CH2C12 are poured into a three-necked bottle equipped as in Example 2. The temperature is brought down to -5 C. 16g of dinitrogen tetroxide, 0.55g of concentrated sulphuric acid and then 1.17g of tetraacetyl dibenzyl hexaazaisowurtzitane (obtained in accordance with Example 1) are introduced into the bottle. After stirring for 1.25 hour at room temperature (about 20 C), the mixture is degassed and concentrated. 15ml of nitric acid (100%) are added. The mixture is heated for 2 days at 65 C. 220ml of freezing water are then poured into the mixture. After filtering, 0.85g of hexanitro hexaazaisowurtaitane is isolated which is identified as in Example 2. It is about 95 /O pure. The yield is 86%. This compound has the same thermal characteristics as those of the compound obtained in Example 2. It has a very good thermal stability under vacuum, nearly the same as hexogen or octogen. The volume of emitted gas is 0.64 cm3/g after 193 hours at 80 C.
The density of the product is 1.95 g/cm3 measured by gas pycnometer, and 1.97 g/cm3 according to the crystallographic data obtained by X-rays. For comparison, the density of octogen is 1.91 g/cm3, and that of hexogen is 1.71 g/cm3.
The detonation velocity of hexanitro hexaazaisowurtzitane is 9.500 m/s whereas that of octogen is 9.100 m/s and that of hexogen 8.500 m/s.
Its burning rate at 2 MPa is 7mm/s (4.5 mm/s for octogen); at 8 MPa is 27. 1 mm/s (12 mm/s for octogen); at 15 MPa is 46.3 mm/s (23 mm/s for octogen) ; and at 25 MPa is 90 mm/s (35 mm/s for octogen).
Its friction sensitivity is 120 N (measured by tjhe Julius Peters equipment). The friction sensitivity of octogen is 100 N and that of hexogen is 113 N. Its electric spark sensitivity is low (above 726 mJ), which is roughly the same as those of octogen and hexogen.
( - 8 ExamDle 4: Synthesis of hexanitro hexaazaisowurtzitane.
480g of gaseous N2O4 are introduced at 0 C into a one-liter, doublewalled reactor vented with nitrogen. 31g of concentrated sulphuric acid are added and then, at 5 C, 60g (0.116 mol) of tetraacetyl dibenzyl hexaazaisowurtzitane (obtained in accordance with Example 1). The temperature is allowed to rise to 20 C, and the mixture is stirred for 23 hours. After degassing the mixture for about 2 hours by mildly bubbling nitrogen through it, 360ml of concentrated nitric acid are added while maintaining the temperature of the reaction mixture below 17 C. The mixture is degassed again and then warmed up to 70 C for 40 hours.
After cooling down to 20 C, 4 liters of freezing water are poured into the reaction mixture. A solid is formed. It is filtered, washed with water and dried under vacuum in a desiccator with P2Os. There is obtained 48.4g (95% yield) of hexanitro hexaazaisowurtzitane, which is identified as in Example 2.
Example 5: Synthesis of hexanitro hexaazaisowurtzitane.
Into a 150ml reactor, there are introduced 63g of bioxide tetrahydrothiophene (solvent), 0.28g of water and 6.3g (5.4 10-2 mol) of nitrosonium fluoroborate. After stirring for 0.5 hour at room temperature, lg (2x10-4 mol) of tetraacetyl dibenzyl hexaazaisowurtzitane (obtained in accordance with Example 1) is added.
The mixture is stirred for 1 hour between 17 C and 20 C and progressively warmed up to 55 C over 0.7 hour.
This temperature is maintained for 1 hour. The mixture is then cooled down to 17 C. Next, 5.16g (3.8x10-2 mol) of nitronium tetrafluoroborate are added. The temperature is progressively raised to 55 C over one hour, and then the mixture is maintained at this temperature for 1 hour. Then it is cooled down to 17 C and 50ml of water are added, drop by drop, while maintaining the temperature below 20 C. The
reaction mixture is poured into a 10-liter beaker and then 5 liters of water are introduced progressively while stirring.
After 12 hours at 5 C, the precipitate obtained is isolated by filtration and dried under reduced pressure in the presence of phosphoric anhydride. 0.73g of hexanitro hexaazaisowurtzitane are obtained and identified as in Example 2. The yield is 86%.
/
Claims (7)
1. 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-
hexaazatetracyclo (5.5.o.o59.031l) dodecane.
2. A process for making 2,4,6,8,10,12-hexanitro-
2,4,6,8,10,12-hexaazatetracyclo (5.5.o.o59.o31l) dodecane, which process comprises nitrozation of 4,10-dibenzyl 2,6,8,12-tetraacetyl-2,4,6,8,10,12hexaazatetracyclo (5.5.0.05 9.311) dodecane, followed by nitration of the product. 3. A process according to claim 2, wherein the nitrozation is effected by reacting the 4,10-dibenzyl-
2,6,8,12-tetraacetyl-2,4,6,8,10,12-hexaazatetracyclo (5.5.o.o59.o31l) dodecane with dinitrogen tetroxide.
4. A process according to claim 3, wherein the nitrozation reaction is effected in the presence of concentrated sulphuric acid.
5. A process according to any claim 2, 3 or 4, wherein the nitration is performed with concentrated nitric acid. 6. A process according to any of claims 2 to 5, wherein the nitrozation reaction is effected at a temperature of 10 C to 35 C, and the nitration reaction is effected at a temperature of 45 C to 75 C.
7. A process according to any of claims 2 to 6,, wherein the 4,10dibenzyl 2,6,8,12-tetraacetyl-2,4,6,8,10,12 -hexaazatetracyclo (5.5.o.o59. 031l) dodecane is obtained by reductive acetylation, in acetic medium and in the presence of hydrogen and palladium hydroxide as catalyst, while the reaction mixture is progressively warmed from a
temperature between 0 C and 20 C up to a temperature between 45 C and 75 C.
8. A process for making 2,4,6,8,10,12-hexanitro-
2,4,6,8,10,12-hexaazatetracyclo (5.5.o.o59.o31l) dodecane substantially as herein described in Example 2, 3. 4 or 5.
9. 2,4,6.8,10,12-hexanitro-2,4,6,8,10,12-
hexaazatetracyclo (5.5.o.o59.03'll) dodecane produced by the process of any of claims 2 to 8.
10. A pyrotechnic composition which comprises 2,4,6,8,10,12-hexanitro-2,4, 6,8,10,12-hexaazatetracyclo (5.5.o.059.031l) dodecane.
11. A composition according to claim 10, which is in the form of a plastic-bonded explosive, a solid propellant or a gun powder.
12. Use of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-
hexaazatetracyclo (5.5.o.o59.o31l) dodecane as an explosive or as an oxidizing charge in a gun powder or a solid propellant.
i
Amendments to the claims have been filed as follows I. A process for making 2,4,6,8,10,1 2-hexanitro-2,4,6,8, 10,12-
hexaazatetracyclo (5.5.0.05'9.03'll) dodecane, which process comprises nitrozation of 4,1 O-dibenzyl 2,6,8,1 2-tetraacetyl-2,4,6,8, 10,1 2hexaazatetracyclo (5.5,0,05'9.03'l i) dodecane with dinitrogen tetroxide, followed by nitration of the product. 2. A process according to claim 1, wherein the nitrozation reactions is effected in the presence of concentrated sulphuric acid.
3. A process according to claim I or 2, wherein the nitration is performed with concentrated nitric acid.
4. A process according to any of claims I to 3, wherein the nitrozation reaction is effected at a temperature of 10 C to 35 C, and the nitration reaction is effected at a temperature of 45 C to 75 C.
5. A process according to any of claims I to 4, wherein the 4,10-
dibenzyl 2,6,8,1 2-tetraacetyl-2,4,6,8, 10,1 2-hexaazatetracyclo (5.5.0. 05'9.03'l l) dodecane is obtained by reductive acetylation, in acetic medium and in the presence of hydrogen and palladium hydroxide as catalyst, while the reaction mixture is progressively warmed from a temperature between 0 C and 20 C up to a temperature between 45 C and 75 C.
6. A process for making 2,4,6,8,10,1 2-hexanitro-2,4,6,8, 10,12-
hexaazatetracyclo (5.5.0.05'9.03'l l) dodecane substantially as herein described in Example 2, 3 or 4.
t3
7. 2,4,6,8,10,1 2-hexanitro-2,4,6,8, 10,1 2-hexaazatetracyclo (5.5.0. 05'9.03't l) dodecane produced by the process of any of claims I to 5.
l
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9212575A FR2831167B1 (en) | 1992-10-21 | 1992-10-21 | NOVEL POLYNITRAMINE, ITS SYNTHESIS PROCESS, NOVEL PYROTECHNIC COMPOSITIONS |
| GB9513427A GB2394222B (en) | 1992-10-21 | 1995-06-29 | A method of making a polynitramine |
| IT1995TO000565A IT1316050B1 (en) | 1992-10-21 | 1995-07-06 | POLYNITRAMIN, ITS SYNTHESIS AND HYDROTECHNICAL COMPOSITIONS. |
| DE19526503A DE19526503B4 (en) | 1992-10-21 | 1995-07-20 | Process for the preparation of hexanitrohexaazaisowurtzitane |
| ES009501473A ES2191500B1 (en) | 1992-10-21 | 1995-07-21 | NEW POLINITRAMINE, ITS SYNTHESIS PROCEDURE, NEW PIROTECHNICAL COMPOSITIONS. |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9212575A FR2831167B1 (en) | 1992-10-21 | 1992-10-21 | NOVEL POLYNITRAMINE, ITS SYNTHESIS PROCESS, NOVEL PYROTECHNIC COMPOSITIONS |
| GB9513427A GB2394222B (en) | 1992-10-21 | 1995-06-29 | A method of making a polynitramine |
| IT1995TO000565A IT1316050B1 (en) | 1992-10-21 | 1995-07-06 | POLYNITRAMIN, ITS SYNTHESIS AND HYDROTECHNICAL COMPOSITIONS. |
| DE19526503A DE19526503B4 (en) | 1992-10-21 | 1995-07-20 | Process for the preparation of hexanitrohexaazaisowurtzitane |
| ES009501473A ES2191500B1 (en) | 1992-10-21 | 1995-07-21 | NEW POLINITRAMINE, ITS SYNTHESIS PROCEDURE, NEW PIROTECHNICAL COMPOSITIONS. |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB9513427D0 GB9513427D0 (en) | 2003-02-26 |
| GB2394222A true GB2394222A (en) | 2004-04-21 |
| GB2394222B GB2394222B (en) | 2004-09-29 |
Family
ID=32777251
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9513427A Expired - Fee Related GB2394222B (en) | 1992-10-21 | 1995-06-29 | A method of making a polynitramine |
Country Status (5)
| Country | Link |
|---|---|
| DE (1) | DE19526503B4 (en) |
| ES (1) | ES2191500B1 (en) |
| FR (1) | FR2831167B1 (en) |
| GB (1) | GB2394222B (en) |
| IT (1) | IT1316050B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2448110C1 (en) * | 2010-10-21 | 2012-04-20 | Российская Федерация, от имени которой выступает Министерство промышленности и торговли Российской Федерации (Минпромторг России) | Method for debenzylation of 2,6,8,12-tetraacetyl-2,4,6,8,10,12-hexaazaisowurtzitane |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2831167B1 (en) * | 1992-10-21 | 2004-04-23 | Poudres & Explosifs Ste Nale | NOVEL POLYNITRAMINE, ITS SYNTHESIS PROCESS, NOVEL PYROTECHNIC COMPOSITIONS |
| FR2830532B1 (en) * | 1996-02-15 | 2005-09-16 | Poudres & Explosifs Ste Nale | PROCESS FOR THE SYNTHESIS OF HEXAAZAISOWURTZITANE DERIVATIVES AND THE ALPHA POLYMERIC FORM OF A HEXAAZAISOWURTZITANE DERIVATIVE |
| CN106946894B (en) * | 2017-04-10 | 2019-03-15 | 中国科学院上海有机化学研究所 | Application of the Pd radicel duplex metal catalyst in HBIW catalytic hydrogenolytic cleavage |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997000873A1 (en) * | 1995-06-22 | 1997-01-09 | Thiokol Corporation | Improved synthesis of 2,4,6,8,10,12-hexabenzyl-2,4,6,8,10,12-hexaazatetracyclo[5.5.0.0?5,9.03,11¿]dodecane |
| EP0753519A1 (en) * | 1995-02-01 | 1997-01-15 | Asahi Kasei Kogyo Kabushiki Kaisha | Hexaazaisowurtzitane derivatives and process for producing the same |
| GB2333292A (en) * | 1988-12-21 | 1999-07-21 | Thiokol Corp | Polycyclic polyamides as precursors for energetic polycyclic polynitramine oxidizers |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2831167B1 (en) * | 1992-10-21 | 2004-04-23 | Poudres & Explosifs Ste Nale | NOVEL POLYNITRAMINE, ITS SYNTHESIS PROCESS, NOVEL PYROTECHNIC COMPOSITIONS |
-
1992
- 1992-10-21 FR FR9212575A patent/FR2831167B1/en not_active Expired - Lifetime
-
1995
- 1995-06-29 GB GB9513427A patent/GB2394222B/en not_active Expired - Fee Related
- 1995-07-06 IT IT1995TO000565A patent/IT1316050B1/en active
- 1995-07-20 DE DE19526503A patent/DE19526503B4/en not_active Expired - Fee Related
- 1995-07-21 ES ES009501473A patent/ES2191500B1/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2333292A (en) * | 1988-12-21 | 1999-07-21 | Thiokol Corp | Polycyclic polyamides as precursors for energetic polycyclic polynitramine oxidizers |
| EP0753519A1 (en) * | 1995-02-01 | 1997-01-15 | Asahi Kasei Kogyo Kabushiki Kaisha | Hexaazaisowurtzitane derivatives and process for producing the same |
| WO1997000873A1 (en) * | 1995-06-22 | 1997-01-09 | Thiokol Corporation | Improved synthesis of 2,4,6,8,10,12-hexabenzyl-2,4,6,8,10,12-hexaazatetracyclo[5.5.0.0?5,9.03,11¿]dodecane |
Non-Patent Citations (4)
| Title |
|---|
| Combustion and Flame (1991), 87(2), 145-151 * |
| J. Phys. Chem. (1991), 95(15), 5858-5864 * |
| Mol. Cryst. Liq. Cryst. Sci. Technol. Sect.A (1992), 219, 139-148 * |
| Propellants, Explosives, Pyrotechnics (1994), 19(3), 133-144 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2448110C1 (en) * | 2010-10-21 | 2012-04-20 | Российская Федерация, от имени которой выступает Министерство промышленности и торговли Российской Федерации (Минпромторг России) | Method for debenzylation of 2,6,8,12-tetraacetyl-2,4,6,8,10,12-hexaazaisowurtzitane |
Also Published As
| Publication number | Publication date |
|---|---|
| DE19526503A1 (en) | 2003-07-17 |
| DE19526503B4 (en) | 2006-06-14 |
| GB2394222B (en) | 2004-09-29 |
| FR2831167A1 (en) | 2003-04-25 |
| IT1316050B1 (en) | 2003-03-28 |
| ES2191500B1 (en) | 2004-07-01 |
| ITTO950565A1 (en) | 1997-01-06 |
| ITTO950565A0 (en) | 1995-07-06 |
| ES2191500A1 (en) | 2003-09-01 |
| GB9513427D0 (en) | 2003-02-26 |
| FR2831167B1 (en) | 2004-04-23 |
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