killswitch
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Explosive stable to over 500ºC: BTDAONAB
BTDAONAB (N,N'-Bis (1,2,4-triazol-3-yl)-4,4'-diamino-2,2',3,3',5,5',6,6'-octanitroazo-benzene) is among the most thermally stable explosives known. It
is stable at up to 550ºC.
The surprising thing is how few specialty chemicals are required. Here is the list of materials used in the synthesis:
chloroform
acetone
ethyl acetate
methanol
oleum (25% SO3 by mass)
nitric acid (98% or higher)
sodium azide
p-chlorobenzoic acid
3-amino-1,2,4-triazole
Since the original journal publication is in password-protected PDF form in an obscure journal, I will manually type out the synthesis instructions
here:
4-Chloro-3,5-dinitrobenzoic acid
40 mL of oleum (25%) was transferred carefully to a 250 mL three-necked round-bottomed flask fitted with a mechanical stirrer, dropping funnel and
reflux condenser and 36 mL of fuming nitric acid was added drop-wise under stirring and maintaining the temperature = 25-30°C (ice bath cooling). To
this nitrating mixture, 4-chlorobenzoic acid (10 g, 63.9 mmol) was added slowly with continuous stirring. After the addition, reaction mixture was
heated on a water bath to achieve a temperature of 92-95°C which was maintained for 4 h under continuous stirring. The reaction mixture was allowed
to cool to ambient temperature followed by pouring into the crushed-ice. The pale yellow compound, thus obtained, was filtered and washed thoroughly
with cold water till it is acid-free. The product was crystallized from ethyl acetate. The yield was 12.8 g (81.2%) and m.p. was 162-63°C.
4-Chloro-3,5-dinitroaniline
20 mL of oleum (25%) was carefully transferred to a three-necked round-bottomed flask fitted with a mechanical stirrer, reflux condenser and dropping
funnel followed by the drop-wise addition of 4 mL of concentrated sulfuric acid (98%) To this, 4-chloro-3,5-dinitrobenzoic acid (10 g, 40.56 mmol) was
added slowly under continuous stirring. After complete dissolution, 40 mL of chloroform was also added through a dropping funnel and the temperature
of the reaction mixture was raised to 35-40° C. Sodium azide (4 g, 61.5 mmol) was added in small portions under vigorous stirring followed by reflux
for 4 h. The reaction mixture was allowed to cool and then poured into the crushed ice. The dark yellow product thus obtained was filtered and washed
with water till it is acid-free. The product was crystallized from ethyl acetate. The yield was 7.4 g {- 84%) with a mp. of 188-190°C.
4,4'-Dichloro-2,2',3,3',5,5',6,6'-octanitroazobenzene
To a 500 mL three-necked round-bottomed flask fitted with a mechanical stirrer, thermometer pocket and dropping funnel 250 mL of concentrated sulfuric
acid (98%) was carefully transferred followed by drop-wise addition of 15 mL fuming nitric acid (98%) under vigorous stirring at 25-30°C (in an ice
bath). 4-chloro-3,5-dinitroaniline (10 g, 45.97 mmol) was slowly added to this nitrating mixture while maintaining the same temperature. The
temperature of reaction mixture was slowly raised to 85-90°C over approximately one hour and maintained for 2.5 hrs. The reaction mixture was
subsequently cooled to ambient temperature and poured into the crushed ice. A light yellow product was obtained, filtered and washed with distilled
water till it became acid-free. It was then dried to yield 11.0 g (~38%) with DTA exotherm at 340°C.
N,N'-Bis (1,2,4-triazol-3-yl)-4,4'-diamino-2,2',3,3',5,5',6,6'-octanitroazo-benzene
In a three-necked mund-bottomed flask fitted with a reflux condenser and additional funnel 4,4'-dichloro-2,2', 3,3', 5,5', 6,6 -octanitroazobenzene (5
g, 8.18 mmol) was transferred followed by addition of 100 mL of methanol. 3-amino-1,2,4-triazole (5 g, 41.66 mmol) was added to this slowly with
occasional swirling. The reaction mixture was refluxed for 5 h followed by cooling to ambient temperature and pouring into the ice-cooled water. The
resulting brown precipitate was allowed to settle overnight. The product was filtered, washed thoroughly with distilled water and dried in a water
jacketed oven at 60ºC. The compound was further washed with acetone to remove any impurities and finally air-dried to yield 3.6 g (64%) and DTA
exotherm at 550ºC.
[Edited on 2-10-2013 by killswitch]
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Trotsky
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What about detonation velocity and impact sensitivity?
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bfesser
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Seriously?
I just found it with a 2-second Google search for "BTDAONAB" (first result)...
<strong>N,N'-Bis(1,2,4-triazol-3-yl-)-4,4'-diamino-2,2', 3,3', 5,5', 6,6'-octanitroazo-benzene (BTDAONAB): A new thermally stable insensitive
high explosive</strong>
Mehilal, N. Sikder, A.K. Sikder, J.P. Agrawal
Attachment: IJEMS 11(6) 516-520.pdf (182kB)
This file has been downloaded 920 times
While I'm sure EM-oriented members appreciate your effort, I ask that you please include a citation next time.
[Edited on 5.10.13 by bfesser]
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Melmoth
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More on thermally stable explosives from Agrawal (including BTDAONAB);
Past, Present & Future of Thermally Stable Explosives
Attachment: Agrawal.pdf (913kB)
This file has been downloaded 698 times
"This species has amused itself to death"
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Ral123
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How is a CHNO explosive so stable? It has double N=N bond in the middle, kinda reminds me of azides. How can the N-N and N-O bonds survive 550C?
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simply RED
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This is because the electron withdraw effect of NO2 groups is compensated by electron donation by the aminotriazine groups. Also because of hydrogen
bonding and bad oxygen balance. Its exoterm being at 550 C does not mean it survives to that point. Most probably it already starts to deteriorate at
250-300 C but at slower rate.
When logic and proportion have fallen sloppy dead...
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Ral123
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Thanks, I'm not to good with chemistry. If that 550C is so far beyond it's comfortable temperature, then I can imagine it.
Does that mean that TATB(TATNB?) is much more stable then TNB?
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simply RED
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Quote: Originally posted by Ral123  | Thanks, I'm not to good with chemistry. If that 550C is so far beyond it's comfortable temperature, then I can imagine it.
Does that mean that TATB(TATNB?) is much more stable then TNB? |
Indeed. Read more about the topic and do not ask "one line answer" questions that spam the topic.
When logic and proportion have fallen sloppy dead...
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