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Author: Subject: RDX synthesis
softbeard
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[*] posted on 25-9-2015 at 15:14


Yet another RDX synthesis paper, but specifically dealing with radioisotope-labelled RDX & HMX synthesis. Contains a good list of references.

Attachment: p512589.pdf (1.2MB)
This file has been downloaded 516 times

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kecskesajt
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[*] posted on 27-9-2015 at 01:05


Hi,It was discribed a lot of time but what abou mixing an excess Ca(NO3)2 with H2SO4,filtering and then nitrating the hexamie in it? I don't want to make it, Ag2C2-DS and ETN is fine for me.
Will it be unstirrable and unfilterable?[SFMBE]
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roXefeller
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[*] posted on 27-9-2015 at 16:18


My first thought without looking it up would be to ask if CaSO4 has any equilibrium products like Na2SO4.
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PHILOU Zrealone
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[*] posted on 28-9-2015 at 01:57


Quote: Originally posted by kecskesajt  
Hi,It was discribed a lot of time but what abou mixing an excess Ca(NO3)2 with H2SO4,filtering and then nitrating the hexamie in it?
Will it be unstirrable and unfilterable?[SFMBE]

Ca(NO3)2 is hygroscopic.
CaSO4 forms gyspum with water... = plaster of Paris

So unless you start from conc H2SO4 and dry Ca(NO3)2...stirrable at first, but not for long, difficult to filter without vaccuum.

Maybe good to try vaccuum distilation of the CaSO4 cake to get the conc HNO3 out of it in the cold to avoid its decomposition.




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Fulmen
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[*] posted on 28-9-2015 at 02:50


Pretty much. I tried it once, and you end up with a CaSO4/HNO3-paste that is pretty much unworkable. You could perhaps add the Ca(NO3)2 in portions, filtering in between, although I suspect the losses will be high. Vacuum distillation should work, but then you could use any nitrate salt and avoid the mess of the insoluble CaSO4.

I think this method would be best for producing mixed acids, that way you can wash out the HNO3 with conc. H2SO4.




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[*] posted on 28-9-2015 at 06:11


Ahh.Alright,I saving for a laptop so I dont have acces to a distillation kit in the near future.
Anyway,thanks for the anwsers.
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hyfalcon
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[*] posted on 28-9-2015 at 13:34


Has this already been uploaded or do I need to make a request?

Methylene-nitramines. Part I. The reaction of hexamine dinitrate with nitric acid at low temperatures

K. W. Dunning and W. J. Dunning
J. Chem. Soc., 1950, 2920-2924

DOI: 10.1039/JR9500002920
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Joeychemist
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[*] posted on 28-9-2015 at 14:59


I don't beleive it has and if you are going to go through the trouble of getting the first one you might as well get parts two and three.

Methylene-nitramines. Part II. An investigation of some properties of 1-alkoxymethyl-3 : 5-dinitro-1 : 3 : 5-triazacyclohexane and of related compounds
K. W. Dunning and W. J. Dunning
J. Chem. Soc., 1950, 2925-2928
DOI: 10.1039/JR9500002925

Methylene-nitramines. Part III
K. W. Dunning and W. J. Dunning
J. Chem. Soc., 1950, 2928-2932
DOI: 10.1039/JR9500002928
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[*] posted on 16-11-2015 at 23:32


Rigged up my melting point apparatus to record video of the process and overlay the temp controller reading simultaneously....turned out pretty cool :)

https://youtu.be/WMJDcE7wS_8

Just need to make the sample well bottom less reflective, otherwise the camera will compensate for the bright surrounding areas and turn the center sample too dark.

[Edited on 17-11-2015 by markx]




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[*] posted on 17-11-2015 at 07:58


Quote: Originally posted by markx  
Rigged up my melting point apparatus to record video of the process and overlay the temp controller reading simultaneously....turned out pretty cool :)

https://youtu.be/WMJDcE7wS_8

Just need to make the sample well bottom less reflective, otherwise the camera will compensate for the bright surrounding areas and turn the center sample too dark.

[Edited on 17-11-2015 by markx]

Thumbs up and hat down!
Beautifull!
Stil I have a question for you:
Is there no risk for your camera lens to be in the axis, in the bad event of a detonation?
Usually melting point apparatus allows one to see perpendicular to the axis...the full melting point is easier to see.




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markx
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[*] posted on 17-11-2015 at 11:55


Quote: Originally posted by PHILOU Zrealone  

Thumbs up and hat down!
Beautifull!
Stil I have a question for you:
Is there no risk for your camera lens to be in the axis, in the bad event of a detonation?
Usually melting point apparatus allows one to see perpendicular to the axis...the full melting point is easier to see.


Thanks for the kind words Philou! :)
This is not a very conventional desing indeed....the means available forced my hand, so to speak. Hence the head on collision course with the sample. But really, the amount measured is so small, on the order of one mg, that even in the unlikely event of a detonation the camera will most likely stay in tact as it sits a good 5cm above the sample well. Even so it is a cheap chinese usb microscope, the loss of which I shall hardly mourn.




Exact science is a figment of imagination.......
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[*] posted on 30-10-2016 at 09:20


I would like to tell ,that I am now ended the China synthesis of RDX-keto RDX mix,preparation vers. B. with HDN.
I take 14 g urea to 65 ml acid 50:50 HNO3 +H2SO4,cooled to 0-5C,past them I gave there 10 g of HDN at minus 5 C.It was white like milk and if I put it to water,then was there nothing,absolut nothing,clear water.
With the same acid and with the same HDN I synthetised RDX without problems.Therefore it was lie.

[Edited on 15-10-2016 by Thraxx]
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[*] posted on 30-10-2016 at 12:37


Quote: Originally posted by Thraxx  
I would like to tell ,that I am now ended the China synthesis of RDX-keto RDX mix,preparation vers. B. with HDN.
I take 14 g urea to 65 ml acid 50:50 HNO3 +H2SO4,cooled to 0-5C,past them I gave there 10 g of HDN at minus 5 C.It was white like milk and if I put it to water,then was there nothing,absolut nothing,clear water.
With the same acid and with the same HDN I synthetised RDX without problems.Therefore it was lie.

[Edited on 15-10-2016 by Thraxx]


Me too, same problem with the China synthesis. But in my case I were unable to keep the temperature below 5 ºC, which is critical for this synthesis.
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[*] posted on 30-10-2016 at 22:38


I had a cooling with ice and 450g of NH4NO3.
In the first step by adding urea I did a mistake -temperature rose to +15 for 5 min.In the second step by adding HDN I was between 0 and +5C.
If I added the HDN into the mixed acid ,it wasnt like if I give the HDN to fuming nitric acid,it was too mild,it was like without reaction.It diluted only.
Fedoroff under Hexamethylene dinitrate described similar reaction with histamine giving to mixed HNO3 and sulfuric
acid for to prepare HDN.
May be ,that this China reaction should be done in two steps after longer time,because the first undercooled step could be Dinitrourea and it could be reaction between Hexamine and this stuff in the fuming nitric acid.(?)


[Edited on 15-10-2016 by Thraxx]

[Edited on 15-10-2016 by Thraxx]
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[*] posted on 4-11-2016 at 11:54


So in the effort of figuring out ways to produce RDX at a decent cost and with relative ease i at one point stumbled upon a synthesis using Acetic Anhydride, but through looking into it futher I discovered that Ac₂O is very hard to purchase because of its linkage to illegal drugs.

I went stumbling around tring to find a decent synth for Ac2O but even its precursors were not that easy. But today i found this patent:Patent US1425500-Manufacture of Acetic anhydride
From what it says there is a possible route to Ac2O using high purity Acetic acid and acetylene gas. From what i can tell in the procedure this method is much easier.

Thoughts?
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[*] posted on 5-11-2016 at 11:49


Quote: Originally posted by cryomancer  
So in the effort of figuring out ways to produce RDX at a decent cost and with relative ease i at one point stumbled upon a synthesis using Acetic Anhydride, but through looking into it futher I discovered that Ac₂O is very hard to purchase because of its linkage to illegal drugs.

I went stumbling around tring to find a decent synth for Ac2O but even its precursors were not that easy. But today i found this patent:Patent US1425500-Manufacture of Acetic anhydride
From what it says there is a possible route to Ac2O using high purity Acetic acid and acetylene gas. From what i can tell in the procedure this method is much easier.

Thoughts?


Interesting, but you'll dealing with acetic acid vapours and a mercury salt, so be careful. Also keep in mind that acetylene from calcium carbide is contaminate with other compounds, so your AA won't be pure.
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[*] posted on 5-11-2016 at 13:05


^

Right, the dangers of mercury salts, if you are using good lab practice, can be avoided. I would say it would be easier (maybe more expensive) to go and buy a tank of commercial acetylene gas from a welding company (I think tractor supply sells the tanks and gas) That way you would reduce contamination to near negligible amounts. It would be very simple to just pump the gas straight from the tank into the acid while outdoors or in a very well ventilated room in case the gas escapes.
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[*] posted on 6-11-2016 at 07:14


Quote: Originally posted by cryomancer  
^

Right, the dangers of mercury salts, if you are using good lab practice, can be avoided. I would say it would be easier (maybe more expensive) to go and buy a tank of commercial acetylene gas from a welding company (I think tractor supply sells the tanks and gas) That way you would reduce contamination to near negligible amounts. It would be very simple to just pump the gas straight from the tank into the acid while outdoors or in a very well ventilated room in case the gas escapes.

Or Calcium carbide direct into the acetic acid....although the acid must be in 3X excès to take care for the CaC2, CaO and CaCO3 neutralisation into Ca(acetate)2...




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[*] posted on 7-11-2016 at 01:07


For to make the nitrolysis of hexamine more economic ,I tryied use the spent acid for pentaerythritole esterification in situ.
After the nitrolysis which should be in ratio 1:8 and by 20 C I gave there into the reaction pentaerythritol by the 20-30 C in ratio 1:5 .
75 ml (112g)Nitric acid + 14 g Hexamin (1:8)... + 22 g pentaerythritol (1:5).After reaction stand it half of hour and I throw it into 400 ml of water.Result was 15 g of product.
May be this is not the right way.

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[*] posted on 7-11-2016 at 10:06


Quote: Originally posted by Thraxx  
For to make the nitrolysis of hexamine more economic ,I tryied use the spent acid for pentaerythritole esterification in situ.
After the nitrolysis which should be in ratio 1:8 and by 20 C I gave there into the reaction pentaerythritol by the 20-30 C in ratio 1:5 .
75 ml (112g)Nitric acid + 14 g Hexamin (1:8)... + 22 g pentaerythritol (1:5).After reaction stand it half of hour and I throw it into 400 ml of water.Result was 15 g of product.
May be this is not the right way.


Sorry but I don't understand what you are trying to do.

-Your 75 ml HNO3 are at wat %?
-What are Hexamin (1:8) and PE (1:5)?
-15g of what product?

1°) PE should lead to PETeN, but into this case, you may have also PETriN, PEDN, PEMN...
2°) the Hexamin may lead to hexamine dinitrate or to cyclo-N,N'-dinitro-triazahexane nitrate...and of course HMX and precursors...
3°) Not counting with the oxydation products from PE and the possible hemi-acetal and acetal formation between alcohol (HO) groups from PE (or intermediary nitrated PE) and formaldehyde resulting from Hexamine breakdown.

--> An horrible mix...probably hard to purify, crystallize and most likely unstable for storage.

Better synthetise appart and mix afterwards to avoid complexification/multiplication of the side products.

[Edited on 7-11-2016 by PHILOU Zrealone]




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[*] posted on 7-11-2016 at 10:10


Quote: Originally posted by cryomancer  
^

Right, the dangers of mercury salts, if you are using good lab practice, can be avoided. I would say it would be easier (maybe more expensive) to go and buy a tank of commercial acetylene gas from a welding company (I think tractor supply sells the tanks and gas) That way you would reduce contamination to near negligible amounts. It would be very simple to just pump the gas straight from the tank into the acid while outdoors or in a very well ventilated room in case the gas escapes.

Not to neglect:
1°) the use of acetylen at about 2.5 atm/bars...
Over 2 bars acetylen becomes quite explosive on its own or to shock/surface catalyst ... owing to its endothermic nature
H-C#C-H --> 2 C + H2 + heat

2°) some acetylenic compounds of Hg are explosive

3°) Commercial tanks of acetylen usually contains aceton in which C2H2 is quite soluble and it reduces the risk of spontaneous explosion/shock explosion while pressurized.
--> Maybe is aceton detrimental to the proces?


[Edited on 7-11-2016 by PHILOU Zrealone]




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[*] posted on 8-11-2016 at 00:34


Quote: Originally posted by PHILOU Zrealone  


-Your 75 ml HNO3 are at wat %?
-What are Hexamin (1:8) and PE (1:5)?
-15g of what product?

[Edited on 7-11-2016 by PHILOU Zrealone]


-I used freshly distilled fuming nitric stabilised whith urea.
-According to Orlova,which citate from work of Di Cerrione L.A.-Am, Chim.appl.38,5,(1948),-„ is the RDX by the nitrolysis constitute in the range between (H:Acid) 1:3 to 1:500,where optimum is between 1:8-1:30 with best yield by 1:26.“
Because the acid must be in excess for to equalize diluting during the reaction(3 mol watter from each mol of hexamine).This problem is by the nitrolysis of hexamine not possible to solve through sulfuric acid as usually. And therefore is in the spent acid too much nitric acid in too high concentration for to throw it .
Because the Pentaerythritol could be esterificate with nitric acid without sulfuric acid like in WWII. production methodes in Germany, Japan and Soviets and each of these methods used ratio 1:5 by the temperature abbout 20 C ,I thought,that the spent acid after the nitrolysis of Hexamin,could be used and exploatate for esterification of Petn.
-15g of what product?-I dont know what it is,it should be 11g of RDX and over 20 g of Petn.Perhaps is there the RDX and some lower nitrates of PE.


[Edited on 15-10-2016 by Thraxx]
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[*] posted on 8-11-2016 at 12:08


Maybe recover the "diluted" HNO3 from reaction by using it with hexamine to make hexamine dinitrate...and allow to dry
Or from urea to make urea nitrate and recover crystals for keto-RDX.




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[*] posted on 9-11-2016 at 09:16


RDX from sulfamic acid like GB pat.899692:

Aminosulphamic acid (ASA) H3NSO3 mol= 97,10
NH4OH 24% mol =35,05
Formaldehyd 40 % mol= 30,03
HNO3 =63,01

I.Step :
10g ASA diluted in 30 ml watter neutralised with 14 ml aquous Ammonia .Evaporated .Yield 15g crystals looking like mica.
This step is not necessary,because the Ammonium ASA is possible to buy by Aldrich.
II. Step:
Into 10 ml of formaldehyd giving 15 g crystals of ammonium ASA .Reaction mild but exothermic.
After adding ethanol for to precipitate the product ,there extruded white liquid on the bottom looking like NG.
Other clear dilution should crystalised , and after two days there was nice crystals,but still wet.Added Ethanol,filtered,dryied.Complicate to dry it.After drying there was 15 g of ammonium methylene amino sulphonate
III.Step:
15 g of ammonium methylene amino sulphonate added into 30 ml of cold fuming acid (vacuum made).Mild reaction,throwed into 150 ml of ice watter =yield poor-2g RDX





[Edited on 15-10-2016 by Thraxx]

[Edited on 15-10-2016 by Thraxx]
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[*] posted on 10-11-2016 at 08:15


Quote: Originally posted by Thraxx  
RDX from sulfamic acid like GB pat.899692:

Aminosulphamic acid (ASA) H3NSO3 mol= 97,10
NH4OH 24% mol =35,05
Formaldehyd 40 % mol= 30,03
HNO3 =63,01

I.Step :
10g ASA diluted in 30 ml watter neutralised with 14 ml aquous Ammonia .Evaporated .Yield 15g crystals looking like mica.
This step is not necessary,because the Ammonium ASA is possible to buy by Aldrich.
II. Step:
Into 10 ml of formaldehyd giving 15 g crystals of ammonium ASA .Reaction mild but exothermic.
After adding ethanol for to precipitate the product ,there extruded white liquid on the bottom looking like NG.
Other clear dilution should crystalised , and after two days there was nice crystals,but still wet.Added Ethanol,filtered,dryied.Complicate to dry it.After drying there was 15 g of ammonium methylene amino sulphonate
III.Step:
15 g of ammonium methylene amino sulphonate added into 30 ml of cold fuming acid (vacuum made).Mild reaction,throwed into 150 ml of ice watter =yield poor-2g RDX





[Edited on 15-10-2016 by Thraxx]

[Edited on 15-10-2016 by Thraxx]

Maybe use the Na or K salt instead of the NH4 salt?
Anyway, it is not the favoured synthesis pathway for a reason...probably the low yield.




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