Hexamethylenetetramine Dinitrate

[Detonator]

Got this from http://flashbangboom.homestead.com/procedures.html

Maybe some of you knows the site and maybe not.

Hexamethylenetetramine Dinitrate

I don't have much information on this explosive at the moment, but I'll keep looking... I think I heard that VoD was around 6000-7000 m/s, with a lead block expansion of 230 cm3, but I can't remember. I will find out. It is a similar sort of explosive to Urea Nitrate and M.M.A.N., i.e. it is a nitrate salt.
It's another that doesn't involve nitric acid, but I think it could be forming M.M.A.N. I don't think it is, but if it is then it might be a better method for it.


You will need:


5g of hexamethylenetetramine,
65mL of 15% hydrochloric acid,
10g of ammonium nitrate,
A 150mL beaker,
A filter funnel,
A filter paper,
A glass rod,
A fridge.


1) Pour the hydrochloric acid into the beaker and add the ammonium nitrate.
2) Stir the solution with the glass rod until all the ammonium nitrate has dissolved.
3) Cool the solution to 5*C in the fridge.
4) Add the hexamethylenetetramine. Stir it with the glass rod until it has all dissolved. A white crystalline precipitate should form.
5) Quickly filter out the precipitate.
6) Leave it in a warm, dry place to dry fully.

[Detonator]

Anyone tried this method?

[Mr Cool]

Yes, me! (It's my site by the way)
It seems to work pretty well for me, but you do need to filter the precipitate quickly (in a few minutes) or it will redissolve. So use a "fast" filter, like a few layers of T-shirt or some coffee filters etc. I haven't tried it recently, but IIRC I got about 3 grams of hex. dinitrate from 5 grams of hexamine, which is not a good yield (c. 30%) but it's very quick and easy. It is forming the dinitrate, not MMAN as I thought it might be.

I did a big bit of updating yesterday, but my shite computer crashed before I could save it. So I'll re-do it later today, with TMDD, CTMTNA, RDX from CTMTNA and from HMTD and maybe a few others... but I need to buy a few things before I can actually try them and put the yields up for these.

Oh, and there's no link to the home-page on that page, so if you want to go to the home-page (and the yields section etc) then go to: http://www.flashbangboom.homestead.com/home_page.html

[10fingers]

I like your sight Mr. Cool. I was wondering if anyone has tried using Hexamethylenetetramine Dinitrate to make RDX? I did see a formula in one of the KIPE books where it was used for this with acetic anhydride but I wonder if it would work in the K-Process.

[This message has been edited by 10fingers (edited October 25, 2001).]

[cutefix]

Try this out,
Preparation of RDX from Hexamethylenetetramine Dinitrate.

Prepare a solution by combining alternately and proportionately ,27 gram of hexamethylenetetramine dinitrate and 68 grams of 90% H2SO4 at 8-15 C for 30 minutes.Stir it at 15C for 45 minutes.
Pour this mixture into 110 grams of preferably 99+% nitric acid slowly within the 10 minute period,while maintaining temperature at 10C.Then let the temperature rise to 25C and stir for 25 minutes.
Pour it into 10 times its weight of ice and water mixture.This will precipitate crude cyclonite...

[Detonator]

Mr Cool i like your site, cant wait for the updating...

[Mr Cool]

Cutefix: if H2SO4 is used to dehydrate the hexamine dinitrate (I assume that's what it's doing, or maybe it's decomposing it to something else), then would it be OK to use an H2SO4/nitrate mixture instead of the HNO3? I've always heard that RDX will be decomposed by, and cannot be formed in, H2SO4, but there will be some present in the method you posted, so it can't be too critical. What do you think? Yields might be low, but it's simple.

I'm glad you like my site! It's not very well put together, but I'll concentrate on how it looks when I've got some good content. Unfortunately updates are quite rare...

[Mr Cool]

And it would probably help to use hexamine dinitrate instead of hexamine in the HNO3/NH4NO3/hexamine method (I can't remember the name of that process).

[10fingers]

That's what I was thinking. If you can make hexamethylenetetramine dinitrate with your method using hydrochloric acid/ammonium nitrate and then use the dinitrate to make RDX it may be possible to use much less nitric and/or slightly lower concentration.

[Berserker]

Does anyone have a better estimate of detonation velocity than "6000-7000mps"? This sounds like a very novel explosive that could be made from stuff you pick up at your local gardening and hardware store. http://theforum.virtualave.net/ubb/smilies/biggrin.gif

Plus, when -someone I know- http://theforum.virtualave.net/ubb/smilies/wink.gif is going to try this, -they'll- use potassium nitrate instead, or is the NH₄⁺ important to the reaction somehow?

[cutefix]

There are alternative means of preparing RDX that uses H2SO4 but the yields are not high such as using propionitrile and trioxane.Using sulfuric acid/inorganic nitrate mixture is an alternative methods,I anticipate that the yields are lower.That formula I give could achieve 30-45 % yields of the theoretical,of crude RDX(containing HMX and other homologues)…..It should preferably be digested with 70% nitric acid and the final yield would be around 30%-35%but the purity will be higher(m.p.,>200 C).

[Detonator]

Is there is a way for a better yield (Hexamine Dinitrate)?
Looks like there isn't alot of information about this HE!!

[Mr Cool]

The ammonium ion isn't important, I simply chose NH4NO3 since it's very soluble.

A better yield could be achieved by using nitric acid (use about 50%) and hexamine, in a 2:1 molar ratio. Maybe 2.1:1 might be better. I devised my method because I didn't have any HNO3 at the time because my retort broke (and I still don't have a new one!), and also HNO3 is hard for many people to get so I thought this method would be more useful.

Hey, maybe every procedure I have on my site should have a no-HNO3 version, because many people just can't get it...

Well, I'm off to try RDX from hex. dinitrate and H2SO4/KNO3... I'll tell you how it goes. I don't really mind low yields, not when the product is as good as RDX! It makes the shitty reaction worthwhile if it's easy. I've also go to try that TMDD, it sounds quite promising. Oh, and I've just remembered another RDX method using H2SO4, the R-salt oxidation one...

The lead block expansion was actually 220cm/3 IIRC.

[Mr Cool]

To anyone else that's tried this: do you also get an odour of formaldehyde?

[10fingers]

How much shittier can the yields be than using some of the standard methods?
I was under the assumption that H2SO4 and RDX were incompatible so I'm interested in learning the results.
My friend tried the process in KIPE for hexamethylenetetramine dinitrate using 70% nitric(I think), and it worked fairly well except he had problems drying the stuff.

[cutefix]

Hexamine dinitrate can be made to produce more yields of RDX by including acetic anhydride and ammonium nitrate in the nitration process.Therefore it will need less nitric acid than using straight hexamine.Have a look at this: Hexamine to RDX
C6H12N4 + 4HNO3 + 2NH4NO3 +6 (CH3CO)2O----> 2C3H6N6O6 + 12CH3COOH
Hexamine Dinitrate to RDX
C6H12N4(NO3)2 + 2HNO3 + 2NH4NO3 +6(CH3CO)2O-------> 2C3H6N6O6 + 12CH3COOH

Yields about 80% can be obtained from this process while less than half can be produced with sulfuric acid as solvent for the hexamine dinitrate.With these combination process it is even possible to make RDX with less concentrated nitric acid(ex 70%)provided that the water in the acid is considered by increasing the amount of acetic anhydride correspondingly.in the ingredients feed....

[Hex]

I suspect that careful neutralisation of these reaction liquors with ammonia (taking care not to go beyond ph6) will precipitate DPT, which is a handy HMX precursor, though not an explosive in it's own right.

[Mr Cool]

I tried the hexamine + KNO3 + H2SO4 --> DPT, then DPT + KNO3 + H2SO4 --> RDX, without first purifying the DPT, but it didn't work.
Look in the DINGU/SORGUYL thread for a bit more info on what I did...

[Detonator]

I tried Hexamine dissolved in cold water then added to 70% NA. Temp raised but nothing showed up???!

What is the wrong with this method?

Mr Cool when are you gona update your site?

[cutefix]

First ,I would like to confirm ,if did you really do it this way?Why waste precious hexamine in this way when the procedure for making it is clear(adding solid reactant to the acid)and not the liquid- liquid approach.
With lower acid concentration and hydration of hexamine plus uncontrolled reaction temperature upon additon, you cannot expect formation and much more anticipate desirable precipitation of hexamine dinitrate(which is also water soluble).

[Mr Cool]

Detonator: I've updated my site three times in the past few days, but it always crashes before I can save it! In other words, it'll be updated as soon as my computer starts behaving...

[Berserker]

Would the dehydration of HMDN via H₂SO₄ create anything interesting? Perhaps a useful precursor or some other exotic explosive? Seeing as the dehydration of urea⁺NO₃^- and guanidine⁺NO₃^- will yield nitrourea and nitroguanidine respectively, compounds of much more interest than the former.

[This message has been edited by Berserker (edited September 01, 2001).]

[Mr Cool]

There's some stuff on this sort of thing in the DINGU/SORGUYL thread. HDN and H2SO4 creates DPT. If you add DPT to 99% HNO3 you get HMX. If you add DPT to H2SO4 and then add HNO3, you get RDX!! I assume a KNO3/H2SO4 mixture would work, giving a lower yield of RDX. Or DPT + AN + Ac2O + HNO3 (IIRC) gives a roughly 50:50 ratio of RDX to HMX.
Check out the DINGU/SORGUYL thread for the exact details, it's quite interesting...

[Berserker]

But where on earth could one obtain actinium oxide?

[Detonator]

Then what is the method you make HD using 70% NA ?

[Berserker]

Detonator: According to KIBC2, 50g hexamine is dissolved in 150ml of water. To this 70ml NA is added until litmus paper says the solution is acidic. Apparently the HMDN should precipitate out.

[Mr Cool]

Sorry, not actinium oxide! Ac2O is a kinda shorthand way of writing acetic anhydride, since that's two acetyl groups joined by an oxygen. In the same shorthand, MeOH is methyl alcohol, EtOH is ethyl alcohol, etc etc.

[CodeMason]

Haha, stupid me. That shorthand always confuses me. :\

[10fingers]

*

[This message has been edited by 10fingers (edited October 19, 2001).]

[Mr Cool]

Yield should be 95 grams from 50 grams of hexamine I believe, so that would be a 53% yield, which is better than mine!
I think he should boil off the water from the filtrate, to get more HDN out of solution.

[Detonator]

I think that HD doesnt dissolve in Aceton so you can decant the acidic water carefully then wash the HD with aceton, this will help it to dry faster.

Because HD is hygroscopic do you think adding wax, vasline, oil..etc will solve the problem? maybe plasticizes it.

If it has 6000-7000 DV i think it is a good choice because of making it is easy as UN and ANFO. It has a higher detonation velocity than ANFO and UN.

Maybe it can find a use in making improvised boosters for ANFO.

What is its sensitivity?
Can it be stored for a long time?
Did anyone try to detonate it?

I searched alot but no info available on the net.

[10fingers]

*

[This message has been edited by 10fingers (edited October 19, 2001).]

[Mr Cool]

I'm afraid I really don't have any more information on this explosive, but maybe someone else does. I'm not even sure about that VoD.
I think one drawback might be that it could corrode metals, but it should be storage stable.
Yes, for me it's main use would be for making HMX and/or RDX. You react it with H2SO4, precipitate the DPT and nitrate that. Or I might try it in the K-process...

[Detonator]

After heating it for 20min at 100c HD melted! and got darker color.
When it was cooled a liqued appeared above it.???!

And by the way it looks like the Aceton dissolves HD!!
So it would be hard to make it dry easily.
Any ideas?

[CodeMason]

I tried it, and it didn't work at all. First off, I used fertilizer grade KNO₃ for the first time in one of my reactions, and I think that was the main problem. First off, it barely dissolved in the HCl at all. I used around 4.5g, and half of it remained undissolved. So I wasted a filter paper. Then I chilled it in an ice bath to 5C, nothing special. Then I added around 5g hexamine. It dissolved rather rapidly, but after 10 minutes waiting no precipitate formed! Arg! I just wasted expensive hexamine. The things I could think of were a) impurities in the acid somehow interfered with this delicate reaction or b) I used TOO MUCH HCl, about 80mls (if this is possible).

I'll try again tomorrow, then if it works I'll do some tests to deduce things like behavior to flame, relative power to AP and sensitivity to impact and initiation. If I'm unsuccessful, maybe you more lucky people can try these tests out so we can build up a reasonable amount of knowledge on this exotic explosive.

[Mr Cool]

I think your problem is this:
you used KNO3, which isn't soluble enough so you didn't get enough in the solution. Therefore in your solution you had too much hydrochloric acid and not enough nitric acid, so hexamine dihydrochloride formed instead, which would be more soluble and wouldn't precipitate.
I use fertiliser grade NH4NO3 and 15% HCl which is sold as a brick cleaner in DIY stores. It's green! So I don't think impurities will matter too much.

Edit: wow, 4.5 grams of KNO3 in 80mL of HCl is definitely not enough nitrate!!
Also, are you using less than 15%? If so you may have too much water present for it to precipitate.

[This message has been edited by Mr Cool (edited September 03, 2001).]

[CodeMason]

Yeah, I think you're right. I'll use ammonium nitrate next time.

I used 30% HCl.

[10fingers]

Here are the results of my friends attempt to use Hexamine Dinitrate in the K-Process instead of plain hexamine.
1. 80 ml's nitric acid, density 1.51.
2. 32 grams ammonium nitrate was added to the nitric and the mixture was cooled to 15 degrees C.
3. 30 grams hexamine dinitrate were added slowly while stirring and keeping the mixture below 20 C.
4. The mixture was slowly heated to 75 C and held there for 1/2 hr.
5. The mixture was then cooled down, at this point something strange happened, the mixture was sitting in ice water and had cooled down to around 30 C. RDX was precipitating out of the solution. At this point it was not being attended and for some reason the mixture began to heat up again. When he came back it was quite hot and a small amount had overflowed out of the container.
6. The mixture was dumped into cold water and the precipitate was filtered out.
7. Yield=CRAPPY! About 10 grams.

[Mr Cool]

75*C? Most methods I've seen keep the temperature lower, about 50*C to 60*C.
Strange about it heating up again...

[Kdogg]

<font face="Verdana, Arial" size="2">Originally posted by Mr Cool:
Yes, me! (It's my site by the way)
It seems to work pretty well for me, but you do need to filter the precipitate quickly (in a few minutes) or it will redissolve. So use a "fast" filter, like a few layers of T-shirt or some coffee filters etc. I haven't tried it recently, but IIRC I got about 3 grams of hex. dinitrate from 5 grams of hexamine, which is not a good yield (c. 30%) but it's very quick and easy. It is forming the dinitrate, not MMAN as I thought it might be.

I did a big bit of updating yesterday, but my shite computer crashed before I could save it. So I'll re-do it later today, with TMDD, CTMTNA, RDX from CTMTNA and from HMTD and maybe a few others... but I need to buy a few things before I can actually try them and put the yields up for these.

Oh, and there's no link to the home-page on that page, so if you want to go to the home-page (and the yields section etc) then go to: http://www.flashbangboom.homestead.com/home_page.html</font>

How much is £1.31?? In $ Do you know??

------------------
Monkeyman

[Mr Cool]

In $US that's about $1.85 I think, but I don't know about any other kind of dollar.
What was the point in quoting all that?!

[10fingers]

Mr. Cool, I think in the process that just uses hexamine and nitric acid the temperature is only 50-55 C. In the K-process it is 75-80 C.

[Detonator]

But how you make this thing dry?????????????!

[Mr Cool]

How do you dry it? I normally use a water bath, and then just leave it in a warm place (airing cupboard) to dry fully.

[10fingers]

I think if there is too much residual acid left in the product it is hard to dry and it breaks down into formaldehyde plus other things. You can't rinse it with water because it readily dissolves. It does not seem to be soluble in methanol but I don't know if the acid would react with the methanol and create other impurities.

[CodeMason]

HMDN mark 2 failed. http://theforum.virtualave.net/ubb/smilies/tongue.gif
Yes, yes, it was a stupid mistake on my part. I did everything right up until adding the hexamine. It was very coursely powdered rubbish I use for HMTD, so it didn't dissolve fast enough, so the "precipitate" was mostly just hexamine. Oh well. Third time's a charm, eh?

[DBSP]

CodeMason I've had just the same problem with the hexamine not dissolving fast enough.
I tried vaporizing the solution it works but it hurts like hell when you get the fumes into your lungs. I tried this a couple of weaks ago but I didn't vaporize it until yesterday, everything went ok until I was to filter it, I forgot that it dissolves in water, STUPID me poured some water on the crystals to wash them. In a matter of seconds every crystal dissolved. So I started vaporizing the water then the FUCKING beaker broke, so now I don't have any
hexamethylenetetramine dinitrate as I was supposed to have!

The crystals was quite large, are they supposed to big like an 1/8 of a needle-head?

------------------
¤monte¤

[Hex]

I've not been following this thread, (and I can't be arsed to read all of it) but I don't understand where the problem in making Hexamine dinitrate is. Dissolve 40g in about 100ml deionised water, chill it in ice, and add 43.5ml of 70% nitric dropwise with good stirring, adding the acid slowly enough to keep the temperature below 15C. Filter off the solid, and wash it a few times with cold alcohol before drying. You could probably get away with washing it with cold water first - HDN isn't that soluble. The yield is about 92%. It's worth keeping the filtrate in the fridge, and using this to dissolve your hexamine in for the next batch.I've got a batch made like this that's 6 months old, and has no formaldehydey smell.
Maybe the hexamine is the problem - perhaps you haven't removed all the crap from your heating tablets?
Does anyone know where this detonation velocity of 6-7000 comes from? I find that amazingly high, indeed I'm surprised it detonates at all.

[This message has been edited by Hex (edited October 05, 2001).]

[DBSP]

What if you can't get 70% nitric acid? thought about that!. What do you do then? the logical thing would be to try it with the ingridients you have. In this case Mr Cools prucedure works fine.

I didn't think it was that suluble in water but it was, about two seconds after the water hit the crystals everything was dissolved.

------------------
¤monte¤

[Mr Cool]

I can't remember where I heard that figure, but I definitely did...
My c. 65% HNO3 will be arriving on Monday, so I'll be able to make it more efficiently then. I plan on making RDX/HMX via the DNPMTA route with it.
My HDN doesn't smell of CH2O at all, but it does seem to make some during the reaction. But once washed it's fine. I believe acetone would work well for the washing.
This reminds me, my site must have been closed by now http://theforum.virtualave.net/ubb/smilies/frown.gif. I'll trim it down to under the requirements for having a free site until I can find a different place to have it.

[CodeMason]

I have heard PHILOU mention a figure close to that, and also on an alt.engr.explosives newsgroup article.

[CodeMason]

Yep, it was closed on October 1st. Why not try brinkster.com? 30mb free, no ads. Just no good for pictures as they don't allow indirect linking. Or lunarpages.com, 50mb space, no ads, only files must be under 250kb each, which is ok. (Both of these quotes are from last time I check, these companies could have changed their policies by then.) And if the above aren't to your liking, freewebspace.net is a search engine and directory of free web hosts. http://theforum.virtualave.net/ubb/smilies/smile.gif

[Mr Cool]

Thanks, I'll check out those places...

[Hex]

Mr Cool,
What procedure are you using to get to DNPMTA? With 90% sulphuric? I've done that one, and it's another one of those reactions where you need really good stirring, or the HDN just sits on the surface and frazzles. You need to be extremely careful with the neutralisation as well -the pH wanders about as you get near to the precipitation point - going over pH 7 is very bad news.
The best yield I ever got was only about 30%. The product dropped out good and pure though.

[Mr Cool]

Yeah, I'd be using sulphuric. God that's a shite yield - well, thanks for the tips on pH!
Got my NaNO2 today, perhaps I'll have a go at the Hexamine => R-Salt => RDX rxn some time soon.

[CodeMason]

I'd fed up with the ammonium nitrate+HCl method for making HMDN. It was just a waste of expensive hexamine for me. Next time I try it I'm using nitric acid. And I'm going to cook up some Na/K nitrite and try out the nitrosamine reactions, and maybe work out a scaled up procedure.

[ALENGOSVIG1]

first couple timed i attempted the synthesis it failed, i found that when using 28% hcl when the hex is added it creates too much heat and it doesnt seem to completely dissolve, so just remember to dilute your hcl to 15% and make sure the hexmaine is very finely powdered. i also have to use an ice bath with my reaction for some reason when i do it it gets quite hot without it.

------------------
How much power will you lose if you do not know what they already know?


Explosives Archive (http://surf.to/alexplo)

[This message has been edited by ALENGOSVIG1 (edited 11-20-2001).]

[nbk2000]

6CH2O + 4NH4NO3 + 4NaOH = C6H12N4 + 4NaNO3 + 10H2O

The formaldehyde (20% neutral solution) and ammonium nitrate are mixed and heated to 60&deg;C, prior to addition of the sodium hydroxide solution (1N).

You can use phenolphthalein as an indicator for the end-point of the reaction.

If the lye is added without heating, the reaction proceeds slowly, but heating greatly decreases reaction time. If heated much higher than 60&deg;C, the yields are low, as the hexamethylenetetramine decomposes into ammonia gas.

What I'd like to know is, what would the equivalent amount of paraformaldehyde be, as that's much easier to find and more convenient to measure.

[nbk2000]

6CH2O + 4NH4NO3 + 4NaOH = C6H12N4 + 4NaNO3 + 10H2O

The formaldehyde (20% neutral solution) and ammonium nitrate are mixed and heated to 60&deg;C, prior to addition of the sodium hydroxide solution (1N).

You can use phenolphthalein as an indicator for the end-point of the reaction.

If the lye is added without heating, the reaction proceeds slowly, but heating greatly decreases reaction time. If heated much higher than 60&deg;C, the yields are low, as the hexamethylenetetramine decomposes into ammonia gas.

What I'd like to know is, what would the equivalent amount of paraformaldehyde be, as that's much easier to find and more convenient to measure.

[hereno]

6CH2O + 4NH4NO3 + 4NaOH = C6H12N4 + 4NaNO3 + 10H2O

What I'd like to know is, what would the equivalent amount of paraformaldehyde be

Ummm. Same empirical formula, thus same weight needed. :confused:

[hereno]

6CH2O + 4NH4NO3 + 4NaOH = C6H12N4 + 4NaNO3 + 10H2O

What I'd like to know is, what would the equivalent amount of paraformaldehyde be

Ummm. Same empirical formula, thus same weight needed. :confused:

[Diabolique]

Urbanski gives the following on making hexamine dinitrate in volume 3 (on RDX):

Hexamine dinitrate is prepared by adding 65 parts of 70% nitric acid to a solution of 40 parts hexamine in 70 parts water at 15* C. Cool to 5*C and filter the product. Yield stated to be ~95%.

As for MMAN, my LLNL sources say it is Monomethylamine nitrate.

[mil&co]

I was planning to produce HMX with the HDN->DPT->HMX procedure.

I succeeded in producing HDN (roughly 90 grams, HNO3 method), but now I have some questions on the dehydration of HDN to DPT.
I have searched, but I couldn't find details.

Urbanski vol 4 states:
The best method of obtaining DPT consists in introducing hexamine dinitrate to 90% sulphuric acid at 8 - 15 °C. After 45 min. all is poured on ice and the solution is filtrated. The filtrate is neutralized with 28% ammonia to pH = 5.5-6.5 DPT precipitated [165].

1. What exactly is the ratio HDN/H2SO4? Is it 1:1 by moles as one can assume because 2 moles water are dehydrated from 1 mole HDN (1 mole of sulphuric acid being capable of absorbing 2 moles of water), or is it better to use an excess of sulphuric acid?

2. The solution is poured on ice, is this just to cool it? Or does the solution have to be dilluted (does the ice have to be melted before filtering)?

3. The filtrate is neutralized with 28% ammonia. What is the solubility of DPT in water? I assume the neutralizing is done to drive the DPT out of solution from H2SO4? Is 5% ammonia not concentrated enough because the DPT will dissolve in the additional water?

[Hex]

DPT is essentially insoluble in water. In fact, it's not soluble in many solvents at all, a little bit in acetone and ethyl acetate.
The ammonia addition is probably more complex than a straight neutralisation - I guess that by dunking HDN in to sulphuric, you create a soup of nitramine, methylolnitramines, ammonium sulphate etc etc. Ammonia, formaldehyde and nitramine can be condensed to form DPT pretty instantly - I suspect that's what's going on here. i.e. the nitrogen of the ammonia is actually ending up as the bridgehead nitrogens of the DPT.