Tetramethylenediperoxidedicarbamide, TMDD

[Mr Cool]

Here it is, in Swedish:

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TMDD
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Denna för oss nya medlem i peroxidfamiljen har det rationella namnet
1,3,8,10-tetraaza-5,6,12,13-tetraoxocyklotridekan-2,9-dion, eller
enklare TetraMetylenDiperoxidDikarbamid (TMDD). Det framställs genom att
behandla urea med en formaldehyd/väteperoxid-blandning i närvaro av en syra.
Ämnet upptäcktes 1914 av tyskarna Girsewald och Siegens. Ämnet som sådant är
liksom HMTD och TCAP ett vitt kristallint pulver, och är också det mycket
känsligt för stötar och slag, dock är friktionskänsligheten lägre.

Fysikaliska och kemiska egenskaper

TMDD har följande strukturformel:


HN-CH2-O-O-CH2-NH
/ \
O=C C=O
\ /
HN-CH2-O-O-CH2-NH


Ämnet är olösligt i vatten och de flesta organiska lösningsmedel, och
liknar även i detta avseende HMTD. Densiteten hos ämnet är mycket låg, ej
packat upptar 12 gram mer än 50 cm3. Stabiliteten är större än hos HMTD,
och kan förvaras i över ett år utan att sönderfalla betydande.

Explosiva egenskaper

Liksom alla peroxider så måste man behandla TMDD med stor respekt. Inga
värden är funna angående detonationshastighet eller blyblockexpansion.
Ämnet verkar inte vara överdrivet känsligt för friktion. Vid antändning av
friliggande (liten mängd) TMDD så brinner det upp med hög hastighet, men
exploderar inte. Större mängder friliggande exploderar med stor
sannolikhet. Sönderfallet bör se ut som följer:

C6H12N4O6 --> 6CO + 6H2 + 2N2

Detta är det teoretiska sönderfallet, men i verkligheten bildas det också
varierande mängd vatten, koldioxid och kväveoxider.

Tillverkning

Eftersom detta är ett initialsprängämne så bör man inte framställa mer än
runt 10g per sats. Metoden nedan ger 8-10g utbyte så den är alldeles lagom,
dessutom blir kylningen av reaktionen besvärligare ju större sats man gör.
Lagra heller inte större mängder, utan använd det mesta du kan i anslutning
till tillverkningen.

1. Mät upp 16ml 35%-ig formaldehydlösning och blanda detta med 22ml
35%-ig väteperoxid i en bägare, och lös 6g urea i vätskan.

2. Sätt bägaren i ett vattenbad med isbitar eller snö (tillsätt ev. även
salt till vattenbadet för att få ännu effektivare kylning) och när
temperaturen sjunkit till under 10°C så tillsätt mycket sakta (droppvis)
12ml 65-70% salpetersyra (eller 10ml 50% svavelsyra) under omrörning med
magnetomrörare, eller i nödfall termometern. Temperaturen låter du inte
stiga över 20°C under tillsatsen av syra. Under tiden du tillsätter syra
kan kristaller att falla ut, som sedan åter löser sig. Detta är inte TMDD.

3. När all syra är tillsatt så tas bägaren ur kylbadet och ställs i
rumstemperatur i två timmar innan reaktionsblandningen, som nu ser ut
som en gröt, späds med 100ml vatten. Låt bägaren stå i ytterligare 24
timmar innan du filtrerar av de bildade kristallerna. Denna reaktionstid
ger runt 70 procents utbyte, och 48 timmars reaktionstid ger 90 procent,
alla utbyten beräknade på urean.

4. Tvätta kristallerna med rikliga mängder vatten, och sedan med aceton,
innan du lägger dem att torka på några lager hushållspapper.


Procedure VERY ROUGHLY AND SHITTILY translated by me because I had never read any Swedish before today! (please correct any mistakes that you see!):

1) Mix 16mL of roughly 35% formaldehyde solution with 22mL of roughly 35% hydrogen peroxide solution in a beaker, and dissolve 6 grams of urea in it.

2) Sit the beaker in a water bath with ice or snow (?!) until the temperature is below 10*C and add (dropwise) 12mL of 65-70% nitric acid (or 10mL of 50% sulphuri acid) while stirring magnetically, or with the thermometer. (The next sentence, I think, is either: "After the addition of the acid, let the solution warm up to 20*C" OR "While adding the acid, do not let the solution go above 20*C"). After adding the acid, crystals will begin to fall out of the solution. These are TMDD.

3) ???? I think this paragraph basically says that after 24 hours the yield will be 70% and after 48 it will be 90%, based on the urea used.

4) ???? I think this is telling you to wash the crystals with water, recrystalise from acetone and filter.

PLEASE, someone that can speak Swedish, TRANSLATE THIS!!

Sounds like good stuff from what I can understand. Has anyone ever heard of/tried it?

[kingspaz]

cool. looks interesting. maybe it could have better stability andlonger shelf lives than the other peroxides or maybe it could be super sensitve. definately worth looking into though!!

[Lagen]

I know a guy who makes it, according to him it is a good choice of peroxide. I do not make peroxides, so I can't tell you. Anyway, here's a translation of a post on TMDD by him:

It is a very powerful initiation agent, suitable for the manufacture of detonators. It is a white powder resembling powder sugar in appearance, only a bit greasy to the touch. Chemically it is a peroxide, therefore exhibits a much lower stability compared to the other conventional primary explosives. You can store it safely for 1 year (store it longer at your own risk). When ignited in the open it burns quickly with a large flame. It detonates when confined. No. 8 cap equivalent: 1.7g. Its initiation ability is about halfway between MF and lead azide.

Manufacture: Three different methods are possible:
1) using HNO3
2) without the use of HNO3
3) by action of H2O2 and HNO3 upon hexamine

According to 1) the preparation is fast and gives a high yield. According to 2) you avoid the need for HNO3. [He doesn't detail on method #3]

1) Materials: Urea (pro analysi), H2O2 35%, formaldehyde 37-38%, HNO3 65%
Procedure: Place 25ml of formaldehyde solution in a beaker and dissolve 15g of urea in it. In a separate beaker place 45ml of the H2O2 solution. Carefully add 12ml of the HNO3. Blend the two solutions and let them react at a temperature of about 40°C. The TMDD will precipitate in the course of about 30 mins. Filter out the TMDD and wash with a sodium bicarbonate solution. The yield is nearly quantitative, around 99% (much higher than usual for a primary explosive preparation). Dry the product thoroughly before use.

2) Materials: Urea (pro analysi), H2O2 35%, formaldehyde 37-38%
Procedure: Place 20ml of formaldehyde solution in a beaker and dissolve 10g of urea in it. Add 50ml of the H2O2 solution to it and let the mixture react at a temperature of about 40°C for about two days. The TMDD will precipitate. Filter out the TMDD and wash with water. The yield is about 70%. Dry the product thoroughly before use.

Both of the methods have been tried several times.

[Mr Cool]

Thanks Lagen!
99% yield in 30 minutes? That's pretty good! I'll try this asap, but I need to buy urea and formaldehyde first.
I'll use 9% H2O2 (it's all I have right now), and let it react longer.
Sounds like good stuff too...

[Alchemist]

Hello gang,

Good find! I'll also try the TMDD, asap and then we can compare notes later. I'll use the 27% H2O2 I just bought! Later then........................................

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[DBSP]

I just found this topic. here is the translation:
This for us new member in the peroxide-family have the the name
1,3,8,10-tetraaza-5,6,12,13-tetraoxocyklotridekan-2,9-dion, or
simpler TetraMetylenDiperoxidDikarbamid (TMDD). It is made by
treating urea with a formaldehyde/hydrogenperoxide solution in the presence of an acid.
The subject was discovered in 1914 by the germans Girsewald and Siegens. The subjectis just
like HMTD and TCAP is a white crystaline powder, and it is very
sensitive for shock and flame, however it's friction sensitivity is lower than for HMTD.

fysicalic and chemical properties

TMDD has the following structure:


HN-CH2-O-O-CH2-NH
/ \
O=C C=O
\ /
HN-CH2-O-O-CH2-NH


The subject is unsuluble in water and most organic solvents, and
is similar to HMTD. the density of the subject is very low,
unpacked 12 grams take more than 50 cm3.the Stability is better than HMTD,
and it can be stored in over a year without (decomposing...?)

explosive properties

Like all peroxides you must treat TMDD with great respect. No
rates about detonation velosity or leadblock expension is found.?
The subject doesn't seem to be extremly sensitive for friction. igniting
a small quantity) of TMDD it burns with high speed, but
doesn't explode. Larger ammounts ignated in the open will
probably explode. the decomposion should lock something like this

C6H12N4O6 --> 6CO + 6H2 + 2N2

This is the theroreticall decomposion but in reality a
varying quantity of water, carbon dioxide and nitrogendioxide.

manufacture

Since this is a primary explosive you shuldn't make more than
around 10g per synthesis. The method below gives about 8-10g.
don't store larger ammounts, make up as neded
1. measure up 16ml of 35% formaldehydsolusion -and mix this with 22ml of
35%hydrogenperoxide -in a beaker, and dissolve 6g urea in the liquid

2.put the beaker in a salted ice bath and when the
temperature has sunk to under 10°C very slowly (drop by drop) ad
12ml 65-70% nitric acid (or 10ml 50% sulfuric acid) stirring with
a magnetic stirrer, or with the thermometer. dont let the temperature
go over 20°C during the adition of acid. while adding acid some
crystals may occur This is not TMDD.

3. When all acid is added take the beaker out of the ice bath
let the beaker stand for two hours at rom temperature, the solution now shuld look like a slurry when it has been standing for two hours at rom temperature ad 100ml of water then let the solution stand for 24 hours before you filter the the solution and collect the crystals.
If you let the solution stand for 24h you will get a 70% yield.
48h you will get a 90% yield.
yields calculated on the urea.

4. Wash the crystals with lots of water and then with acetone,
before you put the crystals on some paper towels to dry.

To Mr Cool. where did you find that text?

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¤monte¤

[a_bab]

I bet this comes from some Swedish Infomania file, wich really worth downloaded, as it seems to contain good info. It looks to be Megalomania's like work in swedish pyro field !
Here is the link :

http://swi.1av10.nu/

It would be great for all of us a translation of these files !


________________________
http://move.to/pyromania


[This message has been edited by a_bab (edited August 28, 2001).]

[Berserker]

That's an AWESOME info archive a_bab, thanks for that. http://theforum.virtualave.net/ubb/smilies/biggrin.gif

[Tony Montana]

a_bab you can translate using this link:
http://www.translation-experts.com/intert.htm

[Mr Cool]

Yeah, it's a great source of info. I found the link to it in a short thread in the HE section about DINGU.

Edit: are there any free sites that will translate Swedish --> English? Looks like you have to pay on the link Tony gave.

[This message has been edited by Mr Cool (edited August 30, 2001).]

[Berserker]

http://www.tranexp.com - click on "intertran" under services. This tends to be unstable and slow and not very good, but it does the job... eventually.
http://www.elingo.com - was simply the best online translator but I think they're still down at the moment. http://theforum.virtualave.net/ubb/smilies/frown.gif

[Oh, it looks like Tony already posted the former link. http://theforum.virtualave.net/ubb/smilies/tongue.gif]

[This message has been edited by Berserker (edited August 30, 2001).]

[Q]

Could you use HCl instead?A cheaper more common alternative.Is formaldehyde available in chemists?I've never seen it before.

[Mr Cool]

I'd bet just about anything that hydrochloric, citric, sulphuric, nitric, ethanoic, formic etc etc etc would all work as the acid.

It depends where you live... I've never seen formaldehyde in any UK chemist's (or in any UK chemists), but in some places if you ask for something they can order it for you. It is commonly used as a disinfectant for toilets in caravans or something, and it can be found as a 27% solution in water/methanol in big camping shops. It is also available as a disinfectant in the dairy industry, and as a mildewcide, fungicide and killer of just about any microbe in garden centres and some DIY/hardwear stores.

[DBSP]

I must thank you a_bab those files are the first files i have found about explosives in swedish. They are great and the best of all is that there were a list of chemical suppliers in sweden that sell to anyone that is 18. They have everything i need but concentrated acids.

Again thank you!!!

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¤monte¤

[Detonator]

Anyone tried it?
Is it less sensitive than AP,HMTD?
Any data?

[CodeMason]

If you're brave, you can rescue formaldehyde from paraformaldehyde, its polymer, which is available even at the supermarket as a common mildewcide. I believe there has been a thread or two in the past along these lines.

[Mr Cool]

Hopefully I'll try to make it later today. I'm going in to town so I'll look around for camping shops and in the supermarkets...

[Detonator]

My friend tried it but it didn't work, he said he had a white powder and after he dried it he tried to detonate some of it but it didnt even burn.

[simply RED]

I just made the TMDD succesfully!
The formula is right but i din't make it all the time at 40 degrees but at 25. Only the first 30 minutes at 40 and not all the product was formed. I used 15 gram urea, 45ml 30%H2O2, 25ml 35%CH2O, and 20 ml 60% HNO3. just dissolved the urea at the CH2O solution and then mixed with the mixed H2O2 and HNO3. Then put the mix in 40 degrees for half an hour(it may have not been just 40)...
I filterred the product after 6 hours. It is white fine powder similar to HMTD. I haven't dried all the TMDD but i dried small quantity and it burned like HMTD(exactly like HMTD). I'm waiting for all other to dry(about 10-15 grams). An tomorrow if its dried i'm gonna detonate some.

[Mr Cool]

Damn! All local sources of CH2O appear to have dried up... maybe they'd just sold out, I'll look again later.

Well, tell us how it goes when it's dry...

[simply RED]

I just detonated 4 grams TMDD. First i tried with 2 grams and pressed it so high that it couldn't give full detonation. This expolsive can easily get dead pressed!
the second time i just fill 4 grams in a paper cylinder and closed the ends with toilet paper. it detonated more than good. But this explosive is really less powerful than TCAP and HMTD, although it seems a good choice if you use it with PETN of nitroglycerine, maybe gelled nitroglycerine secured with nylon in the blasting cap.

[Alchemist]

Hello all,

Well I just completed a bath of TMDD without the use of any acid! The yield was a little low, about 5 grams when starting with 10 grams of Urea, 20 of Formaldehyde, and 50ml of 30% H2O2. I let it sit for a whole two weeks at about 40*C by using a coffee cup warmer.

It does NOT seem to be real shock sensitive at all! I hit a few grains with a 10lb slug hammer with no results. This is NOT to say that it will NEVER be, but this batch was not. Lighting it in the open it popped/flashed quit good for 1/2 gram. Then I tried about 1 gram in a plastic straw with ends plugged with paper. This detonated VERY well. This seems like another real good Peroxide! I am sure that there are many more to discovery so keep looking and experimenting!

Well that's it. I am now making a batch with ACID. More later, so by for now!



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[VasiaPupkin]

Hmmm. I tried to make this matter half year ago, but finaly found it not useful. At first I knew only formula and non-detailed preparing. I prepared it by adding urea to formaldehyde/weak HNO3 solution. Filtered amorphis polymethyleneurea. Then dissolve polymer in 60% HNO3, add some urea and 50%H2O2. Mixture kept a 5 days at room temperature. Then added water and wash precipitate powder with acetone. Also I tried other ways... This powder burns like HMTD. Momentary decomposes to gas without ignition (CH2O smell) when slowly heated. I check it friction by rubing. I found its very insensitive to shock and friction. Then I tried to check its detonation susceptibility. Matter was pressed (Density near 0.7) to 120 MM special strong paper pipe with 8 mm diametre and 3 mm thickness (14 MM overall D). In one end some HMTD was pressed. It exploded in special closed box with sand. The great smoke and sound was here. I make it on my balcony :-) But other end with 40-50 mm of TMDD was undamaged. Later I didt make TMDD. What do you thing about it? Maybe TMDD was not pure or effect of overpressing was present?

[simply RED]

I also find TMDD unusable at all...I tried to detonate 20 grams in matchbox(about 10-20 grams). It wasn't overpressed but it only boomed less powerful than black powder.
This seems not to be a good choice becosue of the low power and disastrous oxigen balance but for "research" it was good.
btw:Vasia, i write you an e-mail, have you recieve it?

[Detonator]

Less than BP!? are you serious...? Is it this bas?

It looks like its not dangerous as AP but still sensitive so maybe adding it to ANFO or UN will help to achive a better detonation ( like a booster! ) with a small detonator.

what you think?

[CodeMason]

Judging the power of an explosive by how loud it booms is a mistake. Heck, heavily confined AP can make a measly pop comparable to a cap gun cap (although the high decibel noise that you don't hear does make your ears ring).

[VasiaPupkin]

And when TMDD exploded always many white smoke is present (strong smeel CH2O) isnot it? And I think its not possible when detonate.
To Simply RED: I change mail, because I had some problems. My new "pyro" mail is crv@hotbox.ru. send again please.

[Detonator]

So is it strong or not?!!

[simply RED]

TMDD is impossible to use in actual device. It is not powerful at all, extremely easy gets overpressed. Yes, it is impossible to judge explosive by the sound it makes, it was my mistake i didn't explained that i put 1mm thin witness plate benieth the matchbox full of TMDD. The witness plate was not scratced at all. I have noticed the white smoke too. Vasia, the mail was only to say "hello". I'm working on shaped charge with NG now but i don't know when will i accomplish it. I have 20 grams nitrocellulose and 20 grams NG till now, but a lot more NG is necessary...(by the way about 5 ml NG detonated in a test tube blasted a small brick in powder).
sorry for the late reply...

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With love and hatred i brought her chrystal vase!
When she got home immediately broke it and was spread on the floor...
The strange thing inside was C-4...