1,3-diaminopropane perchlorate...

[anthracis]

I have two friends also interested in high explosives and they managed to get a wide range of useful chemicals, including 4 bottles of 1L HClO4~70% (Merck). They also got some 1,3-diaminopropane, and they made these two substances to react. They call the product "perchlorate of 1,3-diaminopropane" or "1,3-diaminopropane perchlorate-DAPP". It is a colourless substance, slightly higroscopic. It burns in open air with a bright, white flame and a noise. They first tried to use it as a rocket propellant, and this was a bad idea also because the engine casing was an aluminium cylinder. As soon as they ignited the DAPP, the "rocket" exploded and little shrapnels flew all over the place, but only a few small pieces hit them, as they weren't too close but not far enough, too. After that they tried to detonate it and discovered it's a great explosive, quite powerful and stable. I saw such a detonation and I can say that the noise is strong and sharp, and there is no need for much confinement (this was a small charge inside a photographic film can). That's all I can say about, but I would like to know if any of you is familiar with this substance. I've searched the Internet but I found nothing on this particular substance.

[cutefix]

It is pretty simple.
Any strong oxidant such as perchloric acid mixed with fuel such as diamino propane will likely produce a reactive material.
I have not seen a data about that combination but the principle remains the same .
Generally organic perchlorates are hygroscopic and more potentially powerful explosive than inorganic perchlorates which are more of an oxidants.

[simply RED]

This is gonna be a nice explosive.
NH2-CH2-CH2-CH2-NH2 + 2HClO4 = O4ClH3N-CH2-CH2-CH2-NH3ClO4 (C3 H12 N2 Cl2 O8)
The density should be high for such easy to make substance, the energy output will be great too.
Unfortunately the matereal will be slightly more sensitive than PETN, storage unstable and incompatable with metals. It will be strongly acidic and prone to full hydrolysis.
The power should be 120-150% TNT.
The diperchlorate of : CH3-NH-CH2-NH-CH3 is more stable. And more powerful.
If NH2-CH2-CH2-CH2-NH2 is easily available, this explosive will be much much better choice than urea nitrate!

[anthracis]

Yes, it is very possible that it was 1,3-diaminopropane diperchlorate, the acid they used was quite concentrated...I'd be interested to see if it could give a good plastic explosive. In pure form the detonation was quite impressive, as I rememeber. I hope I won't be sorry for sharing this.

[frogfot]

A wild guess, shouldnt HClO4 oxidise the amino groups giving NO2 groups? The final product should then be: O2NCH2CH2CH2NO2
HClO4 is a strong oxidiser after all.. in which way did they carry out reaction?

[Maniak]

I don´t think that perchloric salts of organic bases are fully usable as explosives..I don´t know exactly sensitivity of yours explosive, but I think that it´s high. One man in our country made explosives only from perchlorates - he used hexamine perchlorate as a primer and in plastic explosives too...he used methylamine perchlorate (it´s from us patent 3,976,522) and others.
But now he´s maybe death...
Perchlorates are really much sensitive for me and maybe quite unstable...
I use only anorganic perchlorates - sodium perchlorate in fluid explosive (68%NaClO4+4%H2O+28%ethylenglykol) and amonium perchlorate in cast with DINA (50%DINA+15%elektron+35%perchlorate).

[Mr Cool]

What are "DINA" and "elektron"?

[simply RED]

Elektron is an alloy of Mg and Al used in fire bombs.
DINA is : (O2N-O-CH2-CH2-)2N-NO2. DINA has found no practical use. DINA is less powerful than RDX.

[Maniak]

DINA is one of my favourite explosives;)
it´s m.p. is 51deg.C,
detonation vel.=7600m/s (dens.1,48 after casting),
max. dens.=1,67,
stability and sensitivity are between PETN and EGDN...
I usually use DINA in cast with 60%RDX and sometimes with perchlorate. DINA can be made easy from diethanolamine, 90+%nitric acid and acetanhydride with ZnCl2 catalyzator.

[anthracis]

My friends used this substance for quite a long time and they had no problems, other than that accident when the rocket exploded... I had a few grams to play with, and considering my experience and from the discussions with my friends I am pretty sure that 1,3-diaminopropane (di)perchlorate is less dangerous than acetone peroxide or HMTD...And more powerful.

[Microtek]

Maniak: I have just recently become interested in DINA as a more powerful alternative to TNT for use as melt-castable energetic binder (It is described in US 2461582 for those who want more info). Anyway, Maniak could you tell me about the ZnCl2 catalyst ? Is it allright to use some hydrated form from Zn + HCl (aq) or do you have to chlorinate Zn directly ?
Perhaps this deserves a thread of its own.

[Maniak]

I have ZnCl2.2H2O, and it can be made from Zn and HCl. My DINA preparation is similar to
US patent 4450110, but I use ZnCl2 catalyst instead of acetylchloride which is recomended.
The yield was 76% theory - 55g DINA from 30g diethanolamine...Second I tried preparation with HCl catalyst only, but yield wasn't exceed 61%. The yield can be higher (about 90%), but it needs no water in reaction mixture and I have only 95%HNO3...
One of disadvantages of dina is low density of cast product - casted DINA with 60%RDX has got a density only 1,57, but det. vel. is quite good - 7800-8000m/s and it has good sensitivity (I usually use 0,7gRDX or PETN detonator)...

[Maniak]

Anthracis: yes, this substance is quite stable, it has easy and stable base - diaminopropane.
And sensitivity must be lower than peroxides - they are really sensitive (and unstable too), I never use them. But what about comparation with brizants like PETN and RDX?
I think, that sensitivity to shock is near PETN (about 20cm/kg)...yes, it isn´t bad.

[anthracis]

Maniak: I only had a few grams, as I've said. On the other hand I never had PETN and RDX, only TNT, picric acid and nitrocellulose. So I can only compare it with these explosives - from the sound and the effects I've seen, I'd say it is stronger than any of them. You seem pretty sure about that sensitivity to shock. Have you made 1,3-diaminopropane (di)perchlorate and test it? I'd do it myself but I have no diaminopropane and my friends are in the Army now...

[Mr Cool]

DINA does sound interesting, but I'd be more inclined to use erythritol tetranitrate if you want a melt-castable HE, Microtek. It has the power of MHN, better stability, and melts below 70*C. A pound of erythritol costs about £5 from places selling sugar substitutes, and you can use the normal mixed-acid or acid-nitrate (cheap) methods of nitration.

Although it would be nice to try something new (DINA)...

[Maniak]

erythrit tetranitrate really has slightly higher det. parameters than DINA:
Name: ETN DINA
Energy 6439 5384
Det.vel. ? 7580(dens.1,47)
Vol. of gases 704 943
oxygen bal. +5,4 -26,6
density 1,6 1,67
m.p. 61°C 51°C
impact sens. 2Nm 6Nm
deflagr.p. 160°C 200°C

literature: UrbanskiII,III,IV , Meyer-Explosives , US pat.2461582
Stability of DINA is better,it's near PETN and maybe tetryl(UrbanskiIV) - stability of ETN is near NG(UrbanskiII).
I think, that DINA is safer for use, but when you need the most brizant explosive, ETN is really better...
And maybe, precursor for ETN is cheaper, but not in our country:)

[megalomania]

As I have never heard of DINA before I did some digging. A quite interesting explosive it is, been around since the late 19th century it seems, although it wasn't until the 40's that it could be made with any good yield. Please see also US patents 2686804, 4761250, and 5482581 for synths of DINA, DINA and DANPE, and DINA and NINA respectively.

I gather that DINA is not intended to be used as a high explosive all by it lonesome, but is used as an energetic binder/plasticiser in plastic explosives or propellants.

[FrankRizzo]

Kinda OT, but since DINA has been mentioned: What is a good/common source for diethanolamine?

[nbk2000]

From patent #2461582


EXAMPLE 4
(Preparation of DINA from diethanolamine using nitric and hydrochloric acids)
105 g. (1.0 mole) of diethanolamine was added dropwise to 954 g. (15 moles of 99% nitric acid maintained at 20° C. The resulting solution was cooled to 0-5° C., and hydrochloric acid gas passed into the solution until the increase in weight was
36.5 g. (1.0 mole of hydrochloric acid).

The reaction mixture was then heated to 55° C. for 20 minutes and poured onto 1900 g. of ice. The crude DINA was filtered off; it melted at 49-51° C. and weighed 100.8 g., corresponding to a yield of 42% of the theoretical.

Small yields of DINA were obtained when the hydrochloric acid was replaced by phosphorus pentachloride, phosphorus trichloride, phosgene, and chlorine while no yield was obtained with sulfuryl chloride or thionyl chloride.


This seems the best process from the home experimenters viewpoint, since it obviates the need for acetic anhydride (difficult to obtain) and zinc chloride (one less thing to mess with), while using things that are readily available. :)

And it doesn't even use much more acid than the catalyzed method.

DEA is fairly common in products, but I've been looking for an OTC source of fairly pure DEA and haven't found one listed (yet) on the 'net. Though I'm sure a sample scam can obtain some. :)

[Balurg]

Hello, duys! This is my first post to this forum (and I am not sure that my English is good - but I sure that my English is bad, thougth :) - please excuse me).
I am interesting DINA, this is a very good casting explosive. But I very amazed by your data about PETN, about its melting point of PETN: "below 70 °C", "61 °C"…
This is a 99% mistake or misprint. A melting point of PETN is 141 °C! And working with melted PETN is very dangerous! You can do lower MP of PETN, of course, by adding some components (13% a-trinitroroluene, for example - MP is 76 °C, this is eutectic alloy), but this still dangerous in many cases (in home preparation of explosives - in 99% of cases ;) ) because decomposition of PETN may occurred even with small overheat of this alloy (and many similar alloys with PETN)… So PETN is NOT a casting explosive! It is recommended that PETN will be pressed to charges instead.

[Maniak]

Balurg: there is no discussion about PETN! The explosives, which I compared were DINA and ETN.
ETN is erythrit tetranitrate, not pentaerythritol tetranitrate. Melting p. of PETN is really 141 degreeC.

[Balurg]

Maniak: I even not heard about ETN :). In Russia erithritol does not used as sweet substitute, I think (mannit and ksilit instead).
But I see that ETN even closer to NG, then nitrosorbit, for example. So ETN must be dangerous in look at decomposition... So this is a good idea - to use difenilamine or so stabilizer for castable mixes with ETN... :rolleyes:

[Hystrix]

RED:
I'm almost sure that 1,3-diaminopropane diperchlorate will be more stable than bis-methylamino-methane diperchlorate. Anyway, it will be rather sensitive (sensitivity of methylammonium perchlorate is similar to LA).

anthracis:
Didn't you try to make 1,3-diaminopropane dinitrate? I think it'll form an eutectic mixture with AN which should have mp less than 100 deg. C. Thus you can obtain castable explosive and it will be rather powerful.

Balurg:
In english "nitrosorbit" is named sorbitol hexanitrate, its mp is 55 deg. C. As for ETN, it really melts at 61 deg. C. And eutecticum you meant consists of 13% of PETN and 87% of TNT.

BTW I've recalled two melt castable explosives. The first is MNO, N,N'-dimethyl-N,N'-dinitro-oxamide: CH3-N(NO2)-CO-CO-N(NO2)-CH3. Pure stuff melts at 124 deg. C but it can form an eutecticum with picric acid (45% PA, mp 78.6 deg.C). The second is DMMD, 2,4-dinitro-2,4-diaza-pentane: CH3-N(NO2)-CH2-N(NO2)-CH3. Its mp is 57 deg. C. IIRC both explosives have power similar to tetryl; the raw for them is methylamine.

[Maniak]

I read some informations about MNO in Urbanski III and it´s really interesting for me...the precursors for this explosive are methylamine and diethyloxalate, which I´m going to have:)
But I have got ethylamine, not methyl- and I don´t know about product of reaction diethyloxalate with ethylamine :rolleyes: It won´t be the same as with methyl-, but some derivate, which has lower power and so:(
MNO is very strong and "fast" explosive, det.vel. can be over 9000m/s:D

[Hystrix]

Maniak, MNO is not so powerful as you're writing. Maximum VoD I saw for it was 8500 m/s (for cast sample), and I'm not quite sure that this data is correct. According to Urbanski its VoD is 7130 m/s @ 1.33 g/cm3. Dinitro-diethyl-oxalate is much weaker; it gives 220 ml in Trautzl's test (therefore it's similar to DNT).

[Maniak]

Sorry, it was my mistake:rolleyes: max vod is really 8500m/s.
Now I read Urbanski and I see dinitrodiethyloxamide, which I will make:) Trauzl test is poor, but I think, that VoD mustn´t be so bad...

[nbk2000]

7,000+ m/s isn't shabby. :)

[simply RED]

Secondary amines are stronger bases than primary so the 1,3 must be less stable.
See the structure : CH3-NH-CH2-NH-CH3 , you have 5 atoms. The geometry of the molecule will be like cyclohexane, only not cyclic. All atoms in sp3, after the nitrate is formed its again in sp3. The two amino groups are too distant and the interaction between the negative charged oxigen atoms in the nitrate ions will not be noticable.

[Hystrix]

Hmm :). RED, look better at your "stronger base". It's formed from 2 moles of CH3NH2 and 1 mole of HCHO, isn't it? Therefore, it should be readily hydrolysable. BTW, condensation is in use for producing DMMD (2 CH3NHNO2 + HCHO) and not nitration (you can find the description of this process in US patents Nos. 4,469,888 and 4,476,322). I think it's caused by low stability of 2,4-diaza-pentane.

PS Thus if you want to have stable secondary amine you need at least 2 atoms of carbon between amino groups.

[Balurg]

Hystrix: "C. IIRC both explosives have power similar to tetryl" - what is IIRC, please?

[zaibatsu]

If I Remember/Recall Correctly

[anthracis]

Hi guys!

Regarding 1,3 diaminopropane diperchlorate: I've talked to my friend and he told me that both reactants (diaminopropane and concentrated HClO4) must be cooled before you put them together. He even kept the diaminopropane in the freezer. The reaction is very exothermic. :(

[KABOOOM [pyrojustforfun]]

why the guys didn't use the more common ethylenediamine. it's a very slightly weaker base than 1,3-propylene diamine. EDDP is ofcourse more powerful than PDDP. has better OB as well (zero!)

[anthracis]

Because they only had 1,3-diaminopropane and made some experiences with this substance...Your idea is quite interesting, anyway!...

[Wydarr]

Well... reading through these extremely interesting things I have uncovered, I have encountered an extremely familiar experience (the one anthracis told you about). The reason it is so familiar is because I was one of the lucky bastards to come clean after the DAPP incident (isn't the world small and this the best forum for guys like us? :D )

This being my first post I have decided to clarify some things:

1) It was all we could get our hand on in terms of di-amines. Of course Ethylene-diamine is more powerfull.. but no luck in obtaining the stuff... YET.
2) The reaction is SO exothermic that besides putting the DAP in the freezer before the experiment we had to add the perchloric acid drop by drop because of the spraying that occurs there.
3) I have a pretty solid history with this explosive (I have used it for some 7 years). First we detonated it in a very hand on manner: the explosive in a tightly sealed can, attach a fuse and light it. Because of the rapid combustion inside the tube there would be enough pressure to tigger a detonation. When we learned how to detonate it ( we only use custom made blasting caps with silver acetylide) there was a dramatic increase in the effectiveness of the charges. I find it a VERY powerful explosive in comparison with what I worked in the military (a 50 gr. charge has more effect that a 100gr standard TNT stick) The downside is that we only use it in tightly sealed containers.
The only indication I can give you about the power of the explosive is that a 50 gr charge penetrated a 1 cm thick concrete slab. Furthermore the bang is much more powerfull than the standard 100 gr TNT stick we use in the Romanian army.