Sciencemadness Discussion Board

"DINA", the nitration product of diethanolamine

PLSHY - 2-11-2023 at 11:28

I have heard of it a long time ago, but recently I came across it in a book. As an amateur energetic material, it has the following advantages.
1. It can be cast (melting point 50 degrees), this is the best advantage! Because I didn’t think of anything more suitable for shaped perforating bombs than casting!
2. It is powerful, at least 150% of the power of TNP (lead mass test), with an explosion velocity of more than 7700 at a casting density of 1.67.
3. Lower cost, if you have fuming nitric acid, it can be manufactured at a lower cost than petn, and the purification process is easy.
4. The mechanical sensitivity is low. For the above three advantages, etn can do better than it. But this advantage separates it from etn. It has a similar sensitivity to tetryl, which means it can be cast in a safer manner.
But similarly, he also has the following shortcomings.
1. The stability is poor. The stability test at 72 degrees Celsius lasts for more than 30 minutes, but the decomposition temperature is only 160 degrees, and the stability is much worse than tetryl.
2.It can only be made with fuming nitric acid. Due to the special nitramine structure, it can only be made with nitric acid with a mass fraction greater than 95%.
3. There is less information. For energetic material enthusiasts, information on a substance is very important, but there is less information on dina.
Overall, this is a very nice substance. It is possible to replace etn as the first choice for amateur casting and casting explosives, greatly improving safety. And due to its high energy, it can also be used as a component of high-energy explosives

[Edited on 2-11-2023 by PLSHY]

PLSHY - 2-11-2023 at 11:37

What interests me the most is its simple production method. For enthusiasts, synthesizing some petn is always easier than synthesizing tnt. But the cost of TNT in industry is lower than PETN. For dina, all you need is some diethanolamine, fuming nitric acid, sodium chloride and magnesium oxide. The ratio is approximately 1:4.5:0.032:0.4. And all you have to do is mix them together! It’s almost as simple as petn’s nitrification. There is no need for a lot of glass instruments and complex three-stage nitrification waste acid recovery!

DennyDevHE77 - 2-11-2023 at 20:32

As far as I know, acetic anhydride is needed for the production of DEAN, without it it turns out (O2NOCH2CH2)NH*HNO3. To separate water from amine, acetic anhydride is needed, well, maybe phosphoric will do.

PLSHY - 2-11-2023 at 21:51

Quote: Originally posted by DennyDevHE77  
As far as I know, acetic anhydride is needed for the production of DEAN, without it it turns out (O2NOCH2CH2)NH*HNO3. To separate water from amine, acetic anhydride is needed, well, maybe phosphoric will do.
There is a method that does not require acetic anhydride and is called the magnesium nitrate method.

E8C2861D-D8BB-4AE3-AE87-1760D307AF7E.jpeg - 203kB

EF2000 - 2-11-2023 at 23:28

Then the main problem is DEA itself. It's widely used in things like cosmetics, but is it available OTC? I checked chemcraft, they have only triethanolamine (TEA) and ethanolamine O-sulfate, though I haven't searched for other suppliers

PLSHY - 2-11-2023 at 23:49

In China, you can purchase analytically pure reagents through 999 Chemical Network, which is equivalent to about US$5 for a 500ml bottle. I also know that it is available on the Chinese chemical website "1688" at a very cheap price. As far as I know, diethanolamine is a bulk industrial product and may be easier to find on chemical trading websites. It has many uses such as lubricant, coolant, corrosion inhibitor.

dettoo456 - 3-11-2023 at 07:00

https://doi.org/10.1021/acs.oprd.9b00300 -This paper outlines the Ac2O/HNO3 method but PLSHY is correct in that there are other methods to produce it cheaply. The DEA is cheap too, but sourcing is a little more tricky than finding MEtOHA or TEtOHA. If making though, it is paramount to nitrate all the way to the nitramine (not just the nitrate di-ester) because there are apparently much larger stability issues with the free amine.

Stability is an issue though; as cheap as the DINA may be, pentaerythritol is cheap too (around $1.5/lb) and PETN is far more stable, easy to synthesize, easier to handle, and more powerful. If you want a cheap, stable liquid EM I’d just recommend a simple ammonium salt like ethyl- or methylamminium nitrate or a cyclic nitrate ester like IHN. Now that sugar-free sweeteners are becoming more popular, the market is bigger than ever for cheap polyols for nitration.

Microtek - 6-11-2023 at 01:13

I think the appeal is that DINA is melt castable unlike PETN and most of the nitrate esters. If you look at the NENO thread, the strategy there is to convert the primary amine to a secondary one which is more easily nitrated without forming salts. NENO does require quite harsh conditions to nitrate fully though.

EF2000 - 6-11-2023 at 08:06

Quote: Originally posted by Microtek  
I think the appeal is that DINA is melt castable unlike PETN and most of the nitrate esters.

That's true, and DINA is interesting for sure, but there're melt castable derivatives of PETN: https://doi.org/10.1002/chem.202204013

Melt Castable Derivatives of Pentaerythritol Tetranitrate.jpg - 677kB

Microtek - 6-11-2023 at 13:38

But they are much more difficult to prepare than DINA (at least the ones in that paper)...

I did see references to pentaerythritol TRInitrate once. I forget the energetic properties, but I would guess in the vicinity of NG. I could imagine that it would be quite difficult to only nitrate three of the hydroxy groups, though.

DennyDevHE77 - 6-11-2023 at 22:47

I found a mention of trinitrate on one dead forum.
Quote from one of the participants:

"There is an interesting field for pyromaniac activity for those who like to get involved with pentaerythritol.
For those in the tank: Petrin is a viscous liquid with a solidification temperature of about 20°C and a density of 1.54 g/ml.
The ability to plasticize nitrocellulose is superior to nitroglycerin, while only slightly losing to it in power is much less sensitive (like tetryl)
and less poisonous, because it penetrates the skin worse and is less volatile. In the USA, at one time, all kinds of plastisols were made on it and used in gunpowder instead of nitroglycerin...

In general, how it is done (recipe from JACS 1955): 480g of pentaerythritol for 10 minutes is added to 1980 g of 80% concentration of nitric acid cooled to 0°C
(with the addition of 3 g of urine). During the addition and after, make sure that the temperature does not become higher than 5°C.
After 15 minutes of stirring, add 1980g of 80% sulfuric acid, cooled to -10°C. The mixture is continued to be stirred for 2 hours.
The mixture is poured into half a kilogram of ice and the sediment is filtered out. Wash it with water.
After that, the precipitate is dissolved in 2.5 liters of boiling acetone containing 75 g of ammonium carbonate.
The acetone solution is diluted with water and alcohol to a mixture containing 7 hours of acetone, 3 hours of water and 2 hours of ethanol.
After an hour of holding the mixture, the dropped PETN (!) is filtered out. Another 7L of water is added to the filtrate and left for 16 hours.
The water layer is decanted and the organic layer is filtered out. The precipitate is combined with the resulting PETN and used for its intended purpose :)
The filtrate is diluted with 1 liter of water and mixed well. The liquid organic layer is separated again.
Since vacuum distillation for household chemicals is often exotic, then in my opinion it is necessary to pour the mass into a saucepan, cover the pan with gauze and take
it outside for a couple of days so that any volatile stuff evaporates, after which we dry it with anhydrous magnesium sulfate or calcium chloride.
The result is 450g of petrine, which has a 47% yield... Not counting the side-highlighted PETN" End quote.

There are other ways, for example, to obtain trinitrate through mono-acetate, but it is in turn prepared from tetraacetate, and here acetic anhydride is already needed, and not every household chemist has it.

And someone even successfully obtained PETRIN by saponification of PETN with sodium hydroxide in alcohol.

By the way, penta monoacetate-trinitrate has a melting point of 87°C and probably also forms eutectic with PETN. Monoformate-trinitrate generally melts at 60°C.

EF2000 - 8-11-2023 at 05:50

Quote: Originally posted by DennyDevHE77  

(with the addition of 3 g of urine).

Read as "3 g of urea".
And "JACS 1955" is that paper: A New Synthesis of Pentaerythritol Trinitrate (full text).
Cool method, gives you both desired liquid explosive and PETN as pleasant bonus. 404 g of PETN, actually, not much less than main product.:cool:
Was it on some Russian/Eastern European forum? "For those in the tank" idiom sounds very familiar.

Note: 80% acid concentration is very important:
Quote:

The use of 90% nitric acid gave almost quantitative yields of pentaerythritol tetranitrate while a slight reduction in concentration of nitric acid gave negligible quantities of both pentaerythritol tetranitrate and trinitrate.



[Edited on 8-11-2023 by EF2000]

DennyDevHE77 - 8-11-2023 at 22:55

Quote: Originally posted by EF2000  

Was it on some Russian/Eastern European forum? "For those in the tank" idiom sounds very familiar


Yes, it's from the Russian forum "exploders.info". It's dead now, and is only available in the archive. And the specific article is here: http://web.archive.org/web/20160418231346/http://www.explode...

I'll note that it opens far not always and not immediately, apparently because of problems on the web archive itself. It is not commercial and lives on donations.

Quote: Originally posted by EF2000  
Read as "3 g of urea".



I apologize for the urea, I translated it just like that, although it was mentioned as a metonymy.