Sciencemadness Discussion Board - TETRYL

TETRYL

quicksilver - 21-9-2006 at 17:19

I found out that today (the 21st) is Tetryl's birthday. The structure of tetryl was established by Romburgh in 1883 but the very first time it was used as an energetic material was Sept. 21 1906...thus making it 100 yrs old as an energetic (Happy B-Day)
I have read countless times that dimethylanaline is nitrated with a non-aziotropic 80% nitric acid but yet when 70% is used to nitrate dimethylanaline the material seems just fine. Is there some reason why the 80% figure is used....why not use the clearest highest grade available? Yet most every patent points to a pre-sulfanated dimethylanaline just above the 70% mark...why?

a_bab - 22-9-2006 at 12:36

...because a higher concentration will oxidise the crap out of dimetylaniline. This is how I ruined half of my reserves in my futile atempts to synthesize the tetryl. I eventually gave up. At that time I didn't have access to Internet, nor to books describing the procedure.

If you ever tried to make TNP out of phenol, imagine that mass twice as fast. All I could get was a yellow liquid with a horrible viscous-sticky-black mass.

quicksilver - 23-9-2006 at 05:44

I had thought the pre-mixing with H2SO4 reduced the oxidsation rate. I knew that was the reason that why dimethylanaline could not be nitrated alone but you say that any concentration above 80% will have the same effect...(oxidizing the crap out of the analine))
Am I jumping to conclutions that the real difference between 70 and 80% is yield alone? I just can't see industry attempting to alocate 80% HNO3 when 70% would be effective. And I know that 70% will produce tetryl - the problem is it has impurities in it from the high H2O level which need to be delt with. But it's rearly used in it's crude form anyway, so I don't see the $ savings in using other than standard HNO3.
Those firms that use analine dyes are a great source for dimethylanaline, by the way.

Boomer - 24-9-2006 at 23:21

Analine, Alanine, Aniline or what? Any reason you call it ANAL-ine?

"because a higher concentration will oxidise..." Funny, I always thought that very high conc. nitric is more of a nitrating agent than an oxydiser compared to medium conc (70ie-ish). Just remember PETN, where *below* a certain conc you get runaways, above you get product, further below nothing.

quicksilver - 25-9-2006 at 06:31

Exactly. That's what I was thinking when I asked. It appears superficially that one should get better yields, etc. I take it for granted that temp needs firm control etc - but not one mention of a higher concentration and why the fixation on just higher than 70% (80)?
I have read many times that it must be sulfanated due to a very vigorous reaction (oxcidation most likly) but once that is in place why not use the strongest possible HNO3? I have found reasons for not using HNO3 with niterous acid (red) in nitrations (RDX) but the focus was on an obvious introduction of an extrenal impurity / byproduct during the synth.
I have a similar idea that there must be a certain amount of H2O during the nitration. My idea is that due to the molecular structure of tetryl a certain amount of available H needs to be available. If one were to step too high and / or there is not enough available, the end result would either not be solid or simply not hold together as a nitrated molicule. If there is too much water; you would get tetryl but with other non-desirable components in the final yield. It's just off the top of my head, I have no idea really that's why I thought someone would have had the same question, etc.

You know I can't spell worth a Damn .....the "analine" must have been a slip....

[Edited on 25-9-2006 by quicksilver]

quicksilver - 4-2-2010 at 16:07

Bringing back a very old thread I found a company that supplies dimethylanaline to industry (can't find their web site yet (and they may not have one!) at a pretty filthy high cost (250ml @ 80+ € ). I think because it's fallen from favor industrially as an energetic (& it's likely to be a struggle), it's availability is overlooked.
However I am not too tempted to invest and deal with moving higher than the azotropic level of HNO3 as it simply may not be worth the hassle. Apparently industrial dye firms do use it on a very limited basis, although I do not know if they provide a "sample"; that would be the only way I could think of trying it. With the rate of exchange now, that's some serious money.

Another annoyance is that it appears tempting due to the possibility of using mixed acids to achieve a "higher than 70%" nitric level; recognizing that H2SO4 would be in the mix to begin with.
Has anyone really been successful making Tetryl? Some less than technical-level publications have written of using 70% but unless I could purchase 1/2 a liter, the issue seems like an exercise in wasting HNO3, money, time and a lot of testing to get a (most likely) yellow dye.

If anyone did have some knowledge of it's synthesis in a non-professional environment I'd like to hear about it.

blazter - 4-2-2010 at 16:41

A hint for those looking for dimethylanaline, look into polyester resin curing agents as used in marine applications. It is used as an accelerator often in combination with cobalt napthelate and a peroxide initiator.

Ral123 - 20-9-2012 at 23:21

http://www.youtube.com/watch?v=jGTtUvRpz7Q&feature=youtu...
Used the method from digitalprecursor. If you have dimethylaniline, it's better then mixing hexogen with tnt-single stage nitration. I associate tetryl with TNB/RDX mixture.

Ral123 - 21-9-2012 at 23:46

http://www.youtube.com/watch?v=RGY1pPwyduE&feature=youtu...
come on, why nobody cares about this exotic (for home pyros) explosive, look how military sounding name it has.

Ral123 - 2-10-2012 at 12:24

Looking at my test targets for my tetryl and picric acid tests I'm wondering why these two burn so differently? They seem not too far as brisanse. They are with similar melting points. My tetryl burns like a rocket fuel. Fast with bright white flame. The picric acid can't sustain it's own combustion(witch is kinda cool

). Even my lead picrate burns strangely slow and unstable because of picric acid contaminants. Seems like these aromatics are pretty stable with up to 3 nitro groups and story get totally different after there's another nitro group. My R-salt also burns quite slow.

niertap - 9-10-2012 at 16:27

I'm under the impression that nitric acid in the 50-65% range is most oxidizing. I think it has something to do with how ionic the solution is and how much the nitric acid deprotinates into the nitrate ion.

Ral123 - 9-10-2012 at 19:46

Well, to nitrate something like benzene, you have to oxidize it first right?? And then the nitrogen bonds to the carbon. But definitely mixture with 60% nitric can make bad ass runaways. I underestimated it one or two times

The last time I wanted MNT and ended up with stuff spilled everywhere and a fire.

Motherload - 17-10-2012 at 08:15

If 50-60% HNO3 is more oxidizing .... Has anyone tried using it to oxidize the R-Salt to RDX ?

Geraldinehenry - 18-10-2012 at 19:47

Quote: Originally posted by a_bab

...because a higher concentration will oxidise the crap out of dimetylaniline. This is how I ruined half of my reserves in my futile atempts to synthesize the tetryl. I eventually gave up. At that time I didn't have access to Internet, nor to books describing the procedure.

If you ever tried to make TNP out of phenol, imagine that mass twice as fast. All I could get was a yellow liquid with a horrible viscous-sticky-black mass.

OF COURSE, I THINK YOU ARE RIGHT

PHILOU Zrealone - 24-10-2012 at 02:49

Does someone here have infos on the following molecules somehow related to Tetryl?
I wasn't able to find those.

They stil must display interesting properties high densities and VOD but also, probably higher sensitivity to shock than Tetryl...

1)Tetryl = 1-nitraminomethyl-2,4,6-trinitrobenzene
2) 1,3-bis-nitraminomethyl-2,4,6-trinitrobenzene
3) 1,3,5-tris-nitraminomethyl-2,4,6-trinitrobenzene
4) 1,3,5-tris-nitraminomethyl-2,4,6-triazine
5)?
6)?

Bert - 22-3-2014 at 18:19

Tetryl has come up repeatedly recently- An old standard material with good explosive properties that fell by the wayside, victim of newer and less toxic, longer lasting and safer materials by accounts.

Along with Pentryl (thanks, Axt!) and several other useful things, not a difficult synthesis once 2,4-dinitrochlorobenzene (or 2,4-dinitrobromobenzene) is available, and OTC is achievable if you can deal with the hygiene and avoid sensitization.

http://www.sciencemadness.org/talk/viewthread.php?tid=28480

I've found a good bit on industrial tweaks and patented improvements to tetryl synthesis, including Tenney Davis' observation that it would probably be made from 2,4-dinitrochlorobenzene going forward. Plenty on industrial hygiene and studies on how it injured the plant workers exposed to it too.

What I'm not turning up so much on is the nuts and bolts of how these compounds were used and industrially handled. Such things as compatibility issues with other energetic materials. Best choices for metals in contact with Tetryl or Pentryl. How the compressed pellets were made and details of crystal size choices for the pellet and cap pressing. Details on the fine crystals mentioned in some centerfire primer mixtures.

Does anyone have a suggestion for period literature with such information?

Here's a start on the crystallization question-
Recrystalization of Tetryl from dichloroethane:
http://patentimages.storage.googleapis.com/pages/US1940811.p...

This looks enticing- Love to read the rest.
Tetryl, pentyl, hexyl, nonyl- Preparation & Explosive Properties
http://pubs.acs.org/doi/abs/10.1021/je60016a042

Well! Shiny!!!
Got an old microwave oven I don't mind blowing up somewhere around here...
http://nopr.niscair.res.in/bitstream/123456789/7380/1/JSIR%2069(3)%20208-210.pdf

[Edited on 23-3-2014 by Bert]

Pentryl

Bert - 24-3-2014 at 21:57

http://pubs.acs.org/doi/pdf/10.1021/ie50288a601

Once again, love to see the rest of this-

Here yield from amination of the 2,4-dinitrochlorobenzene is claimed to be 70%-
Axt has 45%. Clearly there are a few details left to tweak- After going to the effort of OTC synthesis of that rather unpleasant dinitrochlorobenzene, shame to be less efficient with the stuff.

The final nitration yield given is 90%, pretty much in line with Axt's figure of 84%.

Hennig Brand - 1-12-2014 at 09:31

I got a present for you Bert.

Attachment: Tetryl, pentyl, hexyl, nonyl- Preparation & Explosive Properties.pdf (1.5MB)
This file has been downloaded 1430 times

Bert - 1-12-2014 at 10:30

Thanks, nice well documented present there! Plenty to think about.

Hennig Brand - 4-12-2014 at 13:06

The following is a copy/paste from the following site. There is a bit of information on how tetryl was pressed into pellets.
http://archive.hnsa.org/doc/ordnance/index.htm

"Tetryl (Trinitrophenylmethylnitramine): Tetryl, because of its combination of high power, brisance, and sensitivity, is the standard U. S. booster charge, although the Navy still uses an appreciable amount of granular TNT. It has been tried for main charge loads in small caliber projectiles, but has proved too sensitive to withstand the setback in all but 20-mm. It is used as a base charge in compound detonators. This, in effect, makes it a small booster in intimate contact with the initiating explosive. The melting point of Tetryl (130 degrees C.) is too high to allow it to be melted and cast. It is loaded by being mixed with small quantities of graphite or stearic acid which serve to lubricate it while it is being pressed into pellets. Tetryl is quite safe to handle and is extremely stable in stowage. Exposed or loose Tetryl should not ')e handled, as it may cause dermatitis.

The velocity of detonation is 24,400 ft./sec. at a density of 1.55. Its color is light yellow, but it is usually gray because of the graphite. It is more powerful than TNT. Its Laboratory Impact Value is 45. Its Bullet Impact Value is 61."

Rosco Bodine - 5-12-2014 at 20:53

While tetryl is interesting for its historical significance, as a practical matter it has been essentially made obsolete by what has replaced it, which is the more simple and economical, more stable, more powerful, and far less toxic RDX.

PHILOU Zrealone - 16-12-2014 at 10:27

Does someone here have the density of heptryl under hand, the experimental/real value?
Heptryl = (O2NOCH2)3C-N(NO2)-C6H2(NO2)3)

I'm making a lot of density calculations of tetryl, pentryl and heptryl related compounds ...but I need some real values to correlate and validate results.
So I will be able to present here probable datas for the previously exposed unknown molecules and more.

I have made calculations (additivity groups) for the density of heptryl and the method I use allows two possibilities...one at 1,81 g/ccm and the second one at 1,91 g/ccm.
So I need real data to find out which one is closer to the reality and extends the properties for unknown compounds.

[Edited on 17-12-2014 by PHILOU Zrealone]

Itchy - 14-4-2016 at 09:22

Hi
I have recently begun volunteering as a tour guide at an Ex MOD explosive manufacturing/research site just north of London which was the scene of a fatal accident involving the manufacture of tetryl, part of my tour goes past the remains of the building. I was hoping to be able to give a little more information on the cause of the accident at that point of the tour but unfortunately very little information seems to be available about it, i'm fairly sure it was hushed up at the time (70+ years ago) by the MOD and the people that worked there after are either not allowed to say wat happened, official secrets act and all that, or they just don't know or indeed both.
Anyway it is my understanding that tetryl is a intermediate explosive so, and i'm guessing here, not particularly shock sensitive. I'm kinda thinking it must have taken a little more than someone dropping some, but wat ?? The place was very static aware and there was obviously a naked flame ban. Any suggestions would be greatly appreciated.

PHILOU Zrealone - 14-4-2016 at 09:41

Quote: Originally posted by Itchy

Hi
I have recently begun volunteering as a tour guide at an Ex MOD explosive manufacturing/research site just north of London which was the scene of a fatal accident involving the manufacture of tetryl, part of my tour goes past the remains of the building. I was hoping to be able to give a little more information on the cause of the accident at that point of the tour but unfortunately very little information seems to be available about it, i'm fairly sure it was hushed up at the time (70+ years ago) by the MOD and the people that worked there after are either not allowed to say wat happened, official secrets act and all that, or they just don't know or indeed both.
Anyway it is my understanding that tetryl is a intermediate explosive so, and i'm guessing here, not particularly shock sensitive. I'm kinda thinking it must have taken a little more than someone dropping some, but wat ?? The place was very static aware and there was obviously a naked flame ban. Any suggestions would be greatly appreciated.

Tetryl is a final stage powerful explosive not an intermediate one.
It is quite sensitive to impact and is/was used in practice as secondary propagation (booster) charge of the detonator just prior the main charge. Sometimes it was used as main charge as mixture.
It is more powerful, brisant and sensitive than TNT.

Here are some datas from Explosives 4th ed by Rudolph Meyer and Josef Kholer:
Max density: 1.73 g/cm³ (vs 1.654 for TNT)
Sensitivity to impact 3 Nm (vs 15 Nm for TNT)
Deflagration point 185°C (vs 300°C for TNT)
Melting point 129.5°C (vs 80.8°C for TNT)
Lead block test expansion for 10g: 410 cm³ (vs 300 cm³ for TNT)
Velocity of detonation @ 1.71g/cm³ = 7570 m/s (vs 6900 m/s @1.60 g/cm³ for TNT)
Specific energy: 133 mt/kg (89 mt/kg for TNT)

In large quantities working with Tetryl is thus risky! The explosion might come from a fire, overheating, shock or runaway reaction during nitration process...

[Edited on 14-4-2016 by PHILOU Zrealone]

Itchy - 14-4-2016 at 10:11

Thank you.

So basically it could of been anyone of the usual suspects that set it off.

I think i may have misunderstood the information i was given about it, i assumed intermediate was the wording used for the explosive compound used between the detonator and the main charge.

The site was a big producer of cordite would i be right in thinking tetryl was sometimes mixed with cordite ?

Just looking for something interesting to say about it to the people on the tour really

PHILOU Zrealone - 15-4-2016 at 05:00

Quote: Originally posted by PHILOU Zrealone

Does someone here have infos on the following molecules somehow related to Tetryl?
I wasn't able to find those.

They stil must display interesting properties high densities and VOD but also, probably higher sensitivity to shock than Tetryl...

[bad img]http://imageshack.us/a/img221/1237/tetryl.jpg[/bad img]

1)Tetryl = 1-nitraminomethyl-2,4,6-trinitrobenzene
2) 1,3-bis-nitraminomethyl-2,4,6-trinitrobenzene
3) 1,3,5-tris-nitraminomethyl-2,4,6-trinitrobenzene
4) 1,3,5-tris-nitraminomethyl-2,4,6-triazine
5)?
6)?

For an unknown reason my picture has dissapeared from previous 2012 post.
So I post it again here.

PHILOU Zrealone - 15-4-2016 at 08:14

Quote: Originally posted by Itchy

Thank you.

So basically it could of been anyone of the usual suspects that set it off.

I think i may have misunderstood the information i was given about it, i assumed intermediate was the wording used for the explosive compound used between the detonator and the main charge.

The site was a big producer of cordite would i be right in thinking tetryl was sometimes mixed with cordite ?

Just looking for something interesting to say about it to the people on the tour really

Yes any of the usual suspects.

Cordite with tetryl mixture, I doubt it.
The manufactury plant was obviously busy with various receipts for various final uses...propellant, bombs, detonators, grenades...

Itchy - 16-4-2016 at 13:00

Quote: Originally posted by PHILOU Zrealone

Quote: Originally posted by Itchy

They didn't actually make any f the final products on site, just the explosives. Mostly cordite but also a few others on a smaller scale up until the early 1940's then from 1945 it was used as a research facility, the site became a visitor attraction after it closed in 1991.