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Kid Orgo
June 23rd, 2003, 02:07 AM
I was driving back from CT tonight thinking about AP.

If the trimeric form is more desirable because it is both more powerful and more stable, would it be worthwhile to purify an obtained mix of dimer and trimer? I'm assuming one could seperate the two by dissolving them in a solvent and using the freezing point difference, or any of the established methods of seperating two organic compounds.

The perfectionist in me would want my first dreams of illicit synthesis to be perfect, with testable purity.

grendel23
June 23rd, 2003, 02:56 AM
If your goal were stability and performance, AP would not be my first choice, but if you want the most stable isomer of AP, you can use tin chloride, SnCl4 as a catalyst to produce tetrameric AP.
I have only dreamed up trimeric myself, but I have a PDF of a paper published in the Journal of Chemical Research describing its preparation. If anyone is interested, I could post it.
I don’t remember where I got this PDF; it may have been from a member’s website, if so I apologize for not giving attribution.

nbk2000
June 23rd, 2003, 03:59 AM
Being isomers of the same chemical, and having essentially similar physical properties, it'd be VERY difficult to seperate di- from tri-.

It'd be much simplier to just make your batch while cooling it as much as possible to ensure the production of only the trimeric form in the first place.

THErAPIST
June 23rd, 2003, 04:43 AM
I've actually made both dimeric and trimeric and there didn't appear to be much if any difference at all. I usually make AP by mixing in small amounts with cold H2O2, cold acetone, and cold HCL but I wanted to see what the difference was once. I put 50ml of acetone in a 500 ml beaker with 50ml of 34% HCL. I next added 100ml of 24% H2O2 all at once, stirred if for a couple seconds, and then I ran away. I put the beaker in a bucket that had about 3 inches of water in it (which wasn't even cold) in case it boiled over or anything. I stood a ways away watching it for about 10 minutes, It didn't run away so I gave it another 20 minutes and then I walked over to it. The beaker looked like it had almost no liquid in it anymore and it looked like all I had was AP. I touched the beaker and found that it was REALLY warm (more like hot). I filtered, washed, and dried the AP, and then looked at it a good bit. the crystals were no smaller than if they were made in the freezer. I hit some with a hammer... I had to hit it just as hard as I had to hit the AP that I made in the freezer. (I had also made a batch in the freezer a couple days before so that I could test this). The products appeared to be the same thing. I had alwasy been under the impression that if AP had been made at even slightly warm temperatures I would get the much less stable and less powerful form... Anyone seen the pics of the mini AP shaped charges that were made to test the mini EFP device with pennies thats in the water cooler? The supposedly less powerful AP was used in those charges... A half gram of it threw the metal backing 176 feet and 9 inches down the road... The flight of the metal backing was parallel with the road too. the board the charge was set on was set 90º to the ground..

Kid Orgo
June 23rd, 2003, 01:43 PM
Tetrameric AP? What are the properties? Has anyone ever dreamed of that before?

NBK: I thought that since the trimeric contains an additional bit of acetone peroxide that it'd have a different molecular weight, and so on.

Grendel: Yes, i'd like to see that pdf a lot.

IPN
June 23rd, 2003, 02:09 PM
Has anyone ever dreamed of that before?

I'm not sure but the reason it isn't in wide use is probably because getting pure tin isn't easy and making tin tetrachloride (clear liquid, melting point -33C, boiling point 115C) is even more difficult.
And I don't think there is much of a difference between trimeric and tetrameric acetone peroxide.
I would try it out but I cant get pure tin anywhere.. (Well I could order it from Acros but it costs 16€ per 100g)

Mr Cool
June 23rd, 2003, 03:02 PM
Lead-free solder: 95% Sn, 5% Sb. Not pure, but close.

megalomania
June 23rd, 2003, 10:39 PM
You have broached a very interesting topic, VoD. The greater sensitivity and decreased detonation velocity of the dimmer is not so egregious to the improvisational experimenter. Indeed most amateurs would probably desire increased yields over the safety factor. I suppose as long as the dimmer product is immediately disposed of (utilized), the increased safety of the trimer would not be paramount. That you have offhandedly noticed an increase in yield leads me to believe there is a vast difference. Tel me, have you actually measured your product, or is your observation speculative?

nbk2000
June 24th, 2003, 01:01 AM
VoD is no longer among us, having also been ElectricJesus, and one person can't have two identities here.

grendel23
June 24th, 2003, 07:06 AM
Kid Orgo, here is the url for that PDF, you need to paste it into your browser.
http://www.geocities.com/sulfuric23/tetrameric_AP.pdf
I have been told you can disolve tin in HCl, and boil off the liquid to obtain SnCl4. I have not tried that myself.
grendel

Mr Cool
June 24th, 2003, 08:37 AM
That will make hydrated SnCl2, but IIRC that works too, although not as effectively. You'd have to read the .pdf to find out, because I can't be bothered to check right now...
SnCl4 needs hot tin and dry chlorine, and you condense and collect the SnCl4 vapours. Dry HCl might work too, I think, instead of chlorine. Even if the hydrated SnCl2 is not as effective, if it works then I'd use that instead since it's so much easier to make.

megalomania
June 24th, 2003, 03:14 PM
From what you have just described Mr Cool, the process of making SnCl4 sounds exactly like the method I have on my website for making aluminum chloride. Chlorine gas is passed over a heated tube filled with aluminum turnings. Aluminum chloride is collected in a flask, and that's about it. Chemically Sn is quite simlar, which leads me to believe the reaction is similar.

frogfot
June 24th, 2003, 04:53 PM
Yp, my chem book tells this too. Sn is heated in a rounbottomed flask to 250-280*C and a stream of dry chlorine is directed on it. Formed SnCl4 goes to condencer. Problem would be to get rid of excess Cl2...

Following anhydrous chlorides can be made this way too: FeCl3, AlCl3, CdCl2, ZnCl2. Could any of those show catalytical properties for tetra-AP?

megalomania
June 25th, 2003, 05:18 PM
Actually my procedure for aluminum chloride uses hydrogen chloride gas, not chlorine. Although I do think chlorine will work, I don't think it works as well. The chloride product should condense quite nicely in a chilled flask, excess chlorine will continue and should be vented through a long hose. Hydrogen chloride gas can be bubbled into water and recycled as hydrochloric acid.

Actually with chlorine gas I have devised a creative setup to recirculate the gas through the system. I have a small $5 fish pump that does a pretty good job of circulating air around. This could be set inside a sealed wood or plastic box, like a tupperware box, with a hole drilled at one end for the gas tube and another for the cord. This box is then sealed. Another hole allows for chlorine to enter from a chlorine generater. The exit gas from the reaction can be passed back into the generator, and into box where it is picked up by the pump and sent through again. I am sure this is not good for the pump, but for the price it seems like a good idea.

I am archiving that PDF file here:

metal dragon
August 16th, 2003, 08:18 PM
Hello,
The rapist said that when he made AP with out any temp control, it got really hot. I was thinking that it could actually increase yields or the time it takes to form. Here’s how, 24% H2O2 contains 76% water so as the reaction is hot the water should be evaporate at fast rate so as this happening the H2O2 is slowly concentrating. Would this happen?
There is however bad side to heating it the acetone would evaporate but this could easily be countered by the addition more acetone. If it has no sensitivity issues according to rapist and shockwave so why isn’t it more widely used? Sure VOD is an issue but instead of 0.5 grams you use 0.6 grams problem solved.

Thanks

Desmikes
August 17th, 2003, 01:03 AM
Dragon whatever you said made absolutely no sense however I do agree that when you need a detonator quick then you can resort to making AP with a lot of acid.

Nevermore
August 17th, 2003, 05:46 PM
Originally posted by metal dragon
Hello,
The rapist said that when he made AP with out any temp control, it got really hot. I was thinking that it could actually increase yields or the time it takes to form. Here’s how, 24% H2O2 contains 76% water so as the reaction is hot the water should be evaporate at fast rate so as this happening the H2O2 is slowly concentrating. Would this happen?
There is however bad side to heating it the acetone would evaporate but this could easily be countered by the addition more acetone. If it has no sensitivity issues according to rapist and shockwave so why isn’t it more widely used? Sure VOD is an issue but instead of 0.5 grams you use 0.6 grams problem solved.

Thanks

Well, i must say that this looks very dangerous, VOD is not an issue in this case, safety is. Dimeric acetone is more unstable than trimeric one, considering how instable is the trimeric already i do not see the point of increasing the danger of handling such compound.
Anyway, that's true, mixing acetone and H2O2 get really hot, operating w/o a temperature control could led to dimeric peroxide mainly that is what we DON'T want, of course, the reaction will be lot faster when hot, but, really, i don't see the point.
AP is a dangerous compound, no need to make it even more dangerous unless you have spare fingers.

nbk2000
August 17th, 2003, 08:42 PM
Don't use the quotes function to quote an entire post. :rolleyes:

It's only for specific lines or passages. Be selective. :)

me234
August 18th, 2006, 08:02 AM
OK, I'm in a rush so I'm buggered if I can find a more appropriate thread to put this in, so here goes:

A while ago I got the IR spectrum of AP and put it in the "Holy Grail Peroxide" thread and someone suggested that an NMR would be better, so here you have it, the proton NMR of (mostly) trimeric acetone peroxide run in CDCl3. And as no big surprise to those who know a bit about NMR's, one giant -CH3 peak, and a bit of junk.

The line list for the spectrum's main peaks is as follows (along with my suggestions about what they are/should/ might be):

PPM possibility

7.261 Chloroform peak (7.250 = theoretical chemical shift)
1.567 Junk/maybe dimeric AP -CH3 peaks (doubtful though)
1.459 -CH3 peak trimeric AP
1.444 More junk

If people really want it (and I can get up the nerve) I suppose mostly dimeric AP could be run.

Besides that, is there anything else people really want the NMR of (something easy that I can get hold of, like, I can maybe get a touch MHN, or I could do some HMTD etc.)

FUTI
August 18th, 2006, 10:28 AM
me234 did you try to run NMR of your sample at different dillution/concentration. If some of those peaks change position it can be some strayed HO-. Water or maybe open form product, hydroperoxyde etc.? Did you find spectrum of H2O2 or t-Bu-OOH to compare?