Sciencemadness Discussion Board - Diphoronepentaperoxide (DPPP)

Diphoronepentaperoxide (DPPP)

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Rosco Bodine - 6-1-2005 at 11:24

In a test of my "scorched" precursor , I added 30 ml acetone and swirled the mixture . Within 5 minutes the color has deepened to a purer tint and the mixture is forming the bright yellow film similarly as was observed in the first experiment .
The indication is that the ratio of acetone to HCl is important . Very unusal to "thin" a mixture with acetone and observe a viscosity *increase* but that is exactly what it appears to do . Anyway , I am wondering whether to ditch this batch and adjust quantities , or try to peroxidize it . I am trying to get a repeatable process worked out with no snags like this to complicate matters .
Aside from the unknown effect of the bit of peroxide I added , the HCl amount seems to contradict j-scan's 2 to 3 volume amounts for acetone to HCl . What adjustments or refinements if any have you found useful during the batches you have completed ?

Ok, hope my math is right, OB =

Mickhael - 6-1-2005 at 13:47

Early on in this threat it was suggested that its hexa, not penta, and I haven't heard that disproved...so:

Diphoronhexaperoxide's OB = -255% O2. As far as I can tell from counting the mol's of the C, H and O2.

What do you all think? Pretty deficient for its power...how does that work?

chemoleo - 6-1-2005 at 14:37

I think not too many pages back, someone tried to make the peroxide with Sigma phorone , and this didn't seemingly work.
Thus it seems possible, if not likely, that pure phorone on its own is not a suitable substrate for peroxidation.
Also, I'd assume that the chloro derivative of phorone is more reactive than phorone on its own.

Dodoman - 6-1-2005 at 15:28

Quote:

Originally posted by chemoleo
I think not too many pages back, someone tried to make the peroxide with Sigma phorone , and this didn't seemingly work.
Thus it seems possible, if not likely, that pure phorone on its own is not a suitable substrate for peroxidation.
Also, I'd assume that the chloro derivative of phorone is more reactive than phorone on its own.

Which I think is in favor of my reactions

. I don't think that these reactions are correct anyway but they seem as a possiblity never the less.

I think the key to understanding the reaction is analysis of that black oil. And I shall do that when I have the time. I think spectral analysis using NMR, UV and IR should do the trick

.

I'll try to make friends with professors at my universty which could probably help me with this. BUT NOT BEFORE I FINISH MY EXAMS. Which is in 10 days

Rosco Bodine - 6-1-2005 at 16:19

The "black oil" which accumulates as an upper layer during a long heating of the acetone and HCl mixture actually only looks black against the dark red lower layer . When separated , it is a brownish yellow resinous material which leaves a light tan colored stain on white paper towel . It is extremely adhesive in nature and has an odor and other properties something like a vegetable oil which has been partially polymerized from overheating and then gells upon cooling .
It is insoluble in alcohol , but dissolves readily in acetone . I believe the composition is predominately phorone with some impurity of triacetone dialcohol and higher acetone polymers . The material would seem to make an excellent component for paints and glues . It sticks to glass tenaciously like urethane or epoxy resin , really gummy stuff , and in thin layers exposed to air it gradually hardens much the same way as does linseed oil .

Chris The Great - 6-1-2005 at 17:16

I remember getting in the -155% range for it's O/B, I think. I remember that it was within a few % of APs O/B.

I is more powerful because it releases it's energy much faster than AP.

great now we can try and undo all our work. BUT!!

Matsumoto_Hideki - 6-1-2005 at 17:59

Hey guys have you checked on the Organic sytheses site for phorone production?
look at this http://www.orgsyn.org/orgsyn/chemname.asp?nameID=33576

quote:
There are two general methods for the preparation of mesityl oxide: the action of condensing agents (hydrochloric acid, etc.) on acetone, 1 and the dehydration of diacetone alcohol. 2 The action of acid condensing agents is very unsatisfactory; the yields are poor and considerable quantities of **phorone and similar substances** are invariably produced.
this other substance this person was reffering to is Phorone HCl?

[Edited on 7-1-2005 by Matsumoto_Hideki]

Rosco Bodine - 6-1-2005 at 19:43

Organic Syntheses has a primitive idea about hydrazine sulfate synthesis too .
They should really update some of their labs

But yeah if you keep cooking the stew . so to speak , the stew being the acetone and HCl mixture , that upper layer that separates is likely chock full of phorone , if phorone is what you want . Of course that needs to be confirmed for certainty .

Anyway I have a clean batch of acetone and HCl reacting , in which I made a far less excess acidity than the earlier batch that I think I scorched with too much acid .
I remembered when I was observing the first sealed bottle experiment that I had the idea that this reaction is pH sensitive , so I tried to measure very carefully the acetone and HCl to achieve
just a 3% excess of theory of HCl to acetone . The results are distinctly superior in terms of color development and the purity of the color is striking at
3 1/2 hours . The color is that of "ruby glass" pure red , brilliant red , not any "tea color" to this batch . I have a good feeling about this ratio just based on
the clarity and depth of color . If nothing else it is pretty . What I used was exactly
112 ml acetone and exactly 105 ml HCl 31.45% , mixed and allowed to stand in a sealed bottle for 1 1/2 hours without supplemental heating , and then heated for 2 hours still in the sealed bottle , in a 75 C water bath . I have removed it from the bath , and am allowing it to cool and stand overnight .

I must say that quite different reaction rates and color developments are being observed with small changes in the acetone to HCl proportions , so obviously
some exactness is needed about these
measurements and reaction times and temperatures . And then when to proceed with the peroxidation and at what rate and temperature and other conditions are important also . This synthesis is not one which is likely to work across a wide range of conditions ,
as is the synthesis of regular AP . So please , those of you who are having success make careful and detailed notes of what you are doing and what you are getting out the other end as yields .

Ok, my first official DPPP (or is it DPHP?)

Mickhael - 6-1-2005 at 22:55

Alright well I to do not believe that the top filmy layer has anything to do with forming the peroxide, here are my results and why I think that:

To 100ml of chilled to -15 "black stuff" I slowly added 200ml almost exactly of h2o2, by the time I had added a third of my h2o2, the tempature had risen from -15 to +5! So I stopped adding, and left the mixture in the freezer for about a half hour, when i came back, the "liquid" had turned into a solid mass of yellow crystals, however there was chunks of black film, which seems to slowly harden, still in the mix, and no matter how much I mixed it (hand stirred) the film never seemed to break up and just stayed in little dark flakes/chunks, I then slowly added the rest of the h2o2, I don't know how many more crystals formed, but when I was done, I left it for another half hour to make sure things were done percipatating, the container was still pretty much stuffed with crystals, I'd say at least a 90% batch, I then dumped the whole thing slowly into another larger glass container filled with bi-carb, I think I lost some product here, it became all foamy and filled with air bubbles, I then strained and washed several times with fresh water (through a coffee filter) and now i've spread it out on newspaper to dry, I'd say I have about a half cup of solid crystals if they were packed tight, I haven't weighed yet, since obviously they are not dry

...So, all in all a pretty good turnout!

Quick question however, since this is my first high explosive...and only second batch of crystal peroxide: I have it drying on newspaper, how safe will it be to collect after its dry? and how can I get it into another container without scraping it at all? I want to mix it instantly with MEKP...but I also want to be able to move it around safely, any suggestions so i don't kill myself with this stuff. For its power, I probly have enough sitting beside me to destroy the room I'm sitting in....Eeep!

[Edited on 7-1-2005 by Mickhael]

Pyroz - 6-1-2005 at 23:27

There are many variables that we cannot be sure about until we do further testing.

My questions that I'd like answered: i keep harping on:

•is real DPPP yellow or is that unreacted material mixed in with DPPP.
•while the power of this substance is substantly more powerful than AP or MEKP/AN what is the yellow materials true VoD?
•how much more powerful would DPHP (hexaperoxide) than DPPP(pentaperoxide)?

Dodoman - 7-1-2005 at 03:24

Quote:

Originally posted by Pyroz
•is real DPPP yellow or is that unreacted material mixed in with DPPP.

I think that's its color because when you wash it with water its color doesn't change. This means that if there are any imuprities at least they are not water soluble.

You can try recrystalizing it from acetone. I don't think that's a good idea though Because if its similar to AP (forming diffrent isomers at diffrent tempretures) then that would be a problem regarding both the physical properties of the product (color and stuff) and also senstivity.

Rosco Bodine - 7-1-2005 at 03:44

The color of the still wet DPPP which I am getting is a light yellowish tan . The shade is about the same color as the default color scheme for every other message posted here on this page , the background color .

Many more experiments will be required before these ideas can be regarded
as conclusive findings about the synthesis of DPPP , however I am willing to
share some early observations so that others may do their own tests
to see if these ideas square with their own results .

First of all the molar ratio of HCl to acetone is important , as is the time and
temperature they are reacted before the peroxidation . It is the soluble or
finely dispersed portion of that digested acetone HCl mixture which will be
reactive with the peroxide . The resins or oils which may precipitate represent
a loss of precursor and should be filtered before peroxidation using a double
thicknes of coffee filter wetted with water before filtration . There isn't much
of anything to be gained by excessive temperatures or extended hours of heating
the acetone and HCl to the point it becomes so dark as to contain suspended
or separated resinous precipitate . Such "black oily" material will not be converted
to DPPP , but will only precipitate as clumps of sticky insoluble goo contaminating
the more and more aqueous peroxidation mixture . This is why filtering before
peroxidation is a good strategy for removing the bulk of such suspended material.
Molar ratio of HCl to acetone should be 2 to 3 , with only very slight excess of theory
for the HCl on the order of 3 % seems in the ballpark . Using more HCl or heating
the mix too high or too long causes resinous insoluble products to precipitate and this
should be avoided to the extent possible . Exact optimums for ratio and times have not been yet determined so this can be an area for close measurement and comparison of
results .

The greatest exotherm during the peroxidation occurs during the addition of the first
10 to 15% of the total peroxide to be added . This initial peroxidation should be done
with efficient stirring and slow , even dropwise addition of the peroxide . I have used no
cooling during this initial addition , or only a shallow plain water bath , and allow the
stirred mixture to heat up from the exotherm to about 65 C . The addition of peroxide
is stopped and then ice is added to the bath to cool down the mixture to 10 C , the stirring
being continued the entire time , and then addition of the peroxide resumed more rapidly
at such a rate as to maintain about 15 C to the end of the addition . The stirring is continued for thirty minutes after the end of the addition and stopped . The crystals
will form a floating raft , from adherent bubbles of oxygen which make them buoyant and
may be skimmed from the surface using a plastic spoon and transferred to the filter .
The crystals should be rinsed on the filter , and neutralized with only dilute alkali . Strong
ammonia will decompose the DPPP . The material is very aromatic and the vapor is irritating
and perhaps intoxicating , and should not be considered harmless until more is known .

[Edited on 7-1-2005 by Rosco Bodine]

Pyroz - 7-1-2005 at 10:58

Rosco that jives with what i have experienced

[Edited on 7-1-2005 by Pyroz]

Rosco Bodine - 7-1-2005 at 13:59

Great to have confirmation on those things . The major points of the synthesis
are now known , and all that remains really are the tweaks and refinements
that are likely to be discovered from many
experiments . This whole thread will probably be reduced to a few paragraphs
on one page when the optimized synthesis tried and true is set down in
its finished details . I was looking back
at this thread and it is like a 200 plus page transcript if printed . This has been one
BIG ASS SCIENCE EXPERIMENT

Somebody ought to drop an e-mail to BASF , aka Hoffman LaRoche who started the thread and see if he has
been aware of the recent developments since the mid December post by Dr. Boom
which breathed new interest into these DPPP experiments .

Where is Dr. Boom exactly anyway ?

I sort of have this mental picture of
Dr. Boom having catnapped Mackowiak's
kitty , and then a call is made to Wolfgang
saying
" Okay listen up professor , we have your cat and it is okay for now anyway . So give up all the lab notebooks and the patent dossier ,
or else the cat gets it "

Dr.Boom returns as a re-incarnate

Matsumoto_Hideki - 7-1-2005 at 14:16

Well I will tell you Pyroz is Dr.Boom
Pyroz has many cats and trhey are all fucked up from DPPP vapours some are even some bristle with their own electric current. unfortnate no German wolfgang cats though. ie) none that could lend a paw to your experiments anyway.

?

Mickhael - 7-1-2005 at 20:36

Just wondering, how long does it usually take to dry peroxide crystals? I've had the DPPP sat out in a 70f room for 24 hours now, and it seems quite dry, however a test proved it to not make a very loud bang, so obviously its not dry, whats the usual number of days before dryness reaches its max?

Pyroz - 7-1-2005 at 21:25

Quote:

Originally posted by Mickhael
Just wondering, how long does it usually take to dry peroxide crystals? I've had the DPPP sat out in a 70f room for 24 hours now, and it seems quite dry, however a test proved it to not make a very loud bang, so obviously its not dry, whats the usual number of days before dryness reaches its max?

Even slightly damp DPPP will explode with considerable energy. What did you pack the material into? Was it compressed tightly or was it in loose form? You my wish to try the rifle shell casing test and make a blasting cap from it!

[Edited on 8-1-2005 by Pyroz]

Mickhael - 7-1-2005 at 21:58

Quote:

All I did was put about a 1/2g into a film container (yes it was loose) and stick a fuse into it, with a little papertowel to hold it in the bottom, it made a sharp crack, but nowhere near the noise the same amount of MEKP makes...which led me to believe it needs quite a bit of drying still.

I take it from your compression question, that compressing it helps alot? I'm hoping to mix it 50/50 with MEKP and test that shortly.

I unfortunatly do not have access to any rifle casings, strange as that may sound, rifles are pretty uncommon around me, so unless I could get to a range...or find someone who has them, I'm out of luck.

Do you have any idea what would happen if I put some slightly damp DPPP into MEKP? would it desolve the crystals and seperate the water out?

The_Davster - 7-1-2005 at 21:58

Rosco, I tried a slight variation on your method of reacting the HCl and acetone. 26mL of HCl and 28mL of acetone were mixed at room temp (18C) in a 250mL flask. The flask was outfitted with a 2 hole stopper with a thermomehter in one hole and in the other hole was a 3' lenght of glass tubing. Upon mixing the HCl and acetone in the flask the temperature shot up to 36C. THis was allowed to sit at room temperature for 1.5h, at the end of which the solution was only very slightly yellow. Still mostly clear. What color was your solution after sitting at room temp for 1.5h, Rosco? This flask was transfered to a hot water bath. Since I was doing this outside and had set up the bath earlier when the flask was put in the bath the temp of the flask dropped to 15C. over a period of 20min the temp of the hotplate was adjusted to end up with a fairly constant temperature of 60-63C. Acetone condensing was noticed at around 60C in the piece of glass tubing. The acetone stopped condensing after around 20 min. Total heating time was just under 2.5h( 30 min @ 55-65C +2h@60-63C). After this time The solution was an incredible deep red, like you Rosco, no tea like color. If one swirls the flask the residue on the flask walls appear deep yellow. There was a very slight slick of oily substance on the surface.

When peroxidizing this what is a good temp to keep it at maximum? I think I will try 0C or 10C. Any ideas?

Mickhael - 7-1-2005 at 22:02

Quote:

When peroxidizing this what is a good temp to keep it at maximum? I think I will try 0C or 10C. Any ideas?

Just for the record, I peroxidized mine at -15c, and it seemed to have a perfectly good yeild *shrugs* maybe it could be better, but the container seemed packed with crystals.

Pyroz - 7-1-2005 at 22:16

thats how you do it! Low temperature synth seems to do fine.

Hum hhuuum, excuse me but !

Matsumoto_Hideki - 7-1-2005 at 23:59

Pyroz, I have to admit damp DPPP will explode but not anything like when it is dry. When I compress it I always moisten it with pure distilled water but that water (slight moisture) is expelled when I compress my caps or explosive devices... I would recccomend anyone useing large amounts of DPPP in metal containers to give a good solid coat of urathane to the inside of your device to prevent any sensitization by any AP impurties. I would hate to see what a 150g - 250g shaped charge could do to a person if it prematurely detonated while you were holding it!
A FUCKING MESS!

froot - 8-1-2005 at 00:14

After browsing this wickedly immense thread I cannot seem to find any confirmed info on the sensitivity and storage stability of the products being made here. It has been mentioned that it gives off an odour which indicates that it probably decomposes during storage like most other org. peroxides. Good storage stability was mentioned in the original patent,-hmmmm.

Shouldn't you folks be making this 'relatively untested and therefore mysterious' explosive substance in much smaller sample quantities????????
Im sure nobody here wants to have to type their posts using a pen in his mouth.

Otherwise good work so far.

Well to answer your question

Matsumoto_Hideki - 8-1-2005 at 00:54

Actually it does store well over long periods of time and is stable at room temperature. I have even taken this material to 70c without it subliming or decomposing. By the way the smell does fade after a while.
If you take DPPP up to 170-200c you risk detonation and or if you were to hit it hard with a hammer on concrete about 30-40lbs of force. I am still investigating DPPP's sensitivity to metals ie) copper.. and alloys like brass. So far brass will not sensitize DPPP as I have discovered in making many blasting caps with it. Still I am careful while loading..

So far nothing much to report... still determining this thought.

Smarten up man!

Joeychemist - 8-1-2005 at 05:23

It does react with brass, and copper and every other metal I have tested it on. Don’t you think you should actually do both short and long term tests in order to see if it reacts with metals before you go telling people it is ok, Christ man! What if it’s going to ignite after a moth or two of being “seemingly dormant” and kill a kid that read you’re post saying that it’s perfectly fine to store DPPP in brass for a month or two?

Hideki you really need to stop making all these assumptions before someone (YOU) gets hurt. I mean fuck man. It’s bad enough that you’re making hundreds of grams of a *PRIMARY* explosive. But to do so with out the proper knowledge is *STUPID, NEGLEGENT, and IMMATURE*

You ask anyone here if they have ever made that much of a primary explosive of which they know *NOTHING* about and see what they’re answer is.
Before you hurt yourself or even worse someone else, slow the fuck down and smarten up PLEASE.

Rosco Bodine - 8-1-2005 at 05:51

Quote:

Originally posted by rogue chemist
Rosco, I tried a slight variation on your method of reacting the HCl and acetone. 26mL of HCl and 28mL of acetone were mixed at room temp (18C) in a 250mL flask. The flask was outfitted with a 2 hole stopper with a thermomehter in one hole and in the other hole was a 3' lenght of glass tubing. Upon mixing the HCl and acetone in the flask the temperature shot up to 36C. THis was allowed to sit at room temperature for 1.5h, at the end of which the solution was only very slightly yellow. Still mostly clear. What color was your solution after sitting at room temp for 1.5h, Rosco?

That is the same color I saw . The size of the batch is going to cause variations in the color development because of the difference in conservation or radiation of the exotherm from the self-heating . A bigger batch would tend to develop a higher temperature and react for a longer time from its own heat of reaction . The idea is simply to let the solution self-heat from its own reaction , and when that self-heating diminishes to add gentle supplemental heating to sustain the reaction until the color is fully developed to that intense deep ruby red color that sheets into a bright yellow film when it is swirled against the walls where a thin layer can be observed . There can be exceptions , but often it is true that such an intense coloration is an indication of a high concentration of a particular compound , so this was thought to be a likely visual indicator as a "marker" for the reaction point where there is substantially a single product in solution , hopefully the desired precursor . Experiments will show what is the exact point of color development which provides best yields , but my guess is that this intense coloration is very close to that point if not perfect .

Quote:

This flask was transfered to a hot water bath. Since I was doing this outside and had set up the bath earlier when the flask was put in the bath the temp of the flask dropped to 15C. over a period of 20min the temp of the hotplate was adjusted to end up with a fairly constant temperature of 60-63C. Acetone condensing was noticed at around 60C in the piece of glass tubing. The acetone stopped condensing after around 20 min. Total heating time was just under 2.5h( 30 min @ 55-65C +2h@60-63C). After this time The solution was an incredible deep red, like you Rosco, no tea like color. If one swirls the flask the residue on the flask walls appear deep yellow. There was a very slight slick of oily substance on the surface.

Your description matches what I saw . After removing from the heat , I allowed my mixture to stand overnight at about 15 C and then refrigerated it . I
wanted to observe how much further the reaction would go over the next few hours without heating , to get an idea how close the timing of the peroxidation
needs to be . It appears that the further reaction of the acetone and HCl slows down greatly once removed from the gentle heating of even a couple of hours ,
following the initial self-heating , and the reaction virtually stops altogether when the mixture is refrigerated . This is good
because it allows for "taking a break" from the experiment or starting one batch of precursor and keeping it refrigerated to
resume the reaction later , being able to simply watch for and use the color development as an indicator of the reaction progress .

Quote:

When peroxidizing this what is a good temp to keep it at maximum? I think I will try 0C or 10C. Any ideas?

It depends on what method of stirring and how closely you control the addition rate of peroxide , what is your strategy . I don't know what is the ideal so I just made a guess as to how I should proceed . I haven't yet peroxidized the
same mixture as we are discussing here .
My strategy will be to add 2 or 3 ml of HCl to the stirred precursor , in a container
sitting in a not yet filled water bath , and then to add by drops the peroxide , while
allowing the stirred mixture to heat up
slowly from its own exotherm , controlling
the heating by rate of addition to a peak of about 65 C , when about 10% of the
peroxide should have been added . Then
I would add the ice to the bath and allow the temperature in the stirred mixture to fall to 10 C before resuming addition of the peroxide at such a rate as to not exceed 15 C for the mixture to the end of the addition , continuing the stirring for 30 minutes past the end of the addition .
The stirring is stopped and the suspended
crystals clump together in suspension looking similar to curdled milk which is not
yet separated into layers . After standing
the crystals should rise to the top as a floating raft . I simply dumped the entire
mixture into its melted cooling bath and then skimmed the crystals after a partial neutralization of the bath with the calculated amount of ammonia water .
You need to calculate the neutralization equivalent because any great excess will start to decompose the DPPP . If you go to far with the ammonia , vinegar seems to be good for bringing the pH back to slight acidity . The crystals skimmed from the top are rinsed on the filter with distilled water .

P.S. This is an interesting material , but I know already that its deficiency is going to be its odor and its irritating vapor . This shit absolutely reeks of a capsacin like vapor which irritates the eyes , and generally fucks up your sense of smell and taste for a day after being near the stuff . It is for damn certain physiologically active . Sprinkle some DPPP around any shrubbery you don't want dogs to frequent as a place to pee and you can be guaranteed they will get the message ! This stuff would make a better fumigant than formaldehyde . It
first seems to have a sort of "light" odor
until you are near it for awhile and realize that it literally permeates everything . I personally don't like the odor of the stuff so my own experiments will be dutifully scientific , but there will likely be no long term fascination with DPPP for me simply because of its disagreeable damn shitty odor . It's in the same category with methylene chloride and formaldehyde and
some other unpleasant materials . So that is going to diminish interest in the material .

[Edited on 8-1-2005 by Rosco Bodine]

that sqaures with me

Joeychemist - 8-1-2005 at 08:16

Ok, it sounds as if every ones stories are squaring up pretty close, I agree with all of the above and will second that.

Rosco, you're right, this stuffs smell is by far its least appealing quality. Have you tested the product yet???Hmmm..???

Rosco Bodine - 8-1-2005 at 08:51

Other than to light off a small amount that was a residue on some still damp filter paper , I haven't fired any of the stuff . The damp material did flash quite
energetically with the usual AP whoomp and a little bit of snap crackle pop included that was interesting

Chloramine could be what is causing the trouble with these reactions where ammonia is used for the neutralizer .
I'm going to use a basic sodium salt
next time and see if a lot of the "mysterious" irritant vapor will happily
not be a problem .

I wish

Joeychemist - 8-1-2005 at 09:01

Sadly to say I don't think that there is a way to fully get rid of that awful odor.

I can tell you that I have used ample sodium bi-carb and ammonia to wash this stuff and nothing, the smell still remains and I still cry every time I get too close. The last batch I had was about 4 days ago and it still stinks in my laundry room still stinks of it.

The metal witness plates I used also still stinks of the DPPP smell too. Fucking fowl.

Rosco Bodine - 8-1-2005 at 09:05

So are you saying the eye and nose stinging "mace" like vapor is present even if you don't use any ammonia at all , but
neutralize with soda instead ?

that's what I'm saying

Joeychemist - 8-1-2005 at 09:18

Yeah, that's what I’m saying

I washed this stuff under countless portions of water and sodium bi-carb and it would still irritate my eyes and mucus glands and make me dizzy if I was around it too much.

I also tried washing one batch with both ammonia then the bi-carb and there was no noticeable change in the odor or the manner in which I was affected by it.

I really firmly believe that this stuff is dangerous and slightly if not very toxic. I think I'm going to go to the pet store and buy some rats to test some things out. I wonder what the LD.50 for a rat would be?

Rosco Bodine - 8-1-2005 at 09:22

You know that's exactly what I was thinking is that DPPP may be a better poison than it is an explosive , and I plan
to introduce some ant mounds to the
saved filtrate to see how well they like it

The smell of DPPP has an uncanny similarity to some strong insecticide odors
like chlorodane or the fungicide orthenex .
In fact I have wondered if perhaps some
chlorinated byproduct may be responsible for the odor and effects , or if perhaps the
DPPP itself may not be accurately described by the patent , and there may
perhaps be a chlorine somewhere on the molecule .

I wonder if urea would have any reaction with DPPP or would be of any value in the rinsing .

[Edited on 8-1-2005 by Rosco Bodine]

Pyroz - 8-1-2005 at 09:44

I too had a serious problem with the smell. So I washed the DPPP crystals in pure water w/ bicarbonate (I tried sodium hydroxide and water and that does seem to work well too)--- and then I allowed DPPP to air dry inside of a plastic bag filled with bicarbonate in a plastic container.

After 1 week the smell was less noticable when the product was fully dry. Right now DPPP product that I have made does not smell that much--- its much weaker like mildly acidic Camphenol.

Is DPPP toxic?--- likely it is a very mild poison--- I doubt it could be used as a poison. It isn;t really corrosive either if you get it on your skin like AP does nor does it seem to form metal peroxides with copper or most other metals--- fairly intert i think.

In fact I have wondered if perhaps some
chlorinated byproduct may be responsible for the odor and effects...

I have often wondered this myself--- it seems that the left over liquid in the DPPP product maybe resposable for causing the acidic smell.

[Edited on 8-1-2005 by Pyroz]

Wait a second!

Joeychemist - 8-1-2005 at 10:09

You may be onto something there pyroz.

There is air indeed trapped inside these crystals (that’s why they float) so there may indeed be chlorine or something becoming trapped in these crystals as they are forming. I think I’m going to go buy some more desiccant and see if I can drive all the moisture out after I recrystallize in acetone. This could also explain the crackling when it is burned.

[Edited on 8-1-2005 by Joeychemist]

Crackling when it burns? really?

Matsumoto_Hideki - 8-1-2005 at 10:34

I haven't noticed this when DPPP is fully dry!
I was also wondering if a small amount of chlorinated product was leftover, and I think I know what it might be "chloroxylitol" ? what ever the substance is, it is a waxy gummy yellowish material and you will see it during your peroxidation sticking to the sides of the container. This makes up the majority of the smell.

[Edited on 8-1-2005 by Matsumoto_Hideki]

Rosco Bodine - 8-1-2005 at 11:01

A urea solution rinse still seems like a good idea to me . Urea can complex
both chlorine and hydrogen peroxide .

But one of the first things I want try with
the fully dried DPPP is to make some putty .

A good binder syrup is 20 grams of Bullseye pistol powder allowed to gelatinize on long standing with 60 ml acetone in a sealed bottle . For AP putty
about 1.5 to 1.75 parts by weight of the binder syrup to 1 part AP , mixed well
with a popsicle stick on a baggie seems
about right . The partially dried material can be shaped and then hardens into a rigid mass as the residual solvent evaporates after a couple of days . But the AP putty , while powerful , doesn't really have the brisance
to make a good detonating composition and is more of a very noisy novelty than anything else . It seems almost , but not quite quick enough as a detonator charge . So I am curious as to how DPPP might perform if substituted for AP in such a putty . Maybe a DPPP putty would be a more useful composition .

Pyroz - 8-1-2005 at 12:47

Quote:

Originally posted by Joeychemist
You may be onto something there pyroz.

The DPPP that I made sinks like a stone in water. So it is quite dense. I think their is some gas left over in your product...

Rosco:
You are definetly on the right track with your DPPP putty! I'd like to try some too--- the NC, NG, HMTN binder present in rifle power could certainly help. I've just made a length of DPPP detcord and we will see what comes of that. No new tests yet--- I'm under 1' of snow at the moment and I'm making use of the low temperature outside for various exploding projects

[Edited on 8-1-2005 by Pyroz]

what???

Joeychemist - 8-1-2005 at 13:06

Quote:

Originally posted by Pyroz
The DPPP that I made sinks like a stone in water--- it is also denser than vegetable canola oil. So it is quite dense.

How can DPPP crystals have a higher density than a thick heavy viscous liquide like vetable oil?

Pyroz - 8-1-2005 at 13:24

sorry, that was an error... pls ignore it... it is heavy material. i put a compressed tube of 1 gram DPPP in ethyl alcohol it sunk, I placed it in water---it sunk---, I place the same material in light vegtable oil and it appeared to sink--- and then bobbed up to the surface.

---sorry, i was mistaken.

i'm trying that whole density test thing--- humm ,what else can I use for a liquid medium?

[Edited on 8-1-2005 by Pyroz]

The whole density thing?

Joeychemist - 8-1-2005 at 13:41

Quote:

Originally posted by Pyroz
i'm trying that whole density test thing

You don’t know how to calculate the density?

Well then, I suppose it’s time you learn.
http://www.nyu.edu/pages/mathmol/textbook/density.html

[Edited on 8-1-2005 by Joeychemist]

Rosco Bodine - 8-1-2005 at 14:27

Quote:

Originally posted by Pyroz
Rosco:
You are definetly on the right track with your DPPP putty! I'd like to try some too--- the NC, NG, HMTN binder present in rifle power could certainly help.

Bullseye pistol powder is what most folks use for AP putty because it is the highest nitroglycerine content commercial powder that is commonly available just about anywhere . There are a couple of other brands that are similar . High nitro content powders are usually pistol powders or maybe a few shotshell powders , not rifle powders which must burn much slower because of the heavier powder charge and steep initial pressures .

Pyroz - 8-1-2005 at 14:47

hold on--- measurements coming. I was mearly testing the visable density.

now for the math: I did a calculation with acetone peroxide first. I got 1.192 gram/cc ---- makes sense right?

The DPPP product gives 1.836 gram/cc
hummm..maybe someone esle can varify my findings?

Rosco Bodine - 8-1-2005 at 15:14

Quote:

Originally posted by Pyroz
hold on--- measurements coming. I was mearly testing the visable density.

I wonder if DPPP sinks or floats in molten Erythritol Tetranitrate

If anyone cares to test that pleeeeeease only a very small sample for that experiment .

The_Davster - 8-1-2005 at 15:58

I did the peroxidation of the solution I prepared yesterday.

The deep red solution was left overnight(13h) in the garage at around 0C. It was then cooled to -12C via freezer. At the same time 50mL of 35% H2O2 was coolded in the same freezer for the same length of time(1h). 2mL of HCl was added to the dark red solution. The flask was placed in a slush bath(salt, water, ice cubes, snow) and ther peroxide was added dropwise. Adding the first 10mL of peroxide dropwise caused the temp to increase to around 8C. The flask was swirled a few times after the addition of each drop. Adding the next 20mL of peroxide was done by squirting a dropper of peroxide in then swirling. The temperature increse was no where near as great per addition as during the addition of the first 10mLs. The remalining 20 mL of peroxide was added in 5mL increments with swirling in the bath. The temperature actually decreased during this. Over the entire course of peroxidation the maximum temp reached was 8C. After the final addition the flask was allowed to sit in the slush bath for 30 min. The crystalls of DPPP were everywher in the mother liquor,not floating or sinking. It was then filtered and the filtrate was removed before neutralizing because it was still a deep yellow. The DPPP is now drying.

The yellow filtrate has been sitting aroud for a few hours and has gone completly clear. DPPP has floated to the surface, buoyed up by bubbles of (probally) oxygen. The source of this oxygen is probally decomposition of H2O2 caused by Fe(II) and (III) impurities in the OTC HCl used.

[Edited on 9-1-2005 by rogue chemist]

[Edited on 9-1-2005 by rogue chemist]

Rosco Bodine - 8-1-2005 at 16:17

That sounds like it went very smoothly .

Did that reaction mixture stay pretty clean and free from droplets of insoluble goo ?

Were the crystals suspended throughout the mixture and clumping like curdled milk
with regions of light yellow liquid between the hanging chains of crystals sort of suspended in the liquid like dense growths of seaweed hanging vertically in the ocean . A sort of Kelp-like crystal suspension ?

Are you going to weigh your yield and do the math to get the percentage ?
( 27.57 grams would be 100% of theoretical ) 24.8 grams would be 90% of theoretical .

[Edited on 9-1-2005 by Rosco Bodine]

The_Davster - 8-1-2005 at 17:07

Quite smoothly. I wonder what causes the massive temp increase and vaporization of reactants that was reported a while back?

The reaction mix stayed quite clean, the red liquid( is this phorone dihydrochloride or pentachlorophorone?) had a slight oil slick on the surface, reminiscent of a bit of gasoline on a wet road, but there was a very minor ammount of it and there were no signs of this after peroxidization. There were a few balck bits of rubber but that is remanents from enlarging the stopper hole for the thermometer during the heating of the acetone/HCl.

I think that I understand what you are refering to here but I observed none of this. Perhaps it is caused by DPPP crystallizing upon some of the insoluble oily droplets? My DPPP was freeflowing and spread equally throughout the mother liquor.

The yield will be weighed, but may not be completly accurate. I had done a trial testtube sized peroxidation of the dark red liquid before attempting the entire batch. And a little(very little) of the DPPP was lost onto the table during filtering by accidently overfilling the funnel :mad:

. And, of course, I could not resist a flame test of the damp DPPP

. I estimate that at maximum 0.5g of DPPP was lost.

The origional patent did claim black smoke if I am not mistaken? I recieved some of this. Not large ammounts, but a black outline was visible on the edge of the flame during deflagration and a few black carbonaceous particles were noticed floating out of the air soon after the deflagration.

[Edited on 9-1-2005 by rogue chemist]

Rosco Bodine - 8-1-2005 at 17:26

That temperature spike at the very start of peroxidation is what was causing the runaway reported for early experiments . According to the patent that would be the formation of the pentachlorophorone from
the phorone dihydrochloride via HCl and H2O2 .

The intensely red liquid is phorone dihydrochloride . Conversion to pentachlorophorone which forms next is where the heat spike occurs .

I always start a reaction slowly so as to get an idea what kind of addition rate
can be used and still keep control of the exotherm . It was clear that the reaction has a rapid rate in that initial 10-15% of the peroxide addition so that is where you
have to make the addition literally by drops , and watch the temperature to keep from getting trouble .

Probably the crystal clumping which I observed was related to a bit of the insoluble oily material and the action of the stirrer . The precursor mixture for my
last peroxidation experiment was one I had used an excess of acid , and then balanced with some added acetone later in an effort to salvage the batch . It was a darker mixture than the one I have in the cooler now that is like the ratio and color you used , which is evidently an improvement giving a cleaner reaction mixture . I am a step behind you fellows who are doing new reactions working from information I just posted , plus I'm taking a break while my last batch is still drying . It's okay if somebody else proves or disproves any theory I have , it just saves me work

[Edited on 9-1-2005 by Rosco Bodine]

The_Davster - 8-1-2005 at 18:12

Has anyone tried recrystalizing DPPP? I am wondering whether the cream color of DPPP is actually the color of the DPPP or could possibly be attributed to unreacted phorone dihydrochloride or pentachlorophorone trapped within the crystall latice of the DPPP. Time permitting, I may have a chance to dissolve DPPP in a solvent(acetone?) and add ammonia to destroy any phorone dihydrochloride or pentachlorophorone. I know from experiance in failed DPPP reactions that ammonia does destroy phorone dihydrochloride and/or pentachlorophorone. Then crashing into water to precipitate the DPPP.

EDIT: Damn, I will need concentrated ammonia or ammonia gas to try this, the commercial ammonia I have contains too much water for this.

[Edited on 9-1-2005 by rogue chemist]

Mickhael - 8-1-2005 at 18:17

I'm still letting mine dry, and hoping to get the MEKP made shortly, any thoughts yet on how much water the MEKP would expell from damp DPPP?

Also to comment on the fumes, I would recamend a good mask, I noticed how bad the fumes were right away, and since whenever I'm working around it I wear my S10 gas mask, it seems to block everything out perfectly, plus gives some head protection...I got it off ebay for $70 cdn.

Ps:Is it possible for someone to get a close look at DPPP in a lab, to see finally what the thing looks like? Hexa? Penta? Phorone? Clorine??

[Edited on 9-1-2005 by Mickhael]

Rosco Bodine - 8-1-2005 at 18:18

The ammonia will also destroy the DPPP , at least at a certain pH . So activated charcoal would be a plan , or simply precipitating the DPPP slowly by a dropwise addition of cold water to the
stirred acetone would purify it also . DPPP
is the least soluble component in water so it should crystallize out first in pure form . I tend to believe it is pure already
because the color is so even and the crystals are uniformly sized .

Ammonium Hydroxide decomposes DPPP?

Matsumoto_Hideki - 8-1-2005 at 18:45

Rosco and others can you explain why Ammonia decomposes DPPP? I did for all my other sucessful batches use NaOH to nutralize the DPPP. It worked very well. I have noticed that Ammonia attacks DPPP, I just don't know why and what forms as a result of this. Does it start to form an amine of Phorone ?

BTW I am not going to be able to do a video of my detcord and BIG shaped charge since the weather in my parts is very DANGEROUS, too much ice and snow on the roads. I FUCKING HATE FUCKING SNOW! I AM PISSED OFF :mad:

maybe next week????
[Edited on 9-1-2005 by Matsumoto_Hideki]

[Edited on 9-1-2005 by Matsumoto_Hideki]

Rosco Bodine - 8-1-2005 at 19:16

It is the elevated pH caused by free ammonia which destroys the DPPP . And it is so easy to overshoot neutralization using any hydroxide , that it is best to calculate the neutralization equivalent and then add somewhat less of a very diluted hydroxide than needed and then complete the neutralization with a separate addition of much milder base like sodium bicarbonate in slightly greater amount than needed to effect the neutralization . Adding too concentrated of a hydroxide creates a local caustic concentration which destroys the organic peroxide it contacts . Good stirring and using a diluted hydroxide added quickly limits the decomposition . Most peroxides tend to be decomposed by alkali and stabilized by acid , except for HMTD which is an exception . Phosphoric acid is actually added to hydrogen peroxide solutions to stabilize the solutions against decomposition in storage , while any alkalinity accelerates the decomposition .
Organic peroxides behave the same way , generally speaking , being stabilized by slight acidity and destabilized by alkalinity . Evidently DPPP follows the general rule . But in a way this is good because in compositions containing Ammonium Nitrate for example the natural acidity will probably enhance the stability of the DPPP , MEKP , AP which may be part of such compositions , while the same acidity would be detrimental for the stability of HMTD .

Breakthrough???

Joeychemist - 8-1-2005 at 20:16

Rosco, you might want to try re-crystalizing this stuff. I just recystalized 1g by dissolving in acetone and was left with half the volume of crystals but they still weighed almost .9g still. Also the smell is not as bad as before, it's more sweet now and not as iritating, the crystals ar whiter but still with the slight yellow tan color. All I can say is you must try this for yourself.

Rosco Bodine - 8-1-2005 at 20:48

What method exactly did you use to
perform the recrystallization ? Did
you precipitate using water dropwise ,
or let the acetone evaporate , or saturate
hot acetone with DPPP and cool ? Please everybody , be precise .

Joeychemist - 8-1-2005 at 21:01

Sorry I was exited and kind of busy playing with the stuff.

I dissolved the DPPP crystals with a few ml of Acetone at room temp then allowed the acetone to evaporate until most was gone and I was left with a thick “slurry” I poured onto a paper towel, the remaining acetone very quickly evaporated as I gently “kneaded” and powdered the crystals to avoid large crystals from forming. The remaining crystals burned pretty nice with a Whoomp!

Rosco Bodine - 8-1-2005 at 21:10

Yeah letting the solvent evaporate or
slowly cooling hot solutions will both
grow the crystals bigger , so will watering out the crystals very slowly from acetone ,
or using alcohol if the substance is alcohol insoluble . Dittos for toluene or naphtha .
There are a half dozen ways this could be tried . Conversely , dumping a hot saturated acetone solution of DPPP into
cold water would give you a dust like product . The most dense granular composition may be an aggregate of the
the coarse and the fine , just enough to fill the spaces between the larger crystals .

Wow thanx rosco!

Matsumoto_Hideki - 8-1-2005 at 22:48

Ya, that is what I was thinking about free NH3 destroying the DPPP yet when I added my Ammonium nitrate nothing happend. hmm this is looking better and better. NExt question is what does DPPP decompose into when it has reacted with ammonia???
I am tring a crystal seeding method with cool forming Pentachlorophorone to see if there is any difference in quality of the crystals.. keep you posted..

[Edited on 9-1-2005 by Matsumoto_Hideki]

Pyroz - 8-1-2005 at 23:49

Quote:

Originally posted by Joeychemist
Sorry I was exited and kind of busy playing with the stuff.

Thats excellent news...and may I add thats a smart idea. I used 100% pure Isoproplyene and found that it dissolves the DPPP rather easily as well but it does not vapour as quickly as Acetone. Good work Joey

Jome - 9-1-2005 at 08:29

I came up with some strange results. I had to keep my acetone-HCl mix on hold for a few days, and now it has turned from red, almost black back to bright yellow.

I tried to peroxidise 2 ml of it, I performed the experiment in such a small scale because my freezer was filled with food (!) and the weather warm so I had to use a small ice-salt bath.

1ml H2O2 19,5% was added to 2ml of the mixture after cooling it down to -10 C. Temperature only rised to -5. After a few minutes temperature was down at -10 again, and the rest of the peroxide, 3ml, was added.

No crystalls formed whatsoever. No gasbubbles either.
I'm going to keep it in the icebath, so it will stay at a temperature of about 0 C for a time. Perhaps stupid HCl completely left the solution, but I find this unlikely. I will try again with some HCl added later.

The big question: What happened to my solution? Why is it bright yellow again? (Tarry shit is on the jar walls)

I used 20ml of pure acetone, and 26ml of 30% muriatic acid (aq HCl). It was heated in a closed container to 60-70 for an hour (It did not leak) and later heated to 35-35 C for two more hours. Then the jar lid was opened and the solution was heated to 35-45 C for another six hours.

By the end of that heating (to evaporate exc. acetone) the solution divided into brown-red tar goo on the walls and on top of the solution and the liquid itself, now bright yellow. What is this?

The lid was corroded, and it was made of plastic covered iron. Perhaps the solution was iron-contaminated but one would think that'd make H2O2 fizzle when added.

I know what happend!

Matsumoto_Hideki - 9-1-2005 at 09:51

Jome, this yellow you speak of has occured in my peroxidations before and may related to a couple of things
I think you are looking at what happens when you over heat your Phorone HCl and or what happend when impurities react with leftover HCl and cause secondary reactions with metal ions Fe+causing your Phorone HCl to decompose?
More detail is needed. Never use ANY metal near H2O2 or HCl as you can really get some nasty reactions, especially when they are mixed.
My experience leads me to beleive that your iron lid caused your problem. USE nitrile or rubber to seal your reaction next time.

Summary of Experimental Findings related to Chemistry of DPPP

Rosco Bodine - 9-1-2005 at 10:24

Phorone Dihydrochloride Precursor :

The sealed bottle reaction has definite advantages . If a bottle or jar
has a metal lid it will not withstand the corrosive effects of direct contact
with vapors of acetone and HCl , and its gasket liner will likely detach
and contaminate the reaction . This can be overcome by laying flat across
the opening of the glass jar , one of the heavier thickness ziplock freezer bags
and then pressing the metal cap downward to engage the threads and tightening
securely . The polyethylene sheets of the bag will act as a gasket and prevent
the inner surface of the metal lid from being attacked by the vapors .
A completely polyethylene or polypropylene cap with compatable liner
or friction seal , or most desirable a teflon seal is actually the best option .
The precursor can be prepared in any shape of bottle , even a wine bottle
and transferred to another vessel of more convenient shape and volume
for performing the peroxidation .

From several slightly different experiments it has been found
the preparation of the acetone and HCl reaction mixture is the
secret for producing good yields of DPPP . The molar ratio of
HCl to acetone must be 2 to 3 , with the HCl limited to only a
very small excess of theory on the order of 2 to 3 % . The volumes
of acetone and HCl must be measured very precisely for the reaction
to produce the precursor in a concentrated and pure form . The
* exact volumes * for HCl 31.45% and acetone to accomplish a
correct mixture are 104 ml of HCl and 112 ml acetone . For convenience
in measuring using a 100 ml graduated cylinder , for exactly 100 ml acetone ,
use exactly 93 ml HCl 31.45% to achieve the correct ratio . Small
departures from these amounts will produce disproportionately
larger changes in the quality of the precursor produced by the reaction
which appears to be sensitive to pH . If you are using a different
concentration of HCl , then you need to calculate the amount of
your HCl to achieve the same molar ratio as above . The mixture
should be done in a glass jar or bottle and sealed immediately to
prevent the loss of acetone and thereby preserve the reaction mixture
proportions unchanged during the time of reaction , which involves
gentle heating of the mixture . The first heating which occurs is the
exotherm of the self-reaction , immediately upon mixing the acetone
and HCl . This self-reaction is allowed to continue for 1 and 1/2 hours
and then supplemental heating for 2 to 2 and 1/2 additional hours is
performed by placing the still sealed bottle into a 75 C water bath ,
to complete the reaction which forms an intensely red tinted but transparent
solution of phorone dihydrochloride . The beam of a flashlight shined
through the deep red solution gives the appearance of "ruby glass"
and if the solution is swirled so that a thin film of liquid sheets across
the inside walls of the bottle , the thin film appears bright yellow .
This color development is the marker for the endpoint of the reaction
producing the phorone dihydrochloride precursor . The supplemental
heating should be ended at this point and the sealed bottle removed
from the water bath and allowed to cool . A very slight oil slick may be
seen on the surface of the intensely red liquid if light is reflected from its
surface , and it will have the shimmering rainbow irridescent appearance
which is similar to the effect seen when a drop of oil strikes the surface
of still water in sunlight . The trace of oily material is insoluble higher
polymerization and precursor decomposition product which would increase
in amount with continued heating of the acetone HCl mixture , and the
oily surface precipitate therefore represents a loss of the desired precursor .

Higher acid to acetone ratios and higher reaction temperatures
and longer reaction times increase the amount of the oily precipitate ,
so these factors are to be avoided . The cooled reaction mixture
may be kept in good condition by refrigerating it until the peroxidation step
is performed later . The mixture in the sealed bottle does continue to react
after being removed from the heat , only at a much reduced rate , and the
further reaction nearly ceases under refrigeration . If the reaction has been
allowed to proceed beyond the desired point and becomes very dark from
precipitated material or has a distinct upper layer of oily material forming on
its surface , then it should be filtered through a double thickness of coffee filter
which has been pre-wetted with plain water before filtering . The filter will
trap most of any the oily precipitate and the solution can then be used for the
peroxidation without precipitation of the insoluble impurites which would
otherwise occur if they are not removed by filtration .

Peroxidation of Precursor to DPPP :

Generally this has been done by first adding 2 or 3 ml
of fresh HCl to the cold precursor solution before proceeding with the peroxidation .
The greatest exotherm during peroxidation will occur during the addition of
the first 10 to 15% of the total peroxide to be added . The initial exotherm is quite
energetic and must be done dropwise , very slowly with swirling or stirring ,
drop by drop additions are imperative here . This initial peroxidation converts
the phorone dihydrochloride to pentachlorophorone , and the reaction is ten times
as exothermic as is the remainder of the peroxidation . So it cannot be too
much emphasized to go * slowly * with the first additions of peroxide in order to
control the thermal spike which everyone observes to occur at this point in the
reaction . If peroxide is carelessly dumped into the mixture at this point , a
full blown steam explosion has been reported to eject the contents of the mixture
from the reaction vessel . A salted ice bath is a good idea here , and keeping the
reaction below 10 C thoughout the addition of peroxide is good practice . The reaction
mixture is allowed to stand in the cold for at least 30 minutes to complete the precipitation . One hour would perhaps be better .

I have tried an alternate method which has also worked , using a magnetic stirrer
but I have not compared the yields of the alternate method to the cold method
just described . The alternate method is to perform the initial peroxidation having
the reaction vessel in an unfilled cooling bath containing a shallow layer of plain water , and allowing the precursor mixture to warm at a fair rate during dropwise addition of the first 10 to 15 % of the peroxide , controlling the rate of addition so that the reaction mixture attains a peak temperature of 65 C at the end of the addition of the 10 to 15 % of the total peroxide . The addition is stopped and the bath is filled with ice so that the stirred mixture is cooled below 10 C before the addition of peroxide is resumed . The rate of peroxide adddition is increased cautiously so as to maintain the reaction temperature below 15 C to the end of the addition , and stirring continued for thirty minutes beyond the last addition . Stirring is then stopped and the mixture allowed to stand for a few minutes , and the mixture is dumped into the now melted cooling bath and neutralized . Slightly less than the calculated amount of ammonium hydroxide required for neutralizing is dumped into the well stirred mixture , since it has been observed that excess alkalinity of free ammonia decomposes the DPPP . Local caustic concentrations decompose the DPPP , so the neutralization mixtures should be dilute and mixed quickly , and perhaps it is best to then complete the neutralization using a small excess of theory of a milder alkali like sodium bicarbonate .

That pretty well summarizes where things are at this point in the experiments
so far regarding the synthesis of DPPP . The material evolves extremely irritating
vapors which should be avoided , as they are quite similar to the irritant effects
of "tear gas" . The effect is noticeable to put it mildly , even at low concentrations
where the smell is not noticeable . There has been consistent observation and agreement by everyone reporting that good ventilation and / or other protection
is a must . DPPP is one of those materials which will render an area vacant quicker than a fart filled elevator , you have to experience it to believe it

[Edited on 10-1-2005 by Rosco Bodine]

THings still to be done?

chemoleo - 9-1-2005 at 11:27

Good work everyone!

Having been away for a few days, this thread has grown yet by another couple of pages !

Anyway, regarding odour, and the purity of the putative DPPP - am I correct in reading that noone actually tried to dissolve it in isopropanol or acetone (i.e. a saturated solution of DPPP) and then to precipitate it with an excess of water?
I strongly suspect that this may partially remove the bad smell, and as rosco said, produce a more powdery precipitate.

Also, has someone determined the solubilities at this point? I.e. in ethanol, ethylacetate, methanol, IP, acetone, and less polar ones such as toluene, trichloroethylene, chloroform etc??

Then, did anyone do some friction tests? I really would like to know how it behaves when it is scraped with a spoon against stone or something. That way I always managed to ignite small amounts of chlorate/sugar (had to press very hard), which is otherwise fairly friction insensitive.

Rosco, you give a very detailed summary of the procedure - but I wonder where you got your thoughts on the importance of stoichiometry from (i.e. to quote your 2-3% excess). Did you do detailed yield studies, i.e. measure the yield at various stoichiometries (acetone vs HCl), to find the optimum yield?

That brings this to another point: yield.
What is the yield, from the quantities you describe? How many grams from 112 ml acetone?

Then, you all seem to be making very large batches. Did anyone try making small amounts, producing only a couple of grams worth of DPPP? Did this work ok? Or was the yield considerably less?

Oh, and Axt, we need you for the old drop test! As far as I remember you have it nicely calibrated against PETN and various others

Stability: it might be wise to take, say, 5 grams, and leave it at RT in a safe place, for several weeks, to then weigh it again to determine whether and how much DPPP decomposes/sublimes.
This is of course a function of purity, so, the recrystallised stuff is desired.

[Edited on 9-1-2005 by chemoleo]

The_Davster - 9-1-2005 at 11:48

I have been working with smaller batches. 26mL of HCl and 28 of acetone. It is still drying.

Rosco, you are quite excellent at those long writeups.

However I have some conflicting evidence on the aroma of DPPP. I (kinda) LIKE IT, it does not bother me. The worst smells I noticed during this reaction is of the phorone dihydrochloride. Sure the DPPP has a smell, but it does not seem lachramatory as you have been making it out to be. I used bicarbonate for my neutralization which could be a factor in this. Perhaps ammonia somehow complexes with the DPPP? I used gloves and goggles during the peroxidation and filtering of the DPPP and the smell was noticeable but not terrible, and I was doing this in a closed basement room without the window open. The smell of DPPP is different from that of AP but they both have the same intensity( if that makes sense, neither was stronger than the other). Is there a danger of decomposition of DPPP when too much Na-bicarb is used to neutralize it?

Dodoman - 9-1-2005 at 12:09

Regarding the smell I too noticed that irretating smell (that's why I got rid of the ppt). I too used ammonia to neutralize it. But my prepration faild as I ended up with AP.

So I think its correct to assume that ammonia doesen't react with the DPPP (my yeild didn't seem to contain any) but rather with the phorone dihydrogen chloride or other crap that may exist in the mixture.
Please someone correct me on this if I'm wrong.

Pyroz - 9-1-2005 at 12:16

DPPP is soluable in acetone, Isoproplyene, methyl and ethyl alcohol. It is insoluable in water.

--becomes extremely dangerous around 150C when it begins to melt---it will explode without warning at 200C unconfined state
--is much less sensitive when fully dry in comparion to other organic peroxides and it take a significant amount of force from a 5lb sledge hammer to explode it. Unlike dry AP or HMTD which takes very little force.
--in explosion tests 2grams of compressed DPPP inside of a 2.5" X 1/2" copper tube blasting cap has more than double the explosive power than the same amount of AP.
--DPPP charge: Brass casing punctured the steel plate completely--sharpnel peirced the steel plate in several area, indication of extremely high velocity sharp fragments
--AP charge: Brass casing chunked and moderately indented the steel plate---no penitration. Slight scoring on the plate from sharpnel.

[Edited on 9-1-2005 by Pyroz]

Na bi-carb seems the best

Joeychemist - 9-1-2005 at 12:32

R chemist
I have not noticed any decomp while using sodium bi-card to bring the ph down and I am glad that you did wear goggles while filtering, the filtering does seem to be the worst part. I am shocked to find that you like this smell? I guess each to their own, I don’t like the smell.

Pyroz, what’s with the gigantic quote? The thread is large enough as is.
I have done some friction tests between two rocks and between a rock and a spoon and well, what can I say?, it’s a primary explosive, it is friction sensitive in the way that it seems to perform like the rest of the explosive peroxide family, similar to TCAP but a little more stable and requires a heavier blow to detonate compared to AP.

I think getting Axt to do a test is a simply marvelous idea

Rosco Bodine - 9-1-2005 at 13:00

Quote:

Originally posted by chemoleo
Rosco, you give a very detailed summary of the procedure - but I wonder where you got your thoughts on the importance of stoichiometry from (i.e. to quote your 2-3% excess). Did you do detailed yield studies, i.e. measure the yield at various stoichiometries (acetone vs HCl), to find the optimum yield?

Usually it doesn't take old Rosco long to get the lowdown on a reaction from empirical data , eyesight and intuition , and then apply the amount of theory that seems to fit the experimental observations . Yeah I know that's doing things the old fashioned way , but in the absence of pricey equipment to do the analytical work , I have to do what I can with the data I do have and then go out on a limb with a best guess interpretation . It's early I know to be making some bold conclusions about the chemistry , but it seemed that the priority at this point is really the physical chemistry of making the synthesis work and then the details and tweaks can be debated later .

Quote:

That brings this to another point: yield.
What is the yield, from the quantities you describe? How many grams from 112 ml acetone?

The yield is very good .
I haven't weighed my last batch because it isn't fully dried yet . It's been raining here and its taking its time drying . But this yield won't be definitive because some was lost during neutralization by
taking the pH too far past 7 , not knowing it would cause some loss of product . It will take some more work to get good numbers from a clean , error free procedure .

Quote:

Oh, and Axt, we need you for the old drop test! As far as I remember you have it nicely calibrated against PETN and various others

I second that . The professional services of one wacky Aussie are required at this point

Also we need to get Philou Zrealone in here for another chemistry lesson

rogue chemist :

Quote:

Originally posted by rogue chemist
I have some conflicting evidence on the aroma of DPPP. I (kinda) LIKE IT, it does not bother me. The worst smells I noticed during this reaction is of the phorone dihydrochloride. Sure the DPPP has a smell, but it does not seem lachramatory as you have been making it out to be. I used bicarbonate for my neutralization which could be a factor in this. Perhaps ammonia somehow complexes with the DPPP?

Actually my first idea was that
* Chloramine * is the likely culprit arising from a mixture of ammonium hydroxide , HCl , and unreacted H2O2 ......But Joeychemist reported that the irritant vapor was present even if no ammonia was used but only sodium bicarbonate ,
so that shot down my theory about chloramine . So now rogue chemist and Joeychemist are providing contradictory information . Guess that leaves the question unresolved , until somebody tries both ways . It would get sort of "foamy" using bicarb for the entire neutralization so I will likely go with NaOH for 97 % neutralization and finish the process with bicarb .

[Edited on 9-1-2005 by Rosco Bodine]

damb!

Joeychemist - 9-1-2005 at 13:51

Yes that does conflict!Arg!!!
I did do it both ways ammonia and sodium bi-carb, the smell remained in or on the crystals stronger and slightly different than the bi-carb even after washing with additional portions of water and the smell did remain. And as I did mention yesterday after I recrystalized the DPPP in acetone the smell was considerably less but still remained. But you know Rogue chemist also said that he’s doesn’t mind the smell.Hmm... maybe it just does not affect him like it does us.

Rosco,You reported the same as I have experienced when I comes to this odor, the eyes become agitated and the nose and mucus glands become slightly inflamed and agitated causing a runny nose.

Rogue, you experienced no effects like a runny nose or soar throat? You didn’t even shed one tear? I’m not sure what to say or what to do now? This thread is going to be 50 pages before we figure this one out.

[Edited on 9-1-2005 by Joeychemist]

Rosco Bodine - 9-1-2005 at 14:04

Maybe rogue chemist has fondness for cajun food , three alarm chili , and slices onions with a smile

You know the sort that eats hot peppers like they were celery sticks , peppers which would be lethal to the average person

[Edited on 9-1-2005 by Rosco Bodine]

The_Davster - 9-1-2005 at 14:46

Joey, Nope, absolutely no effects.

And now for my most recent "holy shit" observation.

All of you may remember how I said that I kept my filtrate after filtering out the DPPP but before neutralizing. Well yesterday it was still yellow, with some DPPP crystalizing on the surface. Well, today I go back to it and the solution and the crystalls are completly white.

I filtered it out and neutralized it. It was still completly white. So, I decide to take a whiff of the crystals after filtering and IT SMELLED NOTHING LIKE DPPP AT ALL IT SMELLED LIKE CHLOROBUTANOL. Of course I flame test the still wet crystals and I get the nice fwump(no diference from the usuall DPPP). I smelled my vial of chlorobutanol, then smelled my "DPPP" the DPPP was like a slightly milder version of the chlorobutanol.

My theory on this is that the colour and smell of the origional pale yellow DPPP is a result of phorone dihydrochloride/ pentachlorophorone entrapped within the crystall latice of DPPP. Allowing the crystalls to sit in the mother liquor at room temperature overnight frees the unreacted precursors through use of the solubility equilibrium, the precursors then react with the remaining H2O2. This process occurs untill all the precursors have been used up, indicated by a clear solution.

EDIT: Rosco, I cannot stand very spicy food, I have acid reflux

I am fine with moderatly spicy though.

[Edited on 9-1-2005 by rogue chemist]

Rosco Bodine - 9-1-2005 at 15:17

The DPPP that I have is nearly dry and the odor / irritant property is at least 75% decreased for the relatively dry material , so it appears the offending substance is something else which has attached itself as an impurity or is a byproduct in the reaction mixture . Whatever it is appears to be more volatile than the DPPP since it slowly dissipates from a layer of the damp crystals exposed to air . It could well be occluded pentachlorophorone trapped in the crystal matrix of rapidly forming crystals , in which case slowing down the
precipitation , and I mean slowing it way down could result in much purer crystals not containing so much of the "tear gas"
component . This could also be related to the temperature at which the reaction is
performed and the level of agitation . The precipitation of DPPP crystals could be slowed by simply slowing down the rate of addition of the peroxide . The presence of some nonreactive solvent added to the reaction mixture could help also , possibly some methylene chloride or chloroform or methanol in small amount would be useful in precipitation of purer crystals .

It is possible that the 90% yield reported by the patent is because the other 10 % of reaction product is some undesired and
perhaps unavoidable byproduct , and that this byproduct is the irritant material . If we can determine what it is or how to eliminate it , by any sort of neutralization or crystallization strategy , even to substantially reduce its concentration would represent a great improvement .

Perhaps there is improvement from simply letting the reaction mixture stand , which could be complicated because of "rafting" of the crystals , after which they rise like bread dough and overflow the container , remedied by keeping the mixture stirring moderately for an extended time to keep any bubbles dispersed . Perhaps limiting
the excess of H2O2 used to only a minimum excess , or other strategies could clean up the product .

The_Davster - 9-1-2005 at 15:52

Quote:

Originally posted by Joeychemist

Rogue, you experienced no effects like a runny nose or soar throat? You didn’t even shed one tear? I’m not sure what to say or what to do now? This thread is going to be 50 pages before we figure this one out.

I had a family member go into the lab and they did not experiance an overpowering smell either. Just to test that I am not somehow resistant to it.

Does anyone have any thoughts on what the white chlorobutanol smelling substance is? I heard mention of diphorone hexaperoxide on roguesci could this be it? Or is just a purer form of DPPP? DPPP could be cream colored as a result of incomplete peroxidation which allows a chlorine atom or two to stay on the carbon chain of the phorone part of the DPPP molecule. I have no idea what this is...

[Edited on 9-1-2005 by rogue chemist]

Rosco Bodine - 9-1-2005 at 16:13

The very surface edges of the crystals of DPPP which I have been air drying have
tinged with white or very nearly white ,
as if the color was faded and the edges
of the yellow crystals were bleached out nearly white . It looked sort of like a thin
layer of white frost on the surface of the crystals exposed to the air . But of course it isn't cold enough for it to be frost so it is evidently a loss of color on drying , and
all the crystals are somewhat lighter in color , even those not directly on the surface . I noticed this when stirring the
drying crystals to smooth out any clumps and speed the drying .

The_Davster - 9-1-2005 at 16:37

I too noticed that loss of colour in my DPPP while it is drying, the assumption I made on the previous page of this thread may have been correct about unreacted precursor within the crystall. However I am still looking for an explanation for the smell of my new crystalls, it is nothing like DPPP. The smell of the pale yellow DPPP will have to be determined after a long period of time. It is possible that the smell of the more volatile component overpowers its actuall smell. Anyone who has experianced nearly lachramatory DPPP, when you made your phoronedihydrochloride, was there an oil slick on the surface? the milder odor of mine could be attributed to only a very small oil slick. Perhaps this oil acts as nucleation centres for the precititation of the DPPP, and then evaporates slowly later.

Most of this could be wrong...

Pyroz - 9-1-2005 at 17:20

I just recrystallised my DPPP in 100% pure rubbing alcohol. The yellow tinge is completely gone and the smell has decreased quite a bit--- it looks slightly green and smells similar to AP. When detonated--- this material maintains its high power and no smell or smoke is produced.

this is one way of doing things

Rosco Bodine - 9-1-2005 at 17:26

Hmmm , white DPPP , imagine that

Soooo exactly what method of recrystallization did you use , and I presume by "rubbing alcohol" you mean denatured ethanol ?

What one minute!

Joeychemist - 9-1-2005 at 17:50

You guys know that wax like insoluble junk that forms as the phorone dihydrochloride is being peroxidated (the upper "oily waste" layer)? Well when it burns it produces a very thick *black* smoke ok. The “smelly” “yellow” DPPP produces a small amount of black smoke when burned but the re-crystallized DPPP does *not* smell as bad, it is *white* and now that you mention it pyoz it *DOES NOT* produce the small amount of black smoke. Any one else get what I’m saying here???

[Edited on 10-1-2005 by Joeychemist]

Pyroz - 9-1-2005 at 18:10

DPPP after filtration using pure rubbing alcohol or ISOPROPLYENE ALCOHOL Color is ever so slightly green---much whiter than before and smells similar to AP ---but smell isn't as intense. It violently explodes in a compressed clump in open air but will catch fire uncompressed.

[Edited on 10-1-2005 by Pyroz]

100_2636.jpg - 106kB

Rosco Bodine - 9-1-2005 at 21:05

It still seems possible to me that adding
some chloroform or methylene chloride or trichlorethylene to the mixture before the peroxidation may result in precipitation of the DPPP in pure form . Such solvents should be inert to the peroxidation mixture but somewhat soluble in it , and would therefore tend to act sort of like an emulsifier and solubility increaser for the suspended or dissolved materials , to make the reaction more complete while slowing crystallization . And because they are highly volatile , they would easily disappear from evaporation after they have served their
purpose . If the DPPP could be precipitated pure from the reaction and require no subsequent purification it would be desirable for saving the work and expense of solvents for recrystallization . And what I am thinking is it shouldn't require much of the solvent
added to the reaction mixture to do the
job if the strategy works , maybe 10% or
less of the volume of the acetone and HCl mixture should be sufficient .

The_Davster - 9-1-2005 at 21:15

It may be unnecessary to use other solvents during the peroxidation. As I mentioned before letting my filtrate sit at room temperature for 24h yielded a pure white precipitate with no other solvents needed. Perhaps if after peroxidation, the reaction mix is allowed to sit for 24h at room temperature the same result could be observed.

Those of you who have recrystalized your DPPP, was the smell after just a milder version of how it smelled before or was it a new smell?

Rosco Bodine - 9-1-2005 at 21:30

You are probably right about just letting the mixture stand . But I have some chloroform on hand , and I feel it is only fair that I should chloroform some DPPP just to get back at it for what it has aleady done to me

That's right ...
take that you little molecular m'f#!*kers .

It really could make a difference also to simply slow down the addition of the H2O2 to a crawl , which would by itself
slow the growth of crystals and perhaps result in a crystal having less occluded impurities . So I'll probably check out that
strategy first , maybe let it stand afterwards for a good while too .

Before=shit smell After=good

Joeychemist - 9-1-2005 at 21:44

Rogue Chemist
I can’t describe the smell, It smells absolutely awful before I re-crystallized it, but after, O dear god, after I re-crystallized the DPPP it was almost pleasant to smell the stuff. It has a weak sweet smell, somewhat like chlorobutanol, yeah, I guess I can see where you’re coming from with that, but it more so smells like really “funky” AP to me.

So flat out, before I re-crystallized it smelled fowl

but after it smelled like peaches compared to before.

Maybe even using less concentrated H2O2 will allow the crystals to form at the ideal pace, of course one would have to adjust the amounts used and it might totally fuck the reaction up. But I doubt it, besides I really want to know what type of a yield is possible with say 3 and 6% H2O2 anyways, so I’ll try that tomorrow perhaps.

[Edited on 10-1-2005 by Joeychemist]

I also filtered my remaining 300g and also discovered...

Matsumoto_Hideki - 9-1-2005 at 21:53

I would not say the filtered end product it completely white but very very very light yellow, almost the colour of the post reply box..
Coloured material I am drying and sending to university tommorrow, get some sort of answer on...
Indeed it looks as though I was wrong about dppp's colour after all... hmmmm.

chemoleo - 10-1-2005 at 10:02

May I just ask what you plan to have done with it at the university? You are dealing with an explosive substance, and if anything, just anything happens to it in the form of an explosion/little fireball, while being handled from lab assistants etc, you will undoubtedly be in big trouble.

I myself considered giving it to our NMR people, but the risk it entails is too large - at least for me.
Anyway, if you are giving a sample to the NMR people, make sure it is dissolved, i.e. in a saturated solution of methanol. Not many people do solid-state NMR, and aside this it is safer. You won't have deuterated methanol, so you will have to live with massive peaks from the methanol.

Else... try to chase down an electrospray massspec. It won't take long to run a sample, and also you won't have to disclose its identity - i.e. you could say it's a dye you made or something. Calibrate from 0-1000 Dalton.

But NMR would be best of course.

[Edited on 10-1-2005 by chemoleo]

rogue chemist is probably correct , irritant is unreacted precursor

Rosco Bodine - 10-1-2005 at 11:02

The crystals of DPPP which I have been drying for several days are continuing to
gradually lighten in color and lose the irritating vapor which was an unmistakable presence on the freshly made DPPP . The level of the irritant has steadily decreased around the crystals exposed to the air , and it is now barely detectable after three days of
"airing out" . When the crystals were freshly made , the irritant vapor was quite overpowering even several feet away from the crystals resting on the filter and spread out for drying . And now after several days the vapor has nearly vanished completely ,
so it is evident the impurity is volatile , and whatever is the impurity , it is not the DPPP

, but is a nuisance impurity which by some means is accompanying the DPPP crystals from synthesis , like fleas on a dog . So there is probably some change which can be made in the way the synthesis is being done , to minimize or exclude the impurity . Rogue chemist may be correct in that simply letting the mixture stand will allow the reaction to finish more completely and eliminate the impurity which consists of unreacted precursor . That looks like a very good theory at this point .

In the early part of the discussion at E&W Forum I suggested that reversing the order of addition may have advantages and this still seems like it may be logical as a possible way of addressing this specific problem . If the precursor was added very slowly to the cold peroxide , and * IF * the reaction would proceed the same path in spite of this reversal of the order of addition , then the precursor would be exposed to H2O2 in great excess of its requirement during the early part of the reaction . Normally this
would tend to drive the reaction more assertively in the direction of complete conversion of the precursor , resulting in a more pure product . And because it appears that the presence of any unreacted precursor accompanying the end product is an
offending impurity due to its lachrymatory properties , then this provides incentive for formulating a strategy for reducing or eliminating that unreacted precursor from the end product . I am tempted to try the reverse order of addition simply to see if this will
clean up the reaction . I know I asked about this earlier and was told that reversing the order of addition produces AP instead of DPPP , but frankly I doubt the accuracy of that report . What I suppose and hope could be true is that a white product resulted which was mistakenly identified as AP , when it may have actually been pure white DPPP .
That would be very nice if that turned out to be true and clarification on this is no matter of any trivial significance .

chinamen_6 - 10-1-2005 at 12:10

Allright after all these 20 pages, has someone really have a good synthesis with a high yield, no lying which everyone could follow?

No!

Joeychemist - 10-1-2005 at 12:22

No we don't, if you would have bothered to read the last 20 pages you would know that we are still tweaking and playing around with things trying to figure all that out. All I can tell you I the basic procedure is out lined many times in this thread. If you're not even going to bother reading this whole thread (I don't blame you) at least read a couple pages back.

Hey guys I'll confirm that my crystals are much whiter after letting the reaction continue at room temperature over night. I'm not sure how bad they are going smell after filtering and drying, but they have gone almost to the color of AP in less than 12hours, it would appear that the reaction actually does need extra time to finish.

How about a reverse order of addition peroxidation ?

Rosco Bodine - 10-1-2005 at 12:35

I am going to check it out , just for shits and giggles to see what happens .

Will get back later on the results .

Axt - 10-1-2005 at 13:12

Why not try distill the acetone/HCl mixture, and try peroxidation on both the distillate and the mother liquid. I speculate that you will find that the black condensation product doesn't create a peroxy precipitate, but the distillate will form a precip (which I call AP

).

Yeh, im still a full blown skeptic! But whatever the case, distillation would provide interesting results.

Rosco Bodine - 10-1-2005 at 13:35

AXT :

Distilling is definitely an idea , but the heat of an atmospheric distillation is likely going to decompose the the phorone dihydrochloride , so vacuum and low temp
would be a good idea , and even that may
not work or be conclusive , since it is possible that the phorone dihydrochloride
is an unstable transitional compound that
will decompose if boiled at any temperature , existing only in solution .
I do believe that it does exist however ,
and the dyestuff like quality which lends a yellow tint to dilute solutions as surely as does picric acid , lets you know there is more there than just a simple solution of acetone and HCl . The byproduct which is so irritating is also something not associated with AP , and the dried material thought to be DPPP looks nothing like AP , and smells nothing like AP . The thermodynamic of the peroxidation isn't the same as for AP either . So why do you suppose what we have made is just some "tinted" AP ?

Axt - 10-1-2005 at 14:38

Quote:

Originally posted by Rosco Bodine
So why do you suppose what we have made is just some "tinted" AP ?

Because everyone is assuming large yeild of condensation product, whose to say that there is still not significant quantities of acetone still in the mix, which I believe their would be. A quick evaporation session won't release it all! not when dissolved in that quantity of liquid.

The decription of the peroxidation of DPPP closely resemble what would happen if one was to add 1 part peroxide into cold 1 part HCl and 1 part acetone (the DPPP ratio's), Temperature jumps sharply and a precip of AP forms instantly as a fine powder.

The colour/smell/look of it can be explained by interference from the condensation product.

Anyway, thats why im a skeptic, I'll wait for your performance reports before believing any power claims. Which I really think should be confirmed first.

Not AP, not 9000m/s

Joeychemist - 10-1-2005 at 14:48

Axt, You may be right, but then again…I would like it if you checked this stuff out under a microscope at about 100X, I would not be surprised if you changed you’re tune.

I don’t think 7000m/s let alone 9000m/s is possible with this peroxide, but it is not AP.

Axt - 10-1-2005 at 15:02

Quote:

Originally posted by Joeychemist
I would not be surprised if you changed you’re tune.

The large mix of condensation solutes in the liquid could explain the interference with crystal growth, thats my point, it can all be explained more logically then looking at the complex reactions proposed for DPPP.

Im not saying im right, people have looked into this far harder then I have, but distilling it to see if AP can be reclaimed from the "DPPP" mix would answer a lot of questions. Getting a confirmation on "power" would dismiss my theory.

chemoleo - 10-1-2005 at 15:19

And who's the man well-known for calibrating the power of various energetic materials? *hint*hint*

PS Axt- one thing that seemingly doesnt add up with the AP theory is its stability and friction sensitivity - so far noone reported friction sensitivity. But I don't know if anyone tested it.
Also, if someone did a comparative test on its volatility, that would be great. AP should lose a significant amount of weight during a few days, while the putative DPPP wouldnt. Should be a simple matter.

[Edited on 10-1-2005 by chemoleo]

Joeychemist - 10-1-2005 at 15:20

Quote:

Originally posted by AxtIm not saying im right, people have looked into this far harder then I have, but distilling it to see if AP can be reclaimed from the "DPPP" mix would answer a lot of questions. Getting a confirmation on "power" would dismiss my theory.

Ahh..., but this is why you have been called in Axt, I do believe that Rosco asked for a crazy Aussie.

We want you to test the power among other things, not only do you have the proper tools but you are trusted and very experienced, plus you provide visual proof(movies)_(I love you’re movies). I think that you’re tests and findings will prove the most useful in determining the question of whether or not this is the “holy grail” organic peroxide or not, ( I think not, I think MEKP rules over DPPP but I have yet to test this).

No tests? What

Matsumoto_Hideki - 10-1-2005 at 15:47

I guess you people never bothered to download the test.pdf that has picts of DPPP and AP both at 1.93g being detonated. ie) the witness plate tests, I guess people have just ignored them? DPPP is very slightly friction sensitive, but will ignite/detonate upon hard impact of a strong hammer blow, unlike AP which is highly friction sensitive.

BTW I am now having some organic chemists looking into the molecule and synthesis at my university officially, and they are really interested!!!
There should be some answers in a matter of weeks about if this DiPhorone Pentaperoxide is as energetic as the pattent claims!!
Already I have talked with a physics prof and showed him my pics of the witness plate damage, he was really surprised by just how much brissiliance this material (DPPP) had especially the damage had come from an organic peroxide. :mad:

[Edited on 10-1-2005 by Matsumoto_Hideki]

Sublimation / Condensation test anyone ?

Rosco Bodine - 10-1-2005 at 15:48

Suppose we put a small amount of "suspected" DPPP in the bottom of a test tube
( maybe a poly tube ) and then put the bottom of that test tube in some near boiling or boiling hot water .

AP would melt , sublime from the heated portion of the tube and then condense as
rectangular white crystals on the cooler portion of the tube ......right ?

The_Davster - 10-1-2005 at 15:51

Well I returned today to check the odor of both the white DPPP and the standard pale yellow variety. The pale yellow DPPP has lost even more smell, my nose must be inches away to detect any smell. The odor detected at this range is like "funky AP" as origionally described by Joey. The smell of the white DPPP which I origionally reported to be surprisingly close to that of chlorobutanol has now subsided to again "funky AP" but this smell is stronger than that of the pale yellow DPPP. But this is to be expected because of the different times of filtering(1day apart).

Sublimation should work

Joeychemist - 10-1-2005 at 15:51

Rosco, yes, in theory that sounds pretty good. Are you going to be trying it now perhaps????

Rosco Bodine - 10-1-2005 at 16:02

Quote:

Originally posted by Joeychemist
Rosco, yes, in theory that sounds pretty good. Are you going to be trying it now perhaps????

Yeah I'll give it a go if I can find my bag
of 15 ml clear polypropylene culture tubes , give me awhile and I'll dig through
my stored junk to find what I need . I have glass test tubes handy , but I hate heating primaries in glass for tests . So I'll go find the poly tubes . I know I have a full box , just can't remember where in the hell they are , something I rarely use .
But I got 'em somewhere .

UPDATE : Well there's some good news and some bad news . I'm getting a slight
dusting of glitter on the cool part of the tube as there was a * partial * melting of the quarter gram sample , along with some water vapor . But the "dusting" of glitter appears to be less than 1% of the sample which first melted and then solidified again after "off gassing" the little bit it did . I am going to get it a bit warmer for a longer time and see if anything else comes off the sample .
UPDATE : Subsequent heating for a longer period produced no melting and only a bit more moisture and a little more of the same dusting of glitter of sublimed crystals as the first time . A comparison sample of authentic AP is undergoing the identical test right now .
UPDATE: Well that test told me a big fat nothing because the AP behaved exactly the same way , slight condensation of moisture and a dusting of glitter of sublimed crystals . I expected the AP to make the larger crystals which sometimes
will grow from its vapor , but no such luck .
Partial melting in boiling water , looks like it would melt completely on a second heating . But I have sealed up both tubes
and put them in a warm water bath for overnight to see what may sublime and crystallize slowly over time . One thing I did note was the difference in bulk density for the loose crystals , the suspected DPPP is twice as heavy per volume as is the loose crystals of AP ,
that is for the pouring volume without tapping the crystals down at all .

[Edited on 11-1-2005 by Rosco Bodine]

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