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Author: Subject: Diphoronepentaperoxide (DPPP)
BASF
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"the determination of blasting power relies on comparative methods. A possibility is the determination of the lead block expansion after trauzl."(roempp)
There is a good picture, but i cannot copy it, i would need a capturing prog.
But i can give you the diameters.
The standard Trauzl block is 20cm in diameter and height and has a vertical hole with 2.5cm diameter 12.5cm deep.
Exactly 10g of the explosive are placed in the hole.

Assuming lead has a density of 11.3g/ccm,
you´ll need at least
11.3*[(10*10*3.14*20)-(2.5*2.5*12.5*3.14)]=68.2kg(!)

You see, it would be quite wise to make a smaller lead block 1-5g.

HLR
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I think the sand test would (as vulture proposed) also be a good method to give DPPP some experimental brisance value.
After the detonation, the sand will consist of bigger and smaller particles.

To determine a represantative value i´d propose filling the whole sand into a small bucket and shake it for a defined time, say 15min, so that the bigger sand particles seperate from the smaller ones.
(the bigger ones are on top)

Then determine the big-particles to small particles-weight-ratio by weighing the upper half and the lower half seperately.

HLR
vulture
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I would think the sand has to be perfectly dry for the sand test, because otherwise water could interfere, not only by absorbing energy, but also by changing the weight. True or not?

One shouldn't accept or resort to the mutilation of science to appease the mentally impaired.
BASF
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For sure, using dry sand would be "a good idea" indeed...

The biggest difficulty in the sand crush test will be the determination of a value that correlates with the size of the particles.
I guess that the shaking of the crushed sand should be done as long as possible, but always for the same time.

And don´t forget: one test is not sufficient.-One test is no test!
At least 3 tests would be necessary to
1)prove the reproducability
2)give a more reliable value

We need reproducable results.
2)the initiation charge has to have a standard size and loading density
3)always use the same sand.
Possibly sand of a particle size of 3-5mm would be best.
BASF
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Or just juse a sieve to seperate the crushed particles from the rest.....more realistic and better for reproducability.
Abramellin
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Crystal Formation

Anyone should determine the content of the different AP isomers in the endproduct which formed in the side reactions of the AP synthesis.

tricyclo isomer [ C9H18O6 ] and the
dicyclo isomer [ C6H12O4 ]

How are the size difference between the crystals of the different AP isomers ?

I dont know its possible to make DPPP direclty from pure phorone,
more likely a similar cyclic peroxide from
4-oxoisophorone.
BASF
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I think the crystal size would be a very unreliable method to determine the content of different isomers...i did not get into thin sheet chromatography, but maybe this would be a thinkable method(has to be UV-assisted as they are colourless).

Further i also believe peroxidation of pure phorone is impossible from my empirical point of view:

 Quote: Peroxidation of commercial phorone I recently bought 97% phorone at Sigma-Aldrich, which seems to be the only supplier of small quantities. At first, the phorone was very pure, could easily be melted in a warm water bath and crystallized upon cooling(room temperature) in the form of long yellow needles. Solubility tests: -Insoluble in 30% HCl -soluble in commercial acetone -exzellent solubility in 98% acetic acid -Insoluble in commercial ethanol(absolute ethanol needed?) The phorone does not crystallize at room temperature if surrounded by an aqueous (immiscible) phase. I tried to peroxidize the phorone(1ml) by first dissolving it in 98% acetic acid (5ml=excess to prevent seperation upon addition of the peroxidation-mix) and then adding a mix of 1ml HCl and 1ml 30%H2O2, but although the batch heated up very strong and this was then later repeated with proper cooling, no precipitate occured. Maybe the DPPP is very soluble even in aqueous solutions of acetic acid, like phorone. -Or the reaction just failed. So i added some ml of water to make it seperate along with the rest of unreacted phorone, but nothing remarkable happened. The last experiment i did was to dissolve phorone in acetone and then tried to peroxidize both. I was surprised that the phorone seemed to prevent peroxidation of the acetone(no AP-precipitate).
DeusExMachina
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I didn't get a chance to read the whole topic because it'sso long and I apologize in advance if someone has alread asked or anwsered this question already but how would you know if you had diphoronepentaperoxide without detonating it when you have it? does it look any different than acetone peroxide or is it just the detonation velocity and a few other stuff that have nothing to do with the appearance of DPPP?
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The answers are in this thread... let's not have discussion going in circles.

I weep at the sight of flaming acetic anhydride.
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http://apanshock.tripod.com/phoron_dppp.htm
magnum
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hi

i did a search on the phonebook and there lives a wolfgang mackowiak in bielefeld (the inventer of the procedure) the phone number is
+49 5 21 33 41 44 . possible he know how it's done. let's call him.

bye
BASF
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Sublimation and prevention of same

Recently i did a little "study" on the sublimation of "DPPP" and tricyclic AP.
(AP and DPPP were made with great care, using an AN-icebath at below 5°C)

At 21+/-0.5°C samples(filter cakes, thouroughly dried and weighed with 0.01g accuracy) of

1)tricyclo acetone peroxide(TCAP) showed a loss of 26% after 13 1/4 days

2)"DPPP"; 49% loss after 13 1/4 days

To me, this is a strong indication, that the "DPPP"-product is a indeed a different compound, not just another form of acetone peroxide.

I also made two experiments with coating substances to slow down sublimation of TCAP. (Same conditions and time as above)

1)TCAP was impregnated with 16% phorone (from Sigma-Aldrich); the weight loss was now only 15% as opposed to 26% uncoated.

2)TCAP was impregnated with less than 45% of an ethanol-soluble grease(non-volatile) obtained by cooking acetone with concentrated sulfuric acid.

The unexpected result was a weight loss of 38%, even more than of pure TCAP.

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lol

thats very tempting, it would be great if someone called him

Most people outgrow their pyro tendencies, we are the ones who\'s tendencies outgrew us.
BASF
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......and it´s not gonna be me.

It would have to be someone speaking german. I just speak german with a freaky dialect hehe, so i´m not the right one.

But maybe someone could say he examines different peroxides in their capabilities as polymerization starters and spin a story from that....

For sure, if someone could also record the whole thing on tape this would be a cool thing.
Eternal glory to the brave one!
PHILOU Zrealone
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I have some words to say here!

Tetracene has a density of 1,7 and as a bluk may have a lower density!

I don't have the patent under the eyes but from what I have understood:

(CH3)2C=O + CH3-CO-CH3 -H(+)-> (CH3)2C=CH-CO-CH3 + H2O

Then
(CH3)2C=CH-CO-CH3 + O=C(CH3)2 -H(+)-> (CH3)2C=CH-CO-CH=C(CH3)2 + H2O + (CH3)2C=CH-C(CH3)=CH-CO-CH3 +(-C(CH3)=CH-)3 + ...

It seems very advisable to isolate the phorone!
The more you wait, the more crotonisation will occure!
If you let aceton and concentrate NH4OH stand for monthes it will make yellow, then orange, then brown then a black solid precipitate...thus a high polymer of the kind
(-C(-R)=CH-)x.

Thus phorone is made aside with other trimers condensate and the more you wait; the more you go to higher polymers!

Phorone is submitted to addition of 2 molecules of HCl and follows markovnikov's rule!The phorone resonates and display CH3 inductive giver effect and enol-cetone shift-both effects goes in the same way!
(CH3)2C=CH-CO-CH=C(CH3)2 + 2HCl -->
(CH3)2CCl-CH2-CO-CH2-CCl(CH3)2
Then HCl oxydises with H2O2 and heat to generate Cl2!
2HCl + H2O2 --> Cl2 + 2H2O
Cl2 may react directly with phorone to add 2 moles of Cl2!
(CH3)2C=CH-CO-CH=C(CH3)2 + 2Cl2 --> (CH3)2CCl-CHCl-CO-CHCl-CCl(CH3)2
Anyway assuming the way they propose is right:
Cl2 and HCl will yield monohalogenation of hydrogens alfa oriented vs the ceto carbon!
Looking at ((CH3)2CCl-CH2-)2C=O the more favourable sites of halogenation is thus the inner methylene and not the external CH3 that are far from the C=O!
And this said it bring to the same as Cl2 addition on phoron!
((CH3)2CCl-CH2-)2C=O + 2Cl2 --> ((CH3)2CCl-CHCl-)2C=O + 2HCl
This is a good assumption since the phoron is symetrical molecule why would it give an unsymetrical product now?
I don't see a reason why if they have terminal halogenation on one side why not on 2,3 or 4 terminal CH3?
Anyway:
((CH3)2CCl-CHCl-)2C=O + 4H2O2 --> ((CH3)2C(OOH)-CH(OOH)-)2C=O + 4HCl

As a conclusion, you see that ALL HCl involved is recovered and it serves as a catalyst!
Thus there is no significant increase of acidity; also in 33% HCl pH = -1, no pHmeter can work well in such concentration; since it is in excess, you will not notice any change!

Finally if this works for phorone it should work aswel with Cl-CH2-CO-CH2-Cl to replace the Cl by peroxydes to get 3,4dioxacyclopentanone (DACP) then peroxidise it to cyclotri(DACP).
With Cl-CH2-CH=O

It should also work with the intermediary
mesityl oxyde (CH3)2C=CH-CO-CH3 via the chlorinated (CH3)2CCl-CHCl-CO-CH2Cl

So in this patent basic organic rules seems to be broken!
The best way to make the stuff is to isolate intermediaries!
Mesityl oxyde, phorone (via distillation) then add HCl on both; then isolate the chlorocetons; then chlorinate with Cl2 bubbled in H2O2 solution of the chlorocetons!

The trauzl test is a bit tricky because it deals with 10g of explosive!So if you have an explosive that is 10 times denser than another one you will compare let say 10 ccm of a HE of density 1 and 1ccm of a HE of density 10!
Of course this explains why high density lead primaries display so bad in Lead Block test vs pure HE of much lower density!
A good alternative would be to make both LBT with same weight and with same volume of HE and with molar weight multiple!

Same problem with brisance it is based on a given sample of known weight!

PH Z (PHILOU Zrealone)

"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
IgnorantlyIntelligent
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Damn where was I while this thread was so hot and in testing??? Damnit! Well this compound interests me even though I seriously doubt DPPP is a possibility. 9000m/s? Come on now, if the germans really invented a compound THIS easy to make and this powerful they'd either tell no one or it would become their new main HE for blasting and such. If it truly has th properaties described earlier than it would not be hard to make it fairly insensitive by the addition of NC paste or something. 9,000m/s is..to say the least, aww inspiring.. I will begin tests tomarow. I read somewhere that the HCL/acetone mix must sit in a warm place for about 72 hours atleast for the phorone to form. You all talked about just letting it sit for 10 min or so...I doubt that would work.

[Edited on 24-3-2004 by IgnorantlyIntelligent]

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Blind Angel
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Not registred, this thread is over 1year old and has procreated to create some offsprings
IgnorantlyIntelligent
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A year old..... smeone must have a conclusion. IS or IS IT NOT possible?

\"People fear from ignorance what they do not have the intelligence to understand\"

\"Religion is the sigh of the oppressed creature, the heart of a heartless world, just as it is the spirit of a spiritless situation.\"

\"A fool would rather not question, a soldier is taught not to question, a slave dares not question.\"

\"To fight for nothing is to love nothing, to die for something is to have lived for something.\"
Polverone
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I don't think the compound, as described, exists. But of course this is just my opinion. It's been a year, and many people have tried this one way or another and failed. But if the challenge were "perform a total synthesis of quinine," everyone here would fail too. That is no proof that it is impossible that a substance having the claimed properties of quinine exists. Still, I think DPPP is a chimera, since it has unusually good claimed properties and a given synthesis that either does not work at all or that works only by some tricky modification not mentioned in the patent.

PGP Key and corresponding e-mail address
braegler
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Phoronsynth. Still works:-)

Hallo,
mix 100ml Aceton and 100 mlHCl konz (37%).
Boil under reflux for 2 Hours (70°C schould be best).
Cool down to 5°C an slowly add
48 g powdered Sodiumhydroxyd until the liquid becomes yellow and the pH is >7.
Cool meanwhile, so the Temp cannot rise above 10°C (realy good cooled and slowly added).

Cool down in a Ice/Salt-Bath to appr. 0°C and filter.

To wash the residue, rinse with Icewater at 0°C.

The yield of Phorone is not bad in this way.
BASF
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? is this from a book or what ? ... its not quite scientific to write sth without naming any source or at least saying "this is just an idea of mine or this from the Organikum or book xy"...
however, it seems to be a detailed procedure to me.
I have once bought some phorone; if someone wants to make a DC-comparison and lives in Germany or Austria, i could eventually send him some mg in a letter or something...
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BLAST_X wrote --------------------

I've tested preparation of DPPP and i can say its a very interesting and varied explosive.
You can use it as a primary explosive and as a high energetic secondary explosive.
You can never classify DPPP in the same category as AP or HMTD.
The question is, at which density you use DPPP and at which method you use to ignite DPPP.

preparation:
To a 1000 ml erlenmeyer flask add 185 ml of 20% HCl (i dont
have 35% HCl at this time). To a second flask add 100 ml of aceton.
To an third flask add 200 ml of 30% H2O2. Cool all to 5 C.
After cooling, slowly add the aceton to the HCl and stir the mixture
for 5 minutes.(very slight yellow colouring over a few minutes)
The patent dont say heat at this time and the patent dont say
some product (poron) should precipitate from the solution at this time.
If you heat or not, the content of AP are always present at end of the synthesis. On the contrary, if you heat to much or to long, the reaction fails.
Cool the mixture to 5 C for 2 hours and stir occasionally.
After standing, set the mixture to magnetic stirring at room
temperature and slowly (over 10 minutes) add the H2O2 to the
aceton/HCl mixture. The temperature can rise over 40 C and
the mixture become a sligth green colouring.
(second reaction-step, formation of pentachlorporon and free
Cl with H2O2 as catalyst)
The DPPP should precipitate on top of the mixture and some fumes bubble of.
You can distinguish this of AP crystalls, which formes in the reaction-mixture and which are a bit larger than crystals of DPPP.
Ive look at the crystals exactly through a microscope.
(look at attachment DPPP.jpg)

After all H2O2 is adding, continue stirring for 2 hours an more till the liquid on the bottom of the flask are clear and no fumes bubble of.
Filter out the crystals, wash them with 1 L of 10 % sodium bicarbonate solution, and again with water.
Dry crystals of DPPP at room temperature for 48 hours.
The next step are very important to remove all traces of acid and AP in the product, that you can handle safe with DPPP.
Dissolving the crystals in minimum amount of hot ethyl alcohol (60 C),
let cool to 5 C, filter, add a large volume of cold distilled water, let sit for 1-2 hours below 10 C and filter again.
Let dry DPPP at room temperature for 1-2 weeks to decompose and evaporate the rest of AP on the air.
final yield: 65 g
(at this reaction temperature and with delute 20% HCl, i think you can get much more yield with reaction temperatures below 10 C and a longer reaction time, the patent say around 90%)

Be careful with large quantities because DPPP is somewhat sensitive
to friction, shock and heat.

Ive tested the DPPP in 3 different charges.

1. Ive made a blasting-cup (hard-paper) with 5 g charge low pressed
DPPP and ignite with a match.
No detonation, only flash, the blasting-cup bursts only.
Consequently, if you ignite DPPP at powdered density or with flame,
its flashes only, you can use it as a primary explosive similar
to AP and HMTD, it detonates only at this density when strongly heated.
(very storage stable and lower sensitive to friction and shock)
2. Ive made a stable blasting cup (hard-paper) with 50 g charge high
pressed DPPP and ignite with a match.
It datonates hazardous and id feel strong the detonation pressure
still the distance of over 50 m between the blasting-cup and me.
3. Ive made a stable blasting cup (hard-paper) with 10 g charge high
pressed DPPP and ignite with a match.
It datonates correctly as well.
Consequently, in high pressed density or under pressure in a
stable blasting-cub - DPPP is a high qualtity and high energetic
explosive, it detonates without a primary igniter.

- somewhat sensitive to friction and shock
- low detonation temperature, ~ 200 C
- density of DPPP are not very high

- required chemicals for synthesis are cheap
- its easy to produce (no expensive lab-equipment required)
- large volume of gas and high explosive velocity, ~ 9000 m/s
(conditioned military usage, cut of steel ...)
- storage stable and great chemical stability

DPPP is my new favourite peroxide. Its safer to handle as AP or HMTD and more powerful and brisant.
Its a very good primary explosive to ignite very insensitive explosives (hexogen,octogen,TNT,HNIW) or a energetic single explosive.

------------------------------------------------------

Does this procedure actually work and did anyone try to make DPPP by this method ?
KABOOOM(pyrojustforfun)
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<blockquote>quote:<hr>After cooling, slowly add the aceton to the HCl and stir the mixture
for 5 minutes.(very slight yellow colouring over a few minutes)
The patent dont say heat at this time and the patent dont say
some product (poron) should precipitate from the solution at this time.<hr></blockquote>the mixture needs to stay for days to obtain a considerable amount of phoron. plus phoron is just slightly soluble in water so if he had no precipitate it simply means he hadn't much phoron in his solution (just enough to give it a <i>very slight yellow colouring</i>.
heating the aceton/HCl mix has the advantages of accelerating the reaction and removing the unreacted aceton (tho I'm not sure about the former)

<blockquote>quote:<hr>Disadvantage: .... - low detonation temperature, ~ 200 C ....<hr></blockquote>as mentioned by others already it's the temperature at which it explodes when it is heated slowly (with a particular rate).
.... - large volume of gas and high explosive velocity, ~ 9000 m/s (conditioned military usage, cut of steel ...)
- storage stable and great chemical stability<hr></blockquote> almost everyone agreed that 9000 m/s is too much for such explosive.... I bet 9000 f/s is closer to its real VOD (not meaning it had been a misprint or such).... BASF's experiments proved DPPP to be even less storage stable than AP!

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Can you explain a bit more storage sensitivity ?

Do you have experiences with DPPP ?
KABOOOM(pyrojustforfun)
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