BASF
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DPPP-the legendary Mackowiak patent
After that the DPPP thread has grown too big to handle, i thought it was time for a new one, making it more easily to take part in the discussion for
other members.
I have picked out the most important points and put it into a huge summary.
A translation of the patent can be found here:
http://sciencemadness.org/library
The additional drawing of the reaction mechanism provided by the inventor here:
http://www.pirotechnika.one.pl/hedm/foron/foron4.GIF
The original patent can easily be found using espacenet, or the german patent server.
For the brave ones, the telephone number of Wolfgang Mackowiak, inventor of the patent: +49 5 21 33 41 44 ; Bielefeld, Germany
Thanks to vulture for building the DPPP-molecule using chemsketch:
http://sciencemadness.org/talk/viewthread.php?action=attachm...
Chemsketch predicts a density of 1.3g/ccm, which is in accordance with the density of the product obtained by following the patent(1.0-1.3g/ccm).
It has been argued many times that the obtained product has to be the common TCAP, but our experiments showed at differs very much from AP in the rate
of sublimation-it sublimizes nearly double as fast as AP.
I have to add that i made the peroxidation step for DPPP (and AP) below 5°C, so we can exclude dimeric acetone peroxide as the reason for higher rate
of sublimation.
Possibly, the storage stability claimed in the patent points only means chemical stability, also a big problem for organic peroxides.-Even more
thinkable considering organic peroxides are usually stored under alcohol or very moist anyway.
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
The second difference many of us already experienced, was that the same quantities being sufficient for AP to detonate upon lighting it with a match,
only caused DPPP to flash.
It seems that DPPP is less sensitive than TCAP so it needs a bigger quantity of it to manage the deflagration-detonation-transition(DDT).
This would be in accordance with TCAP has a detonation temp of 130°C and DPPP about 200°C, claimed by the patent.
Conclusion: For a comparative brisance test between TCAP and DPPP a blasting cap for both would be necessary because DPPP spends a lot of mass for
DDT.
There were various attempts for synthesizing phorone as starting material out of acetone and HCl, but although a lot of time and material has been
invested, so far no satisfactory results in the preparation could be achieved, although lots of interesting things, such as the formation of fluffy
flakes upon neutralization and a nice play of colours could be observed.
Also, my own attempt with pure phorone from sigma-aldrich failed:
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 1:1 mix of 30%H2O2 and 30%HCl(total of 2ml) in a test tube.
It heated up very strong and i repeated the whole procedure with proper cooling(ice bath), but so far 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).
Last but not least, the opinion of a professional chemist on the topic(LOUIS):
http://groups.google.at/groups?dq=&hl=de&lr=&ie=UTF-8&oe=UTF...
The logs of dozens of experiments, especially on the synth of phorone can be found spread throughout the original thread:
http://sciencemadness.org/talk/viewthread.php?tid=179&page=1
More news to come.
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BASF
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sorry for the fucked up post.
After that the DPPP thread has grown too big to handle, i thought it was time for a new one, making it more easily to take part in the discussion for
other members.
I have picked out the most important points and put it into a huge summary.
A translation of the patent can be found here:
http://sciencemadness.org/library
The additional drawing of the reaction mechanism provided by the inventor here:
http://www.pirotechnika.one.pl/hedm/foron/foron4.GIF
The original patent can easily be found using espacenet, or the german patent server.
For the brave ones, the telephone number of Wolfgang Mackowiak, inventor of the patent: +49 5 21 33 41 44 ; Bielefeld, Germany
Thanks to vulture for building the DPPP-molecule using chemsketch:
http://sciencemadness.org/talk/viewthread.php?action=attachm...
Chemsketch predicts a density of 1.3g/ccm, which is in accordance with the density of the product obtained by following the patent(1.0-1.3g/ccm).
It has been argued many times that the obtained product has to be the common TCAP, but our experiments showed at differs very much from AP in the rate
of sublimation-it sublimizes nearly double as fast as AP.
I have to add that i made the peroxidation step for DPPP (and AP) below 5°C, so we can exclude dimeric acetone peroxide as the reason for higher rate
of sublimation.
Possibly, the storage stability claimed in the patent points only means chemical stability, also a big problem for organic peroxides.-Even more
thinkable considering organic peroxides are usually stored under alcohol or very moist anyway.
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
The second difference many of us already experienced, was that the same quantities being sufficient for AP to detonate upon lighting it with a match,
only caused DPPP to flash.
It seems that DPPP is less sensitive than TCAP so it needs a bigger quantity of it to manage the deflagration-detonation-transition(DDT).
This would be in accordance with TCAP has a detonation temp of 130°C and DPPP about 200°C, claimed by the patent.
Conclusion: For a comparative brisance test between TCAP and DPPP a blasting cap for both would be necessary because DPPP spends a lot of mass for
DDT.
There were various attempts for synthesizing phorone as starting material out of acetone and HCl, but although a lot of time and material has been
invested, so far no satisfactory results in the preparation could be achieved, although lots of interesting things, such as the formation of fluffy
flakes upon neutralization and a nice play of colours could be observed.
Also, my own attempt with pure phorone from sigma-aldrich failed:
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 1:1 mix of 30%H2O2 and 30%HCl(total of 2ml) in a test tube.
It heated up very strong and i repeated the whole procedure with proper cooling(ice bath), but so far 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).
Last but not least, the opinion of a professional chemist on the topic(LOUIS):
http://groups.google.at/groups?dq=&hl=de&lr=&ie=UTF-8&oe=UTF...
The logs of dozens of experiments, especially on the synth of phorone can be found spread throughout the original thread:
http://sciencemadness.org/talk/viewthread.php?tid=179&page=1
More news to come.
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DeusExMachina
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CH3COCH3 + HCl= CH3COCH3 -> C9H14O (there will be HCl left over)
H2O2 goes into mix, causing 2 HCL molecules to bond with 2 phorone molecules. H2O2 causes chlorine atoms to
come off phorone and the peroxide (the H202- giving off H2O2) joins the phorone.
thats what I wrote from what I know about DPPP's reaction. My chemistry isn't very good so I didn't understand the other part about the peroxy bond
and stuff. Would someone explain the other part of it to me?
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vulture
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CH3COCH3 + HCl= CH3COCH3 -> C9H14O (there will be HCl left over)
I don't quite understand what you mean with this, would you please clarify?
I described the reaction manufacture *somewhere*  in the DPPP thread. I don't
blame you for not finding it though...
Anyways, if you clarify to me what's written above I'd be happy to explain. Or drop me a mail.
One shouldn't accept or resort to the mutilation of science to appease the mentally impaired.
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DeusExMachina
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no, I saw it vulture. I was just trying to write something to make it easier for me to understand.
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DeusExMachina
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sorry about the double posting again but what I said will not make sense to a lot of people. What I meant was that when the HCl and the
acetone come together phorone is formed? please correct me if I'm wrong.
and when I said "CH3COCH3 -> C9H14O (there will be HCl left over)"
I just put that there to let me remember that the acetone turns into phorone and some HCl is left over that's why this says: "1 part of acetone are added to 1 part hydrochloric acid, through which acetone polymerizes to phorone; then 2 parts of hydrogen
peroxide are added, through which two molecules of HCl bond with the two C-double-bonds of the phorone." the HCl still stays there and does something
with the H2O2.
after the H2O2 part comes in, it gets confusing. maybe clearing up what you wrote in a way that people very new to chemistry (like me  ) will understand
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vulture
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What I meant was that when the HCl and the acetone come together phorone is formed?
True. The HCl catalyses this reaction which is called a condensation.
the HCl still stays there and does something with the H2O2.
The H2O2 oxidizes the HCl to form very reactive chlorine which then chlorinates the phorone.
After the HCl is consumed, there will be excess H2O2 which will then replace the chlorine with oxygen because oxygen is a more powerful oxidizer than
chlorine.
One shouldn't accept or resort to the mutilation of science to appease the mentally impaired.
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DeusExMachina
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thanks a lot!
would you mind (or somone else can) answering one more question? what is a peroxy-bond?
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vulture
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A peroxy bond is a bond where two oxygen atoms are bonded together.
Example: H2O2 H--O--O--H
The --O--O-- part is the actual peroxy bond. Peroxy bonds are usually unstable because the bond is rather weak.
Organic peroxy compounds are usually explosive because the peroxy bond will break easily, thereby shattering the molecule and releasing oxygen the
oxidize other atoms.
I hope that's clear enough.
One shouldn't accept or resort to the mutilation of science to appease the mentally impaired.
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BASF
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Anyone got some time and a thermometer?
1)The decomposition temperature claimed by the patent is about 200°C.
There are relatively cheap mercury thermometers which could be used for this action.
1)make (or just buy) a 0.5-1mm-diameter capillary by pulling out a hot glass pipe(just break it at the desired lenght), sealed on the other end
2)set up an oil bath with ethylene glycol or glycerine (anti freeze) and heat with 5-10°C/min and place the capillary with some mg of the peroxide in
it
*Take care not to exceed 5°C in your DPPP-synth (higher temp. favours formation of dimeric AP).
4)protective glasses needed; hot oil and fragments from the capillary
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vulture
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I've been thinking lately, how could the inventor know what he made? Did he run his product through NMR?
Maybe he made a peroxide of diacetone alcohol or a mesitylene peroxide (or hydroperoxide?). Where does the VoD come from? I think we'd better
shift the priority to finding out if these claims in the patent are true and verified instead of isolating phorone.
One shouldn't accept or resort to the mutilation of science to appease the mentally impaired.
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Iv4
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On BS a few tests were run and most seem to think it's overrated with 9km/s(Bidget pyro is RogueSci's Bryan,btw).They seem to be missing the
point that VoD is'nt everything but I ran it myself and yes I think it's not quite as powerfull as you'd think somewhat stronger than
acetone peroxide but nothing to right home about.Maybe we just put too much expectations in it.
BTW,the BS estimate is 7-7.5km/s
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KABOOOM(pyrojustforfun)
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what is BS?
vulture I agree with u. I assume he did quantitative analytical experiments and found the approx percentage of elements then tried to design the most
acceptable structure that he could explain its mechanism! I'm not belittling him but making a hypothesis.
peroxidisation of t-butanol in acidic media leads to formation of di(t-butyl)peroxide (and t-butyl hydroperoxide?) t-butanol is a typical terciary
alcohol.we can hypothesize tertiary alcohols can be peroxidised with H<sub>2</sub>O<sub>2</sub> in acidic media. so what you
ask? hydrated phoron is a t-alcohol. the following piture shows hydration of phoron acording to Markownikoff's rule:
<img src="http://www.angelfire.com/rnb/pjff/phoron_PJFF.gif">
It's strange nobody mentioned thatphoron like other ketons forms peroxides involving the carbonyl group. knowing mentioned 2 rules various
compounds may be present. <b>if</b> it's supposed to have 5 -OO- then the 2 most possible structures I suggest are as
follows:<br><pre><img src="http://www.angelfire.lycos.com/rnb/pjff/dppp_PJFF.gif"> <img
src="http://www.angelfire.lycos.com/rnb/pjff/dppp2_PJFF.gif"></pre><br>edit: corrected previous pic, added another pic
[Edited on 3-8-2003 by KABOOOM(pyrojustforfun)]
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Iv4
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BS is bombshock.So you'r saying that the reaction is basically the sae as acetone peroxide,MEK peroxide?
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KABOOOM(pyrojustforfun)
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you asked me what I had just said . phoron when hydrated is both a ketone and a tertiary alcohol (IIRC such compounds are named ketols), its
peroxidation is similar to other ketons but there's a slight difference. I don't wanna repeat it again (read the post).
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