| Pages:
1
..
7
8
9
10
11
..
37 |
vulture
Forum Gatekeeper
Posts: 3330
Registered: 25-5-2002
Location: France
Member Is Offline
Mood: No Mood
|
|
I don't need multiple egos fending for me.
J-scan and Matsewhatever are banned. You crossed the line.
One shouldn't accept or resort to the mutilation of science to appease the mentally impaired.
|
|
|
Rosco Bodine
Banned
Posts: 6370
Registered: 29-9-2004
Member Is Offline
Mood: analytical
|
|
Maybe it escaped notice , but in one of the posts by one of the various aliases of what has become a tiresome "clown club" was the
declaration " I am a *chemist* " ,
( not a chemist wannabe mind you , but a genuine , goggles and glove equipped , *thermometer literate* , hour and minute and second hand time telling
, actual for real chemist ) So.....you have to keep wondering about why there isn't a somewhat conventional writeup giving a step by step in
concise language , describing the parameters of the experiment in the usual way .
|
|
|
Smoer
Harmless
Posts: 16
Registered: 24-5-2004
Location: Belgium
Member Is Offline
Mood: Relaxed
|
|
DPPP synth
So,I tried to make phoron first ,but the solution didn't turned red,but just orange.Then after I added the H2O2(30%) it just turned clearless
with a yellow shine.
No crystals found....
What could be the problem?
cheerz
|
|
|
The_Davster
A pnictogen
Posts: 2861
Registered: 18-11-2003
Member Is Offline
Mood: .
|
|
Well, more experimentation 
1. 25mL of 31.45% HCl was mixed with 25mL of acetone in a 150mL beaker. This was heated on a waterbath for 2h at 55->65C the tremp was stable at
around 62C most of the time. The beaker was covered with saran wrap to prevent evaporation of the acetone
2. After 2h had elapsed the saran wrap was removed and the temp was increased to a max of 80C over a period of 10min to drive off the excess acetone.
I was left with an incredibly deep red solution.
3. This is being cooled to -20C
More to come soon.....
When the red solution of dichlorophorone was at -10C an eyedropper full of it was removed and placed in a small testtube. To this was added an equell
volume of 35% H2O2. Some heating was noticed after around 10s, by 20s the solution was yellow, but there was no ppt, the solution was quite warm, but
not too hot to touch. 4mL of commmercial ammonia was added, the solution cleared up but still no ppt  .
I am letting the rest of the DCP solution cool to at least -20 before coninuing experimentation.
[Edited on 22-12-2004 by rogue chemist]
|
|
|
Dodoman
Hazard to Self
Posts: 79
Registered: 2-8-2004
Member Is Offline
Mood: No Mood
|
|
My experience
I've decided to give it a go. And here is what I did, and I'll try to give as much details as I can so please bare with me.
Chemicals:
100 ml acetone
100 ml 30% HCl
200 ml 50% H2O2 (the bottle says 50% but I don't trust that to be correct because it was opened and laying for a couple of month)
I added 10 ml of HCl to the 100 ml acetone and the temp rised 10 c. 40 ml more and 10 c more, the rest was added. The temp was raised a total of 20 c.
I heated the solution in a 900 ml beaker. There wee some nasty fumes of HCl and Acetone. I saw the beaker was refluxing the acetone so I transferred
the sol to a 250 ml beaker and used the 900 ml one as a water bath.
The color of the solution started to change around 65 C. And I noticed the sol boils at 70 c (at that time). The color doesn't seem to get darker
below 70C because I held it at 65C for 10 mins with almost no change in color. So the temp was held at 75C for 15 mins. The solution started to turn
orange and dark orange at the end of the 15 mins. And noticed that the HCl fumes has stoped only acetone is fuming now. The boiling point has changed
and I let the temp rise to 80C (the new boiling point). The reaction was held at 80C for 10 more mins. At the end of the 15 mins the solution have a
tea color. I decided to stop the heat and left the solution in the hot water bath to cool slowly (for 30 mins) to drive as mush acetone off as
possible. At the end of the 30 mins the sol smelled like acetone but the smell was very strong.
The mixture was then cooled in a freezer to 2C and H2O2 to the same temp. The liquid now have a volume of 145 ml ( 55 ml acetone seem to have
evaporated). I started adding the H2O2 dropwise and kept the temp under 30C. As I added the solution started to become lighter in color. After adding
about 30 ml of H2O2 I thought that was enough (the H2O2 seems to be still potent). After a few seconds the solution started to turn white without any
rise in temp. The smell was not like AP a decided to add ammonia to neutralize the solution (didn't test the pH but it should be acidic with all
that HCl in it). So I spilt a few mls of ammonia. White fumes of NH3 smothered me for a few minutes the temp didn't rise though. I'm pretty
sure that what I ended up with is plain old AP. The damp crystals weighted 43 gm. But the strange thing is that when I scarped the crystals with a
spoon they turned yellow and the spoon was covered by a white layer that doesn't come off. The spoon isn't made of stainless steel it looks like tin. Sorry for the length of the post.
|
|
|
leopard
Harmless
Posts: 12
Registered: 14-11-2002
Member Is Offline
Mood: No Mood
|
|
DPPP synthesis ?
About 3 months before reading Matsumoto Hideki's posts I was dabblling with DPPP also and as my results were so similar to his I found his posts
interesting. Please bear with me as this is not very scientific and I worked with very small quantities for safety reasons.
My first try involved 10 ml each of acetone and 31.5% HCL heated to 90 degree C for about 30 minutes. The result was a very dark red/brown almost
opaque liquid. After cooling to room temperature I added 10 ml of 25% h2o2 fairly quickly. The solution went clear/transparent within about 10 seconds
and after about 1 minute began to boil. I left it alone for about 1 hour and found it had stopped boiling and had cooled. I left it sitting for 2 days
and I got about 1 small spoonfull ofwhat appeared to be a very fine powdery AP. It behaved the same and smelled the same so probably was the same!
I decided to try someting different and mixed 10 ml each of acetone and 31.5% HCL together and let this sit for 3 days at room temperature. There was
a very gradual change of colour to light yellow, orange, light red, dark red, and finally very dark red/brown almost opaque like the heated sample
previously. I seperated this into 2 equal quanties and added the first sample drop by drop to an equal volume of h2o2. The colour faded quickly as I
added the red liquid and I was left with a clear liquid that did not heat up. I covered it and set it aside.
I took the 2nd sample of red liquid and added h2o2 to it drop by drop (reverse of previous). Almost immediately the dark red liquid began to lighten
and after adding about 1/3rd of the total h2o2 the liquid had taken on a pale yellow colour and appeared to be filled with suspended particulate
matter. I added the rest of the h2o2 which caused the liquid to lose all colour and it had a small amount of crystal in it.
I left both samples for 3 days and gradually they both developed precipate (a small spoonfull each). The first samples precipitate floated on top and
bubbled. The 2nd samples precipited sat on the bottom with no bubbling. I placed both precipites on a filter paper and let them air dry for a week.
Upon inspection the 1st sample was a very white sugar crystal powder that looked just like AP. Upon flame it woomphed with flash of flame (very short
lived and clean burning). The hammer test set it off easilly with the characteristic smell of AP.
The second sample had a very light yellowish tint to it and was a very fine talcum like powder. Upon flame it woomphed but noticeably slower and with
a dark sooty orange fireball. The hammer test set it off but not easilly and there was no detectable AP odour or much of anything else for that
matter!
I have not had time for further testing but I recognized some similarities between what I experienced and Mr. Hideki experienced. I feel this warrants
further exploration. One note; When I added the h2o2 to the red liquid I noticed the crystal precipate occured allmost immediately and at very low
h2o2 amounts. I should mention that I tried another sample of h2o2 added to the red liquid but accidently added double the recommended amount and I
was left with a water clear liquid that never produced any precipitate. I conclude that there is allmost no minimum point where precipate begins to
form but there is a critical point which if exceeded prevents precipitate from forming.
One last note: I found the treatment of Hideki exccesive, vulgar, unkind and immature. It destroyed the enthusiasm of the thread and left me with a
poor opinion of some members. This board has been a terrific forum for the exchange of mature subject matter. A little more maturity and patience
please, lets get long a little better and get excited about discovering.
Leopard
|
|
|
The_Davster
A pnictogen
Posts: 2861
Registered: 18-11-2003
Member Is Offline
Mood: .
|
|
All righty then.... I think I got some DPPP.
The solution that I mentioned in my last post was cooled all the way down to near -30( an estimate because my thermometer ends at -25). An eyedropper
of this was transfered to a small testtube and an eyedropper of room temp 35% hydrogen peroxide was slowly added. I recieved a precipitate . I let it react for around 30s more and halted the reaction with an ammonia
solution. The yield did not seem as good as was mentioned earlier. Despite the very small volume I filtered it. I was rewarded with a small ammount
of powder, about the size of 1/4 a .177 BB. It was a cream color. It had a unusual smell that I cannot describe, the english language is severly
lacking in words to describe smells, the smell was nothing like that of AP. When it deflagrates a new smell is formed, very different from the smell
of AP when it deflagrates, the smell seemed 'related' ( If that makes any sense when describing smells) to that of the solid DPPP powder.
I repeated the testtube sized test with similar results.
The problems occured when scaling it up... I used the rest of the DCP and poured it into the 1.5L beaker that was in a salt ice bath. I then slowly
added the -30C peroxide, after around 30s I recieved a precipitate. Nowhere near the high yields reported earlier. 300mL of a cold solution of 10g
NaOH in 300mL commercial ammonia was added an the residual orange yellow color disappaared. I filtered out the ppt of (hopefully) DPPP. Unfortunatly
around 1/2 of the ppt was lost as a result of inadvertantly overfilling the funnel ( thanks to a lungfull of ammonia fumes). I am estimating the mass
of powder formed to be at most 0.2g
[Edited on 23-12-2004 by rogue chemist]
|
|
|
Dodoman
Hazard to Self
Posts: 79
Registered: 2-8-2004
Member Is Offline
Mood: No Mood
|
|
I think i failed to explain what happened in my experiment. At the end of the addetion of the 30 ml H2O2 the ppt (which started to form from the first
drop) had a pale yellow color (off white) that didn't look or smell like AP. It smelled like a mixture of acetone and HCl but much stronger and
made my eyes tear. Did you get the same resultes rogue......?
Then it started to turn white (without any rise in temp). That's when i decided to add the ammonia. And after the addition the ppt conteniued to
turn white. I lost alot of the ppt also thatnks to the ammonia fumes. But the remaining whighed 43 gms.
|
|
|
Joeychemist
Hazard to Others
Posts: 275
Registered: 16-9-2004
Location: Canada
Member Is Offline
Mood: Sedated
|
|
43g,good show!
You have 43gms??? Great, would you mind purifying half of the batch?
Weigh out say 20gms and place in a coffee filter or two, then fold the coffee filter over and dip it in a bowl of hot water (like a tea bag) and let
it sit for several minutes at about 100°C.Then wash remaining crystals with distilled water and dry the crystals and measure out how much is left
from the original 20gms, The product left should be almost pure DPPP and mostly AP free. (As I’ve said in previous posts, this will work since AP
readily decomposes at 90°C and DPPP will stand up to higher temperatures than AP will). Doing this would give crucial info about yields and purity,
plus it’s nice to have credible people to compare findings with.
|
|
|
Dodoman
Hazard to Self
Posts: 79
Registered: 2-8-2004
Member Is Offline
Mood: No Mood
|
|
I'm pretty sure it's pure AP with no DPPP in it.
The yellow crystals (probably DPPP) decomposed and I think the components left in the beaker gave AP. Althou i didn't see the crystals dissapear
and new ones form.
I don't have any time to do further testing my term exapms are next week. Besides the smell of AP hurt my eyes and chest (inspite of being left
outside) so I threw them away.
I'll probably give it another go but not before I finish my exams (in a month).
|
|
|
KemiRockarFett
Hazard to Self
Posts: 84
Registered: 23-7-2004
Member Is Offline
Mood: No Mood
|
|
| Quote: | Originally posted by Joeychemist
You have 43gms??? Great, would you mind purifying half of the batch?
Weigh out say 20gms and place in a coffee filter or two, then fold the coffee filter over and dip it in a bowl of hot water (like a tea bag) and let
it sit for several minutes at about 100°C.Then wash remaining crystals with distilled water and dry the crystals and measure out how much is left
from the original 20gms, The product left should be almost pure DPPP and mostly AP free. (As I’ve said in previous posts, this will work since AP
readily decomposes at 90°C and DPPP will stand up to higher temperatures than AP will). Doing this would give crucial info about yields and purity,
plus it’s nice to have credible people to compare findings with. |
According to Federof TATP, acetoneperoxide, is stable in boiling water for 6 hours !!!
|
|
|
Joeychemist
Hazard to Others
Posts: 275
Registered: 16-9-2004
Location: Canada
Member Is Offline
Mood: Sedated
|
|
| Quote: | | Originally posted by KemiRockarFettAccording to Federof TATP, acetoneperoxide, is stable in boiling water for 6 hours !!!
|
It may be stable, but It will still decompose in hot water, (try it) the dimmer version decomposes at lower temperature than the trimer form dose. (I
don't know exactly how much lower) But I can assure you it dose. As I said, try it for yourself.It's AP, it's not that hard to make
some and find out if i'm right or if i'm wrong.
|
|
|
KemiRockarFett
Hazard to Self
Posts: 84
Registered: 23-7-2004
Member Is Offline
Mood: No Mood
|
|
| Quote: | Originally posted by Joeychemist
| Quote: | | Originally posted by KemiRockarFettAccording to Federof TATP, acetoneperoxide, is stable in boiling water for 6 hours !!!
|
It may be stable, but It will still decompose in hot water, (try it) the dimmer version decomposes at lower temperature than the trimer form dose. (I
don't know exactly how much lower) But I can assure you it dose. As I said, try it for yourself.It's AP, it's not that hard to make
some and find out if i'm right or if i'm wrong. |
Okey but I think that the info about DPPP sucks, so where to read about the properties of that compound if its even exist. I think you will end up
with pure tremericacetoneperoxide and that is what you have left after boiling, say I am wrong and Federof telling lies why should the DPPP be stable
to boiling?
|
|
|
Rosco Bodine
Banned
Posts: 6370
Registered: 29-9-2004
Member Is Offline
Mood: analytical
|
|
Federoff is generally accurate but it does contain erroneous information in isolated places . One of those places which comes to mind relates to an
imaginative synthetic method for nitroguanidine from ammonium nitrate which states a reaction that can be found nowhere else but in Federoff and
likely has no validity .
In the early portion of this thread someone stated that they had found a telephone listing for the inventor , and that someone should give him a call
. That sounds like a great idea , if for nothing else but to get a good e-mail or FAX number to exchange some business correspondence pertaining to
the patent .
Has anyone made an effort to communicate directly with the inventor ?
If anyone knows the details of the process , it is certain to be the inventor . Any developer interested in the technology of the invention would of
course need to be able to confirm that the process is technically feasible and reproducible results are necessary to be demonstrated before any
negotiations may be considered with regards to royalties or other compensations . An inventor may have a prepared package of detailed information
ready to send out in response to any inquiries from potential developers , and the information contained may be more extensive and detailed than the
information supplied by the patent . A developer must be assured that a process described by a patent can be reduced to practice .
[Edited on 23-12-2004 by Rosco Bodine]
|
|
|
Joeychemist
Hazard to Others
Posts: 275
Registered: 16-9-2004
Location: Canada
Member Is Offline
Mood: Sedated
|
|
Lets find him
I never said federof was lying, in fact I have never read the book, but that is irrelevant. I don’t think this info about DPPP is “crap” I just
think that we had made due with what was given to us. I don’t know why DPPP is more stable or why it has a higher VoD or why it dose not decompose
as fast as other peroxides. I ADDMIT IT, I don’t know. I spent all last night trying to find this out and I came up with little more than what was
already stated in this thread.
I think that Rosco has brought fourth the solution too this problem. We must find the creator/inventor which first synthesized this explosive. I
cannot track this guy down unless he’s in or around one of the northern states. But we have members from everywhere in the world so I’m sure If we
could just get a name we could go from there.
We could surly track this man down after the holidays. But we need a name first, I looked in the beginning of the thread and could not find any links
or copies of the patent.(not to mention I can’t speak German so I wouldn’t know what I was even looking at) So I ask who has a copy??? Or who at
least knows this guys name???
|
|
|
Rosco Bodine
Banned
Posts: 6370
Registered: 29-9-2004
Member Is Offline
Mood: analytical
|
|
| Quote: | Originally posted by magnum page 5 of this thread on 12-26-2002
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 |
Now why didn't I think of that ?
The address is in Germany .
Wolfgang Mackowiak
4800 Bielefeld
Meller Str. 59 a
The German patent is DE1951660
( see attached file )
There is an idea I have been wondering about concerning the initial condensation reaction of three molecules of acetone under acidic conditions . It
is known that two molecules of acetone will condense under very slight basic conditions to form diacetone alcohol , ( GB356609 ) , and the first
reaction shown on page 1 of GB362204 . I have been thinking that perhaps the first 2 molecules of acetone are condensed under basic conditions to
first form diacetone alcohol , and then the diacetone alcohol is futher reacted with a third molecule of acetone under acidic conditions which results
in the phoron precursor of the patent .
Well I think I may be on the right track . Indeed the precursor shown by the patent in the first reaction condensing three acetones is a compound
called triacetone dialcohol , which is a known precursor for phorone , see GB830813 , page 1 line 58 . GB616740 and GB583863 are phorone from acetone
related synthesis . Hmmmm , alkaline conditions not acid , very strange . And the conditions described by such patents for condensation of three
acetones to triacetone dialcohol then subsequently dehydrated to phorone , all use autoclave extreme pressure and high temperature alkaline conditions
which are low yield per pass , multiple pass processes . It could be that there are autoclave conditions required for the Mackowiak acid catalyzed
condensation and dehydration of acetone to phorone or phorone dihydrochloride .
[Edited on 25-12-2004 by Rosco Bodine]
Attachment: DE1951660.pdf (155kB)
This file has been downloaded 1221 times
|
|
|
Rosco Bodine
Banned
Posts: 6370
Registered: 29-9-2004
Member Is Offline
Mood: analytical
|
|
Earlier in the thread PainKilla suggested use of free chlorine as possibly being useful in producing the chlorinated phorone intermediates for DPPP .
The suggestion is interesting and it caused me to consider a source for chlorine which may have value in this reaction . There is a high chlorine
content compound which is used as a chlorinator for swimming pools , and it is highly soluble in acetone , which dissolves 385 grams per liter of
acetone . The chlorinator is called trichloroisocyanurate or trichloro-triazine-trione . The material is very soluble in concentrated H2SO4 , from
which it may be recrystallized . But in the presence of moisture the compound slowly hydrolyzes with the evolution of free chlorine . It would seem
to be a promising candidate for facilitating the formation of the chlorophorone intermediates of the Mackowiak patent , where trichloroisocyanurate
might substitute for much of the HCl / H2O2 used as a source for free chlorine . Some free cyanuric acid added to such a reaction system might also
be useful . It would be an interesting experiment to dissolve in acetone some trichloroisocyanurate and see what may occur when this is mixed with
hydrogen peroxide , in reaction systems where is also present HCl or H2SO4 , or both . This may provide a new area of experimentation for pursuit of
DPPP by a modified approach . Or perhaps other interesting cyclic peroxides may result . On an entirely different subject , an acetone solution of
trichloroisocyanurate may have interest as to possible reaction with urea . Just off the top of my head it would seem there may be potential there
perhaps as a route to hydrazones or hydrazine . I have not drawn the first reaction diagram to see if this seems plausible so this is pure
speculation on my part .
[Edited on 25-12-2004 by Rosco Bodine]
|
|
|
kclo4
National Hazard
Posts: 916
Registered: 11-12-2004
Location:
Member Is Offline
Mood: No Mood
|
|
There may be a way with sodium percarbonate
|
|
|
Rosco Bodine
Banned
Posts: 6370
Registered: 29-9-2004
Member Is Offline
Mood: analytical
|
|
At last it would seem the Mackowiak patent for DPPP is gaining some validity , even though certain details remain to be fully understood . My
contemplation of the process has been based entirely upon reading with interest the threads here and at E&W , and deliberately not doing the first
experiment of my own , until I have confidence in the theoretical basis for the compound attempted to be synthesized . This is my typical method
following years of time and wasted reagents with purely trial and error experiments , to spend much more time with the theory of reactions being
worked out on paper , before proceeding with the more fun part of actually attempting the synthesis . It is much easier to perfect a synthesis when
observations can be made with the benefit of some understanding derived from a plausible theory concerning the reaction being observed . This is at
the heart of the matter when the task at hand is knowing how to get the most of the purest product desired from the precursors , by an efficient
method whose details are unknown , but being discovered by way of experiment . From the reading of these threads , an understanding has developed for
me , now sufficient to describe what I believe are logical conclusions in summary of the various experiments done by others concerning DPPP .
First of all , phorone itself is *not* a valid precursor for diphoronepentaperoxide ( DPPP ) . This is one of those cases where the structure of the
DPPP "derivative" is related in name only to the "parent" compound as a compliance with naming convention only , to designate
structural similarity for the derivative , but *not* to suggest that the route of synthesis must involve the "parent" phorone itself , but
rather another derivative of phorone . This sort of occurrence is not uncommon in chemistry . The actual "phorone related" precursor for
DPPP is "phorone dihydrochloride" not phorone itself . Since phorone was reported to be insoluble in HCl , then it would seem likely that
"phorone dihydrochloride" is also a derivative of phorone in name only , not to sugggest it is synthetically derived directly from phorone ,
but from a phorone related structure , the hydrated form of phorone , which is triacetone dialcohol . The triacetone dialcohol is initially formed
from the condensation of 3 acetone molecules in the presence of HCl , and then further combines with 2 HCl's while at the same time losing 2
H2O's to form phorone dihydrochloride .
So we see that "phorone dihydrochloride" does *not* form from phorone and hydrochloric acid , but does derive instead from triacetone
dialcohol and 2 HCl's with the loss of 2 H2O's .
The phorone dihydrochloride is then chlorinated further by the action of free chlorine to form pentachlorophorone , according to a chlorination scheme
described by the patent , which involves a side reaction between HCl and H2O2 .
This chlorination mechanism appears to be speculative , and the actual reaction may involve hypochlorous acid as an intermediate , or the reaction
with "free chlorine" stated by the patent may be a gross oversimplification for a complex reaction involving HCl and H2O2 and the
phorone dihydrochloride through the formation of an undefined and unspecified unstable intermediate for the end product DPPP which precipitates
spontaneously from that unknown transition species .
This seems likely to me since the mixing of H2O2 and HCl does not produce clouds of free chlorine , in my experience , but simply produces a mixed
solution of HCl and H2O2 in H2O . Generally reaction of such a mixture is observed only after some additional material is added to the system , as
would be occurring with the process of peroxidation of some organic material added to the solution , which we have in the process for DPPP . Further
experiments would be required for clarification of the actual reaction mechanism involving the formation of pentachlorophorone from phorone
dihydrochloride .
Following the controversy in the heated discussion here which has led to some members being blocked or banned from posting , the discussion was
carried a bit further with similar controversy at another forum where the same topic has been followed with interest . Since a more lucid writeup of
the synthesis has been provided , which has pertinence to the development of the topic originating in this forum , including my own investment of time
studying these reported experiments , I hope it is allowable to quote with credit and provide a link to the more detailed information about the latest
efforts at a synthesis of DPPP . Some difference will be noted in the identification and naming of intermediates in the description below , but the
discrepancies are reconcilable and it is the process being described in detail which is significant . The following updated description of the
synthesis of DPPP is credited to j-scan , and quoted from his post at E&W ,
http://www.roguesci.org/theforum/showthread.php?p=68338&...
| Quote: |
j-scan December 26th, 2004 04:09 PM
--------------------------------------------------------------------------------
Here is my write up...
I started with a 1:1 ratio of HCL and Acetone and added heat until the color changed to a dark orange. I continued the boil on a low setting and got
the color down to a dark red -black) and then cooled it down over a period of days "freezer would have sufficed just fine".. The solution
changed color again and the viscosity also changed to a motor oil consitency(very thick). This oily liquid is relitivly pure Pentacholorphorone (dark
yellow orange.. looks black in standard light) say 90-95% and about 10-5% H20.. Ok I am guessing here... It has not much acidity to it anymore. You
then have to add a few mls of HCL to get the peroxidation happening. After adding the HCl you then add H2O2 and give the solution a stir.
Cl2 is immediatly ejected from the solution (you can smell this)which turns bright yellow ( heat climbs up rapidly) and a yellowish orange precip is
immediatly formed at the bottom of the flask... this then eventually migrates to the top of the flask where you can scoop it out with a plastic spoon.
The more pure the liquid the better the yeild.. a small flask say 100ml SHOULD optimally yeild you around 80ml of crystals.
---problem occured the first time I tried this: because the solution was not completely reacted , TC AP formed with the DPPP... ALL of the left over
acetone must be evaporated in open air for their to be pure DPPP.
-------------------------------------
more info and improved method as of 11pm Dec 25th:
--------------------------------------
Please follow carefully:
For the best results--->
200mL Acetone
300mL Muriatic Acid (30% HCL)
Mix together into a glass container and place into a hot water bath to 100C
Boil for 45 minutes until solution changes to a dark orange-red. Remove heat.
Allow the solution to cool off to 2 C or so for at least 10 hours without a lid. I left my solution for 24hours at room temperature. The solution
should at this time be almost black as the HCL will have converted the majority of the acetone onto thick viscous Chloro-Phorone. Left over HCL
content should be minimal.
The next step is to reintroduce 30ml of HCL catalyst into the Chloro-Phorone solution and add 500mL of chilled 35% H202. Chlorine gas will be
expelled. A mass of yellowish -orange crystals should appear almost instantously, The temperature should increase slightly but should not boil over.
Dry the crystals using distilled water and ammonia/ or bicarbonate solution. rinse and dry.
-----the end product is quite stable when dry---not as shock sensitive as AP but highly explosive in the presence open flame or any surface
temperature above 190C. |
Hopefully these additional details and ideas of my own are helpful in further experiments seeking to confirm the Mackowiak patent for DPPP , and
resolve some of the valid questions which have ben raised by earlier experiments in that effort .
|
|
|
Pyroz
Hazard to Self
Posts: 76
Registered: 27-12-2004
Member Is Offline
Mood: curious...
|
|
The mistake that most people make while creating Phorone diHydrogen Chloride is in leaving the material to cool off. You have to leave the
"chloro-Phorone" to sit in open air to evapourate any unreacted acetone. The result will be a highly vicous oily liquid which has a fruity
smell to it..it doesn't smell like HCL or acetone in anyway. Once the liquid has been cooled to 5C add in HCL to prime the reaction and them add
30% H202--- precip will form immediately.
|
|
|
Matsumoto_Hideki
Banned
Posts: 103
Registered: 27-12-2004
Member Is Offline
Mood: detonated
|
|
pics related to J-SCAN's developments
Alright, I know I am posting from the Same IP adress
but again I am on a router so don't kill me. Ok?
look at the pics at my webshot account.
http://community.webshots.com/user/matsumoto_hideki
see the 2nd to last pic... I assume this is pretty pure DPPP as the characteristics were way different.
[Edited on 28-12-2004 by Matsumoto_Hideki]
|
|
|
Rosco Bodine
Banned
Posts: 6370
Registered: 29-9-2004
Member Is Offline
Mood: analytical
|
|
There is almost certain to be an optimum ratio of acetone to HCl , combined and then heated to a specific temperature and held there for a specific
time to produce the optimum yield of phorone dihydrochloride with least amount of higher polymerization products or other undesired byproducts . My
guess is that
it requires a bit less HCl for the initial stage of the reaction producing phorone dihydrochloride , than is being used presently . Of course on a
molar basis ,
the minimum requirement of HCl is 2 moles of HCl for every 3 moles of acetone . And probably a little excess of that theoretical amount of HCl , on
the order of perhaps 5 % excess of theory should be plenty to drive the reaction .
For use of pool grade muriatic which is 31.45% HCl , that would amount to 210 ml of the HCl mixed with 220 ml acetone , which is very close to the
patents equivalent volumes . The actual theoretical proportion without any excess for HCl would be 200 ml of HCl 31.45% for each 220 ml acetone . What
we don't want is any large excess of HCl since it is catalytic in an already vigorous reaction . And the volatility of acetone insures that some
of the acetone is going to be lost to evaporation , which will result in an excess of unreacted HCl as a given . The volatility of the acetone would
make this a reaction better suited to being done in a closed system , with some provison for
reflux , that is for condensing and returning any acetone vapors back to the heated reaction mixture . Something as simple as a smaller jar or bowl
filled with ice cubes and set into the opening of the container in which the acetone and HCl mixture is being heated would be helpful in keeping the
acetone from escaping and
not only reducing the yield by its loss but causing an overly acidic residue to be what remains when the heating is finished .
[Edited on 28-12-2004 by Rosco Bodine]
|
|
|
Pyroz
Hazard to Self
Posts: 76
Registered: 27-12-2004
Member Is Offline
Mood: curious...
|
|
end product
..this was my end product---after peroxidization of the Phorone dihydrogen chloride. I compaired the color to standard AP--- here is what it looks
like.
|
|
|
Joeychemist
Hazard to Others
Posts: 275
Registered: 16-9-2004
Location: Canada
Member Is Offline
Mood: Sedated
|
|
Sweet!!
It looks like Rosco is doing most of the work here. I think that you are correct with most of what you said and upon a second glancing of the patent
it is actually quite obvious now what reaction is happening. But why the hell don’t they specify and elaborate, I mean why the hell wouldn’t
patent specify such important details, I guess they felt it wasn’t necessary. I do however think that the procedure mentioned above is working but
it is rather vague and some mistakes need to be fixed but I think we have something to go by now, something to build on. This latest information you
have provided is the most crucial piece of the puzzle we needed.
I tried j-scan’s procedure, although I must say I did produce some fine DPPP crystals, I have to report good, bad and strange results.
I used the exact specifications in the procedure mentioned above by j-scan. only I scaled the procedure down to 50ml Acetone and 75ml HCl 30%. I
slowly heated the mix for 2 ½ hrs with a plastic sheet over the reaction vessel to minimize the evaporation of the phorone. (I noticed the phorone
was condensing on the plastic sheet quite a bit, so I had to put a 1g weight in the middle to cause the condensation to run back into the reaction
vessel). After letting the phorone cool and sit for 12hrs without the plastic sheet the phorone smelled very sweet and slightly acidic and was very
dark red.
Next I split the solution into two beakers, beaker A and beaker B, I added 7.5ml of 30%HCl to the phorone in beaker A which caused some heat, I did
nothing to beaker B. I then chilled both to 2C and added 62.5ml 35%H2O2 to both beakers. The heat increased 10 C in both beakers. Beaker B formed a
few yellow crystals almost immediately but then stopped and started a very slow bubbling precip (AP), but not for long. But beaker A with the
additional HCl added beforehand formed very nice yellow crystals, but they smelled acidic! I washed in sodium-bicarb 2 times and dried on a paper
towel, 2g is what I ended up with. That’s not too good. The dried crystals smelled weird. It was a soft smell not like phorone and not like AP.
I noticed a very peculiar smell before and after burning. This was is not AP, the two were nothing alike. The substance recovered was a very light
yellow/green in color and smelled like umm… I can’t really describe it, but I like it, it’s a weird odor and it’s not very strong. The
collected crystals will detonate with sharp report when held 3” above a Bunsen burner in quantities less than 0.2g and only produce a miniscule
amount of smoke, no real smoke to report thought. A hammer test proved it to be more stable than AP but not much. Density was higher than AP but only
slightly.(I can’t really tell with my crapy method and scale). Upon examination of 0.1g under a microscope at 100X I could clearly see DPPP
crystals. Not only that but I could see both TCAP and DCAP and I could also see broken DPPP crystals that broke when I put the sample between the
glass sample slides.
After I was done with the usual tests I had enough left for a brisance and power test. I packed 1g of the suspected DPPP into a tube with exactly 2½
kg pressure (I have a press) I did the same with 1g AP. I drilled a hole in two red masonry bricks and placed the mini charges in the holes, they fit
snug. The AP broke the brick into several large pieces while the DPPP shattered the brick into many smaller pieces. It was quite clear who the winner
of this test was.
I don’t like the fact that I only produced 2g with all that H2O2 I dumped into the mix I should have made more. I would have made atlest 10 grams of
AP with the same amount.
In conclusion, this procedure works but not well. We now have to solve the other side of this “rubrics cube”, the details of j-scan’s procedure
are sketchy, but I think that we are on the right track now, but this is going to take a lot of testing now to set the difinative synthesis for DPPP
down on paper. We now need to find temperature and time range, how to increase total product yield and I would really like to know if this explosive
could be prepared from other precursors.
Rosco, since you do not wish to waste you’re reagents and you have obviously put fourth you’re time and effort into identifying the reaction which
occurs, I am willing to waste mine to further our knowledge and understanding of DPPP as well. Just let me know if there is something you would like
me to try or test. I have used the last of my acetone and must get more to further the testing.
Sorry for the long post
Edit] I just realized why the yield was so shity. J-scan is off on his measurements and I followed his instructions carefully so while scaling down
the procedure I didn’t even notice the error. That tard J-scan is using two parts 35% H2O2 when the patent calls for two parts 30% H2O2, so I
wasted precious H2O2 because this fool mis-calculated and I assumed he was right. But still that little miscalculation did not affect my total yield
that much. Like I said there are problems that need ironed out.
[Edited on 28-12-2004 by Joeychemist]
[Edited on 28-12-2004 by Joeychemist]
|
|
|
Rosco Bodine
Banned
Posts: 6370
Registered: 29-9-2004
Member Is Offline
Mood: analytical
|
|
That AP / DPPP comparison picture looks very interesting indeed
It seems to me that once the synthesis of DPPP is well understood in all its variables and the optimum ratios and temperatures , ect. are established
, that it would be valuable to then investigate the possibility of coprecipitation of DPPP with MEKP and perhaps even AP as well , given the
possibility of producing a high density product which is a binary or tertiary composition . If DPPP is difficult to obtain as dense crystals , as
some have reported , then that is one way to solve that problem . Another idea for slowing the precipitation of the DPPP and improving its crystal
density is to dilute the "red oil" with methanol before its peroxidation , and see if dropwise addition of the peroxide with stirring will
result in more dense "gritty" crystals of DPPP . Keeping any added HCl to a minimum may also help slow the precipitation and aid crystal
growth .
|
|
|
| Pages:
1
..
7
8
9
10
11
..
37 |
![[*]](images/xpblue/default_icon.gif){kind=icon}
