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Pyroz
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| Quote: | Originally posted by Mickhael
I'm just double checking here, i have read hundreds of posts...but done very little of my own synths, so i want to get it right.
Also, that still didn't answer my question about how much bi-carb (water + powder) to use, and if the speed is you need to add it withen 5
seconds, that i've read...that makes timing very crucial! I may have missed it in reading, but i didn't notice anyone who gave conclusive
amounts...or timing.
[Edited on 3-1-2005 by Mickhael] |
I didn't add in any base to my DPPP synth. I tested the acidity before I started my reaction and it was really mild.
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Matsumoto_Hideki
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I don't think you have read the recent posts
The current method of DPPP production is dropping the temperature down as cold as possible (-25c to -30c) in a freezer then slowly adding the H2O2
over the course of several hrs. This method yeilds the most amount of DPPP per ml. Heating is a nonissue with this current method.
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Rosco Bodine
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Yes with enough cooling , reaction heating is a non-issue . But doesn't a very low temperature also complicate things by introducing a
miscibility issue , which itself can cause surges in temperature that may not occur for a more dispersed mixture at a slightly warmer temperature ?
That has been my line of thinking on this , but I can tell more when I observe the temperatures on a peroxidation in progress , and actually see
better the
effect of temperature and rate of stirring and rate of addition , knowing such things all work together harmoniously within a range that will give
good results . Then you sort of choose the median values for those variables as your "target" reaction condition , which allows your control
error some space to vary a bit up or down , while still giving good results . Maybe the reaction does work best working with the highly viscous
precursor at very low temperature for this particular case , but generally it would be worth investigating whether this is certain , since the
physical
considerations suggest a more moderate
reaction condition may work also with certain benefits , from the milder conditions . Of course the milder conditions may not work at all , but it
seems probable it would do okay . How you go about this reaction may be influenced also by what equipment you use and how closely you can control the
reaction .
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Pyroz
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too cold--- no good
I'd say if you were to keep the temperature somewhere in the neighbourhood between -5C to 1C this would be optimal. I get the best crystal
growth at 1C.
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Rosco Bodine
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"Thinking outside the box" is something I deliberately do when trying to analyze a complex reaction . And in that spirit , there is one
thing that I must say I have wondered about all along concerning this reaction , with specific regard to the conversion of the phorone dihydrochloride
to pentachlorophorone , I have wondered if perhaps this first part of the reaction using hydrogen peroxide sufficient to accomplish the chlorination ,
should be a reaction run *hot* , and then the actual
peroxidation reaction run at room temperature or just slightly cooler . There is no reaction condition specified by the patent , so
it is only guessing how the inventor performed the synthesis , and there may even be different ways of performing the synthesis which will work
equally well , or some better than others , or only one way which works at all . I do not dispute the findings of others experiments , but only have
some uncertainty that their conclusions are entirely correct , when such conclusions may be premature . I wish to not leave a stone unturned in
considering what possible experiments with variations on the methods may shed light on the details not disclosed by the patent .
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Pyroz
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| Quote: | Originally posted by Rosco Bodine
"Thinking outside the box" is something I deliberately do when trying to analyze a complex reaction . And in that spirit , there is one
thing that I must say I have wondered about all along concerning this reaction , with specific regard to the conversion of the phorone dihydrochloride
to pentachlorophorone , I have wondered if perhaps this first part of the reaction using hydrogen peroxide sufficient to accomplish the chlorination ,
should be a reaction run *hot* , and then the actual
peroxidation reaction run at room temperature or just slightly cooler . There is no reaction condition specified by the patent , so
it is only guessing how the inventor performed the synthesis , and there may even be different ways of performing the synthesis which will work
equally well , or some better than others , or only one way which works at all . I do not dispute the findings of others experiments , but only have
some uncertainty that their conclusions are entirely correct , when such conclusions may be premature . I wish to not leave a stone unturned in
considering what possible experiments with variations on the methods may shed light on the details not disclosed by the patent .
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I was having a similar discussion with several chem grads over the weekend. H202 may infact create a phorone of sorts when heated.--- never tried it
though.
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Mickhael
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Ok, I did miss some posts...sorry, I must have been trying to speed-read and skipped them  Anywho's I'm going to try re-heating and bringing my remaining liquid (and covering the flask) down to the dark, thick quaility
needed. I have noticed the sheeting of the liquid on the glass as I swirl it as well rosco, I can't see any seperation as of yet however...more
results when I've completed them.
I might not be doing anything today, as its my 21st birthday  wohoo!
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Pyroz
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| Quote: | Originally posted by Mickhael
Ok, I did miss some posts...sorry, I must have been trying to speed-read and skipped them Anywho's I'm going to try re-heating and bringing my remaining liquid (and covering the flask) down to the dark, thick quaility
needed.... |
Thats the idea Mickhael. If you do this and you get a very thick liquid that is nearly black--- then I'd say cool it off to -3C and add HCL and
H2O2--- make sure the reaction temperature doesn't go above 5C or you'll get TCAP forming with DPPP.
I froze my canning jar with phorone into a block of ice to keep the temperture cool while i began the peroxidation process.
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Rosco Bodine
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| Quote: | Originally posted by Pyroz
--- make sure the reaction temperature doesn't go above 5C or you'll get TCAP forming with DPPP.
I froze my canning jar with phorone into a block of ice to keep the temperture cool while i began the peroxidation process. |
This is one of those matters about which I have uncertainty , as I can see no
reason why AP should be produced at all at any moderate temperature in such a mixture . It is a long way back to acetone from the precursor being
peroxidized , and difficult to see that such a hydrolysis would be favored by the mild temperatures . I could see it easier if someone said that
extended boiling with NaOH causes the precursor to revert to acetone . But it just seems unlikely under the conditions described . If you got AP
forming simultaneously with DPPP , then the first idea I would have is that you have free acetone mixed in with the precursor , rather than the
precursor would be reverting back into acetone at 5 C . It just seems unlikely and very strange .
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Pyroz
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When i first tried making this material--- I tried keeping the tempertaure at 5C--- and it ran away on me. I got lots of white crystalline precip HCL
gas which was quite nasty--- i could NOT keep the reaction under control.
in a cold environment thing seem to work better.
DPPP reaction is very odd...
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Rosco Bodine
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Agreed it is a strange synthesis , peculiar solubilities and generally wierd stuff .
What conditions of agitation were you using , hand stirring or magnetic , ect . ?
And what rate of addition is best for the H2O2 , also was that rate limited by temperature rise from reaction , or was it limited because of other
reasons like miscibility , gas evolution , or some combination ?
Do you think perhaps it was actually DPPP that was the crystals you were getting , and that more efficient stirring and close control of the addition
rate could control the exotherm , preventing runaway , or was the product itself decomposing after it precipitated at above 5 C ?
[Edited on 4-1-2005 by Rosco Bodine]
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Matsumoto_Hideki
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freezing phorone in ice brick works the best!
I just tried to make another very tiny batch of DPPP without ice and it seems to really not work very well. I do think heating occurs either way but,
the heating is able to be dissipated into the ice than say water at above 5c.
However I just use a 450ml container ultra pure Phorone HCl and made cold formed DPPP with it.. My yeild is in excess of 300g and is right now drying
as we speak. Yay.. I am going to attempt to make DPPP detcord as soon as all my DPPP has fully dried. I am still thinking what I need to make an
explosive past from it... hmm... I think MEKP is out of the question as it is a bit too toxic and reactive to vinyl plastics..
hmm, any ideas?
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Mickhael
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Drying?
Whats the recamended method of drying Peroxide crystals? any suggestions? I would tend to think that as soon as they are dry, making a slush solution,
by mixing them with Acetone or even possibly MEKP would make the movement and storage much safer...any thoughts?
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Joeychemist
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IMO, I don't think temperature will affect the amount of formation of AP but it will affect the type of AP formed. The patent says 90% yield so
we figure the other 10% has some amount of AP forming and the rest is waste, but since we and I don't think even the inventor even knows the
exact reaction which is happening or how to separate and purify all the active chemicals from the waste, I don’t really have a solid basis for my
conclusions or anything else to really back this up, as I see it there are two possibilities which I have derived from my experiments and
observations.
One;
We cannot achieve anything greater than a 90%DPPP yield, no matter what, so we can either control the temperature to control the amount of trimer vs.
dimer AP forming with our DPPP. And again, just because the temperature might not affect the amount of AP formed it obviously does affect the amount
of DPPP formed and the time it takes to form it.
Or option two, we more than likely have to continue to conduct the necessary tests to understand the reaction fully and the exact chemicals involved
and can find a way to purify and separate the active and waste chemicals. Then try to achieve a better than 90% total DPPP yield. Tracking down and
making contact with Wolfgang Mackowiak still sounds like something that has to be done.
Rosco, the gas evolution is a problem with most reactions but it is only minimal, the only really visible gas evolution I notice during the procedure
is during the initial mixing of HCl and Acetone and the peroxidation step, and the only gas I can really smell is chlorine, but that is what one would
expect when attempting this reaction. The only other gases produced IMO is H, O, Cl, and these occurred only as a result of being lighter than the
solution there in. therefore during the reaction the molecules split and the oxygen and hydrogen starts into accent and some of these gas molecules
escape the solution taking some additional chlorine and *possibly* something else with them too.
Hideki, I now believe you when you say you and pyroz are two different people, it is quite obvious when reading you’re posts. You might want to try
making a putty or paste by adding and kneading together 1 part NC (smokeless powder) with 1 part acetone and 2 parts DPPP. You can use a slight excess
of acetone, as it will evaporate. And you might want to watch freezing you’re reaction vessel in ice, have you no idea how much pressure that puts
on you’re beaker?
And pyroz, please note that Hydrochloric acid is spelled HCl, notice the lower case l.
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Matsumoto_Hideki
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Hey joey...
Well I know it took long enough for people to start to understand that 2 people can infact share the same IP address via the "magic router"
...... Vulture is a prime example of this.
Yes it is possible to get a 90% yeild, I have got this on several occasions only when I concentrated the solution at 30c for 1 week. patent says
nothing about a yeild greater than 90% being possible.
Anyway, I agree that high temperatures affect the kind of AP if at all that co-form with the DPPP. So far I can tell you that concentrating your
Phorone HCl at 30c or better for 1 week results in no AP being co-formed when using the cold formation method. All that forms as a result of this is
pure brilliant sulphur yellow crystalline DPPP.
I think for safety's sake cold formed DPPP method is best since it decreases the risk of a caustic boil over or steam explosion, i think this
is due inpart by too much Cl2 being given off at one time in the reaction.. I have seen a couple nasty ones
, I will tell you!
[Edited on 4-1-2005 by Matsumoto_Hideki]
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Rosco Bodine
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Is it possible that when you see white crystals , you are influenced by the assumption this must be AP , for believing that DPPP is yellow ? What I
have been thinking is that the white crystals are possibly not AP at all , but simply DPPP which is precipitating in purer form above a certain
temperature , but perhaps too close for comfort to the temperature where you are having problems with temperature . In remedy for that , you are
running the reaction colder which solves the instability ,
but perhaps at the expense of purity of the DPPP precipitate , which is tinted with some precursor at the lower temperature .
Does this scenario seem possible ?
Also when you have seen a runaway , exactly what happens ? Have you had a thermometer immersed in the reaction mixture itself to observe at what
temperature where the reaction sours ?
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Matsumoto_Hideki
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| Quote: | Originally posted by Rosco Bodine
Is it possible that when you see white crystals , you are influenced by the assumption this must be AP , for believing that DPPP is yellow ? What I
have been thinking is that the white crystals are possibly not AP at all , but simply DPPP which is precipitating in purer form above a certain
temperature , but perhaps too close for comfort to the temperature where you are having problems with temperature . In remedy for that , you are
running the reaction colder which solves the instability ,
but perhaps at the expense of purity of the DPPP precipitate , which is tinted with some precursor at the lower temperature .
Does this scenario seem possible ?
Also when you have seen a runaway , exactly what happens ? Have you had a thermometer immersed in the reaction mixture itself to observe at what
temperature where the reaction sours ? |
first of all the white crystals have got to be AP as they sublime after 10-15min in near boiling water 70-80c
were as the yellow material WILL not sublime at all.
secondly a boil over seems to occur when the liquid Phorone HCl is above 5c. The moment H2O2 is added the solution immediatly heats up +30c than
liquid temp, there is an instant smell of chlorine and the bottom of the container vessel turns clear and a black oil appears at the bottom of the
flask. Is this a phorone derivative? After this you a have a few seconds before the temperature jumps to beyond boiling point. I have measured the
temp in just about every instance, and in one such occasion the temp whent from 32c to a full out steam explosion (reminded me of a geyser) in mere
seconds. I guess we are dealing with too much chlorine too fast being released at a single moment which = BIG HEATING.?
This make sense to you? Yet the same amount if chilled into the -30c range refuses to get above -15c and has a much better amount of product.
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Rosco Bodine
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Does the runaway you describe happen even when the H2O2 is being added dropwise to the rapidly stirred precursor at 5 C ? Or is it something that
occurs when a large amount of peroxide is added in one portion ?
BTW the molecular weight of DPPP is about 434.50 and for 100% yield based on acetone , that works out to .98486 grams of DPPP from each 1 ml of
acetone .
The 90% yield reported for the patent works out to .8864 grams of DPPP from each 1 ml acetone .
[Edited on 4-1-2005 by Rosco Bodine]
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Matsumoto_Hideki
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Finally a mole weight.
Ok what you describe for %iles makes sense and explains the monsterous yeilds I have been getting.
My 250ml jar yeilded me 156g total when it was dry of course.
My most recent 450ml yeilded me 400g but it is still wet so i am guessing more like 300-350g? Still this is quite a bit product.
next thing... about runaways happening above +5c .. these seem to start when
a) too much H2O2 is added at once
b) too much unreacted HCl is present in the Phorone HCl.
c) too little H2O2 is added and allowed to form a bottom layer which then encourages the rest of the material to decompose from the heating.
[Edited on 4-1-2005 by Matsumoto_Hideki]
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mr.pyro
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Hideki,
To get these huge yields, your just using Rserts Synthesis, but just very cold and slow H202 addition? How much H2O2 do you recommend I add for the
first peroxidation, I have about 400 Ml of Black Phorone? And the second? I really would like to get a good yield out of this batch, because I am
running down my Hydrogen Peroxide supply.
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Rosco Bodine
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| Quote: | Originally posted by Matsumoto_Hideki
Ok what you describe for %iles makes sense and explains the monsterous yeilds I have been getting. |
The
acetone is the starting material , from which all the intermediate precursors form , and therefore on which the final yield is based . So every
milliliter of acetone that escapes as vapor is lost to the reaction , and makes for less DPPP in the filter at the end . That's why the good
yields will require preventing the loss of acetone , especially during the first couple of hours until it is polymerized to a less volatile form .
Very little pressure is produced if the mixture is incubated below 70 C , so about any sort of lightly sealed container could be used to prevent
evaporation loss of acetone while the mixture is gently heated . | Quote: |
My 250ml jar yeilded me 156g total when it was dry of course.
My most recent 450ml yeilded me 400g but it is still wet so i am guessing more like 300-350g? Still this is quite a bit product.
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Multiply the amount of acetone in milliliters by .9849 to see what 100% yield would be . Measure your
actual weight in grams of dried crystals and divide that by the first number you got for what would be 100% yield and the number you get will be your
actual yield based on acetone . | Quote: |
next thing... about runaways happening above +5c .. these seem to start when
a) too much H2O2 is added at once |
breaking the law of mass action gets everybody busted every time | Quote: |
b) too much unreacted HCl is present in the Phorone HCl. |
catalytic and then autocatalytic action to make
matters worse , yes I saw that one coming , and that agrees with the reaction theory . | Quote: |
c) too little H2O2 is added and allowed to form a bottom layer which then encourages the rest of the material to decompose from the heating.
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stratification , insufficient mixing , until it mixes itself by decompositon from "hot spots"
which churns the mixture and then geometrically progresses , "the avalanche effect" or "snowball effect" , classics all which can
be managed with good technique .
This reaction behaves a lot like nitrations of an easily oxidized material , touchy about temps and addition rates and agitation , but probably the
usual strategies would keep it controllable .
There is probably a "smooth reaction temperature" at which the reaction will proceed at a rate controlled by rate of addition of the
peroxide , and in keeping with the cooling capacity a steady reaction at a steady temperature will yield crystals of uniform size in predictable yield
. Nothing so far there looks insurmountable in regards to scaleup concerns , or repeatability . The next free time I get , I'm going to run
this reaction a few different ways and see what develops . There are likely some small improvements that will get discovered and refinements added to
the process as many people experiment and track the results .
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Matsumoto_Hideki
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That sounds a bit better,,
1# 250ml x .9849 = 246.225g
250ml x _____ = 156g (.624) - .0151= 60.89%
2# 450ml x.9849 = 393.96g
450ml x ____ = 350g (est) (.780) -.0151=76.49%
?? this right?
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Swedish Chef
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Can anyone try the following test?
Try heating some crude DPPP with 1% CuCl in 5% HCl for 2 hours at 80 °C. After cooling extract any remaining DPPP with ether (or something else that
doesn't mix with H2O) and crystallize. If the product is still explosive, you can be sure it's not AP!
This should decompose any RCOH(OOH)R type compound, like AP and AP-isomers. ROOR type compounds like DPPP should not be affected. 
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Jome
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AP is a "ROOR" compound... Its composed of three C(CH3)2 connencted in a ring with -O-O-'s between. Or what do you mean?
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Dodoman
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Just until I have some time to do my own experiments. But why not instead of purifying the product from AP, eliminate the possiblelity of it forming
in the first place by removing the excess acetone if there is any.
I think this could be done by adding water to the water insoluble dark oil. You could add NaHCO3 to the water to neutralize the excess HCl. Use a
separetory funnel to separate the two liquid repeat the process several times. Discard the aqueous layer and save the organic for peroxidation.
If you add sod. Bicarbonate to the water you would need to add HCl again before the peroxidation.
Please correct me if this sounds like a stupid thing to do.
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