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chemoleo
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Can you provide us with any reliable reference on mesitylen peroxide? I don't see how this would work, it's fairly unreactive and aromatic;
the chemistry behind these peroxides (made with acid) is that carbonyls or alcohols are required (except HMTD). Mesitylene has neither.
Now if you meant mesityl oxide peroxide, and if you manage to make it yourself, from diacetone alcohol, and subsequent peroxidation, then create a
new thread. I posted references above re. the synthesis of mesityl oxide.
[Edited on 17-1-2005 by chemoleo]
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Pyroz
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---not to confuse the issue but I wonder if Mesityl Oxide can be peroxidized into dicumyl peroxide C18H22O2?
http://www-ilo-mirror.cornell.edu/public/english/protection/...
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PainKilla
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I have no direct information to it's forming of peroxides, but many msds list that it is capable of forming peroxides. Perhaps, methyl isobutenyl
ketone is somehow formed as intemediary. I tried adding 1:1:1 ratio, and got crystals? I am not sure, since it began to also smell of ap (this was
sepearture from the mesitylene smell) and I poured baking soda on it. So basically it was like this:
h2so4+acetone -->room temp etc-->ap smell plus mesitylene and other goodies---->+h2o2-->crystals and bubbles that smelled stronger of ap
now I know that's like nothing at all but this was out of curiosity and boredom. I will try a much better synth with heatng etc. I will heat
h2so4
EDIT: hmm h2so5?
and acetone to exact same temps as DPPP synth. We will see then. I won't peroxidise any large amounts of it though. 1ml at a time until i can
verify chemical stability.
-------------------regarding DICUMYL PEROXIDE-----
I would not be surprised.... its structure looks like this:
benzene ring with a tricross at the "2" position...eh screw it ill get a pic....
http://www.inforubber.com/product/peroxide/pic5.jpg
[Edited on 17-1-2005 by PainKilla]
[Edited on 17-1-2005 by PainKilla]
[Edited on 17-1-2005 by PainKilla]
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chemoleo
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No, I think you still mean mesityl oxide, not mesitylene. The latter is stable, and only incompatible with conc HNO3- which is probably true for any
aromatic. I checked all MSDS's on mesitylene, no mention of peroxides.
Further, since you keep going on about it - mesitylene isn't rapidly formed. Check OrgSyn's method. It's a water-insoluble oil anyway, and you'd need to separate it away from unreacted acetone. But it won't
react with H2O2 anyway...
Also, in case you don't know, H2SO4 and acetone does NOT produce mesitylene as a sole product.
By the way, mesitylene is also produced by HCl and acetone, check the references from the orgsyn method above!
This one really is a killer, so many products from heating acetone and HCl! How are we ever to know what is forming the crystals? 
PS Rosco, I don't mind updates or anything. But yes, it does get confusing, and I felt it was necessary to point out again what we are after -
which is to validate whehter the new product(s) have greater power than AP, or indeed, if they are just something but NOT AP. I am looking forward to
the results from the tests you will do tomorrow!
[Edited on 17-1-2005 by chemoleo]
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
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PainKilla
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Yea I know that it can form various products, but mesitylene is the main one. It's ok. I will post results on my reaction probably Tuesdayish.
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Rosco Bodine
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| Quote: | Originally posted by chemoleo
This one really is a killer, so many products from heating acetone and HCl! How are we ever to know what is forming the crystals? |
Most chemistry is experiments which follow a
sort of algebraic logic where you work the unknowns against each other in a bit of detective work to learn exactly what the unknowns most likely are .
Each experiment chips away at the unknown "big picture" sort of like the pieces of a jigsaw puzzle being connected until a visualization can
materialize . | Quote: |
PS Rosco, I don't mind updates or anything. But yes, it does get confusing, and I felt it was necessary to point out again what we are after -
which is to validate whehter the new product(s) have greater power than AP, or indeed, if they are just something but NOT AP. I am looking forward to
the results from the tests you will do tomorrow! |
Actually I got a phone call about some other business which will require my time tomorrow . But I will try to get something done if time permits . I
had only a small sample on hand of regular AP leftover from several years ago from other experiments , so I have a new batch in the freezer to produce
some fresh material for use as an AP control sample . My storeroom is getting low on materials for experiments so I need to restock some items before
continuing much further anyway . When I get to the detonation tests I will probably be comparing several sample materials to get a good indication of
what is occurring . One of the definitive tests I like to do on a detonator candidate is to load 2.5 grams of it into a capsule and see if it will
fully detonate urea nitrate , which is an excellent challenge . A hot cap with sassy material will surely detonate the urea nitrate every time . AP
would never even come close to delivering the impulse required . 2.5 grams of HMTD is about the threshold quantity for a single component charge ,
moderately pressed in a charge column diameter of 9.5 mm , modest confinement such as provided by a 5 ml 12 mm X 75 mm polypropylene culture tube
with a piece of visco inserted through a hole drilled in the culture tube closure and secured in place with tape . This is sort of a test bench
reference standard cap which can be used as a control for comparison with other configurations .
[Edited on 17-1-2005 by Rosco Bodine]
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Matsumoto_Hideki
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japanese website translation says nothing about peroxides
This website painkilla found is about the degredation/allteration of diethyl ether's crystal structure to light at +2MV. ie) shortwave UV
Not about peroxidation.. sorry guys..
Fukou ni mo, DPPP no nazo ga tsuzuiteiru........
[Edited on 18-1-2005 by Matsumoto_Hideki]
[Edited on 18-1-2005 by Matsumoto_Hideki]
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PerFecTioNisT
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I did.....but.....
Ok I made DPPP yesterday.
100ml acetone+100ml 30%HCL+175ml 30%H202.And how to look that is sure DPPP?Matsumoto_Hideki could you writte your DPPP proportion, I want to try make
by your method.
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Matsumoto_Hideki
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Ok this is what I did.
Step 1#
340ml HCl (muratic acid) 35%Vol
2% below regent grade.
340ml Acetone
Step 2#
cover your mix flask with a balloon or bag
to trap HCl and acetone vapours, this will concentrate your reaction.
Step 3#
Put your flask in a hot water bath
and heat until the colour changes to a dark red. This should take about 30mins. after the dark red/ almost black colouration has been reached let the
flask cool down on it's own. empty out the balloon back into the flask.
4#
After the flask has cooled off, remove the balloon
carefully and lt the flask stand at room temperature for at least 48hrs. This allows any unreated acetone to vapour off.
5#check the flask against a light source, there should be no light passing through it. There may be a small reddish transparent layer at the bottom,
this is usually leftover HCl and can be removed with a pipet.
6# Peroxidation
****You are advised at this point to put the entire flask into a bucket of cold water and freeze it in a freezer down to around -25c -30c before ANY
35% vol Hydrogen peroxide is added***** You are freeing the flask into a block of ice.
The Phorone HCl is viscous like honey at this point.
7# Adding the peroxide.
680ml H202 is added in total.
Add your first 200ml of H2O2 while you stir you mix with a glass or nitrile rod (acid and solvent intert material)
The colour changes immediatly to a red orange and crystaline rafts start to become instantly visible.
let the temperature cool off after 1-2hrs
8# Add your remaining H2O2 480ml to the crystalizing DPPP, colour now is BRIGHT YELLOW ! give your flask a good stir and leave for at least 9hrs in
the freezer. This yellow is mesitlyene and is indicative of phorone production.
9# After 9hrs you need to filter and neutralize your crystals with baking soda, then again in a wash of distilled H2O. note your yeild will be
slightly over 300g with this method when dry.
10# Using pure Isopropyl alcohol you can remove the left over mesitylene form the crystals, this is what stains your end product. I would also keep a
bit of Isoproylene to wet your yeild for safetys sake.
[Edited on 19-1-2005 by Matsumoto_Hideki]
[Edited on 19-1-2005 by Matsumoto_Hideki]
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Rosco Bodine
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Hold on just a minute , Let's do some math
The gram molecular weight of DPPP is 434.40 , formation of which requires 6 gram moles of acetone , which is 441.2 ml of acetone . Therefore a 100 %
yield of DPPP would be 434.4 / 441.2 = .9845875 grams of DPPP per each 1 ml acetone .
A yield of 100% of theory from 340 ml acetone would be 334.75 grams of DPPP .
Sooooo , if you got 400 grams yield , then it is definitely not dry 
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PainKilla
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I dont think we can apply stoichimetry yet as we have not determined what this is. Friday I will be trying my project.
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Rosco Bodine
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Agreed that we have not confirmed structure . We need to be accurate about the dry weight however so we can account for anomalies . I thought I had
my samples pretty dry , and yet when they were heated in the culture tubes where I am subliming the samples , a pretty good puff of water vapor came
off the powder and condensed in the tubes ,
confirming that there is some moisture remaining in the loose powder I thought was fully dried . I have some freshly made AP for a control sample ,
and may have some preliminary tests on detonations of small amounts in the next few days . I will be stepping up charge amounts , doing some witness
plates , and some direct initiation test comparisons with AP at least , and possibly comparisons with some other primaries as well , using carefully
weighed quantities . I also plan to make some molded putty comparisons , and some loose powder deflagration comparisons .
Among the initiation tests I plan is to test whether or not the supposed DPPP will initiate pressed crystalline picric acid in an unreinforced
compound detonator . Ordinary AP won't do the job in an unreenforced cap , but HMTD will . So if
DPPP has the power and brisance HMTD ,
If I put 2 grams of picric acid in a 5 ml culture tube , pressed in half gram increments with about 10 Kg of pin pressure , and top it with 1 1/2
grams of DPPP , pressed the same way , if the DPPP even matches the performance of HMTD , a full detonation of the 9.5 mm diameter column of picric
acid will occur . Garden variety cold formed AP fails this test .
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Pyroz
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...I think the absolute maximum I have achieved in terms of yield is ---- scale---
my scale says: 363.85 grams that is bone dry DPPP and kept warm. It has very little smell and from 510mL acetone --- so it is not the 90% yield talked
about in the patent, but close* i am positive the yield would have been much better if the temperature had not been so cold and I have left the
phorone-isomer to peroxidize longer say several more hours.
-----------------------------------------------------
I hope to conduct a (((blast))) test on DV on the weekend! This is my chance to show you what I have been seeing in the last few detonation attempts.
[Edited on 19-1-2005 by Pyroz]
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Rosco Bodine
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I haven't done any tests except to simply ignite small amounts of the powder , but just from the subjective impression I had on first glance the
DPPP looks faster , makes a briefer and quicker flash and makes a different sound when a small pile is ignited compared to regular AP . I will repeat
the tests in the dark with weighed
samples more carefully dried , but to me the visible flash from the DPPP is more white yellow color and quick like a camera flash or flashpowder ,
while the flash from AP is darker yellow orange burning more like a quick gunpowder .
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Pyroz
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| Quote: | Originally posted by Rosco Bodine
visible flash from the DPPP is more white yellow color and quick like a camera flash or flashpowder , while the flash from AP is darker yellow orange
burning more like a quick gunpowder . |
It has very different burning characteristics--- and won't hesitate to explode in small amounts with heat gradually and liquified--- it then
reaches max temperature and then detonates. If lit directly it will burn with an intense white-yellow flame. AP seems to be very orange-yellow by
comparison in a flame test.
I agree Rosco, this is what I have seen as well..
[Edited on 19-1-2005 by Pyroz]
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Rosco Bodine
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Now that you mention stoichiometry .......
| Quote: | Originally posted by PainKilla
I dont think we can apply stoichimetry yet |
Anybody else notice that the stoichiometry is incorrect in the patent itself ? Because the amount of H2O2 30% which is specified by Mackowiak in his
own patent is only sufficient for producing a maximum yield of 78.4% if the reactions proceed according to the way Mackowiak has them written . There
are 11 moles of H2O2 required for each 6 moles of acetone , and for 30% H2O2 that would require about 2.55 volumes of H2O2 for each 1 volume of
acetone .
2.75 volumes of H2O2 30% would be more likely as a minimum , and for 27.5% H2O2 , 2.9 or even 3 volumes of H2O2 per 1 volume of acetone would not be
unduly excessive . If the peroxidation reactions do proceed in the way Mackowiak has them written , then there is no way to get 90% yields unless
the quantity of H2O2 is increased to or near to these ratios .
[Edited on 19-1-2005 by Rosco Bodine]
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Pyroz
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hey, maybe the patent yield could be increased with a more concentrated peroxide--and a little more of it
35% as apposed to 30% -- I wonder why I'm getting such good yields ~80%. It seems to work for me. As well I'm sure temperature has a lot to
do with yield and so does time! I'll try leaving the material for 48 hours @ 0 degrees Celcius and see if I can't get more crystals forming.
Mackowaik patent is very interesting indeed but I still think 90% yields are possiable with some tweeking. Maybe the patent should indicate 3:1 or 3X
the peroxide to acetone --- so if you had 500mL's acetone/HCL --- you would need 1500 mL's of peroxide? Thats does sound a little
excessive---but hey who knows.
[Edited on 19-1-2005 by Pyroz]
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Rosco Bodine
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With stoichiometry , it is purely mathematical for solving for minimum molar amounts . And I did the math above . Mackowiak said to use 2 volumes
30% H2O2 for each 1 volume of acetone , but that is not sufficient to balance the reaction equations he wrote , 2.55 volumes of 30% H2O2 would be the
minimum for each 1 volume of acetone .
Generally , then there is some excess of theory used for the peroxide , maybe 3 to 10% more than the minmum requirement .
There may be some guesswork there in choosing the optimum excess , but usually the minimum molar amounts are just simple arithmetic , arithmetic which
in this case does not square with the ratios Mackowiak stated . The reason it takes more than twice as much peroxide as for making ordinary AP is
because more than half of the peroxide 6/11 of it is used in the chlorination reaction which precedes the actual peroxidation . Actually this
provides a method of chemical identification of the peroxide formed , knowing how much peroxide would have ben consumed to produce whatever number of
grams of DPPP you believe you have , the unreacted peroxide should be found in the filtered reaction mixture , where it may be decomposed and the
volume of oxygen produced can be measured . Then a fairly good idea can be gotten of how much of the consumed peroxide is chemically bound in the
number of grams of the product obtained ,
and a speculation on its structure can be justified .
These discrepancies concerning the stoichiometry cause me to question if the parts per volume interpretation of the quantities is correct translation
. I think I will run the numbers through again on the basis of parts by weight and see if the result better reconciles with the equations as
Mackowiak has them written .
UPDATE: The numbers were run on parts by weight basis and the results were not even close to being right so the parts per volume translation is
correct , but the volume figure for the peroxide is definitely off by the amount I said .
[Edited on 19-1-2005 by Rosco Bodine]
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Matsumoto_Hideki
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Wait a sec,
| Quote: | Originally posted by Rosco Bodine
The gram molecular weight of DPPP is 434.40 , formation of which requires 6 gram moles of acetone , which is 441.2 ml of acetone . Therefore a 100 %
yield of DPPP would be 434.4 / 441.2 = .9845875 grams of DPPP per each 1 ml acetone .
A yield of 100% of theory from 340 ml acetone would be 334.75 grams of DPPP .
Sooooo , if you got 400 grams yield , then it is definitely not dry
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Yes, I understand this 400g would be wet, dry more like closer to 300g or so.
BTW After having a close call with DPPP today when it was dry I do suggest the use of dampening the dPPP with a bit of Isopropylene just to add a bit
of safety margin.
Details about my horrific encouter will be posted shortly, that is when I can hear myself again..
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Mickhael
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Update
Just a quick note to everyone, to update my testing to see the stablity of DPPP with MEKP, So far everything is completely fine, the DPPP has settled
into the lower part of the test tube, making a smooth silt-like mixture. I imagine I could add quite a bit more...to make a stiff paste, which I will
do shortly. No signs of seperation...or decomp has been noticed, its been sitting open to the air, in a 60f garage for a week now.
Detonation results so far have been nothing special, however I am redesigning the electric dets for my BC's, so the results should be more
conclusive and powerful when I do the next set of tests.
\"I shall not fear, fear is the mind killer...\"
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Matsumoto_Hideki
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Nothing special?
Well I tell you make the paste 90/95% DPPP and 10/5% MEKP and you wont be saying that for much longer!!
BTW my accident yesterday was in trying to heat DPPP to 160c in a metal spoon and getting it to liquify. Shortly after this DPPP liquified I then let
the material recystalize/cool off... this is when it self detonated. The spoon blew itself into a u shape and flew across the room. the amount i was
using was maybe 1-3mg.
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The_Davster
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Can we see a pic of the spoon? Did the DPPP going off in the spoon cause any
deformation in the actuall spoon part of the spoon(the round part), any holes blown through? or was the handle just badly bent.
Mainly I want to compare it to the picture posted by blaster a while back which showed the results of 1 drop of ethyl perchlorate going off in a
spoon.
I think the DPPP likely detonated while cooling as a result of posible crystall fracture causd by expansion and contraction of the cooling DPPP.
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Rosco Bodine
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1 to 3 mg wouldn't do that to a spoon .
These exaggerations about effects and yields are serving no constructive purpose and are in fact serving to discredit what useful * F A C T S * you
might wish to share with others who are in good faith trying to get at the unvarnished truth about DPPP . So PLEASE knock it off with such
"reports" on the "awesome damn nearly thermonuclear POWER of "DPPP" , and stick to the FACTS .
One FACT we do know at this point is that there is an error in the stoichiometry in the patent , and this can be mathematically proven before the
first drop of any reagent is measured or the first crystal made . So the accuracy of the other numerical data in the patent is instantly thrown into
doubt by that one error in stoichiometry . Actual chemists rarely make errors in stoichiometry in something like a journal or patent publication
where peer review is certain to discover and expose the error , which is then usually corrected as an "erratta" declaration page of later
publication which then becomes a permanent attachment or insert and an embarrassment to the author for imprecision .
Now Hideki , you don't want to have to go back and do "erratta" corrections on your posts , so let's stick to the facts PLEASE
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WaveFront
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My English is not very good, and since I am not a chemist I didn´t want to write for now.
Just to say that it´s extremely dangerous the melted "dppp", can explode without any confinnement if the amount is not tiny. I believe
cause I have experienced an accident, but the amount was a little more than a few mg. You can see the spoon:
http://webs.ono.com/rym/cuchara.jpg
You have permission to call me stupid.
My "dppp" was made without the phase separation by freezing (my freezer is not enough powerful). The results for this product (tested by
putting small amounts in aluminum foil and perforating metal plates) are better than TCAP, improve much when mixed with KClO3, but from my viewpoint
it does not reach the brissance of HMTD. Sorry for the imprecissions.
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Joeychemist
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Shouldn't the spoon be bent the other way?
I only ask because it just doesn't look right to me. Could you please explain in further detail what happened?
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