menchaca
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can polyestyrene be nitred?
hello again!
waht I mean is posible that phenil groups of polyestyrene be separated and then nitred or even better can phenil groups of polyestyrene be nitred
directly? i mean whiout breaking de polyestyrene molecule? would that give a "plastic explosive"?
thanks again!!
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Darkfire
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Is english your first language?
CTR
\"I love being alive and will be the best man I possibly can. I will take love wherever I find it and offer it to everyone who will take it. I
will seek knowledge from those wiser and teach those who wish to learn from me.\" Duane Allman
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Haggis
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No, for some reason I think he is from South America.
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Blind Angel
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It's not so hard to understand, he wanna know if you can create nitrated polymers...
/}/_//|//) /-\\/|//¬/=/_
My PGP Key Fingerprint: D4EA A609 55E4 7ADD 8529 359D D6E2 33F6 4C76 78ED |
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DDTea
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I know that styrene itself can be nitrated. Polystyrene can too, it would form Dinitrostyrene. Megalomania has a synthesis for htis on his website.
The explosive velocity is 1510 m/s. According to Mega:
| Quote: | | This material has found a home as a mining explosive since it is stable and somewhat low powered. It will burn in the open and requires a suitably
powerful explosive plus confinement to detonate. |
The formula for it would be [C6H3(NO2)2(CHCH2)]200 .
And yes, his post was quite understandable...it would be more helpful to answer the questions rather than ask, "Is English your first
language." 
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Madog
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i saw that on megalomanias site a long time ago, looked interesting cauuse it was so weird, i mgith try it sometime.
Most people outgrow their pyro tendencies, we are the ones who\'s tendencies outgrew us.
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Darkfire
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 Well i couldnt answer the question with any real confidence, i would assume so,
but i didnt really know.
It wasnt an insult, i was just curius because of "breaking de polyestyrene molecule?" i noticed a "de" which i figured ment he
speaks some other language.
Im just trying to get to know my board members better  .
CTR
\"I love being alive and will be the best man I possibly can. I will take love wherever I find it and offer it to everyone who will take it. I
will seek knowledge from those wiser and teach those who wish to learn from me.\" Duane Allman
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PHILOU Zrealone
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Of course PS can be nitrated twice or three times!
One would need a lot of heat and very fine dust of PS + a solvant for both PS, HNO3 and H2SO4... I would suggest CH2Cl2 or CH3-CCl3.
One could also depolymerise PS by heating (sort of cracking) and collecting Styrene/styrol ina cold flask.
Then submit styrene to nitration; more than certainly side chain will be oxydised.
But of course it would be much more interesting to trinitrate ethyl benzene; then react Cl2 under light and heat to get CH3-CHCl-C6H2(NO2)3.
And finally to perform HCl elimination in NaOH media to get TNS ... a subsequent polymerisation will lead to PTNS... a cristaline HE of low
sensitivity and very good thermal stability used is some UHE compositions (unsensitive HE).
VOD is arround 7km/s.
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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unicorn
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I bought some styrene resin from my local model shop the other day (the one that comes with a methyl ethyl ketone peroxide catalyst to get the
polymerisation going). I was thinking of a couple of uses for it:
Hydrogenation to make ethylbenzene
Hydrogen from the Al/NaOH reaction passed through conc H2SO4 and into the liquid styrene with a Ni catalyst. I have some nickle plated chain to use
for that, though I'm worried that anything approaching a decent rate needs Raney Ni and high pressures.
Ethyl benzene nitrated to a mix of its di- and tri-nitro forms is known as K10 and is used as an energetic plasticizer.
Hydration to make (1-hydroxyethyl)benzene
Conc H2SO4, then water. Nitrate to the tri-nitro form. This could possibly be used as is, esterified with commonly available organic acids such as
acetic or stearic, but preferably reduced back to 2,4,6-trinitrostyrene and polymerised.
Using both methods one could make an energetic polymer and plasticizer for plastique that would otherwise have something like 10% of its mass wasted
in inert materials.
Just a few thoughts, I might work out a few more detailed synthesis for both when I have more time.
Also found a route from styrene to toluene but it requires ozonolysis and hydrazine!
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Kutsenko
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POLYMER SIGMA ASSOCIATES OBTAINED FROM 2,4,6-TRINITROSTYRENE AND 4-VINYLPYRIDINE.
A. D. Kutsenko, K. A. Krasnov, B. V. Chernitsa
Institute of Macromolecular Compounds RAS, 199004 St.-Petersburg,
E-mail: adkut@mail.ru
Mechanisms of both the anionic polymerization of 2,4-dinitrostyrene (DNS) and 2,4,6-trinitrostyrene (TNS) under the action of bases in polar solvents
and the zwitter-ionic spontaneous copolymerisation of TNS with 4-vinylpyridine (VP) have been studied. Initiation and propagation steps of the
polymerization of DNS and TNS were shown to include the new reactions 1 of Meisenheimer sigma complexes (MSC), instead of charge transfer complexes,
as thought early. Anionic vinyl growth reactions followed by condensation stages led to living ionic polymers, containing MSC formed by an addition
reaction of polynitrostyryl anions to the internal units of oligomeric fragments of a polymer sigma associate (PSA). The peculiarity of PSA structure
is a labile conjunction of chains with covalent C-C bonds, giving rise to a new type of mobility (chemical mobility). The PSA structure reversible
varies under the action of external factors such as temperature, the acidity of a solvent etc. The initiation of TNS with polyetheleneimine or
aluminium oxide results in a PSA-containing graft copolymer or a composite.
The initiation of the copolymerization of TNS with VP occurs through the coupling of zwitter-ions (ZI-1) formed at an attack of a pyridyl moiety on
TNS into a novel zwitter-ion (ZI-2), containing the pyridone-4-methide growth center. By analogy with the polymerization of vinylpyridinium salts,
this center was supposed to be able to react with the double bond in ZI-1. ZI-1 was regarded as a combined monomer engaged in a competition with TNS.
The reaction of ZI-2 with TNS initially produced a novel sigma complex, then rearranged into a quadrupole-ione, containing an anionic trinitrobenzyl
growth center. A distinctive feature of the copolymerization has been found to be an easy expulsion of the anionic beta- ( 2,4,6-trinitrophenyl )
ethenyl substitute from the positively charged N-atom of pyridinium rings of copolymer. By analogy with the homopolymeriza- tion of DNS and of TNS,
the condensation stage has been detected to produce a PSA net-work at long reaction times. Evidence for the presence of charged (pyridinium and
trinitrocylohexadienyl) and uncharged (pyridine and trinitroben- zene) rings were obtained in molar ratio 1: 8-10. The mobility of breathing net-work
of the PSA was presumed to be due to the lability of covalent C-C bonds in the novel pyridonemethide sigma complexes.
References:
( 1 ) K. K. Kalninsh, A. D. Kutsenko, Ju. E. Kirsh, N. A. Barba, I. D. Korzha. Vysokomolek. Soed. 1990. V. 32À, ¹ 6. P. 1268-1275.
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AndersHoveland
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Dinitropolystyrene has a variable detonation velocity, depending on density and extent of nitration. At 0.25 g/cm3, the detonation velocity is 1510
m/sec. When the density is increased to 0.95 g/cm3, the detonation velocity increases to 2 km/s.
The density could probably be increased by squeezing in a vice. The styrofoam precursor used in both measurements was probably the foam form, which
would explain why the nitrated products ended up with low measurements for density. However beginning with a denser form of polystyrene is likely to
sterically hinder nitration to a greater degree, so for measurements of the denser forms of polynitrostyrene, it should be assumed that the polymer is
not fully nitrated to the full theoretic dinitro ratio. This leaves unanswered the question of what the maximum theoretic detonation velocity would be
of High-Density nitropolystyrene in a with a complete dinitro average ratio. It is very difficult to significantly increase the density of a low
density polymer after it has formed. An idea would be to melt the polymer with a melt-castable filler, to fill in the "spaces" between the molecular
chains.
DinitroBenzene from Polystyrene (styrofoam)
If a nitration of limited duration, using concentrated acids is done, poly-dinitrostyrene will form, and the extent of side oxidation will be limited.
Using potassium permanganate, and keeping the temperature from rising above 50degC, the polydinitrostyrene can be oxidized, allow 2 hours for the
reaction. Note that the potassium permanganate is not absolutely required, but more nitric acid will be required if it is not used. Cool the mixture
and allow crystals of dinitrobenzoic acid to crystallize out. Remove the crystals, wash in cold water, then add the crystals to boiling water.
Dinitrobenzene should form, which will crystallize out. Benzoic acid, when there is another electron withdrawing group on the ring, such as a chlorine
or nitro group, can be easily "de-corboxylated" by heating, the carboxyl group coming off as CO2. There will inevitably be some unwanted further
oxidation of the dinitro-benzoic acid to Dinitrophenol during the oxidation. For improved yields, the polydinitrostyrene (first removed from the
water) can be nitrated to the trinitro with Cupric Nitrate dissolved in Acetic Anhydride. Trying to use nitric acid to add the third nitro group will
cause significant undesirable oxidation, and picric acid will be the main product. However, concentrated nitric acid can be used to add a third nitro
to dinitro-toluene without significant oxidation of the methyl group, which is less vulnerable. In the last two cases, trinitro-benzoic acid would
result instead of the dinitro, and the end product would be Trinitrobenzene. Dinitrobenzene can also be further nitrated with concentrated acid to
Trinitrobenzene.
A patent mentions that the nitration temperature should be 160°, and that mainly para-nitrobenzoic acid is formed.
[Edited on 20-9-2011 by AndersHoveland]
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PHILOU Zrealone
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AndersHoveland,
It would be preferable for a better VOD to get the polytrinitrostyrene instead of the polydinitrostyrene.
You will end up with a product with less power a bit like dinitrobenzene (6100 m/s at max density) vs TNB (7100 ms/s at max density)
To get a better density out of the nitrated foam...one can dissolve it into aceton or or a volatile halogenated solvent (CH2Cl2) and allow
evaporation...the resulting solid will be much denser than the foam.
The VOD can be extrapolated from the VOD of trinitroethylbenzene (6600 m/s at max d) or of hexanitrodiphenylethylene (6800 m/s at 1,6g/ccm) . If you
measure the density of your polymer...it must be over 1,6g/ccm then every increase of 0,1g/ccm is equal to a VOD increase of 350m...that is how I
evaluated the VOD of PTNS to be arround 7km/s.
So if your density is:
1,7 you should be arround 7150 m/s
1,8 you should be arround 7400 m/s
1,9 you should be arround 7750 m/s
and even if unlikely in this case...
2,0 you should be arround 8100 m/s
Note that the density is dependant of the degree of polymerisation...a longer polymer induces more Vanderwaals bondings (intermolecular attraction)
and so the density increases...
It is funny to observe that density increases while the relative composition remains the same...so polymerisation is a good way to get more power per
volumic unit.
After a decade of research, I have finally found the rule of density increase as a function of the polymer lenght but I'm stil working on the datas.
This will help me in predicting densities of unknown molecules and their explosive properties....
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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