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DubaiAmateurRocketry
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Quote: Originally posted by roXefeller  | | Has any thought ever been given to a partial polymerization of glycerol, and then forming a nitrate ester with the remaining hydroxyl groups? Or
would the nitrating split the oligomers apart to form NG? |
Good thought however what will we link glycerol with ?
I think it is ok to call Poly-GLYN(poly-glycidol nitrate), poly-glycerol-nitrate, Nitration of glycidol and glycerol both give nitroglycerin, however,
glycidol could be linked together in the reaction of the 2nd picture on this post.
http://www.sciencemadness.org/talk/viewthread.php?tid=28450
poly GLYN is just glycerin connected similar to how diethyleneglycol, tri-tetra, etc, is, however since it have an extra hydroxyl group, it could be
nitrated, which is GLYN. And this is why i find poly-GLYN most potential, except its instability when cured with urethane linkages. My proposal on
that post to solve the instability with urethane linkage also gives the problem of limited plasticizers since the curing is done with azido groups,
any plasticizer containing the azido group most probably could not be used.
polyGLYN have a lot of advantages over GAP, such as significantly higher OB and density, and insensitive at the same time(Impact sensitivity >20J)
[Edited on 1-2-2014 by DubaiAmateurRocketry]
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roXefeller
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The polymerization with phthalic anhydride seems to be a common college-level reaction to form a polyester.
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DubaiAmateurRocketry
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I dont think its more efficient than Poly-GLYN, would it even be a liquid ?
Edit: forgot to add ''dont'' in the sentence.
[Edited on 4-2-2014 by DubaiAmateurRocketry]
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roXefeller
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It does set up to a thermoset, but that's why I'm conjecturing about the partial polymerization. Since it uses equimolar amounts of phthalic
anhydride and glycerol and it's not a catalyzed homopolymer, backing off the phthalic anhydride should keep it as soft oligomers.
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franklyn
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Modern high-energetic polymers
www.chemikinternational.com/pdf/2010/01_2010/chemik_01_2010_018_020.pdf
.
Techniques to Disrupt, Deviate and Seize Control of
an Internet Forum In case you wonder W T F ! is going on here
?
www.zerohedge.com/contributed/2012-10-28/cointelpro-techniques-dilution-misdirection-and-control-internet-forum https://web.archive.org/web/20120814124000/www.washingtonsblog.com/2012/08/the-15-rules-of-internet-disinformation.html
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DubaiAmateurRocketry
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I believe Poly glycidyl nitrate (aka PGN or poly-GLYN or GNP) Should be the future binder. This patent's method for preparing it is much more cost
effective than methods used before and synthesizing GAP.
US patent 6362311
https://docs.google.com/viewer?url=patentimages.storage.goog...
Synthesis of GNP, and DTGNP.
This tells why Glycidyl nitrate polymer is better than GAP.
[Edited on 10-2-2014 by DubaiAmateurRocketry]
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roXefeller
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The butane diol was chosen because it forms a preinitiator complex with the BF3. But it was only one of many diols possible. Will ethylene glycol do
similar? It was presented to cocatalyze oligomers in this patent (http://www.freepatentsonline.com/4409415.html). That substitution is also useful as it increases the nitrogen percent by reducing the size of the
R group.
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DubaiAmateurRocketry
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Roxefeller, Theoretically yes, I am not sure why butane diol is used, but maybe it is more reactive on the terminal hydroxyl groups.
On your question on the increase in energy since the R is smaller for ethylene diol than butane diol, for a molecular weight of 2000 GAP, Ethylene
diol GAP contains 41.15% Nitrogen, meanwhile butane diol GAP have 40.6% N. Small improvement but why not. Glyerol which forms trifunctional GAP is
even more favorable since if makes more elastic and crosslinked binder.
btw i drew the polymer wrong and its fixed now
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roXefeller
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I thought we were talking about Poly GLYN...
The description paragraphs of the patent discuss polymerization in the diol/BF3 etherate as you detailed. The examples also use CaH2, examples
8&9. Have you eliminated this as unnecessary?
[Edited on 11-2-2014 by roXefeller]
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DubaiAmateurRocketry
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| Quote: Originally posted by roXefeller | I thought we were talking about Poly GLYN...
The description paragraphs of the patent discuss polymerization in the diol/BF3 etherate as you detailed. The examples also use CaH2, examples
8&9. Have you eliminated this as unnecessary?
[Edited on 11-2-2014 by roXefeller] |
Oh, I thought you meant GAP since GAP's energy has to do with the nitrogen content, GLYN is the amount of oxygen.
Umm for the CaH2, they mentioned its use to stop the reaction, im pretty sure it is not a necessary step. Cold water can stop the reaction easily,
when water is added, water is miscible with CH2Cl2 and the polymer or glycidyl nitrate is kicked out from the solution (Im pretty sure glycidyl
nitrate have a very bad solubility in cold water).
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Dany
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Just a little correction, dichloromethane CH2Cl2 is not miscible in water. In fact CH2Cl2 is a common
solvent for aqueous phase extraction in organic chemistry lab.
Dany.
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DubaiAmateurRocketry
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| Quote: Originally posted by Dany |
Just a little correction, dichloromethane CH2Cl2 is not miscible in water. In fact CH2Cl2 is a common
solvent for aqueous phase extraction in organic chemistry lab.
Dany. |
Ah, i didnt know that!
Is it possible to have Poly glycidyl nitrate(PGN), the one I drew, to have GAP section terminated polymer? Maybe by polymerizing the glycidyl nitrate
first, and then when the reaction is done, add glycidyl azide? How can we make sure most of the polymer's end have a GAP section?
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roXefeller
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Yeah, that's where I was going (percent oxygen fixed to nitrogen), but I should've said it better.
The CaH2 is a dessicant, so it probably dehydrates the polymerization process since water forms by way of terminating hydrogens reacting with the
hydroxyls of the diol's. It may in fact be necessary as a catalyst. Further it is one of the first additions in the examples, so it cannot logically
be used to stop the reaction according to the patent description. However, it may be that its absence stops the process, e.g. by
selecting a certain molar quantity, the MW of the oligomers can be planned from the beginning when the CaH2 plays out. Further I suspect that given
the choice of dessicant (one that chemically reacts with vigor), one of similar scavenging qualities is needed (Ac2O vice H2SO4 or CaCl2 or other
anyhydrous compounds) if CaH2 is not chosen.
Do you know what sort of viscosity the PGN has prior to curing? It's novel enough that I'm having a hard time finding numbers, only 'viscous liquid'
as descriptor. Possibly the incorporation of a small fraction of glycerol with the diol could be used to tweak the viscosity by adding a third
functional group to increase the branching polymerization.
[Edited on 12-2-2014 by roXefeller]
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roXefeller
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I had this wrong. I'm suprised I wasn't corrected. There isn't water being produced during polymerization, and it is purely a matter of Lewis acid
catalysis of epoxide/hydroxyl additions. It does appear that water present would reduce the glycidyl nitrate to glycerol mononitrate, perhaps the
reason for the CaH2 dessication. Ac2O would be damaging, reacting with the epoxide groups to form acetates. Somehow I thought that alternating units
of epoxide and diol monomers were linked, so the use of glycerol is also mostly wrong. The polyol was just present to initiate the chain and provide
hydroxyl for the first epoxide addition.
[Edited on 25-2-2014 by roXefeller]
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DubaiAmateurRocketry
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| Quote: Originally posted by roXefeller | I had this wrong. I'm suprised I wasn't corrected. There isn't water being produced during polymerization, and it is purely a matter of Lewis acid
catalysis of epoxide/hydroxyl additions. It does appear that water present would reduce the glycidyl nitrate to glycerol mononitrate, perhaps the
reason for the CaH2 dessication. Ac2O would be damaging, reacting with the epoxide groups to form acetates. Somehow I thought that alternating units
of epoxide and diol monomers were linked, so the use of glycerol is also mostly wrong. The polyol was just present to initiate the chain and provide
hydroxyl for the first epoxide addition.
[Edited on 25-2-2014 by roXefeller] |
I dont think glycidyl nitrate + Ac2O = glycidyl acetate and nitric acid ? Will nitric acid really form?
I dont think glycidyl nitrate will not reduce glycidyl nitrate into glycidyl mononitrate because if you read examples of the patent on the synthesis
of glycidyl nitrate, NaOH, CH2Cl2, and nitric acid, all are in solution. NaOH was a dilute 30%, and HNO3 was 90%.
So it means it shouldnt react with water.
If CaH2 is used for dehydration, they will put more than 1 gram on a 1.5 kg batch for example9.
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roXefeller
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I think the acetate doesn't form with the nitrate, but on the group formed when the epoxide opens. Wikipedia mentioned it in the oxirane article for
reactions with anhyrides.
But the glycidyl nitrate was separated from the aqueous phase in the CH2Cl2. Then dried with MgSO4, filtered and evaporated. It is then mixed with
new CH2Cl2 and CaH2 added. It should be anhydrous by that point. But given its reactivity with water to form glycerol mononitrate it will do its own
water scavenging and then provide initiator sites after such. The process of glycidyl nitrate going to glycerol mononitrate looks like the same
process as when ethylene oxide reacts with water to form ethylene glycol, and its a industrial process for such.
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DubaiAmateurRocketry
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Oh, I forgot that the NaOH in the solution will keep glycidyl nitrate's oxirane ring from opening, therefore it was alright for HNO3, CH2Cl2 to
contain water. What you said should be right, however I still kind of disagree about the desiccant part. I have read a handful of papers about GAP and
so on, and none of them used any desiccant? Even if CaH2 was used as desiccant, why 1 gram for such a big batch? GAP's synthesis is very similar
except it is glycidyl azide.
Any ways, Ill try these one day. I am wondering how do I get chemicals when I move to the US...
[Edited on 26-2-2014 by DubaiAmateurRocketry]
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roXefeller
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These are very readily available in the states, at least for the nitrate version. The biggest hurdle will be nitric acid, BF3 etherate, and methylene
chloride. But these can be managed. One thing that startled me today was browsing the nitromethane on Amazon. The 'also purchased by' list included
ice packs, stirring rods, methanol, sulfuric acid, hexamine, aluminum powder, methylene chloride, etc. I can't believe the amount of data logging
that is being done by merchants. It's dangerous.
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DubaiAmateurRocketry
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Just wow, This new paper published just last year has shortened the N2O5 synthesis of Nitro-HTPB into a single step NaNO2-I2 1 step synthesis with
cheapest chemicals possible.
Unfortunately, the amount of nitro groups hanged onto the polymer backbone is not given, however the ease of synthesis is remarkable! NHTPB's
important characteristic is low glass transition temperature(not much difference with HTPB), around 10-20% higher density, and finally the most
important - miscibility with other energetic plasticizers which can help with the OB.
The paper is in the uploads.
https://docs.google.com/viewer?url=patentimages.storage.goog...
This patent shows another plasticizer found in this century, It's claimed to have a TC impact sensitivity of 117cm, and ABL impact sensitivity of
11cm. (I have no idea what is those 2 impact sensitivity measurements are.)
Judging from the structure, I feel this plasticizer should not be impact sensitive. It has yet to report its glass transition temperature but it
require no more oxygen to burn it self, with an amazing density of 1.47. Its melting point is lower than -60 degree Celsius which is a good sign of a
very good plasticizer.
Attachment: phpGT2PHo (703kB)
This file has been downloaded 1333 times
]
[Edited on 3-4-2014 by DubaiAmateurRocketry]
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DubaiAmateurRocketry
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interesting paper published the energetic materials journal in china.
This paper is about epoxy terminated - GYN, removing the initial problem of Glycidyl nitrate polymer's instability.
http://www.energetic-materials.org.cn/hncl/ch/reader/view_ab...
"The reaction between the end hydroxyl of poly(glycidyl nitrate)(PGN) and isocyanates is easily affected by ambient moisture, and the curing
stability is poor. Aiming at these problems, epoxy-terminated poly(glycidyl nitrate) (e-PGN) was synthesized. Its structure was characterized by
infrared spectroscopy(IR), nuclear magnetic resonance(NMR) and gel permeation chromotagraph(GPC), and its major physiochemical properties were tested.
The main physical properties of e-PGN, such as glass transition temperature, viscosity, density, thermal decomposition temperature, were close to
those of PGN. The curing reactions of e-PGN with epoxy curing agents, such as imidazole(IMD), o-phthalic anhydride(PA), n-ethylethylenediamine(NEED)
and isophorone diamine (IPDA) were studied. Results show that the curing reaction of e-PGN with IMD, PA, NEED and IPDA at 60 ℃/70 ℃ can be
performed. When PA is used as curing agent, the mechanical properties of the cured material outperformed; the tensile strength is 0.912 MPa, and the
elongation at break is 354%. In addition, the mechanical properties of the cured samples stored at room temperature for 8 months remained almost
unchanged."
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PHILOU Zrealone
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There is a problem with the reaction after the 4th Arrow...the butylen moeity R is lost...I don't see how the epoxide may form without splitting off
the "polymer"...here it is no more an epoxide but an acetal because one carbon holds 2 oxygen (ether linkage), a H atom and a link to another C...
[Edited on 7-3-2017 by PHILOU Zrealone]
PH Z (PHILOU Zrealone)
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PHILOU Zrealone
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Belive me it does burn with dry ammonium nitrate especially when hyper-reactive ultrafine dendritic Al powder with low oxyd layer is used...
I have experimented with it--> It burns bright spreading star sparks all arround like a sparkler but fiercely and this from the simple flame of a
cigaret lighter .
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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Laboratory of Liptakov
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After reading this thread it seems, respectively I estimate, that will the miracle, if we sometime see only one gram the modern active binder -
plasticizer. From preparations in amateur conditions........ ...Dr.
Development of primarily - secondary substances CHP (2015) Lithex (2022) Brightelite (2023) Nitrocelite and KC primer (2024)
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PHILOU Zrealone
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It is not the -CO2H that is nitrated but the CH2 between the two EWG (electron withdrawing groups) N#C- and -C(=O)-OH...
The Hs from the CH2 are thus more acidic and exchange easier for a N=O(+) or a NO2(+)...
EWG1-CH2-EWG2 + Y(+) --> EWG1-CHY-EWG2 + H(+)
If the Y is N=O it can take the oxime form..
CH-N=O <==> C=N-OH
If the Y is NO2 it is also a stonger EGW and allows for easy (spontaneous?) decarboxylation of the -CO2H into -H + CO2
You thus get EWG1-CH2-NO2 and the Hs are even more acidic and prone to be attacked by an extra NO2 thus leading to EWG1-CH(-NO2)2 itself even more
reactive and leading to EWG1-C(NO2)3...
Into the case Y is equal to -N=O maybe decarboxylation occurs also (first?)or it goes via oxydation of the C-N=O into C-NO2 and then it decarboxylate
like in the previous exposed case Y=NO2...
But further NO(+) attacks the EWG1-CH2-NO2 and makes a nitrolic acid (nitrosonitromethylene) what is not oxidized further into a dinitromethyl-, a
dinitronitrosomethyl or trinitromethyl- group.
EWG1-CH2-NO2 + N=O(+) <--==> EWG1-CH(-NO2)-N=O + H(+)
EWG1-CH(-NO2)-N=O <==> EWG1-C(-NO2)=N-OH
[Edited on 7-3-2017 by PHILOU Zrealone]
PH Z (PHILOU Zrealone)
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PHILOU Zrealone
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| Quote: Originally posted by Laboratory of Liptakov | | After reading this thread it seems, respectively I estimate, that will the miracle, if we sometime see only one gram the modern active binder -
plasticizer. From preparations in amateur conditions...........Dr.
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May be hard for those exposed into the tread but not impossible...
There are indeed many potentially explosive polymers or explosives that could be used alone or in composite mix (to adapt to the requirements of the
use as binders, as crosslinking reagents (curing) or as plasticizers...)
Don't forget that after all nitrocellulose and most of its propellant mixes (double base, single base) are of that kind...and NC is pretty amateur-ish
;-)
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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