Why not nitroglucose?? - Archive File

[megalomania]

Mr Cool
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posted 03-26-2001 12:51 PM
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This has been annoying me for some time now. Starch and cellulose are both polysaccharides, which means they're polymers of glucose. Correct so far? Well, they can both be nitrated to form HE's using very simple methods. I was wondering: can glucose or sucrose or any other common sugar (mono- or disaccharide) be nitrated using the same methods, and if not why not? Are they very sensitive or something? Or is it just that the H2SO4 dehydrates them leaving carbon? If that is the case, then why doesn't that happen to starch or cellulose? And what about smaller polysaccharides, like dextrin? (actually, I'm going to try nitrodextrin when I've posted this. I'll let you know the results as soon as I have them. I think it will be good if it works, because the dextrin can dissolve, meaning that there will be no problems with acid not reaching some of the molecules, which can happen with the large grains of insoluble starches). On Mega's site there is a reference to maltose octanitrate, and it lists it as being very sensitive but gives no other information. This makes me think that as the number of glucose units goes down, the sensitivity of the nitro-compound increases, in which case nitroglucose will be very sensitive, but nitrosucrose might be OK.
Sorry about all the Q's!


Mr Cool
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From: None of your bloody business!
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posted 03-26-2001 12:52 PM
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Actually, I've just thought of a flaw in my logic, but reply if you want!


richl261
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From: uk
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posted 03-26-2001 02:09 PM
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ah i know what "totse" is now..lol
[This message has been edited by richl261 (edited April 05, 2001).]



Alchemist
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From: Woodland hills,Ca.,L.A.
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posted 03-26-2001 10:24 PM
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Mr. Cool,
Here are some doc's I had on Nitro-Sugars!

NITRO_SUGARS

In general Nitro-sugars may be prepared, by adding concentrated sulfuric acid drop by drop to a solution of the corresponding sugar in concentrated nitric acid at 0 degrees.

Nitroglucose (d-Glucose pentanitrate) , C6H7O (ON02) 5

d-Glucose pentanitrate , is a colorless viscous syrup, insoluble in water and in ligroin, readily soluble in alcohol. It becomes hard at 0°. It is unstable above 50°, and if heated slowly to a higher temperature decomposes rapidly at about 135°. It reduces Fehling's solution on warming. Glucosan trinitrate, C6H702 (ON02)s, is produced by the nitration of a-glucosan and by the actioQ for several days of mixed acid on d-glucose. It is readily soluble in alcohol and insoluble in water. It has been obtained in the form of aggregates or crusts of crystals which melted not sharply at about 80° and which were probably not entirely free from glucose pentanitrate

Nitromannose (d-Mannose pentanitrate) , C6H7O (ON02) 5

d-Mannose pentanitrate, transparent rhombic needles from alcohol, melts at 81-82° and decomposes at about 124°. It is soluble in alcohol and insoluble in water and reduces Fehling's solution slowly on warming. It undergoes a rapid decomposition if stored at 50°.

Nitromaltose (Maltose octonitrate), C12H14O3 (ON02) 8

Maltose octonitrate, glistening needles from methyl alcohol, melts with de~omposition at 164-165°. If heated quickly, it puffs off at 170-180°. It decomposes slowly at 50°. If fused and allowed to solidify, it has a specific gravity of 1.62. It is readily soluble in methyl alcohol, acetone, and acetic acid, difficultly soluble in ethyl alcohol, and insoluble in water. It reduces warm Fehling's solution more rapidly than nitrosucrose.

Nitrolactose (Lactose octonitrate), C12H14O3(ON02)8

Lactose octonitrate, monoclinic needles from methyl or ethyl alcohol, melts at 145-146° with decomposition. Its specific gravity is 1.684, It is readily soluble in methyl alcohol, hot ethyl alcohol, acetone, and acetic acid, difficultly soluble in cold ethyl alcohol, and insoluble in water. It reduces Fehling's solution on warming.

Lactose hexanitrate, C12H1605 (ONO2) 6,

has been found in the alcoholic mother liquors from the crystallization of the octonitrate, white, amorphous material melting nQt sharply at about 70°.
Crater in 1934 described explosives containing nitrolactose, one consisting, say, of nitrolactose 25%, ammonium nitrate 65%, sodium nitrate 6%, and vegetable absorbent material 40;0, another made by treating wood pulp with an acetone solution of nitrolactose and dinitrotoluene and containing about 78% nitrolactose, about 9%, DNT, and about 13% wood pulp. For this use the nitrolactose ought to be stabilized with diphenylamine.

Nitrosucrose (Sucrose octonitrate), C12H1403 (ONO2) s

The nitration of cane sugar , yields sucrose octonitrate, white glistening needles, which melt at 85.5°. If heated slowly, nitrosucrose decomposes at about 135° and if heated rapidly deflagrates at about 170°. The fused and solidified material has a specific gravity of 1.67. It is readily soluble in methyl alcohol, ether, and nitrobenzene, difficultly soluble in ethyl alcohol and benzene, and insoluble in water and in petroleum ether. It reduces Fehling's solution on warming. It is relatively stable when pure. Monasterski reports that it gives a feeble puff under a 20-cm. drop of a 2-kilogram weight, a puff with one of 25 cm., and a detonation with one of 30 cm. He states that samples of 10 grams in the Trauzl test gave average net expansions of 296 cc.


P.S., Where do you get your concentrated Nitric Acid from?

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Mr Cool
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posted 03-27-2001 12:52 PM
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Thanks a lot for that info.
I make my HNO3 from H2SO4 drain cleaner and KNO3 fertiliser, and if necessary purge it of NOx with urea fertiliser and dry air.

Why don't people nitrate sugars more often?!?! Why bother looking for pentaerythrite when table sugar will work?! Well, I know it probably isn't quite as good, but when it's that common WHO CARES?

[This message has been edited by Mr Cool (edited March 27, 2001).]



Mr Cool
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posted 03-27-2001 01:13 PM
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When you say "concentrated nitric acid", do you mean the stuff that most people call concentrated which is about 70%, or do you mean CONCENTRATED, 95% or something like that? I want it to work, but I'm worried that if my acid is too concentrated it might react too fast and decompose the product from the heat.
Oh, and nitrodextrin behaves almost exactly like nitrostarch, but it does seem a bit less stable.


Alchemist
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From: Woodland hills,Ca.,L.A.
Registered: NOV 2000
posted 03-28-2001 11:04 AM
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Hello Mr. Cool,
I am sorry, but these crummy text books never say what they mean by concentrated. I may have some more for ya as soon as I remember where I put it. I have to stop cleaning up around here! Bye for now....................


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Mr Cool
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From: None of your bloody business!
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posted 03-28-2001 03:59 PM
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I suppose the concentrations would be the same as those used for hexanitromannitol, since mannitol is similar to sugar.
Thanks again.


Alchemist
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Posts: 211
From: Woodland hills,Ca.,L.A.
Registered: NOV 2000
posted 03-29-2001 03:16 PM
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Hello Mr. Cool,
It's H2SO4 at S.G. 1.84 and HNO3 at S.G. 1.51.

P.S., What brand (manufactory) of NO3 fertiliser are you using for H2SO4. Also is it Ammonium, Calcium, Sodium, or Potassium Nitrate?

Thanks............................

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Mr Cool
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From: None of your bloody business!
Registered: DEC 2000
posted 04-19-2001 06:00 PM
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Potassium nitrate, from chempak. 13.2-0-48.2 I think, I'll have to check though.


CodeMason
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From: Your Nightmares
Registered: NOV 2000
posted 05-28-2001 07:50 AM
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I assume improvised nitrosucrose be made in the same way as MHN, without conc. nitric acid, but instead using conc. sulfuric and ammonium nitrate. Will this work?


the freshmaker
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Posts: 175
From: Heaven
Registered: DEC 2000
posted 05-28-2001 08:24 AM
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Does anyone know how sensitive nitrostarch is? compared with fx tetryl?
Can it be ignited by flame like nitrocellulose?


gcic
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Posts: 80
From: Germany
Registered: OCT 2000
posted 05-28-2001 10:00 AM
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The impact sensitivity of nitrostarch is 11Nm, while the sensitivity of tetryl is 3Nm.




fightclub
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Posts: 39
From: none
Registered: APR 2001
posted 05-30-2001 08:41 PM
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The power, VOD, sensitivity, detonability, etc. varies and increases with increase in
Nitrogen percentage(for Nitrostarch!!). As shown in Urbanski:

|N2|...|Shock-|#..|lead|.......
|%.|...|sens..|..|block|..|VOD*|

13.4%...21cm.....430......6190........
13.1%...23cm.....395......5740........
12.8%...--cm.....375......5300........
12.4%...36cm.....360......4950........
12.1%...38cm.....320......4480........
11.6%...70cm.....300......3880........
11.0%...100cm....260......3020........
10.5%...100cm....230......2880........
9.4%....100cm....160......1500........
8.9%....100cm....125......100.........
7.7%....no det....35.....no det.......


*Detonation velocity in 34/38 mm tube in m/sec. All results using No. 8 Blasting cap. Also:

VOD..9.4% -- 3200m/s (10g picric acid)
.....8.9 -- 300m/s (10g picric acid)
.....7.7% -- no detonation even with 10g picric acid

Lead block test in cm^3/10gm.

# Shock-sensitivity was done with 5kg weight, 8% expl.


Note: The shock-sensitivity in Newton meters is simply: A*B*C,
where:

A= weight of drop hammer (in kg),
B= 10 N/Kg
C= distance of traveling weight (in meters)

meter= cm/100

So for 13.4% SS is 10.5 Nm, 13.1% 11.5 Nm, etc.

[The_Rsert]

I think nitroglucose is not so much powerful as sorbitol-, mannitol-, lactose hexanitrate or maltose octonitrate. So there is reason for using nitroglucose!?
Nitrosuccrose is more puwerful and cheaper, too!

Idea: Maybe fructose will be better instead of glucose!

[Bugger]

How would it compare with nitrocellulose (gun-cotton, which was once dissolved and made into cine film). Being solid and polymeric, I think that nitrocellulose would be somewhat more stable, but even it slowly auto-oxidizes unless stored at low temperatures.

Bugger.

[Boomer]

I started making NG (nitro glucose eehhmm, let’s better call it GPN for glucose pentanitrate) some month ago. It was used to replace the NG (THE NG) in the explosive plasticizer mixes (see plastic explosives thread). Advantage is it still has a positive OB (+2%), and gives no headache if you knead the stuff without gloves. :)

It is easily made by dissolving 1 part glucose in 5 parts 95+% nitric below 0 degree C, then cooling below zero (freezer –20C) and adding an equal volume sulphuric (keep below 0C). The mix is then poured in a big access of cold water like with MHN, PETN etc, but you get a slime instead of crystals (see COPAE quoted in the post above).

You cannot neutralize it unless in solution. I used acetone to dissolve the slime, added soda for a makeshift neutralisation, and evaporated the solvent at RT. Yellow thick syrup, like honey. Stable for a week (a month in fridge), good plasticiser. Stronger that the hexa- hepta- and even octo-nitrates of disaccharides due to better OB.

PROBLEMS:

A small batch (10g G) was put back in the freezer (-27C, lowest setting) after dissolving the G, batch was at 2C then. Gave a bad runaway even then! Freezer fucked again… :p

With another batch, the acetone in the end was evaporated in a hot water bath. From the moment the acetone was mostly gone, it was maybe three minutes until the stuff boilled up unto yellow smoke … :p

MORAL:

Safer than NG, but thermally less stable, and more prone to runaway nitration. Though I remember batches which went to 15C without runaway at the end of the SA addition. Probably the end product is more stable than the sugar-in-nitric solution.

I will try a 2-phase neutralisation soon, using a non-water miscible solvent for the GPN, and water for the soda. This can be processed like NG, then separated and the solvent evaporated. This way the crap stays in the water and does not contaminate the product, as is the case using only acetone.

[Microtek]

Boomer, have you tried using NiBGTN as your energetic plasticizer ? I suggested this in the thread about NiBGTN and have made a few experiments with it since then.
When I first synthesized it, just before posting the thread, I made a plastique consisting of ca. 85 % PETN and 15 % NiBGTN. I did it with heating to avoid the use of solvent, and obtained a soft plastic mass which exhibited good mechanical properties around room temp ( about 0 - 40 C ). At 50-60 C it was more soft like butter at room temp. I didn't experiment with lower temps.
I'm pretty sure that good results could be had with even more PETN, as the plastique has a slightly glossy look, indicating perhaps a slight excess of NiBGTN.
Anyway, I made some sensitivity and initiation tests ( finding that it is somewhat less sensitive to impact and initiation than straight RDX, making it perfect for small charges where a powerful detonator will be a large percentage of the charge weight ), but still had most of it left. I didn't do anything with it except store it at room temp, wrapped in Al foil.
I have checked it for decomposition every once in a while, but so far there is no sign of any NOx smell or swelling of the plastique.
I have handled it barehanded for about 10 minutes at a time and haven't felt any effect at all.

[Boomer]

Yes Microtek, I remember your post. Unfortunately the whole post seems to be gone in the fuckdefense incident, and I do not remember what NiBGTN means (something with glycide?). All I remember is that I did not have the precursors at that time.

In addition, my still broke last month, and while I was able to weld (!) the parts together, it broke in two more places where it was suspended, one of them being the 29/32 ground glass joint. This I cannot repair, as it will never be tight again. :(
Did you know that you can weld (even pyrex-) glass like steel with an oxy torch?

There was also a life discussion going on in your old caseless detonator thread which I had revived, but it was all lost too. All I have are two of my posts stored locally, which I will post there.

But back to GPN: Do you think it can be neutralized in solution the way I mentioned, i.e. with the soda in water and the product in a non-miscible solvent? COPAE says the bad reputation of most nitro sugars was probably based on them being hard to neutralize as a sticky goo, while e.g. nitro sucrose in NG is sufficiently stable in dynamites.

EDIT (to Microtek below):

I suppose it is stable in solution because A: the acid traces are diluted much my the alcohol, and B: any NOx is more likely to oxidize the alcohol to aldehyde than to attack the nitrate ester.

The advantage I want to achieve by using two phases is to get the crap out of the solvent, as it has to be evaporated instead of crushing in water to get crystals, like for solid esters. I hope that at least the acidic compounds (nitrous acid/NOx) will stay in the water.

It works for NG, EGDN etc and also for nitro sucrose in NG solution, why should it not work for a nitro sugar?

[Microtek]

Well, NiBGTN is short for Nitro iso-Butyl Glycerol TriNitrate. It is made by condensing one mol nitromethane with three moles of formaldehyde in the presence of KHCO3. If you have these precursors it is not too difficult to make.
About the GPN, I made some at about the same time I made the NIBTN ( some authors write the acronym this way; it's a little faster ). I dissolved it in ethanol for the neutralization, and left most of it in solution for storage.
A small amount of the soln was mixed with powdered PETN and evaporated. This produced a nicely plastic matter which unfortunately turned yellow and started gassing over the following weeks.
What's interesting, however, is that the GPN that was left in alcoholic solution and stored at room temp hasn't shown any sign of decomposition yet ( and it has been a few months now... ).
I don't know if a two-phase neutralization would work well, but I suppose so. On the other hand, I don't think much is gained by doing it this way; you still need to dissolve the GPN, and I doubt any unstable byproducts will be more soluble in water than in whatever other solvent you were going to use.

[Boomer]

" ... It is made by condensing one mol nitromethane with three moles of formaldehyde ..."

I guess you mean the intermediate is made that way, then the 3 nitrate groups are added (using mixed acids?) ?

Either way, I have neither pure NM, nor do I want to mess with formaldehyde gas. Or can it be condensed by mixing NM with formalin solution? Even then, getting the NM from 15% NM fuel is the problem (not willing to distil).

BTW the method I proposed did not work: Converting to a soluble salt using a base, evaporating all methanol, then separating from the oil with a non-polar solvent. Finally adding an acid to get the NM back. Or perhaps the base I used was too weak (bicarb) or to strong (NaOH). Ammonia did not work either.

[Oktogen]

Hello !
I'm new at this forum, in the past I was only reading the threads...
I tried nitrating glucose once, with standart H2SO4 98% + HNO3 65% mixture , but the temp. was probably too high... the glucose oxidized and red NO2 started fuming , but i poured this mix into cold water...
In my opinion it is possible to nitrate glucose... but carefully, in cold temp., and with fuming nitric acid. The reason why I don't try it again is that the nitroesters are more powerfull than nitrosugars... my favourite explosive is PETN cause it's cheap, safe and powerfull... and I don't need HNO3 99%... I'm simply using 25ml H2SO4 and 35ml of HNO3 for every 10grams of PE... :D

[nbk2000]

You'll have much better luck finding a supplier if you look for "Dextrose", instead of "Glucose", as they're synonyms for the same thing, just that the dextrose is glucose with the water removed. :)

Within the industry dextrose is used to describe 100 % pure glucose. Both the anhydrous and the monohydrate form is used.

Took me a while to find this out about glucose/dextrose. :o

[Marvin]

Since noone else has mentioned the reason.

Why sugars runaway more easily and are generally less chemically stable than nitrates. Theyre aldehydes. Ok, so they have a cyclic form, and ok disacharides are more stable, but they hydrolyse at the drop of a hat in conc acid and an aldehyde is too good a reducing agent to make for an easy nitration or a stable product, its also lattice unfriendly.

This is why polyols are great. You pick a loser sugar molecule with an accidentally good steriochemistry like mannose, and reduce it (for example electrolytically) producing mannitol. The liability aldehyde group now becomes an alcohol, harder to oxidise making for an easier nitration, and also allows an extra nitrate group to be introduced, giving more kick to the molecule, better stability and (steriochemistry dependant) much better physical properties.