Posts: 778Registered: 28-1-2003Member Is OfflineMood: No MoodNitroguanidine from Sulphamic acid and UreaNitroguanidinefrom Sulphamic Acid and UreaBy AxtNitroguanidine is an explosive of some industrial and military significance, where its primary use is as an additive for propellants. The temperatureof explosion for nitroguanidine is low, and when added to nitrocellulose-nitroglycerine powders it has the effect of both reducing muzzle flash andlowering erosion when compared to propellants of comparable power1. These are known as triple based propellants.When used as a high explosive nitroguanidine detonates at a rate of 7650m/s at 1.55g/cm3 and its explosive power is relatively high, comparable toTNT1. Nitroguanidine is insensitive, failing to detonate from a 3.20m drop of a 2.5kg weight where TNT will detonate with a drop of 1.48m.2.
Italso has a low critical diametre of between 1.27-1.43mm2.While the toxicity of nitroguanidine is stated as being “high“ by Dobratz et al.2, a study on its acute oral toxicity in mice by Hyatt et al.3placed it into the category of being practically non-toxic with a dose of 5000mg/kg producing less then 50% mortality.The preparation of guanidine by fusing sulphamic acid and urea was patented by Mackay4 and the mechanism was later studied by Boivin5,6. While nodefinite conclusions were obtained, the probable mechanism is shown in figure 1. The urea and sulphamic acid first fuse to form ammonium ureasulphonate, which dissociates into cyanamide and ammonium bisulphate which reacts to form guanidine bisulphate.Figure 1: Preparation of guanidine bisulphate by fusing urea with sulphamic acid.Nitroguanidine is prepared by dissolving guanidine nitrate in cold concentrated sulphuric acid (figure 2), then precipitating by pouring into icewater7,8.
Though the yield obtained in this study was low, its an easy preparation and the precursors are both cheap and readily available.Figure 2: Preparation of nitroguanidine from guanidine nitrate.Precursors:99% Sulphamic acid was sold in a hardware store as a descaler for removing calcium and rust deposits. Urea was also purchased from the hardware storein a 15kg bag for use as a fertiliser.
Potassium hydroxide is available from hydroponics suppliers for raising pH.Synthesis:200g sulphamic acid and 124g urea were mixed in a shallow Pyrex bowl and placed into a fan forced kitchen oven. The mixture was left in the oven at220°C for 2 hours, where it gave off some ammonia and melted into a clear liquid gradually thickening and forming a white semi-solid due to ammoniumand guanidine sulphate separated of from the melt.
This was then cooled and broken up to leave 302g of crude residue (figure 3).The crude residue was then blended with 240g of potassium hydroxide in 1L of methylated spirits for 30 minutes (figure 3). This freed the guanidineand ammonia bases and precipitated potassium sulphate, 750ml of this free based alcohol solution was recovered by filtering the blended mixture.Figure 3: Crude fusion product (left); Blending with alcoholic KOH solution (centre); Crude ammonium and guanidine nitrate salts(right).The alcoholic solution of guanidine and ammonia was then neutralised with 70% nitric acid, this precipitated residual potassium hydroxide as itsnitrate which was filtered out. On boiling down the alcohol to a concentrated solution, then evaporating dry, 84g of crude ammonium and guanidinenitrates was obtained (figure 3).50g of the crude mixture of nitrates was directly converted to nitroguanidine by slowly dissolving small portions into 75ml of 98% sulphuric acid, thetemperature was maintained from -5 to +10°C throughout the addition which took approximately 1.5 hours. The milky solution (figure 4) was left for 10minutes at 10°C after the last addition then poured into 500ml of iced water. On standing the nitroguanidine precipitated as small crystals (figure4) which were filtered and dried. Posts: 339Registered: 1-7-2005Location: BrothelMember Is OfflineMood: @%&$ing hardcore babyWow fucking awesome find Axt.
I believe this method looks a lot more OTC than the ammonium nitrate + urea + silica gel method of producing Gnitrate. Well except for the fact that my local hardware store only carries naval jelly or some sulfite mixture for rust removal:rolleyes.hmm. Say did you try mixing Metal+ NO3- and the guanidine bisulfate to produce Nitric acid, guanidine nitrate and Metal Sulfate? Or would othervarious nitrates result too(di/trinitrate)?Edited on 31-7-2007 by DeAdFX. Posts: 982Registered: 14-4-2004Location: California, USAMember Is OfflineMood: Catalytic!Quote:Originally posted by DeAdFXWow fucking awesome find Axt.
I believe this method looks a lot more OTC than the ammonium nitrate + urea + silica gel method of producing Gnitrate. Well except for the fact that my local hardware store only carries naval jelly or some sulfite mixture for rust removal:rolleyes.hmm. Say did you try mixing Metal+ NO3- and the guanidine bisulfate to produce Nitric acid, guanidine nitrate and Metal Sulfate? Or would othervarious nitrates result too(di/trinitrate)?Edited on 31-7-2007 by DeAdFXI found pure sulfamic acid in Home Depot; it was near the plumbing area. I never had a use for it. Posts: 5351Registered: Location: Barad-Dur, MordorMember Is OfflineMood: metastableAnother use for sulfamic acid is the neutralization of strong caustic solutions such as gunsmithing 'blueing' salts which are a mixture (highlyconcentrated) of ammonium nitrate and NaOH.Nitroguanidine is the third main component in so called triple base propellants.
As you know, a single base propellant is straight NC nitrocellulose.A double base propellant is NC/NG nitrocellulose/nitroglycerin. When you get up into propellants for artillery, however, bore erosion becomes aserious issue that limits the life expectancy of the gun tubes (barrels) so nitroguanidine is added to reduce burning temperature and therefore boreerosion. That is triple base propellant.Not normally encountered in small or medium caliber firearms applications. Posts: 778Registered: 28-1-2003Member Is OfflineMood: No MoodQuote:hmm.
Say did you try mixing Metal+ NO3- and the guanidine bisulfate to produce Nitric acid, guanidine nitrate and Metal Sulfate? Or would othervarious nitrates result too(di/trinitrate)?I tried a few different ways before resigning myself to free basing the guanidine.I tried dissolving the crude fusion product in water, filtering out the melamine (from trimerisation on cyanamide or decomp. Of guanidine) thenprecipitating the sulphate with calcium nitrate.
After filtering the calcium sulphate I then tried to boil cry to reclaim the supposed AN/GN but aftera very large and volumous crystaline precipitate formed which near solidified the solution, possible a Ca double salt of sorts, I just chucked it out.I also tried direct nitration of the crude fusion product with KNO3/H2SO4 to see if anything could be obtained via the simplest route possible, but Ididnt recieve anything. In hindsight I think i disposed of it to soon as the NQ does take a little while to precipitate from the solution. Possiblyworth another try.I also tried isolating the ammonium urea sulphonate via lower temperatures following the procedure in the Canadian artilcle, same but with out the useof vacuum and only achieved a sticky resin with the consistancy of honey.Quote:I found pure sulfamic acid in Home Depot; it was near the plumbing area. I never had a use for it.Sulphamic acid has many uses for energetic material synthesis, primarily nitramines via condensation with aldehydes and other amines. Its nitrationitself forms dinitramide.Quote:And there is this thread from a bit over a year ago, references the same basic prep but starting with ammonium sulfamate, which may increase the yieldin the first step - be an interesting experiment.Yeh, thats the patent that the canadian article refers to.
The article does say that yields are increased by use of ammonium salt however it onlyreferences to that patent. If you look at the patent, there is an example for fusing the acid with urea, and the yield based on sulphamate ispractically the same.
At least if the patent is to be trusted, as I recieve far lower yields then what they state.Edited on 3-8-2007 by Axt. Posts: 778Registered: 28-1-2003Member Is OfflineMood: No MoodQuote:Originally posted by Rosco Bodinebut the number is incorrect in thatreference #4 which Axt gives above.I think the yield is higher with the ammonium salt of sulphamic acid.Ahh yep sorry, I edited it.
At a quick glance that 6 looks like a 5.Nope the yields are the same, the patent is basing the yields on the urea used but the sulphamic acid is the most expensive so more practical tocalculate the yields off it. Both examples 1 and 3 yield 0.4g of guanidine sulphate from 1g of sulphamic acid. They are using a 2x molar excess of NH4sulphamate in examples 1 and 2, but not for the sulphamic acid.The metaphasphate route looks interesting. Isn't that available as fertiliser, as is?I think I read of a route through chloropicrin and aqueous ammonia somewhere as well, but cant find and other reference to it. This would beinteresting if the needed pressures are low enough.Edited on 4-8-2007 by Axt. Posts: 6334Registered: 29-9-2004Member Is OfflineMood: analyticalWhat caught my notice as interesting about the sulfamic acid plus urea reaction is the theorized.cyanamide. intermediate, and wondering if theprocess could be modified to favor cyanamide as the product, rather than guanidine.The metaphosphate I'm not sure about the availability.The normal othophosphate can be used with the silica gel catalyst.but then less expensive ammonium chloridewould be make more sense.
I have a string of patentsrelated to that silica gel catalytic process which would be the cheapest method. I wonder if it also works with ammonium sulfate.since thereare bagged fertilizerswhich are 50/50 urea/(NH4)2SO4 sold very cheap and it appears to be a white very pure mixture.The catalytic process works with NH4NO3 plus urea to produce guanidine nitrate directly.but there is also the danger associated with heating thatparticular mixture.IIRC there were strategies for handling that in the industrial methods, but it may not be so easy to implement for an improvised process.Granulated silica gel is cheap OTC as a bulk dessicant for drying flowers, or keeping dampness out of gun cabinets. The more coarse material iseven used as ahigh end kitty litter.
Posts: 899Registered: Member Is OfflineMood: ObsessiveI've seen ammonium metaphosphate and polyphosphate listed as fertilizers, but the N-P-K numbers look squirrely. Pure metaphosphate should besomething like 14-73-0, not 12-52-0.My local supplier has mono ammonium phosphate (MAP) at 12-62-0 which is right on the money for 98%+ material. This can probably be dehydrated at200-250 C, but it seems likely to form a viscous melt and loose some of the ammonia.Anyone have numbers for the dehydration of MAP?
Melting points for various intermediates?Edited on 8-4-2007 by Eclectic. Posts: 2724Registered: 12-3-2004Member Is OfflineMood: ' I think we are all going to die. I think that love is an illusion. We are flawed, my darling'.Quote:Nitroguanidinefrom Sulphamic Acid and UreaBy AxtNitroguanidine is an explosive of some industrial and military significance, where its primary use is as an additive for propellants. The temperatureof explosion for nitroguanidine is low, and when added to nitrocellulose-nitroglycerine powders it has the effect of both reducing muzzle flash andlowering erosion when compared to propellants of comparable power1. These are known as triple based propellants.When used as a high explosive nitroguanidine detonates at a rate of 7650m/s at 1.55g/cm3 and its explosive power is relatively high, comparable toTNT1. Nitroguanidine is insensitive, failing to detonate from a 3.20m drop of a 2.5kg weight where TNT will detonate with a drop of 1.48m.2.
Italso has a low critical diametre of between 1.27-1.43mm2.While the toxicity of nitroguanidine is stated as being “high“ by Dobratz et al.2, a study on its acute oral toxicity in mice by Hyatt et al.3placed it into the category of being practically non-toxic with a dose of 5000mg/kg producing less then 50% mortality.The preparation of guanidine by fusing sulphamic acid and urea was patented by Mackay4 and the mechanism was later studied by Boivin5,6. While nodefinite conclusions were obtained, the probable mechanism is shown in figure 1. The urea and sulphamic acid first fuse to form ammonium ureasulphonate, which dissociates into cyanamide and ammonium bisulphate which reacts to form guanidine bisulphate.Figure 1: Preparation of guanidine bisulphate by fusing urea with sulphamic acid.Nitroguanidine is prepared by dissolving guanidine nitrate in cold concentrated sulphuric acid (figure 2), then precipitating by pouring into icewater7,8. Though the yield obtained in this study was low, its an easy preparation and the precursors are both cheap and readily available.Figure 2: Preparation of nitroguanidine from guanidine nitrate.Precursors:99% Sulphamic acid was sold in a hardware store as a descaler for removing calcium and rust deposits. Urea was also purchased from the hardware storein a 15kg bag for use as a fertiliser. Potassium hydroxide is available from hydroponics suppliers for raising pH.Synthesis:200g sulphamic acid and 124g urea were mixed in a shallow Pyrex bowl and placed into a fan forced kitchen oven.
The mixture was left in the oven at220°C for 2 hours, where it gave off some ammonia and melted into a clear liquid gradually thickening and forming a white semi-solid due to ammoniumand guanidine sulphate separated of from the melt. This was then cooled and broken up to leave 302g of crude residue (figure 3).The crude residue was then blended with 240g of potassium hydroxide in 1L of methylated spirits for 30 minutes (figure 3). This freed the guanidineand ammonia bases and precipitated potassium sulphate, 750ml of this free based alcohol solution was recovered by filtering the blended mixture.Figure 3: Crude fusion product (left); Blending with alcoholic KOH solution (centre); Crude ammonium and guanidine nitrate salts(right).The alcoholic solution of guanidine and ammonia was then neutralised with 70% nitric acid, this precipitated residual potassium hydroxide as itsnitrate which was filtered out. On boiling down the alcohol to a concentrated solution, then evaporating dry, 84g of crude ammonium and guanidinenitrates was obtained (figure 3).50g of the crude mixture of nitrates was directly converted to nitroguanidine by slowly dissolving small portions into 75ml of 98% sulphuric acid, thetemperature was maintained from -5 to +10°C throughout the addition which took approximately 1.5 hours. The milky solution (figure 4) was left for 10minutes at 10°C after the last addition then poured into 500ml of iced water. On standing the nitroguanidine precipitated as small crystals (figure4) which were filtered and dried.
Rapopart’s Rules for critical commentary:1. Attempt to re-express your target’s position so clearly, vividly and fairly that your target says: “Thanks, I wish I’d thought of putting itthat way.”2.
List any points of agreement (especially if they are not matters of general or widespread agreement).3. Mention anything you have learned from your target.4. Only then are you permitted to say so much as a word of rebuttal or criticism.Anatol Rapoport was a Russian-born American mathematical psychologist (1911-2007). Posts: 2996Registered: 30-5-2006Location: Da Big AppleMember Is OfflineMood: No MoodReactions of Ammonium Sulphamate with Amides & Ureasnrcresearchpress.com/doi/abs/10.1139/v56-214.
Side note:On article page 1664 ( 3rd pg of pdf ) under the heading Alkylureas' It was found that methylurea and 1,3-dimethylurea reacted with ammonium sulphamatein a manner analogous to that of urea. Methylamine was isolated from the reaction mixtures.' This is also mentioned in the opening abstract, table IV does not show this perhaps an ommision?Table IIIAttachment: (358kB)This file has been downloaded 1957 times. Posts: 1986Registered: 2-3-2011Member Is OfflineMood: No MoodHere are some other interesting compounds that can be made from guanidine:The di-nitrate salt of azobisformamidine, NH2C(=NH)-N=N-C(=NH)NH2, can be prepared by treating aminoguanidine nitrate, with excess dilute nitric acid,with a solution of potassium permanganate. The di-nitrate salt forms yellow plates, which explode at 180-184 °C.2,5-dinitro-azobisformamidine, O2NN=C(NH2)-N=N-C(-NH2)=NNO2, forms redish to orangish-yellow crystals which explode at 165 °C.
It is obtained bynitrating azobischloroformamidine. with 98.8% concentrated nitric acid and acetic anhydride. Wright, Canadian Journal of Chemistry 30, 65-8(1950). The compound was also prepared by oxidation of 1,6-dinitrobiguanidine with calcium permanganate, obtaining an orange-yellow product,melting point 171-172 °C with decomposition. Henry JACS 75, 958 (1953).Azobischloroformamidine, NH2C(=NCl)-N=N-C(=NCl)NH2, crystallizes in bright yellow needles or plates, melting at 152 °C when crystallized out ofwater, or 155.5 °C from ethyl acetate. The compound has toxicity and explosion hazards. Prepared by reaction of NH2C(=NH)NHNHC(=NH)NH2 withhypochlorite or chlorine gas.
Alternatively, aminoguanidine may be oxidized to NH2C(=NH)N=NC(=NH)NH2, then chlorinated with NaOCl, giving a 42% yieldof azobischloroformamidine, the product having a 96% purity.Edited on 12-1-2013 by AndersHoveland» » » Nitroguanidine from Sulphamic acid and Urea.
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Dobratz Llnl Explosives Handbook 1
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