Polverone gave this link in his hydrazine thread
Post 411522
(Polverone: "optimized OTC hydrazine sulfate synth", Chemistry Discourse):
http://www.sciencemadness.org/talk/viewthread.php?tid=470
so I went to this interesting forum website, and found that Mr. Anonymous gave another present in that thread:
""In the previous communication about the usefulness of urea, I failed to mention a patent which shows the usefulness of urea in synthesis of methylamine. EP 0037862 discloses a high yield synthesis for methylamine nitrate. Also see GB1548827 for a closely related synthesis. It is my guess that paraformaldehyde would react with a diluted urea/ammonium nitrate eutectic. There was a mention of the nitrate process at the Hive, but no details or followup information was posted in the methylamine FAQ. Also see GB168333.""
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So, EP0037862 discloses a high yield synthesis for methylamine nitrate:
Description of patent:
Blasting explosive compositions, generally in the form of slurry explosive compositions, which contain ammonium nitrate as the sole or principal inorganic oxidising salt and a methylamine nitrate mixture as the sole or principal sensitizer, are prepared by reacting in the liquid phase ammonium nitrate and formaldehyde to form an oxidizer/sensitizer blend which can then be mixed with other appropriate constituents to form the required blasting explosive composition, the reaction of the ammonium nitrate and formaldehyde being carried out in the presence of urea in order to reduce the amount of free formic acid which is unexpectedly produced in the reaction, since the presence of formic acid in the reaction mixture is undesirable in that it affects the production of a stable gel therefrom and if converted into a formate reduces the strength of the explosive composition.
Procedure:
800g of a 37% by weight aqueous formaldehyde solution were mixed with 48 g of urea and to the resulting mixture were added 800 g of solid ammonium nitrate. On warming the so formed mixture to 60C an exothermic reaction set in and the temperature rose to 90-95C. The reaction mixture was maintained at a temperature of 95-100C by applying heat when necessary for a period of 3 to 4 hours. Considerable quantities of CO2 were released and at the end of the reaction period the reaction mixture had the following composition:
Solids : 67%
Formic Acid: 1%
Water : 32%
The reaction mixture so formed, containing unreacted ammonium nitrate and a methylamine nitrate mixture, can be evaporated in any suitable evaporation system to a desirable water content. The distillate thus obtained contains only a minor quantity of formic acid, which can easily be neutralised with Ammonia and disposed of without causing environmental problems.
Then you can distill the foregoing reaction mixture in vacuo until 250 ml of water has been collected in the receiver. (we go on until all water is removed)
They proceed to add f,ex. solid sodium perchlorate (NaClO4.H2O) for the next steps of producing in the end an explosive mixture. We better forget those steps, we are not interested in explosives in this context.
So after total water removal, you have a mixture of :
Ammonium nitrate
monomethylamine nitrate
dimethylamine nitrate
trimethylamine nitrate
They indicate that the amines content of one of their final explosives was:
monomethylamine nitrate : 16.5 %
dimethylamine nitrate : 4 %
trimethylamine nitrate : 2 %
This gives a rough indication of the percentual content of the amines you can find if you follow the above procedure, which are around the 40% yield, however they didn't give any content of ammonium nitrate, so you have to find out yourself in practice how much methylamine nitrate can be produced. But mr Anonymous said "a high yield synthesis for methylamine nitrate.""
Then you have to choose a practical manner of separating the amines from the Ammoniumnitrate, and then the separation of solely Methylamine-nitrate from the 2 others, which is much more difficult, better said impossible. But their presence is much lower, so therefor it's more logical to remove in later reduction steps their reaction products in that reduction, which could be possible.
I see no reason why this procedure could not be done with Ammonium chloride instead of Ammonium nitrate, as explained in:
https://www.thevespiary.org/rhodium/Rhodium/chemistry/methylamine.html
But then instead an extra addition of Urea to suppress the formation of excess Formic acid.
Here are some exerpts from GB1548827 (no Urea, but Sodium formate addition):
(Please read the whole patent, if you are also interested in a good explanation of the reaction mechanisms of Methylamine salt production (MethylAmmoniumChloride, here often also called Methylaminechloride, MeAmCl) from Formaldehyde and Ammonium Chloride).
It has been found that by the addition of 5% Sodium formate to a reaction mixture of 800 parts by weight of Ammonium nitrate and 620 parts by weight of 37% (commercial grade) Formaldehyde it is possible, by controlling the reaction temperature to lie between 95 C and 105 C, that the yield of the mixed alkylammonium nitrates (mono, di and trimethylamine nitrates) increases considerably from 30% (without formate) to above 40% (with formate).
The reaction mixture at the end is practically free from Formic acid and requires very little alkali to neutralise it.
Procedure:
A mixture of 800 parts by weight of Ammonium nitrate, 620 parts by weight of 37% commercial grade Formaldehyde and 50 parts by weight of Sodium formate is heated slowly untill the temperature reaches about 70 to 80 C and as the reaction is exothermic, it can maintain itself between 95 to 100 C.
The reaction is, however, maintained at 100 to 105 C by additional sparse heating for 2 hours.
At the end of this period the water content of the reaction mixture is reduced by vacuum distillation to about 12% by weight to give after neutralisation with Ammonia an oxidiser blend(used as base for explosive mixtures, we ofcourse drive off all the water then).
Patent GB168333:
This Danish patent from 1920 describes the production of high explosive mixtures of perchlorate compounds and methylamines.
However, there is a nice remark :
""Furthermore, this perchlorate explosive can be produced at low costs,
since the Methylamine may be EASILY obtained by hydrogenation of hydrocyanic acid, or by distillation of sugar residues.""
I see that in those times scientists were not very impressed by HCN : very poisonous
see:
http://www.nsc.org/library/chemical/hydrocy0.htm
,
so forget that, but that distillation of sugar residues is never mentioned here IMHOP. LT/
