| Researchers are searching for advanced replacements for TNT for its disadvantage such as oil seepage and high vapor pressure. 1-amino-3-methyl-1,2,3-triazolium nitrate(1-AMTN) is one kind of energetic ionic liquids, It has appropriate melt point and superior explosive performance over TNT, so it can be used as high-energy liquid carrier in melt castable explosives。1-AMTN was synthesized using glyoxal and hydrazine hydrate as starting materials in four steps including addition-elimination, cyclization, methylation and replacement reaction, the overall yield is 68.1%(based on glyoxal). The reaction conditions of addition-elimination, cyclization and methylation were optimized. The optimal reaction conditions were confirmed: (1). Medium methanol, the ratio of aqueous hydrazine and glyoxal 3:1, the ratio of acetic acid and glyoxal 0.3:100, reaction temperature 70℃, reaction time 5h, to the yield 90.7%; (2) medium acetonitrile, the ratio of activated manganese dioxide and glyoxal bishydrazone 2.8:1, reaction temperature 20℃, reaction time 2.5h, to the yield 87.5%; (3) medium acetonitrile, the ratio of 1-amino-1,2,3-triazole and methyl iodide 1:6, reaction temperature 20℃, reaction time 12h, to the yield 90.1%.The process conditions of cyclization and methylation were improved and optimized: medium acetonitrile, the ratio of glyoxal and methyl iodide 1:5, reaction temperature 20℃, cyclization time 2.5h, methylation time 12h, the yield of cyclization and methylation was 86.7%, the overall yield of 1-AMTN was improved to 74.9%, which indicates that it is a better method than the method reported.The structure of product was confirmed by elemental analysis, IR, MS and NMR. Actived manganese oxide was recycled and its mechanism was discussed. The melt point and decomposition onset temperature are confirmed by DSC. The explosive performances were measured:impact sensitivity 16%, friction sensitivity 24%, explosive velocity 7780m/s, C-J pressure 21.2GPa. |
