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CN-122010652-A - Inner salt type high-energy-density insensitive explosive and preparation method thereof

CN122010652ACN 122010652 ACN122010652 ACN 122010652ACN-122010652-A

Abstract

The invention discloses an inner salt type high energy density insensitive explosive and a preparation method thereof, 9-amino-2, 6-binitro-bis [1,2,4] triazolo [1,3,5] triazine, namely ZDTT, is prepared, has the advantages of high energy density and insensitivity, has the advantage of simple synthesis process, and ZDTT has a unique inner salt type condensed ring structure, and is insoluble in water and conventional organic solvents. ZDTT has the actual measurement density of 1.881g cm ‑3 , the detonation velocity of 8757m s ‑1 , the detonation pressure of 31.7GPa, the initial thermal decomposition temperature of 330 ℃, the impact sensitivity of more than 40J, the friction sensitivity of more than 360N, and has great application potential in the field of insensitive explosives with high energy density.

Inventors

  • WANG KANGCAI
  • WANG HAIFENG
  • CHEN SITONG
  • LIU JIAN
  • ZHANG WENQUAN

Assignees

  • 中国工程物理研究院化工材料研究所

Dates

Publication Date
20260512
Application Date
20260122

Claims (10)

  1. 1. An inner salt type high-energy insensitive explosive is characterized by comprising the following structural formula: 。
  2. 2. The preparation method of the inner salt type high-energy insensitive explosive is characterized by comprising the following steps of: 。
  3. 3. the method for preparing the inner salt type high-energy insensitive explosive according to claim 2, wherein the method comprises the following steps: (1) Adding TCs-Br into H 2 SO 4 water solution, continuously stirring under ice bath condition, then adding the TCs-Br into NaNO 2 water solution, heating the solution after the dripping is completed until a large amount of reddish brown precipitate is separated out, then adding the solution into acid for acidification to obtain light yellow precipitate, namely DNBTA; (2) Adding DNBTA into a proper amount of organic solvent, then adding Cs 2 CO 3 and BrCN, reacting under heating, cooling the solution to room temperature after the reaction is finished, filtering, washing, acidifying the obtained solid by using acid, washing impurities by using the organic solvent, and drying to obtain the target product ZDTT.
  4. 4. The method for preparing an inner salt type high-energy insensitive explosive according to claim 3, wherein in the step (1), the ratio of the amounts of the three reaction raw materials TCs-Br, H 2 SO 4 and NaNO 2 is 1 (7-10): 60-90), and in the step (2), the ratio of the amounts of DNBTA, cs 2 CO 3 and BrCN is 1 (1-2): 1-2.
  5. 5. The method for preparing an inner salt type high-energy insensitive explosive according to claim 3, wherein the aqueous solution of H 2 SO 4 of the raw material is 10-30 wt% of aqueous solution of H 2 SO 4 , and the reaction temperature of the mixing process of the aqueous solution of H 2 SO 4 of the raw material and the aqueous solution of NaNO 2 is kept at 0-5 ℃.
  6. 6. The method for preparing an inner salt type high-energy insensitive explosive according to claim 3, wherein the solution is heated to 58-62 ℃ for reaction after the completion of the dropping in the step (1), and the reaction time is 4-6 hours.
  7. 7. A method of preparing an inner salt type high energy insensitive explosive according to claim 3 wherein the organic solvent in step (2) includes one or more of ACN, DMF, DMSO, and an appropriate amount of organic solvent is used to completely dissolve DNBTA.
  8. 8. The method for preparing an inner salt type high-energy insensitive explosive according to claim 3, wherein the reaction temperature of DNBTA, cs 2 CO 3 and BrCN is 60-80 ℃, and the reaction time of DNBTA, cs 2 CO 3 and BrCN is 1-2 h under the heating condition.
  9. 9. A process for the preparation of an inner salt type high energy insensitive explosive according to claim 3 wherein step (1) is carried out by adding the reddish brown precipitate to an acid for acidification, which means: The reddish brown precipitate prepared from 0.5 g-1 g TCs-Br is acidified with at least 10ml of a 20% wt H 2 SO 4 aqueous solution.
  10. 10. A method of preparing an inner salt type high energy insensitive explosive according to claim 3 wherein the acid used in the acidification of step (2) is concentrated sulfuric acid or trifluoroacetic acid.

Description

Inner salt type high-energy-density insensitive explosive and preparation method thereof Technical Field The invention relates to the technical field of energetic materials, in particular to an inner salt type high-energy-density insensitive explosive and a preparation method thereof. Background Active energetic materials generally cannot meet the requirements of high energy and low sensitivity at the same time, which severely restricts the development of weaponry. The design and synthesis of novel high-energy density insensitive explosive become a core technical problem to be overcome in the field of energetic materials. In recent years, nitrogen-rich heterocyclic compounds have become leading-edge hot spots for research in the field of energetic materials due to their unique molecular characteristics. Numerous high energy compounds have been successfully built by introducing typical explosive groups such as nitro (-NO 2) into the multi-nitrogen backbone, but their safety performance is still limited. The fused ring compound has the advantages of a polycyclic coplanar structure, a larger pi-pi conjugated system, high formation enthalpy and the like, has positive effects on the performances of energy density, sensitivity, thermal stability and the like, and can enable the fused ring energetic material to break through the performance bottleneck of high energy and low sense. Disclosure of Invention The invention aims to break through the contradiction between high energy and low sensitivity of the existing explosive to meet the development requirement of modern weaponry, and therefore provides an inner salt type high-energy insensitive explosive and a preparation method thereof. The invention takes reported 2,3,5, 6-tetramino-9-imino-bis 1,2,4 triazolo 1,3,5 triazine bromine salt (TCs-Br) as a substrate, develops a synthesis method of an inner salt type high-energy insensitive explosive with low process cost, synthesizes the high-energy insensitive explosive ZDTT with novel structure and excellent comprehensive performance, and has great application potential and value in the field of energetic materials. The invention realizes the above purpose through the following technical scheme: an inner salt type high-energy insensitive explosive has the following structural formula: 。 The invention also provides a preparation method of the inner salt type high-energy insensitive explosive, which is prepared by the following synthetic route: 。 the preparation method further comprises the following steps: 2,3,5, 6-tetramino-9-imino-bis 1,2,4 triazolo 1,3,5 triazine bromine salt (TCs-Br) is added into 20 wt% of H 2SO4 aqueous solution, stirring is continued under ice bath condition, after the solution temperature is proper, the solution is added into NaNO 2 aqueous solution, and proper reaction temperature is needed to be maintained in the dropping process. Heating the solution to 60 ℃ after the dripping is completed for enough time to react, precipitating a large amount of reddish brown precipitate, and then adding the precipitate into acid for acidification to obtain light yellow precipitate, namely DNBTA; DNBTA is added into an appropriate amount of organic solvent, cs 2CO3 is added for deprotonation, and BrCN is added for cyclization reaction, and the reaction is carried out for a sufficient time under the heating condition. After the reaction, a large amount of yellow precipitate is precipitated, filtered, and washed with a proper amount of ice water and ethanol, and the obtained solid is ZDTT cesium salt (ZDTT-Cs). The ZDTT-Cs are acidified by using enough trifluoroacetic acid (TFA) or concentrated sulfuric acid, then the impurities are washed off by using an organic solvent, and the target product ZDTT is obtained after drying. Further, the ratio of the amounts of the substances of TCs-Br, H 2SO4 and NaNO 2 is 1 (7-10): 60-90. Further, the reaction temperature in the mixing process of the raw material 20%wt H 2SO4 solution and the NaNO 2 aqueous solution is kept at 0-5 ℃. According to the further scheme, after the dripping is completed, the solution is heated to 58-62 ℃ and the reaction time is 4-6 hours. Further, the organic solvent comprises one or more of ACN, DMF, DMSO. The use of an appropriate amount of organic solvent means that the organic solvent is capable of complete dissolution DNBTA. Further, the ratio of the amounts of DNBTA, cs 2CO3 and BrCN is 1 (1-2): 1-2. Further, the reaction temperature of DNBTA, cs 2CO3 and BrCN is 60-80 ℃. In a further scheme, the DNBTA, cs 2CO3 and BrCN react for 1-2 hours under the heating condition. In the acidification process of the step (1), adding acid for acidification, namely: acidifying the reddish brown precipitate prepared from 0.5 g-1 g of TCs-Br by using at least 10ml of 20%wt H 2SO4 aqueous solution; During the acidification of step (2), ZDTT-Cs is acidified with sufficient trifluoroacetic acid (TFA) or concentrated sulfuric acid, meaning: At least 20ml of TFA