论文总字数：22796字

摘 要

由于含能材料内部能量与稳定性的固有矛盾，高能钝感的含能材料的设计与合成一直是一大挑战。含能金属有机材料（EMOFs）凭借良好的爆轰性能和安全性能为协调能量与感度的矛盾提供了新的方向，受到了广泛关注。本论文选用5-氨基-3-硝基-1,2,4-三唑（ANTA）作为配体，该配体有着高含氮量、良好的热稳定性、丰富的配位点和对环境友好的优点。本文以氰基胍为原料，经过取代、硝化和还原反应制备得到ANTA。本文尝试用ANTA分别与两种金属盐Cu(NO₃)₂·3H₂O、Zn(NO₃)₂·6H₂O反应制备EMOFs：ANTA与Cu(NO₃)₂·3H₂O反应得到的7种粉末状物，通过红外与粉末X射线衍射（PXRD）表征发现，这些产物是相同的，但既不是ANTA也不是Cu(NO₃)₂·3H₂O，粉末衍射实验中发现这些产物只有在低角度时出现了一个较强的峰，说明它们成为晶体的可能性不大；ANTA与Zn(NO₃)₂·6H₂O反应得到5种红色粉末状物，通过红外与PXRD表征发现，这些产物是相同的，但既不是ANTA也不是Zn(NO₃)₂·6H₂O，粉末衍射实验中发现这些产物存在多个较强的衍射峰，说明有进一步制备为晶体的潜力。

关键词：含能分子的设计与合成 含能有机金属框架 三唑衍生物 高能钝感

Preparation of Energetic Organometallic Framework Materials Based on 5-Amino-3-Nitro-1,2,4-Triazole

Abstract

Due to the inherent contradiction between internal energy and stability of energetic materials, the design and synthesis of energetic materials with high energy insensitivity have always been a tremendous challenge. Energetic metal-organic frameworks (EMOFs) have received widespread attention, which provide a new direction for resolving the incompatibility between energy and sensitivity due to their promising detonation performance and safety performance. In this article, 5-amino-3-nitro-1,2,4-triazole (ANTA) is selected as the ligand, which possess the advantages of high nitrogen content, good thermal stability, rich coordination sites and friendly to environment. In this article, ANTA was obtained from cyanoguanidine through substitution reaction, nitrification reaction and reduction reaction. This article uses cyanoguanidine as raw material, through the synthesis of 3,5-diamino-1,2,4-triazole,through the Synthesis of 3,5-dinitro-1,2,4-triazole sodium salt and ANTA prepared by reaction with hydrazine hydrate. This article aims to prepare EMOFs by reacting ANTA with two metal salts Cu(NO₃)₂·3H₂O and Zn(NO₃)₂·6H₂O respectively: seven kinds of powders were obtained though the reaction of ANTA and Cu(NO₃)₂·3H₂O. Infrared and powder X-ray diffraction (PXRD) data suggest that seven products are the same material, but that is different to ANTA and Cu(NO₃)₂·3H₂O, and the PXRD data shows only a strong peak appears at low angles, indicating that this powder is unlikely to become crystals. Five kinds of red powders were obtained through the reaction of ANTA and Zn(NO₃)₂·6H₂O. Infrared and PXRD data suggest that five products are the same material, but that is different to ANTA and Zn(NO₃)₂·6H₂O, the PXRD data shows plenty of strong diffraction peaks, indicating the potential for further preparation of crystals.

KeyWords: Design and synthesis of energetic molecules；Energetic metal-organic frameworks；Triazole derivatives；High energy and insensitivity

目 录

摘 要 I

ABSTRACT II

第一章 绪论 1

1.1 含能材料概述 1

1.2 含能材料几类药剂的研究进展 1

1.2.1推进剂 1

1.2.2烟火剂 1

1.2.3火炸药 2

1.2.4新型绿色的起爆药 3

1.3 含能金属有机骨架概述 4

1.3.1含能小分子金属有机骨架 4

1.3.2富氮杂环含能金属有机骨架 5

1.3.3高能多致爆基含能金属有机骨架 6

1.4 5-氨基-3-硝基-1,2,4-三唑（ANTA）的制备合成 6

1.5 ANTA三唑环的几种典型反应 7

1.5.1 ANTA 1位点的反应 7

1.5.2 ANTA中氨基参与的反应 7

1.6 本课题的研究意义 8

第二章 实验部分 9

2.1 引言 9

2.2 配体5-氨基-3-硝基-1,2,4-三唑的合成 9

2.2.1 3,5-二氨基-1,2,4-三唑的合成 10

2.2.2 3,5-二硝基-1,2,4-三唑钠盐的合成 10

2.2.3 5-氨基-3-硝基-1,2,4-三唑的合成 11

2.3 基于配体ANTA的配合物制备尝试 13

2.3.1与Cu(NO₃)₂·3H₂O的自组装反应 13

2.3.2 与Zn(NO₃)₂·6H₂O的自组装反应 16

第三章 实验结论及展望 20

3.1 结论 20

3.2 展望 20

参考文献 21

致谢 25

请支付后下载全文，论文总字数：22796字