高能低感熔铸炸药液相载体3,3’-联(1,2,4-噁二唑)-5,5’-二甲硝酸酯的合成及性能  

Synthesis and Properties of 3,3’-Bi (1,2,4-oxadiazole)-5,5’-diylbis (methylene) dinitrate (BODN) as A High Energy and Low Sensitivity Melt-casting Explosive

作　　者：薛琪[1,2] 毕福强 周彦水[1,2] 吴敏杰 霍欢[1,2] 张家荣 罗义芬[1,2] 翟连杰 张生勇[1,3] 王伯周 XUE Qi;BI Fu-qiang;ZHOU Yan-shui;WU Min-jie;HUO Huan;ZHANG Jia-rong;LUO Yi-fen;ZHAI Lian-jie;ZHANG Sheng-yong;WANG Bo-zhou(Xi′an Modern Chemistry Research Institute, Xi′an 710065, China;State Key Laboratory of Fluorine & Nitrogen Chemicals, Xi′an 710065, China;School of Pharmacy, Air Force Medical University, Xi′an 710032, China)

机构地区：[1]西安近代化学研究所,陕西西安710065 [2]氟氮化工资源高效开发与利用国家重点实验室,陕西西安710065 [3]空军军医大学药学系,陕西西安710032

出　　处：《火炸药学报》2019年第3期236-241,I0002,共7页Chinese Journal of Explosives & Propellants

基　　金：国家自然科学基金(No.21243007)

摘　　要：以二氨基乙二肟与乙酰氧基乙酰氯为原料,经环化、水解、硝化合成了新型熔铸炸药液相载体3,3′-联(1,2,4-噁二唑)-5,5′-二甲硝酸酯(BODN),总收率为54%,并采用红外光谱、核磁共振、元素分析等进行了结构表征;优化了水解与硝化反应条件;基于分离、鉴定反应副产物的实验结果,探讨了BODN环化反应机理;利用DSC法研究了BODN与RDX、HMX、CL-20的相容性;采用EXPLO5软件预估了RDX、HMX、CL-20为固相的BODN基熔铸炸药的爆轰参数。结果表明,水解反应较优条件为:以碳酸钾为水解试剂在甲醇中回流,其中,3,3′-联(1,2,4-噁二唑)-5,5′-二甲醇乙酸酯和碳酸钾的摩尔比为10∶1,反应2h;硝化反应较优体系为98%发烟硝酸/醋酐体系,其中,98%发烟硝酸、醋酐体系及3,3′-联(1,2,4-噁二唑)-5,5′-二甲醇的摩尔比为10∶5∶1,反应10h;BODN分解峰温203.2℃,与RDX、HMX和CL-20均可良好相容;BODN/CL-20(质量比7∶3)理论爆速达8595m/s,较TNT/CL-20爆速提高约900m/s。Using diaminoglyoxime and 2-chloro-2-oxoethyl acetate as raw materials, a melt-casting explosive, 3,3′-bi(1,2,4-oxadiazole)-5,5′-diylbis(methylene)dinitrate (BODN), was synthesized via coupling-dehydration cyclization, hydrolysis and nitration with an overall yield of 54%, and its structure was characterized by IR, 1H NMR, 13 C NMR and elemental analysis. The reaction conditions of hydrolysis and nitrition were optimized. Based on the separation and identification of reaction by-product, the mechanism of BODN coupling-dehydration cyclization reaction was discussed. The compatibilities of BODN with RDX, HMX and CL-20 were investigated by DSC method. The detonation parameters of BODN-based melt-casting explosives with RDX, HMX and CL-20 as solid phase were predicted by EXPLO5 software. The results show that the preferred hydrolysis conditions are as follows∶ n ([3,3′-bi(1,2,4-oxadiazole)]-5,5′-diylbis(methylene)diacetate)∶ n (K 2CO 3) is 10∶1 and the reacting time is 2h with reflux in CH 3OH and K 2CO 3 as hydrolysis solvent. The preferred reaction conditions for nitrition are: under 98% fuming nitric acid / acetic anhydride system, the molar ratio of the 98% fuming nitric acid / acetic anhydride /[3,3′-bi(1,2,4-oxadiazole)]-5,5′-diylbis(methylene) is 10∶5∶1,reaction time of 10h. The decomposition peak temperature of BODN is 203.2℃ and it has good compatibility with RDX, HMX and CL-20. The theoretical detonation velocity of BODN/CL-20 with a mass ratio of 7∶3 reaches to 8595m/s, 900m/s higher than that of TNT/CL-20.

关 键 词：有机化学 熔铸炸药 [3 3′-联(1 2 4-噁二唑)]-5 5′-二甲硝酸酯(BODN) 热行为 炸药载体 相容性 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O62[理学—有机化学]