|本期目录/Table of Contents|

[1]柴笑笑,李永祥,曹端林,等.耐热炸药TKX-55的合成与热性能[J].火炸药学报,2019,42(2):135-140.[doi:10.14077/j.issn.1007-7812.2019.02.006]
 CHAI Xiao-xiao,LI Yong-xiang,CAO Duan-lin,et al.Synthesis and Thermal Properties of Heat-tesistant Explosive TKX-55[J].,2019,42(2):135-140.[doi:10.14077/j.issn.1007-7812.2019.02.006]
点击复制

耐热炸药TKX-55的合成与热性能()
     
分享到:

《火炸药学报》[ISSN:1007-7812/CN:61-1310/TJ]

卷:
42卷
期数:
2019年第2期
页码:
135-140
栏目:
出版日期:
2019-04-30

文章信息/Info

Title:
Synthesis and Thermal Properties of Heat-tesistant Explosive TKX-55
作者:
柴笑笑 李永祥 曹端林 王建龙 郭昊琪
1. 中北大学环境与安全学院, 山西 太原 030051;
2. 中北大学化学工程与技术学院, 山西 太原 030051
Author(s):
CHAI Xiao-xiao LI Yong-xiang CAO Duan-lin WANG Jian-long GUO Hao-qi
1. School of Environment and Safety Engineering, North University of China, Taiyuan 030051, China;
2. School of Chemical Engineering and Technology, North University of China, Taiyuan 030051, China
关键词:
有机化学55’-双(246-三硝基苯基)-22’-二(134-恶二唑)(TKX-55)246-三硝基甲苯(TNT)双(246-三硝基苯甲酰基)草酰肼耐热炸药
Keywords:
organic chemistry55’-bis(246-trinitrophenyl)-22’-bi(134-oxadiazole) (TKX-55)246-trinitrotoluene (TNT)bis(246-trinitrobenzoyl) oxalohydrazideheat-resistant explosive
分类号:
TJ55;O62
DOI:
10.14077/j.issn.1007-7812.2019.02.006
文献标志码:
-
摘要:
为了寻求新型耐热炸药,以TNT为原料,通过氧化、氯化、缩合、环化4步法合成了5,5’-双(2,4,6-三硝基苯基)-2,2’-二(1,3,4-恶二唑)(TKX-55);通过薄层色谱、傅里叶红外光谱(FTIR)、质谱、元素分析对其4步产物进行了表征,利用差示扫描量热法(DSC)对中间体及TKX-55的热安定性进行了分析。结果表明,氧化反应较佳反应条件为:TNT与氯酸钠(NaClO3)的摩尔比为1:4,反应时间为4 h,反应温度为90℃,与文献[2]相比,使2,4,6-三硝基苯甲酸(TNBA)的收率提高了4%;缩合反应较佳反应条件为:选取四氢呋喃(THF)为溶剂,N,N-二甲基甲酰胺(DMF)为缚酸剂,2,4,6-三硝基苯甲酸(TNBC)与草酰二肼的摩尔比为2:1,反应温度为5℃,反应时间为36 h,与文献[2]相比,使双(2,4,6-三硝基苯甲酰基)草酰肼的收率提高了7%;环化反应较佳反应条件为:以发烟硫酸(质量分数20%)为脱水剂,反应温度为15℃,反应时间为24 h,TKX-55的收率为93%;TKX-55的分解温度为365.5℃,表明TKX-55是一种热安定性良好的耐热炸药。
Abstract:
To seek the novel heat-resistant explosive, 5,5’-bis(2,4,6-trinitrophenyl)-2,2’-bi(1,3,4-oxadiazole) (TKX-55) was synthesized via four steps of oxidation, chloridization, condensation and cyclization using 2,4,6-trinitrotoluene (TNT) as raw material. Four products were characterized by thin-layer chromatography, Fourier transform infrared spectrometer (FTIR), mass spectrometry(MS), elemental analysis and different scanning calorimetry (DSC). The results show that the optimal reaction conditions for the oxidation reaction are as follows:the molar ratio of TNT to sodium chlorate (NaClO3) is 1:4, the reaction time is 4 h, and the reaction temperature is 90℃ to make the yield of 2,4,6-trinitrobenzoic acid(TNBA)increases by 4%. The optimal reaction conditions for the condensation reaction are:taking tetrahydrofuran (THF) as solvent, N,N-dimethylformamide (DMF) as deacid reagent, the molar ratio of 2,4,6-trinitrobenzoic acid (TNBC) to oxalyl dihydrazide as 2:1, the reaction temperature as 5℃, and the reaction time as 36 h to make the yield of bis(2,4,6-trinitrobenzoyl)oxalohydrazide increase by 7%. The optimal reaction conditions for cyclization reaction are as follows:the most suitable dehydrating agent is fuming sulfuric acid (mass fraction of 20%), the reaction temperature is 15℃, the reaction time is 24 h, and the yield of TKX-55 is 93%. The decomposition temperature of TKX-55 is 365.5℃, indicating that TKX-55 is a heat-resistant explosive with good thermal stability.

参考文献/References:

[1] Klapötke T M, Witkowski T G, Wilk Z, et al. Experimental study on the heat resistant explosive 5,5’-bis(2,4,6-trinitrophenyl)-2,2’-bi(1,3,4-oxadiazole)(TKX-55):the jet penetration capability and underwater explosion performance[J]. Centra European Journal Energetic Materials, 2016, 13(4):821-837.
[2] Klap tkeT M, Witkowski T G.5,5’-Bis(2,4,6-trinitrophen-yl)-2,2’-bi(1,3,4-oxadiazole) (TKX-55):thermally stable explosive with outstanding properties[J]. ChemPlusChem, 2016, 81(4):357-360.
[3] 薛长荣, 甘云清.测定2,6-,双(苦氨基)-3,5-二硝基吡啶纯度的研究[J].火炸药学报, 1997, 20(1):21-22. XUE Chang-rong, GAN Yun-qing. Certificated study of 2,6-dipicrylamino-3,5-dinitro-pyridine pureness reference material by potentiometric method[J]. Chinese Journal of Explosives & Propellants(Huozhayao Xuebao), 1997, 20(1):21-22.
[4] 邓明哲.耐热炸药PYX生产中废酸处理[J].火炸药学报, 1998, 21(1):69. DENG Ming-zhe. Treatment of waste acid in production of thermally stable explosive PYX[J]. Chinese Journal of Explosives & Propellants(Huozhayao Xuebao), 1998, 21(1):69.
[5] 邱甬生, 王光碧.国外六硝基茋合成的进展[J].火炸药学报, 1984, 7(4):31-37. QIU Yong-sheng, WANG Guang-bi. Progress in the synthesis of hexanitrostibeneabroad[J]. Chinese Journal of Explosives & Propellants(Huozhayao Xuebao), 1984, 7(4):31-37.
[6] 惠君明.六硝基茋炸药及其应用[J].爆破器材, 1990(4):9-11, 40. HUI Jun-ming. Hexanitrostilbene(HNS) and its application[J]. Demolition Equipments and Materials, 1990(4):9-11, 40.
[7] 陈智群, 郑晓华, 刘子如, 等.HNS的热行为研究[J].含能材料, 2005, 13(4):249-251. CHENG Zhi-qun, ZHENG Xiao-hua, LIU Zi-ru, et al. Thermal behavior of HNS[J]. Chinese Journal of Energetic Materials, 2005, 13(4):249-251.
[8] 周建华, 池钰, 王新锋, 等.超细六硝基茋的热分解性能[J].火炸药学报, 2006, 29(6):38-40. ZHOU Jian-hua, CHI Yu, WANG Xin-feng, et al. Thermal decomposition property of superfine hexanitrostilbene[J]. Chinese Journal of Explosives & Propellants(Huozhayao Xuebao), 2006, 29(6):38-40.
[9] 盛涤纶, 马风娥, 吕巧莉. 2,5-二苦基-1,3,4-恶二唑的制备研究[J].火工品,1998(2):8-15. SHENG Di-lun, MA Feng-e, LU Qiao-li. Study on preparation of 2,5-dipicryl-1,3,4-oxdiazole[J]. Initiators and pyrotechnics, 1998(2):8-15.
[10] 周智明, 王凯, 孙稳稳, 等. 一种由TNT合成TATB的方法:CN, 201010284486.8[P]. 2011. ZHOU Zhi-ming, WANG Kai, SUN Wen-wen, et al. A method of synthesizing TATB by TNT:CN,201010284486.8[P]. 2011.
[11] 何佳,金波,彭汝芳,等.1,1-二(2,4,6-三硝基苯甲酰胺基)-2,2-二硝基乙烯的合成[J].有机化学,2011, 31(10):1643-1647. HE Jia, JIN Bo, PENG Ru-fang, et al. Synthesis of 1,1-dinitro-2,2-di(2,4,6-trinitrobenzoyl amino)ethylene[J]. Chinese Journal of Organic Chemistry, 2011, 31(10):1643-1647.
[12] Wang K,Zhou Z M, Song J H, et al. A metal-free aerobic oxidation of nitrotoluenes catalyzed by N,N’,N"-trihydroxyisocyanuric acid (THICA) and a novel approach to the catalyst[J]. Journal of Hazardous Materials, 2010,184:400-405.
[13] Hassan J, Penalva V, Lavenot L, et al. Catalytic alternative of the ullmann reaction[J]. Tetrahedron, 1998, 54(45):13793-13804.

相似文献/References:

[1]周彦水,李建康,黄新萍,等.3,4-双(4′-氨基呋咱基-3′)氧化呋咱的合成及性能[J].火炸药学报,2007,30(1):54.
[2]彭汝芳,金 波,马冬梅,等.2-(2-硝基苯基)吡咯烷[3′,4′∶1,2][60]富勒烯的合成[J].火炸药学报,2007,30(2):29.
[3]陈 斌,张志忠,姬月萍.偕二硝基类含能增塑剂的合成及应用[J].火炸药学报,2007,30(2):67.
[4]莫洪昌,甘孝贤.3-硝酸酯甲基-3-甲基氧杂环丁烷的合成及表征[J].火炸药学报,2006,29(6):58.
[5]郑晓东,马晓东,邱少君,等.一种新型叠氮含能固化剂的合成及性能[J].火炸药学报,2006,29(5):63.
[6]韩涛,甘孝贤,邢颖,等.3-叠氮甲基-3-乙基氧杂环丁烷及其均聚物的合成与性能[J].火炸药学报,2006,29(5):72.
[7]曹继平,李东林,王吉贵.不饱和聚酯包覆含DNT双基推进剂的研究[J].火炸药学报,2006,29(4):41.
[8]李东林,曹继平,王吉贵.不饱和聚酯包覆层的耐烧蚀性能[J].火炸药学报,2006,29(3):17.
[9]钱华,吕春绪,叶志文.绿色硝解合成六硝基六氮杂异伍兹烷[J].火炸药学报,2006,29(3):52.
[10]赵建民,李加荣,魏筱洁,等.三硝基吡啶及其N-氧化物的合成[J].火炸药学报,2006,29(3):73.
[11]徐容,周小清,曾贵玉,等.TEX的合成研究[J].火炸药学报,2006,29(2):26.
[12]蔡春,吕春绪.五氧化二氮硝解合成1,4,5,8-四硝基-1,4,5,8-四氮杂双环[4.4.0]癸烷[J].火炸药学报,2005,28(2):50.
[13]罗军,李娅琼.用改进的Sollott法合成1,3,5,7-四硝基金刚烷[J].火炸药学报,2011,34(5):13.
 LUO Jun,LI Ya-qiong.Synthesis of 1,3,5,7-Tetranitroadamantane via Modified Sollott′s Route[J].,2011,34(2):13.
[14]史楠,胡炳成,吕春绪.小分子法合成1, 5-二乙酰基-3,7-二硝基-1, 3, 5, 7-四氮杂辛烷工艺研究[J].火炸药学报,2013,36(2):13.
 SHI Nan,HU Bing-cheng,Lü Chun-xu.Study on the Process of Synthesizing 1,5-Diacetyl-3,7-dinitro-1,3,5,7-tetraazacyclooctane by Small Molecule Method[J].,2013,36(2):13.
[15]胡小玲,吴秋洁,钱华.N2O5/HNO3硝解TAIW合成CL-20[J].火炸药学报,2015,38(2):35.[doi:10.14077/j.issn.1007-7812.2015.02.007]
 HU Xiao-ling,WU Qiu-jie,QIAN Hua.Synthesis of CL-20 by Nitrolysis of TAIW with一─3csub>2O5/HNO3 [J].,2015,38(2):35.[doi:10.14077/j.issn.1007-7812.2015.02.007]
[16]王小军,张晓鹏,宋磊,等.5,5′-联四唑-1,1′-二氧氨盐的合成、晶体结构及性能[J].火炸药学报,2015,38(4):35.[doi:10.14077/j.issn.1007-7812.2015.04.008]
 WANG Xiao-jun,ZHANG Xiao-peng,SONG Lei,et al.Synthesis, Crystal Structure and Properties of the Ammonia Salt of 5,5′-Bistetrazole -1,1′-diolate[J].,2015,38(2):35.[doi:10.14077/j.issn.1007-7812.2015.04.008]

备注/Memo

备注/Memo:
收稿日期:2018-7-22;改回日期:2018-9-5。
作者简介:柴笑笑(1992-),男,硕士研究生,从事含能材料及精细化工品的合成研究。E-mail:1987671813@qq.com
通讯作者:李永祥(1964-),男,教授,从事含能材料及其应用研究。E-mail:574732638@qq.com
更新日期/Last Update: 1900-01-01