TKX?55合成工艺优化及性能
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摘要
以三硝基甲苯(TNT)为主要原料,通过氧化、氯代、取代、成环反应合成耐热炸药5,5'?双(2,4,6?三硝基苯基)?2,2'?双(1,3,4?噁二唑)(TKX?55),综合收率60.3%。采用红外光谱(FTIR)、核磁共振(NMR)对产物进行了表征,并对氯代反应、取代反应进行了优化。结果显示以SOCl_2为氯代试剂,产率最高(88.8%);以THF为溶剂、反应时间为24 h时,加入无机碱NaHCO_3,取代效果好于加入其它缚酸剂(NaOH、Et_3N、Na-2CO_3),TKX?55分解温度为335℃。用Gaussian软件在b3lyp/6?31++g(d,p)水平下对TKX?55进行分子优化,并通过Kamlet?Jacob公式计算得到爆速(D=8052 m·s~(-1))和爆压(p=28.6 GPa),均优于2,6?二苦胺基?3,5?硝基吡啶(PYX)(D=7590 m·s~(-1),p=26.2 GPa)和2,2',4,4',6,6'?六硝基二苯基乙烯(HNS)(D=7545 m·s~(-1),p=23.6 GPa)。
5,5'?Bis(2,4,6?trinitrophenyl)?2,2'?bi(1,3,4?oxadiazole)(TKX?55),a thermally stable explosive,was synthesized with a total yield of 60.3% from trinitrotoluene via oxidation,chlorination,substitution and cyclization reactions. The chemical structure of TKX?55 was characterized by infrared(IR)spectroscopy,nuclear magnetic resonance(NMR,~1H and~(13)C). Next,we optimized the chlorine and substitution reaction conditions.When SOCl_2 acted as chlorine reagent,the highest yield was up to88.8%. When THF was used as solvent and the reaction time was 24 h,NaHCO_3 was a better acid?binding agent compared with others(such as NaOH、Et_3 N and Na_2CO_3). The decomposition temperature of TKX?55 is 335 ℃. After optimizing the molecularstructure of TKX?55,its detonation velocity(D=8052 m·s~(-1))and detonation pressure(p=28.6 GPa)are calculated by Kamlet?Jacob formula,which are better than those of PYX(D=7590 m·s~(-1),p=26.2 GPa)and HNS(D=7545 m·s~(-1),p=23.6 GPa).
5,5'?Bis(2,4,6?trinitrophenyl)?2,2'?bi(1,3,4?oxadiazole)(TKX?55),a thermally stable explosive,was synthesized with a total yield of 60.3% from trinitrotoluene via oxidation,chlorination,substitution and cyclization reactions. The chemical structure of TKX?55 was characterized by infrared(IR)spectroscopy,nuclear magnetic resonance(NMR,~1H and~(13)C). Next,we optimized the chlorine and substitution reaction conditions.When SOCl_2 acted as chlorine reagent,the highest yield was up to88.8%. When THF was used as solvent and the reaction time was 24 h,NaHCO_3 was a better acid?binding agent compared with others(such as NaOH、Et_3 N and Na_2CO_3). The decomposition temperature of TKX?55 is 335 ℃. After optimizing the molecularstructure of TKX?55,its detonation velocity(D=8052 m·s~(-1))and detonation pressure(p=28.6 GPa)are calculated by Kamlet?Jacob formula,which are better than those of PYX(D=7590 m·s~(-1),p=26.2 GPa)and HNS(D=7545 m·s~(-1),p=23.6 GPa).
引文
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[3]刘季灯,周新利,王鹏程,等.2,6-二苦氨基-3,5-二硝基吡嗪的合成与表征[J].含能材料,2017,25(6):486-492.LIU Ji-deng,ZHOU Xin-li,WANG Peng-cheng,et al.Synthesis and properties of 2,6-bis(picrylamino)-3,5-dinitropyrazine[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2017,25(6):486-492.
[4]Michal R,Svatopluk Z,Ale?R.Crystallography of 2,2',4,4',6,6'-hexanitro-1,1'-biphenyl and its relation to initiation reactivity[J].ChemMater.2008,20:3105-3109.
[5]曹晓华,陆婷婷,陆明.绿色氧化法制备HNS的催化体系[J].含能材料,2015,23(8):732-736.CAO Xiao-hua,LU Ting-ting,LU Ming.Catalytic system for green synthesis of HNS[J].Chinese Journal of Explosives&Propellants(Hanneng Cailiao),2014,37(3):29-32.
[6]王保国,张景林,陈亚芳,等.超细PYX的制备和性能测试[J].含能材料,2007,15(3):198-200,213.WANG Bao-guo,ZHANG Jing-lin,CHEN Ya-fang,et al.Preparation and performance test of ultra-fine PYX[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2007,15(3):198-200.
[7]Sheremetev A B.Chemistryof furazans fused to five-membered rings[J].Journal of Heterocyclic Chemistry,1995,32:371-385.
[8]Pivina T S,Sukhachev D V,Evtushenko A V,et al.Comparative characteristic of energy content calculating methods for the furazan series as an example of energetic materials[J].Propellants,Explosives,Pymtechnics,1995,20(1):5-10.
[9]Sheremetev A B,Aleksandrova N S,Mantseva E V,et al.Synthesis of chlorofurazans from nitrofurazans[J].Mendeleev Communications,2000,10(2):67-68.
[10]Sheremetev A B,Mantseva E V.One-pot synthesis of 4,4'-diamino-3,3'-bifurazan[J].Mendeleev Communications,1996,6:246-247.
[11]Churakov A M,Semenov S E,Loffe S L,et al.The oxidation of heterocyclic amines to nitro compounds using dinitrogen pentoxide[J].Mendeleev Communications,1995,5:102-103.
[12]卑凤利,张兴明,陈海群,等.高能密度材料1,3,4-噁二唑衍生物的分子设计[J].南京理工大学学报,2015,39(2):246-252.BEI Feng-li,ZHANG Xing-ming,CHEN Hai-qun,et al.Molecular design of 1,3,4-oxadiazole-based high energy density material[J].Journal of Nanjing University of Science and Technology,2015,39(2):246-252.
[13]Klap?tke T M,Witkowski T G.5,5'-Bis(2,4,6-trinitrophenyl)-2,2'-bi(1,3,4-oxadiazole)(TKX-55):thermally stable explosive with outstanding properties[J].Chem Plus Chem,2016,81(4):357-360.
[14]Lee chengteh,Yang Wei-tao,Parr R G.Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density[J].Physical Review B,1988,37:785-789.
[15]KamIet M J,Jacobs S T.Chemistry of detonationⅠ.a simple method for calculating detonation properties of C,H,N,O explosives[J].Journal of Chemical Physics,1968,48(1):23-25.