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摘要
为获得耐热温度大于330℃,并有望替代1,3,5-三氨基-2,4,6-三硝基苯(TATB)的耐热炸药,通过收集63种苯类含能化合物的熔点数据,分析苯环上所含取代基的位置、种类、数量等因素对苯类衍生物熔点的影响规律,并根据这一规律设计出几种有望成为耐热炸药的苯衍生物分子。运用密度泛函理论,计算苯类含能化合物的几何结构、密度、爆轰参数、熔点以及撞击感度。结果表明:设计出的9种化合物,密度均在1.576～2.160g/cm3之间,爆速均在6.630～9.543km/s之间,爆压均在18.231～46.247GPa之间,熔点均在219.982～358.006℃,其中一些化合物的爆轰性能可与优良耐热炸药PYX(爆速=6950m/s)相当。根据理论计算结果,筛选出潜在的新型耐热炸药3,3',5,5'-四氨基-2,2',4,4',6,6'-六硝基偶氮苯(BTAHNAB),其密度为1.868g/cm3,爆速和爆压分别为8.489km/s和33.296GPa,熔点达到358.006℃,特性落高为49.91cm。
Abstract
In order to obtain heat-resistant explosive with heat-resistant temperature greater than 330℃,which is expected to replace 1,3,5-tri-amino-2,4,6-trinitrobenzene(TATB),the melting point data of sixty-three kinds of benzene-containing energetic compounds were collected to analyze the position,type,quantity and other factors of the substituents on the benzene ring.The law of influence on the melting point of benzene derivatives,and based on this law,several benzene derivative molecules that were expected to become heat-resistant explosives were designed.Using density functional theory,the geometric structure,density,detonation parameters,melting point and impact sensitivity of benzene energetic compounds were calculated.The results shown that the densities of the 9 compounds designed were all between 1.576～2.160g/cm3,the detonation speeds were all between 6.630 and 9.543km/s,the explosion pressures were all between 18.231～46.247GPa,and the melting points were all between 219.982～358.006℃,the detonation performance of some of these compounds was comparable to that of the excellent heat-resistant explosive PYX (D=6950m/s).According to the theoretical calculation results,the potential new heat-resistant explosive 3,3',5,5'-tetraamino-2,2',4,4',6,6'-hexanitroazobenzene (BTAHNAB) was screened out.Its density was 1.868g/cm3,the detonation velocity and detonation pressure were 8.489km/s and 33.296GPa,the melting point reached 358.006℃,characteristic drop height was 49.91cm.
关键词
耐热炸药
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苯衍生物
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高熔点
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爆轰参数
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分子设计
Key words
heat-resistant explosive
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benzene derivative
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high melting point
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detonation parameter
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molecular design
苯类耐热炸药分子设计及性能预测[J].
化工新型材料, 2022, 50(10): 241-246 DOI:10.19817/j.cnki.issn1006-3536.2022.10.046
[1] 杨建刚,赵丹丹.耐热炸药的研究现状与进展[J].山东化工,2012,41(12):54-55.
[2] Mehilal M,Sikder N,Sikder A K,et al.N,N'-Bis(1,2,4-triazol-3-yl-)-4,4'-diamino-2,2',3,3',5,5',6,6'-octanitroazobenzene (BTDAONAB):a new thermally stable insensitive high explosive[J].Indian Journal of Engineering & Materials Sciences,2004,11(6):516-520.
[3] 周芙蓉.六硝基茋的合成工艺研究进展[J].化工中间体,2013,10(8):4-7.
[4] 王军,黄靖伦,廖龙渝,等.一种PYX制备新技术[J].含能材料,2008,16(4):480.
[5] Pinal R.Effect of molecular symmetry on melting temperature and solubility[J].Organic & Biomolecular Chemistry,2004,2(18):2692-2699.
[6] Brown R J C,Brown R F C.Melting point and molecular symmetry[J].Journal of Chemical Educaton,2000,77(6):724-731.
[7] 夏泽吉.氢键的键理论及在化学中的应用[J].川东学刊,1996(2):46-52.
[8] 罗洪娟.杂环芳香体系分子间氢键和双氢键的理论研究[D].重庆:西南大学,2009.
[9] 肖鹤鸣,江明,俞马宏,等.单硝基甲苯和多硝基甲苯偶极矩的理论计算和实验测定[J].有机化学,1991(6):595-598.
[10] Dean J A.Lange's handbook of chemistry (15th edition)[M].New York:McGraw-Hil,1999,518-589.
[11] 安华,傅茂武.3,3',5,5'-四氨基-2,2',4,4',6,6'-六硝基联苯的合成[J].火炸药,1983(3):6-10.
[12] 张厚生,胡荣祖,杨德锁.多硝基芳香族化合物的分解热与爆热的关系[J].化学通报,1987(12):30-32.
[13] 张学梅,董海山,周智明,等.苦味酸氨化产物的合成及其性能研究[J].兵工学报,2010,31(10):1341-1345.
[14] 张学梅,董海山,周智明,等.新法合成1,3-二氨基-5-甲氨基-2,4,6-三硝基苯(英文)[J].含能材料,2009,17(5):523-526.
[15] 徐海凤,王娟,李永强,等.2,4,6-三硝基-3,5-二氨基-N-(1,2,4-三唑-4)-苯胺的合成[J].含能材料,2013(6):721-725.
[16] 易景缎,王洪珍.3-苦胺基-1,2,4-三唑的合成[J].火炸药,1992(4):1-5.
[17] 张海昊,贾思媛,王伯周,等.3位氨基或硝基取代5-硝基-1,2,4-三唑衍生物的合成与表征[J].含能材料,2010,18(1):29-33.
[18] 王鸿珍.介绍一种新型耐热炸药[J].火炸药,1981(2):80.
[19] 邱甬生,王光碧.国外六硝基芪合成的进展[J].火炸药,1984(4):31-37.
[20] 郑厦蓉,李永祥,王建龙,等.九硝基三联苯炸药的合成及表征[J].化工进展,2015(3):820-824.
[21] Keshavarz M H.A new computer code for prediction of enthalpy of fusion and melting point of energetic materials[J].Propellants,Explosives,Pyrotechnics,2015,40(1):150-155.
[22] Becke A D.Density-functional thermochemistry.V.systematic optimization of exchange-correlation functionals[J].The Journal of Chemical Physics,1997,107(20):8554-8560.
[23] Lu T,Chen F W.Multiwfn:a multifunctional wavefunction analyzer[J].Journal of Computational Chemistry,2012,33(5):580-592.
[24] Rice B M,Byrd E F C.Evaluation of electrostatic descriptors for predicting crystalline density[J].Journal of Computational Chemistry,2013,34(25):2146-2151.
[25] 王林剑,刘玉存,荆苏明,等.嘧啶类含能化合物的分子设计与性能预测[J].化工新型材料,2021,49(9):179-187.
[26] Byrd E F C,Rice B M.Improved prediction of heats of formation of energetic materials using quantum mechanical calculations[J].The Journal of Physical Chemistry,2006,110(3):1005-1013.
[27] Kamlet M J,Jacobs S J.Chemistry of detonations.I.A simple method for calculating detonation properties of C—H—N—O explosives[J].Journal of Chemical Physics,1968,48(1):23-35.
[28] Pospíšil M,Vávra P,Concha M C,et al.A possible crystal volume factor in the impact sensitivities of some energetic compounds[J].Journal of Molecular Modeling,2010,16(5):895-901.
基金资助
国家自然科学基金(2140316)
