[1]许健,王鹏程,陆明.3,7-二硝基-1,3,5,7-四氮杂双环［3.3.1］壬烷硝解过程的理论研究[J].爆破器材,2014,43(01):1-7.[doi:10.3969/j.issn.1001-8352.2014.01.001]
　XU Jian,WANG Pengcheng,LU Ming.Theoretical Calculation for the Nitrated Process of 3, 7-dinitro-1,3,5,7-tetrazabicyclo［3.3.1］Nonane[J].EXPLOSIVE MATERIALS,2014,43(01):1-7.[doi:10.3969/j.issn.1001-8352.2014.01.001]
点击复制

3,7-二硝基-1,3,5,7-四氮杂双环［3.3.1］壬烷硝解过程的理论研究()
分享到：

《爆破器材》[ISSN:1001-8352/CN:32-1163/TJ]

卷:
43
期数:
2014年01
页码:
1-7
栏目:
基础理论
出版日期:
2014-02-20

文章信息/Info

Title:
Theoretical Calculation for the Nitrated Process of 3, 7-dinitro-1,3,5,7-tetrazabicyclo［3.3.1］Nonane
文章编号:
4681
作者:
许健; 王鹏程; 陆明
南京理工大学化工学院（江苏南京，210094）
Author(s):
XU Jian;  WANG Pengcheng;  LU Ming
School of Chemical Engineering, Nanjing University of Science and Technology (Jiangsu Nanjing, 210094)
关键词:
硝解; DPT; HMX; 密度泛函理论
Keywords:
nitration;  DPT;  HMX;  density functional theory
分类号:
TJ55；O64
DOI:
10.3969/j.issn.1001-8352.2014.01.001
文献标志码:
A
摘要:
在密度泛函理论B3LYP/6-31G**水平下，对3,7-二硝基-1,3,5,7-四氮杂双环［3.3.1］壬烷(DPT)硝解制备1,3,5,7-四硝基-1,3,5,7-四氮杂环辛烷(HMX)的过程进行量子化学研究，主要计算了DPT以及重要反应中间体的电子云密度、键长、键级和二阶微扰能。结果表明，由于受键长和键解离能的影响，DPT在硝解过程中可能同时生成八元环和六元环的中间体；八元环中间体受键解离能与二阶微扰能的影响，在硝解制备HMX的同时有副产物产生。因此，DPT硝解制备HMX不仅受实际实验过程影响，还受到分子本身结构的影响，通过计算可以看出，量子化学参数在微观上体现了HMX的总收率不理想的内在原因。
Abstract:
The nitration process of 3,7-dinitro-1,3,5,7-tetrazabicyclo［3.3.1］nonane (DPT) to 1,3,5,7-Tetranitro-1,3,5,7-tetraazacyclooctane (HMX) was studied using density functional theory at the B3LYP/6-31G** level. Several important factors such as the electron density, bond length, bond order and second-order perturbation energy were calculated. The results show that, because of the influence of bond length and bond dissociation energy, the nitration of DPT not only leads to the intermediate with eightmembered ring but also six-membered ring. Besides that, byproducts would generate in the nitrolysis of the eight-membered ring products to HMX, which was affected by the bond dissociation energies and the secondorder perturbation energy. Therefore, the nitration process is affected both by experiment and molecular structure. Through calculation, the quantum chemical parameters microscopically provide the intrinsic reasonable explanation why the yield of HMX is limited in industrial production.

参考文献/References:

［1］Greenfield M, Guo Y Q, Bernstein E R . Ultrafast photodissociation dynamics of HMX and RDX from their excited electronic states via femtosecond laser pumpprobe techniques［J］.Chemical Physics Letters,2006,430(4-6):277-281. 
［2］任特生.硝胺硝酸酯炸药化学与工艺学［M］.北京:兵器工业出版社，1994:182-185．
［3］Bachmann W E,Jenner E L. 1-acetoxymethyl-3,5,7-trinitro-1,3,5,7-tetrazacycloctane and its reactions. Significance in the nitrolysis of hexamethylenetetramine and related compounds 1［J］. Journal of the American -Chemical- Society,1951,73(6):2773-2775.
［4］Mckay A F, Richmond H H, Wright G F. Nitrolysis of hexamethylenetetramine;nitrolysis of 1,5-endomethylene- 3,7-dinitro-1,3,5,7-tetrazacyclo-ctane［J］.Canadian Joural of Research:Section B,1949,27(5):462-468.
［5］何志勇,罗军,吕春绪,等.3,7-二硝基-1,3,5,7-四氮杂双环［3.3.1］壬烷的硝解副产物及硝解机理［J］.含能材料，2012，20(1):5-8.
He Zhiyong, Luo Jun, Lü Chunxu, et al. Mechanisms and byproducts of nitrolysis of 3,7-dinitro-1,3,5,7-tetrazabicyclo- ［3.3.1］nonane ［J］.Chinese Journal of Energetic Materials, 2012, 20(1): 5-8.
［6］Lee C, Yang Weitao, Parr R G. Development of the colle-salvetti correlation-energy formula into a functional of the electron density［J］. Physical. Review. B, 1988,37(2):785-789. 
［7］Miehlch B, Savin A, Stoll H, et al. Results obtained with the correlation energy density functionals of Becke and Lee, Yang and Parr［J］. Chemical Physies Letters, 1989,157(3):200-206. 
［8］Becke A D. Densityfunctional thermochemistry. II. The effect of the Perdew-Wang generalizedgradient correlation correction ［J］.The Journal of Chemical Physics,1992,97(12):9173-9177.
［9］Becke A D. A new mixing of Hartree-Fock and local density-functional theories ［J］.The Journal of Chemical Physics,1993,98(2):1372-1377.
［10］Zhang Maoxi, Eaton P E, Gilardi R. Heptaund octanitrocubane ［J］.Angewandte Chemie,2000,112(2):422-426.
［11］Ravi P,Gore G M, Sikder A K,et al. A DFT study on the structureproperty relationship of aminonitropyrazole-2-oxides ［J］.International Journal of Quantum Chemistry, 2012,112(6):1667-1677.
［12］ Sharia O, Kuklja M M. Modeling thermal decomposition mechanisms in gaseous and crystalline molecular materials: application to βHMX ［J］.The Journal of Physical Chemistry B,2011,115(44):12677-12686.
［13］Zhang Guohua, Zhao Yongfang, Hao Fengyou, et al. Theoretical study on structures and stabilities of N4X (X=O, S, Se, Te) series ［J］.International Journal of Quantum Chemistry,2009,109(2):226-235.
［14］Zhao Guozheng, Lu Ming.Theoretical studies on high energetic density nitramine explosives containing pyridine［J］. Science China Chemistry ,2012,55(9):1903-1909.
［15］Namboothiri I N，Balasubrahmanyam S N, Pius K.A computational evaluation of bond order and charge distributions in isomeric aminotroponiminiums and their benzo-fused derivatives［J］. Journal of Biophysical Chemistry ,2012, 2(1):15-22.
［16］Zhou Panpan ,Qiu Wenyuan, Jin Nengzhi .Quantification of hyperconjugative effect on the proton donor X-H bond length changes in the red and blueshifted hydrogenbonded-complexes［J］.The Journal of Chemical- Physics,2012, 137(8): 84311-84315. 
［17］Nalewajski R F,Gurdek P.Bondorder and entropic probes of the chemical bonds［J］.Structural Chemistry,2012, 23(5):1383-1398.［18］Tan Xiaojun,Li Zhen,Sun Qiao,et al. Theoretical study on the reaction mechanisms between propadienylidene and RH (R=F, OH, NH2, CH3): an alternative approach to the formation of alkyne［J］.Structural Chemistry,2012,24(1):33-38.

相似文献/References:

[1]张袁斌,陈文靖,叶志文.N2O5/HNO3体系硝解三（N-乙酰基）六氢化均三嗪制备RDX[J].爆破器材,2012,41(04):9.
　ZHANG Yuanbin,CHEN Wenjing,YE Zhiwen.Preparation of RDX by Nitrolysis of 1,3,5-Triacetyl Hexahydro-1,3,5-Triazaine with N2O5/HNO3[J].EXPLOSIVE MATERIALS,2012,41(01):9.

备注/Memo

备注/Memo:
收稿日期：2013-07-02
作者简介：许健（1988~），男，硕士研究生，主要从事含能材料的合成及其理论研究。
通信作者：陆明（1963~），男，教授，博导，主要从事多氮杂环含能材料的设计与合成。
更新日期/Last Update: 2014-02-28