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-《爆破器材》

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Title:: Theoretical Calculation for the Nitrated Process of 3, 7-dinitro-1,3,5,7-tetrazabicyclo［3.3.1］Nonane

Author(s):: XU Jian; WANG Pengcheng; LU Ming; School of Chemical Engineering, Nanjing University of Science and Technology (Jiangsu Nanjing, 210094)

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.