1,3-二硝基六氢嘧啶-5-硝酸酯的合成与性能

(1. 氟氮化工资源高效开发与利用国家重点实验室,陕西 西安710065; 2. 西安近代化学研究所,陕西 西安710065)

有机化学; 含能化合物; 1,3-二硝基六氢嘧啶-5-硝酸酯; DNHM; 晶体结构;

Synthesis and Properties of 1,3-Dinitrohexahydropyrimidin-5-yl Nitrate
YANG Kai-di1,2, ZHAI Lian-jie2, ZHANG Jun-lin2, XUE Qi2, LU Xu2, BI Fu-qiang1,2, WANG Bo-zhou1,2

(1. State Key Laboratory ofFluorine & Nitrogen Chemicals, Xi'an 710065, China; 2. Xi'an Modern Chemistry Research Institute, Xi'an 710065, China)

organic chemistry; energetic compound; 1,3-dinitrohexahydropyrimidine-5-nitrate; DNHM; crystal structure

DOI: 10.14077/j.issn.1007-7812.202001010

备注

为了更好地研究氮杂环己烷骨架的含能材料,以1,3-二氨基异丙醇为起始原料,经缩合、硝化等反应,合成了硝酸酯类含能化合物1,3-二硝基六氢嘧啶-5-硝酸酯(DNHM),并采用红外光谱、1H NMR、13C NMR及元素分析等对其结构进行了表征,并培养其单晶; 优化原硝化条件,利用HNO3/(CH3CO)2O代替原HNO3/P2O5硝化体系; 采用DSC与TG-DTG法研究了DNHM的热行为; 利用DSC法研究了DNHM与传统单质炸药RDX、HMX与CL-20的相容性; 利用Gaussian与EXPLO5软件计算了DNHM的爆速、爆压等爆轰参数。结果 表明,其晶体结构为单斜晶系,空间群为P21,晶体密度1.766g/cm3; 硝化条件优化后收率由79.69%提高至87.93%,且粗品纯度高达99.39%; 其熔点为126.9℃、分解点为197.0℃; 与RDX、HMX及CL-20相容性良好; 理论爆速8412m/s、计算爆压31.59GPa,表明DNHM在混合炸药与推进剂中具有潜在应用前景。

To gain better insight into energetic materials with azacyclohexane skeletons, an energetic compound of 1,3-dinitrohexahydropyrimidine-5-nitrate(DNHM)was synthesized via condensation and nitration reactions using 1,3-diaminoisopropanol as starting material. The structure of DNHM was characterized by FTIR, 1H NMR, 13C NMR and elemental analysis and the single crystal was also prepared. An optimized nitration condition was achieved by replacing the original nitration system of HNO3/P2O5 with HNO3/(CH3CO)2O. The thermal behaviors of DNHM were studied by DSC and TG-DTG methods, and the compatibilities of DNHM with traditional single explosives, including RDX, HMX and CL-20, were investigated through DSC experiments. The detonation parameters of DNHM were predicted by Gaussian and EXPLO5 software. The results showed that DNHM crystallizes in monoclinic with the space group of P21 and a crystal density of 1.766g/cm3. The nitration yield of DNHM was increased from 79.69% up to 87.93% and the purity of its crude product was up to 99.39%. The melting and decomposition temperatures of DNHM were 126.9℃ and 197.0℃, respectively, and DNHM exhibited good compatibility with RDX, HMX and CL-20. Moreover, the theoretical detonation velocity and detonation pressure were 8412m/s and 31.59GPa, respectively. All these results indicated a potential application prospect of DNHM in the formulations of composite explosives and propellants.