CHINESE JOURNAL OF ENERGETIC MATERIALS
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3,5-二硝基-3,5-二氮杂庚烷合成与性能
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西安近代化学研究所

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国家自然科学基金 21303133 21875185国家自然科学基金(No.21303133和No.21875185)


Synthesis and Properties of 3,5-Dinitro-3,5-diazaheptane
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Xi′an Modern Chemistry Research Institute, Xi′an 710065, China

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    摘要:

    以1,3-二乙基脲为原料,经硝化、水解、缩合等反应得到了中间体乙硝胺(ENA)及终产物3,5-二硝基-3,5-二氮杂庚烷 (DNDA7),ENA收率为80.6%,纯度为99.3%,DNDA7收率为67.7%,纯度为99.0%,总收率为54.6%。采用红外光谱、核磁共振及元素分析表征了其结构。优化了硝化、水解和缩合反应条件,确定较佳硝化水解反应条件为:硝化剂为20%发烟硫酸和浓硝酸,硝化温度-5~0 ℃,水解温度20 ℃,水解时间30 min;较佳缩合反应条件为:乙硝胺/多聚甲醛摩尔比1∶0.5,反应温度23~25 ℃,反应时间30 min。利用差示扫描量热技术(DSC)研究了DNDA7热分解特性及与火炸药常用组分的相容性,结果表明,其熔点为77.3 ℃,热分解峰温为260.8 ℃,DNDA7与黑索今相容性较好,与奥克托今、硝基胍和聚叠氮缩水甘油醚基本相容,与硝化棉和1,1-二氨基-2,2-二硝基乙烯的相容性较差;利用国军标GJB772A-1997方法测试其撞击感度H50>125.9 cm,摩擦感度为4%。

    Abstract:

    The intermediate ethyl nitramine (ENA) and the final product 3,5-dinitro-3,5-diazaheptane (DNDA7) were syntheized starting from 1,3-diethylurea via the reactions of nitration, hydrolysis and condensation. The yield and purity of ENA is 80.6% and 99.3% while 67.7% and 99.0% for DNDA7, respectively, the overall yield is 54.6%. The structure of DNDA7 was characterized by IR, NMR and elemental analyses. Meanwhile, the reaction conditions for nitration, hydrolysis and condensation were optimized as follows: 20% fuming sulphuric acid and nitric acid were used as the nitrating agents, and the recation temperature was controlled between -5 ℃ to 0 ℃ for nitration reaction; while the hydrolysis reaction was finished in 30 min at 20 ℃; and the molar ratio of ENA and paraformaldehyde is 1∶0.5, the reaction mixture was stirred at 23-25 ℃ for 30 min for condensation reaction. The thermal decomposition properties of DNDA7 and its compatibility with normal energetic materials were studied by using differential scanning calorimetry(DSC). The melting point and thermal decomposition temperature of DNDA7 is determined to be 77.3 ℃ and 260.8 ℃, respectively. DNDA7 performs good compatibility with RDX, basic compatibility with HMX, NQ and GAP, and poor compatibility with NC and FOX-7. Moreover, the mechanical sensitivities of DNDA7 were tested according to the national standard GJB772A-1997, and it isfound that the impact sensitivity is H50>125.9 cm and the friction sensitivity is 4%.

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引用本文

陈斌,刘亚静,高福磊,等.3,5-二硝基-3,5-二氮杂庚烷合成与性能[J].含能材料, 2019, 27(12):1036-1042. DOI:10.11943/CJEM2018289.
CHEN Bin, LIU Ya-jing, GAO Fu-lei, et al. Synthesis and Properties of 3,5-Dinitro-3,5-diazaheptane[J]. Chinese Journal of Energetic Materials, 2019, 27(12):1036-1042. DOI:10.11943/CJEM2018289.

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历史
  • 收稿日期: 2018-10-14
  • 最后修改日期: 2019-06-13
  • 录用日期: 2019-02-03
  • 在线发布日期: 2019-05-27
  • 出版日期: 2019-12-25