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新型钝感含能增塑剂3-硝基呋咱-4-甲醚的合成与性能研究
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中国航天科技集团四院四十二所,中国航天科技集团四院四十二所,中国航天科技集团四院四十二所,中国航天科技集团四院四十二所

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沈华平(1986-),男,硕士,主要从事航空宇航推进理论与工程研究。e-mail: nerhehe@163.com

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国家重大安全基础研究项目(973)(批准号: 61337-01)


Synthesis and Characterization of Novel Insensitive Energetic Plasticizer 3-Nitrofurazan-4-monomethyl Ether
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The 42nd Institute of the Fourth Academy of CASC,The 42nd Institute of the Fourth Academy of CASC,The 42nd Institute of the Fourth Academy of CASC,The 42nd Institute of the Fourth Academy of CASC

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    摘要:

    以氰基乙酸乙酯为起始原料,用一锅法先行合成了前体化合物3-氨基呋咱-4-羧酸(AFCA),产率46%。再通过NaBH4/ZnCl2还原体系和H2O2/H2SO4氧化体系先后得到了3-氨基呋咱-4-甲醇(AFMA)及3-硝基呋咱-4-甲醇(NFMA)。用SOCl2将NFMA氯化,得到3-硝基-4-氯甲基呋咱(NFCM),NFCM与甲醇钠反应,最终得到目标化合物3-硝基呋咱-4-甲醚(NFME),产率45%。采用傅里叶红外光谱(FT-IR)、高分辨质谱(HRMS)、核磁共振(NMR)和差热-热重联用(DSC-TG)等对其进行了表征,测定了其燃烧热和感度。结果表明,NFME具有-67 ℃的低熔点,且对撞击和摩擦钝感;其分解温度为169.9 ℃,燃烧热16940.8 kJ·kg-1,生成焓407.0 kJ·mol-1,均高于传统硝酸酯类增塑剂丁基硝酸基乙硝胺(Bu-NENA)、三羟甲基乙烷三硝酸酯(TMETN)、1,2,4-丁三醇三硝酸酯(BTTN)和硝化甘油(NG)。

    Abstract:

    With ethyl cyanoacetate as starting materials,3-aminofurazan-4-carboxylic acid(AFCA) was prepared through one-pot reaction in 46% yield. And 3-aminofurazan-4-monomethyl alcohol(AFMA) was synthesized by reduction reaction of AFCA through NaBH4/ZnCl2 system. 3-Nitrofurazan-4-monomethyl alcohol(NFMA) was obtained by oxidation of AFMA through H2O2/H2SO4 system. 3-Nitrofurazan-4-chloromethylene(NFCM) was obtained by chlorination of NFMA and SOCl2. And 3-nitrofurazan-4-monomethyl ether(NFME) was synthesized by etherification reaction of NFCM and sodium methoxide in 45% yield. Their structures were characterized by FT-IR, MS, NMR and DSC-TG, and sensitivity and heat of combustion of NFME were measured. The results show NFME has a low melting point of -67 ℃ and is insensitive to impact and friction. NFME decompose at 169.9 ℃, and its standard combustion heat is 18628.8 kJ·kg-1, formation enthalpy 1694.4 kJ·mol-1, higher than nitrate plasticizer Bu-NENA, TMETN, BTTN and NG.

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沈华平,卢艳华,曹一林,等.新型钝感含能增塑剂3-硝基呋咱-4-甲醚的合成与性能研究[J].含能材料, 2011, 19(6):735-738. DOI:10.3969/j. issn.1006-9941.2011.06.029.
SHEN Hua-ping, LU Yan-hua, CAO Yi-lin, et al. Synthesis and Characterization of Novel Insensitive Energetic Plasticizer 3-Nitrofurazan-4-monomethyl Ether[J]. Chinese Journal of Energetic Materials, 2011, 19(6):735-738. DOI:10.3969/j. issn.1006-9941.2011.06.029.

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  • 收稿日期: 2011-02-11
  • 最后修改日期: 2011-07-14
  • 录用日期: 2011-03-23
  • 在线发布日期: 2012-02-22
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