呋咱醚类含能化合物因其具有熔点低、能量高、塑性强的优点,目前已成为含能材料研究领域的热点之一[1-5]。本文自行设计了呋咱环醚含能化合物三呋咱并氧杂环庚三烯(TFO)分子结构和合成方法,以3, 4-双(3′-硝基呋咱-4′-基)呋咱(BNTF)为原料,在无水乙腈中进行分子内硝基醚化反应,首次合成了呋咱环醚含能化合物TFO(Scheme 1),收率为55.2%,纯度99.3%(HPLC),并采用FT-IR、13CNMR、MS以及元素分析进行了结构表征。TFO熔点为76.5~77.0 ℃, 理论密度1.935 g·cm-3,计算爆速8646 m·s-1,撞击感度24%(10 kg落锤,25 cm), 摩擦感度4%(90°摆角),H50为72.4 cm。TFO综合性能优异,有望用于熔铸炸药中的液相载体组份,也可作为固体推进剂中的含能增塑剂与氧化剂。
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Scheme1 The designed synthetic routes of TFO |
(1) 合成方法
室温条件下,向50 mL的反应瓶中加入25 mL无水乙腈后,再分别加入10.0 g(33.7 mmol)3, 4-双(3′-硝基呋咱-4′-基)呋咱(BNTF)和4.8 g(45.1 mmol)无水碳酸钠,反应约5 min后,升温至回流反应6 h,冷却,倒入80 mL水中,用60 mL二氯甲烷萃取三次,分离收集有机相,无水硫酸镁干燥6 h,过滤、蒸干得白色固体4.2 g,收率55.2%,纯度99.3%(HPLC),m.p.:76.5~77.0 ℃。IR (KBr, cm-1),υ:1569,1481,1003,985(呋咱环); 1165,1087(醚键); 13CNMR (DMSO-d6,500 HMz),δ:160.79,144.01,137.28; MS(EI)m/z(%),220(M+,45),190(23),30(100); Elemental anal(%),calcd for C6N6O4:C 32.73,N 38.18; found C 32.55,N 37.99。
(2) TFO物化与爆轰性能
从表 1可以看出,TFO理论密度1.935 g·cm-3、理论爆速8646 m·s-1、感度较低,特别是熔点较低(76.5~77.0 ℃),可作为熔铸炸药的液相载体,结果表明TFO综合性能优异。
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表 1 TFO的物化与爆轰性能 Tab.1 Properties of TFO |
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Using 3, 4-bis(3′-nitrofurazano-4′-yl)furazan(BNTF) as a starting material, a novel energetic material trifurazanooxacyclohetpatriene was designed and synthesized by intermolecular etherification with a yield of 55.2 % and the purity of 99.3%(HPLC).