单质炸药CL-14的合成及其安全性能研究
摘要
高能量、低感度是现代含能材料的发展趋势。本课题采用两种不同的原料合成出了高能钝感炸药5,7-二氨基-4,6-二硝基苯并氧化呋咱(CL-14),并对其安全性能进行了相关研究。
路线一以3-硝基苯胺为起始原料,通过酰化、硝化、环化-脱氮、VNS胺化反应得到目标化合物；路线二以苦基氯为起始原料,通过叠氮化、环化、脱氮、VNS胺化反应得到单质炸药目标化合物。结合反应机理讨论了影响单元反应的主要因素,研究了反应时间、温度、物料比等因素对单元反应的影响,对单元反应各个因素进行了优化,获得了最佳工艺条件。通过红外光谱、质谱、核磁等手段对合成的化合物进行了表征,确认了所得产物为目标产物。
同时,本文还研究了7-氨基-4,6-二硝基苯并氧化呋咱合成新方法：以2,3,4,6-四硝基苯胺为原料,在碱的作用下与盐酸羟胺反应得到了7-氨基-4,6-二硝基苯并氧化呋咱,并讨论了该反应的反应机理。本方法避免了使用剧毒、易爆的叠氮化钠,使反应过程的的安全性提高,反应条件温和,操作简单,具有一定的理论意义和实际意义。
此外,本文使用不同溶剂对CL-14进行了精制,对精制样品的粒度、感度和DSC特性进行了测试和分析。结果表明,DMF为精制CL-14的最佳溶剂,CL-14的热稳定性较好,机械感度较低,是一种安全性能较好的含能材料。
High energy-low sensitivity is the developmental trend of energetic materials.In this dissertation, the insensitive high explosive 5,7-diamino-4,6-dinitrobenzofuroxan(CL-14) was synthesized with two different raw materials, and the safety performance of this explosive was investigated.
There are two methods to synthesis CL-14.The single compound explosive CL-14 was synthesized from 3-nitroaniline through acetylation, nitration, azidation-denitrogenation and VNS amination in the first route.In the other one, using picryl chloride as the starting material to produce CL-14 through nitration, azidation, denitrogenation and VNS amination. This article discussed major factors such as time,temperature,material ratio which affect reaction by means of reaction mechanism,and optimized each kind factor in elementary reaction, finally optimal reaction conditions was obtained. Moreover, the synthesis compounds were characterized by means of infrared spectrum,mass spectrum,nuclear magnetism,and confirm obtained products as goal products.
Meantime,the reaction intermediate 2,3,4,6-tetranitro-anilines was used as raw material to react with hydroxylamine hydrochloride through the function of alkali, and 7-amino-4,6-dinitrobenzofuroxan was obtained, reaction mechanism was discussed, violently poisonous and explosive reagent sodium azide was avoided, the security of the reaction was enhanced.Temperate reaction conditions and simple operation in the reaction had higher research value for synthesizing CL-14 in security. The method is of importance on theory and practice.
CL-14 was purified by different solvents,the fined sample's sizing, DSC thermal decomposition characteristic analysis, and sensitivity were also explored. The results showed that CL-14 purified by DMF has better thermo stability, weaker mechanical sensitivity, and is a kind of energetic material with better security.
路线一以3-硝基苯胺为起始原料,通过酰化、硝化、环化-脱氮、VNS胺化反应得到目标化合物；路线二以苦基氯为起始原料,通过叠氮化、环化、脱氮、VNS胺化反应得到单质炸药目标化合物。结合反应机理讨论了影响单元反应的主要因素,研究了反应时间、温度、物料比等因素对单元反应的影响,对单元反应各个因素进行了优化,获得了最佳工艺条件。通过红外光谱、质谱、核磁等手段对合成的化合物进行了表征,确认了所得产物为目标产物。
同时,本文还研究了7-氨基-4,6-二硝基苯并氧化呋咱合成新方法：以2,3,4,6-四硝基苯胺为原料,在碱的作用下与盐酸羟胺反应得到了7-氨基-4,6-二硝基苯并氧化呋咱,并讨论了该反应的反应机理。本方法避免了使用剧毒、易爆的叠氮化钠,使反应过程的的安全性提高,反应条件温和,操作简单,具有一定的理论意义和实际意义。
此外,本文使用不同溶剂对CL-14进行了精制,对精制样品的粒度、感度和DSC特性进行了测试和分析。结果表明,DMF为精制CL-14的最佳溶剂,CL-14的热稳定性较好,机械感度较低,是一种安全性能较好的含能材料。
High energy-low sensitivity is the developmental trend of energetic materials.In this dissertation, the insensitive high explosive 5,7-diamino-4,6-dinitrobenzofuroxan(CL-14) was synthesized with two different raw materials, and the safety performance of this explosive was investigated.
There are two methods to synthesis CL-14.The single compound explosive CL-14 was synthesized from 3-nitroaniline through acetylation, nitration, azidation-denitrogenation and VNS amination in the first route.In the other one, using picryl chloride as the starting material to produce CL-14 through nitration, azidation, denitrogenation and VNS amination. This article discussed major factors such as time,temperature,material ratio which affect reaction by means of reaction mechanism,and optimized each kind factor in elementary reaction, finally optimal reaction conditions was obtained. Moreover, the synthesis compounds were characterized by means of infrared spectrum,mass spectrum,nuclear magnetism,and confirm obtained products as goal products.
Meantime,the reaction intermediate 2,3,4,6-tetranitro-anilines was used as raw material to react with hydroxylamine hydrochloride through the function of alkali, and 7-amino-4,6-dinitrobenzofuroxan was obtained, reaction mechanism was discussed, violently poisonous and explosive reagent sodium azide was avoided, the security of the reaction was enhanced.Temperate reaction conditions and simple operation in the reaction had higher research value for synthesizing CL-14 in security. The method is of importance on theory and practice.
CL-14 was purified by different solvents,the fined sample's sizing, DSC thermal decomposition characteristic analysis, and sensitivity were also explored. The results showed that CL-14 purified by DMF has better thermo stability, weaker mechanical sensitivity, and is a kind of energetic material with better security.
引文
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[3]王乃兴,李纪生,张来新.苯并氧化呋咱类化合物研究概述[J].合成化学,1995,3(4)：309-313
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[7]范磊刚,杨晓慧,周跃花.苯并呋咱-N-氧化物及其衍生物合成工艺研究概况[J].西安文理学院学报,2006,9(1)：10-13
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[9]Ross W M, Javid H, Robert E,et al. Approaches to the synthesis of energetic heterocyclic compounds suitable for use in insensitive explosive and propellant compositions[C].2006 Insensitive munitions & Energetic Materials Technology Symposium:2006,5-8
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[11]陈捷,汪佩兰,张孝仪等.含微量杂质的苯并三氧化呋咱安定性能研究[J].含能材料,2003,11(1)：32-36
[12]唐玉海,于天义.制备4,6-二硝基苯并氧化呋咱的新方法[J].火工品,1994(3)：38-39
[13]任志奇,于天义,许碧英.新起爆药4,,6-二硝基苯并氧化呋咱钾的制备及其应用研究[J].含能材料,1995,3(4)：7-12
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[15]Mehilal,Arun K S,Suman P,et al.Synthesis, Characterisation, thermal and explosive properties of 4,6-dinitrobenzofuroxan salts[J].Journal of Hazardous Materials,2002,90: 221-227
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[17]Mehilal A K, Salunke R B.Synthesis, characterization and explosives properties of 7-(1H-1,2,4-triazol-3-amino)-4,6-dinitrobenzofuroxan and 7-(1H-1,2,3,4-terazol-5-amin o)-4,6- dinitrobenzofuroxan[J].Journal of EnergeticMaterials,2002,20(1):39-51
[18]霍欢,王伯周,罗义芬等.7-氯-4,6-二硝基苯并氧化呋咱的合成与表征[J].火炸药学报,2009,32(4)：31-33
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[26]夏云霞.4-氨基苯并二氧化呋咱的合成研究[G].硕士学位论文.绵阳：中国工程物理研究院,2004.
[27]陈博仁,廖支援,松全才等.带乙酰胺基苯并氧化呋咱化合物的合成及其热分解[J].北京理工大学学报,1990,10(1)：65-69
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[29]王乃兴,陈博仁,欧育湘.2,6-双(2,4-二硝基苯并氧化呋咱亚胺基)-3,5-二硝基吡啶的合成[J].北京理工大学学报,1993,13(4)：475-478
[30]王乃兴,陈博仁,欧育湘.2-苦胺基-6-(2,4-二硝基苯并氧化呋咱基)-氨基-3,5-二硝基吡啶的合成[J].应用化学,1993,10(3)：94-95
[31]王乃兴,陈博仁,欧育湘.N,N’-双(2-硝基-苯并氧化呋咱)-3,5-二硝基-2,6-二氨基吡啶的合成[J].化学通报,1994,4：37-39
[32]王乃兴,陈博仁,欧育湘等.5-氨基-7-苦氨基-4,6-二硝基苯并氧化呋咱的合成[J].含能材料,1994,2(1)：12-14
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[36]Klyuchnikov O R, Starovoitov V I, Khairutdinov F G, et al.Synthesis of condensed nitrof uroxanes using hydroxylamine[J].Russian Journal of Applied Chemistry,2004,77(5): 853-854
[37]欧育湘.炸药学[M].北京：北京理工大学出版社,2006.111-120
[38]胡宏纹.有机化学(上册)[M].北京：高等教育出版社,1990.203-204
[39]张铸勇.精细有机合成单元反应[M].上海：华东理工大学出版社,2003,2(1)：309-310
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