臺灣博碩士論文加值系統

目前大部份傳統彈藥仍使用三硝基甲苯(Trinitrotoluene, TNT)系列熔裝炸藥。然而，以TNT系列為主裝藥的彈藥敏感度較高，易因火焰、破片、撞擊等外在因素造成高爆、燃燒等反應。因此，各國目前均致力於尋找物理與化學性能適宜之新型熔裝鈍感炸藥(Insensitive Munitions, IM)替代TNT。其中，2,4-二硝基苯甲醚(2,4-Dinitroanisole, DNAN)是一種性能適宜、敏感度較TNT低，且製備及廢棄物處理均較環保，以致成為國內新型熔裝鈍感炸藥之開發研究目標。
本論文重點在於設計合成開發新型熔裝式鈍感火炸藥DNAN以取代TNT，並對DNAN的製備方法與相對性能進行奠基開發研究。本研究以2種起始物「酚(Phenol)」、「氯苯(Chlorobenzene)」來製備合成2,4-二硝基苯甲醚(DNAN)，並探討由中間體：苯甲醚(Anisole)、2,4-二硝基氯苯(2,4-Dinitro Chlorbenzene)反應後所得最終產物(DNAN)之產率。由「酚」合成「苯甲醚」進行先醚化產率達80.3%；「苯甲醚」於硝化反應產率為71.4%；「氯苯」合成「2,4-二硝基氯苯」進行先硝化產率為53.1%，「2,4-二硝基氯苯」進行醚化取代反應產率為97.7%。
並藉由紅外線光譜譜(FTIR)，核磁共振光譜儀(13C-NMR,1H-NMR)，氣相層析-質譜儀(GC-mass)，液相層析儀(HPLC)，元素分析儀(EA)及熱分析儀(DSC,TGA)等對反應之中間體及2,4-二硝基苯甲醚之化學結構及熱性質作一系列鑑定與分析；另進行落錘及摩擦敏感度之機械敏感度測試，測試結果顯示本研究合成之DNAN具有較TNT更鈍感之特性。

Until now, most of traditional ammunition are still using TNT (Trinitrotoluene) series melt-casting explosive. However, the ammunition filled with TNT as main charges are more sensitive so that they would detonate and ignite easily due to flame, fragments and impact. Nowadays, more and more countries try to research and develop a new kind of melt-casting insensitive munitions(IM) with suitable physical and chemical properties to replace TNT. Because of the suitable properties, lower sensitivity, eco-friendly synthesis process and waste dealing, DNAN (2,4-Dinitroanisole) has become one of the replacing explosives for our country.
The main goal of the study is to develop some synthesis of a new kind of insensitive munitions－DNAN to replace TNT. In this study, we use Phenol and chlorobenzene as starting materials to, prepare DNAN and the yield of DNAN were investigated. The etherification yield of anisole with phenol was 80.3%; the nitrification yield of DNAN with anisole which is Nitrification by mixing HNO3 and H2SO4 solution with two times was 71.4%. The nitrification yield of 2,4-Dinitro Chlorobenzene with chlorobenzene was 53.0%; The etherification yield of DNAN with 2,4-dinitro Chlorobenzene was 97.7%.
The chemical structure and thermal properties of DNAN were sensitivityed by FTIR, 1H-NMR,13C-NMR,GC-mass, HPLC, EA, DSC and TGA. The drop-weight impact loading and frictional sensitivity tests were also investigated and the results suggested that DNAN was less sensitivity than TNT.

目錄
誌謝 ii
摘要 iii
Abstract iv
目錄 v
表目錄 x
圖目錄 xii
1. 緒論 1
1.1 前言 1
1.2 研究動機 3
1.3 研究目的 5
2. 文獻回顧 6
2.1 DNAN基本結構簡介與應用發展 6
2.1.1 DNAN基本結構簡介 6
2.1.2 DNAN的應用發展 7
2.2 DNAN合成反應之可行性方式評估 9
2.2.1 以2,4-二硝基氯苯合成DNAN之反應方法 11
2.2.2 以2,4-二硝基酚合成DNAN之反應方法 11
2.2.3 以氯苯合成DNAN之反應方法 12
2.2.4 以苯甲醚合成DNAN之反應方法 12
2.3 DNAN合成之硝化製備技術探討 13
2.3.1 兩液相反應方式 13
2.3.2 芳香族的硝化反應 16
2.3.2.1 硝酸硝化、硝-硫酸硝化、硝-硫-醋酸硝化 16
2.3.2.2 硝酸酯硝化 17
2.3.2.3 氮氧化物硝化 17
2.3.3 芳香族與催化劑的反應研究 19
2.3.3.1 高分子擔體 19
2.3.3.2 無機擔體（沸石） 20
2.3.3.3 粘土 22
2.3.3.4 離子液體 22
2.3.4 芳香族硝化的反應機制 23
2.3.5 2,4-二硝基苯甲醚(DNAN)之合成反應 25
3. 實驗方法 28
3.1 實驗流程與架構 28
3.2 實驗藥品 29
3.3 實驗器材與儀器設備 30
3.4 儀器檢驗鑑定使用方式 31
3.4.1 傅立葉轉換式紅外線光譜儀(FTIR) 31
3.4.2 核磁共振光譜儀(NMR) 31
3.4.3 元素分析儀(Element Analysis, EA) 31
3.4.4 氣相層析-質譜儀(GC-mass) 31
3.4.5 液相層析儀(HPLC) 32
3.4.6 熱重分析儀(TGA) 32
3.4.7 示差掃描熱量分析儀(DSC) 32
3.5 DNAN合成步驟 32
3.5.1 酚合成「苯甲醚」之實驗步驟 33
3.5.2 苯甲醚硝化合成「2,4-二硝基苯甲醚(DNAN)」之實驗步驟 34
3.5.2.1 苯甲醚一次硝化合成「對-硝基苯甲醚」之實驗步驟 34
3.5.2.2 對-硝基苯甲醚二次硝化合成「2,4-二硝基苯甲醚(DNAN)」之實驗步驟 35
3.5.2.3 苯甲醚連續式硝化合成「2,4-二硝基苯甲醚(DNAN)」之實驗步驟 36
3.5.3 氯苯合成「2,4-二硝基氯苯」之實驗步驟 37
3.5.3.1 氯苯一次硝化合成「對-硝基氯苯」之實驗步驟 37
3.5.3.2 對-硝基氯苯二次硝化合成「2,4-二硝基氯苯」之實驗步驟 38
3.5.3.3 氯苯連續式硝化合成「2,4-二硝基氯苯」之實驗步驟 39
3.5.4 2,4-二硝基氯苯合成DNAN之實驗步驟 40
4. 結果與討論 42
4.1 合成苯甲醚之光譜分析鑑定與產率探討 42
4.1.1 苯甲醚之FTIR光譜分析鑑定 42
4.1.2 苯甲醚之(1H、13C)-NMR光譜分析鑑定 43
4.1.3 苯甲醚之GC-mass光譜分析鑑定 44
4.1.4 合成苯甲醚之產率探討 45
4.2 合成2,4-二硝基氯苯之光譜分析鑑定與產率探討 54
4.2.1 2,4-二硝基氯苯之FTIR光譜分析鑑定 54
4.2.2 2,4-二硝基氯苯之(1H、13C)-NMR光譜分析鑑定 55
4.2.3 2,4-二硝基氯苯之GC-mass光譜分析鑑定 58
4.2.4 合成2,4-二硝基氯苯之產率探討 59
4.2.4.1 氯苯間段式硝化合成2,4-二硝基氯苯之產率探討 59
4.2.4.2 氯苯連續式硝化合成2,4-二硝基氯苯之產率探討 66
4.3 合成DNAN之光譜分析鑑定 70
4.3.1 苯甲醚合成DNAN之光譜分析鑑定 70
4.3.1.1 苯甲醚硝化合成DNAN之FTIR光譜分析鑑定 70
4.3.1.2 苯甲醚硝化合成DNAN之(1H、13C)-NMR光譜分析鑑定 71
4.3.1.3 苯甲醚硝化合成DNAN之GC-mass光譜分析鑑定 74
4.3.2 2,4二硝基氯苯合成DNAN之光譜分析鑑定 76
4.3.2.1 2,4二硝基氯苯醚化合成DNAN之FTIR光譜分析鑑定 76
4.3.2.2 2,4-二硝基氯苯醚化合成DNAN之(1H、13C)-NMR光譜分析鑑定 77
4.3.2.3 2,4-二硝基氯苯醚化合成DNAN之GC-mass光譜分析鑑定 78
4.3.3 合成DNAN之EA元素光譜分析鑑定 79
4.3.4 DNAN之HPLC光譜分析鑑定 80
4.4 合成DNAN相關參數對產率之分析 82
4.4.1 苯甲醚硝化合成DNAN參數之探討 82
4.4.1.1 苯甲醚間段式硝化合成DNAN之產率探討 82
4.4.1.2 苯甲醚連續式硝化合成DNAN之產率探討 95
4.4.2 2,4-二硝基氯苯醚化合成DNAN參數之探討 99
5. 合成DNAN之產率比較分析 104
5.1 醚化反應之產率參數探討 104
5.2 硝化反應之產率參數探討 106
5.3 DNAN合成之物性與機械性能分析 111
5.3.1 DNAN合成之物性分析 111
5.3.2 DNAN合成之機械性能分析 112
6. 結論 114
參考文獻 116
自傳 122

[1]陳俊瑜、夏炎生，火炸藥學，中正理工學院兵器系統叢書，台北，第74-158頁，1991。
[2]Daniel, W. D., Jami, M., Alan, G., and John, B., “Reduced Sensitivity Melt Pourable TNT Replacements,” US Patent: Pub.No.2003/0005988, U.S.A., 2003.
[3]Danie, L. D., Jam, M., and Hanks, A. G., “Reduced Sensitivity Melt Pourable Tritonal Replacements,” US Patent: Pub.No.2003/0140993, U.S.A., 2003.
[4]Voigt, H. W., “Exudation Test for TNT Explosives Under Confinement：Exudation Control and Proposed Standards,” Technical report, AD-AI25476 /2/HDM.
[5]Groupe, S., “International Progress in Insensitive Munitions and Energetic Materials,” 2010 Insensitive Munitions & Energetic Materials Technology symposium, Munich, Germany, 2010.
[6]Department of Defense Test Method Standard., “Hazard Assessment Tests for NON-Nuclear Munitions,” MIL-STD-2105D, 2011.
[7]Phil, J. D., “Characterisation of 2,4-Dinitroanisole: An Ingredient for Use in Low Sensitivity Melt Cast Ormulations,” DSTO-TR-1904, 2006.
[8]Niles, J., Ferlazzo, P., Doll, D., Braithwaite, P., Rausmussen, N., Ray, M., Gunger, M., and Spencer, A., “Recent Developments in Reduced Sensitivity Melt Pour Explosives,” 34th Annual Conference of ICT, June 24-27, pp. 135, 2003.
[9]Arthur, P., and Phil, J. D., “Australian Melt-Cast Explosives R&D DNAN - A Replacement for TNT in Melt-Cast Formulations,” Explosives & Pyrotechnics Group Weapons Systems Division Defence Science and Technology Organisation, http://www.imemg.org/res/IMEMTS%202006_Provatas_paper 3B. (2012.5.20)
[10]王相元、李偉明、王建龍，“炸藥結晶晶形控制技術研究進展”，山西化工學報，第29卷，第1期，第2-5頁，2009。
[11]John, D. V., “Computer Model for the Solidification of Composition B,” AD-A163443.
[12]劉志建，“超細材料與超細炸藥技術”，火炸藥學報，第18卷，第4期，第37-40頁，1995。
[13]Simpson, R., Urtiew, P., and Ornellas, D. L., “CL-20 Performance Exceeds that of HMX and is its Sensitivity is Moderate,” NO. 22, pp. 249-255, 2008.
[14]Larry, S., and Robert, M., “Insensitive Munitions (IM) Enhancement of the 120mm M934A1 High Explosive (HE) Mortar Cartridge,” 2006 Insensitive Munitions and Energetic Materials Technology Symposium, Picatinny Arsenal, New Jersey, USA, 2006.
[15]Groupe, S., “International Progress in Insensitive Munitions and Energetic Materials,” 2010 Insensitive Munitions & Energetic Materials Technology symposium, Munich, Germany, 2010.
[16]譚彥威、劉玉存、楊宗傳、任思國，“熔鑄炸藥的研究進展”，山東化工，第40卷，第5期，第22-24頁，2011。
[17]Chang, A., Daniel, K. C., Byung, J. K., and Seok-Young, O., “Detoxification of PAX-21 Ammunitions Wastewater by Zero-Valent Iron for Microbial Reduction of Perchlorate,” Journal Hazardous Materials, Vol. 192, pp. 909-914, 2011.
[18]William, E. P., David, B., Makram, T. S., and Stephen, W. M., “Biological Transformation Pathways of 2,4-Dinitro Anisole and N-Methyl Paranitro Aniline in Anaerobic Fluidized-Bed Bioreactors,” Journal Chemosphere, Vol. 81, pp. 1131–1136, 2010.
[19]Michael, E., “Development and Performance Characterization of PAX-28: A New Melt Pour Explosive,” Insensitive Munitions ＆Energetic Materials Techno logy Symposium (MEMTS 2003), pp. 10-13 March, Orlando, Florida, USA, 2003.
[20]Mike, A., Wendy, B., and Paul, B., “Characterization of PAX-28 Explosive,” 38th International Annual Conference of ICT, Karlsruhe, Germany, pp. 140-1, 2007.
[21]Nicolich, S., and Niles, J., “Development of A Novel High Fragmentation High Blast Melt Pour Explosive,” Insensitive Munitions ＆ Energetic Materials Technology Symposium (MEMTS 2003), 10-13 March, Orlando, Florida, USA, 2003.
[22]Brian, R., “The Characterization of Explosive Candidates for TNT Replacement,” Insensitive Munitions ＆ Energetic Materials Technology Symposium (MEMTS 2007), October 15-18, Doral Go If Resort and Spa Miami, Florida, USA, 2007.
[23]Rutkowski, J., “Common Low-Cost M Explosive Program to Replace TNT,” Insensitive Munitions ＆ Energetic Materials Technology Symposium (MEMTS 2007), October 15-18, Doral Go If Resort and Spa Miami, Florida, USA, 2007.
[24]Singh, S. J., “The Application of New M Explosive Candidates in the M795 Projectile,” Insensitive Munitions ＆ Energetic Materials Technology Symposium (MEMTS 2007), October 15-18, Doral Go If Resort and Spa Miami, Floridas, USA, 2007.
[25]Wilson, A., “Explosive Ingredients and Compositions for the M M795 Artillery Munition,” Insensitive Munitions ＆ Energetic Materials Technology Symposium (MEMTS 2007), October 15-18, Doral Go If Resort and Spa Miami, Florida, USA, 2007.
[26]Provatas , A., and Phil, J. D., “DNAN A Replacement for TNT in Melt Cast Formulations,” Munitions ＆ Energetic Materials Technology Symposium (MEMTS 2006), 15-28 April, Orlando Bristol, United Kingdom, 2006.
[27]Army Acquisition, Logistics & Technology (AT&L)., “Insensitive Munitions - New Explosives on the Horizon,” ARMY AL&T, JANUARY–MARCH, U.S.A, pp. 33-35, 2008.
[28]王親會，“熔鑄混合炸藥用載體炸藥評述”，火炸藥學報，第34卷，第5期，第25-28頁，2011。
[29]Thomas, K., and Highsmith, H., “Continuous Process for Preparing Alkoxynitro Arenes,” US Patent: Pub.No.2004/ 0133046, 2004.
[30]張光全、董海山，“2,4-二硝基苯甲醚為基鎔鑄炸藥的研究發展”，含能材料，第18卷，第5期，第604-609頁，2010。
[31]Peh, E. A., “Process For the Preparation of 2,4-Dinitrophenyl Ethers,” US Patent：4695656, U.S.A., 1987.
[32]Starks, C. M., Liotta, C., and Halpern, M., “Phase-Transfer Catalysis Fundamentals Applications and Industrial Perspectives,” Chapman ＆ Hall, New York, 1944.
[33]王凱弘，“以有機產物為溶劑之相間轉移催化技術-合成丙烯基苯基醚”，碩士論文，國立成功大學化學工程學系，台南，第1-2頁，2002.
[34]Keith, S., Shifang, L., and Gamal, A. E., “Regioselective Mononitration of Simple Aromatic Compounds Under Mild Conditions in Ionic Liquids,” Industrial Engineering Chemistry Research, Vol. 44, pp. 8611-8615, 2005.

[35]George, A. O., Stephen, J. K., Sylvia, H. F., and John, C., “Aromatic Substitution. XIII. Comparison of Nitric Acid and Mixed Acid Nitration of Alkylbenzenes and Benzene With Nitronium Salt Nitrations,” Nitration of Alkylbenzenes, Oct 5, pp. 3687-3693, 1962.
[36]Smith, K. F., “Para - Selective Mononitration of Alkylbenzenes Under Mild Conditions by Use of Benzoyl Nitrate in the Presence of a Zeolite Catalyst,” Tetrahedron Lett, Vol. 30, No. 39, pp. 5333-5336, 1989.
[37]彭新華，呂春緒，“皂土催化劑上芳烴的硝酸酯硝化反應的區域選擇性研究”，有機化學，第20卷，第4期，第570-573頁，2000。
[38]Xinhua, P., and Hitomi, S., “Regioselective Double Kyodai Nitration of Toluene and Chlorobenzene Over Zeolites High Preference for the 2,4-Dinitro Isomer at the Second Nitration Stage,” Organic Letters, Vol. 3, No. 22, pp. 3431-3434, 2001.
[39]Smith, K., Almeer, S., and Black, S. J., “Para-Selective Nitration Halogenobenzenes Using a Nitrogen Dioxide-Oxygen-Zeolite System,” Journal chemical Society, Chem Commun, Vol. 10, pp. 1571-1572, 2000.
[40]李小青，杜曉華，鄭鶥，陳盛，徐振元，“綠色硝化反應研究進展”，化工進展，第24卷，第10期，第1073-1078頁，2005。
[41]Kwok, T. J., “Application of H-ZSM-5 Zeolite for Regioselective Mononitration of Toluene,” Journal Organic Chemistry., Vol. 49, pp. 4939-4942, 1994.
[42]Smith, K., Musson, A., and Deboos, G. A., “A Novel Method for the Nitration of Simple Aromatic Compounds,” Journal Organic Chemistry., Vol. 63, pp. 8448-8454, 1998.
[43]Keith, S., Shifang, L., and Gamal, A., “Regioselective Mononitration of Simple Aromatic Compounds under Mild Conditions in Ionic Liquids,” Industrial. Engineering Chemistry Research., Vol. 44, pp. 8611-8615, 2005.
[44]Anthony, C. H., and James, L. C., “Novel Synthesis and Spectral Characterization of an N-Acetoxyarylamine：N-Acetoxy-2,4- dinitrophenylamine,” Journal Organic Chemistry., Vol. 52, pp. 4933-4937, 1987.
[45]林經綸、陳昭雄、楊靜儀，有機化學，文京圖書有限公司，台北，第215-344頁，1997年。
[46]方俊民、何東英、徐希白、曾國輝，有機化學，藝軒圖書出版社，台北，第73-131頁，1995年。
[47]邱承美，有機化學概論，新陸書局，台北，第339-413頁，1970年。
[48]Gillespie, R. J., Hughes, E. D., Ingold, C. K., Millen, D. J., and Reed, R. I., “Kinetics and Mechanism of Aromatic Nitration,” Nature Publishing Group, Vol. 163, No. 4146, pp. 599-600, 1949.
[49]曹瑞軍、梅冬，“芳環上親核取代反應-2,4-二硝基氯苯醚化的研究”，西安交通大學學報，第28卷，第8期，第8-11頁，1994。
[50]許馮生、彭耀寰、宋瑩、洪家隆，有機化學，大中國圖書公司，台北，第14-55頁，1980年。
[51]林嘉興，“植物生長調節劑在葡萄栽培上之應用”，植物生長調節劑在園藝作物之應用研討會專集，第203-213頁，1988。
[52]姜絕、席海濤、謝立成，“對硝基苯氧丙酸合成”，江蘇工業學院學報，第17卷，第3期，第10-11頁，2005。