[1]石磊①,孙志杨②,杨超飞①,等.磺酸类催化剂在合成CL-20硝化反应中的应用[J].爆破器材,2018,47(05):16-20.[doi:10.3969/j.issn.1001-8352.2018.05.003]
　SHI Lei,SUN Zhiyang,YANG Chaofei,et al.Application of Sulfonic Acid Catalysts in Nitration in Synthesis of CL-20[J].EXPLOSIVE MATERIALS,2018,47(05):16-20.[doi:10.3969/j.issn.1001-8352.2018.05.003]
点击复制

磺酸类催化剂在合成CL-20硝化反应中的应用()
分享到：

《爆破器材》[ISSN:1001-8352/CN:32-1163/TJ]

卷:
47
期数:
2018年05
页码:
16-20
栏目:
基础理论
出版日期:
2018-09-27

文章信息/Info

Title:
Application of Sulfonic Acid Catalysts in Nitration in Synthesis of CL-20
文章编号:
5263
作者:
石磊①; 孙志杨②; 杨超飞①; 开旺①; 钱华①③
①南京理工大学化工学院（江苏南京,210094）
②浙江永联民爆器材有限公司（浙江杭州，310011）
③国家民用爆破器材质量监督检验中心（江苏南京,210094）
Author(s):
SHI Lei①;  SUN Zhiyang②;  YANG Chaofei①;  KAI Wang①;  QIAN Hua①③
① School of Chemical Engineering, Nanjing University of Science and Technology (Jiangsu Nanjing, 210094)
②Zhejiang Yonglian Civil Explosive Materials Co., Ltd.(Zhejiang Hangzhou,310011)
③ China National Quality Supervision Testing Center for Industrial Explosive Materials (Jiangsu Nanjing, 210094)
关键词:
六硝基六氮杂异伍兹烷（CL-20）; 四乙酰基六氮杂异伍兹烷（TAIW）; 有机磺酸; 镧系金属磺酸盐; 全氟磺酸分子筛
Keywords:
hexanitrohexaazaisowurtzitane (CL-20);  tetraacetylhexaazaisowurtzitane (TAIW);  organic sulfonic acid;  lanthanide sulfonates;  perfluorosulfonic acid molecular sieve
分类号:
TD235.2+1;TQ564;TQ031.2
DOI:
10.3969/j.issn.1001-8352.2018.05.003
文献标志码:
A
摘要:
针对N2O5/HNO3体系硝解四乙酰基六氮杂异伍兹烷（TAIW）、制备六硝基六氮杂异伍兹烷（CL-20）反应收率和纯度低的问题，探讨了有机磺酸、三氟甲磺酸的镧系金属盐以及全氟磺酸分子筛的催化剂效果。结果表明，3类催化剂对合成CL-20硝化反应具有催化作用。CL-20的收率由无催化剂时的80.2％，分别提高到95.1％、94.9％、91.5％，相应纯度由89.8％分别提高到98.9％、97.6％、98.6％。三氟甲磺酸的镧系金属盐和全氟磺酸分子筛催化剂循环使用5次以上，CL-20的收率和纯度均没有明显降低，表现出良好的催化活性和可重复性。
Abstract:
Due to the low yield and purity of hexanitrohexaazaisowurtzitane (CL-20) during the nitration of tetraacetylhexaazaisowurtzitane(TAIW) using N2O5/HNO3 as nitrating agent, the effects of three types of catalysts, in cluding organic sulfonic acid, lanthanide trifluoromethanesulfonates and perfluorosulfonic acid molecular sieve, were studied. Results indicate that all the three catalysts have catalytic effect in nitration of CL-20 synthesis. Yield of CL-20 increases from 80.2% to 95.1%, 94.9%, and 91.5%. And the corresponding purity increases from 89.8% to 98.9%, 97.6%, and 98.6%, respectively. Catalytic performance of lanthanide trifluoromethanesulfonates and perfluorosulfonic acid molecular sieve catalysts do not show remarkable decrease after being reused for more than five times, indicating both catalysts possess desirable catalytic activity and repeatability.

参考文献/References:

-［1］NIELSEN A T. Caged polynitramine compound:US5693794［P］. 1997-12-02.
［2］AGRAWAL J P. Some new high energy materials and their formulations for specialized applications［J］. Propellants, Explosives, Pyrotechnics, 2005, 30(5):316-328.
［3］赵晓锋, 成健, 刘祖亮. ［MIMPS］［HSO4］催化N2O5硝化2,6-二乙酰氨基吡嗪-1-氧化物［J］. 含能材料, 2013, 21(1):12-15.
ZHAO X F, CHENG J, LIU Z L. Nitration of 2,6-diacetamidopyrazine-1-oxide with N2O5 catalyzed by ［MIMPS］ ［HSO4］［J］. Chinese Journal of Energetic Materials, 2013, 21(1):12-15.
［4］张袁斌, 陈文靖, 叶志文. N2O5/HNO3体系硝解三(N-乙酰基)六氢化均三嗪制备RDX［J］. 爆破器材, 2012, 41(4):9-11,15.
?ZHANG Y B, CHEN W J， YE Z W. Preparation of RDX by nitrolysis of 1,3,5-triacetyl hexahydro-1,3,5-triazaine with N2O5/HNO3［J］. Explosive Materials, 2012, 41(4):9-11,15.
［5］胡衍甜, 吕早生, 孙昱,等. N2O5/HNO3/有机溶剂混合体系硝解DPT制备HMX［J］. 火炸药学报, 2016,39(2):50-53,58.
HU Y T, Lǔ Z S ,SUN Y,et al. Preparation of HMX by nitrolysis of DPT in N2O5/HNO3/organic solvent mixed systems［J］. Chinese Journal of Explosives & Propellants, 2016,39(2):50-53,58.
［6］吕春绪. N2O5绿色硝化研究及其新进展［J］. 含能材料, 2010, 18(6):611-617.
?LǔC X. Clean nitrating agent dinitrogen pentoxide and its application in nitration［J］. Chinese Journal of Energetic Materials, 2010, 18(6):611-617.
［7］卜令涛, 董波, 钱华,等. 表面活性剂催化硝化TAIW制备CL-20［J］. 爆破器材, 2016, 45(2):25-28.
?BU L T, DONG B, QIAN H, et al. Economic preparation of CL-20 by nitrolysis of TAIW using surfactants as catalyst［J］. Explosive Materials, 2016, 45(2):25-28.
［8］KAI W, DONG B,YANG C F, et al. Acidic ionic liquids, green and recyclable catalysts in the clean nitration of TAIW to CL-20 using HNO3 eletrolyte ［J］. Canadian Journal of Chemistry, 2017,95(2):190-193.
［9］胡育, 王公应, 杨先贵. SnO2-Al2O3固体酸催化剂的制备及其对苯液相硝化反应的催化活性［J］. 合成化学, 2010, 18(4):441-445.
?HU Y， WANG G Y, YANG X G. Preparation of SnO2-Al2O3 catalyst and its catalytic activity in liquid-phase nitration of benzene［J］. Chinese Journal of Synthetic Chemistry, 2010, 18(4):441-445.
［10］庄明晨. 固体超强酸催化环己烷液相硝化制备硝基环己烷的研究［D］. 湘潭：湘潭大学, 2011.
?ZHUANG M C.Study on the liquidphase nitration of cycloheane to nitrocyclohexane by solid super acid［D］.Xiangtan:Xiangtan University,2011.
［11］SELVAM J J P, SURESH V, RAJESH K, et al. Highly efficient nitration of phenolic compounds by zirconyl nitrate［J］. Cheminform, 2006, 47(15):2507-2509.
［12］SUN H B, HUA R M, YIN Y W. Highly efficient nitration of phenolic compounds in solid phase or solution using Bi(NO3)3·5H2O as nitrating reagent［J］. Journal of Organic Chemistry, 2005, 70(22):9071-9073.
［13］RAJAGOPAL R, SRINIVASAN K V. Regio-selective mono nitration of phenols with ferric nitrate in room temperature ionic liquid［J］. Cheminform, 2003, 33(6):961-966.
［14］SHEEMOL V N, TYAGI B, JASRA R V. Nitration of o-xylene over rare earth cations exchanged zeolite-β with nitric acid and acetic anhydride［J］. Journal of Molecular Catalysis A Chemical, 2006, 252(1/2):194-201.
［15］SHI M, CUI S C. Perfluorinated rare earth metals catalyzed nitration of aromatic compounds［J］. Journal of Fluorine Chemistry, 2002, 113(2):207-209.
［16］周心龙, 刘祖亮, 成健,等. 2,6-二乙酰氨基吡嗪-1-氧化物硝化反应研究［J］. 爆破器材, 2014,43(4):16-21.
ZHOU X L, LIU Z L, CHENG J,et al. Study on the nitration reaction of 2,6-diacetamidopyrazine-1-oxide［J］. Explosive Materials, 2014,43(4):16-21.
［17］SMITH K, LIU S F, EL-HITI G A. Regioselective mononitration of simple aromatic compounds under mild conditions in ionic liquids［J］. Industrial & Engineering Chemistry Research, 2005, 44(23):8611-8615.
［18］LAM E, MAJID E, LEUNG A C, et al. Synthesis of furfural from xylose by heterogeneous and reusable nafion catalysts［J］. Chemsuschem, 2011, 4(4):535-541.
［19］BUZZONI R, BORDIGA S, RICCHIARDI G, et al. Interaction of H2O, CH3OH, (CH3)2O, CH3CN, and pyridine with the superacid perfluorosulfonic membrane nafion: an IR and Raman study［J］. Journal of Physical Chemistry, 1995, 99(31):307-311.
［20］李小青, 杜晓华, 徐振元. 三氟甲磺酸盐催化甲苯硝化反应的研究［J］. 有机化学, 2006, 26(8):1111-1114.
?LI X Q, DU X H,XU Z Y. Toluene nitration catalyzed by metal triflates［J］. Chinese Journal of Organic Chemistry, 2006, 26(8):1111-1114.
［21］WALLER F J, BARRETT A G M, BRADDOCK D C, et al. Lanthanide(III) and group IV metal triflate catalysed electrophilic nitration:‘nitrate capture’ and the role of the metal centre［J］. Journal of the Chemical Society Perkin Transactions, 1999, 8(8):867-872.、
［22］王丽琼, 张正波, 李小永,等. Yb(NTf2)3催化苯甲酸酯化反应［J］. 应用化学, 2003, 20(3):219-222.
WANG L Q, ZHANG Z B,LI X Y,et al. Esterifications of benzoic acid with alcohols over Yb(NTf2)3［J］. Chinese Journal of Applied Chemistry, 2003, 20(3):219-222.

相似文献/References:

[1]孙鹏瞻①,杨敏②,尢淇①,等.Pickering乳液自组装CL-20/n-Al/F2605复合空心微球的制备与性能[J].爆破器材,2024,53(04):9.[doi:10.3969/j.issn.1001-8352.2024.04.002]
　SUN Pengzhan,YANG Min,YOU Qi,et al.Preparation and Characterization of CL-20/n-Al/F2605 Composite Hollow Microspheres Self-Assembled by Pickering Emulsion[J].EXPLOSIVE MATERIALS,2024,53(05):9.[doi:10.3969/j.issn.1001-8352.2024.04.002]

备注/Memo

备注/Memo:
收稿日期：2018-05-18
作者简介：石磊（1982－），男，博士研究生，主要从事含能材料合成研究。E-mail:407925642@qq.com
通信作者：钱华（1981－），男，教授，主要从事含能材料、安全评价和应用化学研究。E-mail:qianhua@njust.edu.cn
更新日期/Last Update: 2018-09-26