微反应技术合成不敏感硝酸酯增塑剂TMETN和PGDN
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摘要
利用微反应技术,分别以1,2-丙二醇、三羟甲基乙烷为原料,硝硫混酸为硝化剂,合成了1,2-丙二醇二硝酸酯(PGDN)和三羟甲基乙烷三硝酸酯(TMETN);采用红外光谱、核磁共振等对其结构进行了表征,同时优化了微反应器硝化反应条件。结果表明,TMETN和PGDN结构与间歇式合成产物一致,合成TMETN的较佳硝化温度为17~20℃,硝酸与三羟甲基乙烷的最佳摩尔比为5.6∶1.0,收率达90.0%以上,纯度达98.5%;合成PGDN的较佳反应温度为20~22℃,硝酸与1,2-丙二醇的摩尔比为2.7∶1.0。该工艺具有反应温度范围宽、硝酸用量少和收率高等优点。
Trimethylethane trinitrate(TMETN)and 1,2-propylene glycol dinitrate(PGDN)were synthesized by micro reaction technology,using 1,2-propylene glycol and trimethylethane as raw materials and nitric acid/sulphuric acid as nitrating agent respectively.Their structures were characterized by FTIR and NMR etc.and nitration reaction conditions of micro reactor were optimized through the micro reactor method developed in this study.The results show that their structures were consistent with those from intermittent synthesis product.The better nitration temperature of TMETN is 17-20℃,and the optimum molar ratio of HNO3 and trimethylethane is 5.6∶1.0.The yield is over 90.0%.The purity is 98.5%.The better reaction temperature of synthesizing PGDN is 20-22℃,and the molar ratio of HNO3 to 1,2-propylene glycol is 2.7∶1.0.The process has the advantages of wide reaction temperature range,low nitric acid dosage and high yield,etc.
Trimethylethane trinitrate(TMETN)and 1,2-propylene glycol dinitrate(PGDN)were synthesized by micro reaction technology,using 1,2-propylene glycol and trimethylethane as raw materials and nitric acid/sulphuric acid as nitrating agent respectively.Their structures were characterized by FTIR and NMR etc.and nitration reaction conditions of micro reactor were optimized through the micro reactor method developed in this study.The results show that their structures were consistent with those from intermittent synthesis product.The better nitration temperature of TMETN is 17-20℃,and the optimum molar ratio of HNO3 and trimethylethane is 5.6∶1.0.The yield is over 90.0%.The purity is 98.5%.The better reaction temperature of synthesizing PGDN is 20-22℃,and the molar ratio of HNO3 to 1,2-propylene glycol is 2.7∶1.0.The process has the advantages of wide reaction temperature range,low nitric acid dosage and high yield,etc.
引文
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[3]刘所恩,陈锦棉,潘葆,等.新型螺压高能改性双基推进剂研究[J].兵工学报,2015,36(6):1123-1127.LIU Suo-en,CHEN Jin-mian,PAN Bao,et al.Study of novel screw extruded high energy composite doublebase propellant[J].Acta Armamentarii,2015,36(6):1123-1127.
[4]齐晓飞,张晓宏,郭昕,等.NENA对NC溶塑作用的实验与模拟[J].固体火箭技术,2013,36(4):516-520.QI Xiao-fei,ZHANG Xiao-hong,GUO Xin,et al.Experiments and simulation on plastication of NENA on NC[J].Journal of Solid Rocket Technology,2013,36(4):516-520.
[5]Arthus P.Energetic Polymers and Plasticisers for Explosive Formulaions-A Review of Recent Advances[M].Comonwealeh:DSTO,2000.
[6]范晓薇,居学海,孙小巧,等.硝化甘油与高分子黏合剂混合体系相互作用的理论研究[J].火炸药学报,2009,32(6):46-49.FAN Xiao-wei,JU Xue-hai,SUN Xiao-qiao,et al.Theoretical studies of interreaction of complex system nitroglycerin-polymer binder[J].Chinese Journal of Explosive&Propellants(Huozhayao Xuebao),2009,32(6):46-49.
[7]姬月萍,李普瑞,汪伟,等.含能增塑剂的研究现状及发展[J].火炸药学报,2005,28(4):15-18.JI Yue-ping,LI Pu-rui,WANG Wei,et al.A review of recent advances of energetic plasticizers[J].Chinese Journal of Explosives&Propellants(Huozhayao Xuebao),2005,28(4):15-18.
[8]Jeong K K,Jin S K,Keun D L,et al.A new energetic mixed formal plasticizer,using diformal as energetic material[C]∥Insensitive Munitions and Energetic Materials Technology Symposium.San Diego:NDIA,2000:421-426.
[9]崔建兰,郭文龙,曹端林,等.1,1,1-三羟甲基丙烷三硝酸酯的合成与表征[J].火炸药学报,2005,28(5):78-79.CUI Jian-lan,GUO Wen-long,CAO Duan-lin,et al.Synthesis and characterization of 1,1,1-trimethylolpropane trinitrate[J].Chinese Journal of Explosives&Propellants(Huozhayao Xuebao),2005,28(5):78-79.
[10]石飞,王庆法,张香文,等.1,2-丙二醇二硝酸酯的绿色合成[J].火炸药学报,2007,30(2):75-77.SHI Fei,WANG Qing-fa,ZHANG Xiang-wen,et al.The green synthesis of 1,2-propylene glycol dinitrate[J].Chinese Journal of Explosives&Propellants(Huozhayao Xuebao),2007,30(2):75-77.
[11]刘兆利,张鹏飞.微反应器在化学化工领域中的应用[J].化工进展,2016,35(1):10-17.LIU Zhao-li,ZHANG Peng-fei.Applications of microreactor in chemistry and chemical engineering[J].Chemical Industry and Engineering Progress,2016,35(1):10-17.
[12]Woodman.Vapor pressure of tiracetin,triethylene glycol dinitrate,and metriol trinitrate[J].Journal of Chemical and Engineering Data,1963,8(2):241-242.