BNTF的合成、单晶结构和性能  

Synthesis,Crystal Structure and Performances of BNTF

作　　者：王珀会 曾炼 谌思嘉 吴金婷 黄明[2] 李鸿波[1] WANG Po-hui;ZENG Lian;SHEN Si-jia;WU Jin-ting;HUANG Ming;LI Hong-bo(School of Materials and Engineering,Southwest University of Science and Technology,Mianyang 621010,China;Institute of Chemical Materials,CAEP,Mianyang 621999,China)

机构地区：[1]西南科技大学材料科学与工程学院,四川绵阳621010 [2]中国工程物理研究院化工材料研究所,四川绵阳621999

出　　处：《含能材料》2021年第1期70-77,I0005,共9页Chinese Journal of Energetic Materials

基　　金：国家自然科学基金(22075260);中央军委装备发展部重大基础研究项目(14021001040305-5);爆炸科学与技术国家重点实验室开放基金(北京理工大学)(KFJJ20-03M)。

摘　　要：以3,4-双(3'-氨基呋咱基-4'-)氧化呋咱(BAFF)为原料,采用廉价易得且绿色环保的丙三醇为溶剂,经氯化亚锡还原合成关键中间体3,4-双(3'-氨基呋咱基-4'-)呋咱(BATF),后经过氧化氢氧化得到3,4-双(3'-硝基呋咱基-4'-)呋咱(BNTF),总收率为59.0%。采用1H NMR、13C NMR、IR、MS和元素分析对BATF和BNTF进行表征,并成功获得BNTF单晶结构数据,BNTF晶体为正交晶系,属P212121空间群,a=0.71437(10)nm,b=0.96839(11)nm,c=1.51555(17)nm,V=1.0484(2)nm^3,Z=4,Dc=1.876 g·cm^-3,F(000)=592;优化BNTF合成工艺,考察投料比、反应时间及反应温度对BNTF产率的影响,获得的最佳工艺条件为n(BATF)∶n(35%H2O2)∶n(98%H2SO4)∶n(Na2WO4·2H2O)=1∶60∶40∶0.86,反应时间3 h,反应温度30℃,收率可达93.3%;采用DSC法和TG-DTG法测定BNTF的热稳定性,分别用Kissinger法、Rogers法和Arrenhis法计算BNTF热分解反应的表观活化能Ea(147.83 kJ·mol^-1)、指前因子A(9.33×10^15 min^-1)和分解速率常数k(2.18×10^-44),计算了BNTF的热爆炸临界温度(Tb=201.36℃);利用Kamlet-Jacobs方程估算得到BNTF的爆速(8.3 km·s^-1)、爆压(31.3 GPa);分别按照GJB772A-1997方法601.2和602.1测试BNTF特性落高(H50=43.0 cm)和摩擦感度(36.0%)。3,4-Bis(3'-aminofurazan-4'-yl)furazan(BATF)was synthesized by reduction with stannous chloride in glycerol using 3,4-bis(3'-aminofurazan-4'-yl)furoxan(BAFF)as raw material.3,4-Bis(3'-nitrofurazan-4'-yl)furazan(BNTF)was prepared from BAFF by using hydrogen peroxide as oxidantwith total yield of 59.0%.The structures of BATF and BNTF were characterized by 1H NMR,13C NMR,IR,MS spectra and elemental analysis,and the single crystal structure data of BNTF was obtained successfully.The crystal belongs to orthorhombic system,space group P212121 with crystal parameters a=0.71437(10)nm,b=0.96839(11)nm,c=51555(17)nm,V=1.0484(2)nm^3,Z=4,Dc=1.876 g·cm^-3,F(000)=592.The influence of molar ratio,reaction time,and reaction temperature on the yield of BNTF was investigated.Results show that the optimum conditions are as follows:n(BATF)∶n(35%H2O2)∶n(98%H2SO4)∶n(Na2WO4·2H2O)=1∶60∶40∶0.86,the reaction time is 3 h,the reaction tem perature is 30℃ and the yield of BNTF is 93.3%.The thermal stability of BNTF was determined by DSC and TG-DTG methods.Apparent activation energy Ea(147.83 kJ·mol^-1),pre-exponential factor A(9.33×10^15 min^-1)and decomposition rate constant k(2.18×10^-44)of thermal decomposition reaction for BNTF were calculated by Kissinger method,Rogers method and Arrenhis method,respectively.The detonation velocity(8.3 km·s^-1)and detonation pressure(31.3 GPa)of BNTF were estimated by Kamlet-Jacobs equation.Characteristic drop height of impact sensitivity(H50=43.0 cm)and friction sensitivity(36.0%)for BNTF were measured according to GJB772A-1997 methods 601.2 and 602.1,respectively.

关 键 词：熔铸炸药 3 4-双(3'-硝基呋咱基-4'-)呋咱(BNTF) 合成 单晶 热分解动力学 性能 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O64[理学—物理化学]