声共振强化HBIW氢解脱苄合成TADB  

Synthesis of Tetraacetyldibenzylhexaazaisowurtzitane from Hydrodebenzylation of Hexabenzylhexaazaisowurtzitane by Resonance Acoustic Technology

作　　者：唐晓飞 张瑶 廉鹏[1] 朱军臣 张圣龙 王锡杰[1] 刘宁[1] 陈松[1] TANG Xiao-fei;ZHANG Yao;LIAN Peng;ZHU Jun-chen;ZHANG Sheng-long;WANG Xi-jie;LIU Ning;CHEN Song(Xi'an Modern Chemistry Research Institute,Xi'an 710065,China)

机构地区：[1]西安近代化学研究所,陕西西安710065

出　　处：《火炸药学报》2022年第5期639-644,共6页Chinese Journal of Explosives & Propellants

基　　金：国家自然科学基金(No.22175139)。

摘　　要：为提高六苄基六氮杂异伍兹烷(HBIW)氢解脱苄反应的“气-液-固”多相间传质效率,以HBIW和H_(2)为原料、Pd(OH)_(2)/C为催化剂,在声共振强化反应器作用下,经氢解脱苄反应合成四乙酰基二苄基六氮杂异伍兹烷(TADB);利用核磁共振谱(^(1)H-NMR,^(13)C-NMR)和高分辨质谱(HRMS)对产物结构进行了表征;通过单因素实验和正交实验研究了反应温度、反应时间、加速度和反应压力对收率的影响,并与传统的釜式反应进行了对比,分析了声共振技术强化反应过程的机理。结果表明,在反应原料为1.5g HBIW、0.15g质量分数10%的Pd(OH)_(2)/C催化剂、5mL Ac_(2)O、7mL DMF和0.1g PhBr的条件下,反应加速度为392m/s^(2),反应压力0.2MPa,18℃反应30min,45℃反应60min,产物TADB收率83%。在以上反应条件下,声共振强化技术与传统釜式工艺相比,产物TADB收率没有变化,但反应时间由18h缩短至90min,时间缩短了91.7%。声共振强化反应传质的原因是改善了氢气在液相中的分散,增大了相间的接触面积,从而提高了反应效率,缩短了反应时间。To improve the“gas-liquid-solid”heterogeneous mass transfer efficiency of the hydrodebenzylation of hexabenzylhexaazaisowurtzitane(HBIW),TADB was synthesized via hydrodebenzylation by using HBIW and H_(2) as raw materials as well as Pd(OH)_(2)/C as catalyst under the effect of resonant acoustic reactor.The structure of TADB was characterized by^(1)H-NMR,^(13)C-NMR and HRMS.The effects of reaction time,reaction temperature,gravitational acceleration and reaction pressure on the yield were investigated by single factor experiment and orthogonal experiment,and the optimized conditions were established.The reaction results based on the resonant acoustic reactor and the traditional tank reactor were compared.The optimized process conditions are as follows:1.5g HBIW,0.15g 10%Pd(OH)_(2)/C,5mL Ac_(2)O,7mL DMF and 0.1g PhBr,the gravitational acceleration is 392m/s^(2),the pressure is 0.2MPa,the reaction is performed at 18℃for 30min and 45℃for 60min,and TADB is obtained with the yield of 83%.Under the above reaction conditions,TADB is obtained on the same yield from the resonant acoustic reactor and the traditional tank reactor.By using resonant acoustic reactor,the reaction time is shortened by 91.7%,from 18h to 90min.The reason for the enhancement of reaction mass transfer by resonance acoustic was that it improved the dispersion of hydrogen in the liquid phase and increased the interfacial area between the phases.Therefore,it improved the reaction efficiency and shortened the reaction time.

关 键 词：有机化学 声共振技术 四乙酰基二苄基六氮杂异伍兹烷 TADB 六硝基六氮杂异伍兹烷 HBIW 氢解脱苄反应 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] TQ56[化学工程—炸药化工]