高能氧化剂ONPP的合成工艺优化  

Synthesis and Performance of High⁃Energy Oxidizer ONPP

作　　者：燕超 孙瑞 朱金利 任晓婷[1] 卢艳华[1] 何金选[1] YAN Chao;SUN Rui;ZHU Jin-li;REN Xiao-ting;LU Yan-hua;HE Jin-xuan(Science and Technology on Aerospace Chemical Power Laboratory,Hubei Institute of Aerospace Chemical Technology,Xiangyang 441003,China)

机构地区：[1]湖北航天化学技术研究所航天化学动力技术重点实验室,湖北襄阳441003

出　　处：《含能材料》2023年第4期332-337,共6页Chinese Journal of Energetic Materials

基　　金：国家自然科学基金(22005090)。

摘　　要：为了解决当前高能氧化剂1,4⁃双(三硝基甲基)⁃3,6⁃二硝基吡唑[4,3⁃c]并吡唑(ONPP)合成工艺的低硝化收率以及使用剧毒物等问题,设计并开发了ONPP的新合成路线。将ONPP溶于乙酸乙酯,采用缓慢溶剂挥发法制备出ONPP的单晶,并对不同配方进行了能量估算。结果表明,在碱和相转移催化剂Bu4NBr(TBAB)的参与下,3,6⁃二硝基吡唑[4,3⁃c]并吡唑(DNPP)与溴丙酮反应,在吡唑环上引入2个丙酮基团,接着使用HNO_(3)/H_(2)SO_(4)/P_(2)O_(5)硝化体系对其进行硝化,合成得到了ONPP,两步总收率为31%。相较原工艺(两步总收率为10.4%),新工艺的产品收率提升了近3倍,且避免了剧毒物丁烯酮的使用,更适合放大化生产。单晶衍射结果为:ONPP的晶体为单斜晶系,P21/c空间群,晶体密度为1.983 g·cm^(-3)(293 K)。经过对端羟基聚丁二烯(HTPB)(占比10%)、Al粉(占比20%)和氧化剂(占比70%)配方进行能量估算,当ONPP和高氯酸铵(AP)作为氧化剂复配使用,分别占比40%和30%时,其配方能量水平达到最佳,显著高于他们分别作为单一氧化剂时的配方能量水平。For the problems of low nitrification yield and the use of highly toxic substances in the synthesis of high⁃energy oxidant 1,4⁃bis(trinitromethyl)⁃3,6⁃dinitropyrazole[4,3⁃c]pyrazole(ONPP),a new synthetic process of ONPP was developed.The sin⁃gle crystal of ONPP was cultivated by slow evaporation from an ethyl acetate solution.The energy levels of different formulations based on ONPP were estimated.In the presence of base and phase transfer catalyst Bu4NBr(TBAB),3,6⁃dinitropyrazole[4,3⁃c]pyrazole(DNPP)reacted with bromoacetone to introduce two acetone groups on pyrazole ring.Followed by nitrating with HNO_(3)/H_(2)SO_(4)/P_(2)O_(5),ONPP was obtained in the total yield of 31%.Compared with the literature(10.4%total yield from two steps),the yield of new synthetic route from DNPP increase by nearly three times.Meanwhile the use of highly toxic butenone is avoided,which is more suitable for large⁃scale production.The crystal structure of ONPP belongs to the monoclinic crystal sys⁃tem,P21/c space group.Its crystal density is 1.983 g cm^(-3) at 293 K.Through the energy estimation of HTPB(10%),Al(20%)and oxidizer(70%)formulations,the energy level is optimal when ONPP(40%)and AP(30%)are used together as oxidizers,which is significantly higher than the formulation energy levels when they used as single oxidant.

关 键 词：含能氧化剂 1 4⁃二(三硝基甲基)⁃3 6⁃二硝基吡唑[4 3⁃c]并吡唑(ONPP) 3 6⁃二硝基吡唑[4 3⁃c]并吡唑(DNPP) 晶体结构 合成工艺 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O62[理学—有机化学]