稠环三氮唑类钝感高能离子盐炸药的设计、合成及性能研究

Based on the needs of being insensitive-high-energetic-low toxic for compound-explosive, using the strategy paying equal attention to the molecular functionality and synthetic simplicity, the anionic structure and its combination with cation forming the corresponding salt are designed. Aiming at excellent stability to the external stimuli (e.g. michanical or heating), by making best of tendency of highly delocalized tetrazole, the favorable structive factors being insensitive and heat-resistant were created. And to meet the needs of being high-energetic, enhancing the characteristics of density, the mult-fused nitrogen heterocycles were designed and constructed matching with diverse cations..Meanwhile, the combination with high enthalpy C-N or N-N bonds, high enthalpy azole framworks, and multi-nitro-groups were optimized, therefore, the inherent character to release high-energy will be produced. The novel cyclization method will be exploided, and it is anticipated to open up a practical way being advantagous of available raw materials, simple operating procedure and short synthetic route. The successful implementation of the present project should be instructive, in view of stimulating new ideas for designing energetic ionic salt, as insensitive high energetic environmentlly friendly explosives, for the purpose of meeting the needs of chinese weapon and equipment modernization.

应用分子功能性—合成简便性并重设计策略，在钝感—高能—低毒平台上，设计离子盐稠氮唑环阴离子及其阳离子组合。针对安定性要求，充分利用稠氮唑阴离子的离域化倾向，创造使离子盐产生钝感耐热的结构因素。针对高能量要求，从提高特征密度入手，构建多元并氮杂环结构，提供其与不同结构不同大小阳离子高密度匹配的有利条件；将桥高焓值的C-N或N-N，及高焓值氮唑环与多氧化性基团优化组合，创造离子盐产生高能量水平的内在条件。创新唑并环化方法，开辟原料易得、操作简便、路线短的合成途径。本项目的成功实施，对创新含能离子盐设计思想和合成策略，发展钝感高能环境友好的新型炸药，有启发意义。

开发能量高、热稳定性好及感度低的新型含能材料是炸药研究领域一直追求的目标。然而含能材料对高能与低感的需求之间通常存在着矛盾，高能量通常导致高感度。设计富氮耐高温唑类化合物含能离子盐是解决这个问题有效策略之一。富氮唑类化合物含有大量N-N和C-N键使其具有很高的正生成焓，较高的密度以及良好的热稳定性。且其含能离子盐具有优良的可调节性，阴阳离子组份均可被独立修饰。通过阴离子和阳离子的精心设计，有望得到爆轰性能优良，耐高温以及低感度的新型含能材料。.成功合成了几十个基于富氮稠环、C-N偶联双杂环化合物和偶氮化合物的含能离子盐，全部化合物经过IR、1H NMR、13C NMR、15N NMR以及元素分析等进行了全面结构表征，其中部分化合物的结构通过单晶X-射线衍射得到了进一步确认。另外，实测了化合物的热稳定性、密度、撞击和摩擦感度，通过软件计算了母体结构和离子盐的生成焓和爆轰性能等参数。其中7,8-二硝基-4-酮-4,6-二氢吡唑并[5,1-d][1,2,3,5]四嗪-2-氧化物（HPCM）的羟胺盐密度达到了1.95g cm–3，表现出优异的爆轰性能（vD= 9228 m s-1, P= 39.4 GPa），优于HMX。而且表现为对撞击低感摩擦钝感（IS= 19 J, FS= 360 N），具有作为高能低感炸药进一步研究的价值。同时为获得含能离子盐的实测爆速数据，并对其它物化及爆轰性能进一步验证，对部分先前工作中获得的理论计算爆轰性能优异的化合物进行了放大制备和工艺改进。