新型肼基四唑含能离子液体的功能化设计与性能研究

This project aims to obtain novel energetic ionic liquids, which are high energetic performance liquid fuels, via functionalized design. Energetic ionic liquids are potential "green" liquid energetic materials. While the energies of the known energetic ionic liquids are generally lower than the traditional energetic materials. Many of them are not stable enough to heat, water or impact. Therefore, functionalized ionic liquids with low melting points, high energies and low sensitivities are needed. In this proposal, we focus on the molecular design, synthesis, and properties of hydrazinyl-tetrazolium/tetrazolate-based energetic ionic liquids. The functionalized hydrazinyl-tetrazolium/tetrazolate structural fragments will be constructed for high performance. Their combustion performance will be investigated. Functionalized groups will be introduced to realize their liquidus properties of low melting point. Both bomb calorimetry method and quantum chemical method will be used to determine their experimental and theoretical combustion of formation, and enthalpies of formation. The detonation velocities and the detonation pressures will be calculated. The effect of ionic liquid structure on their energetic properties will revealed. Sensitivity tests to impact and friction will be used to assess the stability of the prepared energetic ionic liquids, and the relationship of their structures and sensitivities will be explored. Based on the structure-property relationship, the suitable structures for better performances will be designed and selected. This project has important scientific significance in development of novel energetic ionic liquid as liquid fuels.

本项目旨在通过功能化设计方法，探索具有高能液体燃料功能的新型离子液体材料。针对已有含能离子液体能量不高或稳定性能较差的不足，重点围绕离子液体低熔点、高能量和低感度的设计目标，引入兼具多种优良特征的肼基四唑功能骨架，开展含能离子液体的分子设计、合成与液态性质、能量性质及稳定性的研究。拟以肼基四唑为原料，构建功能分子片段，设计合成多种肼基四唑含能离子液体，并考察离子液体的自持燃烧性能；系统研究肼基四唑离子液体的液态性质，探讨不同功能结构对熔点的影响；结合理论计算模拟，评估肼基四唑离子液体的燃烧焓、生成焓等能量性质并预测其爆压、爆速等爆轰性能，在分子层面上揭示能量性能与离子液体结构的关联；测定新型离子液体的感度，归纳影响稳定性的基本结构规律。依据所建立的构效关系，进一步优化功能化分子片段，以提高新型功能化离子液体整体的高能燃料性能。

本项目进行了新型肼基功能化富氮四唑含能离子液体的设计、合成、结构及性质的相关基础研究。先后制备了多种基于肼基四唑结构的富氮含能离子液体。完成了含能离子液体各项结构、组成及物理化学性质表征。.利用实验方法获得了离子液体的实验标准生成焓；采用密度泛函理论，对阴阳离子的气态优化结构、电荷分布等进行分析，并采用等键反应原理和Born-Haber热化学循环理论，计算了离子液体的理论标准生成焓；深入研究了含能离子液体的结构与其能量性能的关系。能量性能的研究证明了该类含能离子液体具有高的能量密度。.通过热力学测试系统，完成了新型肼基四唑含能离子液体热稳定性的测试和分析；借助撞击和摩擦感度测试方法，收集和完善了感度数据，评估了该类离子液体的对撞击和摩擦的机械稳定性。.本项目执行所获得的实验数据证实了采用肼基富电基团与富氮四唑结构配伍可以实现制备高能低感含能离子液体的设计目标，这为设计合成基于富氮四唑结构骨架的新型高能材料提供了理论基础、合成策略和制备技术。.本项目工作已在多种国内外重要学术期刊上发表SCI论文7篇，申请专利4项；培养博士生3人、硕士生3人（已获学位），预期研究目标均已顺利完成。经费使用按预算执行，使用经费未超出预算。