表面接枝含能硼基复合物的构筑及其爆轰加载下的燃烧催化性能研究

Improving the ignition and combustion property of metal power is one of the key problems need to be settled immediately in the studies of explosives, which is extraordinary favorable for the improvement of energy level and damage effect of explosives. In this research project, by organic synthesis and theoretical methods of quantum mechanics and so on, energetic ligands such as derivates of nitrosalicylaldehyde, tetrazole, will be manufactured. With boron as coordination center, the energetic complexes will be grafted on the surface of boron particle, which are used as its combustion catalysts. By altering the ligand stytle, substituent group and bonding atom with boron, the electric density, lewis acidity of the center atom boron, and energetic property will be adjusted accordingly, then the combustion catalytic effect is affected. Utilizing experiments of explosion heat, cyclinder test, DISAR, and detonation test under water, energy release laws of the explosives containing boron power would be obtained, then the structure-activity relationship between substituent group, energy of ligand, electric charge of boron, ligand structure and the combustion catalytic effect would be investigated. At last, the ignition and combustion model of the grafted boron-based energetic composites would be founded. The designed surface-grafted energetic composites are environment friendly, energetic, well-knit, structure stable and so on, and their studies on the combustion catalytic effects under detonation will enrich and prolongate the theory and application of metallized explosives.

改善混合炸药中金属颗粒的点火燃烧性能，是混合炸药研究亟需解决的问题，对于提高炸药的能量水平和毁伤效应具有重要意义。项目拟通过量子力学等理论方法和有机化学合成手段，制备硝基水杨醛、四唑衍生物等含能配体分子。以硼为配位中心，在硼颗粒表面接枝修饰含能硼基配合物分子，将其作为硼颗粒的燃烧催化剂。通过改变配体类型、取代基、硼成键原子，进而调控配位中心原子硼的电子云密度、Lewis酸性和配合物能量特性，从而影响其燃烧催化性能。利用爆热、圆筒、DISAR、水下爆轰等试验方法，获得含硼炸药的能量释放规律，探索取代基、配体能量、硼原子电荷、配体结构与其燃烧催化性能的构效关系，建立爆轰加载下表面接枝含能硼基复合物点火燃烧模型。项目设计的表面接枝含能硼基复合物具有环境友好、含能、界面结合紧密、结构稳定等优点；爆轰加载下的燃烧催化性能研究，将丰富和拓展金属化炸药的理论和应用。

硼粉具有较高的燃烧热，在火药、炸药、推进剂中具有重要应用价值，但由于金属粉表面包覆有致密的高沸点氧化膜，硼粉的点火燃烧性能较差，限制了其在含能材料中的应用。项目设计了含氨基、氯、氟不同取代基团的化合物TATB、TCTNB、DFTNB为助剂的烟火药硼/硝酸钾，添加助剂使烟火药燃烧峰值压力升高、压力持续时间延长、冲量增大，表明硼粉的反应程度提高、点火燃烧性能得到改善，含氟助剂的改善效果最佳；但随着助剂用量的增加，峰值压力、压力持续时间、冲量呈下降趋势。. 设计制备了水杨醛缩氨基脲、水杨醛缩甘氨酸、唑类缩异氰酸酯等表面接枝的含能硼基复合物，优化了唑类缩异氰酸酯表面接枝各步骤的合成工艺参数，硼粉表面含氮量最高达52.2%，固态核磁波谱证明其为共价键连接的复合物材料。通过SEM、TEM、IR、CA和激光粒度，研究了复合物的表面形态、表面化学结构、表面浸润特性和粒度分布，获得了其应用于HTPB粘接体系的流变性能。. 采用TG-DSC研究了氮气、氧气、硝酸钾条件下唑类缩异氰酸酯表面接枝对硼粉点火性能的影响，制备的的含能硼粉具有良好的热稳定性，可以使烟火药硼/硝酸钾临界反应温度提前30℃以上、燃烧压力持续时间延长49.7%，硼粉点火性能明显改善。设计并制备了HMX/B/聚氨酯混合炸药，研究了唑类缩异氰酸酯表面接枝对炸药爆热、反应区宽度、界面粒子速度的影响，对硼粉表面含能接枝修饰，炸药的爆热和界面粒子速度提高、反应区宽度没有明显变化。上述表面含能接枝方法，为含能硼粉复合物的结构设计与制备、硼粉点火燃烧性能的改善、在烟火药和混合炸药中的应用提供了实验和理论依据。