双四唑类含能金属有机框架的构筑及其对双基推进剂燃烧催化机理研究

Increasing energy and improving combustion performance are key technologies for developing new solid rocket propellants, and developing a new type of energetic combustion catalyst is a strategic requirement for solid rocket propellants. The project aims to design bis-tetrazole compounds with many coordination sites, small steric hindrance and high energy density as the energetic ligand framework. Meanwhile, the coordination oxygen atoms are introduced on the tetrazole ring to improve the oxygen balance of the ligand. A novel bitetrazole-based energetic metal organic framework was constructed by combining metal ions effective for propellant combustion catalysis. Then, the compatibility of bistetrazole energetic metal organic framework with the main components of the propellant was studied, and the bistetrazole energetic metal organic framework with good compatibility was screened. Thereafter, the catalytic properties of the bistetrazole energetic metal organic framework for thermal decomposition and combustion of double-base propellants were studied. Comprehensive analysis of experimental parameters such as burning rate, pressure index, temperature distribution of combustion wave, flame structure, flameout surface morphology, adiabatic-explosion time, and thermal decomposition performance of the propellants containing bitetrazole energetic metal-organic framework, combined with theoretical calculations, the catalytic mechanism of bistetrazole energetic metal organic framework for the combustion of double-base propellants were studied. Finally, the bistetrazole-based energetic combustion catalysts with excellent combustion catalytic properties were screened out. Moreover, this project will provide new ideas for the design and research of a new type of insensitive high-energy combustible catalyst.

提高能量、改善燃烧性能是研制新型固体火箭推进剂的关键核心技术，开发新型含能燃烧催化剂是固体火箭推进剂的战略需求。本项目旨在设计以配位点多、位阻小和能量密度高的双四唑化合物为含能配体骨架，同时在四唑环上引入配位氧原子改善配体氧平衡，将其与对推进剂燃烧催化有效的金属离子结合，构筑新型双四唑类含能金属有机框架。通过研究其与推进剂主要组分的相容性，筛选出相容性良好的双四唑含能金属有机框架，开展对双基推进剂热分解和燃烧的催化研究。综合分析含双四唑含能金属有机框架推进剂试样的燃速、压力指数、燃烧波温度分布、火焰结构、熄火表面形貌、绝热至爆时间以及热分解性能等参数，结合理论计算，研究双四唑含能金属有机框架对双基推进剂燃烧的催化作用规律和机理，最终筛选出燃烧催化性能优良的双四唑类含能燃烧催化剂。本项目的实施将为新型钝感高能燃烧催化剂的设计和研究提供新的思路。

提高能量、改善燃烧性能是研制新型固体火箭推进剂的关键核心技术，开发新型含能燃烧催化剂是固体火箭推进剂的战略需求。本项目通过对三唑、四唑和呋咱类富氮含能配体与金属离子的配位方式以及配位后形成含能金属有机框架的结构和性能进行计算，设计了系列理论上合理的富氮含能配体分子及其合成路线；根据优选出的合成路线，以丙二腈、溴化氰、乙二醛、叠氮化钠、羟胺盐酸盐、氯代肟基乙酸乙酯、二氨基马来腈、4,5-二氰基-1,2,3-三唑等为原料，合成得到了13种富氮含能配体；以合成得到的13种富氮含能配体为原料，分别与Co、Ni、Fe、Mn、Pb、Cd、Cu、La、Ce、Nd、Pr、Sm和Eu等过渡金属和稀土金属硝酸盐反应，合成得到48种含能金属有机框架材料；采用FTIR、1H NMR、13C NMR、MS结合X射线单晶衍射等对所合成富氮含能配体和金属有机框架材料结构进行了表征；研究了所合成含能金属有机框架材料的热稳定性、机械感度以及与推进剂主要组分的相容性，并根据这些数据对所合成含能金属有机框架材料进行了初步筛选；采用DTA、DSC、TGA、TG-IR等测试方法研究了所合成含能金属有机框架材料对固体推进剂氧化剂高氯酸铵热分解性能的影响，结果表明，所合成的富氮含能金属有机框架材料对AP热分解具有较好的催化作用，使AP的高温分解峰值温度大幅度降低，显著减少其高温分解活化能；开展了所合成含能金属有机框架材料对双基系推进剂的燃烧催化研究，结果表明，所合成的含能金属有机框架材料能够有效解决现有RDX改性双基推进剂压强指数高的问题，显著降低推进剂的压强指数，提高了其平台燃烧速度；进一步结合其燃烧火焰形貌、燃烧波温度分布以及熄火表面形貌等数据，提出了含能金属有机框架材料可能的燃烧催化作用机制，所研制的含能金属有机框架材料有望作为新型钝感高能燃烧催化剂应用于双基系推进剂。