Ionic Ferrocene-Based Burning-Rate Catalysts with Polycyano Anions: Synthesis, Structural Characterization, Migration, and Catalytic Effects during Combustion: Ionic Ferrocene-Based Burning-Rate Catalysts
Ionic Ferrocene-Based Burning-Rate Catalysts with Polycyano Anions: Synthesis, Structural Characterization, Migration, and Catalytic Effects during Combustion: Ionic Ferrocene-Based Burning-Rate Catalysts
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DOI：
10.1002/ejic.201403023
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发表时间：
2015-03
影响因子：
2.3
通讯作者：
Xuelin Liu;Jizhen Li;F. Bi;Wei‐qiang Zhang;Guofang Zhang;Ziwei Gao
中科院分区：
文献类型：
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作者：
Xuelin Liu;Jizhen Li;F. Bi;Wei‐qiang Zhang;Guofang Zhang;Ziwei Gao
基于烷基二茂铁的燃速（BR）催化剂由于其中性和非极性性质，在固化和储存期间具有很高的迁移倾向。为了克服这些缺点，15个新的离子化合物，1-（二茂铁甲基）咪唑与多氰基阴离子配对，合成和表征。其中11个化合物的结构通过单晶X射线衍射证实。化合物1在四斜晶系空间群I4（1）/a中结晶; 2、12和15在单斜晶系空间群P21/c中结晶，并且3在单斜晶系空间群P21/n中结晶; 4、6-8、13和14在三斜晶系空间群P21/n中结晶。循环伏安法研究表明，大多数化合物表现出准可逆的氧化还原体系。化合物1-10具有高的热稳定性（> 190° C）。迁移研究表明，这些化合物是低迁移材料。采用差示扫描量热法（DSC）和热重分析法（TG）研究了高氯酸铵（AP）、黑索今（RDX）和异硫氰酸根（HMX）在这些化合物催化下的热降解。结果表明，AP的分解峰温度显著下移，并且AP的释放热在新化合物作为添加剂（5 wt. - %）的情况下显著增加。此外，离子型化合物对RDX的热分解有显著的影响。新化合物的催化活性高于其硝酸盐和苦味酸盐类似物，这支持了二茂铁基BR催化剂中高氮含量有利于其燃烧催化活性的结论。
Alkylferrocene‐based burning‐rate (BR) catalysts, have a high tendency to migrate during curing and storage due to their neutral and nonpolar nature. To overcome these drawbacks, fifteen novel ionic compounds, 1‐(ferrocenylmethyl) imidazolium paired with polycyano anions, were synthesized and characterized. The structures of eleven of the compounds were confirmed by single‐crystal X‐ray diffraction. Compound 1 crystallizes in the tetragonal space group I4 (1)/a; 2, 12 and 15 crystallize in the monoclinic space group P21/c, and 3 in the monoclinic space group P21/n; 4, 6–8, 13 and 14 crystallize in the triclinic space group P ̄1. Cyclic voltammetry investigations suggested that most of the compounds exhibit quasireversible redox systems. Compounds 1–10 have high thermal stability (> 190° C). Migration studies revealed that these compounds are low‐migratory materials. The thermal degradation of ammonium perchlorate (AP), hexogen (RDX), and octogen (HMX) catalyzed by these compounds was evaluated by differential scanning calorimetry (DSC) and by thermogravimetric (TG) techniques. The results show that the decomposition peak temperature of AP shifts downwards dramatically and that the released heat of AP increases significantly with the new compounds as additives (5 wt.‐%). Moreover, the ionic compounds exhibit significant effects on the thermal decomposition of RDX. The catalytic activities of the new compounds are higher than those of their nitrate and picrate analogues, which supports the conclusion that high nitrogen content in a ferrocene‐based BR catalyst is favorable for its combustion catalytic activity.