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Ionic Ferrocene‐Based Burning‐Rate Catalysts with Polycyano Anions: Synthesis, Structural Characterization, Migration, and Catalytic Effects during Combustion
Author(s) -
Liu Xuelin,
Li Jizhen,
Bi Fuqiang,
Zhang Weiqiang,
Zhang Guofang,
Gao Ziwei
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201403023
Subject(s) - chemistry , monoclinic crystal system , catalysis , thermogravimetric analysis , differential scanning calorimetry , thermal decomposition , thermal stability , inorganic chemistry , ammonium perchlorate , triclinic crystal system , ferrocene , crystal structure , crystallography , organic chemistry , electrochemistry , physics , electrode , thermodynamics
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 P 2 1 / c , and 3 in the monoclinic space group P 2 1 / n ; 4 , 6 – 8 , 13 and 14 crystallize in the triclinic space group P $\bar {1}$ . 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.