Ferrocene-based polyethyleneimines for burning rate catalysts
Ferrocene-based polyethyleneimines for burning rate catalysts
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用于燃烧速率催化剂的二茂铁基聚乙烯亚胺
DOI：
10.1039/c5nj03171k
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发表时间：
2016
影响因子：
3.3
通讯作者：
Chen Yongsheng
中科院分区：
文献类型：
--
作者：
Zain-Ul-Abdin;Wang Li;Yu Haojie;Saleem Muhammad;Akram Muhammad;Abbasi Nasir M.;Khalid Hamad;Sun Ruoli;Chen Yongsheng
二茂铁基聚合物及其衍生物具有高效催化复合固体推进剂燃烧的能力。然而，简单易挥发的二茂铁在长期储存时会迁移到固体推进剂表面，改变设计的燃烧参数，更严重的是会引起意外爆炸。为了解决聚乙烯亚胺的迁移问题，通过支链聚乙烯亚胺（PEI）与二茂铁甲酰氯的缩合反应，合成了6种新型的二茂铁基聚乙烯亚胺（PEI-Fcs）。采用1H NMR、FT-IR和UV-Vis光谱对合成的PEI-Fcs进行了结构表征。聚合物的氧化还原性能对燃速催化剂（BRC）非常重要。循环伏安法（CV）显示，所有的PEI-Fc显示氧化还原性能，由于存在的二茂铁部分。迁移研究证实，这些PEI-Fc的迁移比2，2-双（乙基二茂铁基）丙烷（茂碳烯）和二茂铁慢得多。采用热重法（TG）和差热重法（DTG）研究了PEI-Fcs对高氯酸铵（AP）热分解的催化作用。发现在PEI-Fcs（1-6）的存在下，AP的峰分解温度显著左移（降低）。TG和DTG分析结果表明，新型PEI-Fcs对AP的热分解具有良好的催化作用，在220 °C以下基本稳定。我们期望这些新型PEI-FC作为高BRC的复合固体推进剂具有很大的应用价值。
Ferrocene-based polymers and their derivatives have the ability to catalyze the burning process of composite solid propellants efficiently. However, the simple and volatile ferrocene migrates to the surface of the solid propellant on prolonged storage, which alters the designed burning parameters and more seriously causes unexpected explosions. To retard migration problems, six novel ferrocene-based polyethyleneimines (PEI-Fcs) were synthesized by the condensation reaction of branched polyethyleneimine (PEI) with ferrocenecarbonyl chloride. The structures of the synthesized PEI-Fcs were characterized using 1H NMR, FT-IR and UV-Vis spectroscopy. The redox properties of the polymers are very important for burning rate catalysts (BRCs). Cyclic voltammetry (CV) revealed that all the PEI-Fcs showed redox properties due to the presence of ferrocene moieties. Migration studies confirmed that the migration of these PEI-Fcs was much slower than that of 2,2-bis(ethylferrocenyl)propane (catocene) and ferrocene. The catalytic effect of PEI-Fcs on the thermal decomposition of ammonium perchlorate (AP) was investigated using thermogravimetry (TG) and differential thermogravimetry (DTG). It was found that in the presence of PEI-Fcs (1–6), the peak decomposition temperature of AP was shifted towards the left (decreased) significantly. The results from the TG and DTG analysis indicated that the novel PEI-Fcs had good catalytic effects of lowering the thermal decomposition temperature of AP and were almost stable up to 220 °C. We expect that these novel PEI-Fcs would have great value as high BRCs for composite solid propellants.