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二茂铁、烷基二茂铁和其他二茂铁衍生物广泛用作复合固体推近剂的燃速催化剂。在推进剂贮存期间,这些化合物有向推进剂表面迁移的倾向,因此会严重降低火箭发动机的弹道性能。有机硅二茂铁衍生物FC—R—SiH(CH_3)_2(R为烷基或苯基)通过硅氢烷化反应把二茂铁基接枝到低分子量端羟基聚丁二烯(HTPB,20% 1,2—双键,80% 1,4—双键)的C=C双键上,合成出新官能团预聚物(取名为Butacene)。这些化合物对燃速的催化能力,至少等于通常的二茂铁衍生物。这项工作开始时,用一些分子模拟化合物和二甲基苯基硅烷做了大量试验研究,前者模拟HTPB中的C=C双键(1,2—,顺—1,4—和反—1,4—双键),后者模拟二茂铁硅烷。用六水合氯铂酸(H_2PtCl_6·6H_2O)的异丙醇溶液作催化剂。这些化合物的硅氢烷化反应动力学的研究,证明了1,2—双键的反应活性比1,4—双键大得多。这个结论与二甲基苯基硅烷和HTPB的加成反应得出的结果相同,硅氢烷化反应并不改变端羟基的功能。此后,合成了多种含Si—H键的有机硅二茂铁衍生物。研究了温度、溶剂性质、催化剂性质和反应条件等各种参数对硅氢烷化反应速率和产率的影响。用红外光谱检验了反应动力学,用~1H核磁共振和火焰光谱法测量了预聚物中的铁含量。预聚物的结构用~1H和~(13)C核磁共振法进行鉴定。从这项研究中可以清楚地看出,Fc(CH_2)_4SiH(CH_3)_2的试验结果最好,它能与全部的1,2—双键反应,从而制得铁含量为10%的预聚物。此外,它的玻璃化温度能满足固体推进剂使用要求。用Butacene预聚物制备的复合推进剂,其燃速特性与使用一般的二茂铁增塑剂的推进剂相同。因为二茂铁基联在预聚物上,不能迁移,这是一个很大的优点,因此,这种推进剂具有良好的老化性能。
Ferrocenes, alkyl ferrocenes and other ferrocene derivatives are widely used as burning rate catalysts for composite solid propellant. During propellant storage, these compounds tend to migrate toward the propellant surface, thereby severely reducing the ballistic performance of the rocket engine. The organofunctional ferrocene derivative FC-R-SiH (CH_3) _2 (R is alkyl or phenyl) is grafted onto the low molecular weight hydroxyl-terminated polybutadiene (HTPB, 20% 1,2-double bond, 80% 1,4-double bond) C = C double bond to synthesize a new functional prepolymer (named Butacene). The catalytic capacity of these compounds for burning rate is at least equal to the usual ferrocene derivatives. At the beginning of this work, a large number of experimental studies were carried out with some molecular modeling compounds and dimethylphenylsilane, the former modeling C = C double bonds in HTPB (1,2-, cis-1,4- and trans-1 , 4-double bond) which mimics ferrocene silane. With hexachloroplatinic acid (H_2PtCl_6 · 6H_2O) isopropanol solution as a catalyst. Studies on the hydrosilylation kinetics of these compounds demonstrate that 1,2-double bonds are much more reactive than 1,4-bis bonds. This conclusion is the same as the result of the addition reaction of dimethylphenylsilane and HTPB. The hydrosilylation reaction does not change the function of terminal hydroxyl groups. Since then, a variety of Si-H bond containing organosilicon ferrocene derivatives have been synthesized. The effects of various parameters such as temperature, solvent properties, catalyst properties and reaction conditions on the hydrosilylation reaction rate and yield were investigated. The reaction kinetics was examined by infrared spectroscopy and the iron content in the prepolymer was measured by ~ 1H NMR and flame spectroscopy. The structure of the prepolymer was characterized by ~ 1H and ~ (13) C NMR. From this study it is clear that the best experimental result for Fc (CH 2) _4SiH (CH 3) _ 2 is that it can react with all 1,2-double bonds to produce a prepoly Things. In addition, its glass transition temperature to meet the requirements of solid propellant use. Compound propellants made with Butacene prepolymers have the same burning rate characteristics as propellants using typical ferrocene plasticizers. Because ferrocene-based prepolymer, can not migrate, which is a great advantage, therefore, this propellant has good aging properties.