二茂鐵衍生物接枝於尾端具有羥基之聚丁二烯之合成與性質探討

Synthesis and Characterization of Hydroxyl Terminated Polybutadiene Grafted with Ferrocene Derivative

陳立恒(Li-Heng Chen)

指導教授 ： 戴子安

國立臺灣大學/工學院/化學工程學研究所/碩士(2012年)

https://doi.org/10.6342/NTU.2012.00439

摘要

Butacene是經由一連串反應製備而成的燃速調節劑，可以應用在固態複合推進器當作催化劑。本研究目的，我們利用 Friedel-Crafts反應乙醯化 ferrocene得到4-chlorobutyrylferrocene (4CByF)，由上述步驟產生的4CByF進行還原反應除去其中之C=O得到產物4-chlorobutyl ferrocene (4CBF)，將4-chlorobutyl ferrocene與鎂反應得到其Grignard reagent，此Grignard reagent與chlorodimethylsilane反應生成4-(ferrocenylbutyl) dimethylsilane，接著以 Pt為催化劑，將此ferrocene的矽烷衍生物接枝在HTPB側鏈雙鍵上，最終生成的產物即是我們想要的Butacene。將所得到的Butacene利用FTIR和NMR分析其結構及性質，其鐵含量則由thermogravimetric analysis (TGA) 量測，並與市售Butacene比較其差異性。

關鍵字

膠合劑 ； 佛瑞德－克來福特醯化反應 ； 還原反應 ； 格林鈉反應 ； 矽烷化 ； 端羥基聚丁二烯 ； 矽氫加成反應

並列摘要

Butacene, which can be prepared in a series of reactions, has been used in solid propellant composite as a catalyst to control the burning-rate of a rocket. At first, we synthesized 4-chlorobutylferrocene by using Friedel-Crafts acylation of ferrocene followed by deoxigenation of the acylated ferrocene. The resulting 4-chlorobutylferrocene was to react with magnesium metal by using Grignard reaction to form a corresponding Grignard intermediate compound which can react with chlorodimethylsilane to produce 4-(ferrocenylbutyl) dimethylsilane. Ferrocenehydrosilane were added to the side chain double bonds of hydroxyl-terminated polybutadiene (HTPB) using hydrosilylation reaction with Pt as a catalyst to form 4-(ferrocenylbutyl) dimethylsilane-grafted HTPB, which is thus called Butacene. The structure of Butacene will be characterized by using FTIR and NMR. The iron content in the Butacene was verified by using thermogravimetric analysis (TGA) and found to be comparable to that of the commercial Butacene (SNPE)

並列關鍵字

Butacene ； Friedel-Crafts reaction ； deoxygenation reaction ； Grignard reaction ； silanation reaction ； HTPB ； hydrosilylation

參考文獻

[40] John F. Garst. Inorganica Chimica Acta, 222 (1994) 365-375.

[21] H. Mimoun, J.Y. de Saint Laumer, L. Giannini, R. Scopelliti, C. Floriani, J. Am. Chem. Soc., 1999, 121, 6158–6166.

[35] JOHN. L. SPEIERJ, A' MES A. WEBSTERA ND GARRETHT. BARNES, RECEIVEDA UGUST20, 1056, 974.

[1] Du Tingfa. Thermochimica Acta 1989, Pages 189–197.

[4] Unver, Dilsiz, A. J. Appl. Polym. Sci., 96: 1654–1661 (2005).