Enlarging the Toolbox: Epoxide Termination of Polyferrocenylsilane (PFS) as a Key Step for the Synthesis of Amphiphilic PFS鈥揚olyether Block Copolymers

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• 作者：Adrian Natalello ; Arda Alkan ; Andreas Friedel ; Ingo Lieberwirth ; Holger Frey ; Frederik R. Wurm
• 刊名：ACS Macro Letters
• 出版年：2013
• 出版时间：April 16, 2013
• 年：2013
• 卷：2
• 期：4
• 页码：313-316
• 全文大小：265K
• 年卷期：v.2,no.4(April 16, 2013)
• ISSN：2161-1653

文摘

Epoxide termination and functionalization of living poly(ferrocenyldimethylsilane) (PFDMS) is introduced by precapping the living PFDMS with a 4/2 molar mixture of 1,1-diphenylethylene and 1,1-dimethylsilacyclobutane acting as a 鈥渃arbanion pump鈥?system. Subsequent addition of allyl glycidyl ether (AGE) leads to quantitatively functionalized PFDMS鈥揂GE polymers with molecular weights between 1500 and 15鈥?00 g mol^鈥? and polydispersity indices 鈮?.10, carrying one hydroxyl group and an additional allylic double bond. PFDMS鈥揂GE was then applied as a macroinitiator for the living anionic ring-opening polymerization of ethylene oxide (EO) to generate amphiphilic and water-soluble poly(ferrocenyldimethylsilane-b-ethylene oxide) block copolymers with a low polydispersity index. All polymers have been characterized by ¹H NMR spectroscopy, DOSY ¹H NMR spectroscopy, size exclusion chromatography (SEC), and MALDI-ToF mass spectrometry. In addition, for the characterization of the morphology of the PFDMS-b-PEO block copolymers transmission electron microscopy (TEM) was performed in methanol, confirming the formation of cylindrical micelles with an organometallic core and polyether corona.