Living Cationic Polymerization of Vinyl Ethers through a Photoinduced Radical Oxidation/Addition/Deactivation Sequence

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• 作者：Mustafa Ciftci ; Yuji Yoshikawa and Prof. Dr. Yusuf Yagci
• 刊名：Angewandte Chemie International Edition
• 出版年：2017
• 出版时间：January 9, 2017
• 年：2017
• 卷：56
• 期：2
• 页码：519-523
• 全文大小：687K
• ISSN：1521-3773

文摘

A new photoinitiating system for living cationic polymerization of vinyl ethers is reported. In the current approach, visible-light irradiation of dimanganese decacarbonyl (Mn₂(CO)₁₀) in the presence of an alkyl bromide results in the formation of carbon-centered radicals. The photochemically generated radicals were then oxidized by diphenyliodonium ions to the corresponding cations. These cations can add vinyl ether monomers, which are then rapidly deactivated by the bromide anions to give α-halide functional end groups. Poly(vinyl ether) chains are then grown through successive photoinduced radical oxidation/addition/deactivation (PROAD) in a controlled manner. The living nature of the system is evaluated through kinetics studies and block copolymer formation.