Synthesis of Poly(3-substituted thiophene)s of Remarkably High Solubility in Hydrocarbon via Nickel-Catalyzed Deprotonative Cross-Coupling Polycondensation

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• 作者：Keisuke Fujita ; Yugo Sumino ; Kenji Ide ; Shunsuke Tamba ; Keisuke Shono ; Jian Shen ; Takashi Nishino ; Atsunori Mori ; Takeshi Yasuda
• 刊名：Macromolecules
• 出版年：2016
• 出版时间：February 23, 2016
• 年：2016
• 卷：49
• 期：4
• 页码：1259-1269
• 全文大小：682K
• ISSN：1520-5835

文摘

Polythiophenes bearing a siloxane moiety in a substituent at the 3-position are prepared by deprotonative polycondensation of 2-bromo-3-substituted-thiophene with a bulky magnesium amide chloromagnesium 2,2,6,6-tetramethylpiperidine-1-yl lithium chloride salt (TMPMgCl·LiCl) catalyzed by a nickel complex. Deprotonation takes place at 60 °C for 1 h to form the corresponding thiophene magnesium species, which is subjected to the polymerization by addition of 0.1–5 mol % NiCl₂(PPh₃)IPr (IPr: 1,3-bis(2,6-diisopropylphenyl)imidazole-2-yl). Polymerization proceeds in a highly regioregular manner, and the molecular weight of the thus-obtained polymer is controllable by the ratio of monomer feed/catalyst loading to indicate M_n of up to 280 000 with narrow molecular weight distribution. Chlorothiophenes are also found to induce polymerization in a deprotonative manner with TMPMgCl·LiCl or nBuLi (the Murahashi coupling polymerization). The obtained polymers bearing a siloxane moiety in the substituent is revealed to be dissolved in a hydrocarbon allowing formation of thin film from hexane.