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Suzuki-Miyaura catalyst-transfer polycondensation of triolborate-type fluorene monomer: toward rapid access to polyfluorene-containing block and graft copolymers from various macroinitiators
Title: | Suzuki-Miyaura catalyst-transfer polycondensation of triolborate-type fluorene monomer: toward rapid access to polyfluorene-containing block and graft copolymers from various macroinitiators |
Authors: | Kobayashi, Saburo Browse this author | Fujiwara, Kaiyu Browse this author | Jiang, Dai-Hua Browse this author | Yamamoto, Takuya Browse this author →KAKEN DB | Tajima, Kenji Browse this author →KAKEN DB | Yamamoto, Yasunori Browse this author | Isono, Takuya Browse this author | Satoh, Toshifumi Browse this author →KAKEN DB |
Issue Date: | 14-Nov-2020 |
Publisher: | Royal Society of Chemistry |
Journal Title: | Polymer chemistry |
Volume: | 11 |
Issue: | 42 |
Start Page: | 6832 |
End Page: | 6839 |
Publisher DOI: | 10.1039/d0py01127d |
Abstract: | In this study, we demonstrated that the Suzuki-Miyaura catalyst transfer polycondensation (SCTP) of the triolborate-type fluorene monomer, viz. potassium 2-(7-bromo-9,9-dihexyl-9H-fluorene-2-yl)triolborate, can be an efficient and versatile approach to the precise synthesis of poly[2,7-(9,9-dihexylfluorene)]s (PFs) and PF-containing block and graft copolymers. SCTP of the triolborate-type monomer proceeded rapidly in a THF/H2O mixed solvent at -10 degrees C using an iodobenzene derivative/Pd-2(dba)(3)center dot CHCl3/t-Bu3P initiating system. Kinetic and post-polymerization experiments revealed that SCTP proceeded via the chain-growth and living polymerization mechanisms. The most important feature of the present polymerization system is that only a small amount of base and water can sufficiently promote the reaction. The well-controlled nature of this polymerization system enabled the synthesis of high-molecular-weight PFs (M-n = 5-69 kg mol(-1)) with narrow dispersity (D-M = 1.14-1.38) and alpha-end-functionalized PFs. Most importantly, PF-containing block and graft copolymers were successfully synthesized, beginning with various iodobenzene-functionalized macroinitiators; this was difficult to achieve by the conventional SCTP of pinacolboronate-type fluorene monomer. One of the key factors for the successful block and graft copolymer syntheses is the reduced water content in the polymerization medium, which suppressed the potential precipitation/aggregation of the macroinitiators. |
Type: | article (author version) |
URI: | http://hdl.handle.net/2115/83279 |
Appears in Collections: | 工学院・工学研究院 (Graduate School of Engineering / Faculty of Engineering) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)
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Submitter: 佐藤 敏文
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