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Suzuki-Miyaura Catalyst-Transfer Polycondensation of Triolborate-Type Carbazole Monomers
| Title: | Suzuki-Miyaura Catalyst-Transfer Polycondensation of Triolborate-Type Carbazole Monomers |
| Authors: | Kobayashi, Saburo Browse this author | | Ashiya, Mayoh Browse this author | | Yamamoto, Takuya Browse this author | | Tajima, Kenji Browse this author →KAKEN DB | | Yamamoto, Yasunori Browse this author | | Isono, Takuya Browse this author | | Satoh, Toshifumi Browse this author →KAKEN DB |
| Keywords: | pi-conjugated polymer | | polycarbazole | | catalyst-transfer polycondensation |
| Issue Date: | Dec-2021 |
| Publisher: | MDPI |
| Journal Title: | Polymers |
| Volume: | 13 |
| Issue: | 23 |
| Start Page: | 4168 |
| Publisher DOI: | 10.3390/polym13234168 |
| Abstract: | Herein, we report the Suzuki-Miyaura catalyst-transfer polycondensation (SCTP) of triolborate-type carbazole monomers, i.e., potassium 3-(6-bromo-9-(2-octyldodecyl)-9H-carbazole-2-yl)triolborate (M1) and potassium 2-(7-bromo-9-(2-octyldodecyl)-9H-carbazole-2-yl) triolborate (M2), as an efficient and versatile approach for precisely synthesizing poly[9-(2-octyldodecyl)-3,6-carbazole] (3,6-PCz) and poly[9-(2-octyldodecyl)-2,7-carbazole] (2,7-PCz), respectively. The SCTP of triolborate-type carbazole monomers was performed in a mixture of THF/H2O using an initiating system consisted of 4-iodobenzyl alcohol, Pd-2(dba)(3)& BULL;CHCl3, and t-Bu3P. In the SCTP of M1, cyclic by-product formation was confirmed, as reported for the corresponding pinacolboronate-type monomer. By optimizing the reaction temperature and reaction time, we successfully synthesized linear end-functionalized 3,6-PCz for the first time. The SCTP of M2 proceeded with almost no side reaction, yielding 2,7-PCz with a functional initiator residue at the alpha-chain end. Kinetic and block copolymerization experiments demonstrated that the SCTP of M2 proceeded in a chain-growth and controlled/living polymerization manner. This is a novel study on the synthesis of 2,7-PCz via SCTP. By taking advantage of the well-controlled nature of this polymerization system, we demonstrated the synthesis of high-molecular-weight 2,7-PCzs (M-n = 5-38 kg mol(-1)) with a relatively narrow (M) (1.35-1.48). Furthermore, we successfully synthesized fluorene/carbazole copolymers as well as 2,7-PCz-containing diblock copolymers, demonstrating the versatility of the present polymerization system as a novel synthetic strategy for well-defined polycarbazole-based materials. |
| Type: | article |
| URI: | http://hdl.handle.net/2115/83901 |
| 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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