2024-03-28T20:08:11Zhttps://eprints.lib.hokudai.ac.jp/dspace-oai/requestoai:eprints.lib.hokudai.ac.jp:2115/832792022-11-17T02:08:08Zhdl_2115_20045hdl_2115_139Suzuki-Miyaura catalyst-transfer polycondensation of triolborate-type fluorene monomer: toward rapid access to polyfluorene-containing block and graft copolymers from various macroinitiatorsKobayashi, SaburoFujiwara, KaiyuJiang, Dai-Hua1000030525986Yamamoto, Takuya1000000271643Tajima, KenjiYamamoto, YasunoriIsono, Takuya1000080291235Satoh, Toshifumiopen accessIn 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.Royal Society of Chemistry2020-11-14engjournal articleAMhttp://hdl.handle.net/2115/83279https://doi.org/10.1039/d0py01127d1759-9954Polymer chemistry114268326839https://eprints.lib.hokudai.ac.jp/dspace/bitstream/2115/83279/1/Main_text%28final%29.pdfapplication/pdf1.29 MB2020-11-14