2024-03-28T16:09:58Zhttps://eprints.lib.hokudai.ac.jp/dspace-oai/requestoai:eprints.lib.hokudai.ac.jp:2115/615022022-11-17T02:08:08Zhdl_2115_20045hdl_2115_139B(C6F5)(3)-catalyzed group transfer polymerization of alkyl methacrylates with dimethylphenylsilane through in situ formation of silyl ketene acetal by B(C6F5)(3)-catalyzed 1,4-hydrosilylation of methacrylate monomerChen, YougenKitano, KodaiTsuchida, ShinjiKikuchi, SeiyaTakada, KenjiSatoh, ToshifumiKakuchi, Toyoji430The group transfer polymerization (GTP) of alkyl methacrylates has been studied using hydrosilane and tris(pentafluorophenyl) borane (B(C6F5)(3)) as the new initiation system. For the B(C6F5)(3)-catalyzed polymerization of methyl methacrylate (MMA) using triethylsilane, tri-n-butylsilane (nBu(3)SiH), dimethylphenylsilane (Me2PhSiH), triphenylsilane, and triisopropylsilane, nBu(3)SiH and Me2PhSiH were suitable for producing well-defined polymers with predicted molar masses and a low polydispersity. The livingness of the GTP of MMA using Me2PhSiH/B(C6F5)(3) was verified by the matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) measurement of the resulting polymers, kinetic analyses, and chain extension experiments. The B(C6F5)(3)-catalyzed GTP using Me2PhSiH was also applicable for other alkyl methacrylates, such as the n-propyl, n-hexyl, n-decyl, 2-ethylhexyl, iso-butyl, and cyclohexyl methacrylates. The in situ formation of the silyl ketene acetal by the 1,4-hydrosilylation of MMA was proved by the MALDI-TOF MS and H-2 NMR measurements of the polymers obtained from the B(C6F5)(3)-catalyzed GTPs of MMA with Me2PhSiH or Me2PhSiD, which was terminated using CH3OH or CD3OD.The Royal Society of ChemistryJournal Articleapplication/pdfhttp://hdl.handle.net/2115/61502https://eprints.lib.hokudai.ac.jp/dspace/bitstream/2115/61502/1/Chen-2.pdf1759-9954Polymer chemistry618350235112015enginfo:doi/10.1039/c5py00294jauthor