2024-03-29T14:33:49Z
https://soar-ir.repo.nii.ac.jp/oai
oai:soar-ir.repo.nii.ac.jp:00019433
2022-12-14T04:27:29Z
1309:1310
Synthesis and post-polymerization reaction of end-clickable stereoregular polymethacrylates via termination of stereospecific living anionic polymerization
Kohsaka, Yasuhiro
Kurata, Takashi
Yamamoto, Kazuki
Ishihara, Shoya
Kitayama, Tatsuki
Polymer Chemistry.6(7):1078-1087(2015) - Reproduced by permission of The Royal Society of Chemistry. There shall be a link from this article to the PDF of the final published article on the RSC's website once this final version is available.
Poly(methyl methacrylate)s with high stereoregularity and clickable end-groups were synthesized via terminating reactions with α-(halomethyl)acrylates in stereospecific living anionic polymerization. The terminating reaction was efficient and tolerant to the reaction conditions to such an extent that almost quantitative end-functionalization was achieved in isotactic- and syndiotactic-specific polymerization systems. The terminating reactions were also achieved in polymerizations of vinyl methacrylate and trimethylsilyl methacrylate. For the polymerization of butyl acrylate, however, the termination efficiency was limited to less than 69%. Furthermore, the quantitative end-functionalization of the incorporated C[double bond, length as m-dash]C double bond at ω-end was achieved with various thiols catalyzed by Et3N. The base-catalysed thiol–ene reaction of the stereoregular poly(vinyl methacrylate) with a ω-end C[double bond, length as m-dash]C double bond selectively proceeded to retain vinyl ester functions, and the subsequent hydrolysis afforded ω-functional stereoregular poly(methacrylic acid). A combination of the terminating agent with a protected lithium amide afforded stereoregular poly(methyl methacrylates) with orthogonally clickable α- and ω-ends.
Article
Polymer Chemistry.6(7):1078-1087(2015)
The Royal Society of Chemistry
2015-02-21
eng
journal article
AM
http://hdl.handle.net/10091/00020194
https://soar-ir.repo.nii.ac.jp/records/19433
https://doi.org/10.1039/C4PY01285B
10.1039/C4PY01285B
1759-9954
Polymer Chemistry
6
7
1078
1087
https://soar-ir.repo.nii.ac.jp/record/19433/files/26620105_04.pdf
application/pdf
401.7 kB
2018-01-22