Proton transfer anionic polymerization with C-H bond as the dormant species.

Autor: Uchiyama M; Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Nagoya, Japan. uchiyama@chembio.nagoya-u.ac.jp., Ohira N; Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Nagoya, Japan., Yamashita K; Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Nagoya, Japan., Sagawa K; Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Nagoya, Japan., Kamigaito M; Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Nagoya, Japan. kamigait@chembio.nagoya-u.ac.jp.
Jazyk: angličtina
Zdroj: Nature chemistry [Nat Chem] 2024 Oct; Vol. 16 (10), pp. 1630-1637. Date of Electronic Publication: 2024 Jul 04.
DOI: 10.1038/s41557-024-01572-3
Abstrakt: Living anionic polymerization-the most common living polymerization and the one with the longest history-generally requires stringent, water-free conditions and one metal initiator per polymer chain. Here we present the proton transfer anionic polymerization of methacrylates using acidic C-H bonds as the dormant species that are activated by base catalysts. The polymerization mechanism involves reversible chain transfer or termination of the growing enolate species. A weakly acidic compound, such as an alkyl isobutyrate, serves as the initiator or chain-transfer agent in the presence of a bulky potassium base catalyst to produce a polymer chain and, thereby, diminishes the metal compound per chain ratio. An added alcohol serves as a reversible terminator to tame the propagation. End-functionalized, star, block and graft polymers are easily accessible from compounds with C-H bonds.
(© 2024. The Author(s), under exclusive licence to Springer Nature Limited.)
Databáze: MEDLINE
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