研究者詳細 - 内山　峰人

論文 - 内山　峰人

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Proton transfer anionic polymerization with C-H bond as the dormant species 査読有り

Uchiyama, M; Ohira, N; Yamashita, K; Sagawa, K; Kamigaito, M

NATURE CHEMISTRY 16 巻 ( 10 ) 頁： 1630 - 1637 2024年10月

担当区分：筆頭著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Nature Chemistry

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. (Figure presented.)

DOI： 10.1038/s41557-024-01572-3

炭素－水素結合をドーマント種としたプロトン移動アニオン重合査読有り

内山峰人

化学と工業 78 巻 ( 3 ) 頁： 192 - 193 2025年3月

Proton Transfer Anionic Polymerization of Methyl Methacrylate with Ligands for Dual Control of Molecular Weight and Tacticity 査読有り

Sagawa, K; Uchiyama, M; Watanabe, H; Homma, C; Kamigaito, M

PRECISION CHEMISTRY 2024年10月

担当区分：筆頭著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Precision Chemistry

Dual control of the molecular weight and tacticity in proton transfer anionic polymerization (PTAP) of methyl methacrylate (MMA) was investigated by using various ligands in the presence of a bulky potassium base catalyst and an organic compound with a weakly acidic C-H bond as dormant species in toluene at 0 °C. The tacticity of the resulting poly(MMA) (PMMA) produced without ligands was nearly atactic (rr/mr/mm = 22/54/24). However, the use of 18-crown-6 as a ligand afforded predominantly syndiotactic PMMA (rr ≈ 58%), whereas the use of chiral bis(oxazoline) ligands gave slightly isotactic-rich PMMA (mm ≈ 32%). Molecular weight control of PMMA was achieved (Đ = 1.1-1.2) by adding 1,1-diphenylethanol as a reversible terminator while maintaining control of the tacticity with the above ligands. Stereoblock PMMA consisting of atactic and syndiotactic segments was successfully synthesized via sequential PTAP using macroinitiator/macro-CTA methods.

DOI： 10.1021/prechem.4c00066

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'Living' anionic polymerization through reversible activation of C-H bonds with a base catalyst 査読有り

Uchiyama, M; Kamigaito, M

NATURE CHEMISTRY 16 巻 ( 10 ) 頁： 1582 - 1583 2024年10月

Synthesis of Degradable Polymers via 1,5-Shift Radical Isomerization Polymerization of Vinyl Ether Derivatives with a Cleavable Bond 招待有り査読有り

M. Uchiyama, M. Imai, and M. Kamigaito

Polym. J. 2024年1月

Cationic β-Scission of C–H and C–C Bonds for Selective Dimerization and Subsequent Sulfur-Free RAFT Polymerization of α-Methylstyrene and Isobutylene 査読有り

T. Tanimoto, M. Uchiyama, and M. Kamigaito

Angew. Chem. Int. Ed. 62 巻 ( 43 ) 頁： e202307791 2023年10月

可逆的連鎖移動に基づくカチオン重合を用いた分子量と立体構造の同時制御招待有り査読有り

内山峰人

高分子 72 巻頁： 276 - 277 2023年6月

Sulfur-Free Radical RAFT Polymerization of Methacrylates in Homogeneous Solution: Design of exo-Olefin Chain-Transfer Agents (R-CH2C(=CH2)Z) 査読有り

Amano Maki, Uchiyama Mineto, Satoh Kotaro, Kamigaito Masami

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 61 巻 ( 12 ) 頁： e202212633 2022年12月

Synthesis and Degradation of Vinyl Polymers with Evenly Distributed Thioacetal Bonds in Main Chains: Cationic DT Copolymerization of Vinyl Ethers and Cyclic Thioacetals 査読有り

Uchiyama Mineto, Murakami Yukihiro, Satoh Kotaro, Kamigaito Masami

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 62 巻 ( 4 ) 頁： e202215021 2022年12月

One-pot synthesis of structure-controlled temperature-responsive polymer gels 査読有り

Sakai Tomoki, Ito Nagisa, Hara Mitsuo, Seki Takahiro, Uchiyama Mineto, Kamigaito Masami, Satoh Kotaro, Hoshino Taiki, Takeoka Yukikazu

POLYMER CHEMISTRY 13 巻 ( 29 ) 頁： 4230 - 4240 2022年7月

Asymmetric Cationic Polymerization of Benzofuran through a Reversible Chain-Transfer Mechanism: Optically Active Polybenzofuran with Controlled Molecular Weights 査読有り

Uchiyama Mineto, Watanabe Daichi, Tanaka Yuhei, Satoh Kotaro, Kamigaito Masami

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 144 巻 ( 23 ) 頁： 10429 - 10437 2022年6月

Acridinium salts as photoredox organocatalysts for photomediated cationic RAFT and DT polymerizations of vinyl ethers 査読有り

Matsuda Marina, Uchiyama Mineto, Itabashi Yuki, Ohkubo Kei, Kamigaito Masami

POLYMER CHEMISTRY 13 巻 ( 8 ) 頁： 1031 - 1039 2022年2月

Cationic RAFT and DT polymerization

Uchiyama Mineto, Satoh Kotaro, Kamigaito Masami

PROGRESS IN POLYMER SCIENCE 124 巻 2022年1月

Cationic RAFT and DT Polymerization 査読有り

M. Uchiyama, K. Satoh, and M. Kamigaito

Prog. Polym. Sci. 124 巻頁： 101485 2021年11月

Hybridization of Step-/Chain-Growth and Radical/Cationic Polymerizations Using Thioacetals as Key Components for Triblock, Periodic and Random Multiblock Copolymers with Thermoresponsiveness 査読有り

Uchiyama Mineto, Osumi Masahiro, Satoh Kotaro, Kamigaito Masami

MACROMOLECULAR RAPID COMMUNICATIONS 42 巻 ( 18 ) 2021年9月

Stereospecific cationic RAFT polymerization of bulky vinyl ethers and stereoblock poly(vinyl alcohol) via mechanistic transformation to radical RAFT polymerization of vinyl acetate 査読有り

Uchiyama Mineto, Satoh Kotaro, Kamigaito Masami

GIANT 5 巻頁： 100047 2021年3月

ポリマーの立体構造制御で物性アップ—キラル触媒を用いた立体選択重合・立体特異性重合査読有り

内山峰人, 上垣外正己

化学 75 巻 ( (11) ) 頁： 70-71. 2020年10月

Epoxy-functionalised 4-vinylguaiacol for the synthesis of bio-based, degradable star polymers via a RAFT/ROCOP strategy 査読有り

McGuire Thomas M., Miyajima Masato, Uchiyama Mineto, Buchard Antoine, Kamigaito Masami

POLYMER CHEMISTRY 11 巻 ( 36 ) 頁： 5844 - 5850 2020年9月

Thiol-Ene Cationic and Radical Reactions: Cyclization, Step-Growth, and Concurrent Polymerizations for Thioacetal and Thioether Units 査読有り

Uchiyama Mineto, Osumi Masahiro, Satoh Kotaro, Kamigaito Masami

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 59 巻 ( 17 ) 頁： 6832 - 6838 2020年4月

Interconvertible and switchable cationic/PET-RAFT copolymerization triggered by visible light 査読有り

Satoh Kotaro, Sun Zhihong, Uchiyama Mineto, Kamigaito Masami, Xu Jiangtao, Boyer Cyrille

POLYMER JOURNAL 52 巻 ( 1 ) 頁： 65 - 73 2020年1月

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