環状構造を高密度に有する新しい炭素主鎖骨格ポリマーの開発

2025-09-01 愛媛大学

＜関連情報＞

• https://www.ehime-u.ac.jp/data_relese/pr_20250901_eng/
• https://www.ehime-u.ac.jp/wp-content/uploads/2025/09/pr_20250901_eng.pdf
• https://pubs.acs.org/doi/10.1021/acs.macromol.5c00704

ペンタエリトリトールから合成される2官能性ジアゾカルボニル化合物のC1環化重合 C1 Cyclopolymerization of Bis(diazocarbonyl) Compounds Derived from Pentaerythritol

Hiroaki Shimomoto,Makoto Ishimoto,Tomomichi Itoh,and Eiji Ihara
Macromolecules  Published: June 25, 2025
DOI:https://doi.org/10.1021/acs.macromol.5c00704

Abstract

C1 cyclopolymerization of a series of bis(diazocarbonyl) compounds derived from pentaerythritol [C(CH₂OH)₄] is described, where two of the OH groups of the tetraol were converted to diazoacetate-containing substituents with or without spacers, and the remaining two OH groups were benzylated or silylated to exert the Thorpe–Ingold effect for the effective cyclization. The cyclopolymerization successfully afforded a new type of cyclopolymer bearing a 9-, 15-, 17-, or 19-membered ring as a repeating unit depending on the spacer structure. For the 19-membered ring formation during the propagation, the two urethane linkages incorporated as spacers were responsible for the effective cyclization, as previously demonstrated for 19-membered-ring-forming cyclopolymerization of divinyl compounds with the urethane linkages. Differential scanning calorimetry analyses revealed that glass transition temperature (T_g) values of the cyclopolymers were 59–68 °C higher than those of their open-chain polymer counterparts.