2025-10-20 京都大学
ケトン骨格が周期的に導入された高分子の合成と分解（左図）と光で分解されるイメージ（右図）
＜関連情報＞
- https://www.t.kyoto-u.ac.jp/ja/research/topics/20251017
- https://www.t.kyoto-u.ac.jp/ja/research/topics/r71017seika_oouchi
- https://pubs.acs.org/doi/10.1021/jacs.5c13090
ラジカル交互共重合と後重合改質によるビニルポリマーへの周期的ケトン単位の導入：バルク状態における配列指向性光分解 Introduction of Periodic Ketone Units on Vinyl Polymers via a Radical Alternating Copolymerization and Postpolymerization Modification: Sequence-Oriented Photodegradation in the Bulk State
Keita Kuroda,and Makoto Ouchi
Journal of the American Chemical Society :Published October 15, 2025
DOI:https://doi.org/10.1021/jacs.5c13090
Abstract
The synthesis and the sequence-oriented bulk-state photodegradation of sequence-controlled polymers with a periodic structure bearing acrylamide, ketone, and vinyl ether units is reported. The alternating terpolymers can be synthesized via a radical copolymerization of a silyl-protected 1,3-butadiene bearing a methyl ether group (SBD) with a pentafluorophenyl acrylate (PFA) monomer in an alternating and 1,4-regioselective fashion. This process is followed by the addition of an amine to trigger a cascade aminolysis–desilylation reaction. The pendant alkyl group on the acrylamide unit, which is derived from the added amine, is crucial for determining the physical properties of a series of polymers, particularly the glass-transition temperature (Tg). Relatively flexible and sufficiently thermally stable polymers with Tg values below room temperature could be degraded under UV irradiation in the bulk state. Control experiments revealed that synergistic interactions between the periodically arranged ketone, vinyl ether, and acrylamide units were essential for promoting the photodegradation.
