POS1-0444
Anionic Homo- and Copolymerization of Thioamide Derivatives
Topic
S1. Polymer Synthesis
When and Where
Sep 29, 2026
08:30 - 09:30
Room 301 (Grand Ballroom)
Session Chairs
Hae Jung SON
Boseok KANG
Presenter(s)
Momo Ishida (Nagoya University)
Co-Author(s)
Abstract
Polymers with sulfur atoms incorporated into their backbones are expected to exhibit unique properties and characteristics different from those of vinyl polymers. To obtain such structures, ring-opening polymerization of sulfur-containing monomers has been widely used. However, this approach limits the available monomers to cyclic structures, making polymer design challenging.
Recently, we reported the radical copolymerization of thioamide derivatives containing C=S double bond with vinyl monomers. Since the C=S double bond in thioamides exhibits electrophilicity, direct anionic polymerization may also be possible. The development of anionic polymerization of C=S double bonds is expected to provide novel sulfur-containing polymers with unique structures and properties. Nevertheless, reported examples of the direct anionic polymerization of thiocarbonyl compounds remain limited, often suffering from poor stability of the monomers and polymers. Furthermore, to the best of our knowledge, the anionic copolymerization of thiocarbonyl compounds with vinyl monomers has not yet been reported.
In this study, we investigated the anionic homopolymerization of thioamides and their anionic copolymerization with methyl methacrylate. The polymerization behavior varied significantly depending on the reaction conditions, including the countercation, polymerization temperature, and additive concentration. Under appropriate reaction conditions, both homo- and copolymerization successfully proceeded. Furthermore, since the resulting polymers contain sulfur atoms in their backbones, they exhibited degradability and unique solubility. Notably, due to their low ceiling temperature, the obtained homopolymers underwent depolymerization, allowing recovery of the thioamide monomer.
Recently, we reported the radical copolymerization of thioamide derivatives containing C=S double bond with vinyl monomers. Since the C=S double bond in thioamides exhibits electrophilicity, direct anionic polymerization may also be possible. The development of anionic polymerization of C=S double bonds is expected to provide novel sulfur-containing polymers with unique structures and properties. Nevertheless, reported examples of the direct anionic polymerization of thiocarbonyl compounds remain limited, often suffering from poor stability of the monomers and polymers. Furthermore, to the best of our knowledge, the anionic copolymerization of thiocarbonyl compounds with vinyl monomers has not yet been reported.
In this study, we investigated the anionic homopolymerization of thioamides and their anionic copolymerization with methyl methacrylate. The polymerization behavior varied significantly depending on the reaction conditions, including the countercation, polymerization temperature, and additive concentration. Under appropriate reaction conditions, both homo- and copolymerization successfully proceeded. Furthermore, since the resulting polymers contain sulfur atoms in their backbones, they exhibited degradability and unique solubility. Notably, due to their low ceiling temperature, the obtained homopolymers underwent depolymerization, allowing recovery of the thioamide monomer.
