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<p>Developing high-performance CO<sub>2</sub>-based polymers is promising to address the challenges of CO<sub>2</sub> sequestration and the environmental impact of petroleum-based plastics. The δ-lactone 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one and its derivatives, synthesized from CO<sub>2</sub> with 1,3-butadiene, have emerged as very promising CO<sub>2</sub>-derived monomers. However, their general ring-opening polymerizations face challenges with thermodynamics and kinetics, generally resulting in long reaction times, low conversions, and low-molecular-weight polyesters with poor mechanical properties. Herein, we report a dual isomerization-driven cationic ring-opening polymerization (DI-CROP) of a CO<sub>2</sub>-derived thionolactone, 3-ethyl-6-vinyltetrahydro-2H-pyran-2-thione, in which the relayed S/O and vinyl isomerizations significantly enhance polymerization activity, enabling the rapid synthesis of high-molecular-weight CO<sub>2</sub>-based polythioesters, achieving near-quantitative conversion within just a few minutes. Also, the relayed S/O and vinyl isomerizations in DI-CROP can easily migrate C=C substituents on the ring of thionolactone into its backbone. These features further enable the production of sustainable CO<sub>2</sub>-based materials through efficient copolymerization and post-polymerization functionalization. This study enriches the realm of isomerization-driven polymerizations, and provides a new synthetic approach to CO<sub>2</sub>-derived polymeric materials.</p>

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S/O and vinyl isomerization enables ultrafast cationic ring-opening polymerization toward CO2-derived polythioester with migrated in-chain C=C substituents

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年10月29日

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  • Zong-Bin Lu,
  • Shun-Ran Peng,
  • Zhe Wang,
  • Yu Xiong,
  • Lei Xia,
  • Guang Chen,
  • Xuan Nie,
  • Chun-Yan Hong,
  • Ze Zhang,
  • Ye-Zi You

摘要

Developing high-performance CO2-based polymers is promising to address the challenges of CO2 sequestration and the environmental impact of petroleum-based plastics. The δ-lactone 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one and its derivatives, synthesized from CO2 with 1,3-butadiene, have emerged as very promising CO2-derived monomers. However, their general ring-opening polymerizations face challenges with thermodynamics and kinetics, generally resulting in long reaction times, low conversions, and low-molecular-weight polyesters with poor mechanical properties. Herein, we report a dual isomerization-driven cationic ring-opening polymerization (DI-CROP) of a CO2-derived thionolactone, 3-ethyl-6-vinyltetrahydro-2H-pyran-2-thione, in which the relayed S/O and vinyl isomerizations significantly enhance polymerization activity, enabling the rapid synthesis of high-molecular-weight CO2-based polythioesters, achieving near-quantitative conversion within just a few minutes. Also, the relayed S/O and vinyl isomerizations in DI-CROP can easily migrate C=C substituents on the ring of thionolactone into its backbone. These features further enable the production of sustainable CO2-based materials through efficient copolymerization and post-polymerization functionalization. This study enriches the realm of isomerization-driven polymerizations, and provides a new synthetic approach to CO2-derived polymeric materials.