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<p>Chemically recyclable polythioesters are of particular interest owing to their unique properties and desired sustainability. By the exploit of a benzo-fusion strategy to <i>ε</i>-thiocaprolactone, we successfully improved the chemical recyclability and regulated the thermal and mechanical properties of the resulting polythioesters. The efficient ring-opening polymerization (ROP) of benzo-fused thiolactone monomers (<b>M</b>) containing different substituents gave rise to high-molecular-weight semi-aromatic polythioesters P(<b>M</b>)s. The resulting P(<b>M</b>)s showcased tunable physical and mechanical properties. The debenzylation of P(<b>M3</b>) was able to generate P(<b>M3</b>-OH) with free hydroxyl sidechains. Notably, chemical recycling of the resulting P(<b>M</b>)s back to their corresponding monomers <i>via</i> bulk thermal depolymerization achieved high efficiency (&gt;95% yield, 99% purity), establishing a closed-loop lifecycle.</p>

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Ring-opening Polymerization of Benzo-fused Thiolactones toward Chemically Recyclable Semi-aromatic Polythioesters

  • 期刊论文

  • 发表日期：

    2025年5月20日

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  • Wei Xiong,
  • Kun Li,
  • Long-Hai Liu,
  • Si-Qi Wang,
  • Zhong-Zheng Cai,
  • Jian-Bo Zhu

摘要

Chemically recyclable polythioesters are of particular interest owing to their unique properties and desired sustainability. By the exploit of a benzo-fusion strategy to ε-thiocaprolactone, we successfully improved the chemical recyclability and regulated the thermal and mechanical properties of the resulting polythioesters. The efficient ring-opening polymerization (ROP) of benzo-fused thiolactone monomers (M) containing different substituents gave rise to high-molecular-weight semi-aromatic polythioesters P(M)s. The resulting P(M)s showcased tunable physical and mechanical properties. The debenzylation of P(M3) was able to generate P(M3-OH) with free hydroxyl sidechains. Notably, chemical recycling of the resulting P(M)s back to their corresponding monomers via bulk thermal depolymerization achieved high efficiency (>95% yield, 99% purity), establishing a closed-loop lifecycle.