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Peer-reviewedCC BY-NCChemical science

Facile synthesis of closed-loop recyclable and crystalline stereoregular poly(ether-alt-ester)s from bio-based commodity chemicals.

  • Tianqi Li1
  • Dongfang Zhao2
  • Sifan Ji3,4
  • Shaofeng Liu2
  • Zheng Li2
  • Zhibo Li1,3,4
4 affiliations
  1. 1Key Laboratory of Optic-Electric Sensing and Analytical Chemistry for Life Science, MOE, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology Qingdao Shandong 266042 China [email protected].
  2. 2State Key Laboratory of Advanced Optical Polymer and Manufacturing Technology, College of Polymer Science and Engineering, Qingdao University of Science and Technology Qingdao Shandong 266042 China [email protected].
  3. 3State Key Laboratory of Chemical Engineering and Low-Carbon Technology, College of Chemical and Biological Engineering, Zhejiang University 866 Yuhangtang Road Hangzhou Zhejiang 310058 China [email protected].
  4. 4Institute of Zhejiang University-Quzhou 99 Zheda Road Quzhou Zhejiang 324000 China.
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Abstract

The microstructure of closed-loop recyclable polyesters, including substituent pattern, stereoregularity, and sequence distribution, plays a pivotal role in determining their thermal and mechanical properties. While stereoregular recyclable polyesters exhibit significantly enhanced overall performance, large-scale access to these materials remains challenging. Herein, we report a scalable one-pot synthesis of enantiopure 3-methyl-1,4-dioxan-2-one (αMDO) from bio-based commodity methyl lactate and ethylene oxide. Further controlled ring-opening polymerization (ROP) of the enantiopure αMDO proceeds with retention of the monomer stereochemistry, yielding semicrystalline closed-loop polyesters with melting temperature up to 100 °C, substantially higher than those of polyesters derived from γ- and δ-substituted MDOs. Moreover, thermodynamic investigations reveal that αMDO exhibits more favorable polymerization thermodynamics than γ- and δ-substituted MDOs, enabling controlled ROP under milder conditions. Crucially, the polyesters enable efficient bulk depolymerization to recover the pristine enantiopure monomer, thus offering a practical pathway toward formation of high-performance, closed-loop recyclable polyesters from sustainable commodity feedstocks.

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Cite

BibTeXRIS
BibTeX
@article{li2026facile,
  title = {{Facile synthesis of closed-loop recyclable and crystalline stereoregular poly(ether-alt-ester)s from bio-based commodity chemicals.}},
  author = {Tianqi Li and Dongfang Zhao and Sifan Ji and Shaofeng Liu and Zheng Li and Zhibo Li},
  journal = {Chemical science},
  year = {2026},
  month = oct,
  doi = {10.1039/d6sc06571f},
  url = {https://europepmc.org/article/MED/42904209},
  note = {CC BY-NC},
}
RIS
TY  - JOUR
TI  - Facile synthesis of closed-loop recyclable and crystalline stereoregular poly(ether-alt-ester)s from bio-based commodity chemicals.
AU  - Tianqi Li
AU  - Dongfang Zhao
AU  - Sifan Ji
AU  - Shaofeng Liu
AU  - Zheng Li
AU  - Zhibo Li
PY  - 2026
DA  - 2026/10/13
JO  - Chemical science
DO  - 10.1039/d6sc06571f
UR  - https://europepmc.org/article/MED/42904209
AB  - The microstructure of closed-loop recyclable polyesters, including substituent pattern, stereoregularity, and sequence distribution, plays a pivotal role in determining their thermal and mechanical properties. While stereoregular recyclable polyesters exhibit significantly enhanced overall performance, large-scale access to these materials remains challenging. Herein, we report a scalable one-pot synthesis of enantiopure 3-methyl-1,4-dioxan-2-one (αMDO) from bio-based commodity methyl lactate and ethylene oxide. Further controlled ring-opening polymerization (ROP) of the enantiopure αMDO proceeds with retention of the monomer stereochemistry, yielding semicrystalline closed-loop polyesters with melting temperature up to 100 °C, substantially higher than those of polyesters derived from γ- and δ-substituted MDOs. Moreover, thermodynamic investigations reveal that αMDO exhibits more favorable polymerization thermodynamics than γ- and δ-substituted MDOs, enabling controlled ROP under milder conditions. Crucially, the polyesters enable efficient bulk depolymerization to recover the pristine enantiopure monomer, thus offering a practical pathway toward formation of high-performance, closed-loop recyclable polyesters from sustainable commodity feedstocks.
SN  - 2041-6520
SN  - 2041-6539
ER  -