Semicrystalline Polyesters Made by Stereoselective Polymerization of a Biobased Bicyclic Lactone
- 1Department of Chemistry, Stanford University, 337 Campus Drive, Stanford, California, 94305
Abstract
Biobased thermoplastics offer sustainable alternatives to petrochemical plastics, but controlling polymer stereochemistry to access biobased materials with desirable thermomechanical properties remains a challenge. Here, we report two new semicrystalline thermoplastics synthesized through the stereoselective ring-opening polymerization of the biobased bicyclic lactone (±)-2-oxo-3,8dioxabicyclo[3.2.1]octane (ODO). Enantiopure bisurea catalysts produced highly syndiotactic poly(ODO) (s-PODO) at low temperatures through an unexpected chain-end control mechanism. Yttrium-catalyzed melt polymerizations afforded high-molecular weight isotactic and syndiotactic PODO. The ductility, strength and modulus of PODO thermoplastics can be tuned through changes in tacticity, processing and crystallinity. By controlling their stereoregularity and processing conditions, we show that semicrystalline PODO films can have exceptional gas barrier properties with enhanced strength and modulus relative to amorphous atactic PODO.
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BibTeX
@misc{dumas2026semicrystalline,
title = {{Semicrystalline Polyesters Made by Stereoselective Polymerization of a Biobased Bicyclic Lactone}},
author = {David M. Dumas and Kai Hin Lui and Hongyi Zhang and Matthew W. Kanan and Robert M. Waymouth},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008674/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008674/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Semicrystalline Polyesters Made by Stereoselective Polymerization of a Biobased Bicyclic Lactone
AU - David M. Dumas
AU - Kai Hin Lui
AU - Hongyi Zhang
AU - Matthew W. Kanan
AU - Robert M. Waymouth
PY - 2026
DA - 2026/09/10
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008674/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008674/v1
AB - Biobased thermoplastics offer sustainable alternatives to petrochemical plastics, but controlling polymer stereochemistry to access biobased materials with desirable thermomechanical properties remains a challenge. Here, we report two new semicrystalline thermoplastics synthesized through the stereoselective ring-opening polymerization of the biobased bicyclic lactone (±)-2-oxo-3,8dioxabicyclo[3.2.1]octane (ODO). Enantiopure bisurea catalysts produced highly syndiotactic poly(ODO) (s-PODO) at low temperatures through an unexpected chain-end control mechanism. Yttrium-catalyzed melt polymerizations afforded high-molecular weight isotactic and syndiotactic PODO. The ductility, strength and modulus of PODO thermoplastics can be tuned through changes in tacticity, processing and crystallinity. By controlling their stereoregularity and processing conditions, we show that semicrystalline PODO films can have exceptional gas barrier properties with enhanced strength and modulus relative to amorphous atactic PODO.
ER -