Highly Isoselective Ring-Opening Polymerization of rac-β-Butyrolactone: Access to Synthetic Poly(3-hydroxybutyrate) with Polyolefin-like Material Properties

We report the highly isoselective ring-opening polymerization (ROP) of racemic β-butyrolactone (β-BL) using in situ-generated catalysts based on Y­[N­(SiHMe2)2]3(THF)2 and salan-type pro-ligands. The catalyst system produces isotactic poly­(3-hydroxybutyrate) (PHB) with record productivity (TOF up t...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2023-05, Vol.145 (21), p.11494-11498
Main Authors: Bruckmoser, Jonas, Pongratz, Stefanie, Stieglitz, Lucas, Rieger, Bernhard
Format: Article
Language:English
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Summary:We report the highly isoselective ring-opening polymerization (ROP) of racemic β-butyrolactone (β-BL) using in situ-generated catalysts based on Y­[N­(SiHMe2)2]3(THF)2 and salan-type pro-ligands. The catalyst system produces isotactic poly­(3-hydroxybutyrate) (PHB) with record productivity (TOF up to 32 000 h–1) and the highest isoselectivity (P m up to 0.89) in ROP of β-BL achieved to date. In contrast to bacterial PHB, the chemically synthesized PHB has beneficial material properties, such as increased melt processing window attributed to a lowered melting temperature (T m ≈ 140 °C) and drastically reduced brittleness. The produced PHB showed an elongation at break of 392%, thus demonstrating promising polyolefin-like thermomechanical material properties.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.3c02348