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

Autor: Bruckmoser J; Catalysis Research Center, Department of Chemistry, Technical University of Munich, 85748 Garching, Germany., Pongratz S; Catalysis Research Center, Department of Chemistry, Technical University of Munich, 85748 Garching, Germany., Stieglitz L; Catalysis Research Center, Department of Chemistry, Technical University of Munich, 85748 Garching, Germany., Rieger B; Catalysis Research Center, Department of Chemistry, Technical University of Munich, 85748 Garching, Germany.
Jazyk: angličtina
Zdroj: Journal of the American Chemical Society [J Am Chem Soc] 2023 May 31; Vol. 145 (21), pp. 11494-11498. Date of Electronic Publication: 2023 May 12.
DOI: 10.1021/jacs.3c02348
Abstrakt: We report the highly isoselective ring-opening polymerization (ROP) of racemic β-butyrolactone (β-BL) using in situ -generated catalysts based on Y[N(SiHMe 2 ) 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.
Databáze: MEDLINE
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