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Stereogradient Poly(Lactic Acid) from meso‐Lactide/L‐Lactide Mixtures

The production of L‐lactide from L‐lactic acid involves a substantial formation of meso‐lactide as an impurity, and, upon polymerization with the industrial catalyst tin octanoate, results in poly(L‐lactic acid) of reduced crystallinity due to stereoerrors randomly distributed along the polymer chai...

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Autores principales: Hador, Rami, Shuster, Michael, Venditto, Vincenzo, Kol, Moshe
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9796763/
https://www.ncbi.nlm.nih.gov/pubmed/35789524
http://dx.doi.org/10.1002/anie.202207652
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author Hador, Rami
Shuster, Michael
Venditto, Vincenzo
Kol, Moshe
author_facet Hador, Rami
Shuster, Michael
Venditto, Vincenzo
Kol, Moshe
author_sort Hador, Rami
collection PubMed
description The production of L‐lactide from L‐lactic acid involves a substantial formation of meso‐lactide as an impurity, and, upon polymerization with the industrial catalyst tin octanoate, results in poly(L‐lactic acid) of reduced crystallinity due to stereoerrors randomly distributed along the polymer chains. We describe a new approach wherein, instead of avoiding stereoerrors by removing the meso‐lactide prior to polymerization, the stereoerrors in the polymer are tolerated, by crowding them in a stereogradient copolymer. A zirconium complex of an amine tris(phenolate) ligand is found to exhibit very high syndioselectivity in the ring opening polymerization catalysis of meso‐lactide at room temperature, and gives rise to stereogradient copolymers in the polymerization of mixtures of meso‐lactide/L‐lactide in the melt at 180 °C. Relative to the stereo‐random copolymers obtained with tin octanoate, the stereogradient copolymers exhibit enhanced crystallinities manifested in lower solubilities and higher melting temperatures and enthalpies.
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spelling pubmed-97967632023-01-04 Stereogradient Poly(Lactic Acid) from meso‐Lactide/L‐Lactide Mixtures Hador, Rami Shuster, Michael Venditto, Vincenzo Kol, Moshe Angew Chem Int Ed Engl Research Articles The production of L‐lactide from L‐lactic acid involves a substantial formation of meso‐lactide as an impurity, and, upon polymerization with the industrial catalyst tin octanoate, results in poly(L‐lactic acid) of reduced crystallinity due to stereoerrors randomly distributed along the polymer chains. We describe a new approach wherein, instead of avoiding stereoerrors by removing the meso‐lactide prior to polymerization, the stereoerrors in the polymer are tolerated, by crowding them in a stereogradient copolymer. A zirconium complex of an amine tris(phenolate) ligand is found to exhibit very high syndioselectivity in the ring opening polymerization catalysis of meso‐lactide at room temperature, and gives rise to stereogradient copolymers in the polymerization of mixtures of meso‐lactide/L‐lactide in the melt at 180 °C. Relative to the stereo‐random copolymers obtained with tin octanoate, the stereogradient copolymers exhibit enhanced crystallinities manifested in lower solubilities and higher melting temperatures and enthalpies. John Wiley and Sons Inc. 2022-07-21 2022-10-04 /pmc/articles/PMC9796763/ /pubmed/35789524 http://dx.doi.org/10.1002/anie.202207652 Text en © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH https://creativecommons.org/licenses/by-nc-nd/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ (https://creativecommons.org/licenses/by-nc-nd/4.0/) License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made.
spellingShingle Research Articles
Hador, Rami
Shuster, Michael
Venditto, Vincenzo
Kol, Moshe
Stereogradient Poly(Lactic Acid) from meso‐Lactide/L‐Lactide Mixtures
title Stereogradient Poly(Lactic Acid) from meso‐Lactide/L‐Lactide Mixtures
title_full Stereogradient Poly(Lactic Acid) from meso‐Lactide/L‐Lactide Mixtures
title_fullStr Stereogradient Poly(Lactic Acid) from meso‐Lactide/L‐Lactide Mixtures
title_full_unstemmed Stereogradient Poly(Lactic Acid) from meso‐Lactide/L‐Lactide Mixtures
title_short Stereogradient Poly(Lactic Acid) from meso‐Lactide/L‐Lactide Mixtures
title_sort stereogradient poly(lactic acid) from meso‐lactide/l‐lactide mixtures
topic Research Articles
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9796763/
https://www.ncbi.nlm.nih.gov/pubmed/35789524
http://dx.doi.org/10.1002/anie.202207652
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