Macromol (Jun 2022)

Poly(L-lactide) Epimerization and Chain Scission in the Presence of Organic Bases

  • Julie Meimoun,
  • Audrey Favrelle-Huret,
  • Julien De Winter,
  • Philippe Zinck

DOI
https://doi.org/10.3390/macromol2020016
Journal volume & issue
Vol. 2, no. 2
pp. 236 – 246

Abstract

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Organocatalysis for polymer chemistry has become a subject of significant interest in the last two decades. In this contribution, we have studied the evolution of the microstructure of poly(L-lactide) in solution in toluene at 105 °C in the presence of various organocatalysts. Weak bases such as triethylamine and DMAP (4-dimethylaminopyridine) lead to a low extent of epimerization and a chain scission reaction. The DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) amidine induces in turn important extents of both epimerization (up to 37% D-stereoisomer formation) and chain scission. This has been tentatively attributed to a nucleophilic mechanism. Cinchona alkaloids lead to only a modest amount of epimerization. Phosphazene bases are in turn rather active, especially for high catalytic loadings (>1 mol %). The chain scission observed in this case is proposed to occur via a base-catalyzed hydrolysis mechanism. Finally, it is shown that combining an organic base with an acid can lead to a synergistic effect regarding notably the chain scission reaction.

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