Issue 32, 2024

Calcium-catalysed ring-opening copolymerisation of epoxides and cyclic anhydrides

Abstract

Novel dinuclear calcium complexes have been employed as bifunctional catalysts for the ring-opening copolymerisation reaction of epoxides and cyclic anhydrides. The catalysts exhibited good performance and quantitative formation of ester linkages for the poly(CHO-alt-PA) production under mild reaction conditions and in the absence of a cocatalyst. Furthermore, these catalysts demonstrated tolerance to a variety of bio-sourced epoxides/phthalic anhydrides, providing access to a range of potentially functionalisable polyesters. On the other, polymerisation kinetic analyses revealed a half-order dependence on catalyst concentration and first-order dependence on cyclic anhydride concentration, whilst MALDI-ToF analyses supported an initiation step involving the ring-opening of the epoxide. Taken together, these findings underpin a mononuclear pathway, with the ring-opening of the cyclic anhydride identified as the rate-limiting step in the process.

Graphical abstract: Calcium-catalysed ring-opening copolymerisation of epoxides and cyclic anhydrides

Supplementary files

Article information

Article type
Paper
Submitted
08 Apr 2024
Accepted
06 Jul 2024
First published
23 Jul 2024

Polym. Chem., 2024,15, 3238-3245

Calcium-catalysed ring-opening copolymerisation of epoxides and cyclic anhydrides

E. Francés-Poveda, M. Martínez de Sarasa Buchaca, C. Moya-López, I. J. Vitorica-Yrezabal, I. López-Solera, J. A. Castro-Osma, F. D. la Cruz-Martínez and A. Lara-Sánchez, Polym. Chem., 2024, 15, 3238 DOI: 10.1039/D4PY00379A

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