Schiff‐Base Aluminum Complexes as Bifunctional Catalysts for the Selective Ring‐Opening Co‐Polymerization of Cyclohexene Oxide and Succinic Anhydride

The ring‐opening copolymerization (ROCOP) of epoxides and cyclic anhydrides is emerging as a powerful method for the synthesis of polyesters with innovative structures and properties. In this work, a series of dialkyl‐aluminum complexes stabilized by Schiff‐base ligands with different functional sid...

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Bibliographic Details
Published in:ChemCatChem 2024-09, Vol.16 (17), p.n/a
Main Authors: Russo, Simona, Isnard, Florence, Costabile, Chiara, Lamberti, Marina, Mazzeo, Mina
Format: Article
Language:English
Subjects:
Aluminum
anhydride
Anhydrides
Catalysts
Chemical synthesis
Copolymerization
Cyclohexene
epoxide
Ligands
NMR
Nuclear magnetic resonance
Phosphines
Polyester resins
polyesters
Ring opening polymerization
Schiff bases
Selectivity
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Summary:The ring‐opening copolymerization (ROCOP) of epoxides and cyclic anhydrides is emerging as a powerful method for the synthesis of polyesters with innovative structures and properties. In this work, a series of dialkyl‐aluminum complexes stabilized by Schiff‐base ligands with different functional side arms (pyridine, amine, or phosphine) and different substituents on the phenoxy moieties have been synthetized and tested as catalysts in the ROCOP of cyclohexene oxide (CHO) and succinic anhydride (SA). The selectivity of the catalysts in the ROCOP was significatively depending on the nature of the pendant arm and/ or of the substituents of the ligand framework. The complexes designed to have a dynamic coordination sphere in which the side arms simulate the role of a neutral cocatalyst favored the desired selectivity, giving poly(CHO‐alt‐SA) with narrow dispersity and negligible ether linkage. NMR investigations and DFT calculations rationalized the observed behavior. Simple bifunctional aluminum catalysts for the ring opening polymerization of cyclohexene oxide and succinic anhydride are described. Their selectivity in promoting an alternated copolymerization of the two monomers is depending on the hemilabile behavior of the nitrogen neutral donor of the pyridine pendant arm: the introduction of electron donating substituents on the phenoxy rings of the ancillary ligand promotes a complete selectivity.
ISSN:1867-3880
1867-3899
DOI:10.1002/cctc.202400508