Ring-Opening Co- and Terpolymerization of Epoxides, Cyclic Anhydrides, and l‑Lactide Using Constrained Aluminum Inden Complexes

Seven constrained aluminum inden complexes having different substituents and diamine backbones were developed for the ring-opening copolymerization (ROCOP) of epoxides and bulky cyclic anhydrides giving alternating polyesters with T g ranging from 49 to 226 °C. Among several catalyst/cocatalyst scre...

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Bibliographic Details
Published in:Inorganic chemistry 2022-12, Vol.61 (50), p.20616-20628
Main Authors: Laiwattanapaisarn, Nattiya, Virachotikul, Arnut, Chumsaeng, Phongnarin, Jaenjai, Tiphanan, Phomphrai, Khamphee
Format: Article
Language:English
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Summary:Seven constrained aluminum inden complexes having different substituents and diamine backbones were developed for the ring-opening copolymerization (ROCOP) of epoxides and bulky cyclic anhydrides giving alternating polyesters with T g ranging from 49 to 226 °C. Among several catalyst/cocatalyst screenings, the aluminum inden complex having a rigid phenylene backbone coupled with 4-dimethylaminopyridine showed the best performance giving linear polyesters. In the case of cyclohexene oxide (CHO) and succinic anhydride (SA), the linear poly­(CHO-alt-SA) could be transformed to cyclic polymer when the polymerization was left under prolonged reaction time to induce intramolecular transesterification. The kinetic studies of the ROCOP revealed a zeroth-order dependence on cyclic anhydride and a first-order dependence on epoxide and the catalyst. The catalysts can be extended efficiently to the one-pot CHO/PA/l-lactide terpolymerization giving uncommon tapered copolymers of poly­(CHO-alt-PA) and PLA via switchable polymerization.
ISSN:0020-1669
1520-510X
DOI:10.1021/acs.inorgchem.2c03532