Tacticity Control of Cyclic Poly(3-Thiobutyrate) Prepared by Ring-Opening Polymerization of Racemic beta-Thiobutyrolactone

Hui Li (1) , Jerome Ollivier (1) , Sophie M. Guillaume (1) , Jean-François Carpentier (1)

1 ISCR - Institut des Sciences Chimiques de Rennes

We report here on the ring-opening polymerization (ROP) of racemic beta-thiobutyrolactone (rac-TBL), as the first chemical synthesis of poly(3-thiobutyrolactone) (P3TB), the thioester analogue of the ubiquitous poly(3-hydroxybutyrate) (P3HB). The ROP reactions proceed very fast (TOF >12 000 h(-1) at r.t.) in the presence of various metal-based catalysts. Remarkably, catalyst systems based on non-chiral yttrium complexes stabilized by tetradentate amino alkoxy- or diamino-bis(phenolate) ligands {ONXOR1,R2}(2-) (X=O, N) provide access to cyclic P3TB with either high isoselectivity (P-m up to 0.90) or high syndiotactic bias (P-r up to 0.70). The stereoselectivity can be controlled by manipulation of the substituents on the ligand platform and adequate choice of the reaction solvent and temperature as well. The cyclic polymer topology is evidenced by MALDI-ToF MS, NMR and TGA. Highly isotactic cyclic P3TB is a semi-crystalline material as revealed by DSC.

Mots clés: Cyclic Polymers; Polythioester; Ring-Opening Polymerization; Stereoselective Catalysis; Yttrium; beta-Thiolactone

Domaines: Chimie

Hui Li, Jerome Ollivier, Sophie M. Guillaume, Jean-François Carpentier. Tacticity Control of Cyclic Poly(3-Thiobutyrate) Prepared by Ring-Opening Polymerization of Racemic beta-Thiobutyrolactone. Angewandte Chemie International Edition, 2022, 61 (21), pp.e202202386. ⟨10.1002/anie.202202386⟩. ⟨hal-03630997⟩