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

We report here on the ring-opening polymerization (ROP) of racemic β-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 (Pm up to 0.90) or high syndiotactic bias (Pr 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.