High-Throughput Approach in the Ring-Opening Polymerization of β‑Butyrolactone Enables Rapid Evaluation of Yttrium Salan Catalysts

Poly(3-hydroxybutyrate) (PHB) is a material produced naturally by bacteria but is also chemically accessible via ring-opening polymerization (ROP) of β-butyrolactone (β-BL). In ROP, catalyst design plays a key role in the production of PHB with different stereomicrostructures, i.e., syndiotactic, isotactic, or atactic PHB. In this work, we demonstrate a simple procedure for generating the catalysts in situ by conveniently combining a suitable yttrium precursor with the respective salan pro-ligand. This approach circumvents the elaborate isolation of the catalyst and enables the high-throughput screening of a library of yttrium salan catalysts for the ROP of β-BL. Electronic and steric influences of the ligand framework on stereoselectivity and activity of the catalyst as well as limitations could be determined, and structure–property relationships were established. Depending on the substitution pattern, these in situ-generated catalysts produced syndiotactic-enriched, isotactic-enriched, or atactic PHB with high activity