Are Well Performing Catalysts for the Ring Opening Polymerization of l-Lactide under Mild Laboratory Conditions Suitable for the Industrial Process? The Case of New Highly Active Zn(II) Catalysts

Poly(lactic acid) (PLA) is one of the best candidates as a sustainable plastic material for a circular economy, being biodegradable, bio-based, recyclable, and displaying good thermal and mechanical properties. The industrial production of PLA is mainly based on the ring opening polymerization (ROP) of l-lactide (l-LA) promoted by tin(II) 2-ethylhexanoate [Sn(Oct)2] in a continuous solvent-free process operating at temperatures between 180 and 200 °C, above the melting point of the resulting isotactic polymer. Despite the huge efforts in the research of alternative catalysts based on less toxic metals, resulting in a plethora of highly active catalysts under laboratory mild conditions, very few candidates can compete with Sn(Oct)2 under industrially relevant conditions. We report a family of new Zn(II) complexes, bearing variously substituted monoanionic [N,O-] (imidazole[1,5-a]pyrid-3-yl)phenolate ligands, as catalysts for the ROP of l-LA under both mild (20 °C, solvent) and industrially relevant (190 °C, in the melt, technical grade unpurified monomer, very low catalyst loading) conditions. Interestingly, the best performing catalyst under mild conditions is the worst performing under harsh conditions, and, on the contrary, the less active catalysts under mild conditions compete well with Sn(Oct)2 under industrially relevant conditions. Kinetic and DFT mechanistic investigations shed light on the non-trivial role of the 2-pyridine substituent in the catalytic performances at different temperatures. Preliminary depolymerization tests on commercial PLLA samples suggested that the new catalysts can also be a suitable candidate for the chemical recycling of PLA under mild conditions.