Highly Active Chiral Zinc Catalysts for Immortal Polymerization of β-Butyrolactone Form Melt Processable Syndio-Rich Poly(hydroxybutyrate)

Highly crystalline poly(hydroxybutyrate) suffers from high melting point and entanglement molecular weight. This leads to low melt strength, limits processing through regular techniques, and precludes many applications. In this work we report a series of racemic and enantiopure zinc catalysts supported by variously substituted diaminophenolate ancillary ligands which form high melt strength PHBs with different molecular weights and microstructure. These complexes are active for the highly controlled polymerization of beta-butyrolactone (BBL); some can polymerize 2000 equiv of BBL in less than 30 min. Changing the steric bulk of the ligand forms PHBs of varied syndiotacticity (P-r = 0.7.5 to 0.5.5). These are highly robust systems capable of polymerizing an unprecedented 20000 equiv of BBL in the presence of 5000 equiv of benzyl alcohol. Therrnorheological investigations reveal that the synthesized PHBs have surprisingly high melt strength at above the melting point. For processable PHBs, high density of entanglements and relatively low crystallinity are crucial. We show that the best PHBs should have high molecular weight and moderate syndiotacticity.