Switch Catalysis To Deliver Multi‐Block Polyesters from Mixtures of Propene Oxide, Lactide, and Phthalic Anhydride

Switchable polymerisation catalysis enables block polymer sequence selectivity from monomer mixtures, resulting in the formation of multiblock polyesters. The aluminium salphen catalyst switches between two different polymerisation mechanisms and selectively enchains mixtures of commercially available monomers: lactide, phthalic anhydride, and propene oxide. Sequential monomer mixture additions yield multi‐block polyesters featuring 3, 7, 11, 15, 19, 23, and 27 blocks. The unparalleled catalytic selectivity can be used to access completely new multi‐block polyesters relevant for future applications.