Steric hindrance ligand strategy to aluminum porphyrin catalyst for completely alternative copolymerization of CO2 and propylene oxide

Aluminum porphyrin complexes are heavy-metal-free and soil-tolerant green catalysts for the copolymerization of CO2 and propylene oxide (PO), but they suffer from relatively poor poly(propylene carbonate) (PPC) selectivity. Herein, steric hindrance porphyrin ligand was used to enhance the PPC selectivity. Typically, a bulky anthracene-like group was incorporated into the porphyrin ring to form 5,10,15,20-tetra(1,2,3,4,5,6,7,8-octahydro-1,4:5,8-dimethanoanthracen-9-yl)porphyrin, the aluminum porphyrin complex with this ligand, in combination with bis(triphenylphosphine)iminium chloride as a co-catalyst, produced completely alternate PPC. Additionally, the obtained PPC showed high regioselectivity, with a head-to-tail linkage content (HT) of 92%. Therefore, we demonstrated that introduction of bulky steric ligand into the porphyrin ring could reduce the propylene oxide homopolymerization activity leading to excellent PPC selectivity, and improve regioselectivity for the PO ring-opening during the copolymerization.