Polymer sequence control is emerging as a novel strategy to control polymer properties. In this sense, we seek to develop high performance polymers with an emphasis on sequence-controlled regio- and stereo-configurations. Assisted by catalyst and monomer design, a series of regio- and stereoselective ring-opening polymerizations were achieved with high sequence fidelity. With the specific sequence design, the resulting polymers exhibit enhanced properties compared to their non-sequence-controlled analogues. The regioselective ring-opening polymerization (ROP) of methyl glycolide was fulfilled by a chiral aluminum alkoxide catalyst. The resulting alternating poly(lactic-<i>co</i>-glycolic acid) exhibits a uniform hydrolytic degradation profile, which is a promising candidate for controlled release drug carrier with predictable and constant drug concentration. Another stereospecific polyester was synthesized from ring-opening copolymerization (ROCOP) of chiral epoxide and cyclic anhydride. An achiral aluminum alkoxide catalyst can realize the regioselective ring-opening at the less hindered site for both monomers, thus retaining the chiral centers and regioregularity. A semicrystalline polymer and stereocomplex was only formed with a certain sequence of stereo configuration. The resulting polymer has an enhanced melting temperature relative to polymers with all other sequences.

Regio- and stereoselective ring-opening polymerization for the synthesis of sequence-controlled polyesters with enhanced properties

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