Alternating Sequence Control for Poly(ester amide)s by Organocatalyzed Ring-Opening Polymerization.

Sequence-controlled polymerization is the forefront of polymer chemistry. Herein, the feasibility of sequence regulation by using organocatalyzed ring-opening polymerization (ROP) is demonstrated. In particular, ring expansion strategy is employed to synthesize pre-organized monomers 1 and 2.

Hyperbranched Aliphatic Polyester via Cross-Metathesis Polymerization: Synthesis and Postpolymerization Modification.

A novel postpolymerization modification methodology is demonstrated to achieve selective functionalization of hyperbranched polymer (HBP). Terminal and internal acrylates of HBP derived from cross-metathesis polymerization (CMP) are functionalized in a chemoselective fashion using the thiol-Michael chemistries. Model reactions between different thiols (benzyl mercaptan and methyl thioglycolate) and acrylates (n-hexyl acrylate and ethyl trans-2-decenoate) by using dimethylphenylphosphine or amylamine as the catalyst are investigated to optimize the modification protocol for HBP.

Precision Aliphatic Polyesters with Alternating Microstructures via Cross-Metathesis Polymerization: An Event of Sequence Control.

Sequence-regulated polymerization is realized upon sequential cross-metathesis polymerization (CMP) and exhaustive hydrogenation to afford precision aliphatic polyesters with alternating sequences. This strategy is particularly suitable for the arrangement of well-known monomer units including glycolic acid, lactic acid, and caprolactic acid on polymer chain in a predetermined sequence. First of all, structurally asymmetric monomers bearing acrylate and α-olefin terminuses are generated in an efficient and straightforward fashion.