Convenient Controlled Aqueous C1 Synthesis of Long-Chain Aliphatic AB, AA, and BB Macromonomers for the Synthesis of Polyesters with Tunable Hydrocarbon Chain Segments

The insertion of long hydrocarbon chains between ester groups in polyester allows for introduction and modulation of crystallinity, which can result in enhanced performance approaching high-density polyethylene. We report a convenient synthesis of building blocks for long-chain aliphatic polyesters via an aqueous C1 polymerization. The macromonomers include ω-hydroxyacid esters, α,ω-diols and α,ω-diacids. The length of hydrocarbon chain segment (C20–C60) can be controlled by the ratio of monomer/initiator in the C1 polymerization. The obtained polyesters from condensation of the long-chain ω-hydroxyacid esters have thermal and mechanical properties indistinguishable from related materials derived from biomass.