Synthesis of Semicrystalline Long Chain Aliphatic Polyesters by ADMET Copolymerization of Dianhydro-D-glucityl bis(undec-10-enoate) with 1,9-Decadiene and Tandem Hydrogenation

Acyclic diene metathesis (ADMET) copolymerization of dianhydro-D-glucityl bis(undec-10-enoate) (M1) with 1,9-decadiene (DCD) using ruthenium-carbene catalyst, RuCl2(IMesH2)(CH-2-OiPr-C6H4) [IMesH2 = 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene, HG2], afforded unsaturated polyesters (Mn = 9300–23,400) under the optimized conditions. Subsequent tandem hydrogenation (H2 1.0 MPa, 50 °C) with the addition of a small amount of Al2O3 resulted in the saturated polymers having a melting temperature of 71.7–107.6 °C, depending on the molar ratio of M1 and DCD.

Sequence-regulated vinyl polymers via iterative atom transfer radical additions and acyclic diene metathesis polymerization

Iterative ATRAs and ADMET polymerization enabled the synthesis of sequence-regulated vinyl polymers without statistical distribution of monomer compositions and sequences.