Fatty Acid–Derived Aliphatic Long Chain Polyethers by a Combination of Catalytic Ester Reduction and ADMET or Thiol‐Ene Polymerization

Aliphatic long-chain polyesters are a common class of renewable polymers and can be obtained by various synthetic routes, most notably from renewable fatty acids. In contrast, for aliphatic long chain polyethers only a few examples are known. Recently, the GaBr3-catalyzed reduction of esters to ethers has been introduced as convenient post-polymerization modification to obtain polyethers directly from polyesters. Here, this reduction is applied to synthesize fatty acid-based omega,omega '-unsaturated diene diether monomers, which are polymerized afterward by thiol-ene or acyclic diene metathesis (ADMET) polymerizations in the "green" solvents methyl-THF (2-methyltetrahydrofuran) and polarclean. After polymerization, the thiol-ene or ADMET polymers are modified by either oxidation or hydrogenation, respectively.