Xylose-Based Polyethers and Polyesters Via ADMET Polymerization toward Polyethylene-Like Materials

One of the challenges developing bioderived polymers is to obtain materials with competitive properties. This study investigates structure-properties relationships polyesters and polyethers that can be derived from d-xylose through metathesis polymerization, in order produce plastic are sourced sustainable feedstocks whose properties compete those polyolefins such as polyethylene. Bicyclic diol 1,2-O-isopropylidene-α-d-xylofuranose was coupled ω-unsaturated fatty acids alcohols different chain lengths (C11, C5, C3), resulting α,ω-unsaturated esters ethers polymerized via an acyclic diene (ADMET) polymerization using a commercial Grubbs second-generation catalyst, obtaining Mn up 63.0 kg mol–1. Glass transition temperatures (Tg) decreased linearly increasing length were lower for (−32 14 °C) compared (−14 45 °C). ADMET could modified postpolymerization by reacting their internal carbon–carbon double bonds. Thiol–ene reaction methyl thioglycolate lowered Tg while allowing insertion additional functional groups. Alkene hydrogenation turned polyester polyether C20 hydrocarbon linkers into semicrystalline Tm ≈ 50 °C. The latter, when cast films, displayed remarkable polyethylene-like Hot-pressed films proved ductile (Young modulus Ey 60–110 MPa, elongation at break εb 670–1000%, ultimate tensile strength σb 8–10 MPa), uniaxially oriented very strong yet flexible (Ey 190–200 160–350%, 43–66 MPa). Gas barrier comparable polyolefins. Polyethers resistant hydrolysis, depolymerized under alkaline conditions.