Improved chemical recyclability of 2,5-furandicarboxylate polyesters enabled by acid-sensitive spirocyclic ketal units

Abstract

Incorporating hydrolytically sensitive functional groups into polymer backbones provides a feasible strategy to trigger their degradation to the starting monomers, thus enabling chemical recycling of the material. Here, we present two series of copolyesters in which a biobased spirocyclic ketal-functional diester monomer was incorporated into poly(butylene 2,5-furandicarboxylate) (PBLF) and poly(hexamethylene 2,5-furandicarboxylate) (PHLF), respectively. A two-step melt polycondensation resulted in copolyesters with moderate to high molecular weights, as confirmed by intrinsic viscosity and size exclusion chromatography data. Thermogravimetric analysis showed a thermal stability up to 275 °C, and increasing char yields upon incorporation of the spirocyclic monomer. The crystallinity and melting points of the copolyesters decreased with an increasing content of the spirocyclic ketal units in the backbone. Copolyesters containing up to 15% of the spiro-ketal units were semicrystalline, while those containing 20 and 50% spiro-ketal units were completely amorphous. The hydrolytic degradation of copolyesters from the PHLF series was investigated using 3–12 M aq. HCl, and were found to degrade faster than the corresponding homopolyesters. Acid-catalyzed cleavage of the randomly distributed spiro ketal units promoted the rapid fragmentation of the polymer chain into small oligomers, which were subsequently hydrolyzed to the original chemical building blocks. The ketone-terminated telechelic oligomers obtained after the degradation of spirocyclic ketal units were also investigated in a direct polymerization with pentaerythritol. The initial results implied that the oligomers can be re-polymerized into the original polymer. Hence, this work demonstrated a feasible pathway towards chemically recyclable 2,5-furandicarboxylate polyesters with a tuneable degree of crystallinity.