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Furanoate polyesters are emerging as promising bioderived polymers that could replace petrochemical-derived polyesters in several applications, for example, the textile field. Here, sustainable and fully bioderived fibers are wet-spun by blending poly(lactic acid) (PLA) and poly(pentamethylene 2,5-furanoate) (PPeF), with up to 50 wt% of PPeF. PLA/PPeF blends result as immiscible, with PPeF domains homogeneously distributed within the PLA matrix, as shown by scanning electron micrographs. The immiscibility is confirmed by differential scanning calorimetry, as the glass transition temperature of PLA is unaffected by PPeF. The immiscibility and poor adhesion between PLA and PPeF are responsible for the decrease in stress at break and elongation at break from 30.1MPa and 127%, of PLA fibers, to 3.5MPa and 1.9%, at high PPeF amounts. However, the addition of PPeF strongly decreases the PLA's tendency to absorb water and retain the processing solvents, showing a mass loss decrease from 3.1% for PLA fibers to 1% for fibers containing 50 wt% PPeF, thereby addressing one of the main drawbacks of PLA. These results, although preliminary, offer new directions for future works on innovative and sustainable fibers based on furanoate polyesters.

The effect of presence of up to 30 mol% diethylene 2,6‐naphthalate (DEN) constitutional defects on the crystallization kinetics and morphology of poly(butylene 2,6‐naphthalate) (PBN) was investigated by differential scanning calorimetry, fast scanning chip calorimetry, polarized‐light optical microscopy, and wide‐angle X‐ray scattering (WAXS). The results indicate that the crystallization behavior of butylene/DEN random copolymers [P(B xDE yN)] is analogous to the PBN homopolymer: at low supercooling direct crystallization from the melt occurs, while at lower crystallization temperature/higher cooling rates, the formation of a liquid crystalline phase precedes the development of the ultimately stable crystal, confirming the validity of Ostwald's rule of stages also for random copolymers. However, the incorporation of DEN counits into the polymer chains retards both crystal and liquid‐crystal formation proportionally to the DEN content. WAXS analysis suggests the exclusion of DEN counits from PBN crystals. Thus, the lower crystallization rate in the copolymers can be associated, with the filtering of crystallizable chain segments at the crystal growth front.