Intending to expand the thermo-physical properties of bio-based polymers, furan-based thermoplastic polyesters were synthesized following the melt polycondensation method. The resulting polymers, namely, poly(ethylene 2,5-furandicarboxylate) (PEF), poly(propylene 2,5-furandicarboxylate) (PPF), poly(butylene 2,5-furandicarboxylate) (PBF) and poly(1,4-cyclohexanedimethylene 2,5-furandicarboxylate) (PCHDMF) are used in blends together with various polymers of industrial importance, including poly(ethylene terephthalate) (PET), poly(ethylene 2,6-naphthalate) (PEN), poly(L-lactic acid) (PLA) and polycarbonate (PC). The blends are studied concerning their miscibility, crystallization and solid-state characteristics by using wide-angle X-ray diffractometry (WAXD), differential scanning calorimetry (DSC) and polarized light microscopy (PLM). PEF blends show in general dual glass transitions in the DSC heating traces for the melt quenched samples. Only PPF–PEF blends show a single glass transition and a single melt phase in PLM. PPF forms immiscible blends except with PEF and PBF. PBF forms miscible blends with PCHDMF and PPF, whereas all other blends show dual glass transitions in DSC and phase separation in PLM. PCHDMF–PEF and PEN–PEF blends show two glass transition temperatures, but they shift to intermediate temperature values depending on the composition, indicating some partial miscibility of the polymer pairs.

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Poly(butylene 2,5-furandicarboxylate) (PBF) constitutes a new engineering polyester produced from renewable resources, as it is synthesized from 2,5-furandicarboxylic acid (2,5-FDCA) and 1,4-butanediol (1,4-BD), both formed from sugars coming from biomass. In this research, initially high-molecular-weight PBF was synthesized by applying the melt polycondensation method and using the dimethylester of FDCA as the monomer. Furthermore, five different series of PBF blends were prepared, namely poly(l-lactic acid)–poly(butylene 2,5-furandicarboxylate) (PLA–PBF), poly(ethylene terephthalate)–poly(butylene 2,5-furandicarboxylate) (PET–PBF), poly(propylene terephthalate)–poly(butylene 2,5-furandicarboxylate) (PPT–PBF), poly(butylene 2,6-naphthalenedicarboxylate)-poly(butylene 2,5-furandicarboxylate) (PBN–PBF), and polycarbonate–poly(butylene 2,5-furandicarboxylate) (PC–PBF), by dissolving the polyesters in a trifluoroacetic acid/chloroform mixture (1/4 v/v) followed by coprecipitation as a result of adding the solutions into excess of cold methanol. The wide-angle X-ray diffraction (WAXD) patterns of the as-prepared blends showed that mixtures of crystals of the blend components were formed, except for PC which did not crystallize. In general, a lower degree of crystallinity was observed at intermediate compositions. The differential scanning calorimetry (DSC) heating scans for the melt-quenched samples proved homogeneity in the case of PET–PBF blends. In the remaining cases, the blend components showed distinct Tgs. In PPT–PBF blends, there was a shift of the Tgs to intermediate values, showing some partial miscibility. Reactive blending proved to improve compatibility of the PBN–PBF blends.

Three samples of biobased poly(ethylene 2,5furandicarboxylate) (PEF) with various molecular weights (MWs) were synthesized. Their crystallization was studied by using differential scanning calorimetry (DSC), modulated temperature DSC (MDSC), wide-angle X-ray diffractometry (WAXD), and polarized light microscopy (PLM). The rates of isothermal crystallization from the melt decreased with increasing MW. One up to three melting endotherms were observed in DSC heating thermograms of samples crystallized isothermally. This behavior was interpreted in the context of recrystallization/reorganization phenomena. Recrystallization and multiple melting were associated with low stability samples crystallized at low crystallization temperatures (T c 's) and with low molecular weight. However, the multiple melting of PEF crystallized after self-nucleation was attributed to a dual morphology. As PEF crystallized slowly, its melt crystallization on cooling at 15 different slow rates ranging from 0.1 to 5.0 °C/min was studied, while the crystallization from the glass was investigated upon heating at 15 different rates from 0.25 to 10 °C/min. A large amount of the collected data was treated using various models. But most importantly, critical observations were made by combining all the available raw data and results from different techniques and methods, allowing for better understanding of the crystallization and melting of thermoplastics under various conditions. The limitations of the experimental techniques and data treatments were evaluated.

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