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Poly(lactic acid) (PLA) is a readily available, compostable biobased polyester with high strength and toughness, and it is excellent for 3D printing applications. Polymer blending is an economic and easy way to improve its properties, such as its slow degradation and crystallization rates and its small elongation, and thus, make it more versatile. In this work, the effects of different 2,5-furan dicarboxylic acid (FDCA)-based polyesters on the physicochemical and mechanical properties of PLA were studied. Poly(butylene furan 2,5-dicarboxylate) (PBF) and its copolymers with poly(butylene adipate) (PBAd) were synthesized in various comonomer ratios and were blended with 70 wt% PLA using melt compounding. The thermal, morphological and mechanical properties of the blends are investigated. All blends were immiscible, and the presence of the dispersed phases improved the crystallization ability of PLA. Mechanical testing revealed the plasticization of PLA after blending, and a small but measurable mass loss after burying in soil for 7 months. Reactive blending was evaluated as a compatibilizer-free method to improve miscibility, and it was found that when the thermal stability of the blend components allowed it, some transesterification reactions occurred between the PLA matrix and the FDCA-based dispersed phase after 20 min at 250 °C.

Poly(hexylene 2,5 furan-dicarboxylate) (PHF) is a relatively new biobased polyester prepared from renewable resources, which is targeted for use in food packaging applications, owing to its great mechanical and gas barrier performance. Since both properties are strongly connected to crystallinity, the latter is enhanced here by the in situ introduction in PHF of graphene nanoplatelets and fumed silica nanoparticles, as well as mixtures of both, at low amounts. For this investigation, we employed Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), X-ray diffraction (XRD) and dielectric spectroscopy (BDS). The fillers were found to improve crystallization in both the rate (increasing T c ) and fraction (CF), which was rationalized via the concept of fillers acting as crystallization agents. This action was found stronger in the case of graphene as compared to silica. BDS allowed the detection of local and segmental dynamics, in particular in PHF for the first time. The glass transition dynamics in both BDS (α relaxation) and DSC ( T g ) are mainly dominated by the relatively high CF, whereas in the PHF filled uniquely with silica strong spatial confinement effects due to crystals were revealed. Finally, all samples demonstrated the segmental-like dynamics above T g , which screens the global chain dynamics (normal mode).

Polyesters based on 2,5-furandicarboxylic acid (FDCA) are a new class of biobased polymers with enormous interest, both from a scientific and industrial perspective. The commercialization of these polymers is imminent as the pressure for a sustainable economy grows, and extensive worldwide research currently takes place on developing cost-competitive, renewable plastics. The most prevalent method for imparting these polymers with new properties is copolymerization, as many studies have been published over the last few years. This present review aims to summarize the trends in the synthesis of FDCA-based copolymers and to investigate the effectiveness of this approach in transforming them to a more versatile class of materials that could potentially be appropriate for a number of high-end and conventional applications.

In the field of polymer chemistry, tremendous efforts have been made over the lastdecade to replace petrochemical monomers with building blocks from renewable resources. In thisrespect, itaconic acid has been used as an alternative to acrylic acid or maleic acid in unsaturatedpolyesters for thermal or UV-curing applications. However, examples of poly(ester amide)s fromitaconic acid are scarce. Under standard polycondensation reactions, the presence of free aminesleads to aza-Michael addition reactions at the α,β-unsaturated double bond of the itaconic acid andisomerization reactions to mesaconic acid. Both reactions make the resulting materials useless asUV-curing polymer resins. To avoid these undesired side reactions, we herein report the use ofpreformed, well-defined diols containing internal amide bonds. The resulting unsaturatedpoly(ester amide) resins were analyzed before and after UV-induced crosslinking. Viscositymeasurements revealed a strong thixotropic behavior induced by the amide groups, which isusually not detected in structurally similar polyester resins.

Plastics are perceived as modern and versatile materials, but their use is linked to numerous environmental issues as their production is based on finite raw materials (petroleum or natural gas). Additionally, their low biodegradability results in the accumulation of microplastics. As a result, there is extensive interest in the production of new, environmentally friendly, bio-based and biodegradable polymers. In this context, poly(ethylene vanillate) (PEV) has a great potential as a potentially bio-based alternative to poly(ethylene terephthalate); however, it has not yet been extensively studied. In the present work, the preparation of PEV is reported. The enthalpy and the entropy of fusion of the pure crystalline PEV have been estimated for the first time. Additionally, the equilibrium melting temperature has also been calculated. Furthermore, the isothermal and non-isothermal crystallization behavior are reported in detail, and new insights on the thermal stability and degradation mechanism of PEV are given.

Poly(propylene 2,5-furan dicarboxylate) (PPF), or poly(trimethylene 2,5-furan dicarboxylate) (PTF), is a biobased alipharomatic polyester that is expected to replace its fossil-based terephthalate (PPT) and naphthate (PPN) homologues. PPF possesses exceptional gas barrier properties, but its slow crystallization rate might affect its success in specific applications in the future. Therefore, a series of PPF based nanocomposites with the nanoclays Cloisite ® -Na (MMT), Cloisite ® -20A (MMT 20A), and halloysite nanotubes (HNT) were synthesized via the in situ transterification and polycondensation method. The effect of the nanoclays on the structure, thermal, and crystallization properties of PPF was studied with several methods including infrared spectroscopy (IR), Nuclear Resonance Spectroscopy (¹H-NMR), Wide Angle X-ray Diffraction (WAXD), Thermogravimetric Analysis (TGA), and Differential Scanning Calorimetry (DSC). The insertion of the nanofillers in the polymer matrix altered the crystallization rates, and TGA results showed good thermal stability, since no significant mass loss occurred up to 300 °C. Finally, the degradation mechanism was studied in depth with Pyrolysis-Gas Chromatography/Mass Spectroscopy, and it was found that β-scission is the dominant degradation mechanism.