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In the present paper, four fully biobased homopolyesters of 2,5-furandicarboxylic acid (2,5-FDCA) with a high molecular weight have been successfully synthesized by two-stage melt polycondensation, starting from the dimethyl ester of 2,5-FDCA and glycols of different lengths (the number of methylene groups ranged from 3 to 6). The synthesized polyesters have been first subjected to an accurate molecular characterization by NMR and gel-permeation chromatography. Afterward, the samples have been successfully processed into free-standing thin films (thickness comprised between 150 to 180 μm) by compression molding. Such films have been characterized from the structural (by wide-angle X-ray scattering and small-angle X-ray scattering), thermal (by differential scanning calorimetry and thermogravimetric analysis), mechanical (by tensile test), and gas barrier (by permeability measurements) point of view. The glycol subunit length was revealed to be the key parameter in determining the kind and fraction of ordered phases developed by the sample during compression molding and subsequent cooling. After storage at room temperature for one month, only the homopolymers containing the glycol subunit with an even number of −CH 2 – groups (poly(butylene 2,5-furanoate) (PBF) and poly(hexamethylene 2,5-furanoate) (PHF)) were able to develop a three-dimensional ordered crystalline phase in addition to the amorphous one, the other two appearing completely amorphous (poly(propylene 2,5-furanoate (PPF) and poly(pentamethylene 2,5-furanoate) (PPeF)). From X-ray scattering experiments using synchrotron radiation, it was possible to evidence a third phase characterized by a lower degree of order (one- or two-dimensional), called a mesophase, in all the samples under study, its fraction being strictly related to the glycol subunit length: PPeF was found to be the sample with the highest fraction of mesophase followed by PHF. Such a mesophase, together with the amorphous and the eventually present crystalline phase, significantly impacted the mechanical and barrier properties, these last being particularly outstanding for PPeF, the polyester with the highest fraction of mesophase among those synthesized in the present work.

Article title: Evidence of a 2D-ordered structure in biobased poly(pentamethylene furanoate) responsible for its outstanding barrier and mechanical properties 5 Pages 6 Figures S2 Figure S1. dP vs. time for O 2 Figure S2. dP vs. time for CO 2 Sample Data Sample No. Order No. Sample Type Sample Name Received Tested by Request°C % Rel. Humidity Pre-conditioning Hrs.°C % Rel. Humidity Room Conditions Test Temperature°C mm³ Volume Device Number cm³/min % Rel. Humidity Gas Stream cm² Layer Sample Area Mask Test Gas Solubility cm³/cm³ bar Diff. Coeff.

The melting behavior and the isothermal crystallization kinetics of linear and randomly branched poly(buty1ene terephthalate)a) (PBT) samples were investigated by differential scanning calorimetry. The multiple endotherms typical of linear PBT were observed also in branched samples and were found to be influenced both by temperature and degree of branching. The isothermal crystallization kinetic constants, obtained applying Avrami's treatment, were analysed on the basis of Hoffman's secondary nucleation theory. A decrease in the crystallization rate was observed as the content of branching units increased. This result was correlated to surface effects: the product of the surface free energies me was found to increase with the ramification content. As far as the nucleation process is concerned, the induction time was determined for all the samples at different crystallization temperatures, and the results suggested that in the presence of branching points the nucleation process is favoured.

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