Abstract
A thorough vibrational spectroscopy and molecular modeling study on poly(ethylene 2,5-furandicarboxylate) (PEF) explores its conformational preferences, in the amorphous and crystalline regions, while clarifying structure–property correlations. Despite the increasing relevance of PEF as a sustainable polymer, some of its unique characteristics are not yet fully understood and benefit from a deeper comprehension of its microstructure and intermolecular bonding. Results show that in the amorphous domains, where intermolecular interactions are weak, PEF chains favor a helical conformation. Prior to crystallization, polymeric chains undergo internal rotations extending their shape in a zigzag pattern—an energetically unfavorable geometry which is stabilized by C–H···O bonds among adjacent chain segments. The zigzag conformation is the crystalline motif present in the α and β PEF polymorphs. The energy difference among the amorphous and crystalline chains of PEF is higher than in PET poly(ethylene terephthalat...
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