Besides maximizing packing efficiency, molecular interactions
also
play an indispensable role upon conformational ordering for crystallization
of long-chain polymers. Herein, structural evolution upon heating
of biobased poly(butylene 2,5-furandicarboxylate) (PBF) is followed
by temperature-dependent infrared (IR) spectroscopy and wide-angle
X-ray diffraction (WAXD) to elucidate the molecular interactions and
conformational preference in its crystalline state. By estimating
the group distances according to atomic coordinates of its crystal
structure, the stronger intermolecular interaction than the van der
Waals force is speculated to exist in crystalline PBF, which is fully
confirmed by the changes of IR absorptions associated with C–H
and CO groups upon heating as an abnormal C–H···OC
hydrogen bonding. The combination of temperature-dependent C–H
band position and crystal lattice expanding supports a good thermostability
of this interaction up to melting, fully defining its nature as strong
hydrogen bonding rather than the generally reported weak H···OC
bonding in biodegradable polyesters. By further analyzing the confirmational
ordering in its crystalline state, it is believed that such intermolecular
C–H···OC hydrogen bonding stabilizes
the energetically inaccessible syn–syn conformer
of 2,5-furandicarboxylic moieties for PBF crystallization.