Influence of Weak Attractive Interactions on Structures and Properties of Poly(trimethylene terephthalate)

Abstract

Conformational analysis of poly(trimethylene terephthalate) (PTT) has been carried out by the refined rotational isomeric state (RIS) scheme with ab initio molecular orbital (MO) calculations for a model compound, trimethylene glycol dibenzoate (TMGDB). Bond conformations of the O−CH2−CH2−CH2−O part of TMGDB were determined from 1H and 13C NMR experiments for unlabeled and 13C-labeled TMGDBs. The MO calculations exactly reproduced not only the experimental bond conformations but also the dipole moment and molar Kerr constant observed from TMGDB dissolved in nonpolar solvents. Comparison of the MO calculations with and without electron correlations revealed that a variety of intramolecular attractions, such as π−π interactions, electrostatic attractions, dipole−dipole interactions, and C═O···H−C and C−O···H−C close contacts, are formed in TMGDB and considerably stabilize its folding conformers with g±g∓ sequences in the central CH2−CH2 bonds. The folding conformers may be sources of dimer fluorescence char...