Semi-empirical molecular orbital calculations and dielectric measurements have been conducted on DPE and DPK molecules and on PEEK films containing these molecular units. The calculations were performed using a modified-CNDO/2 method allowing us to take into account the van der Waals impenetrability zone of the electronic corona of the aromatic rings. From the analysis of the relative energy maps, it is shown, amongst other things, that the most probable route for a molecule to move is through gear rotations. The DPE molecule is also found to move more easily than the DPK molecule. Measurements of the dielectric permittivity and of the refractive index were not possible for the DPE molecule in benzene solution due to its low dipole moment, this being confirmed by theoretical calculations. For the DPK molecule, an experimental mean value of 3.15 D is found for m compared to a calculated value of 3.35 D. The analysis of the dissipation factor isochronal curves shows that the activation energy for the DPK molecule is largely dependent on its concentration in benzene. In the case of PEEK, two relaxations are seen at ¹ 106°C and ¹ 73°C for a frequency of 1 kHz. A parallel is drawn between isolated molecules of DPK in solution and DPK units that are distant from each other in a polymer chain, and between aggregated molecules of DPK in solution and DPK units that are close together in entangled chains. It is finally shown that the DPK molecular unit in a macromolecular chain is only able to reach the permitted conformations in low energy valleys, corresponding to gear rotation motions.
Посилання на статтю:
Semi-empirical calculations and dielectric spectrometry of molecular units in PEEK / Sabine Verot, Pierre Battesti, Gérard Perrier // Polymer. – 1999. – N 40. – P. 2605–2617.