Dielectric experiments are carried out on poly(4-phenoxyphenyl acrylate) (PPOA) and 4-phenoxyphenyl- 2,4-dimethylglutarate (PPODG), a low-molecular-weight analogue of PPOA. The intramolecular dipolar correlation coefficient gintra for the polymer changes from 0.821 at 30°C to 0.835 at 60°C. This coefficient is similar to that of PPODG (0.817 at 30°C), suggesting that the asymptotic value of gintra is reached for rather low molecular weights. The dipolar correlation coefficient g that accounts for both the intramolecular and intermolecular dipolar interactions is smaller than gintra for both the polymer and the low-molecularweight compound. The dielectric spectrum of PPOA in the bulk presents a prominent glass-rubber relaxation followed by a subglass absorption that seems to be the combination of a process in the high-temperature zone (named fl) that overlaps with the glass-rubber relaxation and a well developed absorption (named y) in the low-temperature region. This latter process can be explained in terms of motions of the dipole associated with the C"'-O-C ar bonds whereas motions about the C=-C*O * bonds may also intervene in the fl process. The low-molecular-weight compound only exhibits a prominent glass-liquid absorption followed by a diffuse and weak subglass relaxation; this behaviour cannot be explained in terms of only intramolecular interactions, and therefore intermolecular interactions must play an important role in this process. The mechanical and the dielectric glass-rubber relaxations are interpreted in terms of the coupling scheme. This study suggests that the complexities of both processes are similar, in contrast with what occurs in many other systems.
Посилання на статтю:
Relaxation behaviour and dipolar correlations for polyacrylate-based polymers with aromatic side groups / Ricardo Diaz-Calleja and Evaristo Riande* and Julio San Rombn // Polymer. – 1993. – Vol 34. – P. 3456-3463.