Segmental and Normal Mode Relaxation of Poly(alkylene oxide)s Studied by Dielectric Spectroscopy and Rheology

A series of poly(alkylene oxide)s (PAO’s) with different lengths of the side chains and two different molecular weights were studied by means of differential scanning calorimetry, dielectric spectroscopy (BDS), and rheology. The glass transition temperatures are almost independent of molar mass and the length of the side chains, which is also reflected by the dielectric α-relaxation, which depends only slightly on the different samples. However, the corresponding maxima in the dielectric loss of the samples with longer side chains show a shoulder at high frequencies with a temperature-dependent shape. The shape of the normal mode changes slightly with the molar mass and the length of the side chain. The normal mode relaxation times show a molar-mass-dependent behavior indicating a significant increase of the entanglement molecular weight M e with increasing length of the side group. A Rouse mode analysis incorporating the molar mass distribution was performed but could not reproduce the experimental data of the normal mode process completely. The relaxation times obtained by rheology agree well with the dielectric results, and estimates of M e based on the number of entanglements and on the packing model confirm the values suggested by BDS. A comparison of the estimated chain dimensions with literature data supports the reliability of our calculations.