Influence of cross-linking on the segmental dynamics in model polymer networks

In an attempt to study the specific influence of cross-linking on the alpha relaxation in polymer networks, a series of model heterocyclic polymer net works (HPN) with well-defined cross-link densities and constant concentrati on of dipolar units were studied. Model HPN systems were prepared by simult aneous trimerization of 1,6-hexamethylene diisocyanate (HMDI) and hexyl iso cyanate (HI). These HPN systems were characterized by dielectric relaxation spectroscopy in the 10(-1) Hz < F < 10(5) Hz frequency range and in the 12 3 K < T < 493 K temperature interval. The alpha relaxation in these systems depends on network density and shifts toward higher temperatures as the cr oss-link density increases for high HMDI/HI ratios. Discussion of the alpha -relaxation shape in light of recent models indicates that segmental motion s above the glass transition systematically experience a growing hindrance with increasing degree of cross-linking. Description of the temperature dep endence of relaxation times according to the strong-fragile scheme clearly shows that fragility increases as polymer network develops. (C) 2000 Americ an Institute of Physics. [S0021-9606(00)50724-7].