Journal of Chemical Physics, Vol.113, No.1, 447-452, 2000
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 networks (HPN) with well-defined cross-link densities and constant concentration of dipolar units were studied. Model HPN systems were prepared by simultaneous trimerization of 1,6-hexamethylene diisocyanate (HMDI) and hexyl isocyanate (HI). These HPN systems were characterized by dielectric relaxation spectroscopy in the 10(-1) Hz < F < 10(5) Hz frequency range and in the 123 K < T < 493 K temperature interval. The alpha relaxation in these systems depends on network density and shifts toward higher temperatures as the cross-link density increases for high HMDI/HI ratios. Discussion of the alpha-relaxation shape in light of recent models indicates that segmental motions above the glass transition systematically experience a growing hindrance with increasing degree of cross-linking. Description of the temperature dependence of relaxation times according to the strong-fragile scheme clearly shows that fragility increases as polymer network develops.