Supramolecular polymers, which are non-covalently bonded and formed by self
association of di or trifunctional monomers exhibit, by virtue of quadrupl
e hydrogen bonds, many of the properties of normal high molecular weight po
lymers, e.g a dynamic rubber plateau. We focus on the molecular and coopera
tive dynamics of self-assembled linear polymers and networks, studied by br
oadband dielectric relaxation spectroscopy (DRs) in the frequency range fro
m 10(-2) to 10(6) Hz. The Das analysis was backed up by dynamic mechanical
and theological experiments. In the high temperature region two loss proces
ses (alpha and alpha*) show up, the relaxation times of which obey the Voge
l-Fulcher-Tammann (VFT) law. The dielectric cu process is related to the dy
namic glass-rubber transition and is slightly faster than the corresponding
mechanical or process. A slower (high-temperature) alpha* relaxation is id
entified as chemical corresponding to the mean lifetime of the hydrogen bon
ded linkages in the supramolecular chains. Its relaxation time tau (alpha*)
was found to be 1 to 2 decades larger than the terminal now relaxation tim
e, indicating that the relaxation of an entire chain is dominated by the jo
int dynamics of many hydrogen bonds. The beta relaxation, observed in both
Das and dynamic mechanical analysis (DMA) at temperatures below T-g, arises
from the local junction dynamics of hydrogen bonded units in the glassy st
ate. Details of the temperature dependence and the shape of the loss peaks
of the alpha and alpha* relaxations will be discussed in terms of temporary
physical networks and cooperativity.