RESUMO
The chain and association dynamics of supramolecular polymer ensembles decisively determines their properties. Using neutron spin echo (NSE) spectroscopy we present molecular insight into the space and time evolution of this dynamics. Studying a well characterized ensemble of linearly associating telechelic poly(ethylene glycol) melts carrying triple H-bonding end groups, we show that H-bond breaking significantly impacts the mode spectrum of the associates. The breaking affects the mode contributions and not the relaxation times as was assumed previously. NSE spectra directly reveal the so far intangible H-bond lifetimes in the supramolecular melt and demonstrate that for both the microscopic and the macroscopic dynamics of the supramolecular ensemble the instantaneous average of the M_{w} distribution governs the system response at least as long as the Rouse picture applies.
RESUMO
Controlling the mechanical behavior of novel supramolecular materials is of the utmost importance and requires a fundamental understanding of the underlying physical processes. We present a multimethods approach to the dynamics of entangled transient polyisoprene networks. Small-angle neutron scattering (SANS) on randomly functionalized chains shows homogeneous supramolecular melts with Gaussian chain conformations. The H-bond lifetimes (dielectric α*-process) and the rheological response in terms of the loss modulus Gâ³ differ by 2 orders of magnitude in time. Within the concept of a compact random walk (RW), where the random walker (urazole group acting as a sticker) undergoes multiple returns to its starting point and following the concept of theoretical proposed renormalized sticky bond lifetimes, we quantitatively solve this longstanding and unexplained large discrepancy: While the bond opening gives rise to the dielectric response, for rheological relaxation the association with a new partner is relevant. This takes place only after multiple returns to the original binding partner.