Dynamics of Entangled Linear Supramolecular Chains with Sticky Side Groups: Influence of Hindered Fluctuations

The design and effective application of supramolecular transient polymer networks based on the assembly of entangled polymer building blocks requires not only precise description of relaxation mechanisms of the chain segments but also inclusion of the kinetics of reversible formation and breakage of reversible supramolecular interactions. In this work we extend the tube-based time marching algorithm to the entangled associative polymers with sticky side groups, with special emphasis on the effect of hindered fluctuations, besides sticky Rouse and sticky reptation. Two different approaches are introduced for inclusion of hindered fluctuations comprising fluctuations with extra penalty for deeper segments and stepwise fluctuations by extra friction. It is shown that there is a transition zone in dynamic moduli between the characteristic lifetime of the stickers and emergence of the final relaxation slopes, which can be characterized by almost parallel drop of loss and storage moduli with slope of 0.5 that can be assigned to hindered fluctuations alongside the blinking of stickers. Theoretical guidelines are drawn for practical application of the model by inclusion of secondary association of sticky groups in clusters with longer lifetimes.