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We present hybrid molecular dynamics/Monte Carlo simulations of supramolecular networks formed by unentangled telechelic chains with sticky end monomers (or stickers) of finite functionality. The reversible bonding between sticky monomers leads to the formation of sticker clusters with well-defined size distribution, which in turn work as cross-links for transient polymer networks. We study the kinetics of sticky monomer association, the topological structure, and the resulting dynamic and rheological behavior of the supramolecular systems as a function of the sticker bonding energy e and the parent polymer chain length. Percolated transient networks are formed above a threshold bonding energy around 4.3kBT. At high bonding energies e ≥ 10kBT, the majority of the stickers are fully reacted and the fraction of open stickers is less than 1%. The conventional picture of a single sticker hopping from one cluster to another is energetically unfavorable. We find the dynamic and rheological behavior of such stro...

Dynamics in Supramolecular Polymer Networks Formed by Associating Telechelic Chains