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Hybrid molecular dynamics/Monte Carlo simulations used to study melts ofunentangled, thermoreversibly associating supramolecular polymers. In thisfirst of a series of papers, we describe and validate a model that is effectivein separating the effects of thermodynamics and chemical kinetics on thedynamics and mechanics of these systems, and is extensible to arbitrarilynonequilibrium situations and nonlinear mechanical properties. We examine themodel's quiescent (and heterogeneous) dynamics, nonequilibrium chemicaldynamics, and mechanical properties. Many of our results may be understood interms of the crossover from diffusion-limited to kinetically-limited stickybond recombination, which both influences and is influenced by polymer physics,i. e. the connectivity of the parent chains.

Thermoreversible Associating Polymer Networks: I. Interplay of Thermodynamics, Chemical Kinetics, and Polymer Physics