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

TL;DR

This paper introduces a simulation model for thermoreversible associating polymer networks that effectively separates thermodynamic and kinetic effects, providing insights into their dynamics and mechanical behavior.

Contribution

It presents and validates a novel simulation model capable of analyzing thermodynamics, kinetics, and polymer physics interactions in associating polymer systems.

Findings

Crossover from diffusion-limited to kinetically-limited bond recombination influences dynamics.

Model accurately captures nonequilibrium and nonlinear mechanical properties.

Polymer connectivity affects bond dynamics and material behavior.

Abstract

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