The entropy of the rotational conformations of (poly)isoprene molecules and its relationship to rubber elasticity and temperature increase for moderate tensile or compressive strains

Abstract

Molecular networks comprised of crosslinked cis-1,4 polyisoprene, often referred to as "natural rubber," are one of the most common systems for the study of rubber elasticity. Under moderate tensile or compressive strain, network chains begin to assume straighter paths, as local molecular kinks are removed. Isoprene units along the chain backbone are mechanically forced from their equilibrium distributions of 18 possible rotational states into a smaller subset of states, restricted to more linear conformations with the greatest end-to-end distances. There are two consequences to this change: both the configurational entropy and average internal energy decrease. We find that the change in entropy, and resulting change in free energy, gives rise to an elastic force. We derive an expression for a chain extension force constant that we have incorporated in an explicit, three-dimensional meso-scale network simulation code. Using this force model, our simulations predict a macroscopic stress-strain relationship that closely matches published experimental values. We also predict a slight increase in temperature resulting from the change in average internal energy in the affected isoprene units that is consistent with experiments.