A Tube Model of Rubber Elasticity

Polymer entanglements lead to complicated topological constraints and interactions between neighbouring chains in a dense solution or melt. Entanglements can be treated in a mean field approach, within the famous reptation model, since they effectively confine each individual chain in a tube-like geometry. In polymer networks, due to crosslinks preventing the reptation constraint release, entanglements acquire a different topological meaning and have a much stronger effect on the resulting mechanical response. We apply the classical ideas of reptation dynamics to calculate the effective rubber-elastic free energy of an entangled rubbery network. We then compare the results with other theoretical approaches and establish a particularly close mapping with the hoop-model, with equally good description of experimental data. The present consistent reptation theory allows further development of dynamic theory of stress relaxation.