Statistical mechanics of temporary polymer networks I. The equilibrium theory

In part I of this work (the present article) the equilibrium state of temporary polymer networks is treated in the framework of thermodynamics and statistical mechanics. The network is described as an open system. Thereby we use a modified spring-bead model in which the beads represent junctions that decay and reform thus adding a viscous component to the assumed elastic behaviour of the permanent network. The relevant statistical equation — analogous to Liouville's equation — is solved. The grand-canonical probability density function and two of three equations of state are derived. Explicit formulae are given for several relevant probabilities. For instance the probabilityw (z)dz that a network chain connecting two junctions has a contour length betweenz andz +dz is given by the Wien type formulaw(z) =A z ³ exp {–B z} whereA andB do not depend onz.