Lattice cluster theory of associating telechelic polymers. III. Order parameter and average degree of self-assembly, transition temperature, and specific heat.

The lattice cluster theory of strongly interacting, structured polymer fluids is applied to determine the thermodynamic properties of solutions of telechelic polymers that may associate through bifunctional end groups. Hence, this model represents a significant albeit natural extension of a diverse array of prior popular equilibrium polymerization models in which structureless "bead" monomers associate into chain-like clusters under equilibrium conditions. In particular, the thermodynamic description of the self-assembly of linear telechelic chains in small molecule solvents (initiated in Paper II) is systematically extended through calculations of the order parameter Φ and average degree of self-assembly, the self-assembly transition temperature T(p), and the specific heat C(V) of solutions of telechelic molecules. Special focus is placed on examining how molecular and thermodynamic parameters, such as the solution composition φ, temperature T, microscopic interaction energies (ε(s) and ε), and length M of individual telechelic chains, influence the computed thermodynamic quantities that are commonly used to characterize self-assembling systems.