Solvent effects on model telechelic polymers

A theory to predict the competition between intermolecular and intramolecul ar hydrogen bonding is extended to mixtures and applied to a model telechel ic mixture. The theory is tested by comparing with simulation results for a mixture of fully flexible linear chains that can associate in a hydrogen b onding solvent. The simulation model for the telechelic is a flexible linea r tetramer hard sphere chain with two hydrogen bonding sites, one on each t erminal segment. The solvent is modelled as a hard sphere with four tetrahe drally arranged hydrogen bonding sites. The solvent is seen to affect the a bility of the solute to bond intermolecularly and intramolecularly. The ext ent of hydrogen bonding and thermodynamic properties of the system were stu died using Monte Carlo simulation and compared with predictions from a new statistical mechanics based theory for mixtures. Agreement of simulation an d theory is good over the range of densities, temperatures and compositions studied.