Journal of Chemical Physics, Vol.104, No.16, 6343-6347, 1996
Tricritical Points in Bimodal Polymer-Solutions
The tricritical point of polymer solutions composed by two polymer homologs of different molecular weight in a solvent is studied using the single-chain mean-field theory. The tricritical point is found for a ratio of molecular weights of the two polymers r=N-1/N-2, which decreases as a function of the short chain length N-2 from 51 to approximately 40 for N-2 increasing from 1 to 8. This last value is still much larger than the experimentally measured value for mixtures of polystyrene in cyclohexane, where it was found that r similar or equal to 25. Although a further reduction of r as a function of N-2 seems likely, the chain lengths of the corresponding long chains are beyond the reliability limit of the SAW’s simulation involved. The addition of a small effective repulsion between the polymer homologs, is found to bring down the predicted value to 25.
Keywords:QUASI-BINARY MIXTURES;3-PHASE COEXISTENCE CURVE;ETHANE SYSTEMS;POLYSTYRENE;CYCLOHEXANE;METHYLCYCLOHEXANE;HOMOPOLYMERS;SEPARATION;BEHAVIOR