Abstract
Activation energies of local conformational transitions in polymers were investigated by the fluorescence depolarization method. The mean relaxation time related to the local conformational transitions was measured for dilute solutions of the anthracene-labeled polystyrene (PS), and anthracene-labeled poly(α-methylstyrene) (PαMS) in various solvents. The obtained data were successfully analyzed by use of the generalized formula of Helfand based on the reaction rate theory of Kramers. The results showed that the activation energy is larger in poor solvents than in good solvents which reflects the chain expansion effect. It is clear that the apparent activation energy is influenced by two types of polymer-solvent interactions, i.e., the frictional interaction (short-range interaction) and the chain expansion effect (long range interaction), and that the former can also be evaluated roughly by the present analysis.
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