Abstract
Polystyrene chains having an anthryl group in the middle of its back bone (PSAPS), whose degrees of polymerization are 3200, 2500, and 730, were used to detect orientational relaxation of polymer segments. In order to explain the power law behavior of fluorescence anisotropy decay curves of PSAPS chain, it was assumed that the orientational relaxation of segments is caused by the reaction between segments and solvent molecules. Further the distribution of interval time between relaxation phenomena was considered. According to above two assumptions, a hyperbolic function r(t)∼r0(t/τeff)−β have been derived as an orientational auto-correlation function. We propose the “intermittent process” of polymer segments as one of the probable description for the orientational relaxation process of polystyrene back bone. The hyperbolic exponent β is related to the characteristic activation energy Ea of a polymer segment. The value of Ea=7 kJ mol−1 for polystyrene chain evaluated by β is in good agreement with hitherto reported values. Effective relaxation time τeff corresponds to the minimum reaction radii ξ0 between a segment and a solvent molecule, i.e., the diffusivity of solvent molecules. Temperature dependence of ξ0 is consistent with that of the reciprocal of solvent viscosity.
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Tsunomori, F., Ushiki, H. & Horie, K. Polymer Chain Dynamics. II. Intermittent Process of Orientational Relaxation of Polystyrene Main Chain. Polym J 28, 582–587 (1996). https://doi.org/10.1295/polymj.28.582
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DOI: https://doi.org/10.1295/polymj.28.582
