Abstract
Diffusional changes during the radical bulk polymerization of styrene with and without cross-linker were investigated. Full correlation fluorescence correlation spectroscopy (fcFCS) allowed for the simultaneous detection of rotational and translational diffusion of single fluorescent perylene diimide probes. Small probes show a parallel decrease of both motions whereas for larger probes translation slows down faster than rotation. The latter behavior contradicts the relationship between the Stokes−Einstein and the Stokes−Einstein−Debye equation and is attributed to changes in the microviscosity and mesh size effects of the synthesized polymer chains. The introduction of permanent cross-links results in additional restrictions for translational diffusion whereas rotation is not significantly affected up to high monomer-to-polymer conversions.
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