Non-equilibrium particle morphology in dispersion-polymerized polystyrene particles

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Abstract
The interior particle morphology of dispersion-polymerized polystyrene particles was investigated by freeze fracture TEM (FFTEM) in order to compare the morphology of particles formed under two extreme mechanistic conditions: (a) particle growth by scavenging of dead polymer chains formed in solution (which gives rise to large particles of 5–10 μm) and (b) particle growth by oligomeric radical capture and polymerization inside the particle (giving rise to small particles of 1 μm or less). Although not generally recognized in the literature, ascribing mechanistic significance to an observed morphology requires a demonstration that the morphology is of the non-equilibrium type, i.e., the morphology depends upon how the particle was formed. An equilibrium morphology, by definition, must be independent of the particle formation route, and therefore carries no mechanistic information. In this case, large PS particles of 6.5 μm were found to have a nodular morphology that was unchanged on heating well above Tg, indicating an equilibrium structure (the nodularity of amorphous polymers is briefly rationalized by comparison with literature results over the past 20 years). On the other hand, small PS particles of 1.3 μm had a pronounced radial structure that could be converted into the nodular morphology by the same heat treatment, or by dissolving and precipitating from a suitable solvent combination. This means that the small particles have a non-equilibrium morphology, from which we may attempt to draw mechanistic inferences consistent with the suspected growth mechanism. Keywords: dispersion-polymerized polystyrene, non-equilibrium polystyrene particle morphology, freeze fracture transmission electron microscopy.