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In this paper, we report the separations of large, neutral, synthetic polymers using primarily a nonaqueous mobile phase without the use of a supporting electrolyte. The size- exclusion-based mechanism for separation was achieved on sulfonated polystyrene/divinylbenzene stationary phases. The effect of water, voltage, stationary phase exchange capacity, and pore size were investigated. The stationary phase and solvent interactions were studied by attenuated total reflectance Fourier transform infrared spectroscopy (ATR FT-IR) and a possible mechanism for the generation of EOF in the THF/water system is provided. Linear calibration curves were obtained for polystyrenes ranging in MW from 5K to 2M, for columns made using a combination of high capacity ion exchanger and a neutral polystyrene/divinylbenzene material of varied pore sizes. Analysis of polyurethane, polystyrene, and other polymer samples using CEC correlated well with results obtained by conventional HPLC. The size exclusion CEC separations provide an alternative mode for determining the relative molecular weights of polymers, with reduced solvent consumption.

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