The challenging task of characterizing polydisperse polymer mixtures possessing ultrahigh molecular weight (MW) polymers and microgels in organic solvents is addressed with thermal field-flow fractionation (ThFFF) and multiangle light scattering-differential refractive index (MALS-dRI) detection. In initial experiments, a 350,000 g/mol poly(methyl methacrylate) (PMMA) standard is used to evaluate the effects of temperature gradient and temperature gradient programming on the measurements. dRI baseline fluctuations caused by temperature programming were minimized by using a mobile phase heater to thermostat connecting tubing. ThFFF-MALS-dRI is then used to separate and characterize a complex polyvinyl acetate (PVAc) sample containing ultrahigh MW polymers and microgels. The open channel design employed by ThFFF allowed the PVAc sample to be analyzed with minimal sample preparation. Unfiltered PVAc sample showed components with MWs close to 10(9) g/mol and root mean square radius r(rms) values approaching 400 nm. The same sample, filtered through a 0.5 microm pore-size membrane, yielded a MW that was at least one order of magnitude lower. These results demonstrated that the common practice of prefiltering polymer samples prior to analysis can lead to erroneously low average MWs and polydispersities. The accuracy of MW and r(rms) calculated using standard light scattering equations developed for small scattering molecules and relatively high wavelengths is also examined.
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