Abstract

The determination of molar mass (MM) data for polydisperse polymers by SEC/MALDI involves the fractionation of samples through analytical size exclusion chromatography (SEC). Selected SEC fractions are then analyzed by matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) and the mass spectra of these nearly monodisperse samples allow the determination of the average molar masses. The SEC/MALDI procedure has now been applied to two polycarbonate samples, PC1 and PC2. The results show that the MALDI spectra of the SEC fractions allow not only the detection of linear and cyclic oligomers contained in these samples, but also the simultaneous determination of their average molar masses. Two slightly differing SEC calibration plots were obtained, due to the smaller hydrodynamic volume of the polycarbonate cyclic chains with respect to the linear ones. In agreement with theory, the ratio (M(cycle)/M(linear))(Ve) at a fixed elution volume was found to be 1.22, independent of the molar mass values. Copyright 1999 John Wiley & Sons, Ltd.

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