Characterization of Polymers by GPC-Lalls. I. Computer Simulation of Fractionation of Branched Polymers by GPC
Abstract Simulation formulae are derived for determining polymer structure in an infinitesimal fraction of GPC elution volume. If a sample is ideally fractionated, the MWD of the momentarily eluted polymer depends chiefly on the DNBP of the injected sample. Statistically branched polymer indicates almost monodisperse MWD at the fraction. Separation is always sharper in the higher molecular weight side of a MWD curve than is in the lower side. Even if the DNBP is broader, the average NBP can be correctly estimated by the method proposed by Kurata et al., as far as the DNBP is nearly Gaussian. When a sample is fractionated by a real GPC with axial dispersion, the MWD of the eluted polymer is mainly controlled by the instrumental spreading function, unless the sample has an extremely wide DNBP or a special MWD. The average NBP by the Kurata et al. equations is expected to be more reliable if a polydisperse linear polymer that yields chromatogram similar to the branched sample is applied as a reference material.