New use of size exclusion chromatography in kinetics of mechanical degradation of polymers in solution

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Abstract
A new method to investigate the mechanical degradation of polymers in solution is described that uses size exclusion chromatograms of the initial polymer and of the degraded sample. The incipient parts of these chromatograms are analyzed to obtain kinetic data about degradation at the level of infinitesimal fractions. The procedure is based on the fact that mechanical degradation of the polymers is a first‐order reaction and macromolecules are cleaved mostly in their central region. The rate constant and the variation in the rate constant with molecular weight are determined in a single experiment, avoiding additional fractionation steps. Moreover, the slope of the size exclusion chromatographic calibration curve is derived, opening new ways to determine polydispersities or even to make rapid calibration for unknown polymers. To verify the method, the rate constant and the molecular weight dependence of the rate constant were determined for the sonic degradation of polystyrene in toluene. The rate constant is found to vary with the square of the molecular weight, and its value is in good agreement with results reported using much more laborious methods. © 1993 John Wiley & Sons, Inc.

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