Determination of the degree of swelling and crosslinking of extremely small polymer gel quantities by analytical ultracentrifugation

The degree of crosslinking of very small amounts of polymer gel, encountered in the characterization of the molecular structure of rubber polymers or of polymers in powder form, cannot be determined satisfactorily by measurement of elasticity or conventional swelling. Therefore a method has been developed which enables us to determine the degree of crosslinking of such polymer systems reliably. This method is based on the measurement of equilibrium swelling by sedimentation in the analytical ultracentrifuge. The degree of swelling can either be used directly as a relative measure of the average degree of crosslinking or as basis for calculating the average degree of polymerization of the molecule chains between two crosslink sites according to the theory of Flory and Rehner. The efficiency of the method is demonstrated by several examples of application (differently crosslinked polybutadienes, gel portions of various polychloroprenes and polyurethane foams).Dedicated to Dr. Gerhard Fritz on the occasion of his 60th birthday.