Characterization of non‐homogeneous polymers with size‐exclusion chromatography by implementing an on‐line viscometer

The viscosity distribution of a polymer sample can be obtained by using an on-line viscometer as a detector in size-exclusion chromatography. This newly defined viscosity distribution is closely related to the molecular weight distribution and expresses weight fraction times intrinsic viscosity of species i as a function of the corresponding molecular weight times intrinsic viscosity (wi[ηi] vs. Mi[ηi]). The intrinsic viscosity ([η]) and number-average molecular weight (Mn) can be obtained directly from a viscosity distribution. If the Mark-Houwink exponent a is known (or approximately known) for non-homogeneous polymer the Mw/Mn can be estimated from the viscosity distribution when the molecular weight distribution is approximated with a known distribution function. These estimates are independent of any other detector and are valid even for non-homogeneous polymer samples. The relation between the moments of the viscosity distribution and the Mw/Mn is presented for two widely used distribution functions, the Log-Normal and the Generalized Exponential Distributions. Polymer characterization based on the viscosity distribution is shown to be a robust technique. It is particularly attractive in characterizing non-homogeneous polymers since it is solely obtained from on-line viscometer.