Size‐exclusion chromatography (SEC) is a standard technique for determining molar mass averages and molar mass distributions (MMDs) of polymers. Sometimes the termsgel permeation chromatography (GPC) or gel filtration chromatography (GFC) are also used, but SEC should be preferred, because this term describes the mechanism much better: polymer molecules are separated according to their hydrodynamic volumes (which can be correlated with molar mass), with the larger size molecules exiting first followed by the smaller. Molar masses are determined either from a calibration or using molar mass sensitive detectors. In the case of copolymers, the knowledge of chemical composition along the MMD is required, which can be obtained from combinations of different concentration detectors. As the hydrodynamic volumes of different polymers are typically somewhat different, molecules with different chemical composition and different molar mass will be eluted in the same slice of the chromatogram. Obviously, a discrimination between such molecules requires a two‐dimensional separation, in which one dimension may be SEC, and the other one a chromatographic technique, which separates according to chemical composition rather than molar mass, such as liquid adsorption chromatography (LAC), liquid chromatography at the critical point of adsorption (often also called liquid chromatography under critical conditions, LCCC), supercritical fluid chromatography (SFC), temperature rising elution fractionation (TREF), etc.
In the lower molar mass range, mass spectroscopy competes with SEC. The most frequently used technique is matrix‐assisted laser desorption/ionization time‐of‐flight mass spectroscopy (MALDI/TOF/MS), which cannot, however, provide quantitatively accurate MMDs. Due to its excellent resolution in molar mass, it can be combined with chromatographic techniques in order to increase the reliability of the analysis.
