Enthalpy assisted size exclusion chromatography. Part 2. Adsorption retention mechanism

A novel high performance liquid chromatographic method for separation of synthetic polymers has been tested. It involves combination of the enthalpic and entropic retention mechanisms, resulting in increased selectivity of separation within a specific molar mass range. In this present case, the enthalpic retention mechanism is adsorption of macromolecules on a bare silica gel column packing. Under critical conditions of enthalpic interactions, homopolymers are known to elute irrespective of their molar mass. However, in the vicinity of critical conditions, a situation can be identified when retention volumes (V(R)) rapidly decrease with increasing molar mass. Typically, this happens for polymer species close to or above their exclusion limit observed with the same column in the absence of enthalpic interactions between macromolecules and packing, that is near "ideal SEC" conditions. The dependence of polymer retention volume on molar mass closely resembles size exclusion conditions. However, the witnessed rate of change in V(R )with polymer molar mass is more pronounced, thus indicating increased selectivity of separation. This situation not only offers the benefit of more selective separation according to molar mass but efficient discrimination of macromolecules possessing different nature and interactivity with the column packing can be accomplished as well.