Poly(glycidyl methacrylate-<i>co</i>-ethylene glycol dimethacrylate) Monolith with Dual Porosity for Size Exclusion Chromatography

The use of polymeric monoliths as stationary phases for liquid chromatography has been limited, despite their ability to enhance the convection flow of the mobile phase with respect to particulate-based columns. This is due to a poor balance between the volume of flow through pores and the number of active sites within polymeric monoliths. In this paper, we present the obtainment of poly(glycidyl methacrylate-<i>co</i>-ethylene glycol dimethacrylate) (P(GMA-<i>co</i>-EDMA)) monoliths with dual pore size distributions (with pore sizes of 60 and 550 nm). Hierarchical pore size distributions were achieved by performing the monolith synthesis by reversible addition-fragmentation chain transfer (RAFT) polymerization as well as using ternary porogen mixtures (containing PEG, dodecanol, and dioxane). While the controlled polymerization mechanism promoted mesopores in the monolith, ternary porogen mixtures allowed the formation of macropores. The monoliths obtained were used as stationary phases for size exclusion chromatography (SEC) for the separation of poly(methyl methacrylate) standards with molar masses between 2.50 × 10³ and 3.06 × 10⁶ g/mol, allowing selectivities that were comparable with commercially available SEC columns packed with porous particles. We believe the approach presented in this work could be the first step toward the obtainment of stationary phases for SEC with enhanced accessibility of exclusion pores. Monolithic columns with accessible porous structures can be beneficial for size-based separations of ultrahigh molar mass analytes with low diffusion coefficients.