Effect of monomer mixture composition on structure and chromatographic properties of poly(divinylbenzene-co-ethylvinylbenzene-co-2-hydroxyethyl methacrylate) monolithic rod columns for separation of small molecules

Porous poly(divinylbenzene-co-ethylvinylbenzene-co-2-hydroxyethyl methacrylate) monoliths were synthesized via thermally initiated free-radical polymerization in confines of surface-vinylized glass columns (150 mm × 3 mm i.d.) and applied to the reversed-phase separation of low-molecular-weight aromatic compounds. In order to compensate for the polymer shrinkage during the synthesis and prevent the monolith from detachment from the column wall, polymerization was conducted under nitrogen pressure. The reaction proceeded at 60 °C for 22 h. 2,2′-Azo-bis-isobutironitrile was used as the initiator and 1-dodecanol was used as the porogen. A series of monoliths with different monomer ratios were obtained. All the monoliths had high specific surface areas ranging from 370 to 490 m2/g. In the studied range of monomer mixture compositions, the mechanical stability of the stationary phase in water/acetonitrile eluents was found to be high enough and practically insensitive to the fraction of 2-hydroxyethyl methacrylate (HEMA). Increasing the molar fraction of HEMA from 10.5% to 14.7% resulted in the decrease of column permeability by two orders of magnitude (from 1.1 × 10−12 to 1.8 × 10−14 m2) and led to weaker retention of alkylbenzenes. The higher HEMA content was shown to reduce the plate height of the columns in the separation of small molecules from 160–490 μm to 40–76 μm. This was attributed mainly to the decrease of the domain size of the monoliths leading to lower eddy dispersion and mass transfer resistance in the column.