Influence of different polymerisation parameters on the separation efficiency of monolithic poly(phenyl acrylate-co-1,4-phenylene diacrylate) capillary columns

Monolithic poly(phenyl acrylate-co-1,4-phenylene diacrylate) (PA/PDA) capillary columns were prepared in the confines of 200 μm I.D. fused silica capillaries by thermally initiated free radical copolymerisation of phenyl acrylate (PA) and 1,4-phenylene diacrylate (PDA) in the presence of α,α′-azoisobutyronitrile (AIBN). Variation of polymerisation parameters in terms of total monomer to porogen ratio, nature of the pore-forming agent and polymerisation temperature is shown to have a significant impact on the porous properties of the supports, which was proven by inverse size-exclusion chromatography (ISEC). Monoliths of significantly different porosity (total porosity accessible to the mobile phase (ɛT) = 0.66–0.71, volume fraction of pores (ɛP) = 0.15–0.24) and hence permeability could easily be prepared. The chromatographic efficiency of the PA/PDA monoliths regarding protein and oligonucleotide separation was studied. A correlation between porosity, retention behaviour and efficiency was derived from the obtained separations. In addition to chromatographic evaluation, pressure drop versus flow rate measurements confirmed mechanical stability. Swelling propensity (SP) factors of 0.47–0.87, moreover, indicated a high degree of crosslinking.