Preparation of Porous Poly(Styrene-Divinylbenzene) Microspheres and Their Modification with Diazoresin for Mix-Mode HPLC Separations.

By using the two-step activated swelling method, monodisperse porous poly(styrene-divinylbenzene) (P(S-DVB)) microparticles were successfully synthesized. The influence of porogens, swelling temperatures and crosslinking agents on the porosity of porous microparticles was carefully investigated. Porous P(S-DVB) microparticles were used as a packing material for high performance liquid chromatography (HPLC). Several benzene analogues were effectively separated in a stainless-steel column as short as 75 mm due to the high specific surface area of the porous microparticles. Porous P(S-DVB) microparticles were further sulfonated and subsequently modified with diazoresin (DR) via electrostatic self-assembly and UV (ultraviolet) radiation. After treatment with UV light, the ionic bonding between sulfonated P(S-DVB) and DR was converted into covalent bonding through a unique photochemistry reaction of DR. Depending on the chemical structure of DR and mobile phase composition, the DR-modified P(S-DVB) stationary phase performed different separation mechanisms, including reversed phase (RP) and hydrophilic interactions. Therefore, baseline separations of benzene analogues and organic acids were achieved by using the DR-modified P(S-DVB) particles as packing materials in HPLC. According to the π-π interactional difference between carbon rings of fullerenes and benzene rings of DR, C60 and C70 were also well separated in the HPLC column packed with DR-modified P(S-DVB) particles.