Recent advance in synthesis of monodisperse porous poly(styrene-divinylbenzene) microspheres for chromatographic...

Monodisperse polymer microspheres are widely used as chromatographic packing materials due to their highly controllable morphology and excellent acid-base resistance. Among them, the commonly used monodisperse porous poly(styrene-divinylbenzene) (PS-DVB) microspheres are spherical polymers with abundant pore structures, synthesized by polymerizing styrene monomer and divinylbenzene crosslinker in the presence of an initiator and a porogen. The particle size and pore structure of PS-DVB microspheres can directly affect the specific surface area and mass transfer, thereby influencing their chromatographic separation performance. To precisely control such microstructures, different polymerization methods and synthetic parameters have been reported in recent decades targeting a variety of application scenarios. In spite of all this, there still lacks a timely review summarizing the research progress of PS-DVB microspheres. This work systematically reviews the preparation strategies of PS-DVB microspheres, encompassing suspension polymerization, seed-swelling polymerization, precipitation polymerization, dispersion polymerization, and membrane emulsion polymerization, while detailing their applications across ion chromatography (IC), reversed-phase high-performance liquid chromatography (RP-HPLC), supercritical fluid chromatography (SFC), and hydrophilic interaction chromatography (HILIC). This review reveals that each polymerization strategy entails inherent trade-offs between monodispersity, porosity, and scalability, where particle size and pore structure are critically governed by the type and loading of initiators and porogens-factors that continue to pose central challenges in the customized synthesis of PS-DVB microspheres. In terms of applications, functionalized PS-DVB microspheres exhibit broad compatibility with IC, RP-HPLC, and HILIC separation modes, enabling the efficient separation of anions, organic acids, and natural products. Their exceptional acid-base resistance further imparts unique advantages for the analysis of ultra-pure rare earth elements and rare metals. Looking ahead, three priorities are identified: precise pore/surface engineering assisted by molecular simulation, development of green and sustainable synthesis routes, and expansion into high-value scenarios such as biopharmaceutical purification, industrial wastewater treatment, and clinical blood purification.