The aim of this work was to prepare a new group of aromatic methacrylate monomers, utilise them in preparation of porous microspheres and study the influence of their chemical structure on the textural properties of porous methacrylate microspheres. Polymeric microspheres were prepared by suspension-emulsion polymerisation of four aromatic monomers: methacryloiloxybenzene, 1,2-dimethacryloiloxybenzene, 1,3-dimethacryloiloxybenzene and 1,4-dimethacryloiloxybenzene with another crosslinking agent—trimethylolpropane trimethacrylate. Mass median diameters of obtained beads are in the range 22–35 μm. The polymerisation reactions were carried out in the presence of a pore forming diluent. The influence of the diluent system on the porous structure of microspheres was studied in detail. To determine the textural properties of the studied microspheres, nitrogen adsorption–desorption and inverse sized exclusion chromatography measurements were used. Specific surface area of the obtained microspheres achieves value from 185 to 510 m²/g. Since obtained polymeric materials can be used as chromatographic packings for HPLC their porous structure in a swollen state was investigated. Significant differences in the porous structure parameters for dry and swollen microspheres were observed.

The study describes the thermal properties of functional microspheres composed of glycidyl methacrylate (GMA) and crosslinking agent ethylene glycol dimethacrylate (EGDMA). Copolymeric poly(GMA-co-EGDMA) microspheres were prepared via suspension–emulsion polymerization in the presence of toluene and decan-1-ol as porogens. In order to introduce functional groups, the porous methacrylate network was modified by epoxy ring opening with the use of sodium cyclopentadienide and then the Diels–Alder addition with maleic anhydride. The thermal properties of poly(GMA-co-EGDMA) materials were evaluated by thermogravimetry and differential scanning calorimetry. By TG/FTIR, it was observed that new functional materials exhibited multi-staged decomposition patterns, different from parent poly(GMA-co-EGDMA) microspheres. The synthesized poly(GMA-co-EGDMA) microspheres exhibited rather high thermal stability in inert atmosphere. Their initial decomposition temperature determined at the temperature of 2% of mass loss was about 210 °C; however, after the chemical modification it was slightly lower. The thermal degradation of parent poly(GMA-co-EGDMA) copolymer runs mainly according to the depolymerization mechanism, while functionalized by cyclopentadienyl group and maleic anhydride microspheres decompose through the chain scission mechanism.