Porous Copolymers of 1,4-Di(methacryloxymethyl)naphthalene (DMN) with Trimethylpropane Trimethacrylate (TRIM)—Synthesis, Characterization, and Post-Crosslinking Modification

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Abstract
Porous microspheres based on 1,4-(dimethacryloyloxymethyl)naphthalene (DMN) and trimethylolpropane trimethacrylate (TRIM) were obtained by suspension–emulsion polymerization in the presence of toluene as a porogenic diluent. The obtained copolymers were subsequently modified using tetrachloromethane in the presence of anhydrous AlCl3 via a Friedel–Crafts-type reaction. The influence of monomer composition and post-polymerization modification on the porous structure parameters and thermal stability of the materials was investigated. The synthesized copolymers exhibited well-developed porous structures with surface areas ranging from 368 to 494 m2/g. Increasing the TRIM content resulted in higher crosslinking density, earlier phase separation during polymerization, and formation of a finer porous architecture characterized by increased surface area and lower pore diameters. Chemical modification caused moderate and composition-dependent changes in the porous structure while preserving the mesoporous character of the materials. The highly crosslinked copolymers demonstrated the greatest structural stability during modification. Thermogravimetric analysis performed in helium revealed high thermal resistance of both parent and modified copolymers. The degradation process proceeded in two main stages characteristic of highly crosslinked methacrylate networks. Increasing TRIM content improved resistance toward advanced thermal decomposition, increasing the T50% values up to 415 °C. Post-polymerization modification slightly decreased the temperature of the second degradation stage, probably due to the introduction of thermally less stable chlorinated fragments, while simultaneously increasing char residue formation. The synthesized materials were also evaluated as stationary phases for gas chromatography. Owing to their high thermal stability and the presence of polar ester functionalities, the copolymers enabled efficient separation of aliphatic alcohols at elevated temperatures. The obtained results demonstrate that porous poly(DMN-co-TRIM) microspheres constitute promising thermally stable materials with tunable porous structure and potential applications in chromatographic separation techniques.

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