Małgorzata Maciejewska

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 T_50% 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.

Porous poly(glycidyl methacrylate‐co‐ethylene glycol dimethacrylate) microspheres with tunable functionality were synthesized via suspension–emulsion polymerization and subsequently modified with 5‐aminosalicylic acid (ASA). The influence of copolymer composition (GMA:EGDMA = 1:1–5:1) on porosity, surface chemistry, and thermal properties was systematically investigated. Increasing the GMA content led to higher epoxy group density (2.87–5.02 mmol g ⁻¹ ) but a pronounced decrease in specific surface area (151–39 m ² g ⁻¹ ), indicating a trade‐off between functionality and porosity. Post‐polymerization modification successfully introduced ASA moieties, as confirmed by FTIR spectroscopy and acid number measurements (14.0–30.9 mg KOH g ⁻¹ ), while largely preserving the mesoporous structure. Thermal analysis (TG/DTG and TG–FTIR) demonstrated enhanced thermal stability of ASA‐modified copolymers, attributed to the incorporation of aromatic functionalities and reduced content of thermally labile epoxy groups. The modified materials were evaluated as sorbents for Cr(VI) ions, showing strong pH‐dependent behavior with maximum removal efficiency under acidic conditions. The sorption capacity reached approximately 100 mg g ⁻¹ , and the uptake mechanism was governed by electrostatic interactions between protonated surface groups and anionic chromium species. These results demonstrate that ASA‐functionalized poly(GMA‐co‐EGDMA) microspheres are promising materials for selective sorption applications.

Porous glycidyl methacrylate-based copolymers crosslinked with ethylene glycol dimethacrylate (EGDMA) and trimethylolpropane trimethacrylate (TMPTMA) were synthesized via suspension–emulsion polymerization and subsequently functionalized with triethylenetetramine. The effect of the monomer composition on the epoxy group content and porous structure was systematically investigated by varying the GMA-to-crosslinker molar ratio from 1:1 to 5:1. Increasing the GMA fraction enhanced the epoxy group content (2.8–5.0 mmol/g) but significantly reduced the specific surface area (333–23 m²/g), indicating a trade-off between functionality and porosity. ATR-FTIR and elemental analysis confirmed successful amine functionalization while preserving a considerable degree of porosity. The modified copolymers were evaluated for Cr(VI) removal, showing strong pH dependence, with maximum efficiency at pH 3 due to electrostatic interactions between protonated amine groups and HCrO₄⁻ ions. Equilibrium studies revealed saturation-type behavior, with a maximum sorption capacity of 165.47 mg/g for TMPTMA-based copolymers. Despite the higher nitrogen content in EGDMA-based materials, TMPTMA-crosslinked copolymers exhibited a superior adsorption performance, demonstrating that pore accessibility, rather than functional group density alone, governs adsorption efficiency. These findings provide insight into the rational design of amine-functionalized porous polymer sorbents for efficient chromium(VI) removal.

Porous materials are used in many important applications, such as separation technologies, catalysis, and chromatography. They may be obtained from various monomers via diverse polymerization techniques and a wide range of synthesis parameters. The study is devoted to the synthesis and characterization of crosslinked porous polymeric spheres containing pyrrolidone subunits. To achieve this goal, two methods were applied: direct synthesis from N-vinyl-2-pyrrolidone (NVP) with ethylene glycol dimethacrylate (EGDMA) and via a modification reaction of porous poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) with pyrrolidone (P). The polymerization was carried out with the use of different molar ratios of the monomers. In order to obtain highly porous materials, pore-forming diluents (toluene, dodecane, and dodecan-1-ol) were used. The synthesized copolymers were characterized using size distribution analysis, ATR-FTIR spectroscopy, scanning electron microscopy, thermogravimetry, and inverse gas chromatography. Determined by the nitrogen adsorption/desorption method, the specific surface area was in the range of 55–468 m²/g. The good thermal properties of the poly(VP-co-EGDMA) copolymers allowed them to be applied as the stationary phase in gas chromatography.

Porous polymeric microspheres are among the most effective adsorbents. They can be synthesized from numerous monomers using different kinds of polymerization techniques with a broad selection of synthesis factors. The main goal of this study was to prepare copolymeric microspheres and establish the relationship between copolymerization parameters and the porosity and thermal stability of the newly synthesized materials. Porous microspheres were obtained via heterogenous radical copolymerization using 3-(trimethoxysilyl)propyl methacrylate (TMPSM) as functional monomers and trimethylolpropane trimethacrylate (TRIM) as the crosslinker. In the course of the copolymerization, toluene or chlorobenzene was used as the pore-forming diluent. Consequently, highly porous microspheres were produced. Their specific surface area was established by a nitrogen adsorption/desorption method and it was in the range of 382 m²/g to 457 m²/g for toluene and 357–500 m²/g in the case of chlorobenzene. The thermal degradation process was monitored by thermogravimetry and differential scanning calorimetry methods in inert and oxidative conditions. The copolymers were stable up to 269–283 °C in a helium atmosphere, whereas in synthetic air the range was 266–298 °C, as determined by the temperature of 5% mass loss. Thermal stability of the investigated copolymers increased along with an increasing TMPSM amount in the copolymerization mixture. In addition, the poly(TMSPM-co-TRIM) copolymers were effectively used as the stationary phase in GC analyses.

Rigid porous polymeric monoliths are robust, highly efficient, versatile stationary phases. They offer simple preparation and convenient modification provided by a whole range of synthesis factors, e.g., starting monomers, cross-linkers, initiators, porogens, polymerization techniques, and temperature. The main aim of this study was to synthesize polymeric monoliths and determine the correlation between polymerization parameters and the porosity and thermal stability of the obtained materials. Polymeric monoliths were synthesized directly in HPLC columns using N-vinyl-2-pyrrolidone (NVP) and 4-vinylpiridine (4VP) as functional monomers, with trimethylolpropane trimethacrylate (TRIM) serving as the cross-linking monomer. During copolymerization a mixture of cyclohexanol/decane-1-ol was used as the pore-forming diluent. Polymerization was carried out at two different temperatures: 55 and 75 °C. As a result, monoliths with highly developed internal structure were synthesized. The value of their specific surface area was in the range of 92 m²/g to 598 m²/g, depending on the monomer composition and polymerization temperature. Thermal properties of the obtained materials were investigated by means of thermogravimetry (TG). Significant differences in thermal behavior were noticed between monoliths synthesized at 55 and 75 °C. Additionally, the poly(NVP-co-TRIM) monolith was successfully applied in GC analyses.

This study presents the results of applying the methods of synthesizing mesoporous carbon and mesoporous polymer materials with an extended porous mesostructure as adsorbents for cationic dye molecules. Both types of adsorbents are synthetic materials. The aim of the presented research was the preparation, characterisation, and utilisation of obtained mesoporous adsorbents. The physicochemical properties, morphology, and porous structure characteristics of the obtained materials were determined using low-temperature nitrogen sorption isotherms, X-ray diffraction (XRD), small angle X-ray scattering (SAXS), and potentiometric titration measurements. The morphology and microstructure were imaged using scanning electron microscopy (SEM). The chemical characterisation of the surface chemistry of the adsorbents, which provides information about the surface-active groups, the elemental composition, and the electronic state of the elements, was carried out using X-ray photoelectron spectroscopy (XPS). The adsorption properties of the mesoporous materials were determined using equilibrium and kinetic adsorption experiments for three selected cationic dyes (derivatives of thiazine (methylene blue) and triarylmethane (malachite green and crystal violet)). The adsorption capacity was analysed to the nanostructural and surface properties of used materials. The Generalized Langmuir equation was applied for the analysis of adsorption isotherm data. The adsorption study showed that the carbon materials have a higher sorption capacity for both methylene blue and crystal violet, e.g., 0.88–1.01 mmol/g and 0.33–0.44 mmol/g, respectively, compared to the polymer materials (e.g., 0.038–0.044 mmol/g and 0.038–0.050 mmol/g, respectively). The kinetics of dyes adsorption was closely correlated with the structural properties of the adsorbents. The kinetic data were analysed using various equations: first-order (FOE), second-order (SOE), mixed 1,2-order (MOE), multi-exponential (m-exp), and fractal-like MOE (f-MOE).

Thermal Behavior of Polymeric and Other Advanced Materials is a recently open Special Issue in Materials, which aims to publish original articles, short communications, reviews, and mini-reviews covering the most recent progress in multiple thermal characterizations of diverse materials and provide a platform for scientists from various areas to present their research

Porous materials can be found in numerous essential applications. They are of particular interest when, in addition to their porosity, they have other advantageous properties such as thermal stability or chemical diversity. The main aim of this study was to synthesize the porous copolymers of 9,10-bis(methacryloyloxymethyl)anthracene (BMA) with three different co-monomers divinylbenzene (DVB), ethylene glycol dimethacrylate (EGDMA) and trimethylpropane trimethacrylate (TRIM). They were synthesized via suspension polymerization using chlorobenzene and toluene served as porogenic solvents. For the characterization of the synthesized copolymers ATR-FTIR spectroscopy, a low-temperature nitrogen adsorption–desorption method, thermogravimetry, scanning electron microscopy, inverse gas chromatography and size distribution analysis were successfully employed. It was found that depending on the used co-monomer and the type of porogen regular polymeric microspheres with a specific surface area in the range of 134–472 m²/g can be effectively synthesized. The presence of miscellaneous functional groups promotes divergent types of interactions Moreover, all of the copolymers show a good thermal stability up to 307 °C. What is important, thanks to application of anthracene derivatives as the functional monomer, the synthesized materials show fluorescence under UV radiation. The obtained microspheres can be used in various adsorption techniques as well as precursor for thermally resistant fluorescent sensors.