This work investigates the sulfonation behavior of styrene‐based resins crosslinked with divinylbenzene (DVB) and trimethylolpropane triacrylate (TMPTA) under varying conditions. TMPTA‐formulated resins initially exhibited lower ion exchange capacity (IEC) (∼1.13 mmol g⁻¹) than DVB‐crosslinked resins (∼2.94 mmol g⁻¹). However, optimized sulfonation conditions, including temperature and resin swelling, doubled the IEC of TMPTA‐based resins. Modeling indicated SO₃H groups in both resins, with higher accuracy (R² = 0.9998) when using a sulfonic group molecular weight of 161 g mol⁻¹. Differences in reactivity and degradation rates (6 × 10⁻³ min⁻¹ for STY/DVB and 8 × 10⁻² min⁻¹ for STY/TMPTA) are also highlighted.

This study aimed to synthesize sulfonated polymer resins based on styrene and trimethylolpropane triacrylate (TMPTA) and evaluate their catalytic efficiency in glycerol acetylation. A factorial design was used, with two factors, three levels, and three replicates of the center point. The factors were cross-linker percentage (Y_TMPTA) and cross-linker feed time (T_TMPTA). Ion-exchange capacity, swelling index, and catalytic efficiency were analyzed to characterize each resin. Lower cross-linker percentages resulted in higher catalytic efficiencies, as expected. Resins synthesized with 2, 6, and 10% TMPTA had mean catalytic efficiencies of 215, 176, and 121, respectively. A linear correlation was observed between catalytic efficiency and cross-linker percentage, with R² = 0.9971. Statistical and kinetic models were developed to represent the experimental results and support the development of strategies to improve resin formulation and synthesis conditions. TMPTA feed time at low and high levels positively influenced catalytic efficiency; the result is attributed to the micro- and macrostructure of resins. This finding was corroborated by the kinetic constants provided by the model.