Heterogeneous Brønsted Catalysis in the Solvent-Free and Multigram-Scale Synthesis of Polyalcohol Acrylates: The Case Study of Trimethylolpropane Triacrylate

Abstract

This article presents a thorough investigation into the synthesis of trimethylolpropane triacrylate (TMPTA) via the esterification reaction of trimethylolpropane (TMP) with acrylic acid using Amberlite™ 120 IR (H+), Amberlyst® 15, and Dowex™ 50WX8 resins as heterogeneous catalysts. Preliminary comparative tests explored the impact of air flow on water removal during the reaction and different acid-to-alcohol molar ratios (3:1, 6:1, or 9:1 mol:mol). The findings revealed that introducing air significantly enhances TMPTA yield and -OH group conversion, particularly at a 6:1 acid-to-alcohol molar ratio. Based on cost considerations, Amberlite™ 120 IR (H+) was selected as the preferred catalyst for further optimization. This included evaluating the effect of catalyst loading (10%, 5.0%, and 2.5% w/wtot) and assessing the impact of a pre-drying process on resin efficiency. The study concluded that optimal conditions did not necessitate drying, requiring 120 °C, a catalyst loading of 10% w/wtot, a 4 h reaction time, an acid:alcohol ratio of 6:1 mol:mol, the presence of MEHQ (0.1% mol/molAA), and air bubbling at 6 ± 1 Nl/h. Catalyst recycling was effectively implemented with a slight reduction in catalytic activity over consecutive runs. Furthermore, the study explored a scaled-up system with a mechanical stirrer, demonstrating the potential for multi-hundred grams scale-up. Considerations for optimizing the air flow stripping system are also highlighted. In summary, this study provides valuable insights into designing and optimizing the esterification process for TMPTA synthesis, laying the foundation for potential industrial applications.