One‐pot Fixation of CO2 into Glycerol Carbonate using Ion‐Exchanged Amberlite Resin Beads as Efficient Metal‐free Heterogeneous Catalysts

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AbstractThe one‐pot synthesis of glycerol carbonate from carbon dioxide and glycerol was achieved using ion‐exchanged Amberlite resin beads as metal‐free heterogeneous catalysts. Two commercially available Amberlite resin beads consisting of polystyrene cross‐linked with divinylbenzene and functionalized with either trimethyl ammonium chloride (IRA‐900) or dimethyl ethanol ammonium chloride (IRA‐910) groups were used as starting materials to prepare the catalysts. These polymeric beads were transformed into their iodide (Amb‐900‐I, Amb‐OH‐910‐I) or hydroxide (Amb‐900‐OH and Amb‐OH‐910‐OH) counterparts through straightforward ion‐exchange reactions. First, the two resin bead catalysts in hydroxide form were tested in the base‐catalyzed transcarbonation reaction of glycerol with propylene carbonate. Both resin bead catalysts were more active compared to benchmark basic catalysts as hydrotalcites and attained 80 % yield of glycerol carbonate over Amb‐OH‐910‐OH after 2 h at 115 °C, employing a 4 : 1 ratio between propylene carbonate and glycerol. Then, the one‐pot reaction of CO2, glycerol and propylene oxide to produce propylene carbonate, glycerol carbonate and propylene glycol was investigated as the main target of this study. The reaction involves two steps: the reaction of propylene oxide with CO2 yielding propylene carbonate, and the transcarbonation of the formed cyclic carbonate with glycerol. Amb‐900‐I, Amb‐OH‐910‐I, Amb‐OH‐910‐OH and combinations of the latter two were employed as catalysts. Although Amb‐OH‐910‐I alone is poorly active in the transcarbonation reaction, it showed the highest catalytic activity in the one‐pot cascade reaction, surprisingly surpassing the performance of the Amb‐OH‐910‐I/Amb‐OH‐910‐OH mixtures and reaching high yields of glycerol carbonate (81 %, 115 °C, 4 h). These findings led to proposing a mechanism for the one‐pot reaction using the Amb‐OH‐910‐I catalyst. The bead format led to easy recovery of the catalyst, which displayed good reusability in consecutive runs.