Efficient and Easily Reusable Metal-Free Heterogeneous Catalyst Beads for the Conversion of CO2 into Cyclic Carbonates in the Presence of Water as Hydrogen-Bond Donor

Two porous Amberlite resin beads consisting of ammonium-functionalized polystyrene cross-linked with divinylbenzene were demonstrated to be efficient, easily recyclable, and viable metal-free heterogeneous catalysts for the reaction of CO₂ with epoxides to yield cyclic carbonates. The catalysts were prepared from two affordable, commercially available resin beads, which differ in the nature of their functional groups, i.e., trimethylammonium chloride or dimethylethanolammonium chloride. These materials were converted through a straightforward ion-exchange step into their iodide counterparts (Amb-I-900 and Amb-OH-I-910). The ion-exchanged resin beads were tested as heterogeneous catalysts for the reaction of CO₂ with styrene oxide at different reaction conditions (45-150 °C, 2-60 bar of CO₂, 3-18 h). The effect of the presence of water as a hydrogen-bond donor in combination with a heterogeneous catalyst was systematically investigated here for the first time. With both catalysts, the presence of water led to higher yields of cyclic carbonate (from 12% to 58% with Amb-I-900 and from 59% to 66% with Amb-OH-I-910; ≥98% selectivity). The highest catalytic activity was observed with Amb-OH-I-910, due to the presence of -OH groups in its active site, which together with water enhanced the activity through hydrogen-bonding interactions. This catalytic system attained higher turnover numbers and turnover frequencies (TON = 505, TOF = 168 for reaction at 150 °C) and improved cyclic carbonate productivity compared to the state-of-the-art supported polymeric bead catalysts and was active in catalyzing the synthesis of styrene carbonate also at low temperature (33% yield at 45 °C and 10 bar of CO₂). Additionally, the Amb-OH-I-910 proved to be a versatile catalyst for the conversion of a variety of epoxides into their corresponding cyclic carbonates with good to excellent yields and very high selectivity (≥98%). The two polymeric bead catalysts could be easily recovered and reused without significant loss in their activity and thus represent an easily accessible, environmentally friendly, cost-effective catalytic system for the synthesis of cyclic carbonates from CO₂.