Catalytic and kinetic investigation into 4-dimethylamino pyridine/1,3-diphenyl thiourea catalyzed synthesis of chloromethyl ethylene carbonate under pure CO₂ and simulated flue gas conditions

Eton, Udeme O.; Meredith, Will; Snape, Colin E.

Abstract

Synthesis of chloromethyl ethylene carbonate (CMEC) via CO2 cycloaddition to epichlorohydrin (ECH) has been investigated using a simple metal-free and halide-free catalyst comprising 4-dimethylamino pyridine (DMAP) and N–H type hydrogen bond donors (HBDs). Combining DMAP and 1,3-diphenyl thiourea (DPTU) had the strongest synergistic effect, which resulted in the highest improvement in CMEC yield. DMAP/DPTU was active in the presence of a simulated flue gas (15 % C02 in N2) at low temperatures (30 – 60 °C), reaching a high CMEC yield (93 %) and selectivity (98 %) at 40 °C in 24 h. The presence of O2 in simulated flue gas had no effect on catalytic activity; however, excessive H2O in the reactor had a negative effect, resulting in low yield and selectivity. The reaction obeyed pseudo-first-order kinetics in terms of ECH, DMAP, and DPTU concentrations. The addition of DPTU increased the observed rate constant (kobs) by a factor of 1.52 while decreasing the activation energy (Ea) of the reaction by 7.37 kJ/mol, indicating that the synergistic action of DPTU (HBD) and DMAP (nucleophile) influenced catalytic performance. The positive enthalpy (ΔH‡) and Gibbs free energy (ΔG‡) values indicate an endergonic and kinetically controlled reaction.

Citation

Eton, U. O., Meredith, W., & Snape, C. E. (2025). Catalytic and kinetic investigation into 4-dimethylamino pyridine/1,3-diphenyl thiourea catalyzed synthesis of chloromethyl ethylene carbonate under pure CO₂ and simulated flue gas conditions. Fuel, 382, Part A, Article 133657. https://doi.org/10.1016/j.fuel.2024.133657

• Journal Article Type: Article
• Acceptance Date: Nov 5, 2024
• Online Publication Date: Nov 18, 2024
• Publication Date: Feb 15, 2025
• Deposit Date: Dec 13, 2024
• Publicly Available Date: Dec 18, 2024
• Journal: Fuel
• Print ISSN: 0016-2361
• Electronic ISSN: 1873-7153
• Publisher: Elsevier
• Peer Reviewed: Peer Reviewed
• Volume: 382, Part A
• Article Number: 133657
• DOI: https://doi.org/10.1016/j.fuel.2024.133657
• Keywords: CO2 utilization, Cyclic carbonate, Hydrogen bond donor, Kinetics, Catalytic, Flue gas
• Public URL: https://nottingham-repository.worktribe.com/output/42840385
• Publisher URL: https://www.sciencedirect.com/science/article/pii/S0016236124028060?via%3Dihub