Sustainable synthesis of vinyl methyl ether from biomass-derived ethylene glycol dimethyl ether over solid base catalysts

Vinyl methyl ether (VME) is an important chemical intermediate for the production of functional polymers and fine chemicals. It is primarily produced in industry via the addition of methanol to acetylene, known as Reppe vinylation. However, the requirement for high pressures and caustic bases as catalysts limits its practical applications. Here, we report a novel route for the sustainable synthesis of VME from biomass-derived ethylene glycol dimethyl ether (EGDE) via the methanol elimination reaction catalyzed by CaO-based solid bases at atmospheric pressure. The co-precipitated CaO–MgO catalyst with a Ca/Mg molar ratio of 2 exhibited high efficiency and stability, achieving 100% EGDE conversion and 93.5% selectivity to VME at 400 °C. The strongly basic sites facilitated the formation of VME on the CaO–MgO surfaces, whereas, for comparison, the weakly basic sites on MgO or acidic sites on amphoteric oxides (e.g. CeO2) and solid acids (e.g. H-ZSM-5) were found to promote the degradation of VME. This work provides a viable and sustainable strategy for the synthesis of VME and other high-value vinyl compounds from biomass.