Catalysis Today, Vol.334, 140-155, 2019
Heterogenization of a cyclocarbonation catalyst: Optimization and kinetic study
Different types of heterogeneous catalysts designed for a cyclocarbonation reaction between an epoxidized source and CO2 under supercritical conditions have been synthesized. The process implied a quaternization step where a (haloalkyl) trimethoxysilane reacted with tributylamine leading to a tributyl(trimethoxysilylalkyl) ammonium halide, with iodine and bromine as halogens. Then, a grafting step onto commercial fumed silica through condensation reaction between the silane part and Si-OH surficial groups provided the immobilized catalyst. The efficiency of grafting has been validated by liquid H-1 NMR, solid Si-29 NMR and TG-DSC-MS analyzes. The benchmark cyclocarbonation reaction of polyethylene glycol diglycidylether at 80 degrees C and 100 bar during 4 h showed that the best immobilized catalyst was tributylpropylammonium iodide (IC3Q-EH5). It has also been shown that immobilization provided -surprisingly!- better conversions than the corresponding homogeneous catalyst's: this phenomenon has been explained through an epoxide-ring-opening activating effect thanks to Si-OH surficial groups. Furthermore, kinetic studies performed by in situ Raman spectroscopy on IC3Q-EH5 showed that temperature had a strong influence on the yield of the reaction while CO2 pressure had only a small effect. Recycling of the catalyst has also been considered, but no precise conclusions could be conducted because of the high catalyst dispersion. Finally, the addition of a fluorinated alcohol co-catalyst allowed obtaining a similar yield but at 80 degrees C and 55 bar during only 2,5 h with the best candidate.