Heterogenization of a cyclocarbonation catalyst: optimization and kinetic study

[en] 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 1H NMR, solid 29Si NMR and TG-DSC-MS analyzes. The benchmark cyclocarbonation reaction of polyethylene glycol diglycidylether at 80 °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 °C and 55 bar during only 2,5 h with the best candidate.

Research Center/Unit :

CESAM - Complex and Entangled Systems from Atoms to Materials - ULiège
Center for Education and Research on Macromolecules (CERM)

Disciplines :

Chemistry
Materials science & engineering

Author, co-author :

Léonard, Géraldine L.-M.; Carmeuse Research and Technology SA, Louvain-la-Neuve, Belgium

Belet, Artium ; University of Liège (ULiège), Department of Chemical Engineering – Nanomaterials, Catalysis, Electrochemistry

Grignard, Bruno ; University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM), Center for Education and Research on Macromolecules (CERM)

Calberg, Cédric ; University of Liège (ULiège), Department of Chemical Engineering – Nanomaterials, Catalysis, Electrochemistry

Gilbert, Bernard ; University of Liège (ULiège), Department of Chemistry, Laboratory of Raman Spectroscopy

Jérôme, Christine ; University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM), Center for Education and Research on Macromolecules (CERM)

Heinrichs, Benoît ; University of Liège (ULiège), Department of Chemical Engineering – Nanomaterials, Catalysis, Electrochemistry

Language :

English

Title :

Heterogenization of a cyclocarbonation catalyst: optimization and kinetic study

Publication date :

15 August 2019

Journal title :

Catalysis Today

ISSN :

0920-5861

eISSN :

1873-4308

Publisher :

Elsevier, Amsterdam, Netherlands

Volume :

334

Pages :

140-155

Peer reviewed :

Peer Reviewed verified by ORBi

Funders :

The Walloon Region in the frame of the "CO2Green" project

Available on ORBi :

since 07 December 2018

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