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 :

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

Statistics

Number of views

113 (28 by ULiège)

Number of downloads

4 (4 by ULiège)

More statistics

Scopus citations^®

Scopus citations^®
without self-citations

OpenCitations

Bibliography

Martín, C., Fiorani, G., Kleij, A.W., Recent advances in the catalytic preparation of cyclic organic carbonates. ACS Catal. 5:2 (2015), 1353–1370.
Aresta, M., Dibenedetto, A., Angelini, A., Catalysis for the valorization of exhaust carbon: from CO2 to chemicals, materials, and fuels. Technological use of CO2. Chem. Rev. 114 (2014), 1709–1742.
Alves, M., Grignard, B., Boyaval, A., Mereau, R., De Winter, J., Gerbaux, P., Detrembleur, C., Tassaing, T., Jerome, C., Organocatalytic coupling of CO2 with oxetane. ChemSusChem. 10 (2016), 1128–1138.
Alves, M., Grignard, B., Mereau, R., Jerome, C., Tassaing, T., Detrembleur, C., Organocatalyzed coupling of carbon dioxide with epoxides for the synthesis of cyclic carbonates: catalyst design and mechanistic studies. Catal. Sci. Technol. 7 (2017), 2651–2684.
Chung, G., Kim, H., Jun, S., Kim, M., New cyclic carbonate solvent for lithium ion batteries: trans -2, 3-butylene carbonate. ELECOM 1 (1999), 493–496.
Shim, S., Udayakumar, J., Yu, I., Kim, D., Synthesis of cyclic carbonate from allyl glycidyl ether and carbon dioxide using ionic liquid-functionalized amorphous silica. Catal. Today 148 (2009), 350–354.
Schäffner, B., Schäffner, F., Verevkin, S.P., Börner, A., Organic carbonates as solvents in synthesis and catalysis. Chem. Rev. 110:8 (2010), 4554–4581.
Clements, J.H., Reactive applications of cyclic alkylene carbonates. Ind. Eng. Chem. Res. 42 (2003), 663–674.
Besse, V., Auvergne, R., Carlotti, S., Boutevin, G., Otazaghine, B., Caillol, S., Pascault, J., Boutevin, B., Reactive & functional polymers synthesis of isosorbide based polyurethanes: an isocyanate free method. React. Funct. Polym. 73 (2013), 588–594.
Bahr, R., Mulhaupt, M., Linseed and soybean oil-based polyurethanes prepared via the non-isocyanate route and catalytic carbon dioxide conversion. Green Chem. 14 (2012), 483–489.
Udayakumar, S., Vedarajan, R., Shim, H.-L., Park, D.-W., Cycloaddition of Carbon Dioxide for Commercially-imperative Cyclic Carbonates Using Ionic Liquid-functionalized Porous Amorphous Silica. 2009.
Alves, B., Grignard, S., Gennen, C., Detrembleur, C., Jerome, C., Tassaing, T., Organocatalytic synthesis of bio-based cyclic carbonates from CO2 and vegetable oils. RSC Adv. 5 (2015), 53629–53636.
Adam, F., Batagarawa, M.S., Tetramethylguanidine-silica nanoparticles as an efficient and reusable catalyst for the synthesis of cyclic propylene carbonate from carbon dioxide and propylene oxide. Appl. Catal. A Gen. 454 (2013), 164–171.
Han, H., Choi, S., Choi, B., Liu, D., Park, L.J.J.W., Ionic liquids containing carboxyl acid moieties grafted onto silica: synthesis and application as heterogeneous catalysts for cycloaddition reactions of epoxide and carbon dioxide. Green Chem. 13 (2011), 1023–1028.
Jose, T., Hwang, Y., Kim, M., Kim, D., Park, D., Functionalized zeolitic imidazolate framework F-ZIF-90 as efficient catalyst for the cycloaddition of carbon dioxide to allyl glycidyl ether. Catal. Today 245 (2015), 61–67.
Appaturi, J.N., Adam, F., Facile and efficient synthesis of styrene carbonate via cycloaddition of CO2 to styrene oxide over ordered mesoporous MCM-41-Imi/Br catalyst. Appl. Catal. B Environ. 136–137 (2013), 150–159.
Sun, J., Fujita, S.-i., Zhao, F., Hasegawa, M., Arai, M., Direct synthesis of styrene carbonate from styrene with the Au/SiO2-ZnBr2/Bu4NBr catalyst system. J. Catal. 230 (2005), 398–405.
Naoto, A., Yoshio, F., Takeshi, E., Convenient synthesis of cyclic carbonates from CO2 and epoxides by simple secondary and primary ammonium iodides as metal-free catalysts under mild conditions and its application to synthesis of polymer bearing cyclic carbonate moiety. J. Polym. Sci. Part A: Polym. Chem. 51 (2012), 1230–1242.
Chopade, P.R., Janis, L., [2+2+2] Cycloaddition Reactions catalyzed by transition metal complexes. Adv. Synth. Catal. 348 (2006), 2307–2327.
Gennen, S., Alves, M., Méreau, R., Tassaing, T., Gilbert, B., Detrembleur, C., Jerome, C., Grignard, B., Fluorinated alcohols as activators for the solvent-free chemical fixation of Carbon Dioxide into Epoxides. ChemSusChem. 8 (2015), 1845–1849.
Wang, J.-Q., Kong, D.-L., Chen, J.-Y., Cai, F., He, L.-N., Synthesis of cyclic carbonates from epoxides and carbon dioxide over silica-supported quaternary ammonium salts under supercritical conditions. J. Mol. Catal. A Chem. 249 (2006), 143–148.
Caló, V., Nacci, A., Monopoli, A., Fanizzi, A., Cyclic carbonate formation from carbon dioxide and oxiranes in tetrabutylammonium halides as solvents and catalysts. Org. Lett. 4 (2002), 2561–2563.
Udayakumar, S., Park, S.-W., Park, D.-W., Choi, B.-S., Immobilization of ionic liquid on hybrid MCM-41 system for the chemical fixation of carbon dioxide on cyclic carbonate. Catal. Commun. 9 (2008), 1563–1570.
Yubing, X., Yujiao, W., Hong, W., Rongmin, W., Zipeng, C., Novel one-step synthesis to cross-linked polymeric nanoparticles as highly active and selective catalysts for cycloaddition of CO2 to epoxides. J. Appl. Polym. Sci. 123 (2011), 1486–1493.
Han, L., Choi, H.-J., Kim, D.-K., Park, S.-W., Liu, B., Park, D.-W., Porous polymer bead-supported ionic liquids for the synthesis of cyclic carbonate from CO2 and epoxide. J. Mol. Catal. A Chem. 338 (2011), 58–64.
Hardman-Baldwin, A.M., Mattson, A.E., Silanediol-catalyzed carbon dioxide fixation. ChemSusChem. 7 (2014), 3275–3278.
Sun, L., Wang, S., Zhang, Z., Li, X., Zhang, W., Dai, R., Catalysis, A., Mori, J., ZnCl2/phosphonium halide: an efficient Lewis acid/base catalyst for the synthesis of cyclic carbonate. J. Mol. Catal. A Chem. 256:1–2 (2006), 295–300.
Wang, J.-Q., Dong, K., Cheng, W.-G., Sun, J., Zhang, S.-J., Insights into quaternary ammonium salts-catalyzed fixation carbon dioxide with epoxides. Catal. Sci. Technol. 2 (2012), 1480–1484.
Ju, H.-E., Manju, M.-D., Kim, K.-H., Park, S.-D., Park, D.-W., Catalytic performance of quaternary ammonium salts in the reaction of butyl glycidyl ether and carbon dioxide. J. Ind. Eng. Chem. 14 (2008), 157–160.
Zhuravlev, L.T., The surface chemistry of amorphous silica. Zhuravlev model, Colloids Surfaces A Physicochem. Eng. Asp. 173 (2000), 1–38.
Alves, M., Grignard, B., Gennen, S., Mereau, R., Detrembleur, C., Jerome, C., Tassaing, T., Organocatalytic promoted coupling of carbon dioxide with epoxides: a rational investigation of the cocatalytic activity of various hydrogen bond donors. Catal. Sci. Technol. 5 (2015), 4636–4643.
Alves, M., Mereau, R., Grignard, B., Detrembleur, C., Jerome, C., Tassaing, T., A comprehensive density functional theory study of the key role of fluorination and dual hydrogen bonding in the activation of the epoxide/CO2 coupling by fluorinated alcohols. RSC Adv. 6 (2016), 36327–36335.