[en] Recently, a “greener” approach has been developed to produce bio-sourced polyurethanes by reaction of bio-based cyclic carbonates and amines. Bio-based cyclic carbonates can be synthesised with a total atom economy by chemical fixation of carbon dioxide onto an epoxidized vegetable oil using an appropriate catalyst. Thus, although this area of research has been the subject of many works, catalytic performance must be further enhanced in particular for the carbonatation of vegetable-based precursors while respecting environmental standards. The aim of the present work is to propose new organocatalytic platforms enabling the cycloaddition of CO2 onto epoxidized oils in the most efficient way under mild conditions. For such task, in situ kinetic follow-up of the cycloaddition of model epoxides and epoxidized oils onto CO2 has been performed by FT-IR spectroscopy in order to determine the catalytic activity of new binary organocatalytic systems and to evaluate the influence of various parameters (pressure, temperature catalyst concentration, nature of the epoxide) on the yields and the reaction kinetics. The binary organocatalytic platform is composed of an ammonium salt combined with hydrogen-bond donors. Thanks to this catalyst screening, we have found that new organocatalytic platforms were by far more efficient than that proposed in the literature. Then, few catalytic systems have been investigated by molecular modeling in order to understand the reaction mechanism. The theoretical results put in evidence the key role of the hydrogen bond interaction between the epoxide and the co-catalyst for the enhancement of the catalytic platform’s efficiency.
Research Center/Unit :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Chemistry Materials science & engineering
Author, co-author :
Alves, Margot ; University of Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Gennen, Sandro ; University of Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Grignard, Bruno ; University of Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Detrembleur, Christophe ; University of Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Méreau, Raphaël; University of Bordeaux, Institute of Molecular Sciences, France
Jérôme, Christine ; University of Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Tassaing, Thierry; University of Bordeaux, Institute of Molecular Sciences, France
Language :
English
Title :
New efficient organocatalyst for the synthesis of bio-based cyclic carbonates from CO2 and vegetable oil
Publication date :
May 2015
Event name :
International Symposium on Green Chemistry (ISGC)
Event place :
La Rochelle, France
Event date :
3/05/2015 - 7/05/2015
Audience :
International
Funders :
Univeristy of Bordeaux through the "IDEX"
Commentary :
This oral communication was presented by Thierry Tassaing