[en] The organocatalytic coupling of CO2 with oxetanes is investigated under solvent-free conditions. The influence of the main reaction parameters (type of organocatalytic system, pressure and temperature) on the yield, the product formed and the selectivity of the reaction are discussed. An onium salt combined with a fluorinated alcohol promotes the efficient and selective organocatalytic synthesis of α,ω-hydroxyl oligocarbonates by coupling CO2 with oxetanes at 130 °C and at a CO2 pressure as low as 2 MPa. NMR characterizations were correlated with MALDI-ToF analyses for elucidating the structure of the oligomers. Online FTIR studies under pressure, NMR titrations and DFT calculations allowed an in-depth understanding of the reaction mechanism. Finally, CO2- based poly(carbonate-co-urethane)s were synthesized by step- growth polymerization of hydroxyl telechelic oligocarbonates with MDI. The organocatalytic system described in this paper constitutes an innovative sustainable route to the selective preparation of hydroxyl telechelic carbonates, of high interest for many applications, notably for the polyurethane business, especially for coatings or foams.
Research center :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Materials science & engineering Chemistry
Author, co-author :
Alves, Margot ; 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)
Boyaval, Amélie ; University of Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Méreau, Raophaël; University of Bordeaux, Institute of Molecular Sciences, France
De Winter, Julien; University of Mons (UMONS), Mass Spectrometry Research Group, Interdisciplinary Center of Mass Spectrometry (CISMa)
Gerbaux, Pascal; University of Mons (UMONS), Mass Spectrometry Research Group, Interdisciplinary Center of Mass Spectrometry (CISMa)
Detrembleur, Christophe ; 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
Jérôme, Christine ; University of Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Language :
English
Title :
Organocatalytic coupling of CO2 with oxetane
Publication date :
22 March 2017
Journal title :
ChemSusChem
ISSN :
1864-5631
eISSN :
1864-564X
Publisher :
Wiley-VCH, Weinheim, Germany
Volume :
10
Issue :
6
Pages :
1128-1138
Peer reviewed :
Peer Reviewed verified by ORBi
Name of the research project :
IDEX program CO2Green and Flycoat projects
Funders :
University of Bordeaux [FR] The Erasmus Mundus International Doctoral School IDS-Funmat Conseil Général d'Aquitaine [FR] MESRI - Ministère de l’Enseignement supérieur, de la Recherche et de l’Innovation [FR] Walloon region [BE] BELSPO - Politique scientifique fédérale [BE] F.R.S.-FNRS - Fonds de la Recherche Scientifique [BE]
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