title: Organocatalytic Coupling of CO2with Oxetane.
abstract: The organocatalytic coupling of CO2with 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 CO2with oxetanes at 130 °C and at a CO2pressure as low as 2 MPa. NMR characterizations were correlated with matrix-assisted laser desorption/ionization with time-of-flight mass spectrometer (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 4,4'-methylene diphenyl diisocyanate (MDI). The organocatalytic system described herein 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).
authors.affiliation: Institut des Sciences Moléculaires, UMR 5255, CNRS Université Bordeaux, 351 Cours de la Libération, 33405, Talence Cedex, France.|Center for Education and Research on Macromolecules (CERM), CESAM Research Unit, Université de Liège, Bâtiment B6a, 4000, Liège (Sart Tilman), Belgium.
authors.forename: Margot
authors.initials: M
authors.lastname: Alves
authors.affiliation: Center for Education and Research on Macromolecules (CERM), CESAM Research Unit, Université de Liège, Bâtiment B6a, 4000, Liège (Sart Tilman), Belgium.
authors.forename: Bruno
authors.initials: B
authors.lastname: Grignard
authors.affiliation: Institut des Sciences Moléculaires, UMR 5255, CNRS Université Bordeaux, 351 Cours de la Libération, 33405, Talence Cedex, France.|Center for Education and Research on Macromolecules (CERM), CESAM Research Unit, Université de Liège, Bâtiment B6a, 4000, Liège (Sart Tilman), Belgium.
authors.forename: Amélie
authors.initials: A
authors.lastname: Boyaval
authors.affiliation: Institut des Sciences Moléculaires, UMR 5255, CNRS Université Bordeaux, 351 Cours de la Libération, 33405, Talence Cedex, France.
authors.forename: Raphael
authors.initials: R
authors.lastname: Méreau
authors.affiliation: Mass Spectrometry Research Group, Interdisciplinary Center of Mass Spectrometry (CISMa), University of Mons (UMONS), Place du Parc 20, Mons, 7000, Belgium.
authors.forename: Julien
authors.initials: J
authors.lastname: De Winter
authors.affiliation: Mass Spectrometry Research Group, Interdisciplinary Center of Mass Spectrometry (CISMa), University of Mons (UMONS), Place du Parc 20, Mons, 7000, Belgium.
authors.forename: Pascal
authors.initials: P
authors.lastname: Gerbaux
authors.affiliation: Center for Education and Research on Macromolecules (CERM), CESAM Research Unit, Université de Liège, Bâtiment B6a, 4000, Liège (Sart Tilman), Belgium.
authors.forename: Christophe
authors.initials: C
authors.lastname: Detrembleur
authors.affiliation: Institut des Sciences Moléculaires, UMR 5255, CNRS Université Bordeaux, 351 Cours de la Libération, 33405, Talence Cedex, France.
authors.forename: Thierry
authors.initials: T
authors.lastname: Tassaing
authors.affiliation: Center for Education and Research on Macromolecules (CERM), CESAM Research Unit, Université de Liège, Bâtiment B6a, 4000, Liège (Sart Tilman), Belgium.
authors.forename: Christine
authors.initials: C
authors.lastname: Jérôme
mesh_terms: D001554:Benzene / Q000737:chemistry; D002245:Carbon Dioxide / Q000737:chemistry*; D002384:Catalysis; D004988:Ethers, Cyclic / Q000737:chemistry*; D006860:Hydrogen Bonding; D017953:Isocyanates / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D058105:Polymerization; D011140:Polyurethanes / Q000737:chemistry; D011312:Pressure; D000644:Quaternary Ammonium Compounds / Q000737:chemistry; D013696:Temperature
chemical_list: D004988:Ethers, Cyclic; D017953:Isocyanates; D011140:Polyurethanes; D000644:Quaternary Ammonium Compounds; D002245:Carbon Dioxide; C009405:tetrabutylammonium; C005287:oxetane; D001554:Benzene
keywords: carbon dioxide; oligocarbonates; organocatalysis; oxetane; polyurethanes