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Organocatalytic Coupling of CO 2 with Oxetane
Author(s) -
Alves Margot,
Grignard Bruno,
Boyaval Amélie,
Méreau Raphael,
De Winter Julien,
Gerbaux Pascal,
Detrembleur Christophe,
Tassaing Thierry,
Jérôme Christine
Publication year - 2017
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201601185
Subject(s) - chemistry , oxetane , catalysis , polymer chemistry , polymerization , bifunctional , trifluoromethanesulfonate , solvent , organic chemistry , polymer
The organocatalytic coupling of CO 2 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 CO 2 with oxetanes at 130 °C and at a CO 2 pressure 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, CO 2 ‐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).