[en] We investigate the scope of the organocatalyzed step-growth copolymerization of CO2-sourced exovinylene bicyclic carbonates with bio-based diols into polycarbonates. A series of regioregular poly(oxo-carbonate)s were prepared from sugar- (1,4-butanediol and isosorbide) or lignin-derived (1,4-benzenedimethanol and 1,4-cyclohexanediol) diols at 25 °C with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as a catalyst, and their defect-free structure was confirmed by nuclear magnetic resonance spectroscopy studies. Their characterization by differential scanning calorimetry and wide-angle X-ray scattering showed that most of them were able to crystallize. When the polymerizations were carried out at 80 °C, some structural defects were introduced within the polycarbonate chains, which limited the polymer molar mass. Model reactions were carried out to understand the influence of the structure of alcohols, the temperature (25 or 80 °C), and the use of DBU on the rate of alcoholysis of the carbonate and on the product/linkage selectivity. A full mechanistic understanding was given by means of static- and dynamic-based density functional theory (DFT) calculations showing the determining role of DBU in the stability of intermediates, and its important role in the rate-determining steps is revealed. Furthermore, the origin of side reactions observed at 80 °C was discussed and rationalized by DFT modeling. As impressive diversified bio-based diols are accessible on a large scale and at low cost, this process of valorization of carbon dioxide gives new perspectives on the sustainable production of bioplastics under mild conditions.
Research Center/Unit :
Center for Education and Research on Macromolecules (CERM) CESAM - Complex and Entangled Systems from Atoms to Materials - ULiège
Disciplines :
Materials science & engineering Chemistry
Author, co-author :
Siragusa, Fabiana ; University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM) Research Unit, Center for Education and Research on Macromolecules (CERM), Belgium
Van Den Broeck, Elias; University of Ghent, Center for Molecular Modeling, Belgium
Ocando, Connie; University of the Basque Country, POLYMAT, Donostia/SanSebastian, Spain
Müller, Alenjandro J.; University of the Basque Country, POLYMAT, Donostia/SanSebastian, Spain
De Smet, Gilles; University of Antwerp ; Department of Chemistry, Organic Synthesis Division, Belgium
Maes, Bert U. W.; University of Antwerp ; Department of Chemistry, Organic Synthesis Division, Belgium
De Winter, Julien; University of Mons (UMons), Mass Spectrometry Research Group, Interdisciplinary Center of Mass Spectrometry (CISMa), Belgium
Van Speybroeck, Véronique; University of Ghent, Center for Molecular Modeling, Belgium
Grignard, Bruno ; University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM) Research Unit, Center for Education and Research on Macromolecules (CERM), Belgium
Detrembleur, Christophe ; University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM) Research Unit, Center for Education and Research on Macromolecules (CERM), Belgium
Language :
English
Title :
Access to biorenewable and CO2‑based polycarbonates from exovinylene cyclic carbonates
Publication date :
01 February 2021
Journal title :
ACS Sustainable Chemistry and Engineering
eISSN :
2168-0485
Publisher :
American Chemical Society, Washington, United States - District of Columbia
Volume :
9
Issue :
4
Pages :
1714-1728
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
F.R.S.-FNRS - Fonds de la Recherche Scientifique FWO - Fonds Wetenschappelijk Onderzoek Vlaanderen The "Excellence of Science" (EOS) program
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