Articles producció científica> Química Física i Inorgànica

Solventless Coupling of Epoxides and CO2 in Compressed Medium Catalysed by Fluorinated Metalloporphyrins

  • Identification data

    Identifier: imarina:5131424
    Authors:
    Carrilho, Rui M. B. Dias, Lucas D. Rivas, Raquel Pereira, Mariette M. Claver, Carmen Masdeu-Bulto, Anna M.
    Abstract:
    Metal complexes of meso-arylporphyrins (Cr(III), Fe(III), and Zn(II)) were evaluated in the coupling reaction of cyclohexene oxide (CHO) with CO2 in compressed medium, where the Cr complexes were demonstrated to be the most active systems, leading predominantly to copolymerisation products. It is noteworthy that no addition of solvent was required. To improve the catalytic activity, and to simultaneously increase the solubility in compressed CO2, a new fluorinated catalyst, tetrakis(4-trifluoromethylphenyl)porphyrinatochromium(III) chloride (CrCl-pCF3TPP), was applied to this reaction. The alternating copolymerisation of CHO with CO2, using the Cr(III) fluorinated porphyrin catalyst, required the use of a co-catalyst, bis(triphenylphosphine)iminium chloride (PPNCl), with the best yields of copolymers being obtained at 80 ◦C, and CO2 pressures in the range of 50-110 bar, over a period of 24 h, with a low catalyst/substrate molar ratio (0.07%). The polycarbonate's structure was analysed by 1H NMR, 13C NMR, and MALDI-TOF spectroscopy, which demonstrated high carbonate incorporations (98-99%). Gel permeation chromatography revealed number-average molecular weights (Mn) in the range of 4800-12,800 and narrow molecular weight distributions (Mw/Mn ≤ 1.63).
  • Others:

    e-ISSN: 2073-4344
    Project code: CTQ2016-75016-R
    Keywords: Solventless reaction Polycarbonates Metalloporphyrin Fluorinated catalyst Epoxide Copolymerisation Compressed co2 Compressed co 2 Chromium
    Record's date: 2024-09-07
    Papper version: info:eu-repo/semantics/publishedVersion
    Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
    Papper original source: Catalysts. 7 (7):
    APA: Carrilho, Rui M. B. Dias, Lucas D. Rivas, Raquel Pereira, Mariette M. Claver, Carmen Masdeu-Bulto, Anna M. (2017). Solventless Coupling of Epoxides and CO2 in Compressed Medium Catalysed by Fluorinated Metalloporphyrins. Catalysts, 7(7), -. DOI: 10.3390/catal7070210
    Acronym: ECO2VALCAT
    Publication Type: Journal Publications
    Author, as appears in the article.: Carrilho, Rui M. B. Dias, Lucas D. Rivas, Raquel Pereira, Mariette M. Claver, Carmen Masdeu-Bulto, Anna M.
    Department: Química Física i Inorgànica
    URV's Author/s: Claver Cabrero, Maria del Carmen Orosia / Masdeu Bultó, Anna Maria / Rivas Del Valle, Raquel
    Abstract: Metal complexes of meso-arylporphyrins (Cr(III), Fe(III), and Zn(II)) were evaluated in the coupling reaction of cyclohexene oxide (CHO) with CO2 in compressed medium, where the Cr complexes were demonstrated to be the most active systems, leading predominantly to copolymerisation products. It is noteworthy that no addition of solvent was required. To improve the catalytic activity, and to simultaneously increase the solubility in compressed CO2, a new fluorinated catalyst, tetrakis(4-trifluoromethylphenyl)porphyrinatochromium(III) chloride (CrCl-pCF3TPP), was applied to this reaction. The alternating copolymerisation of CHO with CO2, using the Cr(III) fluorinated porphyrin catalyst, required the use of a co-catalyst, bis(triphenylphosphine)iminium chloride (PPNCl), with the best yields of copolymers being obtained at 80 ◦C, and CO2 pressures in the range of 50-110 bar, over a period of 24 h, with a low catalyst/substrate molar ratio (0.07%). The polycarbonate's structure was analysed by 1H NMR, 13C NMR, and MALDI-TOF spectroscopy, which demonstrated high carbonate incorporations (98-99%). Gel permeation chromatography revealed number-average molecular weights (Mn) in the range of 4800-12,800 and narrow molecular weight distributions (Mw/Mn ≤ 1.63).
    Thematic Areas: Química Physical and theoretical chemistry Farmacia Environmental science (all) Engenharias ii Ciências biológicas ii Chemistry, physical Catalysis Astronomia / física
    licence for use: https://creativecommons.org/licenses/by/3.0/es/
    ISSN: 20734344
    Author's mail: raquel.rivas@urv.cat raquel.rivas@urv.cat annamaria.masdeu@urv.cat carmen.claver@urv.cat
    Author identifier: 0000-0002-2007-7481 0000-0002-2007-7481 0000-0001-7938-3902 0000-0002-2518-7401
    Journal volume: 7
    Link to the original source: https://www.mdpi.com/2073-4344/7/7/210
    Funding program: PROGRAMA ESTATAL DE INVESTIGACIÓN, DESARROLLO E INNOVACIÓN ORIENTADA A LOS RETOS DE LA SOCIEDAD
    Article's DOI: 10.3390/catal7070210
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2017
    Funding program action: VALORIZACION EFICIENTE DE CO2 A COMBUSTIBLES Y COMPUESTOS DE ALTO VALOR AÑADIDO MEDIANTE CATALISIS HOMOGENEA Y NANO-CATALISIS
  • Keywords:

    Catalysis,Chemistry, Physical,Physical and Theoretical Chemistry
    Solventless reaction
    Polycarbonates
    Metalloporphyrin
    Fluorinated catalyst
    Epoxide
    Copolymerisation
    Compressed co2
    Compressed co 2
    Chromium
    Química
    Physical and theoretical chemistry
    Farmacia
    Environmental science (all)
    Engenharias ii
    Ciências biológicas ii
    Chemistry, physical
    Catalysis
    Astronomia / física
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