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

  • Datos identificativos

    Identificador: imarina:5131424
    Autores:
    Carrilho, Rui M. B. Dias, Lucas D. Rivas, Raquel Pereira, Mariette M. Claver, Carmen Masdeu-Bulto, Anna M.
    Resumen:
    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).
  • Otros:

    e-ISSN: 2073-4344
    Código de proyecto: CTQ2016-75016-R
    Palabras clave: Solventless reaction Polycarbonates Metalloporphyrin Fluorinated catalyst Epoxide Copolymerisation Compressed co2 Compressed co 2 Chromium
    Fecha de alta del registro: 2024-09-07
    Versión del articulo depositado: info:eu-repo/semantics/publishedVersion
    URL Documento de licencia: https://repositori.urv.cat/ca/proteccio-de-dades/
    Referencia al articulo segun fuente origial: Catalysts. 7 (7):
    Referencia de l'ítem segons les normes 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
    Acrónimo: ECO2VALCAT
    Tipo de publicación: Journal Publications
    Autor según el artículo: Carrilho, Rui M. B. Dias, Lucas D. Rivas, Raquel Pereira, Mariette M. Claver, Carmen Masdeu-Bulto, Anna M.
    Departamento: Química Física i Inorgànica
    Autor/es de la URV: Claver Cabrero, Maria del Carmen Orosia / Masdeu Bultó, Anna Maria / Rivas Del Valle, Raquel
    Resumen: 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).
    Áreas temáticas: Química Physical and theoretical chemistry Farmacia Environmental science (all) Engenharias ii Ciências biológicas ii Chemistry, physical Catalysis Astronomia / física
    Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/
    ISSN: 20734344
    Direcció de correo del autor: raquel.rivas@urv.cat raquel.rivas@urv.cat annamaria.masdeu@urv.cat carmen.claver@urv.cat
    Identificador del autor: 0000-0002-2007-7481 0000-0002-2007-7481 0000-0001-7938-3902 0000-0002-2518-7401
    Volumen de revista: 7
    Enlace a la fuente original: https://www.mdpi.com/2073-4344/7/7/210
    Programa de financiación: PROGRAMA ESTATAL DE INVESTIGACIÓN, DESARROLLO E INNOVACIÓN ORIENTADA A LOS RETOS DE LA SOCIEDAD
    DOI del artículo: 10.3390/catal7070210
    Entidad: Universitat Rovira i Virgili
    Año de publicación de la revista: 2017
    Acción del progama de financiación: VALORIZACION EFICIENTE DE CO2 A COMBUSTIBLES Y COMPUESTOS DE ALTO VALOR AÑADIDO MEDIANTE CATALISIS HOMOGENEA Y NANO-CATALISIS
  • Palabras clave:

    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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