Articles producció científica> Química Física i Inorgànica

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

  • Dades identificatives

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

    e-ISSN: 2073-4344
    Codi de projecte: CTQ2016-75016-R
    Paraules clau: Solventless reaction Polycarbonates Metalloporphyrin Fluorinated catalyst Epoxide Copolymerisation Compressed co2 Compressed co 2 Chromium
    Data d'alta del registre: 2024-09-07
    Versió de l'article dipositat: info:eu-repo/semantics/publishedVersion
    URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/
    Referència a l'article segons font original: Catalysts. 7 (7):
    Referència 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
    Acrònim: ECO2VALCAT
    Tipus de publicació: Journal Publications
    Autor segons l'article: Carrilho, Rui M. B. Dias, Lucas D. Rivas, Raquel Pereira, Mariette M. Claver, Carmen Masdeu-Bulto, Anna M.
    Departament: Química Física i Inorgànica
    Autor/s de la URV: Claver Cabrero, Maria del Carmen Orosia / Masdeu Bultó, Anna Maria / Rivas Del Valle, Raquel
    Resum: 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).
    Àrees temàtiques: Química Physical and theoretical chemistry Farmacia Environmental science (all) Engenharias ii Ciências biológicas ii Chemistry, physical Catalysis Astronomia / física
    Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
    ISSN: 20734344
    Adreça de correu electrònic de l'autor: raquel.rivas@urv.cat raquel.rivas@urv.cat annamaria.masdeu@urv.cat carmen.claver@urv.cat
    Identificador de l'autor: 0000-0002-2007-7481 0000-0002-2007-7481 0000-0001-7938-3902 0000-0002-2518-7401
    Volum de revista: 7
    Enllaç font original: https://www.mdpi.com/2073-4344/7/7/210
    Programa de finançament: PROGRAMA ESTATAL DE INVESTIGACIÓN, DESARROLLO E INNOVACIÓN ORIENTADA A LOS RETOS DE LA SOCIEDAD
    DOI de l'article: 10.3390/catal7070210
    Entitat: Universitat Rovira i Virgili
    Any de publicació de la revista: 2017
    Acció del programa de finançament: VALORIZACION EFICIENTE DE CO2 A COMBUSTIBLES Y COMPUESTOS DE ALTO VALOR AÑADIDO MEDIANTE CATALISIS HOMOGENEA Y NANO-CATALISIS
  • Paraules clau:

    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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