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Catalysts 2017, 7(7), 210; doi:10.3390/catal7070210

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

1
CQC, Department of Chemistry, University of Coimbra, Rua Larga, 3004-535 Coimbra, Portugal
2
Department of Physical and Inorganic Chemistry, University Rovira i Virgili, Marcel·lí Domingo, Tarragona 43007, Spain
3
Centre Tecnològic de la Química, Marcel·lí Domingo s/n, Campus Sescelades, Tarragona 43007, Spain
*
Authors to whom correspondence should be addressed.
Received: 22 June 2017 / Revised: 22 June 2017 / Accepted: 7 July 2017 / Published: 14 July 2017
(This article belongs to the Special Issue Catalysis in Innovative Solvents)
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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). View Full-Text
Keywords: compressed CO2; solventless reaction; epoxide; copolymerisation; polycarbonates; metalloporphyrin; chromium; fluorinated catalyst compressed CO2; solventless reaction; epoxide; copolymerisation; polycarbonates; metalloporphyrin; chromium; fluorinated catalyst
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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MDPI and ACS Style

Carrilho, R.M.B.; Dias, L.D.; Rivas, R.; Pereira, M.M.; Claver, C.; Masdeu-Bultó, A.M. Solventless Coupling of Epoxides and CO2 in Compressed Medium Catalysed by Fluorinated Metalloporphyrins. Catalysts 2017, 7, 210.

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