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Route to Renewable PET: Reaction Pathways and Energetics of Diels–Alder and Dehydrative Aromatization Reactions Between Ethylene and Biomass-Derived Furans Catalyzed by Lewis Acid Molecular Sieves

Pacheco, Joshua J. and Labinger, Jay A. and Sessions, Alex L. and Davis, Mark E. (2015) Route to Renewable PET: Reaction Pathways and Energetics of Diels–Alder and Dehydrative Aromatization Reactions Between Ethylene and Biomass-Derived Furans Catalyzed by Lewis Acid Molecular Sieves. ACS Catalysis, 5 (10). pp. 5904-5913. ISSN 2155-5435. doi:10.1021/acscatal.5b01309. https://resolver.caltech.edu/CaltechAUTHORS:20150914-125155730

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Abstract

Silica molecular sieves that have the zeolite beta topology and contain framework Lewis acid centers (e.g., Zr-β, Sn-β) are useful catalysts in the Diels–Alder and dehydrative aromatization reactions between ethylene and various renewable furans for the production of biobased terephthalic acid precursors. Here, the main side products in the synthesis of methyl 4-(methoxymethyl)benzene carboxylate that are obtained by reacting ethylene with methyl 5-(methoxymethyl)-furan-2-carboxylate are identified, and an overall reaction pathway is proposed. Madon–Boudart experiments using Zr-β samples of varying Si/Zr ratios clearly indicate that there are no transport limitations to the rate of reaction for the synthesis of p-xylene from 2,5-dimethylfuran and ethylene and strongly suggest no mass transport limitations in the synthesis of methyl p-toluate from methyl 5-methyl-2-furoate and ethylene. Measured apparent activation energies for these reaction-limited systems are small (<10.5 kcal/mol), suggesting that apparent activation energies are derived from a collection of parameters and are not true activation energies for a single chemical step. In addition, 13C kinetic isotope effects (KIE) in the synthesis of MMBC and MPT measured by gas chromatography/isotope-ratio mass spectrometry in reactant-depletion experiments support the Madon–Boudart result that these systems are not transport-limited and the KIE values agree with those previously reported for Diels–Alder cycloadditions.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/acscatal.5b01309DOIArticle
http://pubs.acs.org/doi/10.1021/acscatal.5b01309PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/acscatal.5b01309PublisherSupporting Information
ORCID:
AuthorORCID
Labinger, Jay A.0000-0002-1942-9232
Sessions, Alex L.0000-0001-6120-2763
Davis, Mark E.0000-0001-8294-1477
Additional Information:© 2015 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received: June 22, 2015; Revised: July 29, 2015. Publication Date (Web): September 3, 2015. This work was funded by Toray Industries. We greatly appreciate Dr. Fenfang Wu (Caltech) for performing GC/IR-MS experiments. We also thank Dr. Masaaki Ubukata (JEOL) and Dr. Robert Cody (JEOL) for performing the GC/TOF-MS experiment, Prof. David Sparkman (University of the Pacific) for assisting in the interpretation of mass spectra, and Dr. Mona Shahgholi (Caltech) for use of GC/MS. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
Toray IndustriesUNSPECIFIED
Subject Keywords:terephthalic acid; dimethyl terephthalate; ethylene; 5-(hydroxymethyl)furfural; Diels−Alder cycloaddition; dehydration; zirconium-β; tin-β; kinetic isotope effect
Issue or Number:10
DOI:10.1021/acscatal.5b01309
Record Number:CaltechAUTHORS:20150914-125155730
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150914-125155730
Official Citation:Route to Renewable PET: Reaction Pathways and Energetics of Diels–Alder and Dehydrative Aromatization Reactions Between Ethylene and Biomass-Derived Furans Catalyzed by Lewis Acid Molecular Sieves Joshua J. Pacheco, Jay A. Labinger, Alex L. Sessions, and Mark E. Davis ACS Catalysis 2015 5 (10), 5904-5913 DOI: 10.1021/acscatal.5b01309
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:60229
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:14 Sep 2015 21:31
Last Modified:10 Nov 2021 22:31

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