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dc.contributor.authorOchoa-Gómez, José R.
dc.contributor.authorLorenzo-Ibarreta, Leire
dc.contributor.authorDiñeiro-García, Cristina
dc.contributor.authorGómez-Jiménez-Aberasturi, Olga
dc.date.accessioned2020-05-27T15:32:28Z
dc.date.available2020-05-27T15:32:28Z
dc.date.issued2020-05
dc.identifier.citationOchoa-Gómez, José R., Leire Lorenzo-Ibarreta, Cristina Diñeiro-García, and Olga Gómez-Jiménez-Aberasturi. “Isosorbide Bis(methyl Carbonate) Synthesis from Isosorbide and Dimethyl Carbonate: The Key Role of Dual Basic–nucleophilic Catalysts.” RSC Advances 10, no. 32 (2020): 18728–18739. doi:10.1039/d0ra03552a.en
dc.identifier.issn2046-2069en
dc.identifier.urihttp://hdl.handle.net/11556/926
dc.description.abstractIsosorbide bis(methyl carbonate) (IBMC) is a scarcely studied green chemical with potential applications in the manufacturing of non-isocyanate polyurethanes and bisphenol A-free polycarbonates. Its synthesis by transesterification of isosorbide with dimethyl carbonate (DMC) is very negatively influenced by the presence of small amounts of acidic impurities in isosorbide when heterogeneous inorganic carbonates such as potassium and cesium carbonates are used as catalysts. In this paper it is shown that the problem can be solved by using homogeneous catalysts consisting of nitrogenated bases and superbases having a suitable dual nucleophilic–basic character and able to form a highly reactive acyl intermediate with the electrophilic reactant DMC. Cycloaliphatic secondary and tertiary amines, guanidines and amidines covering a nucleophilicity parameter (N) range between 13.58 and 20.58 in either acetonitrile or dichloromethane, and a pKa range in acetonitrile between 15.68 and 26.02 have been tested in batchwise mode. Highly active catalysts leading to hydroxyl conversions of 84–93% require a minimum N of 16 and a pKa ranging from 18.0 to 26.0. Within this pKa range, N must increase by about 0.5–0.6 units per each unit the pKa falls to keep the catalytic activity, indicating that nucleophilicity has approximately twice as much influence as basicity on the catalytic activity. One guanidine (TBD), one amidine (DBN) and three cycloaliphatic secondary amines (N-methylpyrrolidine, quinuclidine and DABCO) have been found to be excellent catalysts at 5 mol% vs. ISO. The side reaction leading to oligomer formation is not avoided, with oligomers, mainly the dimer, affording 6 wt% of the crude product independently of hydroxyl-conversion and catalyst type.en
dc.description.sponsorshipThis paper is a part of the research carried out within the VIPRISCAR project which has received funding from the Bio Based Industries Joint Undertaking (JU) under the European Union's Horizon 2020 Research and Innovation Programme under grant agreement No. 790440. The JU receives support from the European Union's Horizon 2020 research and innovation programme and the Bio Based Industries Consortium. Thanks are due to research teams involved in VIPRISCAR project for valuable discussion during project meetings: Dr Stefaan De Wildeman et al. (B4Plastics, Belgium), Dr Yaying Chen et al. (Exergy, UK), Dr Daniel Klein et al. (Jowat SE, Germany), Mrs Elena Benedetti et al. (AEP Polymers, Italy), Dr Erasmo Cadena et al. (Vertech Group, France), Dr Jos´e-Mar´ıa Cuevas (Gaiker IK4, Spain) and Dr Sandra Medel (Leitat, Spain). Thanks are also due to Mr Robert Kirschbaum (SakuragiConsult) and Mr Alan Patrick Giles (Rawlings Giles), members of the VIPRISCAR's Advisory Board for valuable advices about market issues. Special acknowledgment is due to Dr Soraya Prieto (Tecnalia) for smooth project management.en
dc.language.isoengen
dc.publisherRoyal Society of Chemistryen
dc.titleIsosorbide bis(methyl carbonate) synthesis from isosorbide and dimethyl carbonate: the key role of dual basic–nucleophilic catalystsen
dc.typearticleen
dc.identifier.doi10.1039/d0ra03552aen
dc.relation.projectIDinfo:eu-repo/grantAgreement/EC/H2020/790440/EU/Validation of an industrial process to manufacture isosorbide bis(methyl carbonate) at pilot level/VIPRISCARen
dc.rights.accessRightsopenAccessen
dc.subject.keywordsSynthesisen
dc.subject.keywordsNon-isocyanate polyurethanesen
dc.issue.number32en
dc.journal.titleRSC Advancesen
dc.page.final18739en
dc.page.initial18728en
dc.volume.number10en


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