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dc.contributor.authorBasterrechea Gorostiza, Andere
dc.contributor.authorGabirondo, Elena
dc.contributor.authorJehanno, Coralie
dc.contributor.authorZhu, Haijin
dc.contributor.authorFlores, Irma
dc.contributor.authorMüller Sánchez, Alejandro Jesús
dc.contributor.authorEtxeberria Lizarraga, Agustín
dc.contributor.authorMecerreyes Molero, David
dc.contributor.authorCoulembier, Olivier
dc.contributor.authorSardon Muguruza, Haritz
dc.date2020-01-25
dc.date.accessioned2019-06-04T15:54:22Z
dc.date.available2019-06-04T15:54:22Z
dc.date.issued2019-01-25
dc.identifier.citationACS Sustainable Chemistry and Engineering 7(4) : 4103−4111 (2019)es_ES
dc.identifier.issn2168-0485
dc.identifier.urihttp://hdl.handle.net/10810/33092
dc.description.abstractPolyethers constitute a well-established class of polymers covering a wide range of applications from industrial man-ufacturing to nanomedicine. Nevertheless, their industrial implementation is limited to short chain aliphatic polyethers such as poly-ethyeleglycol (PEO or PEG), polypropyleneglycol (PPG) or polytetramethylenglycol (PTMG) produced by the ring-opening polymerization of the corresponding cyclic ethers. Herein we report a sustainable and scalable approach for the preparation of medium and long chain aliphatic polyethers by the melt self-polycondensation of aliphatic diols in the presence of non-eutectic acid base mixtures as organocatalyst. These organocatalysts were prepared by forming stoichiometric and non-stoichiometric complexes of methanesulfonic acid (MSA) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as confirmed by NMR spectroscopy and DFT calcula-tions. The non-stoichiometric 2:1 and 3:1 MSA:TBD molar complexes showed superior thermal stability. These non-eutectic acid base mixtures were tested in the bulk-self condensation of 1,6-hexanediol leading to telechelic hydroxy-poly(oxyhexane). The optimized polymerization conditions involved the use of MSA:TBD (3:1) catalyst in a three step polycondensation process at 130 oC - 180 °C and 200 °C respectively. These conditions were applied to the synthesis of a wide range of aliphatic polyethers with a number of methylene units ranging from 6 to 12 units and molecular weights between 5,000 and 22,000 g mol-1. The aliphatic polyethers were highly semicrystalline with melting temperatures ranging from 55 to 85 °C. The synthesis approach was extended to the prepa-ration of value-added copolymers from different lenght chain diols and different functionality, giving rise to different copolymer architectures from linear copolyethers to polyether thermosets. Altogether, this straightforward polymerization strategy enables the access to medium-long chain and cross-linked aliphatic polyethers using easily prepared and recyclable organocatalysts.es_ES
dc.description.sponsorshipThe authors thank the European Commission for its financial sup-port through the projects SUSPOL-EJD 642671. Haritz Sardon and David Mecerreyes gratefully acknowledge financial support from MINECO through project POLYCE. A. J. Müller, O. Coulembier and H. Sardon also acknowledge European funding by the RISE BIODEST project (H2020-MSCA-RISE-2017-778092). The au-thors also thank the technical and human support provided by Mrs. Sofia Guezala (SGIker) of UPV/EHU for the NMR analysis. H. Sardon, A.J. Müller and I. Flores acknowledge funding and beam time from ALBA Synchrotron facility thorugh the project: 2017092338 (2018). O.C is Research Associate for the F.R.S.-FNRS.es_ES
dc.language.isoenges_ES
dc.publisherAmerican Chemical Societyes_ES
dc.relationinfo:eu-repo/grantAgreement/EC/H2020/778092es_ES
dc.rightsinfo:eu-repo/semantics/embargoedAccesses_ES
dc.subjectaliphatic polyetheres_ES
dc.subjectorganocatalystes_ES
dc.subjectpolycondensationes_ES
dc.subjectnon-eutectic acid-base organocatalystses_ES
dc.subjectcopolyetheres_ES
dc.titlePolyether Synthesis by Bulk Self-Condensation of Diols Catalyzed by Non-eutectic Acid Base Organocatalystses_ES
dc.typeinfo:eu-repo/semantics/articlees_ES
dc.rights.holder© 2019 American Chemical Societyes_ES
dc.relation.publisherversionhttps://pubs.acs.org/doi/10.1021/acssuschemeng.8b05609es_ES
dc.identifier.doi10.1021/acssuschemeng.8b05609
dc.contributor.funderEuropean Comission
dc.departamentoesCiencia y tecnología de polímeroses_ES
dc.departamentoeuPolimeroen zientzia eta teknologiaes_ES


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