N-Heterocyclic Carbene-Carbodiimide (NHC-CDI) Betaines as Organocatalysts for β-Butyrolactone Polymerization: Synthesis of Green PHB Plasticizers with Tailored Molecular Weights
The manufacture of poly(3-hydroxybutyrate) (PHB) stands out as a promising alternative to traditional plastics. This polymer is usually produced by bacteria-based biotechnology or metal-catalyzed ring-opening polymerization (ROP) of β-butyrolactone (β-BL). Nevertheless, commercial PHB suffers from d...
| Autores: | , , , |
|---|---|
| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2024 |
| País: | España |
| Institución: | Consejo Superior de Investigaciones Científicas (CSIC) |
| Repositorio: | DIGITAL.CSIC. Repositorio Institucional del CSIC |
| OAI Identifier: | oai:digital.csic.es:10261/356363 |
| Acceso en línea: | http://hdl.handle.net/10261/356363 https://api.elsevier.com/content/abstract/scopus_id/85184811821 |
| Access Level: | acceso abierto |
| Palabra clave: | betaines Flory−Schulz MW distribution organocatalysis ring-opening polymerization PHB plasticizers |
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N-Heterocyclic Carbene-Carbodiimide (NHC-CDI) Betaines as Organocatalysts for β-Butyrolactone Polymerization: Synthesis of Green PHB Plasticizers with Tailored Molecular Weights |
| title |
N-Heterocyclic Carbene-Carbodiimide (NHC-CDI) Betaines as Organocatalysts for β-Butyrolactone Polymerization: Synthesis of Green PHB Plasticizers with Tailored Molecular Weights |
| spellingShingle |
N-Heterocyclic Carbene-Carbodiimide (NHC-CDI) Betaines as Organocatalysts for β-Butyrolactone Polymerization: Synthesis of Green PHB Plasticizers with Tailored Molecular Weights Sánchez-Roa, David betaines Flory−Schulz MW distribution organocatalysis ring-opening polymerization PHB plasticizers |
| title_short |
N-Heterocyclic Carbene-Carbodiimide (NHC-CDI) Betaines as Organocatalysts for β-Butyrolactone Polymerization: Synthesis of Green PHB Plasticizers with Tailored Molecular Weights |
| title_full |
N-Heterocyclic Carbene-Carbodiimide (NHC-CDI) Betaines as Organocatalysts for β-Butyrolactone Polymerization: Synthesis of Green PHB Plasticizers with Tailored Molecular Weights |
| title_fullStr |
N-Heterocyclic Carbene-Carbodiimide (NHC-CDI) Betaines as Organocatalysts for β-Butyrolactone Polymerization: Synthesis of Green PHB Plasticizers with Tailored Molecular Weights |
| title_full_unstemmed |
N-Heterocyclic Carbene-Carbodiimide (NHC-CDI) Betaines as Organocatalysts for β-Butyrolactone Polymerization: Synthesis of Green PHB Plasticizers with Tailored Molecular Weights |
| title_sort |
N-Heterocyclic Carbene-Carbodiimide (NHC-CDI) Betaines as Organocatalysts for β-Butyrolactone Polymerization: Synthesis of Green PHB Plasticizers with Tailored Molecular Weights |
| dc.creator.none.fl_str_mv |
Sánchez-Roa, David Sessini, Valentina Mosquera, Marta E.G. Cámpora, Juan |
| author |
Sánchez-Roa, David |
| author_facet |
Sánchez-Roa, David Sessini, Valentina Mosquera, Marta E.G. Cámpora, Juan |
| author_role |
author |
| author2 |
Sessini, Valentina Mosquera, Marta E.G. Cámpora, Juan |
| author2_role |
author author author |
| dc.contributor.none.fl_str_mv |
Ministerio de Ciencia e Innovación (España) Agencia Estatal de Investigación (España) Junta de Andalucía European Commission Comunidad de Madrid Universidad de Alcalá Sánchez-Roa, David [0000-0001-8172-5764] Sessini, Valentina [0000-0003-1205-4586] Mosquera, Marta E.G. [0000-0003-2248-3050] Cámpora, Juan [0000-0001-7305-1296] Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72] |
| dc.subject.none.fl_str_mv |
betaines Flory−Schulz MW distribution organocatalysis ring-opening polymerization PHB plasticizers |
| topic |
betaines Flory−Schulz MW distribution organocatalysis ring-opening polymerization PHB plasticizers |
| description |
The manufacture of poly(3-hydroxybutyrate) (PHB) stands out as a promising alternative to traditional plastics. This polymer is usually produced by bacteria-based biotechnology or metal-catalyzed ring-opening polymerization (ROP) of β-butyrolactone (β-BL). Nevertheless, commercial PHB suffers from different issues, from poor processability to high production costs. Herein, we report the chemical synthesis of PHB from the ROP of rac-β-butyrolactone promoted by a zwitterionic organocatalyst, an N-heterocyclic carbene-carbodiimide (NHC-CDI) betaine adduct. This reaction has been investigated by a combination of experimental and computational methods. The catalyst cleaves the β-BL via nucleophilic displacement of the C-O(carboxyl) bond followed by intramolecular elimination to give protonated betaine-crotonate ion pairs, the active polymerization initiators. Polymer growth is propagated and controlled by these betaine ion pairs, which render amorphous low-molecular-weight PHBs by an unusual mechanism with rapid chain transfer to the monomer regime, analogous to the well-known mechanism of ethylene oligomerization with late transition-metal catalysts. The resulting material is suitable as a biodegradable and biocompatible plasticizer for commercial bacterial or synthetic PHB. Perfect compatibility between the matrix and the additive and a significant reduction of the crystallinity resulted in a more flexible and resilient material. |
| publishDate |
2024 |
| dc.date.none.fl_str_mv |
2024 2024 2024 |
| dc.type.none.fl_str_mv |
info:eu-repo/semantics/article http://purl.org/coar/resource_type/c_6501 Publisher's version info:eu-repo/semantics/publishedVersion |
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article |
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publishedVersion |
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http://hdl.handle.net/10261/356363 https://api.elsevier.com/content/abstract/scopus_id/85184811821 |
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http://hdl.handle.net/10261/356363 https://api.elsevier.com/content/abstract/scopus_id/85184811821 |
| dc.language.none.fl_str_mv |
Inglés |
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Inglés |
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application/pdf |
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ACS Publications |
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ACS Publications |
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reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC instname:Consejo Superior de Investigaciones Científicas (CSIC) |
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N-Heterocyclic Carbene-Carbodiimide (NHC-CDI) Betaines as Organocatalysts for β-Butyrolactone Polymerization: Synthesis of Green PHB Plasticizers with Tailored Molecular WeightsSánchez-Roa, DavidSessini, ValentinaMosquera, Marta E.G.Cámpora, JuanbetainesFlory−Schulz MW distributionorganocatalysisring-opening polymerizationPHBplasticizersThe manufacture of poly(3-hydroxybutyrate) (PHB) stands out as a promising alternative to traditional plastics. This polymer is usually produced by bacteria-based biotechnology or metal-catalyzed ring-opening polymerization (ROP) of β-butyrolactone (β-BL). Nevertheless, commercial PHB suffers from different issues, from poor processability to high production costs. Herein, we report the chemical synthesis of PHB from the ROP of rac-β-butyrolactone promoted by a zwitterionic organocatalyst, an N-heterocyclic carbene-carbodiimide (NHC-CDI) betaine adduct. This reaction has been investigated by a combination of experimental and computational methods. The catalyst cleaves the β-BL via nucleophilic displacement of the C-O(carboxyl) bond followed by intramolecular elimination to give protonated betaine-crotonate ion pairs, the active polymerization initiators. Polymer growth is propagated and controlled by these betaine ion pairs, which render amorphous low-molecular-weight PHBs by an unusual mechanism with rapid chain transfer to the monomer regime, analogous to the well-known mechanism of ethylene oligomerization with late transition-metal catalysts. The resulting material is suitable as a biodegradable and biocompatible plasticizer for commercial bacterial or synthetic PHB. Perfect compatibility between the matrix and the additive and a significant reduction of the crystallinity resulted in a more flexible and resilient material.This work was supported by the Ministerio de Ciencia e Innovación (Spain) (TED2021-130871B-C22, PGC2018-095768-B-100 and Thematic Network “OASIS” RED2022-134074-T), Comunidad de Madrid (EPU-INV/2020/001), Junta de Andalucía (PY20_0104), and the University of Alcalá (UAH-AE-2017-2). V.S. would like to thank the Ministerio de Ciencia e Innovación (Spain) and the European Community (Grant Number: RYC2021-033921-I) for the financial support. D.S.-R. thanks the Spanish Government for a Predoctoral Fellowship. The authors gratefully acknowledge Dra. Lucía Álvarez Miguel (UAH) for her assistance in the X-ray data collection and Dr. Javier López-Prados and Dra. Gloria Gutiérrez-Alcalá (Mass Spectrometry services, CIC-Cartuja and IIQ) for sample preparation and recording Maldi-TOF and ESI mass spectra of polymers.Peer reviewedACS PublicationsMinisterio de Ciencia e Innovación (España)Agencia Estatal de Investigación (España)Junta de AndalucíaEuropean CommissionComunidad de MadridUniversidad de AlcaláSánchez-Roa, David [0000-0001-8172-5764]Sessini, Valentina [0000-0003-1205-4586]Mosquera, Marta E.G. [0000-0003-2248-3050]Cámpora, Juan [0000-0001-7305-1296]Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202420242024info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10261/356363https://api.elsevier.com/content/abstract/scopus_id/85184811821reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2024/TED2021-130871B-C22info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-095768-B-100info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2024/RYC2021-033921-Iinfo:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2024/RED2022-134074-Thttps://pubs.acs.org/doi/full/10.1021/acscatal.3c05357Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3563632026-05-22T06:33:51Z |
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15,812429 |