N-Heterocyclic Carbene-Induced Zwitterionic Ring-Opening Polymerization of Ethylene Oxide and Direct Synthesis of alpha,omega-Difunctionalized Poly(ethylene oxide)s and Poly(ethylene oxide)-b-poly(epsilon-caprolactone) Block Copolymers
| dc.rights.license | open | |
| hal.structure.identifier | Laboratoire de Chimie des Polymères Organiques [LCPO] | |
| dc.contributor.author | RAYNAUD, Jean | |
| hal.structure.identifier | Institut des Sciences Moléculaires [ISM] | |
| dc.contributor.author | ABSALON, Christelle | |
| hal.structure.identifier | Laboratoire de Chimie des Polymères Organiques [LCPO] | |
| dc.contributor.author | GNANOU, Yves | |
| hal.structure.identifier | Laboratoire de Chimie des Polymères Organiques [LCPO] | |
| hal.structure.identifier | Team 1 LCPO : Polymerization Catalyses & Engineering | |
| dc.contributor.author | TATON, Daniel | |
| dc.date.accessioned | 2020 | |
| dc.date.available | 2020 | |
| dc.date.issued | 2009 | |
| dc.identifier.issn | 0002-7863 | |
| dc.identifier.uri | https://oskar-bordeaux.fr/handle/20.500.12278/20715 | |
| dc.description.abstractEn | An N-heterocyclic carbene (NHC), namely, 1,3-bis-(diisopropyl)imidazol-2-ylidene (1), was demonstrated to bring about the metal-free ring-opening polymerization of ethylene oxide at 50 degrees C in dimethyl sulfoxide, in absence of any other reagents. Poly(ethylene oxide) (PEO) of polydispersities < 1.2 and molar masses perfectly matching the [monomer]/[(1)] ratio could thus be obtained in quantitative yields, attesting to the controlled/living character of such carbene-initiated polymerizations. It is argued that (1) adds to ethylene oxide to form a zwitterionic species, namely 1,3-bis-(diisopropyl)imidazol-2-ylidinium alkoxide, that further propagates by a zwitterionic ring-opening polymerization (ZROP) mechanism. Through an appropriate choice of terminating agent NuH or NuSiMe(3) at the completion of the polymerization, a variety of end-functionalized PEO chains could be generated. In particular, alpha,omega-bis(hydroxy)-telechelic PEO, alpha-benzyl,omega-hydroxy, and alpha-azido,omega-hydroxy-difunctionalized PEOs were synthesized by NHC (1)-initiated ZROP, using H2O, PhCH2OH, and N3SiMe3 as terminating agent, respectively. Characterization of these alpha,omega-difunctionalized PEOS by techniques such as H-1 NMR spectroscopy, MALDI-TOF spectrometry, and size exclusion chromatography confirmed the quantitative introduction of functional groups at both alpha and omega positions of the PEO chains and the formation of very narrow molar mass polymers. Finally, the synthesis of a poly(ethylene oxide)-b-poly(epsilon-caprolactone) diblock copolymer by sequential ZROP of the corresponding monomers was successfully achieved using (1) as organic initiator without isolation of the PEO block intermediate. | |
| dc.language.iso | en | |
| dc.publisher | American Chemical Society | |
| dc.subject.en | MATERIALS SCIENCE | |
| dc.subject.en | GLYCOL) DERIVATIVES | |
| dc.subject.en | CYCLIC ESTERS | |
| dc.subject.en | ONE END | |
| dc.subject.en | ANIONIC-POLYMERIZATION | |
| dc.subject.en | EPSILON-CAPROLACTONE | |
| dc.subject.en | LIVING POLYMERIZATION | |
| dc.subject.en | AQUEOUS-SOLUTION | |
| dc.subject.en | CLICK CHEMISTRY | |
| dc.subject.en | FACILE SYNTHESIS | |
| dc.title.en | N-Heterocyclic Carbene-Induced Zwitterionic Ring-Opening Polymerization of Ethylene Oxide and Direct Synthesis of alpha,omega-Difunctionalized Poly(ethylene oxide)s and Poly(ethylene oxide)-b-poly(epsilon-caprolactone) Block Copolymers | |
| dc.type | Article de revue | |
| dc.identifier.doi | 10.1021/ja809246f | |
| dc.subject.hal | Chimie/Polymères | |
| bordeaux.journal | Journal of the American Chemical Society | |
| bordeaux.page | 3201-3209 | |
| bordeaux.volume | 131 | |
| bordeaux.hal.laboratories | Laboratoire de Chimie des Polymères Organiques (LCPO) - UMR 5629 | * |
| bordeaux.issue | 9 | |
| bordeaux.institution | Bordeaux INP | |
| bordeaux.institution | Université de Bordeaux | |
| bordeaux.peerReviewed | oui | |
| hal.identifier | hal-00380349 | |
| hal.version | 1 | |
| hal.origin.link | https://hal.archives-ouvertes.fr//hal-00380349v1 | |
| bordeaux.COinS | ctx_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.jtitle=Journal%20of%20the%20American%20Chemical%20Society&rft.date=2009&rft.volume=131&rft.issue=9&rft.spage=3201-3209&rft.epage=3201-3209&rft.eissn=0002-7863&rft.issn=0002-7863&rft.au=RAYNAUD,%20Jean&ABSALON,%20Christelle&GNANOU,%20Yves&TATON,%20Daniel&rft.genre=article |
Fichier(s) constituant ce document
| Fichiers | Taille | Format | Vue |
|---|---|---|---|
|
Il n'y a pas de fichiers associés à ce document. |
|||