Multinuclear Magnetic Resonance and DFT Studies of the Poly(chlorotrifluoroethylene-alt-ethyl vinyl ether) Copolymers
| Autor: | Philip Wormald, Bruno Ameduri, Sharon E. Ashbrook, Russell Tayouo, Diego Carnevale |
|---|---|
| Přispěvatelé: | University of St Andrews [Scotland], School of Chemistry [University of St Andrews], Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), collaboration informelle avec l'Univ de Saint Andrews (GB), collaboration avec l'Univ de Saint Andrews (GB) |
| Jazyk: | angličtina |
| Rok vydání: | 2009 |
| Předmět: |
Polymers and Plastics
02 engineering and technology Fluorine-19 NMR 010402 general chemistry J-coupling 01 natural sciences DFT chlorotrifluoroethylene Inorganic Chemistry chemistry.chemical_compound Tacticity Polymer chemistry Materials Chemistry Copolymer ethyl vinyl ether couplng interactions Chemical shift Organic Chemistry Nuclear magnetic resonance spectroscopy 021001 nanoscience & nanotechnology NMR 0104 chemical sciences [CHIM.POLY]Chemical Sciences/Polymers chemistry alternating Copolymers Physical chemistry Density functional theory 0210 nano-technology Chlorotrifluoroethylene |
| Zdroj: | Macromolecules Macromolecules, American Chemical Society, 2009, 42, pp.5652-5659. ⟨10.1021/ma900789t⟩ |
| ISSN: | 0024-9297 1520-5835 |
| DOI: | 10.1021/ma900789t⟩ |
| Popis: | International audience; Chlorotrifluoroethylene (CTFE) and ethyl vinyl ether (EVE) were reacted under radical conditions to produce the poly(CTFE-co-EVE) alternating copolymer, and a full 13C, 1H, and 19F NMR structural interpretation is offered. All spectra were characterized by broad signals resulting from the overlapping of different chemical shifts. This observation was rationalized by considering a complex mixture of diastereomerically related compounds, hence allowing an average assignment to be determined. A density functional theory (DFT) computational study of the isotropic magnetic shieldings with the GIAO and CSGT methods was performed to explore the diasteriomeric relationships between the single building blocks and their mutual influences along the polymer chain. The calculated results totally support the assignment of the experimental chemical shifts of two diasteriomeric sets of resonances indicating chiral center inversion, and not spin-spin J coupling interactions, as the main cause of spectral complexity. |
| Databáze: | OpenAIRE |
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