e-Caprolactone / ZnCl2 complex formation: characterization and ring-opening polymerization mechanism

ε-Caprolactone (ε-CL) has been mixed with ZnCl2 at different mol ratios. The resulting complex was characterized through 1H and 13C NMR spectroscopy in bulk and in solutions, differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), and optical microscopy. Ring-opening polymeriza...

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Detalles Bibliográficos
Autores: Abraham, Gustavo Abel, Gallardo, Alberto, Lozano, Angel E., San Roman, Julio
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2000
País:Argentina
Institución:Consejo Nacional de Investigaciones Científicas y Técnicas
Repositorio:CONICET Digital (CONICET)
Idioma:inglés
OAI Identifier:oai:ri.conicet.gov.ar:11336/35733
Acceso en línea:http://hdl.handle.net/11336/35733
Access Level:acceso abierto
Palabra clave:Ring-Opening Polymerization
Lactones
Zinc Chloride
Mechanism
Quantum-Mechanical Calculation
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
https://purl.org/becyt/ford/2.5
https://purl.org/becyt/ford/2
Descripción
Sumario:ε-Caprolactone (ε-CL) has been mixed with ZnCl2 at different mol ratios. The resulting complex was characterized through 1H and 13C NMR spectroscopy in bulk and in solutions, differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), and optical microscopy. Ring-opening polymerization of ε-caprolactone [M] using ZnCl2 as an initiator [I] at different monomer/initiator ratios has been successfully performed in xylene. The molecular weight of poly(ε-caprolactone) (PCL) as measured by gel permeation chromatografy (GPC) was found to depend linearly on the [M]/[I] ratio. Theoretical calculations were carried out to understand the geometry of the complex and the operating ring-opening mechanism. Both experimental and computational results and the presence of methylene–chloride end group, confirmed by NMR, are in agreement with a coordination–insertion mechanism for the ring-opening polymerization proposed in this article.