Copolymerization of CO2 and Cyclohexene Oxide Mediated by Yb(salen) Based Complexes

New catalysts based on Yb(salen) complexes active for the copolymerization of cyclohexene oxide (CHO) and CO2 to give poly(cyclohexene)carbonate (PCHC) are reported. In combination with co-catalytic, nucleophilic chloride additives these new (binary) catalysts provided good conversion and selectivit...

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Detalles Bibliográficos
Autores: Decortes, Antonello, Haak, Robert M., Martín, Carmen, Martínez Belmonte, Marta, Martin, Eddy, Benet-Buchholz, Jordi, Kleij, Arjan W.
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2015
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2072/356265
Acceso en línea:http://hdl.handle.net/2072/356265
https://doi.org/10.1021/acs.macromol.5b01880
Access Level:acceso abierto
Palabra clave:54
Descripción
Sumario:New catalysts based on Yb(salen) complexes active for the copolymerization of cyclohexene oxide (CHO) and CO2 to give poly(cyclohexene)carbonate (PCHC) are reported. In combination with co-catalytic, nucleophilic chloride additives these new (binary) catalysts provided good conversion and selectivity for PCHC formation with average turnover frequencies of up to 35 h-1 and narrow molecular weight distributions. The best results were obtained with the binary catalyst system 1 (0.1 mol%)/NBu4Cl (0.05 mol%), and at 90 °C a conversion of 57% was reached after 18 h with a TOF of 31 h1, and the polycarbonate had an Mn of 10.2 Kg/mol and a PDI of 1.54. Comparative catalysis studies have also been performed with a series of literature systems based on transition metal/lanthanide salen complexes, and the newly presented catalysts show comparatively good activity as well as copolymerization selectivity. MALDI-ToF mass spectrometric analysis revealed that trace water contamination and/or traces of 1,2-cyclohexane- diol were responsible for chain transfer effects limiting to some extent the maximum molecular weights that can be achieved in the current reactor set up.