Silica-grafted diethylzinc and a silsesquioxane-based zinc alkyl complex as catalysts for the alternating oxirane-carbon dioxide copolymerization

Robbert Duchateau*, Wouter J. van Meerendonkt, Saskia Huijser, Bastiaan B. P. Staal, Marcus A. van Schilt, Gijsbert Gerritsen, Auke Meetsma, Cor E. Koning, Maartje F. Kemmere, Jos T. F. Keurentjes

*Corresponding author for this work

    Research output: Contribution to journalArticleAcademicpeer-review

    28 Citations (Scopus)

    Abstract

    A novel zinc silsesquioxane complex ([(c-C5H9)(7)Si7O11(OSiMePh2)](2)Zn4Me4 (1)) has been used as a model compound for silica-grafted zinc catalysts in the copolymerization of cyclohexene oxide and CO2. Complex 1 exists as a dimer in the solid state and is moderately active in the copolymerization, and polycyclohexene carbonates have been obtained with a carbonate content of 79-98%. Polymerizations with ZnEt2-treated silica particles resulted in polymer particles with (M) over bar (n) and (M) over bar (w) values and carbonate contents comparable to those of the polymers obtained with 1. It was further demonstrated that CO2 consumption can be followed online by monitoring the decrease of system pressure during the reaction. CO2 consumption has been interpreted in relation to both polycarbonate and cyclic carbonate formation. These measurements represent the intrinsic kinetics of this reaction, which appear to be directly related to CO2 pressure.

    Original languageEnglish
    Pages (from-to)4204-4211
    Number of pages8
    JournalOrganometallics
    Volume26
    Issue number17
    DOIs
    Publication statusPublished - 13-Aug-2007

    Keywords

    • OLEFIN POLYMERIZATION CATALYSTS
    • CHROMIUM SALEN COMPLEXES
    • SOLID-STATE STRUCTURES
    • SINGLE-SITE CATALYSTS
    • PROPYLENE-OXIDE
    • CYCLOHEXENE OXIDE
    • POLY(PROPYLENE CARBONATE)
    • MECHANISTIC ASPECTS
    • CYCLIC CARBONATES
    • EPOXIDE/CO2 COPOLYMERIZATION

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