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    Metal-Free Alternating Copolymerization of CO2with Epoxides: Fulfilling “Green” Synthesis and Activity

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    Type
    Article
    Authors
    Zhang, Dongyue
    Boopathi, Senthil
    Hadjichristidis, Nikos cc
    Gnanou, Yves cc
    Feng, Xiaoshuang
    KAUST Department
    Chemical Science Program
    KAUST Catalysis Center (KCC)
    Physical Science and Engineering (PSE) Division
    Polymer Synthesis Laboratory
    Date
    2016-08-26
    Online Publication Date
    2016-08-26
    Print Publication Date
    2016-09-07
    Permanent link to this record
    http://hdl.handle.net/10754/622428
    
    Metadata
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    Abstract
    Polycarbonates were successfully synthesized for the first time through the anionic copolymerization of epoxides with CO2, under metal-free conditions. Using an approach based on the activation of epoxides by Lewis acids and of CO, by appropriate cations, well-defined alternating copolymers made of CO, and propylene oxide (PO) or cyclohexene oxide (CHO) were indeed obtained. Triethyl borane was the Lewis acid chosen to activate the epoxides, and onium halides or onium alkoxides involving either ammonium, phosphonium, or phosphazenium cations were selected to initiate the copolymerization. In the case of PO, the carbonate content of the poly(propylene carbonate) formed was in the range of 92-99% and turnover numbers (TON) were close to 500; in the case of CHO perfectly alternating poly(cyclohexene carbonate) were obtained and TON values were close to 4000. The advantages of such a copolymerization system are manifold: (i) no need for multistep catalyst/ligand synthesis as in previous works; (ii) no transition metal involved in the copolymer synthesis and therefore no coloration of the samples isolated; and (iii) no necessity for postsynthesis purification.
    Citation
    Zhang D, Boopathi SK, Hadjichristidis N, Gnanou Y, Feng X (2016) Metal-Free Alternating Copolymerization of CO2with Epoxides: Fulfilling “Green” Synthesis and Activity. Journal of the American Chemical Society 138: 11117–11120. Available: http://dx.doi.org/10.1021/jacs.6b06679.
    Sponsors
    King Abdullah University of Science and Technology
    Publisher
    American Chemical Society (ACS)
    Journal
    Journal of the American Chemical Society
    DOI
    10.1021/jacs.6b06679
    PubMed ID
    27529725
    Additional Links
    http://pubs.acs.org/doi/full/10.1021/jacs.6b06679
    ae974a485f413a2113503eed53cd6c53
    10.1021/jacs.6b06679
    Scopus Count
    Collections
    Articles; Physical Science and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

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