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    High-speed organocatalytic polymerization of a renewable methylene butyrolactone by a phosphazene superbase

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    Type
    Article
    Authors
    Schmitt, Meghan L.
    Falivene, Laura cc
    Caporaso, Lucia cc
    Cavallo, Luigi cc
    Chen, Eugene You Xian
    KAUST Department
    Chemical Science Program
    KAUST Catalysis Center (KCC)
    Physical Science and Engineering (PSE) Division
    Date
    2014
    Permanent link to this record
    http://hdl.handle.net/10754/563184
    
    Metadata
    Show full item record
    Abstract
    The organic phosphazene superbase, 1-tert-butyl-4,4,4-tris(dimethylamino)- 2,2-bis[tris(dimethylamino)phosphoranylid-enamino]-2λ5, 4λ5-catenadi(phosphazene) (t-Bu-P4), is found to directly initiate high-speed polymerization of the biomass-derived renewable γ-methyl-α-methylene-γ-butyrolactone (MMBL), in contrast to other polymerization systems using t-Bu-P4 which typically require addition of an organic acid or a nucleophile as a co-initiating component. This MMBL polymerization by t-Bu-P4 alone is extremely rapid; even with a low t-Bu-P4 loading of 0.1 mol% or 0.02 mol%, quantitative monomer conversion is achieved in 20 s or 1 min, respectively, affording medium to high molecular weight PMMBL bioplastics in a catalytic fashion. The combined experimental and theoretical/computational studies have yielded mechanisms of chain initiation through abstraction of a proton from a monomer by t-Bu-P 4, essentially barrier-less chain propagation through rapid conjugate addition of the enolate anion stabilized by the nano-size cation [t-Bu-P 4H]+ to the monomer, and chain termination through chain transfer to the monomer which generates a saturated termination chain end and the [t-Bu-P4H]+-stabilized anionic active species that starts a new chain. This journal is © the Partner Organisations 2014.
    Citation
    Schmitt, M., Falivene, L., Caporaso, L., Cavallo, L., & Chen, E. Y.-X. (2014). High-speed organocatalytic polymerization of a renewable methylene butyrolactone by a phosphazene superbase. Polymer Chemistry, 5(9), 3261. doi:10.1039/c3py01579c
    Sponsors
    This work was supported by the US National Science Foundation (NSF-1300267) for the study carried out at Colorado State University. We thank Dr Yuetao Zhang for some initial experiments. LC thanks the HPC team of Enea (http://www.enea.it) for using the ENEA-GRID and the HPC facilities CRESCO (http://www.cresco.enea.it) in Portici, Italy.
    Publisher
    Royal Society of Chemistry (RSC)
    Journal
    Polymer Chemistry
    DOI
    10.1039/c3py01579c
    ae974a485f413a2113503eed53cd6c53
    10.1039/c3py01579c
    Scopus Count
    Collections
    Articles; Physical Science and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

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