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    Mechanism of isotactic styrene polymerization with a C 6F 5-substituted bis(phenoxyimine) titanium system

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    Type
    Article
    Authors
    Caporaso, Lucia cc
    Loria, Marianna
    Mazzeo, Mina
    Michiue, Kenji
    Nakano, Takashi
    Fujita, Terunori
    Cavallo, Luigi cc
    KAUST Department
    KAUST Catalysis Center (KCC)
    Physical Sciences and Engineering (PSE) Division
    Chemical Science Program
    Date
    2012-11-13
    Permanent link to this record
    http://hdl.handle.net/10754/562411
    
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    Abstract
    We report a combined, experimental and theoretical, study of styrene polymerization to clarify the regio- and stereocontrol mechanism operating with a C 6F 5-substituted bis(phenoxyimine) titanium dichloride complex. Styrene homopolymerization, styrene-propene and styrene-ethene-propene copolymerizations have been carried out to this aim. A combination of 13C NMR analysis of the chain-end groups and of the microstructure of the homopolymers and copolymers reveals that styrene polymerization is highly regioselective and occurs prevalently through 2,1-monomer insertion. DFT calculations evidenced that steric interaction between the growing chain and the monomer in the transition state insertion stage is at the origin of this selectivity. The formation of isotactic polystyrene with a chain-end like microstructure is rationalized on the base of a mechanism similar to that proposed for the syndiospecific propene polymerization catalyzed by bis(phenoxyimine) titanium dichloride complexes. Finally, a general stereocontrol mechanism operative in olefin polymerization with this class of complexes is proposed. © 2012 American Chemical Society.
    Publisher
    American Chemical Society (ACS)
    Journal
    Macromolecules
    ISSN
    00249297
    DOI
    10.1021/ma301631b
    ae974a485f413a2113503eed53cd6c53
    10.1021/ma301631b
    Scopus Count
    Collections
    Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

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