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    Metallocene-catalyzed ethylene−α-olefin isomeric copolymerization: A perspective from hydrodynamic boundary layer mass transfer and design of MAO anion

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    Type
    Article
    Authors
    Adamu, Sagir
    Atiqullah, Muhammad
    Malaibari, Zuhair O.
    Al-Harthi, Mamdouh A.
    Emwas, Abdul-Hamid M.
    Ul-Hamid, Anwar
    KAUST Department
    Imaging and Characterization Core Lab
    NMR
    Date
    2015-11-28
    Online Publication Date
    2015-11-28
    Print Publication Date
    2016-03
    Permanent link to this record
    http://hdl.handle.net/10754/595298
    
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    Abstract
    This study reports a novel conceptual framework that can be easily experimented to evaluate the effects of hydrodynamic boundary layer mass transfer, methylaluminoxane (MAO) anion design, and comonomer steric hindrance on metallocene-catalyzed ethylene polymerization. This approach was illustrated by conducting homo- and isomeric copolymerization of ethylene with 1-hexene and 4-methyl-1-pentene in the presence of bis(n-butylcyclopentadienyl) zirconium dichloride (nBuCp)2ZrCl2, using (i) MAO anion 1 (unsupported [MAOCl2]−) and pseudo-homogeneous reference polymerization, and (ii) MAO anion 2 (supported Si−O−[MAOCl2]−) and in-situ heterogeneous polymerization. The measured polymer morphology, catalyst productivity, molecular weight distribution, and inter-chain composition distribution were related to the locus of polymerization, comonomer effect, in-situ chain transfer process, and micromixing effect, respectively. The peak melting and crystallization temperatures and %crystallinity were mathematically correlated to the parameters of microstructural composition distributions, melt fractionation temperatures, and average lamellar thickness. These relations showed to be insightful. The comonomer-induced enchainment defects and the eventual partial disruption of the crystal lattice were successfully modeled using Flory and Gibbs–Thompson equations. The present methodology can also be applied to study ethylene−α-olefin copolymerization, performed using MAO-activated non-metallocene precatalysts.
    Citation
    Metallocene-catalyzed ethylene−α-olefin isomeric copolymerization: A perspective from hydrodynamic boundary layer mass transfer and design of MAO anion 2015 Journal of the Taiwan Institute of Chemical Engineers
    Publisher
    Elsevier BV
    Journal
    Journal of the Taiwan Institute of Chemical Engineers
    DOI
    10.1016/j.jtice.2015.10.031
    Additional Links
    http://linkinghub.elsevier.com/retrieve/pii/S1876107015004721
    ae974a485f413a2113503eed53cd6c53
    10.1016/j.jtice.2015.10.031
    Scopus Count
    Collections
    Articles; Imaging and Characterization Core Lab

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