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

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.