title: Redox-Active Ligands: An Advanced Tool To Modulate Polyethylene Microstructure.
abstract: The ability to control catalytic activity and selectivity via in situ changes in catalyst oxidation-state represents an intriguing tool for enhanced polymerization control. Herein, we report foundational evidence that catalysts bearing redox-active moieties may be used to synthesize high molecular weight polyethylene with tailored microstructure. The ability to modulate branching density and identity is facilitated by ligand-based redox chemistry, and is realized via the addition of chemical reductants into the polymerization reactor. Detailed GPC and NMR analyses demonstrate that branching density may be altered by up to ∼ 30% as a function of in situ added reductant.
authors.affiliation: Department of Chemistry, University of Tennessee , Knoxville, Tennessee 37996, United States.
authors.forename: W Curtis
authors.initials: WC
authors.lastname: Anderson
authors.affiliation: Department of Chemistry, University of Tennessee , Knoxville, Tennessee 37996, United States.
authors.forename: Jennifer L
authors.initials: JL
authors.lastname: Rhinehart
authors.affiliation: Department of Chemistry, Clemson University , Clemson, South Carolina 29634, United States.
authors.forename: Andrew G
authors.initials: AG
authors.lastname: Tennyson
authors.affiliation: Department of Chemistry, University of Tennessee , Knoxville, Tennessee 37996, United States.
authors.forename: Brian K
authors.initials: BK
authors.lastname: Long