title: A fully integrated high-throughput screening methodology for the discovery of new polyolefin catalysts: discovery of a new class of high temperature single-site group (IV) copolymerization catalysts.
abstract: For the first time, new catalysts for olefin polymerization have been discovered through the application of fully integrated high-throughput primary and secondary screening techniques supported by rapid polymer characterization methods. Microscale 1-octene primary screening polymerization experiments combining arrays of ligands with reactive metal complexes M(CH(2)Ph)(4) (M = Zr, Hf) and multiple activation conditions represent a new high-throughput technique for discovering novel group (IV) polymerization catalysts. The primary screening methods described here have been validated using a commercially relevant polyolefin catalyst, and implemented rapidly to discover the new amide-ether based hafnium catalyst [eta(2)-(N,O)[bond](2-MeO[bond]C(6)H(4))(2,4,6-Me(3)C(6)H(2))N]Hf(CH(2)Ph)(3) (1), which is capable of polymerizing 1-octene to high conversion. The molecular structure of 1 has been determined by X-ray diffraction. Larger scale secondary screening experiments performed on a focused 96-member amine-ether library demonstrated the versatile high temperature ethylene-1-octene copolymerization capabilities of this catalyst class, and led to significant performance improvements over the initial primary screening discovery. Conventional one gallon batch reactor copolymerizations performed using selected amide-ether hafnium compounds confirmed the performance features of this new catalyst class, serving to fully validate the experimental results from the high-throughput approaches described herein.
authors.affiliation: Symyx Technologies Inc., 3100 Central Expressway, Santa Clara, California 95051, USA.
authors.forename: Thomas R
authors.initials: TR
authors.lastname: Boussie
authors.forename: Gary M
authors.initials: GM
authors.lastname: Diamond
authors.forename: Christopher
authors.initials: C
authors.lastname: Goh
authors.forename: Keith A
authors.initials: KA
authors.lastname: Hall
authors.forename: Anne M
authors.initials: AM
authors.lastname: LaPointe
authors.forename: Margarete
authors.initials: M
authors.lastname: Leclerc
authors.forename: Cheryl
authors.initials: C
authors.lastname: Lund
authors.forename: Vince
authors.initials: V
authors.lastname: Murphy
authors.forename: James A W
authors.initials: JA
authors.lastname: Shoemaker
authors.forename: Ursula
authors.initials: U
authors.lastname: Tracht
authors.forename: Howard
authors.initials: H
authors.lastname: Turner
authors.forename: Jessica
authors.initials: J
authors.lastname: Zhang
authors.forename: Tetsuo
authors.initials: T
authors.lastname: Uno
authors.forename: Robert K
authors.initials: RK
authors.lastname: Rosen
authors.forename: James C
authors.initials: JC
authors.lastname: Stevens