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
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- 作者：Thomas R. Boussie ; Gary M. Diamond ; Christopher Goh ; Keith A. Hall ; Anne M. LaPointe ; Margarete Leclerc ; Cheryl Lund ; Vince Murphy ; James A. W. Shoemaker ; Ursula Tracht ; Howard Turner ; Jessica Zhang
- 刊名：Journal of the American Chemical Society
- 出版年：2003
- 出版时间：April 9, 2003
- 年：2003
- 卷：125
- 期：14
- 页码：4306 - 4317
- 全文大小：633K
- 年卷期：v.125,no.14(April 9, 2003)
- ISSN：1520-5126
文摘
For the first time, new catalysts for olefin polymerization have been discovered through theapplication of fully integrated high-throughput primary and secondary screening techniques supported byrapid polymer characterization methods. Microscale 1-octene primary screening polymerization experimentscombining arrays of ligands with reactive metal complexes M(CH2Ph)4 (M = Zr, Hf) and multiple activationconditions represent a new high-throughput technique for discovering novel group (IV) polymerizationcatalysts. The primary screening methods described here have been validated using a commercially relevantpolyolefin catalyst, and implemented rapidly to discover the new amide-ether based hafnium catalyst [
2-(N,O)-(2-MeO-C6H4)(2,4,6-Me3C6H2)N]Hf(CH2Ph)3 (1), which is capable of polymerizing 1-octene to highconversion. The molecular structure of 1 has been determined by X-ray diffraction. Larger scale secondaryscreening experiments performed on a focused 96-member amine-ether library demonstrated the versatilehigh temperature ethylene-1-octene copolymerization capabilities of this catalyst class, and led to significantperformance improvements over the initial primary screening discovery. Conventional one gallon batchreactor copolymerizations performed using selected amide-ether hafnium compounds confirmed theperformance features of this new catalyst class, serving to fully validate the experimental results from thehigh-throughput approaches described herein.
2-(N,O)-(2-MeO-C6H4)(2,4,6-Me3C6H2)N]Hf(CH2Ph)3 (1), which is capable of polymerizing 1-octene to highconversion. The molecular structure of 1 has been determined by X-ray diffraction. Larger scale secondaryscreening experiments performed on a focused 96-member amine-ether library demonstrated the versatilehigh temperature ethylene-1-octene copolymerization capabilities of this catalyst class, and led to significantperformance improvements over the initial primary screening discovery. Conventional one gallon batchreactor copolymerizations performed using selected amide-ether hafnium compounds confirmed theperformance features of this new catalyst class, serving to fully validate the experimental results from thehigh-throughput approaches described herein.