4.7 Article

Active Sites in a Heterogeneous Organometallic Catalyst for the Polymerization of Ethylene

期刊

ACS CENTRAL SCIENCE
卷 7, 期 7, 页码 1225-1231

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AMER CHEMICAL SOC
DOI: 10.1021/acscentsci.1c00466

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资金

  1. Chevron Phillips Chemical
  2. National Science Foundation [CBET-1916809, CHE-1800561]
  3. American Chemical Society Petroleum Research Fund [58627-DNI6]
  4. Sloan Foundation
  5. European Research Council (ERC) under the European Union [725686]
  6. Royal Thai Government Scholarships
  7. NWO Domain Science
  8. MRSEC Program of the NSF [DMR-1720256]
  9. NSF

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The study elucidates the reaction mechanism of triisobutylaluminum with aluminum oxide and a zirconocene precatalyst, generating ion pairs to catalyze ethylene polymerization.
Heterogeneous derivatives of catalysts discovered by Ziegler and Natta are important for the industrial production of polyolefin plastics. However, the interaction between precatalysts, alkylaluminum activators, and oxide supports to form catalytically active materials is poorly understood. This is in contrast to homogeneous or model heterogeneous catalysts that contain resolved molecular structures that relate to activity and selectivity in polymerization reactions. This study describes the reactivity of triisobutylaluminum with high surface area aluminum oxide and a zirconocene precatalyst. Triisobutylaluminum reacts with the zirconocene precatalyst to form hydrides and passivates -OH sites on the alumina surface. The combination of passivated alumina and zirconium hydrides formed in this mixture generates ion pairs that polymerize ethylene.

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