Surface science of single-site heterogeneous olefin polymerization catalysts
- *Department of Chemical Engineering, Pennsylvania State University, University Park, PA 16802; and
- †Department of Chemistry, University of California, Berkeley, CA 94720
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Edited by Tobin J. Marks, Northwestern University, Evanston, IL, and approved June 7, 2006 (received for review April 3, 2006)
Abstract
This article reviews the surface science of the heterogeneous olefin polymerization catalysts. The specific focus is on how to prepare and characterize stereochemically specific heterogeneous model catalysts for the Ziegler–Natta polymerization. Under clean, ultra-high vacuum conditions, low-energy electron irradiation during the chemical vapor deposition of model Ziegler–Natta catalysts can be used to create a “single-site” catalyst film with a surface structure that produces only isotactic polypropylene. The polymerization activities of the ultra-high vacuum-prepared model heterogeneous catalysts compare well with those of conventional Ziegler–Natta catalysts. X-ray photoelectron spectroscopic analyses identify the oxidation states of the Ti ions at the active sites. Temperature-programmed desorption distinguishes the binding strength of a probe molecule to the active sites that produce polypropylenes having different tacticities. These findings demonstrate that a surface science approach to the preparation and characterization of model heterogeneous catalysts can improve the catalyst design and provide fundamental understanding of the single-site olefin polymerization process.
Footnotes
- ‡To whom correspondence should be addressed. E-mail: somorjai{at}socrates.berkeley.edu
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Author contributions: G.A.S. designed research; S.H.K. performed research; and S.H.K. wrote the paper.
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Conflict of interest statement: No conflicts declared.
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This article is a PNAS direct submission.
- Abbreviations:
- UHV,
- ultra-high vacuum;
- XPS,
- x-ray photoelectron spectroscopy;
- TPD,
- temperature-programmed desorption;
- Cp,
- cyclopentadienyl.
- © 2006 by The National Academy of Sciences of the USA
