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Highly Stereoregular Syndiotactic Polypropylene Formation with Metallocene Catalysts via Influence of Distal Ligand Substituents

Miller, Stephen A. and Bercaw, John E. (2004) Highly Stereoregular Syndiotactic Polypropylene Formation with Metallocene Catalysts via Influence of Distal Ligand Substituents. Organometallics, 23 (8). pp. 1777-1789. ISSN 0276-7333. doi:10.1021/om030333f. https://resolver.caltech.edu/CaltechAUTHORS:20170807-155218146

[img] PDF (X-ray crystal structure data for Ph2C(OctH)(C5H5), Ph2C(C29H36)(C5H4)ZrCl2 (8), and Ph2C(C21H22)(C5H4)ZrCl2 (10)) - Supplemental Material
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Abstract

Highly stereoregular syndiotactic polypropylene is obtained with the catalyst systems Ph_2C(Oct)(C_5H_4)ZrCl_2/MAO (8/MAO) (Oct = octamethyloctahydrodibenzofluorenyl; MAO = methylaluminoxane) and Me_2C(Oct)(C_5H_4)ZrCl_2/MAO (12/MAO). The syndiotactic polypropylenes obtained are largely devoid of stereoerrors by ^(13)C NMR analysis ([r] > 98%), and melting temperatures as high as 153 or 154 °C (from 8 and 12, respectively) are found for the thermally quenched polymers (without annealing). A related hafnium catalytic system, Ph_2C(Tet)(C_5H_4)HfCl_2/MAO (11/MAO) (Tet = tetramethyltetrahydrobenzofluorenyl), was found to be the most syndioselective of the hafnocenes tested (T_m = 141 °C). The metallocene dichloride precatalysts represent the first examples of transition metal complexes containing the Oct or Tet ligands. Reported are the solid state crystal structures of 8, the diprotio ligand precursor of 8(Ph_2C(OctH)(C_5H_5)), and the zirconium analogue of 11, Ph_2C(Tet)(C_5H_4)ZrCl_2 (10). Distal ligand influences are thus demonstrated to have a dramatic effect on polymer stereochemistry.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/om030333fDOIArticle
http://pubs.acs.org/doi/abs/10.1021/om030333fPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/om030333fPublisherSupporting Information
ORCID:
AuthorORCID
Miller, Stephen A.0000-0002-3181-1426
Additional Information:© 2004 American Chemical Society. Received May 6, 2003. Publication Date (Web): March 18, 2004. This work has been funded by the USDOE Office of Basic Energy Sciences (Grant No. DE-FG03-88ER13431) and by a DOD National Defense Science and Engineering Fellowship awarded to S.M. The authors thank Dr. Michael Day and Mr. Lawrence Henling for obtaining the X-ray crystal structures. The authors also thank Dr. Terry Burkhardt at ExxonMobil for providing molecular weight data. Dr. Luigi Resconi at Montell Polyolefins (now Basell Polyolefins) kindly provided polymer analysis of the sample from entry 15.
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-FG03-88ER13431
National Defense Science and Engineering Graduate (NDSEG) FellowshipUNSPECIFIED
Issue or Number:8
DOI:10.1021/om030333f
Record Number:CaltechAUTHORS:20170807-155218146
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170807-155218146
Official Citation:Highly Stereoregular Syndiotactic Polypropylene Formation with Metallocene Catalysts via Influence of Distal Ligand Substituents. Stephen A. Miller and John E. Bercaw Organometallics 2004 23 (8), 1777-1789 DOI: 10.1021/om030333f
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:79877
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:07 Aug 2017 23:05
Last Modified:15 Nov 2021 17:51

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