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Bimetallic Zirconium Amine Bis(phenolate) Polymerization Catalysts: Enhanced Activity and Tacticity Control for Polyolefin Synthesis

Radlauer, Madalyn R. and Agapie, Theodor (2014) Bimetallic Zirconium Amine Bis(phenolate) Polymerization Catalysts: Enhanced Activity and Tacticity Control for Polyolefin Synthesis. Organometallics, 33 (13). pp. 3247-3250. ISSN 0276-7333. PMCID PMC4216186. http://resolver.caltech.edu/CaltechAUTHORS:20140623-105942813

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Abstract

Binucleating multidentate amine bis(phenolate) ligands with rigid terphenyl backbones were designed to support two zirconium centers locked in close proximity. Polymerizations of propylene or 1-hexene with the synthesized bimetallic precatalysts resulted in polymers with significantly higher isotacticity (up to 79% mmmm) in comparison to the stereoirregular polymers produced with previously reported C_s-symmetric monometallic analogues. The bimetallic precatalysts also display higher activity (up to 124 kg of poly(1-hexene) (mmol of Zr)^(−1) h^(–1)), in comparison to the monometallic analogues, and among the highest activities reported for nonmetallocene catalysts. The stereocontrol is consistent with a bimetallic mechanism involving remote steric interactions with the ligand sphere of the second metal center.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/om500608jDOIArticle
http://pubs.acs.org/doi/abs/10.1021/om500608jPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/om500608jPublisherSupporting Information
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4216186/PubMed CentralArticle
ORCID:
AuthorORCID
Agapie, Theodor0000-0002-9692-7614
Additional Information:© 2014 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received: June 9, 2014. Publication Date (Web): June 18, 2014. We are grateful to Dow Chemical, Caltech, and the ACS PRF for funding. We thank Dr. Mike Takase, Lawrence M. Henling, and Emily Tsui for crystallographic assistance. The Bruker KAPPA APECII X-ray diffractometer was purchased via an NSF CRIF:MU award to Caltech (CHE-063-9094). The 400 MHz NMR spectrometer was purchased via an NIH award (RR027690).
Funders:
Funding AgencyGrant Number
Dow ChemicalUNSPECIFIED
CaltechUNSPECIFIED
American Chemical Society Petroleum Research FundUNSPECIFIED
NSFCHE-063-9094
NIHRR027690
PubMed Central ID:PMC4216186
Record Number:CaltechAUTHORS:20140623-105942813
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20140623-105942813
Official Citation:Bimetallic Zirconium Amine Bis(phenolate) Polymerization Catalysts: Enhanced Activity and Tacticity Control for Polyolefin Synthesis Madalyn R. Radlauer and Theodor Agapie Organometallics 2014 33 (13), 3247-3250
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:46434
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:23 Jun 2014 19:50
Last Modified:20 Jul 2017 23:36

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