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Copolymerization of Ethylene and Long-Chain Functional α-Olefins by Dinuclear Zirconium Catalysts

Sampson, Jessica and Bruening, Meaghan and Akhtar, Muhammed Naseem and Jaseer, E. A. and Theravalappil, Rajesh and Garcia, Nestor and Agapie, Theodor (2021) Copolymerization of Ethylene and Long-Chain Functional α-Olefins by Dinuclear Zirconium Catalysts. Organometallics, 40 (12). pp. 1854-1858. ISSN 0276-7333. doi:10.1021/acs.organomet.1c00126.

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Bimetallic catalysts have shown promise for improving polar comonomer incorporation by late transition metals, but such effects are underexplored using early transition metal catalysts. Herein, the copolymerization of ethylene and α-olefins bearing alcohol groups was performed using mono- and dizirconium bisamine bisphenolate catalysts in the presence of MAO and Al^iBu₃. Under these conditions, catalyst activity was retained with comonomer incorporation trends mirroring those observed with unfunctionalized α-olefins, i.e., lower incorporation by bimetallic catalysts. Although incorporation levels are low, these data provide mechanistic insight for polar comonomer incorporation. These results are consistent with our earlier proposal that larger comonomers sterically clash with the distal metal center of the bimetallic catalysts, leading to lower incorporation. Additionally, a bimetallic mechanism for polar comonomer coordination and incorporation is not supported by the current data.

Item Type:Article
Related URLs:
URLURL TypeDescription
Jaseer, E. A.0000-0002-5385-8778
Agapie, Theodor0000-0002-9692-7614
Additional Information:© 2021 American Chemical Society. Received: March 2, 2021; Published: June 7, 2021. The authors are grateful for the support provided by the King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia, offered under the KFUPM-Caltech Research Collaboration. The authors are also grateful for the assistance of Dr. Dave VanderVelde in acquiring polymer NMR data. The authors declare no competing financial interest.
Funding AgencyGrant Number
King Fahd University of Petroleum and Minerals (KFUPM)UNSPECIFIED
Subject Keywords:Catalysts, Hydrocarbons, Bimetals, Metals, Copolymerization
Issue or Number:12
Record Number:CaltechAUTHORS:20210623-151211923
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Official Citation:Copolymerization of Ethylene and Long-Chain Functional α-Olefins by Dinuclear Zirconium Catalysts. Jessica Sampson, Meaghan Bruening, Muhammed Naseem Akhtar, E. A. Jaseer, Rajesh Theravalappil, Nestor Garcia, and Theodor Agapie. Organometallics 2021 40 (12), 1854-1858; DOI: 10.1021/acs.organomet.1c00126
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:109548
Deposited By: Tony Diaz
Deposited On:23 Jun 2021 18:30
Last Modified:06 Jul 2021 18:05

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