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Polymers 2017, 9(8), 353;

Facile, Efficient Copolymerization of Ethylene with Norbornene-Containing Dienes Promoted by Single Site Non-Metallocene Oxovanadium(V) Catalytic System

Tianjin Key Lab of Composite & Functional Materials, School of Materials Science and Engineering, Tianjin University, Tianjin 300072, China
Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
National Center for Nanoscience and Technology, Beijing 100190, China
Author to whom correspondence should be addressed.
Received: 23 July 2017 / Revised: 8 August 2017 / Accepted: 8 August 2017 / Published: 11 August 2017
(This article belongs to the Special Issue Olefin Polymerization and Polyolefin)
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Non-metallocene oxovanadium(V) complexes bearing either [ONNO]-type amine pyridine bis(phenolate) ligands or [ONN]-type amine pyridine phenolate ligands were employed as efficient catalysts to copolymerize ethylene with several unsymmetrical norbornene-containing dienes, such as 5-vinyl-2-norbornene (VNB), 5-ethylidene-2-norbornene (ENB) or dicyclopentadiene (DCPD), producing copolymers with high comonomer incorporations (VNB: 33.0 mol %; ENB: 30.4 mol %; DCPD: 31.6 mol %, respectively) and high molecular weight (VNB: 86.4 kDa; ENB: 256 kDa; DCPD: 86.4 kDa, respectively). The enchainment of the dienes was proven to be exclusive of vinyl-addition via the C=C double bond of the norbornene ring while the other double bond was retained near the backbone without crosslinking. During the copolymerization of ethylene with ENB, a positive ‘comonomer effect’ was observed. The catalytic activities of the catalysts as well as the molecular weights and comonomer incorporations of the resultant copolymers could be tuned within a wide range by varying the structures of the catalysts and copolymerization conditions. The [ONN]-type oxovanadium(V) complexes showed higher catalytic activities than those of [ONNO]-type oxovanadium(V) complexes, irrespective of the structure of the dienes. In addition, the dominant chain transfer pathway of the non-metallocene oxovanadium(V) catalytic system promoted copolymerization was proven to be transfer to aluminum compounds. View Full-Text
Keywords: cyclic olefin; copolymerization; diene; chain transfer; vinyl addition cyclic olefin; copolymerization; diene; chain transfer; vinyl addition

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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Wang, K.; Wang, J.; Li, Y.; Pan, L.; Li, Y. Facile, Efficient Copolymerization of Ethylene with Norbornene-Containing Dienes Promoted by Single Site Non-Metallocene Oxovanadium(V) Catalytic System. Polymers 2017, 9, 353.

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