Publikation: Ultrahighly Branched Main-Chain-Functionalized Polyethylenes via Inverted Insertion Selectivity
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Branched polyolefin microstructures resulting from 'chain walking' are a fascinating feature of late transition metal catalysts, but so far it has not been demonstrated how any desirable branched polyolefin microstructures can be generated hereby. We show how ultrahighly-branched polyethylenes with exclusively methyl-branches (220 Me/1000 C) and very high molecular weights (~10 6 g mol -1 ), that reach the branch density and microstructure of commercial ethylene-propylene elastomers, can be generated from ethylene alone. At the same time polar groups on the main chain can be generated by in-chain incorporation of methyl acrylate. Key is a novel rigid environment in an α-diimine Pd(II) catalyst with a steric constraint that allows for excessive chain walking and branching, but restricts branch formation to methyl branches, hinders chain transfer to afford a living polymerization, and inverts the regioselectivity of acrylate insertion to a 1,2-mode.
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ZHANG, Yuxing, Chaoqun WANG, Stefan MECKING, Zhongbao JIAN, 2020. Ultrahighly Branched Main-Chain-Functionalized Polyethylenes via Inverted Insertion Selectivity. In: Angewandte Chemie International Edition. Wiley. 2020, 59(34), pp. 14296-14302. ISSN 1433-7851. eISSN 1521-3773. Available under: doi: 10.1002/anie.202004763BibTex
@article{Zhang2020-08-17Ultra-49692, year={2020}, doi={10.1002/anie.202004763}, title={Ultrahighly Branched Main-Chain-Functionalized Polyethylenes via Inverted Insertion Selectivity}, number={34}, volume={59}, issn={1433-7851}, journal={Angewandte Chemie International Edition}, pages={14296--14302}, author={Zhang, Yuxing and Wang, Chaoqun and Mecking, Stefan and Jian, Zhongbao} }
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