Issue 34, 2022

Polar additive triggered chain walking copolymerization of ethylene and fundamental polar monomers

Abstract

Copolymerization of ethylene with polar monomers to produce functionalized polyethylenes is important but is a great challenge by using the seminal cationic α-diimine palladium(II) catalyst. A wide range of polar monomers generally shut down the reaction because of the underlying β-X elimination events and formation of stable chelates. In this contribution, a polar additive strategy was developed to overcome these issues. A large excess of a nitrile compound that acted as a polar additive triggered copolymerizations of ethylene with fundamental polar vinyl and allyl monomers, including methyl acrylate, vinyl acetate, butyl vinyl ether, allyl acetate, tert-butyl 3-butenoate, butyl allyl ether, allyl chloride, acrylic anhydride, allyl acrylate, and allyl methacrylate, mediated by one α-diimine palladium(II) catalyst. This avoided a tedious hunting on a one-to-one catalyst. Catalytic activities, copolymer molecular weights, branching densities and microstructures, and co-monomer incorporations could be modulated by varying the amount of the polar additive. Possible mechanistic insights were proposed on the basis of these copolymerization results.

Graphical abstract: Polar additive triggered chain walking copolymerization of ethylene and fundamental polar monomers

Supplementary files

Article information

Article type
Paper
Submitted
18 jul 2022
Accepted
10 aug 2022
First published
10 aug 2022

Polym. Chem., 2022,13, 4966-4972

Polar additive triggered chain walking copolymerization of ethylene and fundamental polar monomers

Y. Zhang and Z. Jian, Polym. Chem., 2022, 13, 4966 DOI: 10.1039/D2PY00934J

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