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Sterically very bulky aliphatic/aromatic phosphine-sulfonate palladium catalysts for ethylene polymerization and copolymerization with polar monomers

Abstract

A class of sterically very bulky aliphatic/aromatic phosphine-sulfonate ligands L1~L4 and the corresponding neutral palladium complexes 1~4 {[κ2(P,O)-(menthyl)ArP(C6H4SO2O)]PdMe(pyr)} (1: Ar = 2-(2',6'-(MeO)2C6H3)C6H4; 2: Ar = 2-(C6H5)C6H4; 3: Ar = 2-(2',6'-F2C6H3)C6H4; 4: Ar = (MeO)3C6H2) was synthesized and comprehensively identified by NMR spectroscopy, single-crystal X-ray diffraction, and elemental analysis. All these palladium catalysts were employed in ethylene polymerization, generating highly linear polyethylenes (methyl branches < 1/1000C) with high molecular weight (up to 194 kg mol-1) in a high activity of up to 3300 kg mol-1 h-1. More remarkably, in the copolymerization of ethylene and a variety of challenging polar vinyl monomers such as acrylate, acrylic acid, acrylamide, vinyl ether, vinyl acetate, and acrylonitrile, the preferred catalysts 3 and 4 again showed significantly high activity, affording highly linear functionalized polyethylenes with clearly enhanced molecular weight. Especially for the copolymerization of acrylates with ethylene, both the catalytic activity and the copolymer molecular weight are close to the same order of magnitude for ethylene homopolymerization, which are up to 1000 kg mol-1 h-1 and 100 kg mol-1, respectively.

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Publication details

The article was received on 05 Nov 2018, accepted on 06 Dec 2018 and first published on 06 Dec 2018


Article type: Paper
DOI: 10.1039/C8PY01568F
Citation: Polym. Chem., 2018, Accepted Manuscript
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    Sterically very bulky aliphatic/aromatic phosphine-sulfonate palladium catalysts for ethylene polymerization and copolymerization with polar monomers

    J. Xia, Y. Zhang, X. Hu, X. Ma, L. Cui, J. Zhang and Z. Jian, Polym. Chem., 2018, Accepted Manuscript , DOI: 10.1039/C8PY01568F

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