Journal
ACS CATALYSIS
Volume -, Issue -, Pages 9646-9654Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.2c027059646ACS
Keywords
heterogeneous nickel catalyst; ethylene copolymerization; polar monomer; Lewis acid; electron density
Categories
Funding
- National Natural Science Foundation of China [22071023]
- Fundamental Research Funds for the Central Universities [2232020A-05]
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The development of heterogeneous late transition metal-catalyzed olefin (co)polymerization is challenging. This study reports the preparation of heterogeneous anilinonaphthoquinone nickel and palladium catalysts. The nickel catalyst exhibits very high activity and can produce high-molecular-weight semicrystalline polyethylenes. The polymerization behavior is influenced by the electron density of the metal center and the Lewis acidity of the alkylaluminum. The palladium catalyst promotes copolymerization of ethylene with methyl acrylate or polar norbornene derivatives.
The development of the heterogeneous late transition metal-catalyzed olefin (co)polymerization is a challenge in current research. Here, we report the preparation of heterogeneous anilinonaphthoquinone nickel and palladium catalysts by the binding of SiO2-supported alkylaluminums to a quinone oxygen of the ligand (Mt-AlR3/SiO2). The heterogeneous nickel catalyst exhibited a very high activity (up to 10.4 x 106 g mol(-1) h(-1)) for ethylene polymerizations to produce semicrystalline high-molecular-weight (Mn up to 54.3 x 104 g mol-1) polyethylenes with a low degree of branching (< 11.1/1000 C), high Tm values (121-131 ?), and well-regulated particle morphologies. The polymerization behavior depended on the electron density of the metal center modulated by the Lewis acidity of the remotely bound alkylaluminum as can be analyzed and verified through model optimizations and density functional theory (DFT) calculations. Most importantly, these nickel catalysts were able to produce semicrystalline ethylene/5-hexene-1-yl copolymers with a high activity and high molecular weight. The heterogeneous palladium catalyst can promote the copolymerization of ethylene with commercial methyl acrylate or polar norbornene derivatives with a moderate activity, affording a polar functionalized polyethylene and a cyclic olefin copolymer.
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