文献类型：期刊文献

英文题名：Influence of Silica-Supported Alkylaluminum on Heterogeneous Zwitterionic Anilinonaphthoquinone Nickel and Palladium-Catalyzed Ethylene Polymerization and Copolymerization with Polar Monomers

作者：Zhang, Hu[1];Zhang, Zhaoyu[1];Cai, Zhengguo[1];Li, Mingyuan[2];Liu, Zhen[3]

机构：[1]Donghua Univ, Coll Mat Sci & Engn, State Key Lab Modificat Chem Fibers & Polymer Mat, Shanghai 201620, Peoples R China;[2]Guangdong Technion Israel Inst Technol, Dept Chem, Shantou 515063, Peoples R China;[3]East China Univ Sci & Technol, Schoolof Chem Engn, Shanghai 200237, Peoples R China

年份：2022

卷号：12

期号：15

起止页码：9646

外文期刊名：ACS CATALYSIS

收录：;EI(收录号：20223512632893);WOS:【SCI-EXPANDED(收录号:WOS:000834098100001)】；

基金：ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (22071023) and Fundamental Research Funds for the Central Universities (2232020A-05) .

语种：英文

外文关键词：heterogeneous nickel catalyst; ethylene copolymerization; polar monomer; Lewis acid; electron density

摘要：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 10(6) g mol(-1) h(-1)) for ethylene polymerizations to produce semicrystalline high-molecular-weight (M-n up to 54.3 x 10(4) g mol(-1)) polyethylenes with a low degree of branching (< 11.1/1000 C), high T-m values (121-131 degrees C), 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.