Enhancement on Hemilabile Phosphine-Amide Palladium and Nickel Catalysts for Ethylene(Co)Polymerization with Polar Monomers Using a Cyclizing Strategy  

作　　者：Lei Cui Yu-Kai Chu Da-Jun Liu Ying-Feng Han Hong-Liang Mu Zhong-Bao Jian 

机构地区：[1]State Key Laboratory of Polymer Physics and Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022,China [2]School of Chemistry and Environmental Engineering,Changchun University of Science and Technology,Changchun 130022,China [3]Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education,College of Chemistry and Materials Science,Northwest University,Xi’an 710127,China

出　　处：《Chinese Journal of Polymer Science》2022年第3期241-247,I0005,共8页高分子科学（英文版）

基　　金：financial support from the National Natural Science Foundation of China (Nos. 22122110 ad 21871250);the Jilin Provincial Science and Technology Department Program (No. 20200801009GH);Shaanxi Provincial Natural Science Basic Research Program-Shaanxi Coal and Chemical Industry Group Co., Ltd. Joint Fund (No. 2019JLZ-02)。

摘　　要：To address the issue of hemilabile catalyst in olefin polymerization catalysis, a cyclizing strategy was used to construct novel N-bridged phosphine-carbonyl palladium and nickel catalysts, resulting in improvements on ethylene(co)polymerizations. The N-bridged phosphinecarbonyl Pd catalysts(Pd1-Pd5) and Ni catalysts(Ni1-Ni5) bearing five-to eight-membered-ring structures were designed and synthesized.Catalytic performance for ethylene(co)polymerization became better as the size of N-containing bridge increased. The seven-membered-ring bridged catalysts Pd4 and Ni4 exhibited the best performance in terms of catalytic activity, polymer molecular weight and incorporation of acrylates and acrylic acid. The better performance of these catalysts bearing larger-size bridges was tentatively attributed to the methyleneinduced higher electron density around nitrogen, which strenghtens the coordination of carbonyl group to metal center, and also to the steric effect offered by this cyclization. This work provides a new strategy to enhance hemilabile polymerization catalysts.

关 键 词：POLYOLEFINS Cyclizing strategy Phosphine ligands Polar monomers Late transition metal catalysts 

分 类 号：TQ316.3[化学工程—高聚物工业] TQ426