Exploring steric effect of electron-donating group in palladium and nickel mediated ethylene polymerization and copolymerization with polar monomers

被引:17
作者
Xia, Jian [1 ,2 ]
Han, Ying-Feng [3 ]
Kou, Shuqing [1 ]
Zhang, Yixin [2 ]
Jian, Zhongbao [2 ]
机构
[1] Jilin Univ, Roll Forging Res Inst, Coll Mat Sci & Engn, Changchun 130025, Peoples R China
[2] Chinese Acad Sci, Changchun Inst Appl Chem, State Key Lab Polymer Phys & Chem, Renmin St 5625, Changchun 130022, Peoples R China
[3] Northwest Univ, Coll Chem & Mat Sci, Key Lab Synthet & Nat Funct Mol, Minist Educ, Xian 710127, Peoples R China
基金
中国国家自然科学基金;
关键词
Steric effect; Palladium; Nickel; Ethylene polymerization; Polar monomer; PHOSPHINE-SULFONATE PALLADIUM; CATALYZED COPOLYMERIZATION; MOLECULAR-WEIGHT; VINYL MONOMERS; INSERTION; PROPYLENE; LIGAND; (CO)POLYMERIZATION; POLYETHYLENES; REACTIVITY;
D O I
10.1016/j.eurpolymj.2021.110781
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
The influence of steric effect of electron-donating substituents on the phosphine-sulfonate palladium and nickel catalysts was rarely studied in olefin (co)polymerizations. In this contribution, a family of flexible cyclohexyl/ rigid aromatic phosphine-sulfonate palladium and nickel catalysts was designed, synthesized, and comprehensively identified by varying number, position, and size of alkoxy groups on aromatic substituents of phosphine. In ethylene polymerization, the steric effect of alkoxy substituents in palladium and nickel catalysts plays an important role on tuning polymer molecular weight, which gives the high molecular weight of 380 kg mol-1 at 80 degrees C in the palladium system and also provides very high catalytic activity of 16000 kg mol-1 h-1 at 70 degrees C in the nickel system. In ethylene copolymerization with polar monomers, the decrease of steric bulk leads to an increase on the co-monomer incorporation in the obtained copolymers. As a result, the copolymerization of ethylene with methyl acrylate, and acrylic acid using palladium catalysts affords the high incorporation of 9.5 mol% and 8.3 mol%, respectively; and the nickel promoted ethylene copolymerization with vinyl trimethoxysilane, and 6chloro-1-hexene gives the incorporation of 3.7 mol% and 5.0 mol%, respectively.
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页数:7
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