Copolymerization of Nonpolar Olefins and Allyl Acetate Using Nickel Catalysts Bearing a Methylene-Bridged Bisphosphine Monoxide Ligand

Abstract

Bisphosphine monoxide ligand 1 with a methylene linker was applied to the nickel catalyzed olefin polymerization. In situ generated phenylnickel chloride complex 2 and NaBArF 4 mediated the homopolymerization of ethylene and propylene. In addition, complex 2 and NaBArF 4 produced the copolymer of those nonpolar olefins with allyl acetate. Cationic η3-allylnickel complex 3 was successfully isolated and characterized by X-ray crystallographic analysis. Complex 3 exhibited square planar geometry with a bite angle close to 90 deg. Although a strong Lewis acidic cocatalyst such as ZnEt2, B­(C6F5)3, or methylaluminoxane was required for the activation, complex 3 could also copolymerize nonpolar olefins with allyl acetate.

Late Transition Metal Complexes for Olefin Copolymerization with Polar Monomers

“…在氧化膦端引入强给电子性双胺基, 324 和 325 催 化乙烯-丙烯酸甲酯等简单工业大宗极性单体共聚 [13] [186] . [190] , 陈昶乐等 [191] 345 还可以催化乙烯-甲基丙烯酸甲酯共聚 [192] [193] , 催 化 活 性 (50 ～ 2400)和共聚物分子量较低(890～1300), 极性基团位于 链中和链终止端, 插入率为 0.4%～1.5%.…”

2,4,6‐Triphenylpyridinium: A Bulky, Highly Electron‐Withdrawing Substituent That Enhances Properties of Nickel(II) Ethylene Polymerization Catalysts

“…In several cases such analogs have resulted in significant modifications in catalyst performance with respect to microstructural and molecular weight control, thermal stability, and the ability to copolymerize polar and nonpolar olefins. Furthermore, other neutral, bulky bidentate ligands which lead to catalysts possessing cationic metal centers have shown to be competent catalysts for ethylene and α‐olefin polymerizations [10–12] …”

“…Furthermore, other neutral, bulky bidentate ligands which lead to catalysts possessing cationic metal centers have shown to be competent catalysts for ethylene and a-olefin polymerizations. [10][11][12] A second class of important Ni II and Pd II catalysts are those bearing bulky anionic bidentate ligands which result in neutral, uncharged metal centers. Such catalysts are less electrophilic than catalysts of type 1 and, while generally showing higher olefin insertions barriers, often exhibit increased thermal stabilities, greater tolerance of polar media and increased ability to copolymerize polar and nonpolar olefins.…”

Nickel catalysts for the preparation of functionalized polyolefin materials

“…的共聚过程并且制备更高分子量的共聚物 [95] 。随后，五元环镍催化体系受到了广泛关注，Nozaki 课题组 [96] 发展的五元环膦-膦氧镍催化剂F8-5，可以进行乙烯与多种烯丙基类极性单体的共聚合。…”