Ethylene-4-methyl-1-pentene copolymers of complex chain architecture using α-diimine Ni(II) catalysts: synthesis, 13C NMR assignment and understanding the chain-walking mechanism

被引：16

作者：

Losio, Simona ^{[1
]}

Leone, Giuseppe ^{[1
]}

Bertini, Fabio ^{[1
]}

Ricci, Giovanni ^{[1
]}

Sacchi, Maria Carmela ^{[1
]}

Boccia, Antonella Caterina ^{[1
]}

机构：

[1] ISMAC, I-20133 Milan, Italy

来源：

POLYMER CHEMISTRY | 2014年 / 5卷 / 06期

关键词：

METALLOCENE-BASED CATALYSTS; MULTIPLE-QUANTUM NMR; LATE-METAL-CATALYSTS; LIVING POLYMERIZATION; OLEFIN POLYMERIZATION; CHEMICAL-SHIFTS; NICKEL-CATALYST; ETHYLENE; 4-METHYL-1-PENTENE; PROPYLENE;

D O I：

10.1039/c3py01508d

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

Ethylene (E) and 4-methyl-1-pentene (4M1P) are copolymerized using an alpha-diimine Ni(II) catalyst with MAO (methylaluminoxane) or Et2AlCl (diethylaluminium chloride) as the cocatalyst. A series of copolymers with a 4M1P comonomer content ranging from 0.94 to 36.73 mol% are obtained. A detailed C-13 NMR assignment is presented and this thorough analysis has opened up the first full description of this interesting family of copolymers. Manifold branched copolymers are obtained with no noticeable differences in the branching distribution by using MAO or Et2AlCl. The resonance assignments are correlated with the chain-walking mechanism: branching analysis shows that the total amount of 2,1 insertion of the comonomer, followed by backward migration of the nickel active species along the polymer chain, is higher than that of 1,2 inserted 4M1P.

引用

页码：2065 / 2075

页数：11

共 46 条

[1] Living polymerization of ethylene and α-olefins using a nickel α-keto-β-diimine initiator [J].