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INORGANICA CHIMICA ACTA · 2016 · IF 1.918

Novel nickel complexes with hyperbranched structure: Synthesis, characterization and performance in ethylene oligomerization

Cuiqin Li,Fengfeng Wang,Zhiyu Lin,Na Zhang,Jun Wang

Two novel nickel complexes with hyperbranched structure were synthesized with 1.0 generation hyperbranched polyamine molecules (1.0G), salicylaldehyde and anhydrous nickel chloride as materials via the Schiff’s base and the complexation reactions. The structures of the novel hyperbranched ligands and their nickel complexes were characterized by FT-IR, 1 H NMR, UV, ESI-MS and elemental analysis. The hyperbranched nickel complexes were evaluated as catalyst precursors for ethylene oligomerization after being activated with methylaluminoxane (MAO), diethylaluminum chloride (Et 2 AlCl) and ethylaluminum sesquichloride (EASC). The influence of Al/Ni ratio, temperature and ethylene pressure on ethylene oligomerization was also investigated using the novel hyperbranched nickel complexes as pre-catalysts and MAO as co-catalyst. The catalytic activities of the two hyperbranched nickel complexes with dodecyl and octadecyl as cores (R 12 -complex and R 18 -complex) were 2.33   ×   10 5   g/(mol Ni·h) and 1.23   ×   10 5   g/(mol Ni·h), respectively, and the selectivities for C 8+ oligomers of R 12 -complex and R 18 -complex were 56.16% and 88.64% respectively, when the Al/Ni molar ratio was 500:1, the temperature was 25   °C, the pressure of ethylene was 0.5   MPa and the co-catalyst was MAO. The catalytic activities and product distribution were largely dependent on the nature of the co-catalysts and the structures of nickel complexes. The catalytic activities decreased with increasing of the length of alkyl chain of the hyperbranched nickel complexes.

CAS / MDL: 96-10-6 12075-68-2
研究领域: 化学 · 材料科学
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JOURNAL OF APPLIED POLYMER SCIENCE · 2019 ·Vol. 137 ·期 17 ·48620 · IF 2.188

Synthesis of pyrrole-bridged constrained geometry complexes and their application for olefin polymerization

Jianfeng Liu,Lu Shao,Xiu Feng,Sheng Xu,Puke Mi

In this article, four constrained geometry complexes 4a [(η 5 -C 5 H 4 )CH 2 (α-C 4 H 3 N)]Ti(NMe 2 ) 2 , 7a [(η 5 -C 9 H 6 )CH 2 (α-C 4 H 3 N)]Ti(NMe 2 ) 2 , 4b [(η 5 -C 5 H 4 )CH 2 (α-C 4 H 3 N)]Zr(NEt 2 ) 2 , 7b [(η 5 -C 9 H 6 )CH 2 (α-C 4 H 3 N)]Zr(NEt 2 ) 2 with pyrrole-bridged fragment were synthesized and characterized by 1 H NMR, 13 C NMR, MASS, and EA. When combined with MAO, complex 4b given the highest activity, the activity of copolymerizing ethylene and 1-hexene reached 2.48 × 10 6 g polymer/mol·M·h. The effects of temperature, pressure, and ratio of Al/Metal on the polymerization reaction and properties of polymers had been investigated. The polymers with these complexes were characterized by 13 C NMR and DSC, and the results shown that polymer with 4a had the highest α-olefin incorporation, the incorporation of 1-hexene reached up to 9.81 mol%, and the 1-octene was 8.84 mol%. Actually, there was no [HH] or [OO] sequence in the copolymer, according to the formula of reactivity ratio, rE • rH = 0, all these results suggested that the copolymerization mode is alternating copolymerization. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137 , 48620.

CAS / MDL: 16853-85-3 123-75-1
研究领域: 高分子化学 · 催化化学
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