%0 Journal Article %T Simple Preparation of Halogen-Substituted <i>汐</i>-Diimine Nickel Complexes Immobilized into Clay Interlayer as Catalysts for Ethylene Oligo-/Polymerization %A Miru Yoshida-Hirahara %A Shiori Fujiwara %A Hideki Kurokawa %J Modern Research in Catalysis %P 100-120 %@ 2168-4499 %D 2017 %I Scientific Research Publishing %R 10.4236/mrc.2017.62008 %X In the practical use for the production of the 汐-olefins, it is highly desired to develop a novel heterogeneous catalyst system. The metal complexes immobilized into the clay interlayers show a great potential as heterogeneous catalysts due to their excellent processability. In this study, nine types of heterogeneous procatalyst Ln/Ni²⁺-micas were synthesized via a one-pot preparation method, which includes both the condensation reaction of the ligand derivatives and the intercalation of the ligands into the Ni²⁺ ion-exchanged fluorotetrasilicic mica interlayer. The ligand structures of the prepared procatalysts were [Ln: R-N = C(Nap)-C(Nap) = N-R] [(Nap = 1,8-naphthdiyl) (L₁, R = 2-MePh; L₂, R = 2-FPh; L₃, R = 2-BrPh; L₄, R = 4-MePh; L₅, R = 4-FPh; L6, R = 4-BrPh; L7, R = 2,4-F₂Ph; L8, R = 2,4-Br₂Ph; L9, R = 2,6-F₂Ph). At 50⊥ and 0.7 MPaethylene pressure, the triisobutylaluminum-activated L1-L6/Ni²⁺-mica showed a catalytic activity for the ethylene oligo-/polymerization in the range of 334 - 549 g-ethylene•g-cat^每1•h^每1. A high catalyst activity was obtained when the substituent having a larger steric bulk than that of a methyl substituent was introduced at the ortho-position of the aryl rings. The introduction of the fluorine substituent as a strong electron-withdrawing group to the para-position also increased the catalytic activity. The L₂, L₄, L₅, and L₆/Ni²⁺-micas showed moderate selectivities to oligomers consisting of C₄-C₂₀ in the range of 19.9 - 41.6 wt% at 50⊥. The calculated Schulz-Flory constants 汐 based on the mole fraction of C₁₂ and C₁₄ were within 0.61 - 0.78. %K Ethylene Oligo-/Polymerization %K Heterogeneous Catalyst %K Halogen Substituted < %K i> %K 汐< %K /i> %K -Diimine Nickel Complex %K < %K i> %K 汐< %K /i> %K -Olefin Oligomer %K Layered Clay Mineral %U http://www.scirp.org/journal/PaperInformation.aspx?PaperID=75986