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Catalysts 2013, 3(1), 125-136; doi:10.3390/catal3010125

Oligomerization of Ethylene to Produce Linear α-Olefins Using Heterogeneous Catalyst Prepared by Immobilization of α-Diiminenickel(II) Complex into Fluorotetrasilicic Mica Interlayer

1
Graduate School of Science & Engineering, Saitama University, 255, Shimo-okubo, Sakura-ku, Saitama-shi, Saitama, 338-8570, Japan
2
Japan Polychem Corporation, 1 Toho-cho, Yokkaichi-shi, Mie, 510-0848, Japan
*
Author to whom correspondence should be addressed.
Received: 13 December 2012 / Revised: 29 January 2013 / Accepted: 29 January 2013 / Published: 6 February 2013
(This article belongs to the Special Issue Molecular Catalysis for Precise Olefin Polymerization)
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Abstract

Heterogeneous catalysts for production of linear α-olefins from ethylene were prepared by the direct reaction of the α-diimine ligand [L: R-N=C(R')-C(R')=N-R; R' = Me and R = 2,6-Me2Ph (L5), 2,5-Me2Ph (L1), 2-MePh (L2), or Ph (L3); R' = 1,8-naphth-diyl and R = Ph (L4)] and Ni2+ ion-exchanged fluorotetrasilicic mica. Only high molecular weight polyethylene was obtained in the reaction using the L5/Ni2+-Mica procatalyst activated by AlEt3 (TEA) as an activator, whereas the TEA-activated L1- and L2/Ni2+-Mica procatalysts afforded a mixture of a large amount of low-molecular weight polyethylene and a small amount of oligomers having 4-22 carbons. The procatalyst consisting of Ni2+-Mica and the L3 ligand that possesses non-substituted phenyl groups on the iminonitrogen atoms effectively promoted the oligomerization of ethylene after its activation with TEA, resulting in the fact that the ethylene oligomers were produced with a moderate catalytic activity (101 g-ethylene g-cat−1 h−1 at 0.7 MPa-ethylene) in the presence of TEA. When the backbone was varied from the butane moiety (L3) to acenaphthene (L4), the solid product dramatically increased. The weight percentage of the oligomers in the total products increased with the increasing reaction temperature; however, an insignificant increase in the oligomers was observed when the ethylene pressure was decreased. View Full-Text
Keywords: polymerization; polyethylene; clay minerals; intercalation polymerization; polyethylene; clay minerals; intercalation
This is an open access article distributed under the Creative Commons Attribution License (CC BY 3.0).

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MDPI and ACS Style

Kurokawa, H.; Miura, K.; Yamamoto, K.; Sakuragi, T.; Sugiyama, T.; Ohshima, M.-A.; Miura, H. Oligomerization of Ethylene to Produce Linear α-Olefins Using Heterogeneous Catalyst Prepared by Immobilization of α-Diiminenickel(II) Complex into Fluorotetrasilicic Mica Interlayer. Catalysts 2013, 3, 125-136.

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