Oligomerization of Ethylene to Produce Linear α-Olefins Using Heterogeneous Catalyst Prepared by Immobilization of α-Diiminenickel(II) Complex into Fluorotetrasilicic Mica Interlayer
Oligomerization of Ethylene to Produce Linear α-Olefins Using Heterogeneous Catalyst Prepared by Immobilization of α-Diiminenickel(II) Complex into Fluorotetrasilicic Mica Interlayer
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DOI：
10.3390/catal3010125
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发表时间：
2013-02
期刊：
影响因子：
3.9
通讯作者：
H. Kurokawa;Kazuki Miura;Kazuhiro Yamamoto;Tsutomu Sakuragi;T. Sugiyama;Masa–aki Ohshima;H. Miura
中科院分区：
文献类型：
--
作者：
H. Kurokawa;Kazuki Miura;Kazuhiro Yamamoto;Tsutomu Sakuragi;T. Sugiyama;Masa–aki Ohshima;H. Miura
通过α-二亚胺配体[L：R-N=C（R '）-C（R'）=N-R，R' = Me，R = 2，6-Me_2Ph（L_5），2，5-Me_2Ph（L_1），2-MePh（L_2），Ph（L_3）]的直接反应，制备了用于乙烯制直链α-烯烃的多相催化剂; R ′ = 1，8-萘二基和R = Ph（L ~ 4）]和Ni ~（2+）离子交换的氟四氢云母。在使用由AlEt 3（TEA）活化的L5/Ni 2 +-云母主催化剂作为活化剂的反应中仅获得高分子量聚乙烯，而TEA活化的L1-和L2/Ni 2 +-云母主催化剂提供大量低分子量聚乙烯和少量具有4-22个碳的低聚物的混合物。由Ni 2 +-云母和在亚氮原子上具有未取代的苯基的L3配体组成的主催化剂在其用TEA活化后有效地促进乙烯的低聚，导致在TEA存在下以中等催化活性（在0.7 MPa-乙烯下101 g-乙烯g-cat-1 h-1）制备乙烯低聚物的事实。当主链从丁烷部分（L3）变化到苊部分（L4）时，固体产物显著增加。低聚物在总产物中的重量百分比随着反应温度的升高而增加;然而，当乙烯压力降低时，观察到低聚物的不显著增加。
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.