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Nickel Complexes Bearing Bidentate Schiff Base as Ethylene Oligomerization Catalysts

机译:带有双Schiff碱的镍络合物作为乙烯低聚催化剂

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Several nickel complexes [N,N]NiBr2, in which [N,N] indicates bidentate nitrogencontaining ligands (1: [N,N]=N-(2,6-diisopropylphenyl)pyridine-2-carboxaldimine (C1sH22N2); 2: N-(2,6-diisopropylphenyl)-6-methylpyridine-2-carboxaldiminc (C19H24N2); 3: N-(2,4,6-trimethylphenyl)pyridine2-carboxaldimine(C15H16N2); 4: N-(2,4,6-trimethylphenyl)-6-methylpyridine-2-carboxaldimine (C16H18-N2) were synthesized. Some of the nickel complexes exhibit high activity for ethylene oligomerization in the presence of an organoaluminum activator. The main factor affecting the activity and the structure of oligomers is the steric effect of substituents on [N,N] ligands. Methylaluminoxane (MAO) -activated catalysts showed higher activities and produced oligomers with higher molecular weight than Et2AlCl-activated ones. The oligomerization in toluene rather than hexane results in much higher activity, and the oligomers produced in toluene have relatively high molecular weight. With activation of MAO or Et2AlCl,the [N,N]NiBr2 system tended to produce highly branched oligomers with low α-olefin content, but the α-olefin content could be increased by changing the reaction conditions.
机译:几种镍配合物[N,N] NiBr2,其中[N,N]表示双齿含氮配体(1:[N,N] = N-(2,6-二异丙基苯基)吡啶-2-羧二胺(C1sH22N2); 2: N-(2,6-二异丙基苯基)-6-甲基吡啶-2-羧酰亚胺(C19H24N2); 3:N-(2,4,6-三甲基苯基)吡啶2-羧二胺(C15H16N2); 4:N-(2,4,合成了6-三甲基苯基)-6-甲基吡啶-2-羧二胺(C16H18-N2),其中一些镍配合物在有机铝活化剂的存在下对乙烯的低聚反应具有很高的活性,是影响低聚物活性和结构的主要因素是取代基对[N,N]配体的空间效应。甲基铝氧烷(MAO)活化的催化剂显示出更高的活性,并且比Et2AlCl活化的催化剂产生了更高的分子量;在甲苯中而不是在己烷中进行低聚,其活性更高,并且在甲苯中生产的低聚物具有相对较高的分子量,可以通过激活MAO或Et2AlC如图1所示,[N,N] NiBr 2体系倾向于产生具有低α-烯烃含量的高度支化的低聚物,但是通过改变反应条件可以增加α-烯烃的含量。

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