Catalyst composition for ethylene oligomerization and application thereof

Abstract

The invention discloses a catalyst composition for ethylene oligomerization. The catalyst composition comprises a main catalyst (cyclopentadienyl) titanium chlorinated 2-(2-benzimidazolyl)-8-acetanilide quinoline complex as shown in a formula (I) which is described in the specification, an aluminum-containing cocatalyst, water and an organic solvent. The catalyst composition has high oligomerization reaction activity and high alpha-alkene selectivity when applied to ethylene oligomerization, and oligomerization reaction is rapidly initiated, runs stably and has good repeatability; even under the condition of a low aluminum / titanium ratio, good oligomerization reaction activity is maintained; thus, technical biases of the skilled in the art are overcome, unexpected technical effects are obtained, catalysis effect and cost are better balanced, cost for ethylene oligomerization is greatly reduced and the catalyst has good practicality and wide industrialization prospects.

Description

technical field [0001] The invention relates to the field of ethylene oligomerization, in particular to a catalyst composition used in an ethylene oligomerization process. Background technique [0002] Linear α-olefins are widely used in the fields of ethylene comonomers, surfactant synthesis intermediates, plasticizer alcohols, synthetic lubricating oils and oil additives. In recent years, with the continuous development of the polyolefin industry, the worldwide demand for α-olefins has grown rapidly. At present, the vast majority of α-olefins are prepared by ethylene oligomerization. The used catalyst of ethylene oligomerization mainly contains nickel series, chromium series, zirconium series and aluminum series etc., in recent years, Brookhart group (Brookhart, the people such as M, J.Am.Chem.Soc.,1998,120,7143-7144 ; WO99 / 02472,1999), Gibson group (Gibson, V.C. et al., Chem.Commun., 1998,849-850; Chem.Eur.J., 2000,2221-2231) found that some Fe(II) and Co The tridentat...

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Problems solved by technology

[0003] The Institute of Chemistry, Chinese Academy of Sciences reported a catalyst for ethylene oligomerization and polymerization (Organometallics2010, 29, 732–741), which was 2-(2-benzimidazolyl)-8-acetanilinoquinoline chloride (Centrocene) titanium, under the action of the cocatalyst methyl aluminoxane, when the molar ratio of the metal aluminum in the cocatalyst to the central metal in the main catalyst is 10000-35000, and the reaction temperature is 20-100 °C, the polymerization activity up to 10 6 g mol(Ti) -1 h -1 ; and whether it is methylalumoxane or modified methylalumoxane as a co-catalyst, there are problems of high cost and excessive consumption. When the co-catalyst is used in large-scale ethylene oligomerization or polymerization, it will inevitably lead to high production costs

[0004] At present, it is generally believed that water is very unfavorable to the ethylene oligomerization reaction process. CN200810111717.8 discloses a method for ethylene oligomerization, which is strictly controlled in an anhydrous and oxygen-free environment. Therefore, the current ethylene oligomerization reaction is harmful to the process. The requirements are very demanding, resulting in very poor reaction initiation and repeatability of the oligomerization process

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