Catalyst composition for ethylene oligomerization and application thereof

Abstract

The invention discloses a catalyst composition for an ethylene oligomerization reaction process. The catalyst composition contains a main catalyst represented by a formula I shown in the description, i.e., a chlorinated 2,6-di(2-benzimidazoyl)pyridine chromium (III) complex, an aluminiferous cocatalyst, water and an organic solvent. According to the catalyst composition, the catalyst composition disclosed by the invention is applied to the ethylene oligomerization reaction process and has very high oligomerization reaction activity and high alpha-olefin selectivity, and the oligomerization reaction is high in initiating speed, stable in operation and good in repeatability; even if the Al / Cr ratio is low, the catalyst composition has very good oligomerization reaction activity; and thus, the technical prejudice of those skilled in the art are overcome, an unexpected technical effect is achieved, and the catalysis effect and the cost are better balanced, so that the cost of ethylene oligomerization reaction is reduced greatly, the practicability is high, and the industrialization prospect is broad.

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 (Organometallics2006, 25, 1961–1969), which was 2,6-bis(2-benzimidazolyl)pyridine chromium chloride ( III) The complex, under the action of the cocatalyst methylaluminoxane, when the molar ratio of the metal aluminum in the cocatalyst to the central metal in the main catalyst is 100 to 1500, and the reaction temperature is 0 to 80 ° C, oligomerization and polymerization activity up to 10 6 g mol(Cr) -1 h -1 ; and whether methylalumoxane or modified methylalumoxane is used as a cocatalyst, the cost is too high and the consumption is too large. When the cocatalyst is used in large-scale ethylene oligomerization, it will inevitably lead to high cost

[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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