Oligomerization method of ethylene

Abstract

The invention discloses an oligomerization method of ethylene. The ethylene carries out oligomerization reactions in a reaction system composed of a main catalyst, an aluminum-containing co-catalyst, water and an organic solvent; wherein the main catalyst is chlorinated 2-n-butyryl-1,10-phenanthroline amine-Fe (II) represented by the formula (I), the organic solvent is alpha-alkene with n carbons (4<n<=10), and in the formula (I), and the R1, R2, R3, R4, and R5 individually represent a hydrogen atom, an alkyl group with a carbon number of 1 to 6, a halogen atom, an alkyloxy group with a carbon number of 1 to 6, or a nitro group. The provided oligomerization method overcomes the technical bias, and optimizes the oligomerization technology. In the provided method, the oligomerization activity is high, thus the ethylene oligomerization reactions can be triggered rapidly, the operation of the technology is stable, the method is environment-friendly, the toxicity is greatly reduced, the catalytic effect and cost are well balanced, the provided method is very practical and greatly reduces the ethylene oligomerization cost, the catalytic effect and production cost are taken into account as a whole, and the industrialization prospect of the oligomerization method is wide.

Description

technical field [0001] The invention relates to the field of olefin polymerization, in particular to a method for ethylene oligomerization. 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 tridentate pyridine imine complex of (II)...

AI Technical Summary

Problems solved by technology

Whether it is methylalumoxane or modified methylalumoxane, the unit price is relatively high, and when it is used for ethylene oligomerization on a large scale, it will inevitably lead to high production costs

At present, it is generally believed that water is very unfavorable to the ethylene oligomerization process

Secondly, the oligomerization reaction has very strict requirements on the initiation environment, so it is strictly required to be carried out in an anhydrous and oxygen-free environment. Due to the special conditions, it is very difficult to achieve, so the reaction initiation, stability and repeatability of the oligomerization process are also very poor.

In addition, the organic solvent used in the oligomerization process is generally toluene. As we all know, toluene is a toxic aromatic hydrocarbon, which is irritating to the skin and mucous membranes and has an anesthetic effect on the central nervous system; and in the oligomerization products, the toluene content is relatively large , unable to meet the requirements for aromatic hydrocarbon content when used as a comonomer

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