Modified silica gel supported metallocene catalyst and preparation method thereof

Abstract

The invention discloses a supported metallocene catalyst used for vinyl polymerization and a preparation method thereof. The catalyst comprises a metallocene compound, a chlorinated alkyl silicon modifier, alkyl aluminoxane and a silica gel carrier reaction product; the preparation method comprises the following steps: 1) preparation of a chlorinated alkyl silicon modified silica gel carrier, 2) preparation of an alkyl aluminoxane modified silica gel carrier, and 3)preparation of the modified silica gel supported metallocene catalyst; and the obtained metallocene catalyst has high polymerization activity for catalyzing vinyl polymerization or copolymerization. The preparation method of the silica gel carrier is simple, and the obtained supported catalyst particles have good morphology and have adjustable size.

Description

technical field [0001] The invention relates to a preparation method of a modified silica gel supported metallocene catalyst and the application of the obtained catalyst in olefin polymerization. technical background [0002] The development and application of metallocene catalysts is another major breakthrough in the field of olefin polymerization catalysts after the traditional Ziegler-Natta catalysts, especially in the 1980s, Kaminsky and Sinn et al. (Angew.Chem., 1980, 19, 390; Adv. Organoment.Chem., 1980, 18, 99) developed a high-efficiency cocatalyst methylaluminoxane (MAO), making the research on metallocene catalysts enter a stage of rapid development. Because the homogeneous metallocene catalyst requires a large amount of MAO to achieve high activity, the production cost is high, and the obtained polymer is amorphous, which cannot be used in the widely used slurry method or gas phase polymerization process. An effective way is to support the soluble metallocene cat...

AI Technical Summary

Problems solved by technology

Because the homogeneous metallocene catalyst requires a large amount of MAO to achieve high activity, the production cost is high, and the obtained polymer is amorphous, which cannot be used in the widely used slurry method or gas phase polymerization process. An effective way is to support the soluble metallocene catalyst

[0003] At present, there are many reports on metallocene loading research, among which the catalyst using spherical magnesium chloride (containing alcohol) to support metallocene has good particle morphology, such as PCT Int.Appl.99 / 21898; US6,455,647; J.Mol.Catal .A 2002,188,123; PCT Int.APP1.2004 / 078804; CN 101817892; CN 101172988, but the carrier contains alcohol, water, alkoxy and other components, and the preparation of the carrier is complicated; 2 CN 102286114; CN 1174848; CN 1174849; CN 1356343; US 4,808,561; US ​​5,026,797; US 5,763,543; The loading efficiency of the catalyst is low, and a large amount of methylalumoxane is still introduced during the polymerization process. The above shortcomings limit the industrial application of silica gel-loaded metallocene catalysts.

[0004] There are also literatures that use carriers containing magnesium chloride, silica gel, etc. to load metallocenes (Polymer International, 2002, 51, 417-423; US5962360), but the activity is very low, and a large amount of MAO needs to be added during polymerization

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