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, chlorinated alkyl silicon, halogenated alkyl magnesium, 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 a halogenated alkyl magnesium modified silica gel carrier, 3)preparation of an alkyl aluminoxane modified silica gel carrier, and 4)preparation of the 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 particle morphology and have adjustable size.

Description

Technical field [0001] The invention relates to a modified silica gel supported metallocene catalyst, a preparation method, and 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 co-catalyst methylaluminoxane (MAO), making the research of 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, it cannot be used in the widely used slurry method or gas phase polymerization process, which overcomes the above problems The effective method is to support...

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 a lot of research reports on metallocene loading, 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 .A2002,188,123; PCT Int.APP1.2004 / 078804, but the carrier contains alcohol, water, alkoxy and other components, and the preparation of the carrier is complicated; while Si0 2 CN1174849; CN1356343; US4,808,561; US5,026,797; US5,763,543; , a large amount of methylalumoxane must still be introduced during the polymerization process, the above shortcomings limit the industrial application of silica gel-supported metallocene catalysts

There are also reports in the literature that metallocenes are loaded on carriers containing magnesium chloride and silica gel (Polymer International, 51: 417-423, 2002; US5962360; CN102336855A), but the activity is very low, and a large amount of MAO needs to be added during polymerization

The above disadvantages limit the industrial application of silica-supported metallocene catalysts

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