A supported single metallocene catalyst for ethylene polymerization

Abstract

The present invention relates to a supported mono-metallocene catalyst for ethylene polymerization, and a preparation method thereof. The catalyst comprises (a) a mono-metallocene compound; (b) a chlorinated hydrocarbyl silicon modifier; (c) an alkylaluminum oxide alkane; (d) reaction product of silica gel carrier; its preparation method includes: (1) preparation of chlorinated hydrocarbyl silicon modified silica gel carrier, (2) preparation of alkyl aluminoxane modified silica gel carrier, (3) modification The preparation of silica gel supported single metallocene catalyst, the obtained single metallocene catalyst catalyzes ethylene polymerization or copolymerization and has high polymerization activity. The preparation method of the silica gel carrier used is simple, and the obtained loaded catalyst particle has good shape and adjustable size.

Description

technical field [0001] The invention relates to a preparation method of a modified silica gel supported mono-metallocene catalyst and the application of the obtained catalyst in olefin polymerization. Background technique [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. In recent years, in the study of olefin polymerization catalysts, single metallocene catalysts with electron-donating ligands have received more and more attention. Many catalysts with unique properties have been reported in the literature, such as those with aryloxy groups (Organometallics, 1998,17(11):2152-2154...

AI Technical Summary

Problems solved by technology

Because the homogeneous single 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 to overcome the above problems The most effective way is to support the soluble mono-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; 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 single metallocene catalysts.

[0004] There are also literatures that use carriers containing magnesium chloride, silica gel, etc. to load mono-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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