Supported non-metallocene catalyst, preparation method and application thereof

Abstract

The present invention relates to a supported non-metallocene catalyst and a preparation method thereof. The supported non-metallocene catalyst has characteristics of simple and feasible preparation process, adjustable performance, controllable non-metallocene complex content, significant copolymerization effect, and the like. The present invention further relates to an application of the supported non-metallocene catalyst in olefin homopolymerization / copolymerization. Compared to the prior art, the application of the present invention has the following characteristics that: the activity for catalysis of olefin polymerization is high; the produced polymer has high bulk density and controllable molecular weight distribution.

Description

Technical field [0001] The invention relates to a non-metallocene catalyst. Specifically, the present invention relates to a supported non-metallocene catalyst, its preparation method and its application in olefin homopolymerization / copolymerization. Background technique [0002] Non-metallocene catalysts appeared in the mid-to-late 1990s, also known as post-catalysts. The central atom of the main catalyst includes almost all transition metal elements. It has reached or even surpassed metallocene catalysts in some aspects of performance. The fourth generation olefin polymerization catalyst after Ziegler, Ziegler-Natta and metallocene catalysts. The polyolefin products manufactured by this type of catalyst have excellent performance and low manufacturing cost. The coordinating atoms of non-metallocene catalysts are oxygen, nitrogen, sulfur and phosphorus, and do not contain cyclopentadiene group or its derivative groups, such as indenyl and fluorenyl, etc. It is characterized by...

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Problems solved by technology

[0006] 针对专利ZL 01126323.7、ZL 02151294.9ZL 02110844.7和WO03 / 010207所公开的非茂金属催化剂,专利CN200310106156.x、CN200310106157.4、CN200410066070.3、CN200410066069.0、200510119401.x等提供了多种方式进行负载以 Supported non-metallocene catalysts are obtained, but these patents all involve loading non-metallocene organic compounds containing transition metals on the treated carrier, and the catalyst preparation process is relatively complicated

[0007] Catalysts supported by anhydrous magnesium chloride show high catalytic activity in olefin polymerization, but such catalysts are weak and easily broken in the polymerization reactor, resulting in poor polymer morphology

Silica-supported catalysts have good fluidity and can be used in slurry polymerization and gas-phase fluidized-bed polymerization, but the pure use of silica-supported metallocene and non-metallocene catalysts shows low catalytic activity

These two methods use a magnesium compound support, and the particle morphology of the catalyst is difficult to control, which limits the particle morphology of the polymer obtained from the polymerization.

[0013] Patents 200910180603.3, 200910180604.8, 200910210989.8, 200910210986.4, 200910210985.X, 200910210990.0 disclose preparation methods of supported non-metallocene catalysts similar to the above-mentioned patents, all of which use magnesium compounds as carriers. The morphology of polymer particles obtained by this polymerization

[0014] Even so, the ubiquitous problem of the supported non-metallocene catalysts in the prior art is that the preparation process, that is, the loading process is complicated, and it is generally necessary to carry out multi-step treatment of the carrier before loading the non-metallocene complex, and the olefin polymerization activity Low and narrow room for adjustment, and in order to improve its polymerization activity, it must be assisted by a higher amount of cocatalyst when performing olefin polymerization

This loading method is relatively complicated, the process is difficult to control, and there are many factors affecting the batch quality, which is not conducive to large-scale use, and the presence of alcohol in the system will adversely affect the performance of the non-metallocene catalyst loaded on it. , limiting the intrinsic properties of non-metallocene complexes

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