Supported non-metallocene catalyst and preparation method and application thereof

Abstract

The invention relates to a supported non-metallocene catalyst and a preparation method thereof. The supported non-metallocene catalyst has the characteristics that the preparation process is simple, the content of a non-metallocene complex is controllable, and the copolymerization effect is obvious. The invention also relates to the application of the supported non-metallocene catalyst in olefin homopolymerization / copolymerization. And compared with the prior art, the application has the characteristics that activity is high in olefin polymerization catalysis, and a polymer has high bulk density and controllable molecular weight distribution.

Description

technical field [0001] The present 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] The non-metallocene catalysts that appeared in the middle and late 1990s, also known as post-metallocene catalysts, the central atoms of the main catalysts include almost all transition metal elements, which have reached or even surpassed metallocene catalysts in some performance aspects, becoming The fourth generation of olefin polymerization catalysts after Ziegler, Ziegler-Natta and metallocene catalysts. The polyolefin product produced by this type of catalyst has excellent performance and low production cost. The coordination atoms of non-metallocene catalysts are oxygen, nitrogen, sulfur and phosphorus, and do not contain cyclopentadiene groups or their derivative groups, such as ind...

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Problems solved by technology

However, 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

Although silica-supported catalysts have good fluidity and can be used in slurry polymerization and gas-phase fluidized-bed polymerization, pure silica-supported metallocene and non-metallocene catalysts show 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] Patent CN200710162666.7 discloses a supported catalyst, a supported non-metallocene catalyst and its preparation method. In the presence of alcohol, a magnesium compound is dissolved in a tetrahydrofuran solvent, a porous carrier is added, and after direct drying, it is mixed with titanium tetrachloride reaction, and finally load the non-metallocene complex, the catalyst activity is high, and the polymer obtained from this polymerization has a high bulk density. Due to the complex composition, a chemical treatment agent is required to treat the composite support, and due to the presence of alcohol, it will Influence the intrinsic properties of non-metallocene complexes

[0015] Nevertheless, the ubiquitous problems of the supported non-metallocene catalysts in the prior art are that the loading process is complicated, and generally requires multi-step treatment of the support before loading the non-metallocene complexes, and the olefin polymerization activity is low and difficult to adjust. , and in order to improve its polymerization activity, a higher amount of co-catalyst must be assisted in the polymerization of olefins

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 industrial use. Moreover, due to the existence of alcohol in the system and the need for chemical treatment agents for the composite carrier, it will affect the load on other materials. It has an adverse effect on the performance of non-metallocene catalysts, which limits the intrinsic performance of non-metallocene catalysts

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