Supported non-metallocene catalyst, preparation method and application

Abstract

The invention relates to a supported non-metallocene catalyst and a preparation method. The supported non-metallocene catalyst is prepared by the steps of precipitating a magnesium compound slurry containing a non-metallocene ligand and a porous carrier, and treating with an IVB group chemical treating agent; the preparation method is simple and feasible, the load capacity of the non-metallocene ligand is adjustable, and the combination of each compound in the catalyst is close. The invention also relates to the application of the supported non-metallocene catalyst in olefin homopolymerisation / copolymerization. Compared with the prior art, the supported non-metallocene catalyst has the characteristics of less usage of a cocatalyst for catalyzing polymerization of alkene, high polymerization activity, substantial copolymerization effect, high bulk density of polymer, narrow molecular weight distribution, and high and adjustable viscosity average molecular weight of the prepared ultrahigh molecular weight polyethylene.

Description

[0001] This application is based on the ongoing research project of "National Eleventh Five-Year Support Program Topics". The project has been highly valued and strongly supported by the Ministry of Science and Technology of the People's Republic of China. Its goal is to form a new generation of polyolefin catalyst technology with independent intellectual property rights, improve the homogeneity of domestic related products, improve the grade of polyolefin varieties in my country, and promote its development. Development in the direction of diversification, serialization, specialization and high performance. technical field [0002] 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 [0003] The non-metallocene catalysts that appeared in the middle and late 1990s, also kno...

AI Technical Summary

Problems solved by technology

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.

[0010] Chinese patents CN200910180603.3, CN200910180604.8, CN200910210989.8, CN200910210986.4, CN200910210985.X, CN200910210990.0 disclose the preparation method of supported non-metallocene catalysts similar to the above-mentioned patents. Particle morphology in the presence of catalyst is difficult to control, limiting the polymer particle morphology obtained from this polymerization

[0011] Catalysts supported on anhydrous magnesium chloride show high catalytic activity in olefin polymerization, but such catalysts are very brittle and break easily in the polymerization reactor, resulting in poor polymer morphology

Silica-supported catalysts have good fluidity and can be used in gas-phase fluidized bed polymerization, but silica-supported metallocene and non-metallocene catalysts show low catalytic activity

[0018] Patents CN200910210988.3 and CN200910210984.5 disclose that in the absence of alcohol, the non-metallocene ligands are dissolved in the magnesium compound solution, and then the porous carrier is added, dried directly or filtered, washed and dried, and then treated with IVB chemical treatment agents, thereby The preparation method and polymerization application of the supported non-metallocene catalyst, although the non-metallocene ligand exists in the carrier uniformly, due to the channel effect, the non-metallocene ligand and the magnesium compound solution containing the non-metallocene ligand The distribution of magnesium compounds in the pores of the porous carrier is greater than that outside the pores, so when in contact with IVB chemical treatment agents, the non-metallocene ligands and magnesium compounds have equal contact opportunities. Due to the presence of magnesium compounds, the chemical treatment of IVB groups is limited. The sufficient contact of agent and non-metallocene ligand, thereby has reduced the synergy chance of catalyzed olefin polymerization, thereby catalytic ethylene polymerization activity is lower in the embodiment

[0019] Patents CN200910180100.6 and CN200910180607.1 disclose that in the absence of alcohol, the non-metallocene complex is dissolved in the magnesium compound solution, and then the porous carrier is added, dried directly or filtered, washed and dried, and then treated with IVB chemical treatment agents, thereby The preparation method and polymerization application of the supported non-metallocene catalyst are obtained. The non-metallocene complex exists uniformly in the carrier, but in the examples, the activity of catalyzing ethylene polymerization is low, and the similar one is the patent CN200910180601.4 And CN200910180606.7 disclosed supported non-metallocene catalyst preparation method and polymerization application, its main difference is that it is not treated with IVB group chemical treatment agent, thus resulting in lower catalyst polymerization activity

[0020] 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 by this polymerization has a high bulk density, but the preparation process is more complicated, and the reaction between the chemical treatment agent and the carrier will destroy the formed carrier structure. Polymer fines are then produced during the polymerization process

[0021] 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

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