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Supported non-metallocene catalyst, preparation method and application

A non-metallocene, supported technology, applied in the field of non-metallocene catalysts, can solve the problems of complex preparation process, difficult adjustment, low catalytic ethylene polymerization activity, etc., and achieve the effect of simple preparation method

Active Publication Date: 2013-03-13
CHINA PETROLEUM & CHEM CORP +1
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  • Claims
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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 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
[0019] 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
[0020] 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

Method used

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  • Supported non-metallocene catalyst, preparation method and application
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  • Supported non-metallocene catalyst, preparation method and application

Examples

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preparation example Construction

[0104] The invention relates to a preparation method of a supported non-metallocene catalyst, comprising the following steps: dissolving a magnesium compound in a first solvent in the presence of alcohol to obtain a magnesium compound solution; making a chemical compound selected from group IVB metal compounds Dissolving the treatment agent in the precipitant to obtain a chemical treatment agent solution; adding the chemical treatment agent solution to the magnesium compound solution to obtain a modified carrier; making the non-metallocene complex and the modified carrier in the second step contacting in the presence of two solvents to obtain a mixed slurry; and directly drying the mixed slurry to obtain the supported non-metallocene catalyst.

[0105] The magnesium compound will be specifically described below.

[0106] According to the present invention, the term "magnesium compound" refers to an organic or inorganic solid anhydrous magnesium-containing compound conventional...

Embodiment 1

[0322] The magnesium compound adopts anhydrous magnesium chloride, the first solvent adopts tetrahydrofuran, the alcohol adopts butanol, the chemical treatment agent of IVB metal compound adopts titanium tetrachloride, the precipitating agent adopts hexane, and the non-metallocene complex adopts the structure The compound, the second solvent adopts dichloromethane.

[0323] Weigh 5g of anhydrous magnesium chloride, add the first solvent and alcohol, and dissolve completely at room temperature to obtain a magnesium compound solution. Dissolve the chemical treatment agent in the precipitant to obtain a chemical treatment agent solution. Drop the chemical treatment agent solution over 30 minutes. Add it to the magnesium compound solution, stir and react at 60°C for 4 hours to make it completely precipitate, filter, wash twice with the precipitating agent, each time the amount of precipitating agent is 60ml, evenly heat to 60°C and vacuum-dry to obtain the modified carrier.

[03...

Embodiment 1-1

[0328] Basically the same as Example 1, but with the following changes:

[0329] Alcohol adopts ethanol, the first solvent is changed to toluene, and the chemical treatment agent of IVB group metal compound is changed to zirconium tetrachloride (ZrCl 4 ), the precipitant was changed to cyclohexane, and the non-metallocene complexes were The second solvent was changed to toluene.

[0330] Wherein the ratio is as follows: the ratio of the magnesium compound to the first solvent is 1mol: 150ml; the molar ratio of the magnesium compound to the alcohol is 1: 1.64; the molar ratio of the magnesium compound to the non-metallocene complex is 1: 0.15; the precipitation agent and the first solvent The volume ratio is 1:2; the molar ratio of the magnesium compound to the chemical treatment agent in terms of IVB group metal elements is 1:0.20.

[0331] Supported non-metallocene catalysts are designated CAT-1-1.

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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 processing the supported non-metallocene catalyst by a chemical treatment agent and precipitating a magnesium compound solution formed by a magnesium compound, alcohol and a solvent, loading a non-metallocene complex and directly drying. The preparation method is simple and feasible, and the load capacity of the non-metallocene ligand is adjustable. 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, 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...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F10/00C08F4/658C08F4/645C08F4/02
Inventor 李传峰任鸿平柏基业阚林郭峰左胜武梅利陈韶辉
Owner CHINA PETROLEUM & CHEM CORP
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