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Supported non-metallocene catalyst, preparation method and application

A non-metallocene and non-metallocene ligand technology, applied in the field of non-metallocene catalysts, can solve the problems of complex preparation process, difficult adjustment, low catalytic 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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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

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

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preparation example Construction

[0094] 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 the porous The step of contacting the carrier with the magnesium compound solution to obtain a first mixed slurry; dissolving a chemical treatment agent selected from Group IVB metal compounds in a precipitant to obtain a chemical treatment agent solution; adding to the first mixed slurry The step of adding the chemical treatment agent solution to obtain a modified composite carrier; contacting the non-metallocene ligand with the modified composite carrier in the presence of a second solvent to obtain a second mixed slurry; and directly drying the first The second step is to mix the slurry and obtain the supported non-metallocene catalyst.

[0095] The magnesium compound will be specifically described below.

[0096] According t...

Embodiment 1

[0305] Anhydrous magnesium chloride was used as the magnesium compound, tetrahydrofuran was used as the first solvent, butanol was used as the alcohol, and silica gel was used as the porous carrier. The model was ES757 from Ineos Company. Before use, the silica gel was continuously roasted at 600 °C under nitrogen atmosphere for 4 hours. And heat activated. The chemical treatment agent of Group IVB metal compound adopts titanium tetrachloride, the precipitation agent adopts hexane, and the non-metallocene ligand adopts the structure of The compound, the second solvent adopts dichloromethane.

[0306] Weigh 5g of anhydrous magnesium chloride, add the first solvent and alcohol, and dissolve completely at room temperature to obtain a magnesium compound solution, then add heat-activated silica gel, and stir at room temperature for 2 hours to form the first mixed slurry. Dissolve the chemical treatment agent in the precipitant, then drop it into the first mixed slurry at room tem...

Embodiment 2

[0311] Basically the same as Example 1, but with the following changes:

[0312] The porous carrier was changed to Grace's 955, and it was continuously calcined at 400° C. for 8 hours under a nitrogen atmosphere to be thermally activated.

[0313] 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 ligand was The second solvent was changed to toluene.

[0314] 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 ligand is 1: 0.15; the ratio of the magnesium compound to the porous carrier The mass ratio is 1:4; the volume ratio of the precipitant to the first solvent is 1:2; the molar ratio of the magnes...

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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 mixed slurry of a magnesium compound, a porous carrier and a solvent, performing in-situ loading on a non-metallocene ligand 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 mid-to-late 1990s are also call...

Claims

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Application Information

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IPC IPC(8): C08F10/00C08F4/02C08F4/658C08F4/654C08F4/656C08F4/646C08F4/655C08F4/645C08F4/649
Inventor 李传峰任鸿平陈韶辉阚林郭峰左胜武梅利柏基业
Owner CHINA PETROLEUM & CHEM CORP
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