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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, easy breakage, low catalyst polymerization activity, etc., and achieve the effect of simple preparation method

Active Publication Date: 2015-04-22
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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, although the non-metallocene complex exists in the carrier uniformly, due to the channel effect, the non-metallocene complex and the magnesium compound solution containing the non-metallocene complex The distribution of magnesium compounds in the pores of the porous carrier is greater than that outside the pores. Therefore, when in contact with IVB chemical treatment agents, the non-metallocene complexes and magnesium compounds have equal contact opportunities. Due to the presence of magnesium compounds, the chemical treatment of IVB groups is limited. The full contact of the agent and the non-metallocene complex reduces the synergistic chance of catalyzing olefin polymerization, so the activity of catalyzing ethylene polymerization is low in the examples, and similar to that disclosed in patents CN200910180601.4 and CN200910180606.7 The preparation method and polymerization application of the supported non-metallocene catalyst, the main difference is that the polymerization activity of the catalyst is also low without being treated with the IVB group chemical treatment agent
[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

[0105] The invention relates to a preparation method of a supported non-metallocene catalyst, comprising the following steps: dissolving a magnesium compound in a solvent to obtain a magnesium compound solution; making a porous carrier optionally subjected to thermal activation treatment and the magnesium compound solution contacting to obtain a first mixed slurry; contacting the non-metallocene complex with the first mixed slurry to obtain a second mixed slurry; directly drying the second mixed slurry to obtain a modified composite carrier, and A step of reacting a chemical treatment agent selected from group IVB metal compounds with the modified composite carrier to obtain the supported non-metallocene catalyst.

[0106] The magnesium compound will be specifically described below.

[0107] According to the present invention, the term "magnesium compound" refers to an organic or inorganic solid anhydrous magnesium-containing compound conventionally used as a carrier of a supp...

Embodiment 1

[0334] The magnesium compound is anhydrous magnesium chloride, the solvent is tetrahydrofuran, and the porous carrier is silicon dioxide, that is, silica gel, the model is ES757 from Ineos Company. Before use, the silica gel is continuously calcined at 600° C. under nitrogen atmosphere for 4 hours to be thermally activated. The non-metallocene complex adopts the structure The compound, the chemical treatment agent of the IVB group metal compound adopts titanium tetrachloride, and the solvent for the chemical treatment agent adopts hexane.

[0335]Weigh 5g of anhydrous magnesium chloride, add a solvent and dissolve it completely at normal temperature to obtain a magnesium compound solution, then add heat-activated silica gel, stir at normal temperature for 2 hours to form the first mixed slurry, then add a non-metallocene complex to obtain the second 2. Mix the slurry, then stir and react at room temperature for 6 hours, and dry in vacuum at room temperature to obtain a modifi...

Embodiment 1-1

[0340] Basically the same as Example 1, but with the following changes:

[0341] 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.

[0342] The solvent is changed to toluene, and the non-metallocene complex adopts The chemical treatment agent for Group IVB metal compounds was changed to zirconium tetrachloride (ZrCl 4 ), the chemical treatment agent was changed to cyclohexane with a solvent.

[0343] Wherein the ratio is as follows: the ratio of magnesium compound to solvent is 1mol: 150ml; the molar ratio of magnesium compound to non-metallocene complex is 1: 0.15; the mass ratio of magnesium compound to porous carrier is 1: 4; the ratio of magnesium compound to IVB group The molar ratio of the chemical treatment agent in terms of metal elements is 1:0.20.

[0344] 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 employing a magnesium compound, a porous carrier and a solvent to form a mixed slurry, adding a non-metallocene complex for a contact reaction and directly drying, and then treating by a chemical treatment agent. 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 Patents(China)
IPC IPC(8): C08F10/00C08F4/658C08F4/646C08F4/645C08F4/649C08F4/02
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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