Supported non-metallocene catalyst, preparation method and application thereof

A non-metallocene, supported technology, applied in the field of non-metallocene catalysts, can solve the problems of low olefin polymerization activity, limited intrinsic properties of non-metallocene complexes, and difficulty in controlling the shape of catalyst particles.

Active Publication Date: 2012-04-04
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0006] 针对专利ZL 01126323.7、ZL 02151294.9ZL 02110844.7和WO03/010207所公开的非茂金属催化剂,专利CN200310106156.x、CN200310106157.4、CN200410066070.3、CN200410066069.0、200510119401.x等提供了多种方式进行负载以 Supported non-metallocene catalysts are obtained, but 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
Silica-supported catalysts have good fluidity and can be used in slurry polymerization and gas-phase fluidized-bed polymerization, but the pure use of silica-supported metallocene and non-metallocene catalysts shows 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, 20091021098

Method used

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

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[0094] The present invention relates to a method for preparing a supported non-metallocene catalyst, which includes the following steps: reacting a chemical treatment agent selected from group IVB metal compounds with a porous support optionally undergoing thermal activation treatment to obtain a modified support; The step of dissolving the compound in the solvent to obtain a magnesium compound solution; the step of contacting the modified carrier, the magnesium compound solution and the non-metallocene complex to obtain a mixed slurry; adding a precipitant to the mixed slurry to obtain a composite The step of supporting; and the step of reacting a chemical treatment agent selected from the group IVB metal compound with the composite support to obtain the supported non-metallocene catalyst.

[0095] The porous carrier will be specifically described below.

[0096] According to the present invention, as the porous support, for example, those organic or inorganic porous solids conven...

Embodiment 1

[0322] The porous carrier uses silica, namely silica gel, the model is ES757 of Ineos Company. First, the silica gel is calcined at 600° C. under a nitrogen atmosphere for 4 hours to thermally activate.

[0323] The chemical treatment agent uses titanium tetrachloride (TiCl 4 ). Weigh 5g of thermally activated silica gel, add 60ml of hexane, add titanium tetrachloride under stirring at room temperature, after reacting at 60℃ for 2h, filter, wash with hexane 3 times, 60ml each time, and finally vacuum dry to obtain Modified vector.

[0324] The magnesium compound is anhydrous magnesium chloride, and the solvent for dissolving the magnesium compound and the non-metallocene complex is tetrahydrofuran. The structure of the non-metallocene complex is compound of.

[0325] Weigh the anhydrous magnesium chloride and non-metallocene complex, add tetrahydrofuran solvent and completely dissolve at room temperature to obtain the magnesium compound solution, then add the modified carrier, sti...

Embodiment 2

[0330] It is basically the same as embodiment 1, but has the following changes:

[0331] Before the reaction for treating the composite carrier with the chemical treatment agent, the auxiliary chemical treatment agent methylaluminoxane (MAO, 10wt% toluene solution) is used to treat the composite carrier.

[0332] Wherein, the molar ratio of the magnesium compound based on Mg element to the auxiliary chemical treatment agent methylaluminoxane is 1:0.3.

[0333] The supported non-metallocene catalyst is referred to as CAT-2.

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Abstract

The present invention relates to a supported non-metallocene catalyst and a preparation method thereof. The supported non-metallocene catalyst has characteristics of simple and feasible preparation process, adjustable performance, controllable non-metallocene complex content, significant copolymerization effect, and the like. The present invention further relates to an application of the supported non-metallocene catalyst in olefin homopolymerization/copolymerization. Compared to the prior art, the application of the present invention has the following characteristics that: the activity for catalysis of olefin polymerization is high; the produced polymer has high bulk density and controllable molecular weight distribution.

Description

Technical field [0001] The 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] Non-metallocene catalysts appeared in the mid-to-late 1990s, also known as post-catalysts. The central atom of the main catalyst includes almost all transition metal elements. It has reached or even surpassed metallocene catalysts in some aspects of performance. The fourth generation olefin polymerization catalyst after Ziegler, Ziegler-Natta and metallocene catalysts. The polyolefin products manufactured by this type of catalyst have excellent performance and low manufacturing cost. The coordinating atoms of non-metallocene catalysts are oxygen, nitrogen, sulfur and phosphorus, and do not contain cyclopentadiene group or its derivative groups, such as indenyl and fluorenyl, etc. It is characterized by...

Claims

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Application Information

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IPC IPC(8): C08F4/654C08F4/02C08F10/00
Inventor 李传峰郭峰任鸿平阚林柏基业马忠林陈韶辉汪开秀王亚明杨爱武
Owner CHINA PETROLEUM & CHEM CORP
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