Load-type non-metallocene catalyst, preparation method thereof, and application thereof

A non-metallocene and non-metallocene ligand technology, applied in the field of non-metallocene catalysts, can solve the problems of difficult polymerization temperature control, unfavorable stable operation of polymerization production, low olefin polymerization activity, etc.

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

AI Technical Summary

Problems solved by technology

Since the IVB group metal compound is distributed on the surface of the catalyst, the activity is high at the initial stage of polymerization, and it is difficult to control the polymerization temperature, which is also not conducive to the stable operation of polymerization production.
[0015] 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
For the non-metallocene catalyst supported by a single carrier on a porous carrier, the carrier needs to be treated with a chemical reagent such as alkylaluminum after thermal activation treatment. For the non-metallocene catalyst supported by a single carrier of a magnesium compound, the preparation conditions need to be strictly controlled. Polymerization of olefins with good morphology

Method used

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  • Load-type non-metallocene catalyst, preparation method thereof, and application thereof
  • Load-type non-metallocene catalyst, preparation method thereof, and application thereof
  • Load-type non-metallocene catalyst, preparation method thereof, and application thereof

Examples

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preparation example Construction

[0084] The invention relates to a preparation method of a supported non-metallocene catalyst, comprising the following steps: reacting a chemical treatment agent selected from group IVB metal compounds with a porous carrier optionally subjected to thermal activation treatment to obtain a modified carrier; making magnesium Dissolving the compound in the first solvent in the presence of alcohol to obtain a magnesium compound solution; mixing the modified carrier with the magnesium compound solution to obtain a first mixed slurry; adding to the first mixed slurry Precipitating agent, the step of obtaining a composite carrier; reacting a chemical treatment agent selected from the group IVB metal compound with the composite carrier to obtain a modified composite carrier; making the non-metallocene ligand and the modified composite carrier in the second step contacting in the presence of two solvents to obtain a second mixed slurry; and directly drying the second mixed slurry to obta...

Embodiment 1

[0298] The porous carrier is silicon dioxide, that is, silica gel, model ES757 of Ineos Company. First, the silica gel is thermally activated by continuously calcining at 600° C. for 4 hours under a nitrogen atmosphere.

[0299] The chemical treatment agent is titanium tetrachloride (TiCl 4 ). Weigh 5g of thermally activated silica gel, add 60ml of hexane, add titanium tetrachloride under normal temperature stirring conditions, react at 60°C for 2h, filter, wash with hexane 3 times, 60ml each time, and finally vacuum dry to obtain modified carrier.

[0300] The magnesium compound is anhydrous magnesium chloride, the alcohol is ethanol, the solvent (first solvent) for dissolving the magnesium compound is tetrahydrofuran, and the chemical treatment agent is titanium tetrachloride. The non-metallocene ligand adopts the structure compound of.

[0301] Weigh anhydrous magnesium chloride, add the first solvent tetrahydrofuran solvent and ethanol, heat to 60°C to dissolve comple...

Embodiment 2

[0307] Basically the same as Example 1, but with the following changes:

[0308] 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.

[0309] Non-metallocene ligands use The first and second solvents were changed to toluene, the alcohol was changed to n-butanol, the precipitation agent was changed to cyclohexane, and the chemical treatment agent was changed to zirconium tetrachloride (ZrCl 4 ).

[0310] Wherein the proportioning is that the molar ratio of the magnesium compound in terms of Mg element to the non-metallocene ligand is 1:0.15, the molar ratio to the chemical treatment agent is 1:0.30 twice, and the ratio to the first solvent is 1mol: 150ml, the molar ratio to alcohol is 1: 4, the mass ratio of the magnesium compound to the porous carrier in terms of magnesium compound solids is 1: 1, and the volume ratio of the precipitating agent to the first solvent is 1...

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Abstract

The invention relates to a load-type non-metallocene catalyst and a preparation method thereof. The load-type non-metallocene catalyst is characterized by a preparation technology with large adjustment room, controllable non-metallocene content, substantial copolymerization effect, and the like. The invention also relates to an application of the load-type non-metallocene catalyst in alkene homopolymerization/copolymerization. Compared to prior arts, the application is characterized by high alkene polymerization catalytic activity, high polymer bulk density, and narrow and adjustable molecular weight distribution.

Description

technical field [0001] 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 [0002] Non-metallocene catalysts, also known as post-metallocene catalysts, appeared in the mid-to-late 1990s. The central atom of the main catalyst includes almost all transition metal elements, and has reached or even surpassed metallocene catalysts in some aspects. It becomes the fourth generation olefin polymerization catalyst following Ziegler, Ziegler-Natta and metallocene catalysts. The polyolefin product produced by this type of catalyst has excellent performance and low production cost. The coordination atoms of non-metallocene catalysts are oxygen, nitrogen, sulfur and phosphorus, and do not contain cyclopentadiene groups or their derivative groups, such as indenyl and fluorenyl, etc., ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F4/654C08F4/651C08F4/02C08F10/00
Inventor 李传峰任鸿平阚林郭峰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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