Application of supported non-metallocene catalyst in ethene polymerization process by slurry method

A non-metallocene, ethylene polymerization technology, applied in the field of low-pressure slurry ethylene polymerization technology, can solve problems such as low catalytic activity, uneconomical application of supported catalysts, and reduced activity of catalytic olefin polymerization

Inactive Publication Date: 2006-06-21
SINOPEC YANGZI PETROCHEM
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] 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 lower catalytic activity
However, after the non-metallocene catalyst is supported by an inert carrier, the catalyti

Method used

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  • Application of supported non-metallocene catalyst in ethene polymerization process by slurry method
  • Application of supported non-metallocene catalyst in ethene polymerization process by slurry method
  • Application of supported non-metallocene catalyst in ethene polymerization process by slurry method

Examples

Experimental program
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Effect test

Embodiment 1

[0075] Preparation of supported non-metallocene catalysts

[0076] (1) Thermal activation treatment of silica gel

[0077] Take ES70 type silica gel (product of Ineos Company) and bake it under nitrogen atmosphere. The calcination conditions are: heating rate 5°C / Min, constant temperature at 200°C for 0.5h, constant temperature at 400°C for 0.5h, then constant temperature at 600°C for 4h, and finally natural cooling under nitrogen atmosphere. Recorded as ES70-650 carrier.

[0078] (2) Preparation of modified carrier

[0079] Take 10g ES70-650 carrier, add 200ml toluene, add 50ml TiCl under stirring 4 (5v / v%TiCl 4 Hexane solution), stirred and reacted at 20°C for 16 hours, filtered, washed with 150ml of toluene three times, dried and vacuum-dried.

[0080] (3) Preparation of composite carrier

[0081] Anhydrous magnesium chloride is obtained by calcining analytically pure magnesium chloride at 500°C for 3 hours in an air atmosphere. Under an anhydrous and oxygen-free nitro...

Embodiment 2

[0096] Basically the same as Example 1, but with the following changes:

[0097] In the preparation of the catalyst, the silica gel is ES70X, and the catalyst is recorded as CAT-2;

[0098] The slurry polymerization process using the above-mentioned supported non-metallocene catalyst is basically the same as that of Example 1, but the cocatalyst is ethyl aluminoxane (EAO).

Embodiment 3

[0100] Basically the same as Example 1, but with the following changes:

[0101] In the preparation of the catalyst, the silica gel is ES70Y, and the catalyst is recorded as CAT-3.

[0102] The cocatalyst is selected from isobutylaluminoxane (IBAO);

[0103] The solvent of the present embodiment is tetrahydrofuran;

[0104] Magnesium chloride was changed to magnesium ethoxide.

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Abstract

The invention discloses an application of load non- metallocene catalyst in the slurry process for vinyl polymerying, the load non- metallocene catalyst and catalyst promoter forming the catalytic system, the alkene polymerization comprising: vinyl homopolymerization, combined polymerization of vinyl with propylene, butylenes, hexane, octane or norbornene; the catalyst carrier being chosen from: inorganic oxide of metallic oxide from IIA, IIIA, IVA, and IVB groups, or oxided mixture and mixing oxide; the catalyst promoter being chosen from: methylaluoxane, ethylaluoxane, isobutylaluoxane, trimethylaluminum,triethylaluminum,triisobutylaluminum,methylaluoxane-trimethylaluminum or methylaluoxane-triethylaluminum; the mole proportion between the catalyst promoter and catalyst being Al/Ti= 1:1-500. The inventioin is characterized by the less methylaluoxane consumption, stable reaction, easy-to-control polymerization temperature and non still-sticking phenomenon. The produced polyolefine possesses perfect granual shape, and the maximum polymer clamp density can reach 0.385 g/ml.

Description

technical field [0001] The invention belongs to the ethylene polymerization process, and relates to the application method of the supported non-metallocene olefin polymerization catalyst in the slurry ethylene polymerization process, in other words, it is a low-pressure slurry ethylene polymerization process using the supported non-metallocene olefin polymerization catalyst method. Background technique [0002] The coordination atoms of non-metallocene olefin polymerization catalysts are oxygen, nitrogen, sulfur and carbon, etc., and do not contain cyclopentadiene groups. It was discovered and studied in the early 1990s, and its catalytic activity can reach or even exceed Metallocene olefin polymerization catalysts, and at the same time maintain the advantages of metallocene catalyst systems, such as controllable polymers, narrow molecular weight distribution, molecular tailoring of polymers, and controllable molecular weight and branching degree of polymers. Oxygen is weak...

Claims

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Application Information

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IPC IPC(8): C08F10/02C08F2/00C08F4/52
Inventor 戴厚良尤侯平李传峰姚小利李晓强马忠林王亚明柏基业
Owner SINOPEC YANGZI PETROCHEM
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