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Polyethylene catalyst and preparation method thereof

A catalyst and polyethylene technology, which is applied in the field of preparation of supported titanium-based polyethylene catalysts, can solve the problems of difficulty in producing high-quality polyethylene products, large particle size of polymerized products, and high oligomer content, etc., and is beneficial to long-term operation. , Narrow particle size distribution, good copolymerization performance

Active Publication Date: 2018-03-27
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] Chinese patent CN101759817A discloses a method for preparing a solid catalyst for α-olefin polymerization. The preparation method is to add an electron donor composition of dihydroanthracene derivatives and phthalates during the preparation process to prepare The obtained catalyst has low activity and wide molecular weight distribution
Chinese patent CN1814627 discloses an olefin polymerization catalyst suitable for ethylene polymerization or copolymerization of ethylene and α-olefins. During preparation, an electron donor is added, and the electron donor is an organosilicon compound or carboxylic acid anhydride without active hydrogen , or its mixture, the particle size of the catalyst prepared by this method is relatively large, the content of oligomers in the polymerization process is relatively large, and the particle size of the polymerization product is large, so it is difficult to produce high-quality polyethylene products

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] 1) Catalyst preparation

[0040] Under the protection of nitrogen, the raw material Mg(OC 2 h 5 ) 2 10g, 140ml of n-octane, stir and heat up. When the temperature reaches 80°C, drop TiCl 418.7ml. After the dropwise addition, the reaction was continued for 1 hour, and the temperature was lowered. At 55° C., 4.1 ml of ethylene glycol dimethyl ether and 13.3 ml of diisobutyl phthalate were added, and the temperature was kept constant for 30 minutes. Stop heating and cool down to 50°C naturally. After settling for 15 minutes, draw off the supernatant. Add 100ml of hexane, stir and heat up to 60°C, stop stirring after 30 minutes, stop heating, settle for 1 hour, and take out the supernatant. Repeat the above washing step 5 times. The catalyst suspension is dried to obtain a solid catalyst.

[0041] 2) Polymerization reaction

[0042] After the stainless steel reaction kettle with a volume of 2L is fully replaced with nitrogen, add 1L of hexane, 3ml of triethylalumi...

Embodiment 2

[0044] Under the protection of nitrogen, the raw material Mg(OC 2 h 5 ) 2 10g, 280ml of n-octane, stir and heat up. When the temperature reaches 100°C, drop TiCl 4 9.6ml. After the dropwise addition, the reaction was continued for 2 hours, the temperature was lowered, and at 65°C, 0.30 ml of ethylene glycol dimethyl ether and 1.5 ml of dibutyl phthalate were added, and the temperature was kept constant for 30 minutes. Stop heating and cool down to 50°C naturally. After settling for 15 minutes, draw off the supernatant. Add 100ml of hexane, stir and heat up to 60°C, stop stirring after 30 minutes, stop heating, settle for 1 hour, and take out the supernatant. Repeat the above washing step 5 times. The catalyst suspension is dried to obtain a solid catalyst.

[0045] Polymerization is the same as in Example 1. The measured catalyst activity was 2.3×10 4 gPE / gCat, polymer wax content 1.0%, bulk density 0.34g / cm 3 , molecular weight distribution 5.8.

Embodiment 3

[0047] Under the protection of nitrogen, the raw material Mg(OC 2 h 5 ) 2 10g, 200ml n-octane, stir and heat up. When the temperature reaches 85°C, drop TiCl 4 35ml. After the dropwise addition, the reaction was continued for 1 hour, and the temperature was lowered. At 60° C., 2.5 ml of ethylene glycol dimethyl ether and 5.7 ml of diethyl phthalate were added, and the temperature was kept constant for 30 minutes. Stop heating and cool down to 50°C naturally. After settling for 15 minutes, draw off the supernatant. Add 100ml of hexane, stir and heat up to 60°C, stop stirring after 30 minutes, stop heating, settle for 1 hour, and take out the supernatant. Repeat the above washing step 5 times. The catalyst suspension is dried to obtain a solid catalyst.

[0048] Polymerization is the same as in Example 1. The measured catalyst activity was 2.4×10 4 gPE / gCat, polymer wax content 1.3%, bulk density 0.33g / cm 3 , molecular weight distribution 6.2.

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Abstract

The invention relates to a polyethylene catalyst containing a third component and a preparation method thereof. In the preparation process for the catalyst, a composition of an active-hydrogen-free alcohol ether compound and a phthalic acid diester compound are added as electron donors so as to change the coordination of components of the catalyst and the formation of an active center. The prepared catalyst has high activity, sensitivity to hydrogen modulation, good copolymerization performance, uniform particle size distribution, narrow molecular weight distribution (in a range of 5 to 7) andadjustable molecular weight distribution, improves the chlorination performance of resin, and is low in wax content and beneficial for long-term operation of equipment. The polyethylene catalyst canbe applied to conventional slurry-process polyethylene production facilities.

Description

technical field [0001] The present invention relates to a supported titanium-based polyethylene catalyst comprising a phthalic acid diester compound and an alcohol ether compound. The present invention further relates to a preparation method of the supported titanium-based polyethylene catalyst comprising the third component. Background technique [0002] In the industrial process of ethylene polymerization, catalysts are usually required to have high activity and stability to meet the long-term operation of the device and process stability. At the same time, it is required that the polymer has better shape, uniform particle size, less fine powder, controllable molecular weight and molecular weight distribution, and good physical and mechanical properties. In the usual preparation of catalysts, ground magnesium chloride is often used as a carrier, and the catalysts obtained by this method have uneven particle size and poor morphology. The current method mostly uses magnesi...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F110/02C08F4/649
CPCC08F110/02C08F4/6494C08F2500/03
Inventor 鲍永忠张利粉焦金华侯维高嵩冯文元张利仁郭洪元徐丽艳崔月王永年王俊荣王大明刘志军孙辉宇
Owner PETROCHINA CO LTD
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