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Non-metallocene bimetallic catalytic system for synthesizing broad/bimodal polyethylene and application thereof

A bimodal polyethylene and bimetallic catalyst technology, applied in the field of non-metallocene bimetallic catalytic systems, can solve the problems of harsh preparation conditions, difficult process control, and poor thermal stability of metallocene catalysts, so as to overcome the harsh preparation conditions and avoid mutual Good effects of action and interference, thermal stability

Active Publication Date: 2014-03-19
HEBEI UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, most of its catalysts are metallocene catalysts. Metallocene catalysts have problems such as harsh preparation conditions, difficult process control, and poor thermal stability.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025]Dissolve 1.38g (0.01mol) of 2,3-dihydroxybenzaldehyde in 15ml of ethanol, add 10ml of CH dissolved in 0.3g (0.005mol) of ethylenediamine 2 Cl 2 The solution was refluxed for 2 hours, 20ml of solvent was distilled off, filtered, washed with sub-zero ethanol, and vacuum-dried to obtain 1.27g of a dinuclear ligand with the structure of formula III, with a yield of 85%. In a 250ml reaction flask that has been evacuated and replaced by argon, 1.5g (0.005mol) of the dinuclear ligand was dissolved in 20mlTHF, and added dropwise to 0.3g (0.0125mol) of NaH at room temperature, reacted for 5 hours and filtered to obtain The liquid was added dropwise to 1.89 g (0.01 mol) TiCl at -20 °C 4 15ml of THF suspension, the dropwise addition was completed, and the reaction was slowly raised to room temperature for 12 hours, the solvent was drained, and 20ml of CH 2 Cl 2 , stirred for 30 minutes and filtered, the filtrate was concentrated to 2.0ml, then 100ml of n-hexane was added, the pr...

Embodiment 2

[0028] Dissolve 1.38g (0.01mol) of 2,3-dihydroxybenzaldehyde in 15ml of ethanol, add 10ml of CH dissolved in 1.14g (0.005mol) of 1,2-dihexyl-ethylenediamine 2 Cl 2 The solution was refluxed for 4 hours, 20ml of the solvent was distilled off, filtered, washed with sub-zero ethanol, and vacuum-dried to obtain 1.64g of a dinuclear ligand with the structure of formula III, with a yield of 70%. In a 250ml reaction flask replaced by vacuum argon, 2.34g (0.005mol) of the dinuclear ligand was dissolved in 20mlTHF, and added dropwise to 0.3g (0.0125mol) NaH at room temperature, reacted for 5 hours and filtered to obtain The liquid was added dropwise to 4.2g (0.01mol) Ti(OPh) at -20°C 4 15ml of THF suspension, the dropwise addition was completed, and the reaction was slowly raised to room temperature for 12 hours, the solvent was drained, and 20ml of CH 2 Cl 2 , stirred for 30 minutes and filtered, the filtrate was concentrated to 2.0ml, then 100ml of n-hexane was added, the precipit...

Embodiment 3

[0031] Dissolve 1.38g (0.01mol) of 2,3-dihydroxybenzaldehyde in 15ml of ethanol, add 10ml of CH dissolved in 0.58g (0.005mol) of 2,3-diamino-2,3-dimethylbutane 2 Cl 2 The solution was refluxed for 6 hours, 20 ml of solvent was distilled off, filtered, washed with sub-zero ethanol, and vacuum-dried to obtain 1.16 g of a dinuclear ligand with the structure of formula III, with a yield of 65%. In a 250ml reaction flask replaced by vacuum argon, 1.78g (0.005mol) of the dinuclear ligand was dissolved in 20mlTHF, and added dropwise to 0.3g (0.0125mol) NaH at room temperature, reacted for 5 hours and filtered to obtain The liquid was added dropwise to 2.33 g (0.01 mol) ZrCl at -20 °C 4 15ml of THF suspension, the dropwise addition was completed, slowly raised to room temperature and reacted for 6 hours, the solvent was drained, and 20ml of CH 2 Cl 2 , stirred for 30 minutes and filtered, the filtrate was concentrated to 2.0ml, then 100ml of n-hexane was added, the precipitated sol...

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Abstract

The invention provides a non-metallocene bimetallic catalytic system for synthesizing broad / bimodal polyethylene, which is composed of a main catalyst and a co-catalyst, wherein the mol ratio of the co-catalyst to the main catalyst is 300-8000: 1; the main catalyst is a non-metallocene bimetallic catalyst and has a structural formula as a structural formula shown in the specification; the co-catalyst is alkyl aluminoxane or alkyl aluminium. The non-metallocene bimetallic catalytic system provided by the invention has a catalytic activity of 1*10<4>-1*10<7> g PE / mol.h; the molecular weight distribution of the polyethylene obtained by catalysing the ethylene polymerization is broad or bimodal. The non-metallocene bimetallic catalyst has high thermal stability; the molecular weight and the distribution of the polymer can be regulated by changing the structure of the main catalyst and controlling reaction conditions, so the polymer products with different performance indexes are produced. The non-metallocene bimetallic catalytic system provided by the invention has simple polymerization process and is easy to control. A formula I or a formula II of the product is shown in the specification.

Description

technical field [0001] The technical solution of the invention relates to a catalyst system for preparing broad / bimodal polyethylene, specifically a non-bimetallocene catalyst system and its application. technical background [0002] The processability and mechanical strength properties of polyethylene are contradictory. High molecular weight can make the product have better mechanical properties, but at the same time the resin becomes difficult to process. Broad / bimodal polyethylene solves this problem well. The low molecular weight part of the wide / bimodal polyethylene is used to improve the processing performance, and the high molecular weight part ensures the physical and mechanical strength. At the same time, the wide molecular weight distribution makes it resistant to environmental stress cracking and creep performance. Therefore, the wide / bimodal polyethylene It has irreplaceable advantages of other products in terms of strength, stability, low shrinkage, crack resist...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F10/02C08F4/642
CPCY02P20/52
Inventor 杨敏石艳红曲佳燕刘宾元董小芳
Owner HEBEI UNIV OF TECH