Bridged cyclopentadienyl bimetallic catalyst and use thereof

A technology of cyclopentadiene and cyclopentadienyl is applied in the field of catalysts for preparing broad/bimodal polyethylene, and can solve the problems of poor thermal stability, difficult process control, harsh preparation conditions and the like

Active Publication Date: 2014-05-07
PETROCHINA CO LTD +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

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

Method used

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  • Bridged cyclopentadienyl bimetallic catalyst and use thereof
  • Bridged cyclopentadienyl bimetallic catalyst and use thereof
  • Bridged cyclopentadienyl bimetallic catalyst and use thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] In a 250ml reaction bottle after evacuated argon displacement, 6.52g (30mmol) of CpTiCl 3 Dissolve in 200ml of THF, then dissolve 0.28g (16mmol) of water into 40ml of THF, and slowly add it dropwise to the above solution. After the dropwise addition, continue to react for 12 hours at room temperature, and then evaporate most of the THF. Then a large amount of n-hexane was added, solids were precipitated, filtered, recrystallized with carbon tetrachloride and dried in vacuo to obtain (CpTiCl 2 ) 2 O4.25g, yield 75%. In a 250ml reaction bottle after vacuum argon displacement, 1.05g (5mmol) of (Me 2 c) 2 (C 5 h 3 ) 2 Dissolve in 50ml n-hexane, slowly add 10mmol n-BuLi hexane solution dropwise at 0°C, after the dropwise addition, slowly rise to room temperature and react for 6 hours to obtain a white suspension, filter the supernatant, drain the solvent, add 60mlTHF, then add 1.91g (5mmol) of (CpTiCl 2 ) 2 O, after stirring at room temperature for 12h, the solvent ...

Embodiment 2

[0024] 0.507g (1mmol) (Me 2 Si)(Me 2 C)(C 5 h 3 ) 2 (CpZrCl) 2 O was dissolved in 30ml THF, and 3ml (12M, 40mmol) concentrated hydrochloric acid was added under cooling in an ice-water bath, then raised to room temperature and continued to react overnight. The solvent was dried under reduced pressure, and the residue was washed with CH 2 Cl 2 Extract, filter, add appropriate amount of n-hexane after the filtrate is concentrated, freeze, filter and precipitate to obtain after vacuum-drying (Me 2 Si)(Me 2 C)(C 5 h 3 ) 2 (CpZrCl)O(ZrCl 2 ) 0.59g, yield 90%. Elemental analysis found values: C, 40.7%; H, 3.9%.

[0025] Add 50ml of toluene distilled out through reflux of metal sodium to the 250ml reactor filled with ethylene after nitrogen replacement three times, stir and heat up to 0°C, feed ethylene to keep the pressure at 2MPa in the reactor, add the main catalyst (Me 2 Si)(Me 2 C)(C 5 h 3 ) 2 (CpZrCl)O(ZrCl 2 ) (the concentration is 9×10 -4 mol / L), co-cataly...

Embodiment 3

[0027] According to the method described in Example 1, 10.5 g (30 mmol) of CpHfCl 3 React with 0.28g (16mmol) of water to get (CpHfCl 2 ) 2 O 6.9 g, yield 72%. Then 1.95g (5mmol) of (Me 2 SiOSiMe 2 ) 2 (C 5 h 3 ) 2 With 4.72g (5mmol) of (CpHfCl 2 ) 2 O reacts to give (Me 2 SiOSiMe 2 ) 2 (C 5 h 3 ) 2 (CpHfCl) 2 O 2.42g, yield 50%. The measured value of elemental analysis: C, 35.0%; H, 4.3%.

[0028] Add 50ml of toluene distilled out through reflux of metal sodium to the 250ml reactor that has been replaced with nitrogen three times and then filled with ethylene, stir and heat up to 90°C, feed ethylene to keep the pressure in the reactor at 3.5MPa, add the main catalyst (Me 2 SiOSiMe 2 ) 2 (C 5 h 3 ) 2 (CpHfCl) 2 O (at a concentration of 2×10 -4mol / L), cocatalyst MMAO (Al / Hf molar ratio is 4000:1), the polymerization time is 1 hour, then add 10ml of acidified ethanol with a concentration of 10% by volume until the reaction is terminated, wash with water ...

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Abstract

The invention relates to a bridged cyclopentadienyl bimetallic catalyst and a use thereof. A main catalyst is represented by the structural formula. In the main catalyst structural formula, M represents Ti, Zr or Hf, X represents Cl or Br, Rn represents 1-3H or 1-3Me, A1 and A2 represent the same or different bridge groups such as alkylene, silicyl group, siloxy group or germane group, and R1 and R2 represent the same or different groups such as substituted cyclopentadienyl group and halogen atoms. A cocatalyst comprises alkylaluminoxane or alkylaluminium. A mole ratio Al / M of the main catalyst to the cocatalyst is 200-10000: 1. In the catalytic polymerization reaction, the bridged cyclopentadienyl bimetallic catalyst has the characteristic of active center diversification. Polyethylene resin obtained by the catalytic ethylene polymerization has wide molecular weight distribution and even forms bimodal distribution. The bridged cyclopentadienyl bimetallic catalyst has good stability and a large structure adjustment range. The polymer obtained by the bridged cyclopentadienyl bimetallic catalyst has unique performances.

Description

technical field [0001] The invention relates to a catalyst for preparing broad / bimodal polyethylene, in particular bridged cyclopentadienyl bimetallic catalysis and application thereof. Background technique [0002] The processability and mechanical strength properties of polyethylene resin are contradictory. Increasing the molecular weight can make the product have better mechanical properties, but at the same time the resin becomes difficult to process, and broad / bimodal polyethylene can solve this problem well . Among them, the high molecular weight part of polyethylene is used to ensure the physical and mechanical strength, and the low molecular weight part is used to improve the processing performance. The wide molecular weight distribution makes it resistant to environmental stress cracking and creep performance, so the wide / bimodal polyethylene is strong and stable. It has the irreplaceable advantages of other products in terms of durability, low shrinkage, crack res...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F10/02C08F4/6592
CPCY02P20/52
Inventor 杨敏王佰全曲佳燕刘宾元石艳红
Owner PETROCHINA CO LTD
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