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Montmorillonite carrier-formed double-function catalysis system, its preparation method and application

A technology of bifunctional catalysis and catalytic system is applied in the application of the above-mentioned catalytic system in the preparation of linear low-density polyethylene, the preparation of the above-mentioned catalytic system, and the preparation of a montmorillonite carrier-supported copolymerization catalyst in the catalytic system, which can solve the problem of forming Copolymers, ethylene oligomerization catalysts are unstable, etc., and achieve the effects of low melting point, inhibition of sticking kettle phenomenon, and high catalytic activity

Inactive Publication Date: 2005-11-23
INST OF CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

But, the weak point of this method is that the ethylene oligomerization catalyst used is unstable, and the α-olefin selectivity is only 40-90%, and its oligomerization product is 1-alkene, 2-alkyl-1-alkene and 2-Alkenes, of which 2-alkyl-1-alkenes and 2-alkenes cannot form copolymers with ethylene

Method used

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  • Montmorillonite carrier-formed double-function catalysis system, its preparation method and application
  • Montmorillonite carrier-formed double-function catalysis system, its preparation method and application
  • Montmorillonite carrier-formed double-function catalysis system, its preparation method and application

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Experimental program
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Effect test

Embodiment 1

[0028] 1. All operations are carried out under anhydrous and oxygen-free conditions, and the solvents used need to be dehydrated and deoxidized.

[0029] 2. Catalytic system

[0030] (a) Oligomerization catalyst (homogeneous)

[0031]

[0032] (b) Preparation of montmorillonite carrier: Dry montmorillonite in vacuum for 8 hours at 60°C, add 1.8mol / L methylalumoxane solution (the weight ratio of methylalumoxane solution to montmorillonite is as follows: 6:1) was stirred at 60° C. for 8 hours, and the unreacted methylaluminoxane was washed with toluene three times, filtered, and dried to obtain a montmorillonite carrier.

[0033] The preparation of montmorillonite-supported ethylene copolymerization catalyst: take 4 grams of above-mentioned montmorillonite, add 30 milliliters of toluene and 0.1gEt(Ind) 2 ZrCl 2 The solution was reacted at 50°C for 12 hours; unsupported Et(Ind) was washed away with toluene 2ZrCl 2 ; Remove the toluene solvent in vacuum, and vacuum-dry at ...

Embodiment 2

[0037] 1. All operations are carried out under anhydrous and oxygen-free conditions, and the solvents used need to be dehydrated and deoxidized.

[0038] 2. Catalytic system

[0039] (a) Oligomerization catalyst (homogeneous)

[0040]

[0041] (b) Preparation of montmorillonite carrier: Dry montmorillonite in vacuum for 8 hours at 60° C., add 1.8 mol / L methylalumoxane solution (the weight ratio of methylalumoxane solution to montmorillonite is as follows: 6:1) was stirred at 60° C. for 8 hours, and the unreacted methylaluminoxane was washed with toluene three times, filtered, and dried to obtain a montmorillonite carrier.

[0042] The preparation of montmorillonite-supported ethylene copolymerization catalyst: take 2 grams of above-mentioned montmorillonite, add 10 milliliters of toluene and 0.5g Me 2 Si(Ind) 2 ZrCl 2 The solution was reacted at 50 °C for 14 hours; unloaded Me was washed away with toluene 2 Si(Ind) 2 ZrCl 2 ; Remove the toluene solvent in vacuum, and...

Embodiment 3

[0046] 1. All operations are carried out under anhydrous and oxygen-free conditions, and the solvents used need to be dehydrated and deoxidized.

[0047] 2. Catalytic system

[0048] (a) Oligomerization catalyst (homogeneous)

[0049]

[0050] (b) Preparation of montmorillonite carrier: Dry montmorillonite in vacuum for 8 hours at 60° C., add 1.8 mol / L methylalumoxane solution (the weight ratio of methylalumoxane solution to montmorillonite is as follows: 6:1) was stirred at 60° C. for 8 hours, and the unreacted methylaluminoxane was washed with toluene three times, filtered, and dried to obtain a montmorillonite carrier.

[0051] The preparation of montmorillonite-supported ethylene copolymerization catalyst: take 8 grams of above-mentioned montmorillonite, add 40 milliliters of toluene and 0.3g Et(Ind) 2 ZrMe 2 The solution was reacted at 70°C for 9 hours; unsupported Et(Ind) was washed away with toluene 2 ZrMe 2 ; Remove the toluene solvent in vacuum, and vacuum-dry...

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Abstract

The present invention relates to a double-function catalytic system by using montmorillonite clay as catalyst. It uses homogeneous transition-metal catalyst as oligomerization catalyst, uses inorganic material loaded metallocene catalyst with laminar structure as copolymerization catalyst, uses alkylaluminoxane as unique catalyst promotor and uses ethylene as unique monomer. Its preparation method includes the following steps: firstly, preparing montmorillonite clay carrier, then making the montmorillonite clay catalyst be loaded on copolymerization catalyst so as to obtain the copolymerization catalyst using montmorillonite clay as carrier. Said invention utilizes the regulation of proportion of two catalysts so as to can control the density, degree of branching and other physical mechanical properties of different linear low density polyethylene.

Description

technical field [0001] The invention relates to a montmorillonite-supported dual-function catalytic system. [0002] The present invention also relates to the preparation method of the above-mentioned catalytic system, in particular to the preparation method of the montmorillonite carrier-supported copolymerization catalyst in the catalytic system. [0003] The present invention also relates to the application of the above catalyst system in the preparation of linear low density polyethylene. Background technique [0004] Copolymerization of ethylene and α-olefins to prepare linear low-density polyethylene (LLDPE) with metallocene catalysts or constrained geometry catalysts is a research hotspot in recent years. The required α-olefins are usually generated by ethylene oligomerization, and then refined Distillation to obtain hexene, octene, decene and so on. If a dual-functional catalyst system can be used to oligomerize ethylene into α-olefins through an oligomerization ca...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F4/02C08F4/70C08F10/02
Inventor 胡友良张志成郭存悦陈商涛李化毅
Owner INST OF CHEM CHINESE ACAD OF SCI
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