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Application of a chromium-based metal-organic framework material in olefin polymerization

A metal-organic framework and olefin polymerization technology, applied in the field of metal-organic framework material catalysis, can solve the problems of poor selectivity and low catalytic activity, and achieve the effects of good selectivity, high selectivity and reduced polymerization cost.

Active Publication Date: 2020-12-15
BEIJING INSTITUTE OF TECHNOLOGYGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, in catalytic applications, more focus is on the catalysis of small organic molecules. There is no report on the direct use of MOF materials as catalysts to catalyze the polymerization of olefin monomers into high molecular weight polymers. Only a small amount of ethylene is used to prepare C 4 、C 6 、C 8 Other low molecular weight alpha olefins have been reported, but the catalytic activity is not high and the selectivity is not good

Method used

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  • Application of a chromium-based metal-organic framework material in olefin polymerization
  • Application of a chromium-based metal-organic framework material in olefin polymerization
  • Application of a chromium-based metal-organic framework material in olefin polymerization

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0073] (1) Stir the chromium metal organic framework material Cr-MIL-101 with ethanol and water at 75°C for 30 minutes to clean the impurity, and treat it in vacuum at 200°C for 2 hours to obtain the high temperature activated chromium metal organic framework material, the catalyst;

[0074] (2) Add 25 μmol catalyst and 5ml toluene to the eggplant bottle placed in the glove box, and stir evenly with a magnetic stirrer; add 50 μmol AlMe 3 , continue magnetic stirring evenly; add 5mmol isoprene and 25μmol [PhNHMe 2 ][B(C 6 f 5 ) 4 ], stirred and reacted for 5h at 20°C, and the above steps were carried out in an anhydrous and oxygen-free environment provided by a glove box;

[0075] (3) The catalyst is filtered out from the eggplant bottle, and 30 mL of ethanol solution of 2,6-di-tert-butyl-4-methylphenol with a mass fraction of 5% is added to terminate the reaction; the reaction solution is carried out with absolute ethanol Settled, precipitated solid matter, vacuum-dried t...

Embodiment 2

[0086] (1) with embodiment 1 step (1);

[0087] (2) [PhNHMe 2 ][B(C 6 f 5 ) 4 ] The addition of 50 μ mol is changed into, all the other are with embodiment 1 step (2);

[0088] (3) With embodiment 1 step (3).

[0089] The following tests were carried out on the chromium metal-organic framework material and the polymerization product after high-temperature activation prepared in this example:

[0090] (1) Powder X-ray Diffraction Detection

[0091] The peak position of the chromium metal organic framework material after high temperature activation is completely consistent with the standard map of the chromium metal organic framework material Cr-MIL-101, which proves that the chromium metal organic framework material after high temperature activation has not collapsed and can be used for catalysis in subsequent steps .

[0092] (2) NMR detection

[0093] The ppm of the NMR spectrum of the polymerization product prepared in this example is the integration at 5.12 and 4.78...

Embodiment 3

[0099] (1) with embodiment 1 step (1);

[0100] (2) [PhNHMe 2 ][B(C 6 f 5 ) 4 ] The addition of 75 μ mol is changed into, and all the other are with embodiment 1 step (2);

[0101] (3) With embodiment 1 step (3).

[0102] The following tests were carried out on the chromium metal-organic framework material and the polymerization product after high-temperature activation prepared in this example:

[0103] (1) Powder X-ray Diffraction Detection

[0104] The peak position of the chromium metal organic framework material after high temperature activation is completely consistent with the standard map of the chromium metal organic framework material Cr-MIL-101, which proves that the chromium metal organic framework material after high temperature activation has not collapsed and can be used for catalysis in subsequent steps .

[0105] (2) NMR detection

[0106] The ppm of the NMR spectrum of the polymerization product prepared in this example is the integration at 5.12 and ...

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Abstract

The invention relates to application of a chromium metal organic framework material to olefin polymerization, and belongs to the technical field of metal organic framework material catalysis. The chromium metal organic framework material is applied to catalysis of a polymerization reaction of olefin polymerization as a catalyst and preparation of a high-polymer composite material coated with the chromium metal organic framework material as a raw material. When the chromium metal organic framework material is applied to catalysis of the polymerization reaction of olefin polymerization as the catalyst, the framework material has high polymerization activity and high selectivity, and an obtained olefin polymer has a high molecular weight; in particular, when the framework material is appliedto catalysis of polymerization of isoprene, the selectivity of cis-1,4-polyisoprene is up to 95 percent, the molecular weight is up to 1,880,000, the molecular weight distribution is narrow, and the dispersion coefficient can be up to 1.17; the chromium metal organic framework material can be taken as a raw material in olefin polymerization, and is used for preparing the high-polymer composite material coated with the chromium metal organic framework material, so that the problems of complex preparation process and high cost are solved, and the obtained composite material has high heat stability and high carbon dioxide adsorption amount, and is environmentally friendly and economical.

Description

technical field [0001] The invention relates to the application of a chromium-based metal-organic framework material in olefin polymerization, and belongs to the technical field of metal-organic framework material catalysis. Background technique [0002] Metal-Organic Frameworks (MOFs) are a class of crystalline materials with pores formed by self-assembly of metal ions or metal clusters and organic ligands through coordination bonds or intermolecular forces. Due to its regular channels, high porosity, large specific surface area and rich spatial topology, it is widely used in the fields of gas adsorption and separation, drug release, photoelectric materials and chemical catalysis. Among them, in the field of chemical catalysis, it mainly focuses on the use of the Lewis acid active sites exposed by the MOF metal central site to catalyze organic chemical reactions and realize the regulation of yield and selectivity of organic reactions by MOF. In addition, in the industriali...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F10/00C08F136/08C08F4/69
Inventor 李晓芳高飞
Owner BEIJING INSTITUTE OF TECHNOLOGYGY
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