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Metal organic framework with polymer grafted on surface and preparation method thereof

A metal-organic framework and surface grafting technology, applied in separation methods, chemical instruments and methods, medical preparations with inactive ingredients, etc. Improve the effect of practical application, the effect of fewer method steps and low cost

Inactive Publication Date: 2020-05-15
TIANJIN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the existing preparation methods of MOF / polymer composites involve multi-step chemical reactions, and the cost of polymers is relatively high. For example, the bromine-containing linking agent required for atom transfer radical polymerization is expensive, the operation is complicated and the polymerization conditions are harsh. , cannot be adapted to industrial production, and is only applicable to specific MOF materials and monomers, there are still many areas for improvement

Method used

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  • Metal organic framework with polymer grafted on surface and preparation method thereof
  • Metal organic framework with polymer grafted on surface and preparation method thereof
  • Metal organic framework with polymer grafted on surface and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0042] Using methacrylic anhydride as linker in UiO-66-NH 2 Surface grafted polystyrene, it comprises the following steps:

[0043] 1) Add UiO-66-NH 2 (56mg) ultrasonically dispersed in CH 2 Cl 2 (8 mL), to the resulting solution was added methacrylic anhydride (500 μL). The reaction system was placed in a constant temperature water bath at 25° C. and stirred for 2 days at a stirring speed of 200 rpm. The product was obtained by suction filtration under reduced pressure and washed with CH 2 Cl 2 Wash 3 times. Dry in a vacuum oven at 45°C for 48 hours to obtain a light yellow solid, which is UiO-66-NH modified with methacrylic anhydride linker 2 (MAA-UiO-66-NH 2 ).

[0044] 2) Add the MAA-UiO-66-NH obtained in step 1) into the three-necked flask 2 (50mg) and anhydrous acetonitrile (26ml), sonicate at room temperature for 0.5h. Then, styrene (25ml) was added into the three-neck flask under nitrogen. Nitrogen gas continued to flow through the whole system for 20 minut...

Embodiment 2

[0050] Using acrylic anhydride as linking agent in MIL-125(Ti)-NH 2 Surface grafting polymethyl methacrylate, it comprises the following steps:

[0051] 1) MIL-125(Ti)-NH 2 (48 mg) was ultrasonically dispersed in acetonitrile (12 mL), and acrylic anhydride (500 µL) was added to the resulting solution. The reaction system was placed in a constant temperature water bath at 25° C. and stirred for 3 days at a stirring speed of 300 rpm. The product was obtained by suction filtration under reduced pressure and washed 4 times with acetonitrile. Dry in a vacuum oven at 80°C for 6 hours to obtain a yellow solid, which is MIL-125(Ti)-NH modified with acrylic anhydride linker 2 (AA-MIL-125(Ti)-NH 2 ).

[0052] 2) Add AA-MIL-125(Ti)-NH obtained in step 1) into the three-necked flask 2 (50mg) and anhydrous acetonitrile (24ml), sonicated at room temperature for 1h. Then methyl methacrylate (24ml) was added into the three-necked flask under nitrogen. The whole system continued to flo...

Embodiment 3

[0055] Using acrylic anhydride as linking agent in MIL-101(Fe)-NH 2 Surface grafted polystyrene, it comprises the following steps:

[0056] 1) MIL-101(Fe)-NH 2 (48 mg) was ultrasonically dispersed in acetonitrile (12 mL), and acrylic anhydride (500 µL) was added to the resulting solution. The reaction system was placed in a constant temperature water bath at 25° C. and stirred for 3 days at a stirring speed of 350 rpm. The product was obtained by suction filtration under reduced pressure and washed 5 times with acetonitrile. Dry in a vacuum oven at 60°C for 24 hours to obtain a brown solid, which is MIL-101(Fe)-NH modified with acrylic anhydride linker 2 (AA-MIL-101(Fe)-NH 2 ).

[0057] 2) Add AA-MIL-101(Fe)-NH obtained in step 1) into the three-necked flask 2 (50mg) and acetonitrile (25ml), sonicate at room temperature for 2h. Then, styrene (27ml) was added into the three-necked flask under nitrogen. The whole system continued to flow nitrogen for 35 minutes. After a...

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Abstract

The invention provides a metal organic framework with a polymer grafted on the surface and a preparation method thereof. A linear polymer is grafted on the surface of the metal organic framework containing amino through a small molecular connecting agent, wherein the weight-average molecular weight of the polymer is 5,000-500,000, and the particle size of the metal organic framework is 50-1000nm;and the small molecular connecting agent is anhydride containing double bonds. Based on post-synthesis chemical modification, the provided preparation method of the metal organic framework has the advantages of few steps, low cost, simple operation, high density of grafted polymer, and wide weight-average molecular weight range, and is suitable for preparing a plurality of amino-containing metal organic frameworks and olefin or olefin derivative monomers. The prepared metal organic framework not only has the advantages of an existing metal organic framework / polymer composite material, but alsoimproves the dispersity of the metal organic framework in a polymer body material, so that the actual effect of doping the polymer body material by the metal organic framework is improved.

Description

technical field [0001] The present invention relates to the field of metal-organic framework / polymer composites, specifically based on metal-organic frameworks involving novel surface-grafted polymers through post-synthesis chemical modification and methods for their preparation. Background technique [0002] Metal organic framework (Metal organic framework, MOF) is a three-dimensional network structure formed by metal ions or inorganic oxide clusters through coordination bonds with multi-dentate organic ligands. It has a regular pore structure and precisely adjustable pore size. size, ultra-high specific surface area, and rich chemical modifiable properties. MOF has excellent application potential in gas adsorption separation and storage, catalysis, and environmental sewage treatment. However, problems such as poor chemical stability, especially hydrolytic instability, poor mechanical properties, and difficult processing and molding of amino-containing metal-organic framew...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J20/22B01J20/30B01D53/02C02F1/28B01J31/22C08F289/00C08F212/08C08F220/14C08F220/34A61K47/32C02F101/20C02F101/30
CPCA61K47/32B01D53/02B01J20/226B01J31/1691C02F1/285C02F2101/20C02F2101/30C08F289/00C08F212/08C08F220/14C08F220/34
Inventor 吴松海曹香慧张珍坤
Owner TIANJIN UNIV
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