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Monodisperse porous organic metal polymer material as well as preparation method and application thereof

A polymer material and organometallic technology, applied in the preparation of organic compounds, organic compound/hydride/coordination complex catalysts, organic chemistry, etc., can solve the problem of affecting the performance of catalytic materials, increasing the cost of catalysts, and poor recycling performance problems such as good industrial application prospects, good universality, high reactivity and stability

Active Publication Date: 2019-11-22
FUDAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Aiming at the problems that homogeneous catalysts are difficult to recycle, and the catalyst may be deactivated due to polypolymerization during the reaction process, researchers have successfully developed many heterogeneous catalytic systems, but these heterogeneous catalysts have low activity, poor selectivity, and poor stability. , poor recycling performance, etc., and the catalyst often needs to be modified and synthesized in multiple steps, which not only increases the cost of the catalyst, but also affects the performance of the catalytic material

Method used

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  • Monodisperse porous organic metal polymer material as well as preparation method and application thereof
  • Monodisperse porous organic metal polymer material as well as preparation method and application thereof
  • Monodisperse porous organic metal polymer material as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040] Embodiment 1, the preparation of porous organometallic polymer material POMP 1a:

[0041]

[0042] Add 1mmol of bisbenzimidazole nitrogen heterocyclic carbene iridium compound (0.63g) into a 50mL Schlenk tube, vacuum and change nitrogen three times, then add 10mL of 1,2-dichloroethane and 3mmol of benzene (0.23g) successively, and stir at room temperature After a period of time until the solids were completely dissolved, 9 mmol of dimethylformal (FDA, 0.68 g) and anhydrous ferric chloride (1.46 g) were added. After sealing, put the reaction system into an oil bath at 30-80 degrees to react for 1-72 hours. After the reaction was complete, it was cooled to room temperature, filtered, washed, and the obtained solid was extracted by Soxhlet for 24 hours, and vacuum-dried at 60° C. for 24 hours to obtain the porous organometallic polymer POMP1a. The TEM spectrum of the solid is attached figure 1 shown. Yield: 0.58 g, 60%.

Embodiment 2

[0043] Embodiment 2, the preparation of porous organometallic polymer material POMP 1b:

[0044]

[0045] Add 1mmol of bisbenzimidazole nitrogen heterocyclic carbene iridium compound (0.63g) into a 50mL Schlenk tube, vacuum and change nitrogen three times, then add 10mL of 1,2-dichloroethane and 3mmol of benzene (0.23g) successively, and stir at room temperature After a period of time until the solids were completely dissolved, another 12 mmol of dimethylformal (FDA, 0.91 g) and anhydrous ferric chloride (1.95 g) were added. After sealing, put the reaction system into an oil bath at 30-80 degrees to react for 1-72 hours. After the reaction was complete, it was cooled to room temperature, filtered, washed, and the obtained solid was extracted by Soxhlet for 24 hours, and vacuum-dried at 60° C. for 24 hours to obtain the porous organometallic polymer POMP1b. Yield: 0.70 g, 70%.

Embodiment 3

[0046] Embodiment 3, the preparation of porous organometallic polymer material POMP 1c:

[0047]

[0048] Add 1mmol of bisbenzimidazole nitrogen heterocyclic carbene iridium compound (0.63g) into a 50mL Schlenk tube, vacuum and change nitrogen three times, then add 10mL of 1,2-dichloroethane and 3mmol of benzene (0.23g) successively, and stir at room temperature After a period of time until the solids were completely dissolved, another 15 mmol of dimethylformal (FDA, 1.14 g) and anhydrous ferric chloride (2.43 g) were added. After sealing, put the reaction system into an oil bath at 30-80 degrees to react for 1-72 hours. After the reaction was complete, it was cooled to room temperature, filtered, washed, and the obtained solid was extracted by Soxhlet for 24 hours, and vacuum-dried at 60° C. for 24 hours to obtain the porous organometallic polymer POMP1c. Yield: 0.83 g, 80%.

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Abstract

The invention belongs to the technical field of heterogeneous catalysts, and particularly relates to a monodisperse porous organic metal polymer material and a preparation method and application thereof. The polymer is prepared by taking homogeneous double carbene iridium, palladium, gold, copper, cobalt and manganese compounds as monomers and aromatic hydrocarbon as a comonomer in a manner of adding a cross-linking agent and carrying out Friedel-Crafts alkylation under the catalysis of Lewis acid. The polymer can be used for catalyzing hydrogenation cyclization of levulinic acid to prepare gamma-valerolactone, or catalyzing oxidative dehydrogenation of polyol and derivatives thereof and carbohydrate compounds to efficiently prepare lactic acid and derivatives thereof, and dehydrogenationcoupling of alcohol compounds and amine to efficiently prepare pyrrole and derivatives thereof. The polymer material completely holds intrinsic high activity and high selectivity of a homogeneous catalyst precursor and has the characteristics of heterogeneous catalysis stability and easiness in recovery, so that biomass can be converted into various fine chemicals with high efficiency, high selectivity and a large amount; the catalyst can be recycled for multiple times and has a good industrial application prospect.

Description

technical field [0001] The invention belongs to the technical field of heterogeneous catalysts, and in particular relates to a monodisperse porous organometallic polymer material and its preparation method and application. Background technique [0002] The development of modern society relies heavily on fossil energy, not only as a source of power energy, but also as a basic raw material for the preparation of bulk chemicals. However, these resources are non-renewable. With the overexploitation of these fossil energy sources, their reserves are gradually depleted. Therefore, it is imminent to seek a green and environmentally friendly renewable resource as a substitute. Biomass is an important part of renewable resources, and the efficient development and utilization of biomass will play a very positive role in solving energy and ecological environment problems. Among them, plant cellulose, lignin, polysaccharide and its downstream product levulinic acid, as important biomas...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G83/00B01J31/22C07C51/295C07D207/323C07D307/33C07C59/08B01J35/10
CPCC08G83/008B01J31/1691B01J31/2273C07D307/33C07D207/323C07C51/295B01J2531/827B01J2531/16B01J2531/824B01J2231/76B01J35/61C07C59/08Y02P20/584
Inventor 涂涛申雅靓郑庆舒
Owner FUDAN UNIV
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