Viologen-based ion type porous organic polymers and preparation method and application thereof

An ionic and polymer technology, applied in the direction of organic compound/hydride/coordination complex catalysts, chemical instruments and methods, chemical/physical processes, etc., can solve problems such as cumbersome methods, and achieve simple equipment and low catalyst consumption The effect of less, excellent catalytic performance

Inactive Publication Date: 2019-06-11
XUZHOU NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the methods for preparing these viologen-based covalent organic polymers are cumbersome, and most of the synthetic processes require the participation of metal catalysts.

Method used

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  • Viologen-based ion type porous organic polymers and preparation method and application thereof
  • Viologen-based ion type porous organic polymers and preparation method and application thereof
  • Viologen-based ion type porous organic polymers and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] Example 1: Preparation of viologen-based ionic porous organic polymer V-iPOP-Cl

[0036]

[0037] Weigh 4,4'-bipyridyl, biphenyl benzyl dichloride and add 5mL of acetonitrile respectively, stir to dissolve completely, mix the two solutions into a polytetrafluoroethylene-lined stainless steel reaction kettle, place in a 100°C oven, Reaction 48h. After the reaction was completed, the reactor was cooled to room temperature, and the solution was transferred into a beaker, then suction filtered, and washed with DMSO, deionized water and ethanol respectively. Finally, the filter cake was dried in a vacuum oven (80° C.) for 12 hours to obtain the viologen-based ionic porous organic polymer V-iPOP-Cl. The XRD spectrum of V-iPOP-Cl is as follows figure 1 As shown, the infrared IR spectrum is shown as figure 2 As shown, the SEM image is shown in image 3 As shown, V-iPOP-C under 77K N 2 The adsorption-desorption curve is as Figure 4 shown.

[0038] The viologen-based ...

Embodiment 2

[0039] Example 2: Catalytic conversion of CO by V-iPOP-Cl 2 Typical reaction optimization process and reusability

[0040] Add 2mmol epichlorohydrin and 0.05g of the catalyst V-iPOP-Cl in Example 1 into a 25mL reaction tube, stir at 40°C-80°C, and connect the CO 2 The vent tube of the gas cylinder discharges the air in the reaction tube, and then inserts a balloon (0.1MPa) filled with carbon dioxide into the reaction tube, and reacts for 48-120h. After the reaction was completed, a certain amount of ethyl acetate was added for dilution, and stirred at room temperature for 20 min. The solution was taken out, centrifuged, and the supernatant was taken out, and the yield was analyzed and calculated by gas chromatography (GC). The results are shown in Table 1. As can be seen from Table 1, V-iPOP-Cl is a very efficient heterogeneous catalyst.

[0041] Table 1 CO catalyzed by viologen-based ionic porous organic polymer V-iPOP-Cl 2 Results of cycloaddition reaction with epichloro...

Embodiment 3

[0047] In this example, the V-iPOP-Cl catalyst is used as a substrate to carry out CO 2 Research on the expansion of substrates in cycloaddition catalytic reactions, epoxy compounds are

[0048]

[0049] Wherein, R is chloromethyl, bromomethyl, phenyl, benzyloxy, n-butyl, n-hexyl or n-decyl. The experimental results are shown in Table 3.

[0050] Table 3 CO catalyzed by viologen-based ionic porous organic polymer V-iPOP-Cl 2 Cycloaddition reaction performance with different epoxy compounds

[0051]

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Abstract

Viologen-based ion type porous organic polymers and a preparation method and application thereof are disclosed. The viologen-based ion type porous organic polymers have a structural formula represented by a formula shown in the specification, and are prepared by quaternization reaction of 4,4'-bipyridine respectively with 4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(bromomethyl)-1,1'-biphenyl. Since a nitrogen cation and a halogen anion are introduced into the polymer in situ, the prepared viologen-based porous organic polymer has excellent catalytic activity, and can realize efficient catalytic conversion of carbon dioxide under mild conditions. The viologen-based porous organic polymer in the invention has excellent catalytic performance in a cycloaddition reaction of an epoxy compound and CO2 under the condition of no solvent and no cocatalyst, and the reaction also has the characteristics that the catalyst is small in usage amount, and easy to separate and recycle.

Description

technical field [0001] The invention relates to the fields of preparation and catalytic application of organic polymers, in particular to a viologen-based ionic porous organic polymer and its preparation method and application. Background technique [0002] As the global environment deteriorates, the greenhouse gas CO 2 The capture and utilization of CO2 is becoming more and more important, and CO 2 It has abundant sources and can be used as a renewable C1 resource to synthesize high value-added chemical products. Currently, the CO 2 Insertion into the molecule of epoxy compounds to produce cyclic carbonates of five-membered ring compounds is the realization of CO 2 One of the most promising avenues for chemical fixation. At present, many homogeneous and heterogeneous catalysts have been developed for CO 2 conversion, in which porous organic polymers (POPs) with large specific surface area have both adsorption and catalytic functions, have been widely used for CO 2 Cap...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G73/06C07D317/36B01J31/08
Inventor 陈国建徐婧语张亚东刘晓青
Owner XUZHOU NORMAL UNIVERSITY
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