A kind of porphyrin-based self-contained microporous polymer and its synthesis method

A microporous polymer and porphyrin-based technology, which is applied in the field of porphyrin-based microporous polymers and their synthesis, can solve the problems of difficult modification of active sites, instability of active sites, and limited applications. Rich pore size distribution, conducive to large-scale mass production, and the effect of simple steps

Active Publication Date: 2021-09-07
JIANGNAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the active sites of PIMs reported so far are unstable, and the modification of the active sites in the pores of the material is difficult and the abundance is low, which greatly limits the application of such materials in electrochemical technology.

Method used

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  • A kind of porphyrin-based self-contained microporous polymer and its synthesis method
  • A kind of porphyrin-based self-contained microporous polymer and its synthesis method
  • A kind of porphyrin-based self-contained microporous polymer and its synthesis method

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Experimental program
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Effect test

Embodiment 1

[0040] The synthetic steps of present embodiment polymer P1 are as follows:

[0041] 1) Under the conditions of argon protection and ice-water bath, the porphyrin-based P1 was synthesized by a one-pot method, and 193.4 mg of 5,15-bis(4-aminophenyl)-10,20 was weighed into a 25 mL round bottom flask -diphenylporphyrin (B10) (0.3mmol), then add 10mL of trifluoroacetic acid to the bottle, stir for 5 minutes, after B10 is uniformly dispersed, add 0.132mL of dimethylformal to the solution, and react at room temperature 3 days.

[0042] 2) After the reaction is finished, slowly add 2.5% ammonia water dropwise to the blue-black solution to quench the reaction until the pH of the solution is adjusted to 7-8, continue to stir for 4 hours, the solution becomes viscous, pour the reaction solution into 400mL methanol solution , settling to settle for half an hour, and filtered with suction to obtain a blue-black solid.

[0043] 3) Rinse the obtained solid three to five times with deioniz...

Embodiment 2

[0048] The synthetic steps of present embodiment polymer P2 are as follows:

[0049] 1) Under the conditions of argon protection and ice-water bath, the porphyrin-based P2 was synthesized by a one-pot method, and 202.4 mg of 5,10,15,20-tetraaminophenylporphyrin (TAPP ) (0.3 mmol), and then add 10 mL of trifluoroacetic acid into the bottle, and stir for 5 minutes. After TAPP is uniformly dispersed, add 0.265 mL of dimethylformal to the solution, and react at room temperature for 5 days.

[0050] 2) After the reaction is completed, slowly add 2.5% ammonia water dropwise to the blue-black solution to quench the reaction until the pH of the solution is adjusted to 7-8, and continue to stir for 3 hours. The solution becomes viscous and black solids are precipitated. Pour it into 500mL of methanol solution, let it settle for half an hour, and filter it with suction to obtain a blue-black solid.

[0051] 3) Rinse the obtained solid three times with deionized water and three times wi...

Embodiment 3

[0056] The synthesis of present embodiment polymer P3 is as follows:

[0057]

[0058] 1) Under the conditions of argon protection and ice-water bath, use a one-pot method to synthesize porphyrin-based P3, and weigh 293.5 mg of 5,10,15,20-tetrakis(4-aminobiphenyl) into a 25mL round bottom flask )-21H,23H-porphyrin (B11) (0.3mmol), then add 10mL of trifluoroacetic acid to the bottle, stir for 5 minutes, after B11 is uniformly dispersed, add 0.265mL of dimethylformal to the solution, at room temperature The next reaction was 4 days.

[0059] 2) After the reaction is completed, slowly add 2.5% ammonia water dropwise to the blue-black solution to quench the reaction until the pH of the solution is adjusted to 7-8, and continue to stir for 4 hours. Black solids are precipitated from the solution, and the reaction solution is poured into 400 mL of methanol The solution was left to settle for half an hour, and filtered with suction to obtain a blue-black solid.

[0060] 3) The o...

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Abstract

The invention discloses a porphyrin-based self-porous polymer and a synthesis method thereof, belonging to the field of functional materials. The present invention takes the porphyrin base unit as the core, and prepares the porphyrin base microporous polymer by aromatic electrophilic substitution polymerization under solvothermal through structural design and group control. The porphyrin-based self-porous polymer of the present invention is formed by a rigid "V"-shaped base structure bridging porphyrin units. The rigid skeleton structure and spatial distortion make this type of material rich in permanent micropores and The large specific surface area, through group regulation, realizes the regulation of the pore size and specific surface area of ​​the polymer, and the covalent bond structure endows the material with excellent stability. At the same time, the abundant porphyrin rings on the polymer backbone can realize functional adjustments in different directions and in different fields through the "post-modification" strategy, which makes the material have practical application value in the fields of photocatalysis, electrocatalysis and biomimetic catalysis.

Description

technical field [0001] The invention belongs to the field of functional materials, and in particular relates to a porphyrin-based self-porous polymer and a synthesis method thereof. [0002] technical background [0003] Porphyrin is a macromolecular heterocyclic compound formed by the conjugation of four carbon atoms to interconnected pyrroles. Because there are four functional nitrogen atom groups in the middle of the ring, the metal ion with catalytic activity is easily coordinated with the nitrogen in the middle. A stable catalytic active site is formed, and at the same time, the highly conjugated structure of 26 π electrons makes the material have excellent photoelectric properties, thus becoming an important functional building block. In recent years, the use of porphyrin building blocks to construct POPs materials and endow them with catalytic performance through the "post-modification" strategy is in a stage of rapid development. POPs constructed from porphyrins have...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08G12/26
CPCC08G12/26
Inventor 顾志国申锐刘勇李涛路惠舒符秋婷晏晓东
Owner JIANGNAN UNIV
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