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Covalent Triazine Framework Organic Polymer Functionalized with Phosphorus Atoms and Its Preparation and Application

A covalent triazine and functionalization technology, applied in the direction of material electrochemical variables, can solve the problems of high heteroatom doping concentration, inability to react to obtain CTFs, etc., and achieve the effect of high gas sensing sensitivity

Active Publication Date: 2021-02-02
LANZHOU INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, reports on the introduction of other heteroatoms into CTFs are still very rare. Some studies uniformly mixed elemental sulfur (sulfur) or phosphorus (red phosphorus) with monomers, and then obtained sulfur or phosphorus-doped CTFs, but this form of doping has the problem of heteroatom uniformity, which often leads to too high or too low local heteroatom doping concentration
In view of the relatively harsh reaction conditions of high-temperature ionic thermal polymerization, higher requirements are placed on the thermal stability of monomers. Binary or polyaryl cyanide monomers containing thermally unstable functional groups cannot be obtained by ionic thermal polymerization. Corresponding CTFs, so this also limits the introduction of heteroatoms in CTFs from another aspect

Method used

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  • Covalent Triazine Framework Organic Polymer Functionalized with Phosphorus Atoms and Its Preparation and Application
  • Covalent Triazine Framework Organic Polymer Functionalized with Phosphorus Atoms and Its Preparation and Application
  • Covalent Triazine Framework Organic Polymer Functionalized with Phosphorus Atoms and Its Preparation and Application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Example 1 The preparation method of phosphorus atom-functionalized covalent triazine framework organic polymer refers to: put 0.164g (0.5mmol) 4,4'-phenylphosphoryl dibenzonitrile into a glass sealed tube, and Put 0.68g (5.0mmol) anhydrous zinc chloride into the glove box, then use an oil pump to evacuate for 10min~60min, and melt the sealed tube under vacuum conditions; burn the sealed tube at 400°C in a muffle furnace for 40h, After the completion, break the glass and seal the tube to obtain the product; the product is ground in a mortar to obtain a black powder, which is washed with boiled deionized water several times to remove the residual zinc chloride, and finally fully dried under vacuum at 120°C. After drying, 0.156 g of covalent triazine framework organic polymer functionalized with phosphorus atoms (represented by CTF-P-1-400) was obtained, with a yield of 95%.

[0029] 4,4'-Phenylphosphoryldibenzonitrile has the chemical structure shown below:

[0030] . ...

Embodiment 2

[0042] Example 2 The preparation method of phosphorus atom-functionalized covalent triazine framework organic polymer refers to: put 0.164g (0.5mmol) 4,4'-phenylphosphoryl dibenzonitrile into a glass sealed tube, and Put 6.80g (50mmol) of anhydrous zinc chloride into the glove box, then use an oil pump to evacuate for 20min, and melt and seal the tube under vacuum conditions; burn the sealed tube in a muffle furnace at 450°C for 60h, knock Broken glass was sealed and opened to obtain the product; the product was ground in a mortar to obtain a black powder, which was washed with boiled deionized water several times to remove residual zinc chloride, and finally fully dried in a vacuum at 120°C. That is, 0.154 g of a covalent triazine framework organic polymer functionalized with phosphorus atoms (represented by CTF-P-1-450) was obtained, with a yield of 94%.

[0043] 【Gas sensing test】

[0044] Disperse 10mg of CTF-P-1-450 powder in 5mL of absolute ethanol, drop the dispersed l...

Embodiment 3

[0046] Example 3 The preparation method of covalent triazine framework organic polymer functionalized with phosphorus atoms refers to: put 0.177g (0.5mmol) 4,4',4''-phosphoryl tribenzonitrile into a glass sealed tube , put 0.068g (0.5mmol) anhydrous zinc chloride in the glove box, then use an oil pump to vacuum for 30min, and melt the sealed tube under vacuum conditions; burn the sealed tube at 600°C in a muffle furnace for 10h, polymerize After the completion, break the glass and seal the tube to obtain the product; the product is ground in a mortar to obtain a black powder, which is washed with boiled deionized water several times to remove the residual zinc chloride, and finally fully dried under vacuum at 120°C. After drying, 0.168 g of phosphorus atom-functionalized covalent triazine framework organic polymer (represented by CTF-P-2-600) was obtained, with a yield of 95%.

[0047] 4,4',4''-phosphoryltribenzonitrile has the chemical structure shown below:

[0048] .

...

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Abstract

The invention relates to a phosphorus atom functionalized CTF (covalent triazine framework) organic polymer. The polymer has the specific surface area of 370-1109 m<2> / g and the constitutional unit shown in the description, wherein R1 is shown in the description, and R2 is H or R1. The invention further discloses a preparation method and an application of the polymer. The polymer shows higher gassensitivity for acid toxic gas nitrogen dioxide, and a material basis is provided for designing and preparing a nitrogen dioxide gas sensor with high selectivity and high sensitivity.

Description

technical field [0001] The invention relates to the technical field of covalent triazine frame organic polymers, in particular to phosphorus atom-functionalized covalent triazine frame organic polymers and their preparation and application. Background technique [0002] Porous materials widely exist in nature, such as sponge, zeolite, wood, etc. are typical porous materials. The most notable feature of porous materials is large specific surface area and diverse structures, which makes porous materials have broad applications in the aspects of gas selective adsorption and separation, ion exchange, photoelectric materials, heterogeneous catalysis, toxic gas sensing, energy storage and conversion, etc. application prospects. With the advancement of science and technology, porous materials have also developed from the initial natural acquisition to artificial synthesis, from inorganic porous materials to organic porous materials. Covalent Triazine Frameworks (CTFs) have large ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08G73/06G01N27/26
CPCC08G73/0644C08G73/065G01N27/26
Inventor 陶立明张耀明王廷梅王齐华
Owner LANZHOU INST OF CHEM PHYSICS CHINESE ACAD OF SCI