CN108794743A - A kind of preparation method of the organic covalent frame material in large aperture - Google Patents
A kind of preparation method of the organic covalent frame material in large aperture Download PDFInfo
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- CN108794743A CN108794743A CN201810782775.7A CN201810782775A CN108794743A CN 108794743 A CN108794743 A CN 108794743A CN 201810782775 A CN201810782775 A CN 201810782775A CN 108794743 A CN108794743 A CN 108794743A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
Abstract
The present invention provides a kind of preparation method of the organic covalent frame material in large aperture.Cuprous chloride catalyst with nanoscale is prepared using solvent-thermal method, select [the 4- amino (1 of 1,3,5- tri-, 1- biphenyl -4- bases)] benzene and benzidine is monomer molecule, issuing ammonifying base coupling reaction in the catalysis of stannous chloride nanocrystal prepares organic polymer.The method disclosed in the present can carry out at room temperature, reaction condition is mild, have prepare it is simple, at low cost, be easy to the characteristics of industrialized mass production, the polymer of preparation has big aperture, higher chemical stability and thermal stability, can be applicable to many fields such as combination electrode material, organic dyestuff, biological medicine.
Description
Technical field
The invention belongs to the organic covalent frame materials of organic covalent frame material preparation field more particularly to a kind of large aperture
Preparation method.
Background technology
Covalent organic frame material, which is one kind, to be had periodically with crystalline polymer, passes through covalent bond by lightweight element
Connection, possesses lower density, high thermal stability and intrinsic porosity, has intrinsic flexibility, low cost, light weight etc.
Many merits.Covalent organic frame material has important answer in research fields such as gas absorption, heterogeneous catalysis, energy stores
With value and vast market prospect, the strong research interest of scientific circles is caused.
Covalent organic frame material has the attribute that can be designed, can cut.But up to the present covalent organic frame material
The preparation of material is only limitted to be easy to the chemical reaction carried out, is related to that reactive species are very limited, limits new construction and new material
Exploitation.With the development of two-dimentional organic polymer material, type and the function of synthetic polymer also proposed and more want
It asks, there is an urgent need to develop novel two-dimentional organic polymers to meet various actual demands.Gas of the size in aperture for material
Body absorption, proton conduction, photoelectric property, reaction yield, the uniformity of related compound material and chemical property all have very big
Influence, prepare large aperture covalent organic frame material have important practical significance.
Invention content
Propose a kind of preparation method of the organic covalent frame material in large aperture.The present invention adopts the following technical scheme that：
A kind of preparation method of the organic covalent frame material in large aperture, includes the following steps：
(1) chlorination copper powders are placed in autoclave, ethyl alcohol is added, be uniformly mixed, react one at a certain temperature
It the section time, is cooled to room temperature, decompression filters, and vacuum drying obtains the cuprous chloride catalyst with nanoscale；
(2) 1,3,5- tri- [4- amino (1,1- biphenyl -4- bases)] benzene (TABPB), benzidine and stannous chloride is nanocrystalline
Body is distributed in acetonitrile equal solvent, and reaction temperature is selected as room temperature, is continuously agitated in reaction process, through ammonia scrubbing, dries
To the organic covalent frame material of ultra-large aperture.
For a period of time, temperature is preferably 160 DEG C for reaction at a certain temperature in step (1), and the time is preferably for 24 hours.
Cuprous chloride catalyst size is 2~10nm in step (1).
[4- amino (1,1- biphenyl -4- bases)] benzene 1,3,5- tri- in step (2), benzidine and stannous chloride nanocrystal
Mass ratio is preferably 0.6: 0.2: 0.2.
The reaction process duration is 6h~48h in step (2), and the preferred time is 10h.
Solvent for use is the organic solvents such as acetonitrile, n,N-Dimethylformamide and dimethyl sulfoxide (DMSO) in step (2), preferably
Solvent is acetonitrile.
The present invention has following advantage：
(1) it is room temperature that the amino coupled that the present invention selects, which reacts required temperature, and reaction condition is mild, has preparation letter
It is single, at low cost, be easy to the characteristics of industrialized mass production.
(2) polymer prepared by the present invention has big aperture, higher chemical stability and thermal stability, can be applicable to
Many fields such as combination electrode material, organic dyestuff, biological medicine.
Description of the drawings
Fig. 1 is reaction process schematic diagram and the structural representation of the organic covalent frame material in large aperture prepared by the method for the present invention
Figure.
Fig. 2 is the transmission electron microscope photo of the organic covalent frame material in large aperture prepared by the method for the present invention.
Specific implementation mode
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is used only for helping to understand the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
(1) 0.8524g Copper dichloride dihydrates are weighed, the autoclave that volume is 50mL polytetrafluoroethyllining linings is placed in
In, 25mL ethyl alcohol is added, is uniformly mixed, kettle cover is covered tightly.
(2) autoclave is put in Muffle furnace, is reacted for 24 hours at 160 DEG C.It is cooled to room temperature, decompression filters, product
It is dried in vacuo 12h at 50 DEG C.Under nitrogen protection atmosphere, it is placed in shady place preservation, obtains the stannous chloride with 2~10nm
Nanocrystal.
(3) by 10mg cuprous chloride crystals powder, 1,3,5- tri- [4- amino (1,1- biphenyl-of 10mg benzidine and 30mg
4- yls)] benzene is dissolved in 5.0mL acetonitriles, 10h is stirred at room temperature.
(4) reaction mixture therein is taken out, is washed respectively with 25% ammonium hydroxide, water, acetone, kept dry.
Fig. 1 includes reaction process schematic diagram and the structural representation of the organic covalent frame material in large aperture manufactured in the present embodiment
Figure.
Fig. 2 includes the transmission electron microscope photo of the organic covalent frame material in large aperture manufactured in the present embodiment.
Embodiment 2
(1) 0.8524g Copper dichloride dihydrates are weighed, the autoclave that volume is 50mL polytetrafluoroethyllining linings is placed in
In, 25mL ethyl alcohol is added, is uniformly mixed, kettle cover is covered tightly.
(2) autoclave is put in Muffle furnace, is reacted for 24 hours at 160 DEG C.It is cooled to room temperature, decompression filters, product
It is dried in vacuo 12h at 50 DEG C.Under nitrogen protection atmosphere, it is placed in shady place preservation, obtains the stannous chloride with 2~10nm
Nanocrystal.
(3) by 20mg cuprous chloride crystals powder, 1,3,5- tri- [4- amino (1,1- biphenyl-of 10mg benzidine and 30mg
4- yls)] benzene is dissolved in 5.0mL acetonitriles, 10h is stirred at room temperature.
(4) reaction mixture therein is taken out, is washed respectively with 25% ammonium hydroxide, water, acetone, kept dry.
Embodiment 3
(1) 0.8524g Copper dichloride dihydrates are weighed, the autoclave that volume is 50mL polytetrafluoroethyllining linings is placed in
In, 25mL ethyl alcohol is added, is uniformly mixed, kettle cover is covered tightly.
(2) autoclave is put in Muffle furnace, is reacted for 24 hours at 160 DEG C.It is cooled to room temperature, decompression filters, product
It is dried in vacuo 12h at 50 DEG C.Under nitrogen protection atmosphere, it is placed in shady place preservation, obtains the stannous chloride with 2~10nm
Nanocrystal.
(3) by 10mg cuprous chloride crystals powder, 1,3,5- tri- [4- amino (1,1- biphenyl-of 10mg benzidine and 30mg
4- yls)] benzene is dissolved in 5.0mL acetonitriles, 48h is stirred at room temperature.
(4) reaction mixture therein is taken out, is washed respectively with 25% ammonium hydroxide, water, acetone, kept dry.
Embodiment 4
(1) 0.8524g Copper dichloride dihydrates are weighed, the autoclave that volume is 50mL polytetrafluoroethyllining linings is placed in
In, 25mL ethyl alcohol is added, is uniformly mixed, kettle cover is covered tightly.
(2) autoclave is put in Muffle furnace, is reacted for 24 hours at 160 DEG C.It is cooled to room temperature, decompression filters, product
It is dried in vacuo 12h at 50 DEG C.Under nitrogen protection atmosphere, it is placed in shady place preservation, obtains the stannous chloride with 2~10nm
Nanocrystal.
(3) by 10mg cuprous chloride crystals powder, 1,3,5- tri- [4- amino (1,1- biphenyl-of 15mg benzidine and 30mg
4- yls)] benzene is dissolved in 5.0mL acetonitriles, 10h is stirred at room temperature.
(4) reaction mixture therein is taken out, is washed respectively with 25% ammonium hydroxide, water, acetone, kept dry.
Applicant states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological processes, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, the selection etc. of concrete mode all fall within the present invention's
Within protection domain and the open scope.
Claims (6)
1. a kind of preparation method of the organic covalent frame material in large aperture, includes the following steps：
(1) chlorination copper powders are placed in autoclave, ethyl alcohol is added, be uniformly mixed, when reacting one section at a certain temperature
Between, it is cooled to room temperature, decompression filters, and vacuum drying obtains the cuprous chloride catalyst with nanoscale；
(2) 1,3,5- tri- [4- amino (1,1- biphenyl -4- bases)] benzene, benzidine and stannous chloride nanocrystal is distributed to second by choosing
In nitrile equal solvent, reaction temperature is selected as room temperature, is continuously agitated in reaction process, and ultra-large aperture is obtained through ammonia scrubbing, drying
Organic covalent frame material.
2. preparation method according to claim 1, which is characterized in that step reacts one at a certain temperature described in (1)
The section time, temperature is preferably 160 DEG C, and the time is preferably for 24 hours.
3. preparation method according to claim 1, which is characterized in that cuprous chloride catalyst size described in step (1)
For 2~10nm.
4. preparation method according to claim 1, which is characterized in that 1,3,5- tri- described in step (2) [4- amino (1,
1- biphenyl -4- bases)] mass ratio of benzene, benzidine and stannous chloride nanocrystal is preferably 0.6: 0.2: 0.2.
5. preparation method according to claim 1, which is characterized in that the reaction process duration described in step (2) is
6h~48h, preferred time are 10h.
6. preparation method according to claim 1, which is characterized in that solvent described in step (2) is acetonitrile, N, N- diformazans
The organic solvents such as base formamide and dimethyl sulfoxide (DMSO), preferred solvent are acetonitrile.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110305319A (en) * | 2019-07-05 | 2019-10-08 | 福建师范大学 | The preparation method of microporous polymer |
| CN110305320A (en) * | 2019-07-05 | 2019-10-08 | 福建师范大学 | Micropore organic polymer containing abundant nitrogen site |
| CN113045722A (en) * | 2021-03-11 | 2021-06-29 | 兰州大学 | Imino covalent organic framework polymer, preparation method and application thereof, ammonia gas sensor and preparation method thereof, and ammonia gas sensing detection method |
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| CN113045722A (en) * | 2021-03-11 | 2021-06-29 | 兰州大学 | Imino covalent organic framework polymer, preparation method and application thereof, ammonia gas sensor and preparation method thereof, and ammonia gas sensing detection method |
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