CN108503853A - A kind of covalent organic frame material and its preparation method and application based on secondary amine bonding - Google Patents
A kind of covalent organic frame material and its preparation method and application based on secondary amine bonding Download PDFInfo
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Abstract
The present invention discloses a kind of covalent organic frame material and its preparation method and application being bonded based on secondary amine with high chemical stability, belongs to porous crystalline material preparation field.First conventional method is used to synthesize the COF materials based on imine bound, three-dimensional frame structure COF 300 and 366 M of two-dimensional framework structure C OF are realized by solid-state to solid conversion by the method for sodium borohydride reduction, the COF materials by being bonded based on secondary amine have been synthesized for the first time, on the one hand the material remains the original orderly crystalline state pore structure of COF materials based on imine bound, on the other hand its chemical stability has obtained great reinforcement compared to the COF based on imine bound, also orderly NH is introduced in the frame, for the broader application prospect of the materials open.
Description
Technical field
The invention belongs to porous crystalline material preparation field, and in particular to it is a kind of with high chemical stability based on secondary amine
The covalent organic frame material and its preparation method and application of base bonding.
Background technology
Covalent organic frame material (Covalent Organic Framework, COF) is one kind by between organic molecule
The novel porous crystalline material [Wiki.Covalent Organic Frameworks] formed by covalent bonding, because of its phase
To the Modulatory character of higher specific surface area and duct environment, COF gas store with detach, be catalyzed, drug loading and conveying
Etc. have a wide range of applications [Science, 2015,310,1166-1170；Chem.Soc.Rev.,2012,41,
6010-6022；Chem.Soc.Rev.,2013,42,548-568].
However, the invertibity that the formation and synthesis COF due to crystalline state are reacted in the process has the limitation of larger correlation, pass
The bonding pattern of the COF materials of system is only several, such as boric acid ester bond, imine linkage, hydrazides key, azophenlyene key and amido bond, and
Its chemical stability is also all corresponding limited.
Invention content
For the limitation of existing COF synthetic systems, the present invention proposes by way of rear modification, first uses tradition side
COF material of the method synthesis based on imines (- CN-) bonding, three-dimensional frame structure is realized by the method for sodium borohydride reduction
The conversion of COF-300 and two-dimensional framework structure C OF-366-M (M=Co, Cu, Zn) " by solid-state to solid-state " have synthesized logical for the first time
The COF materials based on secondary amine (- NH-) bonding are crossed, on the one hand which remains the COF materials based on imine bound original
Orderly crystalline state pore structure, its chemical stability of another aspect have obtained great reinforcement compared to the COF based on imine bound,
Also orderly-NH- is introduced in the frame, for the broader application prospect of the materials open.
The COF materials that this kind is bonded based on secondary amine have compared to traditional amine polymer in terms of cystalline order
It is promoted from scratch, and there is relatively-stationary pore structure；On the other hand contain-NH with end group2COF materials compare, should
The chemical stability of kind of material is well upper very much, and in skeleton ordered arrangement secondary amine (- NH-) compared to Amino End Group (-
NH2) with orderly, pore structure that can also be orderly with material matches more horn of plenty, is created favorably to widen its application prospect
Condition.
Technical scheme of the present invention is specific as follows：
A kind of preparation method of the covalent organic frame material based on secondary amine bonding, includes the following steps：By 1 equivalent pair
Phthalic acid, the powders A containing 1 equivalent imine linkage are added in methanol, are uniformly mixed；Then delay under -25~-5 DEG C of stirring conditions
It is slow that the sodium borohydride powder for being no less than 38 equivalents is added, continue stirring at -25~-5 DEG C 0.5~2 hour, then at room temperature
Stirring is abundant to reaction；Reaction system is filtered after the completion of reaction, washs solid crude product with methanol and hot water successively, is removed secondary
Product and catalyst, obtain pale yellow powder；By pale yellow powder Ethanol activation in Soxhlet extractor, then at room temperature
Degassing, obtains the covalent organic frame material being bonded based on secondary amine；
The powders A is the COF-300 powder of activation or the COF-366-M powder of activation；
In the COF-366-M, M=Co, Cu or Zn.
The COF-300 powder of the activation is prepared in the following manner：It is 25 by mass ratio:16 tetramino benzene
Methylmethane is dissolved in terephthalaldehyde in Isosorbide-5-Nitrae-dioxane, is added in glass tube；Atmosphere in glass tube is exchanged for argon
Gas carries out tube sealing processing after liquid nitrogen frozen；Glass tube is placed in 120 DEG C of baking ovens and is reacted 3 days, leaching solid；Gained is consolidated
Body carries out reflux activation in Soxhlet extractor with the mixed solvent of Isosorbide-5-Nitrae-dioxane and acetone, then uses above-critical state dioxy
Change carbon to be activated, the COF-300 powder activated.
The COF-366-M powder of the activation is prepared in the following manner：It is 9 by mass ratio:5 tetramino benzene
Base Metal porphyrin is dissolved in terephthalaldehyde in Isosorbide-5-Nitrae-dioxane, is added in glass tube；Atmosphere in glass tube is exchanged
For argon gas tube sealing processing is carried out after liquid nitrogen frozen；Glass tube is placed in 120 DEG C of baking ovens and is reacted 3 days, leaching solid；By institute
It obtains solid and carries out reflux activation with the mixed solvent of Isosorbide-5-Nitrae-dioxane and acetone in Soxhlet extractor, then use above-critical state
Carbon dioxide is activated, the COF-366-M powder activated；The tetrakisaminophenyl metalloporphyrin is tetrakisaminophenyl
Cobalt Porphyrin, tetrakisaminophenyl porphyrin copper or tetrakisaminophenyl zinc porphyrin.
Continue stirring 1 hour at -15 DEG C after sodium borohydride powder is added.
The time being stirred at room temperature is 12 hours.
A kind of covalent organic frame material based on secondary amine bonding, is prepared by above-mentioned preparation method.
The above-mentioned covalent organic frame material based on secondary amine bonding gas store with detach, be catalyzed, drug loading and
The application of transportation art.
COF in the present invention uses solvent structure, and cleans the solvent point in the ducts removal COF by exchange of solvent
Son forms the COF powder after activation.
The present invention has the following advantages and beneficial effect：
(1) present invention is provided can both keep original based on imine bound based on the covalent organic frame material that secondary amine is bonded
COF crystalline state pore structure, and substantially increase the chemical stability of COF materials so that its application range is widened.
(2) it is that COF skeletons introduce-NH- groups by reduction reaction, is that COF is adsorbed in gas-selectively, energy environment
Direction provides potential application prospect.
(3) preparation process of the present invention is easy, can easily be accommodated, and is a kind of the effective of the COF materials of the new Bonding Type of synthesis
Method.
Description of the drawings
Fig. 1 is the synthetic route schematic diagram that COF-300 is converted into COF-300-AR.
Fig. 2 is the synthetic route schematic diagram that COF-366-M is converted into COF-366-M-AR.
Fig. 3 is that the powder x-ray diffraction (PXRD) of COF-300 series characterizes；Wherein, Fig. 3 (A) represents COF-300's
PXRD diffraction and the pawley refine being applied thereon, Fig. 3 (B) represent the PXRD diffraction of COF-300-AR and are applied thereon
Pawley refine, Fig. 3 (C) is illustrated be soaked in strong acid or highly basic after COF-300-AR PXRD spectrograms and COF-300, COF-
A series of comparisons of 300-AR.
Specific implementation mode
Sodium borohydride used in following embodiment is all that analysis is pure, and used hydrochloric acid and sodium hydroxide are molten with methanol
Liquid is prepared with deionized water through volumetric flask with analysis pure hydrochloric acid solution or sodium hydrate solid respectively.
Embodiment 1
1. the synthesis and activation of the three-dimensional covalent organic frame material (COF-300) based on imine bound
The method in document [J.Am.Chem.Soc., 2009,131,4570-4571] is continued to use, by 100mg tetrakisaminophenyls
Methane is dissolved in 64mg terephthalaldehydes in 2mL Isosorbide-5-Nitraes-dioxane, is then added in glass tube, and will be in glass tube
Atmosphere is exchanged for argon gas, after liquid nitrogen frozen, carries out tube sealing processing；Glass tube is placed in 120 DEG C of baking ovens and reacts 3 days, then
Obtained solid is carried out reflux activation by leaching solid in Soxhlet extractor with the mixed solvent of Isosorbide-5-Nitrae-dioxane and acetone,
Then it is activated with the supercritical carbon dioxide, obtains covalent organic frame material of the yellow based on imine bound, that is, activate
COF-300 powder.
2. the preparation of the COF-300-AR based on secondary amine bonding
The COF-300 powder that 57.6mg (1 equivalent) terephthalic acid (TPA), 50mg (1 equivalent, in terms of imine linkage quantity) are activated
It is added in 25mL methanol, is stirred 5 minutes at -15 DEG C；Then divide in 10 minutes and be repeatedly slowly added to hydroboration sodium powder on a small quantity
The total 0.5g (38 equivalent) in end, and continue to stir 1 hour at -15 DEG C, it is then stirred at room temperature 12 hours and reacts fully
It carries out；Reaction solution is filtered after the completion of reaction, is washed successively with methanol and hot water, by-product and catalyst is removed, obtains yellowish
Color powder；By pale yellow powder Ethanol activation in Soxhlet extractor, then deaerate at room temperature, the COF- activated
300-AR powder samples, the i.e. covalent organic frame material based on secondary amine bonding.
Fourier transform infrared spectroscopy, solid state nmr carbon are carried out to restoring front and back COF-300 and COF-300-AR
The spectrum methods such as spectrum and nitrogen spectrum and x-ray photoelectron spectroscopy are tested, and qualitative and quantitative analysis reduction reaction is " by solid-state to admittedly
The performance level of the feasibility and progress of state ", the conversion that discovery COF-300 is converted into COF-300-AR this imines to secondary amine can
To carry out, and it is almost 100% to verify conversion ratio by spectrum method, the COF materials based on secondary amine bonding after reduction
It is maintained the crystal structure and order of original COF materials based on imine bound, as a result as shown in Fig. 3 (A) and Fig. 3 (B).
Determine that COF-300 and COF-300-AR changes (heating rate in the front and back thermal stability of reduction by thermogravimetric analysis：
10 DEG C are per minute), it finds until 490 DEG C, COF-300-AR and COF-300 can be stabilized.
Embodiment 2
1. the synthesis and activation of the two-dimentional covalent organic frame material (COF-366-M) based on imine bound
The method in document [Science, 2015,349,1208-1213] is continued to use, i.e., by 18mg tetrakisaminophenyl metals
(cobalt, copper or zinc) porphyrin is dissolved in 10mg terephthalaldehydes in 1mL o-dichlorohenzenes and 1mL n-butanols, is added in glass tube, and
Atmosphere therein is exchanged for argon gas, after liquid nitrogen frozen, tube sealing processing is carried out, tube sealing is placed in 120 DEG C of baking ovens and reacts 3
It, then filters and takes insoluble matter, reuses Soxhlet extractor and is activated as solvent refluxing using Isosorbide-5-Nitrae-dioxane and acetone；And
Last activation is carried out using the supercritical carbon dioxide afterwards, royal purple is obtained and obtains that machine frame is covalently had based on imine bound
Frame material, that is, the COF-366-M powder activated.
2. the preparation of the COF-366-M-AR based on secondary amine bonding
The COF-366- that 57.6mg (1 equivalent) terephthalic acid (TPA), 50mg (0.16 equivalent, in terms of imine linkage quantity) are activated
M powder is added in 25mL methanol, is stirred at -15 DEG C 5 minutes, then divides in 10 minutes and be repeatedly slowly added to hydroboration on a small quantity
Sodium powder end amounts to 0.5g (38 equivalent), and continues to stir 1 hour at -15 DEG C, and being then stirred at room temperature 12 hours makes reaction
Fully carry out；Reaction solution is filtered after the completion of reaction, is washed successively with methanol and hot water, by-product and catalyst is removed, obtains
Aubergine powder；By aubergine powder Ethanol activation in Soxhlet extractor, then deaerates, activated at room temperature
COF-366-M-AR powder samples, the i.e. covalent organic frame material based on secondary amine bonding.
Embodiment 3：Stability test is tested
50mg COF-300-AR powder is added in 1mL 6M hydrochloric acid solutions and 1mL 6M sodium hydroxide solutions respectively,
It stirs 12 hours, centrifuges and supernatant collection lower layer insoluble matter of going out at room temperature, be washed with deionized 5 times, acetone washing 5
It is secondary, it deaerates at room temperature.PXRD is carried out to COF-300, COF-300-AR and by the COF-300-AR that acid-base solution impregnates
Test uses identical characterization method to COF-366-M systems.It was found that COF-300-AR, COF-366- based on secondary amine bonding
M-AR and COF-300-AR, COF-366-M-AR for being impregnated by acid-base solution can keep the crystal of original COF containing imine linkage
Structure and order, it was confirmed that COF-300-AR and COF-366-M-AR has preferable chemical stability.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description
To make other variations or changes in different ways.There is no necessity and possibility to exhaust all the enbodiments.It is all this
All any modification, equivalent and improvement etc., should be included in the claims in the present invention made by within the spirit and principle of invention
Protection domain within.
Claims (7)
1. a kind of preparation method of the covalent organic frame material based on secondary amine bonding, which is characterized in that include the following steps：
1 equivalent terephthalic acid (TPA), the powders A containing 1 equivalent imine linkage are added in methanol, are uniformly mixed；Then in -25~-5 DEG C of stirrings
Under the conditions of be slowly added to the sodium borohydride powder of no less than 38 equivalents, continue stirring at -25~-5 DEG C 0.5~2 hour, then
It is stirred at room temperature abundant to reaction；Reaction system is filtered after the completion of reaction, washs solids crude production with methanol and hot water successively
Object removes by-product and catalyst, obtains pale yellow powder；By pale yellow powder Ethanol activation in Soxhlet extractor, so
It deaerates at room temperature afterwards, obtains the covalent organic frame material being bonded based on secondary amine；
The powders A is the COF-300 powder of activation or the COF-366-M powder of activation；
In the COF-366-M, M=Co, Cu or Zn.
2. preparation method according to claim 1, it is characterised in that：The COF-300 powder of the activation passes through following
Mode is prepared：It is 25 by mass ratio:16 tetrakisaminophenyl methane is dissolved in terephthalaldehyde in Isosorbide-5-Nitrae-dioxane, is added
Enter into glass tube；Atmosphere in glass tube is exchanged for argon gas, after liquid nitrogen frozen, carries out tube sealing processing；Glass tube is set
It is reacted 3 days in 120 DEG C of baking ovens, leaching solid；By obtained solid with 1,4- dioxane and acetone in Soxhlet extractor
Mixed solvent carries out reflux activation, is then activated with the supercritical carbon dioxide, the COF-300 powder activated.
3. preparation method according to claim 1, it is characterised in that：The COF-366-M powder of the activation by with
Under type is prepared：It is 9 by mass ratio:5 tetrakisaminophenyl metalloporphyrin is dissolved in 1,4- dioxane with terephthalaldehyde
In, it is added in glass tube；Atmosphere in glass tube is exchanged for argon gas, after liquid nitrogen frozen, carries out tube sealing processing；By glass
Pipe, which is placed in 120 DEG C of baking ovens, to react 3 days, leaching solid；Obtained solid is used into 1,4- dioxane and third in Soxhlet extractor
The mixed solvent of ketone carries out reflux activation, is then activated with the supercritical carbon dioxide, the COF-366-M powder activated
End；The tetrakisaminophenyl metalloporphyrin is tetrakisaminophenyl Cobalt Porphyrin, tetrakisaminophenyl porphyrin copper or tetrakisaminophenyl porphin
Quinoline zinc.
4. preparation method according to claim 1, it is characterised in that：Continue at -15 DEG C after sodium borohydride powder is added
Stirring 1 hour.
5. preparation method according to claim 1, it is characterised in that：The time being stirred at room temperature is 12 hours.
6. a kind of covalent organic frame material based on secondary amine bonding, it is characterised in that：Described in claim any one of 1-5
Preparation method be prepared.
7. the covalent organic frame material based on secondary amine bonding described in claim 6 stores in gas and detaches, is catalyzed, medicine
Object loads the application with transportation art.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109354697A (en) * | 2018-10-10 | 2019-02-19 | 复旦大学 | The method of covalent organic frame material is prepared in a kind of supercritical fluid |
| CN109575308A (en) * | 2019-01-02 | 2019-04-05 | 南京大学 | A kind of fluorine-containing covalent organic frame compound of two dimension without catalysis high efficiency preparation method |
| CN110227550A (en) * | 2019-06-25 | 2019-09-13 | 河南科技学院 | A kind of porphyrin COF and the preparation method for nitrogenizing carbon composite and the application in terms of photocatalytically degradating organic dye |
| CN110511391A (en) * | 2019-08-09 | 2019-11-29 | 武汉大学 | Covalent organic frame material and preparation method thereof with optical dynamic therapy effect |
| CN111303442A (en) * | 2020-02-22 | 2020-06-19 | 吉林大学 | Nitroxide-free-radical-functionalized three-dimensional covalent organic framework material and preparation method thereof |
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| CN113563551A (en) * | 2021-06-24 | 2021-10-29 | 山东师范大学 | Covalent organic framework material based on metalloporphyrin and preparation method and application thereof |
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| CN116023282A (en) * | 2023-03-30 | 2023-04-28 | 吉林省卓材新研科技有限公司 | Covalent organic framework material and ligand thereof and application of covalent organic framework material in drug delivery |
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| CN113563551B (en) * | 2021-06-24 | 2024-03-01 | 山东师范大学 | Covalent organic framework material based on metalloporphyrin and preparation method and application thereof |
| CN115894947A (en) * | 2021-09-30 | 2023-04-04 | 浙江工业大学 | Two-dimensional covalent organic framework material with micropore and kgd topological network structure and preparation and application thereof |
| CN115894947B (en) * | 2021-09-30 | 2023-10-20 | 浙江工业大学 | Two-dimensional covalent organic framework material with micropore and kgd topological network structure and preparation and application thereof |
| CN116023282A (en) * | 2023-03-30 | 2023-04-28 | 吉林省卓材新研科技有限公司 | Covalent organic framework material and ligand thereof and application of covalent organic framework material in drug delivery |
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