CN109734930A - A kind of preparation method and application of acid response off-color material - Google Patents
A kind of preparation method and application of acid response off-color material Download PDFInfo
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Abstract
The invention belongs to the preparation fields of covalent organic frame material, and in particular to a kind of preparation method of covalent organic frame material and its membrane module with low pH response discoloration.Preparation method is by " three tooth aldehyde " class compound three (4- formylphenyl) amine and " two tooth amine " class compound 4,4'- diaminodiphenyl-methane or m-phenylene diamine (MPD) or anti-form-1,4- cyclohexanediamine assembles to obtain covalent organic frame material by the aldehyde condensation reaction of schiff bases amine, and further that it is compound with polyvinyl alcohol (PVA) can obtain corresponding membrane module and improve practical application value.Meanwhile present invention gained covalent organic frame material and its membrane module have apparent colorimetric phenomenon under the acid condition of low pH, and the response time is short, it is easy to operate.
Description
Technical field
The invention belongs to the preparation fields of covalent organic frame material, and in particular to a kind of being total to low pH response discoloration
The preparation method of valence organic framework materials and its membrane module.
Background technique
Covalent organic frame material is that one kind is connected by way of covalent bond by lightweight element (C, H, O, N, B etc.) completely
Organic material made of connecing [Chemical sciety Reviews, 2012,41,6010-6022.].Before 150 years, Hugo
Schiff has found the condensation reaction of amine aldehyde, compared to other dynamic covalent bonds, by the dehydration condensation of aldehyde radical and amino and with
As catalyst synthesis schiff bases series, covalently organic frame material has extraordinary chemical stability [Chemical to acetic acid
Reviews, 2006,106,3,652 3711], assembled early in Cram and Quan first passage amine aldehyde condensation reaction in 1991
High yield, stable configuration covalent organic organic framework materials [Nature, 1992;356 (6364): 29-36.].Then
There is researcher to assemble the covalent organic frame material of various shapes, size using reversible reaction, and to them in ion/molecular
Selective recognition, the capture of reactive intermediate and the application in the fields such as absorbing and storing of gas molecule carry out in-depth study
[Angewandte Chemie International Edition, 2005,44 (14): 2068-2078; Chemistry,
2012,18 (40): 12864-12872;Chemical Communications, 2011,47 (31): 8919-
8921.].Compared to other field, exploration of the researcher to covalent organic frame material in chemical sensor field is less, especially
It is the pH detection field being of great significance to environmental protection and industrial development.Many chemicals or biomolecule are in the solution
Solubility and speed or the rate of (biology) chemical reaction each depend on pH value, and lake, river and ocean and factory is useless
The pH value variation of water can all impact local even environment, thus pH value determination is of great significance.Traditional pH detection
As there is muting sensitives for indicator, pH test paper, metal electrode method (hydrogen electrode, quinone hydrogen electrode and antimony electrode method) and glass electrode method
Sense, the reaction time is long, naked eyes are invisible, complicated for operation, equipment price is expensive, not reproducible, environmental pollution etc. is one or more
Limitation.Therefore, there is an urgent need to a kind of response time is short, easy to operate, price is lower, it is reusable, environmental-friendly and
The material of soda acid variation can be indicated within the scope of certain pH value.And in the New-type detector occurred in recent years, there is Gao Ling
Sensitivity, quick response, the easily operated especially chemical sensor with naked eye colorimetric phenomenon are considered to have application
One of pH detector [Bi Chemical Biophysical Methods, 2005,63,1-9.].2013, Yang Yingwei
Seminar by 2,5- dimethoxy -1,4- terephthaldehyde acid dihydrazide and 1,3,5- trihydroxy -2,4,6- trifonnyl benzene into
Row condensation reaction synthesizes pH response type fluorescent optical sensor COF-JLU4 of the first case based on covalent organic framework, this is covalently organic
Frame compound has very strong crystallinity, good porosity, photoluminescence performance and good wetability.Meanwhile it grinding
Discovery is studied carefully within the scope of wide pH (pH=0.9-13.0), and the fluorescence intensity and wavelength of COF-JLU4 occurs as the pH of solution changes
Significantly " closed-open " and " blue shift " phenomenon, the main reason for causing such phenomenon be due in skeleton N- protonation and
Caused by deprotonation process.And the appearance color that can be observed by " naked eye " changes to detect the variation of pH value, this is
Application study of the first covalent organic frame material in pH detection, to expand the application model of covalent organic frame material
It encloses, meaning [Chemical Communications, 2016,52 (74): 11088] with milestone.Hereafter, based on altogether
The naked eye discoloration pH chemical sensor of valence frame material becomes the new hot spot of research of pH detector.But since they may be deposited
In the excessive problem of structural rigidity intensity, their machinability is inevitably limited, i.e. device manufactures.
2018, the recessed project of king's an ancient weapon made of bamboo was combined into the COF-HQ of the 8-hydroxyquinoline functional group containing luminophore, this is
Second case other than COF-JLU4 answers reversible color and fluorescence phenomenon to change based on the pH double-bang firecracker of covalent organic frame material
Chemical sensor.Fluorescence data show pH be 1 to 5 in the range of, the emissive porwer of COF-HQ with the reduction of pH value of solution and
Weaken, and good linear relationship is presented with pH value.In addition, COF-HQ shows recognizable color change, with acidity
Increase, becomes black from original yellow, all these variations are all reversible and can be recycled.In addition, the project
Group prepares COF-HQ and polyvinyl alcohol (PVA) solution with mechanical strength to prove the potential industrial application of COF-HQ
Hybrid films COF-HQ-MMM(Mixed Matrix Membrane), will COF-HQ-MMM immerse gradient acid solution after show
Color change out is consistent with COF-HQ, has further demonstrated that the pH response chemical sensor based on covalent organic frame material
With huge application potential.It is worth noting that, building is that functional material is carried out the significant of application based on COF membrane module
Possible strategy, early in gas separation field, proton conduction, membrane reactor, HCl detector is widely studied [ACS
Applied Materials & Interfaces, 2018:acsami.8b05484.].And there is a variety of acid responses and width
The material of concentration range pH response is almost without appearing in the newspapers.
Thus, how to design, efficiently synthesizes with quick response, high sensitivity, ease of Use and naked eye metachromatism
Covalent organic frame material pH detector is simultaneously further still challenging by its device application.
The present invention by the covalent organic frame material that amine aldehyde is condensed to yield there is apparent low pH to respond metachromatism, phase
Compared with COF-JLU4 and COF-HQ, the present invention have precursor raw material is easy to get, preparation method is simple, purification step is few, it is environmental-friendly,
The advantages that pH response time is short.And its device is expanded into such covalent organic frame material answering in chemical sensor field
With for follow-up study, personnel provide foundation.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of preparation side with acid response off-color material
Method and application, be using amine aldehyde it is legal carry out covalent organic frame material assembling, synthetic reaction system is mildly simple,
Post-reaction treatment process is simple, can offer reference for the preparation of such covalently organic caged chemical combination frame compound.Meanwhile the material
Material by with polyvinyl alcohol (PVA) binder is compound corresponding membrane module is made improves it in the reality in chemical sensor field
Application value.
For achieving the above object, the present invention adopts the following technical scheme:
A kind of preparation method of acid response off-color material, is contracted in anhydrous solvent by amine aldehyde by compound A and compound B
It closes reaction and obtains Schiff bases covalent organic frame material, and gained covalent organic frame material is prepared into membrane module；
The chemical structural formula of the compound A are as follows:
；
The chemical structural formula of the compound B is、、One of.
Its specific preparation process are as follows:
1) compound A is dissolved in compound B according to certain mol proportion and being mixed in anhydrous solvent C, and be added with anhydrous solvent C at
The acetic acid solution D of certain volume ratio, at 25 DEG C stir 2 ~ 6 h, filter after complete reaction, obtained solid through deionized water,
Ethanol washing is dried in vacuo 24 h at room temperature and covalent organic frame material is made.
2) resulting covalent organic frame material is stirred at 100 DEG C with polyvinyl alcohol (PVA) aqueous solution with certain proportion
0.5-3 h is mixed to after evenly dispersed, mixed liquor is poured into the glass dish of 60 mm, is cooled to room temperature, 24 h of vacuum freezedrying
~ 26 h obtain the mixing membrane module based on covalent organic frame material.
Wherein, the molar ratio of compound A described in step 1) and compound B is 1:1 ~ 2；The matter of compound A and compound B
Amount and be 1:6 ~ 15 with the mass ratio of anhydrous solvent C；The anhydrous solvent C includes halogenated hydrocarbons and alcohol；Halogenated hydrocarbons is specially three
Chloromethanes or methylene chloride；Alcohol is specially methanol or ethyl alcohol；Wherein the volume ratio of halogenated hydrocarbons and alcohol is 1:5 ~ 10；The acetic acid
Solution D is 3M or 6M acetic acid solution, and the volume ratio of acetic acid solution and anhydrous solvent C are 1:100 ~ 200；
Covalent organic frame material described in step 2 and the ratio of polyvinyl alcohol (PVA) aqueous solution are the mL of 1 mg:1 ~ 2.
The present invention with solid carbon nuclear magnetic resonance technique (13C Solid-state NMR), electron spray-high resolution mass spectrum (HR-
MS, ESI) the prepared covalent organic frame material of characterization, covalently there is machine frame prepared by ultraviolet spectra (UV-Vis) characterization
The naked eye metachromatism that the pH response of frame material occurs.
Compared with present technology, the present invention has the advantage that:
(1) preparation system of middle covalent organic frame material is simply mild in the present invention, and last handling process is convenient, and purity is excellent,
It is stable in the air, thinking is provided for the design synthesis of such covalent organic frame material；
(2) covalent organic frame material prepared by the present invention has the naked eye metachromatism of low pH response, and the response time is fast, behaviour
Make it is simple, be covalent organic frame material in pH chemical sensor field using providing reference.
(3) membrane module is made in resulting covalent organic frame material by the present invention, is improved covalent organic frame material and is existed
Value in practical application.
Detailed description of the invention
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment
Attached drawing is briefly described:
Fig. 1 is present invention gained Schiff bases covalent organic frame material Compound-1, Compound-2 and Compound-3
Structural schematic diagram.
Fig. 2 is covalent organic frame material Compound-1 provided in an embodiment of the present invention in 0.001M-10M HCl(~ pH
=-1-3) the interior naked eye metachromatism figure responded of range.
Fig. 3 is covalent organic frame material Compound-2 provided in an embodiment of the present invention in 0.001M-10M HCl(~ pH
=-1-3) the interior naked eye metachromatism figure responded of range.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to following embodiment, can also there is many variations.
The synthesis of 1. covalent organic frame material Compound-1 of embodiment
Three (4- formylphenyl) amine of 66 mg, the 4,4'- diamino hexichol of 60 mg are sequentially added into 25 mL stand up reaction bottle
Methylmethane adds the ethyl alcohol of 2 mL chloroforms and 10 mL, and 0.01 mL 6M acetic acid is added after mixing；At 25 DEG C
After stirring 2 h, after complete reaction, reaction solution is filtered, filter cake is through deionized water, ethanol washing, by the glassy yellow after washing
Solid powder is dried in vacuo 24 h at room temperature, obtains the covalent organic frame material Compound-1 of 116 mg, and yield is
59%.Solid nuclear magnetic resonance of carbon (13C solid state NMR) display covalent organic frame material Compound-1 feature official
Energy group-C=N- absorption peak is at 158 ppm；Electron spray-high resolution mass spectrum (HR-MS, ESI): [C68H50N6O2 +H+] m/z
, calculated value: 983.75 m/z；Experiment value: 983.41 m/z.
The synthesis of 2. covalent organic frame material Compound-2 of embodiment
Three (4- formylphenyl) amine of 66 mg, the m-phenylene diamine (MPD) of 35 mg are sequentially added into 25 mL stand up reaction bottle, are added
0.01 mL 6M acetic acid is added in the ethyl alcohol of 2 mL methylene chloride and 10 mL after mixing；After stirring 3 h at 25 DEG C, to
After fully reacting, reaction solution is filtered, filter cake is through deionized water, ethanol washing, by the bright yellow solid powder after washing in room
Temperature is lower to be dried in vacuo 24 h, obtains the covalent organic frame material Compound-2 of 109 mg, yield 68%.Solid carbon core
Magnetic resonance (13C solid state NMR) display covalent organic frame material Compound-2 characteristic group-C=N- suction
Peak is received at 157 ppm；Electron spray-high resolution mass spectrum (HR-MS, ESI): [C54H38N6O2 +H+] m/z, calculated value: 803.31
m/z；Experiment value: 803.55 m/z.
The synthesis of 3. covalent organic frame material Compound-3 of embodiment
Three (4- formylphenyl) amine of 66 mg, the anti-form-1 of 22 mg, 4- hexamethylene two are sequentially added into 25 mL stand up reaction bottle
Amine adds the ethyl alcohol of 2 mL methylene chloride and 20 mL, and 0.02 mL 3M acetic acid is added after mixing；It is stirred at 25 DEG C
After 5 h, after complete reaction, reaction solution is filtered, filter cake is through deionized water, ethanol washing, by the bright yellow solid after washing
Powder is dried in vacuo 24 h at room temperature, obtains the covalent organic frame material Compound-3 of 53 mg, yield 32%.Gu
Body nuclear magnetic resonance of carbon (13C solid state NMR) display covalent organic frame material Compound-3 characteristic group-C=
The absorption peak of N- is at 159 ppm；Electron spray-high resolution mass spectrum (HR-MS, ESI): [C54H50N6O2 + H2O+H +] m/z,
Calculated value: 833.42 m/z；Experiment value: 833.42 m/z.
The synthesis of film Compound-1-MMM of the embodiment 4. based on covalent organic frame material Compound-1
The cotton-shaped polyvinyl alcohol of 1g (PVA) is added into 25 mL single-necked flasks and is dissolved in 10 mL deionized waters, at room temperature
Stirring is warming up to 100 DEG C, and stirring to PVA is dissolved completely in hot water in clear shape.10 mg Compound-1 are added
In PVA aqueous solution, stirs to be uniformly dispersed, uniform mixed liquor is poured into the glass dish of 60 mm after stirring 1 h, be cooled to room
Temperature, 24 h of vacuum freezedrying obtain diameter 4-5 cm, the glassy yellow film Compound-1-MMM of thickness 2-3 mm, and the film
With fabulous elasticity, the uniform zero defect in surface.
The synthesis of film Compound-2-MMM of the embodiment 5. based on covalent organic frame material Compound-2
The cotton-shaped polyvinyl alcohol of 1g (PVA) is added into 25 mL single-necked flasks and is dissolved in 10 mL deionized waters, at room temperature
Stirring is warming up to 100 DEG C, and stirring to PVA is dissolved completely in hot water in clear shape.5 mg Compound-2 are added
In PVA aqueous solution, stirs to be uniformly dispersed, uniform mixed liquor is poured into the glass dish of 60 mm, be cooled to after stirring 0.5 h
Room temperature, vacuum freezedrying obtain diameter 4-5 cm, the glassy yellow film Compound-2-MMM of thickness 2-3 mm for 24 hours, and should
Film has fabulous elasticity, the uniform zero defect in surface.
The pH of 1. covalent organic frame material Compound-1 of Application Example responds experiment
To gained covalent organic frame material Compound-1 carry out pH value transformation range (0.001M HCl-10M HCl ~ pH=-
It 1-3) tests, it is found that the material changes with pH value and color change occurs, and under low ph value (pH≤1), color is by glassy yellow
Obviously it is changed into peony, as shown in Figure 2.The color change interval of ultraviolet spectra (UV-Vis) is in the nm of 420 nm~600.
The pH of 2. covalent organic frame material Compound-2 of Application Example responds experiment
To gained covalent organic frame material Compound-2 carry out pH value transformation range (0.001M HCl-10M HCl ~ pH=-
It 1-3) tests, it is found that the material changes with pH value and color change occurs, and under low ph value (pH≤2), color is by glassy yellow
It is changed into peony under one's name, as shown in Figure 3.The color change interval of ultraviolet spectra (UV-Vis) is in the nm of 420 nm~600.
The pH of 3. covalent organic frame material membrane module Compound-1-MMM of Application Example responds experiment
PH value transformation range (0.001M HCl-10M is carried out to gained covalent organic frame material membrane module Compound-1-MMM
HCl ~ pH=- 1-3) test, it is found that with pH value variation obvious color change occurs for the material, and under low ph value (pH≤1),
Color is changed into Chinese red by glassy yellow.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (6)
1. a kind of preparation method of acid response off-color material, it is characterised in that: by compound A and compound B in anhydrous solvent
Schiff bases covalent organic frame material is obtained by amine aldehyde condensation reaction, and prepared by gained covalent organic frame material formed a film
Device；
The chemical structural formula of the compound A are as follows:
；
The chemical structural formula of the compound B is、、One of.
2. a kind of preparation method of acid response off-color material according to claim 1, it is characterised in that: its specific preparation process
Are as follows:
1) compound A is dissolved in compound B according to certain mol proportion and being mixed in anhydrous solvent C, and be added with anhydrous solvent C at
The acetic acid solution D of certain volume ratio, at 25 DEG C stir 2 ~ 6 h, filter after complete reaction, obtained solid through deionized water,
Ethanol washing is dried in vacuo 24 h at room temperature and covalent organic frame material is made；
2) resulting covalent organic frame material and PVAC polyvinylalcohol aqueous solution are stirred into 0.5-3 at 100 DEG C with certain proportion
Mixed liquor is poured into the glass dish of 60 mm, is cooled to room temperature, vacuum freezedrying 24 h ~ 26 h is obtained to after evenly dispersed by h
To the mixing membrane module based on covalent organic frame material.
3. a kind of preparation method of acid response off-color material according to claim 2, it is characterised in that: described in step 1)
The molar ratio of compound A and compound B are 1:1 ~ 2, the quality of compound A and compound B and with the mass ratio of anhydrous solvent C are
1:6 ~ 15.
4. a kind of preparation method of acid response off-color material according to claim 2, it is characterised in that: described without water-soluble
Agent C includes halogenated hydrocarbons and alcohol；Halogenated hydrocarbons is specially chloroform or methylene chloride；Alcohol is specially methanol or ethyl alcohol；It is wherein halogenated
The volume ratio of hydrocarbon and alcohol is 1:5 ~ 10；The acetic acid solution D is 3M or 6M acetic acid solution, acetic acid solution and anhydrous solvent C's
Volume ratio is 1:100 ~ 200.
5. a kind of preparation method of acid response off-color material according to claim 2, it is characterised in that: described in step 2
Covalent organic frame material and the ratio of PVAC polyvinylalcohol aqueous solution are the mL of 1 mg:1 ~ 2.
6. application of the covalent organic frame material of method preparation as described in claim 1 on membrane module.
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| CN110684203A (en) * | 2019-10-25 | 2020-01-14 | 南京大学 | Two-dimensional bromine-containing covalent organic framework compound and preparation method thereof |
| CN111333858A (en) * | 2020-04-17 | 2020-06-26 | 福州大学 | Covalent organic material with acid gas molecular response, and preparation method and application thereof |
| CN111909389A (en) * | 2020-08-06 | 2020-11-10 | 山东师范大学 | Covalent organic framework material and preparation method and application thereof |
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| CN113429583A (en) * | 2021-08-19 | 2021-09-24 | 东北师范大学 | Covalent organic framework nanowire material and preparation method thereof |
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