CN113461889B - Organic porous material with mixed ion framework structure, membrane material and preparation method - Google Patents
Organic porous material with mixed ion framework structure, membrane material and preparation method Download PDFInfo
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Abstract
The invention discloses an organic porous material with a mixed ion skeleton structure, a membrane material and a preparation method thereof, wherein 4,4 '-diamino-2, 2' -disulfonic acid-biphenyl, ethidium bromide and 2,4, 6-trihydroxy-1, 3, 5-benzene trimethyl aldehyde are put into a reaction container, and a reaction solvent and a catalyst are added for reaction to obtain a mixed solution; respectively washing the mixed solution with N, N-dimethylformamide and methanol solution to remove soluble organic matters, soaking the obtained insoluble product in N, N-dimethylformamide and continuously stirring, sequentially carrying out soxhlet extraction on the product with tetrahydrofuran and methanol, finally carrying out vacuum drying under a heating condition to obtain an organic porous material with a mixed ion framework structure, and dispersing, centrifuging and carrying out suction filtration on the organic porous material with the mixed ion framework structure to obtain the membrane material.
Description
Technical Field
The invention belongs to the field of preparation methods of organic porous materials and films thereof, and particularly relates to an organic porous material with a mixed ion framework structure, a film material and a preparation method.
Background
The membrane separation process plays an important role in the separation and purification fields due to the advantages of no phase change, no secondary pollution, energy conservation, high efficiency, compact device, simple operation, easy automation, low cost, wide use scene and the like. The membrane material is used as a core unit of the membrane separation technology, and the quality of the performance of the membrane material directly influences the separation efficiency, stability, service life and the like of a separation system, so that the design and synthesis of a high-performance separation membrane material is always the key of the development of the membrane separation technology.
The ideal separation membrane material should have high permeation flux, excellent selectivity, excellent mechanical stability, thermal stability, chemical stability, and good acid and alkali resistance and pollution resistance. Among the existing membrane materials, organic polymer membrane materials have attracted extensive attention of researchers due to their abundant compositions and structural forms, good stability and excellent separation performance. A series of organic polymer membrane materials represented by cellulose acetate membranes, polytetrafluoroethylene membranes, polyimide membranes, aromatic polyamide composite membranes, sulfonated polyether sulfone membranes and the like are widely used in the fields of gas separation, water treatment and the like. The polymer membranes have good mechanical and chemical stability and excellent separation performance, but the following problems still exist when the traditional polymer membranes are used for the selective separation of molecules or ions: 1) most of the traditional polymer membrane materials are obtained by cross-linking and winding polymer chains, so that the pore sizes of the polymer chains are difficult to accurately regulate and control, the pore sizes are not uniform, the pore channel structures are disordered and irregular, and the phenomena of bending, complexity, discontinuity and the like exist, so that molecules or ions to be separated are easy to gather in small pore diameters to cause membrane pore blockage, and the permeability is reduced; 2) the contradiction between the selectivity and the permeability of the traditional polymer high-molecular membrane material is difficult to reconcile, and particularly, the high-molecular membrane is easy to swell when separating and purifying substances in an organic solvent system, so that the separation effect and the efficiency are greatly reduced; 3) the skeleton structure of the traditional polymer high-molecular membrane material has the neutral property characteristic, so that the nanometer pore channel of the traditional polymer high-molecular membrane material cannot effectively identify and screen molecules or ions with different ion properties, and the selectivity of the membrane is poor; 4) the neutral framework structure also causes the poor anti-pollution capability of the membrane material, difficult regeneration after membrane pollution and the like. Therefore, the deep research and development of novel high-performance separation membrane materials are the key points of the development of membrane separation technology, and have very important scientific value and practical significance.
Disclosure of Invention
The invention aims to provide an organic porous material with a mixed ion framework structure, a membrane material and a preparation method thereof, so as to solve the defects of irregularity, bending, complexity, changeability, uneven size and the like presented by the pore structure and the pore passage size in the existing high molecular polymer membrane material, thereby overcoming the defects of low separation efficiency, poor selectivity, weak pollution resistance and the like of the traditional organic high molecular polymer membrane material, the organic porous material with the mixed ion framework structure and the membrane material thereof prepared by the invention have excellent physical and chemical stability, good mechanical property, excellent ionic structure attribute, through ordered pore channel structure and uniform pore size, the method has the advantages of excellent selective separation performance, good solvent permeation flux, excellent pollution resistance and wide use scene.
In order to achieve the purpose, the invention adopts the following technical scheme:
an organic porous material with a mixed ion framework structure, wherein the organic porous material with the mixed ion framework structure simultaneously has two functional groups of an anionic type and a cationic type, and the structural formula of the organic porous material is shown as the formula (I):
a preparation method of an organic porous material with a mixed ion framework structure comprises the following steps:
the method comprises the following steps: putting 4,4 '-diamino-2, 2' -disulfonic acid sodium-biphenyl, ethidium bromide and 2,4, 6-trihydroxy-1, 3, 5-benzene triformal into a reaction container, adding a reaction solvent and a catalyst, and reacting for 5-7 days at 100-130 ℃ to obtain a mixed solution;
step two: washing the mixed solution obtained in the step one by using N, N-dimethylformamide and a methanol solution respectively to remove soluble organic matters, soaking the obtained insoluble product in the N, N-dimethylformamide and continuously stirring for 2 days, then filtering to obtain insoluble solid powder, sequentially carrying out soxhlet extraction on the solid powder for 2 days by using tetrahydrofuran and methanol, and finally carrying out vacuum drying under a heating condition to obtain the organic porous material with the mixed ion framework structure.
Furthermore, the molar ratio of the 4,4 '-diamino-2, 2' -disulfonic acid sodium-biphenyl to the ethidium bromide to the 2,4, 6-trihydroxy-1, 3, 5-benzene triformal is 1:2:2, and 20mL of reaction solvent is required to be added for each 1mmol of 2,4, 6-trihydroxy-1, 3, 5-benzene triformal reaction monomer.
Further, the reaction solvent is one or a mixture of more of dichlorobenzene, butanol, N-dimethylformamide, 1, 4-dioxane and 1,3, 5-trimethylbenzene.
Further, the catalyst is acetic acid solution or p-toluenesulfonic acid;
when an acetic acid solution is used as the catalyst, the concentration of the acetic acid solution is 6mol/L, and the volume ratio of the addition amount of the catalyst to the reaction solvent is 1: 5;
when the p-toluenesulfonic acid is used as the catalyst, the molar ratio of the added amount of the catalyst to the 2,4, 6-trihydroxy-1, 3, 5-benzene triformal serving as a reaction monomer is 3: 1.
Further, the stirring time and the soxhlet extraction time in the second step are both 2 days, and the vacuum drying in the second step specifically comprises the following steps: drying the mixture in a vacuum drier for 12 hours at the temperature of 60-100 ℃.
A preparation method of a membrane material based on an organic porous material with a mixed ion framework structure is provided, wherein the organic porous material with the mixed ion framework structure is prepared by adopting the preparation method, and comprises the following steps:
the method comprises the following steps: adding methanol into the organic porous material with the mixed ion framework structure, and then fully grinding;
step two: putting the material ground in the first step into deionized water or a mixed solvent consisting of deionized water and methanol, and performing ultrasonic dispersion;
step three: standing and precipitating the ultrasonic dispersion mixed solution obtained in the step two to remove large particle substances, further centrifuging the supernatant to remove undispersed fine particles, and collecting the supernatant;
step four: and (4) carrying out suction filtration on the supernatant collected in the step three to obtain the membrane material of the organic porous material with the mixed ion framework structure.
Further, the grinding is specifically: adding organic porous material powder with a mixed ion framework structure into a mortar, adding methanol, and fully grinding for 1-3 hours.
Further, the ultrasonic dispersion specifically comprises: and placing the ground material powder into a container, adding deionized water or a mixed solvent of the deionized water and methanol, and then placing the container into an ultrasonic cleaner for ultrasonic treatment for 2-5 hours, wherein the volume ratio of the deionized water to the methanol in the mixed solvent is 1: 1.
Further, the centrifugation process is specifically as follows: and (3) placing the supernatant subjected to ultrasonic dispersion and standing in a centrifuge, and setting the rotation speed to be 6000-10000 rpm and the centrifugation time to be 8-12 minutes.
Compared with the prior art, the invention has the following beneficial technical effects:
the organic porous material with a mixed ion framework structure and the membrane material thereof prepared by the invention simultaneously contain two kinds of sites with positive and negative charges in the structure, and the sites are simultaneously distributed in the nanometer pore channel framework structure of the material, so that the nanometer pore channel of the material simultaneously has two kinds of functional groups with positive and negative charges, the material is endowed with unique physicochemical properties different from a neutral framework structure material or a single positive charge or single negative charge framework material, and the pore channel structure with positive and negative charges can generate electrostatic interaction (attraction or repulsion) on molecules or ions with different ion properties close to or entering the pore channel, thereby realizing the efficient selective separation and purification of different charged molecules or ions under the charge control.
The membrane material prepared by the organic porous material with the mixed ion framework structure has high-efficiency selective separation performance, can realize the selective separation efficiency of more than 99 percent to molecules or ions with positive charges or negative charges, and simultaneously, the anti-pollution capability of the membrane is obviously improved by virtue of a large number of functional group sites with charges in the pore channels. In addition, the organic porous material and the membrane material with the mixed ion framework structure also have good physical and chemical stability, which provides possibility for further wide application of the material and the membrane material thereof.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a powder diffraction (PXRD) pattern of an organic porous material having a mixed ion framework structure prepared in example 1;
FIG. 2 shows N of the organic porous material having a mixed ion skeleton structure prepared in example 12An adsorption-desorption isotherm diagram, wherein a square connecting line is an adsorption curve and a circular connecting line is a desorption curve;
FIG. 3 is a pore size distribution diagram of the organic porous material having a mixed ion skeleton structure prepared in example 1;
FIG. 4 is a scanning electron microscope image of the organic porous material powder with a mixed ion skeleton structure prepared in example 1;
FIG. 5 is a scanning electron microscope image of the membrane surface of the organic porous membrane material with a mixed ion framework structure prepared in example 1;
fig. 6 is a spectral diagram and an optical photograph of selective separation of three dye molecules with different ionic properties by the organic porous membrane material with a mixed ion skeleton structure prepared in example 1, wherein (a) is a filter graph and a spectral diagram of a membrane material for an anionic dye MO, (b) is a filter graph and a spectral diagram of a membrane material for a cationic dye MB, and (c) is a filter graph and a spectral diagram of a membrane material for a neutral dye NR.
Detailed Description
The invention will be described in further detail below:
the invention provides an organic porous material with a mixed ion framework structure, which has a structural formula shown as a formula (I):
the invention provides a preparation method of an organic porous material with a mixed ion framework structure, which comprises the following steps:
the method comprises the following steps: putting 4,4 '-diamino-2, 2' -disulfonic acid sodium-biphenyl, ethidium bromide and 2,4, 6-trihydroxy-1, 3, 5-benzene triformal into a reaction container, adding a reaction solvent and a catalyst, and reacting for 5-7 days at 100-130 ℃ to obtain a mixed solution;
the preferable molar ratio of the 4,4 '-diamino-2, 2' -disulfonic acid sodium-biphenyl, ethidium bromide and 2,4, 6-trihydroxy-1, 3, 5-benzene triformal is 1:2:2, and 20mL of reaction solvent is required to be added to each 1mmol of 2,4, 6-trihydroxy-1, 3, 5-benzene triformal reaction monomer.
The reaction solvent is preferably one or more of dichlorobenzene, butanol, N-dimethylformamide, 1, 4-dioxane or 1,3, 5-trimethylbenzene.
The catalyst is preferably acetic acid solution or p-toluenesulfonic acid; wherein when an acetic acid solution is used as the catalyst, the concentration of the acetic acid solution is 6mol/L, and the volume ratio of the addition amount of the catalyst to the reaction solvent is 1: 5. When the p-toluenesulfonic acid is used as the catalyst, the molar ratio of the added amount of the catalyst to the 2,4, 6-trihydroxy-1, 3, 5-benzene triformal serving as a reaction monomer is 3: 1.
Step two: washing the mixed solution obtained in the first step with N, N-Dimethylformamide (DMF) and methanol solution respectively to remove soluble organic matters, soaking the obtained insoluble product in N, N-dimethylformamide and continuously stirring for 2 days, then sequentially carrying out Soxhlet extraction on the product with tetrahydrofuran and methanol for 2 days, and then carrying out vacuum drying at 60-100 ℃ for 12 hours to obtain the powder of the organic porous material with the mixed ion framework structure.
The invention also provides a preparation method of the membrane material of the organic porous material based on the mixed ion framework structure, which comprises the following steps:
the method comprises the following steps: placing the prepared organic porous material powder with the mixed ion skeleton structure into a mortar, adding methanol, and fully grinding;
the amounts of the porous material powder and methanol added to the mortar and the grinding time are not limited.
Step two: putting the material ground in the first step into deionized water or a mixed solvent consisting of deionized water and methanol for ultrasonic dispersion;
wherein the volume ratio of deionized water to methanol in the mixed solvent used for dispersion is 1:1, and the time of ultrasonic dispersion is 2-5 hours.
Step three: standing and precipitating the ultrasonic dispersion mixed solution obtained in the second step to remove large particle substances, further centrifuging the supernatant to remove undispersed fine particles, and collecting the supernatant;
and placing the supernatant collected after ultrasonic dispersion and standing in a centrifuge for centrifugation, wherein the standing and precipitating time of the obtained ultrasonic dispersion mixed solution is not limited, the set rotating speed is 6000-10000 r/min, and the set centrifuging time is 12 min.
Step four: carrying out suction filtration on the supernatant collected in the third step to obtain an organic porous membrane material with a mixed ion framework structure;
the pressure of the suction filtration operation is not limited.
The present invention will be described in detail with reference to examples. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
The following detailed description is illustrative of the embodiments and is intended to provide further details of the invention. Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention.
Example 1
The method comprises the following steps: adding 0.5mmol of monomer 4,4 '-diamino-2, 2' -disulfonic acid sodium-biphenyl, 1.0mmol of monomer ethidium bromide and 1mmol of monomer 2,4, 6-trihydroxy-1, 3, 5-benzene trimethyl aldehyde into a polytetrafluoroethylene reaction vessel, then sequentially adding 10mL of 1, 4-dioxane solvent and 10mL of 1,3, 5-trimethylbenzene solvent, uniformly stirring, then adding 4mL of 6mol/L acetic acid solution as a catalyst, putting the polytetrafluoroethylene reaction vessel into a stainless steel reaction kettle, and reacting for 6 days at 120 ℃ to obtain a mixed solution;
step two: washing the mixed solution obtained in the step one with N, N-Dimethylformamide (DMF) solution and methanol solution respectively to remove soluble organic matters, soaking the obtained insoluble product in N, N-dimethylformamide and continuously stirring for 2 days, then filtering, performing Soxhlet extraction on the obtained insoluble powder with tetrahydrofuran and methanol sequentially for 2 days, and performing vacuum drying on the Soxhlet-extracted product at 80 ℃ for 12 hours to obtain the powder of the organic porous material with the mixed ion framework structure.
And D, placing a proper amount of the material powder obtained in the step two into a mortar, adding a proper amount of methanol, fully grinding immediately, dispersing the fully ground powder into deionized water, and then placing the system into an ultrasonic cleaner for ultrasound for 3 hours. Fully standing after the ultrasonic treatment is finished, collecting supernatant, centrifuging the obtained supernatant to remove undispersed fine particles, setting the rotation speed of a centrifuge to 8000 revolutions per minute for 12 minutes, collecting supernatant, and carrying out suction filtration on the obtained supernatant by using a filtering device to obtain the organic porous membrane material with the mixed ion framework structure.
Fig. 1 is a powder diffraction (PXRD) pattern of the organic porous material having a mixed ion skeleton structure prepared in example 1, and it can be known from the existence of a significant diffraction peak in the pattern that the organic porous material having a mixed ion skeleton structure prepared in example 1 has good crystallinity.
FIG. 2 shows N of the organic porous material having a mixed ion skeleton structure prepared in example 12Adsorption-desorption of the attached drawing by N2The BET specific surface area of the organic porous material with the mixed ion framework structure obtained by the adsorption-desorption isotherm reaches 582m2/g。
Fig. 3 is a pore size distribution diagram of the organic porous material having a mixed ion framework structure prepared in example 1, and it can be seen that the average pore size of the material is 16.2.
FIG. 4 is a scanning electron microscope image of the organic porous material with a mixed ion skeleton structure prepared in example 1, and it can be seen that the material has an irregular sheet structure.
Fig. 5 is a scanning electron microscope image of the membrane surface of the membrane material of the organic porous material with the mixed ion skeleton structure prepared in example 1, which shows that the surface of the membrane material is flat and has no cracks, and the membrane shape is good.
FIG. 6 is a spectrum chart and an optical photograph of the membrane material of the organic porous material with a mixed ion skeleton structure prepared in example 1 for the selective separation of three dye molecules with different ion properties; wherein (a) is a filtering picture and a spectrogram of a membrane material to an anionic dye MO, (b) is a filtering picture and a spectrogram of a membrane material to a cationic dye MB, and (c) is a filtering picture and a spectrogram of a membrane material to a neutral dye NR. As can be seen from the spectrograms shown in (a), (b) and (c) of fig. 6, the membrane material exhibits different selective retention performances for dye molecules with different ionic properties, wherein the retention rate of the membrane material for anionic and cationic dyes reaches over 99%, compared with the retention efficiency of the membrane material for neutral dye molecules of only 16.2%. The experimental result shows that the membrane material of the organic porous material with the mixed ion framework structure can effectively and selectively intercept dye molecules with different ion attributes, thereby realizing the selective separation of the molecules with different ion attributes.
Example 2
The method comprises the following steps: adding 0.5mmol of monomer 4,4 '-diamino-2, 2' -disulfonic acid sodium-biphenyl, 1.0mmol of monomer ethidium bromide and 1mmol of monomer 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic acid into a polytetrafluoroethylene reaction vessel, then sequentially adding 10mL of dichlorobenzene and 10mL of butanol solvent, uniformly stirring, then adding 3mmol of p-toluenesulfonic acid as a catalyst, then placing the polytetrafluoroethylene reaction vessel into a stainless steel reaction kettle, and reacting for 5 days at 130 ℃ to obtain a mixed solution;
step two: washing the mixed solution obtained in the step one with N, N-Dimethylformamide (DMF) solution and methanol solution respectively to remove soluble organic matters, soaking the obtained insoluble product in N, N-dimethylformamide and continuously stirring for 2 days, then filtering, carrying out soxhlet extraction on the obtained insoluble powder with tetrahydrofuran and methanol sequentially for 2 days, and carrying out vacuum drying on the soxhlet extracted product at 100 ℃ for 12 hours to obtain the powder of the organic porous material with the mixed ion framework structure.
And D, placing a proper amount of the material powder obtained in the step two into a mortar, adding a proper amount of methanol, fully grinding, dispersing the ground powder into a mixed solvent of deionized water and methanol in a volume ratio of 1:1, and then placing the system into an ultrasonic cleaner for ultrasonic treatment for 5 hours. Fully standing after the ultrasonic treatment is finished, collecting supernatant, centrifuging the obtained supernatant to remove undispersed fine particles, setting the rotation speed of a centrifuge to 10000 rpm, wherein the centrifugation time is 12 minutes, collecting supernatant, and performing suction filtration on the obtained supernatant by using a filtering device to obtain the organic porous membrane material with the mixed ion framework structure.
Example 3
The method comprises the following steps: adding 0.5mmol of monomer 4,4 '-diamino-2, 2' -disulfonic acid sodium-biphenyl, 1.0mmol of monomer ethidium bromide and 1mmol of monomer 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic acid into a polytetrafluoroethylene reaction vessel, then adding 20mL of N, N-dimethylformamide solvent, uniformly stirring, then adding 4mL of 6mol/L acetic acid solution as a catalyst, then placing the polytetrafluoroethylene reaction vessel into a stainless steel reaction kettle, and reacting for 7 days at 100 ℃ to obtain a mixed solution;
step two: washing the mixed solution obtained in the step one with N, N-Dimethylformamide (DMF) solution and methanol solution respectively to remove soluble organic matters, soaking the obtained insoluble product in N, N-dimethylformamide and continuously stirring for 2 days, then filtering, performing Soxhlet extraction on the obtained insoluble powder with tetrahydrofuran and methanol sequentially for 2 days, and performing vacuum drying on the Soxhlet-extracted product at 60 ℃ for 12 hours to obtain the powder of the organic porous material with the mixed ion framework structure.
And D, placing a proper amount of the material powder obtained in the step two into a mortar, adding a proper amount of methanol, fully grinding, dispersing the ground powder into a mixed solvent of deionized water and methanol in a volume ratio of 1:1, and then placing the system into an ultrasonic cleaner for 2 hours by ultrasound. Fully standing after the ultrasonic treatment is finished, collecting supernatant, centrifuging the obtained supernatant to remove undispersed fine particles, setting the rotating speed of a centrifuge to be 6000 rpm, setting the centrifuging time to be 12 minutes, collecting supernatant, and carrying out suction filtration on the obtained supernatant by using a filtering device to obtain the organic porous membrane material with the mixed ion framework structure.
The organic porous material with the mixed ion framework structure and the surface of the inner pore channel of the membrane of the organic porous material contain functional group sites with positive charges and negative charges, the structure endows the membrane material of the organic porous material with the mixed ion framework structure with the selective separation performance of dual control of the charges and the nanometer pore channels, so that the high-efficiency selective separation and purification of charged molecules or ions with different sizes can be realized, and the membrane filtration experiment result proves that the membrane material of the organic porous material with the mixed ion framework structure can realize the interception effect of more than 99 percent on positive charges and negative charges, and compared with the membrane material, the interception efficiency of neutral dye molecules is only 16.2 percent. In addition, the anti-pollution performance of the membrane material is also remarkably improved by a large number of charged functional groups in the pore channel structure.
The organic porous material with the mixed ion framework structure and the inner pore channel surface of the film of the organic porous material contain functional group sites with positive and negative charges, the functional group sites are simultaneously distributed in the nanometer pore channel structure of the material in a staggered manner, the structural form endows the organic porous material with the mixed ion framework structure with unique properties and functions different from neutral framework structure materials or organic porous materials with single positive charges or single negative charges, for example, the pore channel structure with the positive and negative charges in the material can generate electrostatic attraction or repulsion action on molecules or ions with different ion properties approaching or entering the pore channel. The membrane material prepared by the material has the selective separation performance of dual control of charge and a nanometer pore channel, so that the membrane material can realize high-efficiency selective separation and purification of charged molecules or ions with different sizes, and the membrane filtration experiment result proves that the membrane material of the organic porous material with the mixed ion framework structure can realize the retention effect of more than 99 percent on positive charge molecules and negative charge molecules, and compared with the membrane material, the retention efficiency of the membrane material on neutral dye molecules is only 16.2 percent. In addition, a large number of charged functional groups in the pore structure also obviously improve the pollution resistance of the membrane material, and in addition, the material and the membrane thereof have good physical and chemical stability, so that the organic porous material with the mixed ion framework structure and the membrane material thereof become excellent candidate materials of high-performance and high-selectivity separation membranes.
The embodiments described above are only preferred technical solutions of the present invention, and should not be considered as limitations of the present invention, and the features in the embodiments and examples in the present application may be arbitrarily combined with each other without conflict. The protection scope of the present invention is defined by the claims, and includes equivalents of technical features of the claims. I.e., equivalent alterations and modifications within the scope hereof, are also intended to be within the scope of the invention.
Claims (9)
1. The organic porous material with the mixed ion framework structure is characterized in that the organic porous material with the mixed ion framework structure simultaneously has two functional groups of anion type and cation type, and the structural formula of the organic porous material is shown as the formula (I):
2. a preparation method of an organic porous material with a mixed ion framework structure is characterized by comprising the following steps:
the method comprises the following steps: putting 4,4 '-diamino-2, 2' -disulfonic acid sodium-biphenyl, ethidium bromide and 2,4, 6-trihydroxy-1, 3, 5-benzene triformal into a reaction container, adding a reaction solvent and a catalyst, and reacting for 5-7 days at 100-130 ℃ to obtain a mixed solution; the molar ratio of the 4,4 '-diamino-2, 2' -disulfonic acid sodium-biphenyl to the ethidium bromide to the 2,4, 6-trihydroxy-1, 3, 5-benzene triformal is 1:2:2, and 20mL of reaction solvent is required to be added into each 1mmol of 2,4, 6-trihydroxy-1, 3, 5-benzene triformal reaction monomer;
step two: washing the mixed solution obtained in the step one by using N, N-dimethylformamide and a methanol solution respectively to remove soluble organic matters, soaking the obtained insoluble product in the N, N-dimethylformamide and continuously stirring for 2 days, then filtering to obtain insoluble solid powder, sequentially carrying out soxhlet extraction on the solid powder for 2 days by using tetrahydrofuran and methanol, and finally carrying out vacuum drying under a heating condition to obtain the organic porous material with the mixed ion framework structure.
3. The method of claim 2, wherein the reaction solvent is a mixture of one or more of dichlorobenzene, butanol, N-dimethylformamide, 1, 4-dioxane and 1,3, 5-trimethylbenzene.
4. The method for preparing the organic porous material with the mixed ion framework structure according to claim 2, wherein the catalyst is acetic acid solution or p-toluenesulfonic acid;
when an acetic acid solution is used as the catalyst, the concentration of the acetic acid solution is 6mol/L, and the volume ratio of the addition amount of the catalyst to the reaction solvent is 1: 5;
when the p-toluenesulfonic acid is used as the catalyst, the molar ratio of the added amount of the catalyst to the 2,4, 6-trihydroxy-1, 3, 5-benzene triformal serving as a reaction monomer is 3: 1.
5. The method for preparing the organic porous material with the mixed ion framework structure according to claim 2, wherein the stirring time and the Soxhlet extraction time in the second step are both 2 days, and the vacuum drying in the second step specifically comprises the following steps: drying the mixture in a vacuum drier for 12 hours at the temperature of 60-100 ℃.
6. A method for preparing a membrane material based on an organic porous material having a mixed-ion framework structure, which is prepared by the preparation method according to any one of claims 2 to 5, comprising the steps of:
the method comprises the following steps: adding methanol into the organic porous material with the mixed ion framework structure, and then fully grinding;
step two: putting the material ground in the first step into deionized water or a mixed solvent consisting of deionized water and methanol, and performing ultrasonic dispersion;
step three: standing and precipitating the ultrasonic dispersion mixed solution obtained in the step two to remove large particles, further centrifuging the supernatant to remove undispersed fine particles, and collecting the supernatant;
step four: and (4) carrying out suction filtration on the supernatant collected in the step three to obtain the membrane material of the organic porous material with the mixed ion framework structure.
7. The method for preparing a membrane material based on an organic porous material with a mixed ion framework structure according to claim 6, wherein the grinding is specifically as follows: adding organic porous material powder with a mixed ion framework structure into a mortar, adding methanol, and fully grinding for 1-3 hours.
8. The preparation method of the membrane material based on the organic porous material with the mixed ion framework structure according to claim 6, wherein the ultrasonic dispersion is specifically as follows: and placing the ground material powder into a container, adding deionized water or a mixed solvent of the deionized water and methanol, and then placing the container into an ultrasonic cleaner for ultrasonic treatment for 2-5 hours, wherein the volume ratio of the deionized water to the methanol in the mixed solvent is 1: 1.
9. The method for preparing a membrane material based on an organic porous material with a mixed ion framework structure according to claim 6, wherein the centrifugation process specifically comprises the following steps: and (3) placing the supernatant subjected to ultrasonic dispersion and standing in a centrifuge, and setting the rotating speed to be 6000-10000 rpm and the centrifuging time to be 8-12 minutes.
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