CN107759802B - Preparation method of high-molecular organic ligand, preparation method of high-molecular metal organic framework, ion separation membrane and preparation method of ion separation membrane - Google Patents
Preparation method of high-molecular organic ligand, preparation method of high-molecular metal organic framework, ion separation membrane and preparation method of ion separation membrane Download PDFInfo
- Publication number
- CN107759802B CN107759802B CN201711007346.4A CN201711007346A CN107759802B CN 107759802 B CN107759802 B CN 107759802B CN 201711007346 A CN201711007346 A CN 201711007346A CN 107759802 B CN107759802 B CN 107759802B
- Authority
- CN
- China
- Prior art keywords
- preparation
- ion separation
- separation membrane
- metal organic
- organic framework
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4006—(I) or (II) containing elements other than carbon, oxygen, hydrogen or halogen as leaving group (X)
Abstract
The invention provides a preparation method of a high-molecular ligand, which comprises the following steps: reacting diester terephthalate, a dibromo alkane compound and potassium carbonate in a solvent to obtain a reaction product; reacting the reaction product with alkali to obtain an intermediate product; and reacting the intermediate product with acid to obtain the high molecular organic ligand. The invention coats the macromolecule organic metal framework layer on the surface of the porous substrate, and effectively realizes the function of selective ion separation by using the aperture screening effect, and the macromolecule organic metal framework in the invention is coated on the surface of the porous substrate in a solution state, thereby greatly enhancing the acting force of the macromolecule organic metal framework and the substrate, and further improving the applicability of the ion separation membrane. The invention also provides a preparation method of the high molecular metal organic framework, an ion separation membrane and a preparation method thereof.
Description
Technical Field
The invention relates to the technical field of ion separation, in particular to a preparation method of a high-molecular organic ligand, a preparation method of a high-molecular metal organic framework, an ion separation membrane and a preparation method thereof.
Background
Metal organic frameworks are attracting attention as a new porous material because of their wide application fields. The Metal Organic Framework (MOF) material has outstanding performance in the fields of gas separation and storage, drug delivery, ion separation and the like, and has pores with various forms in the structure, which is an advantage that other materials do not have. However, the MOF material is a cavity coordination polymer with certain pore size and framework obtained by a method of molecular assembly and crystal engineering of transition metal ions or metal clusters and organic ligands, and contains free anions to neutralize charge, and due to the irregularity of organic molecules, the lattice energy of the MOF material is far inferior to that of the traditional crystal material. At the same time, the fragility of the coordination bonding results in MOF materials that also do not have the stability of covalent bonding. Consequently, MOF materials have been faced with great difficulties in practical application due to the apparent lack of stability.
The composite material is a method for solving the problems, is compounded with a soft and tough polymer material, combines the advantages of the polymer material and a metal material, and forms a polymer metal organic framework (PolyMOF) material, so that the material can play a role in a harsher environment, which is very important for ion separation work. The composition of the MOF material and the polymer material is mainly divided into two ways, namely the MOF material is compounded by taking a polymer as a main body and the polymer material is compounded by taking the MOF material as a main body. In the first approach, a high polymer is taken as a main body to compound the MOF material, and a large number of regularly distributed pore channels exist in the MOF material, so that the ordered distribution and assembly of the high polymer in the MOF material are facilitated. In most cases, the polymer chain segments in the polymer material are randomly entangled, so that from the perspective of polymer assembly, the proper and ordered pore channels standardize the chain segment sequence, chain segment length and chain segment orientation of the polymer material, and the performance of the polymer material can be improved, so that the whole composite material shows unique properties that a single component cannot embody due to synergistic effect. In the second approach, the MOF material is used as a main composite polymer material. The film-shaped or film-like MOF material has wide application prospect in many fields. Therefore, compounding MOF materials with polymeric materials and assembling them into films has been the focus of research in the art, in response to the problem of MOF materials that are difficult to process and apply due to crystallization. The composite material has better performances such as gas adsorption selectivity, hydrolytic stability and biocompatibility than a pure MOF material.
However, the two approaches are basically to combine the polymer material and the MOF material in a physical blending manner, and the long-term stability of the polymer metal organic framework is still to be improved. Meanwhile, the improvement of membrane performance, such as separation performance and the like, is also greatly limited due to the problem of a phase interface between two incompatible materials, namely a polymer and a metal framework.
The method for synthesizing the PolyMOF material by adopting the coordination of the metal ions and the macromolecular ligand can completely avoid the incompatibility problem when the macromolecular material and the metal material are compounded, and simultaneously greatly improves the stability of the material. However, no reports about the soluble PolyMOF material are found at present, and the soluble property can greatly expand the application range of the PolyMOF and facilitate the preparation of the PolyMOF thin layer.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a polymeric organic ligand, a method for preparing a polymeric metal organic framework, and a method for preparing an ion separation membrane, and the polymeric metal organic framework prepared by the methods provided by the present invention has good solubility.
The invention provides a preparation method of a high-molecular organic ligand, which comprises the following steps:
1) reacting diester terephthalate, a dibromo alkane compound and potassium carbonate in a solvent to obtain a reaction product;
2) reacting the reaction product with alkali to obtain an intermediate product;
3) and reacting the intermediate product with acid to obtain the high molecular organic ligand.
In the present invention, the terephthalic acid diester is preferably diethyl 2, 5-dihydroxyterephthalate.
In the present invention, the carbon chain in the dibromoalkane compound is preferably a long carbon chain, and more preferably a linear alkane of nonane to dodecane. In the present invention, the dibromoalkane compound is preferably 1, 9-dibromononane, 1, 10-dibromodecane, 1, 11-dibromoundecane or 1, 12-dibromododecane. The inventor finds that the carbon chain length from nonane to dodecane is appropriate for the dibromoalkane compound, the formation of a metal organic framework is influenced when the carbon chain is too short, and the entanglement phenomenon is caused when the carbon chain is too long.
In the present invention, the solvent in the step 1) is preferably dimethyl sulfoxide (DMSO).
In the present invention, the reaction in the step 1) is preferably a heating reaction; the reaction temperature is preferably 90-110 ℃, more preferably 95-105 ℃, and most preferably 100 ℃; the reaction time is preferably 22 to 26 hours, and more preferably 24 to 25 hours.
In the present invention, after the step 1) is completed, it is preferable to add water to the obtained reaction product and then to perform centrifugal separation, and then to wash the obtained centrifugal product. In the present invention, the washing reagent is preferably methanol and acetone, and the present invention preferably washes the centrifuged product three times with methanol and acetone, respectively.
In the present invention, the alkali in the step 2) is preferably potassium hydroxide.
In the invention, the temperature of the reaction in the step 2) is preferably 80-90 ℃, and more preferably 85 ℃; the reaction time is preferably 7 to 9 hours, and more preferably 8 hours.
In the present invention, the acid in the step 3) is preferably hydrochloric acid. Preferably, the reaction product obtained in the step 2) is acidified by acid, so that the pH value is 1-3, and more preferably 2.
In the invention, after the reaction in step 3) is completed, the obtained reaction product is preferably washed with an organic solvent to obtain a high-molecular organic ligand with high purity, thereby improving the separation effect of the prepared ion separation membrane. In the present invention, the organic solvent is preferably methanol and acetone, and the present invention preferably washes the reaction product obtained in step 3) with methanol and acetone, respectively.
The invention provides a preparation method of a high-molecular metal organic framework, which comprises the following steps:
reacting the high molecular organic ligand with soluble zinc salt in a solvent to obtain the high molecular metal organic framework.
In the present invention, the polymer organic ligand is prepared by the method described in the above technical scheme, and is not described herein again.
In the present invention, the soluble zinc salt is preferably zinc nitrate, more preferably zinc nitrate hexahydrate.
In the present invention, the basic organic solvent is preferably an amide-based organic solvent, and more preferably one or both of N, N-dimethylformamide and N, N-diethylformamide.
In the invention, the reaction temperature of the high molecular organic ligand and the soluble zinc salt is preferably 85-135 ℃, more preferably 110-130 ℃, and most preferably 120 ℃; the reaction time of the high molecular organic ligand and the soluble zinc salt is preferably 42-50 hours, and more preferably 48 hours. In the present invention, the temperature for reacting the polymeric organic ligand and the soluble zinc salt can be reasonably selected by one skilled in the art according to different soluble zinc salts used.
The invention provides a preparation method of an ion separation membrane, which comprises the following steps:
and dissolving the macromolecular metal organic framework and coating the dissolved macromolecular metal organic framework on the surface of a porous substrate to obtain the ion separation membrane.
In the present invention, the polymer metal organic framework is prepared by the method described in the above technical scheme, and is not described herein again.
In the present invention, the agent for dissolving the high molecular metal organic skeleton is preferably N, N-Dimethylformamide (DMF).
In the invention, the thickness of the coating is preferably 200 to 300nm, more preferably 220 to 280nm, and most preferably 240 to 260 nm.
In the present invention, the porous base film is preferably a porous alumina film, such as a positive metal alumina film having uniform pores on the surface, which is commercially available. In the invention, the pore diameter of the porous base membrane is preferably 45-80 μm, more preferably 50-70 μm, and most preferably 55-65 μm. According to the invention, the porous base membrane with the aperture of 45-80 μm is adopted, so that most ions can directly pass through the porous base membrane, ion separation is not influenced, ions can be helped to diffuse in the membrane structure, ion flux is helped to be improved, and the prepared ion separation membrane can better play a role in ion separation.
The high molecular metal organic framework prepared by the invention is used for preparing the ion separation membrane, the stability of the high molecular metal organic framework is better, and the high molecular chain is used for enabling the high molecular metal organic framework to be densely distributed on the surface of the porous base membrane in a group mode, so that the ion separation effect of the separation membrane is better.
The present invention provides an ion separation membrane comprising:
a porous matrix;
a polymer metal organic framework layer attached to the surface of the porous matrix.
In the present invention, the polymer metal organic framework layer is formed of a polymer metal organic framework, and is preferably formed by coating a polymer metal organic framework solution on the surface of the porous substrate.
In the present invention, the thickness of the polymeric metal organic framework layer is preferably 200 to 300nm, more preferably 220 to 280nm, and most preferably 240 to 260 nm.
In the present invention, the preparation method of the ion separation membrane is the same as that of the ion separation membrane in the above technical scheme, and is not described herein again.
Compared with the prior art, the macromolecular metal organic framework prepared by the invention has a macromolecular organic chain segment in the structure, the stability of the metal organic framework is obviously improved, the advantages of a macromolecular material and the metal organic framework are combined, and the macromolecular metal organic framework has separation performance and certain toughness. The macromolecule in the macromolecule metal organic framework prepared by the invention is linked with the framework of the metal organic framework, so that the pore structure of the metal organic framework is stabilized, the determination of the separation pore diameter of the separation layer membrane is facilitated in the ion separation process, and the purpose of separating a certain specific ion is achieved.
In addition, the high molecular metal organic framework prepared by the invention has good solubility, so that the preparation method is completely different from the method for combining the MOF to the base membrane in the prior art, the preparation of the PolyMOF separation layer can be easily realized by utilizing the solubility of the high molecular metal organic framework, and the preparation of the ion separation membrane is greatly simplified. Meanwhile, the PolyMOF prepared by the invention has better stability, so that the combination of the PolyMOF on a base film is better than that of a metal organic framework in a solution system, and the coverage rate on the base film is higher, thereby effectively improving the separation coefficient of the ion separation membrane.
The preparation method of the high molecular organic ligand, the preparation method of the high molecular metal organic framework and the preparation method of the ion separation membrane provided by the invention are simple and effective, the synthesis steps are simple, the construction of the separation membrane is simple and effective, and a theoretical basis and a reference practical basis can be provided for the application of the high molecular metal organic framework, namely a novel porous material, in the field of ion separation.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a schematic structural view of an ion separation membrane prepared in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the polymeric organic ligand prepared in example 1 of the present invention;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of the polymeric organic ligand prepared in example 2 of the present invention;
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of the polymeric organic ligand prepared in example 3 of the present invention;
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of the polymeric organic ligand prepared in example 4 of the present invention;
FIG. 6 is an X-ray diffraction pattern of a polymeric metal organic framework prepared in example 2 of the present invention;
FIG. 7 is an X-ray diffraction pattern of an ion separation membrane produced in example 2 of the present invention;
FIG. 8 is a scanning electron microscope image of the surface of the soaked ion separation membrane prepared in example 1 of the present invention;
FIG. 9 is a scanning electron microscope image of a cross section of the ion separation membrane prepared in example 1 of the present invention after soaking;
FIG. 10 is a scanning electron microscope image of the surface of the soaked ion separation membrane prepared in example 2 of the present invention;
FIG. 11 is a scanning electron microscope image of a cross section of the ion separation membrane prepared in example 2 of the present invention after soaking;
fig. 12 is a schematic structural diagram of an electrodialysis device for detection according to an embodiment of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The raw materials used in the following examples of the present invention are all commercially available products, and the used inorganic porous base film is a positive metal aluminum oxide film with a pore size of 45-80 nm, which is provided by Hefei Puyuan nanotechnology Co.
Example 1
Preparation of high molecular organic ligand:
diethyl 2, 5-dihydroxyterephthalate (1.2g, 4.7mmol), 1, 10-dibromodecane (4.7mmol) and potassium carbonate (2.6g, 19.0mmol) were mixed and added to 33mL of DMSO to form a suspension, which was then reacted at 100 ℃ for 24 hours with stirring.
And (3) cooling the reaction system to room temperature, adding 50mL of water into the reaction system, separating the obtained reaction product through centrifugation, and washing the product with methanol and acetone for three times respectively, wherein 35mL of detergent is used each time.
The product of the above step was collected by centrifugation and dried overnight at 60 ℃. The resulting dried product (1.0g) was added to a total of 30mL of a 1:1 volume ratio mixed solution of water and DMSO, 4.0g of KOH was added, and the mixed solution was heated to 80 ℃ and reacted for 8 hours to obtain a clear solution.
The resulting clear solution was acidified to pH 2 with 1.0mol/L HCl solution to give a white slightly yellowish precipitate. After collecting the precipitate by centrifugation, the product was washed three times with 35mL of detergent each time with methanol and acetone, respectively. And drying the washing product at 60 ℃ overnight to obtain the macromolecular organic ligand.
The nuclear magnetic resonance detection of the macromolecular organic ligand prepared in example 1 of the present invention is performed, and the detection result is shown in fig. 2, and as can be seen from fig. 2, a strong peak of carboxylhydroxyl hydrogen is evident near 12.8ppm, which indicates that the hydrolysis reaction is complete, the original carboxylic ester has been hydrolyzed into carboxylic acid, and the macromolecular organic ligand can be used for coordination. Meanwhile, a characteristic peak of methylene group having a certain shift due to the linkage with oxygen atom is present in the vicinity of 7.26ppm, indicating that the original hydroxyl group has been substituted with an alkoxy group. Therefore, the synthesis of the high molecular organic ligand is successful, and the 2, 5-dihydroxy diethyl terephthalate and the 1, 10-dibromodecane successfully react to form the high molecular ligand with a certain molecular weight.
Synthesis of high molecular metal organic framework
High molecular organic ligand (0.05mol) and Zn (NO)3)2·6H2O (0.05mol), 2mL of N, N-Dimethylformamide (DMF) is added into a 20mL reaction bottle, and after ultrasonic dispersion and dissolution, the reaction system is placed at 85 ℃ for reaction for 48 hours to obtain a reddish brown solid-liquid mixture.
And (3) placing the obtained reddish brown solid-liquid mixture on a heating plate at 60 ℃ to dry the liquid to obtain a brownish yellow solid, namely the macromolecular metal organic framework complex.
Preparation of ion separation membranes
Dissolving the high molecular metal organic framework complex in N-methylpyrrolidone (NMP) at a concentration of 0.1g/mL, coating the obtained solution on the surface of an organic porous base membrane, drying on a heating plate at 60 ℃, and coating the solution to a thickness of 2 μm to obtain the ion separation membrane.
The schematic structural diagram of the ion separation membrane prepared in embodiment 1 of the present invention is shown in fig. 1, and includes: a layer of porous material (organic porous base film) and a layer of PolyMOF material (polymeric metal organic framework layer).
The ion separation membrane prepared in the embodiment 1 of the present invention is soaked in water for 7 days, and then a scanning electron microscope is used for detection, and the detection results are shown in fig. 8 and 9, which shows that the separation layer of the ion separation membrane prepared in the embodiment of the present invention is still clearly visible and has no obvious damage. The separation layer film formed by the polymer metal organic framework prepared in the embodiment 1 has high stability.
The performance of the ion separation membrane prepared in example 1 of the present invention was tested by using an electrodialysis apparatus (the schematic structural diagram is shown in fig. 12), and the specific method was:
the solution of the anode chamber and the cathode chamber is 0.3mol/L of Na2SO4The solution in the desalting chamber is 0.1mol/L NaCl and Na2SO4Solution, concentration chamber is deionized water. The anion exchange membrane is AMX of ASTOM company of Japan, and the PolyMOF membrane is the ion separation membrane prepared by the embodiment of the invention. The electrodes at two ends of the electrode chamber of the electrodialysis device are connected with constant direct current of 0.04A, and along with the continuous progress of the experiment, cations in the solution of the desalting chamber continuously move to one end of the negative electrode. The ion separation membrane prepared by the embodiment of the invention has different barrier effects on different cations, and the flux ratio of different cations passing through the membrane shows the separation effect of the ion separation membrane prepared by the embodiment on different cations. The flux of different cations can be obtained by detecting the concentration of different cations passing through the ion separation membrane within a certain time under the constant current.
As a result of the examination, the flux of sodium ions of the ion separation membrane prepared in example 1 of the present invention was 5.72X 10- 8mol·cm-2·s-1Flux of magnesium ion is 1.7X 10-9mol·cm-2·s-1The separation coefficient is 34.3, and the good single-multivalent cation separation performance is shown.
Example 2
Polymeric organic ligands, polymeric metal organic frameworks and ion separation membranes were prepared as described in example 1, except that 1, 9-dibromononane was used.
The nuclear magnetic resonance detection result of the polymeric organic ligand prepared in example 2 of the present invention is shown in fig. 3. As can be seen from FIG. 3, a strong peak of carboxylhydroxyl is evident in the vicinity of 12.8ppm, which indicates that the hydrolysis reaction is complete, the original carboxylic ester has been hydrolyzed to carboxylic acid, and the polymeric organic ligand is available for coordination. Meanwhile, a characteristic peak of methylene group having a certain shift due to the linkage with oxygen atom is present in the vicinity of 7.26ppm, indicating that the original hydroxyl group has been substituted with an alkoxy group. Therefore, the synthesis of the high molecular organic ligand is successful, and the 2, 5-dihydroxy diethyl terephthalate and the 1, 10-dibromodecane successfully react to form the high molecular ligand with a certain molecular weight.
The X-ray diffraction test results of the polymeric metal organic framework and the ion separation membrane prepared in example 2 of the present invention are shown in fig. 6 and 7, and it can be seen from fig. 6 and 7 that, in the X-ray diffraction pattern, sharp diffraction peaks of MOF crystals are evident in the range of 2 θ of 5 to 10 °. Meanwhile, in the interval of 15-25 degrees of 2 theta, there are multiple peaks which represent polymers and are relatively smooth and disordered. The X-ray diffraction images show that the polymeric metal organic frameworks and the ion separation membranes prepared in the examples have the characteristics of MOF crystals and polymeric compounds, and the combination of the two is successful.
The results of the scanning electron microscope test after the ion separation membrane prepared in example 2 of the present invention is soaked are shown in fig. 10 and 11, and as can be seen from fig. 10 and 11, on the surface of the base membrane positive alumina porous material, a high molecular organic framework grows to be denser and to have a relatively obvious crystal morphology, and at the same time, a stable separation layer with a certain thickness is formed on the surface of the base membrane.
The performance of the ion separation membrane prepared in example 2 of the present invention was tested according to the method of example 1, and as a result, the flux of sodium ions of the ion separation membrane prepared in example 2 of the present invention was 4.72 × 10-8mol·cm-2·s-1Flux of magnesium ion is 1.5X 10-9mol·cm-2·s-1The separation coefficient is 31.5, and the good single-polyvalent cation separation performance is shown.
Example 3
Polymeric organic ligands, polymeric metal organic frameworks and ion separation membranes were prepared as described in example 1, except that 1, 11-dibromoundecane was used.
The nuclear magnetic resonance detection result of the polymeric organic ligand prepared in example 3 of the present invention is shown in fig. 4. As can be seen from FIG. 4, a strong peak of carboxylhydroxyl is evident in the vicinity of 12.8ppm, indicating that the hydrolysis reaction is complete, the original carboxylic ester has been hydrolyzed to carboxylic acid, and the polymeric organic ligand is available for coordination. Meanwhile, a characteristic peak of methylene group having a certain shift due to the linkage with oxygen atom is present in the vicinity of 7.26ppm, indicating that the original hydroxyl group has been substituted with an alkoxy group. Therefore, the synthesis of the high molecular organic ligand is successful, and the 2, 5-dihydroxy diethyl terephthalate and the 1, 10-dibromodecane successfully react to form the high molecular ligand with a certain molecular weight.
The ion separation membrane prepared in example 3 of the present invention was tested for performance according to the method of example 1, and as a result, the ion separation membrane prepared in example 3 of the present invention had a flux of sodium ions of 4.3 × 10-8mol·cm-2·s-1Flux of magnesium ion is 1.5X 10-9mol·cm-2·s-1The separation coefficient is 28.7, and the good single-multivalent cation separation performance is shown.
Example 4
Polymeric organic ligands, polymeric metal organic frameworks and ion separation membranes were prepared as described in example 1, except that 1, 12-dibromododecane was used.
The nuclear magnetic resonance detection result of the polymeric organic ligand prepared in example 4 of the present invention is shown in fig. 5. As can be seen from FIG. 5, a strong peak of carboxylhydroxyl is evident in the vicinity of 12.9ppm, indicating that the hydrolysis reaction is complete, the original carboxylic ester has been hydrolyzed to carboxylic acid, and the polymeric organic ligand is available for coordination. Meanwhile, a characteristic peak of methylene group having a certain shift due to the linkage with oxygen atom is present in the vicinity of 7.26ppm, indicating that the original hydroxyl group has been substituted with an alkoxy group. Therefore, the synthesis of the high molecular organic ligand is successful, and the 2, 5-dihydroxy diethyl terephthalate and the 1, 10-dibromodecane successfully react to form the high molecular ligand with a certain molecular weight.
The ion separation membrane prepared in example 4 of the present invention was tested for performance according to the method of example 1, and as a result, the ion separation membrane prepared in example 4 of the present invention had a flux of sodium ions of 3.2X 10-9mol·cm-2·s-1Flux of magnesium ions is 2X 10-10mol·cm-2·s-1The separation coefficient is 15.5, and the good single-polyvalent cation separation performance is shown.
From the above examples, the present invention provides a method for preparing a polymeric ligand, comprising: reacting diester terephthalate, a dibromo alkane compound and potassium carbonate in a solvent to obtain a reaction product; reacting the reaction product with alkali to obtain an intermediate product; and reacting the intermediate product with acid to obtain the high molecular organic ligand. The separation layer film formed by the metal organic framework prepared by the invention can effectively realize the selective separation effect of ions by utilizing the aperture sieving effect of the separation layer film, and the adhesion stability of the separation layer film on the base film is obviously improved because the metal organic framework and the high polymer material are combined with each other to play respective advantages. In the structure of the macromolecule metal organic framework separation layer membrane, the metal organic frameworks are remarkably distributed on the base membrane in a group mode due to macromolecules, and the efficiency of the metal organic framework separation layer membrane in ion separation is effectively improved.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A method of making an ion separation membrane, comprising:
dissolving a high molecular metal organic framework and coating the dissolved high molecular metal organic framework on the surface of a porous base membrane to obtain an ion separation membrane;
the porous base membrane is a porous alumina membrane;
the preparation method of the high molecular metal organic framework comprises the following steps:
reacting a high-molecular organic ligand with soluble zinc salt in a solvent to obtain a high-molecular metal organic framework;
the preparation method of the organic ligand comprises the following steps:
1) reacting 2, 5-dihydroxy diethyl terephthalate, a dibromoalkane compound and potassium carbonate in a solvent to obtain a reaction product;
2) reacting the reaction product with alkali to obtain an intermediate product;
3) and reacting the intermediate product with acid to obtain the high molecular organic ligand.
2. The method according to claim 1, wherein the dibromoalkane compound is 1, 9-dibromononane, 1, 10-dibromodecane, 1, 11-dibromoundecane or 1, 12-dibromododecane.
3. The method according to claim 1, wherein the temperature of the reaction in the step 1) is 90-110 ℃; the reaction time is 22-26 hours.
4. The method according to claim 1, wherein the temperature of the reaction in the step 2) is 80-90 ℃; the reaction time is 7-9 hours.
5. The method according to claim 1, wherein the temperature for the reaction of the polymeric organic ligand and the soluble zinc salt in the solvent is 85-135 ℃; the reaction time of the high molecular organic ligand and the soluble zinc salt in the solvent is 42-50 hours.
6. The method of claim 1, wherein the coating has a thickness of 200 to 300 nm.
7. An ion separation membrane prepared by the method of claim 1, comprising:
a porous base film;
a polymer metal organic framework layer attached to the surface of the porous base membrane;
the polymer metal organic framework layer is formed by a polymer metal organic framework.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711007346.4A CN107759802B (en) | 2017-10-25 | 2017-10-25 | Preparation method of high-molecular organic ligand, preparation method of high-molecular metal organic framework, ion separation membrane and preparation method of ion separation membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711007346.4A CN107759802B (en) | 2017-10-25 | 2017-10-25 | Preparation method of high-molecular organic ligand, preparation method of high-molecular metal organic framework, ion separation membrane and preparation method of ion separation membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107759802A CN107759802A (en) | 2018-03-06 |
| CN107759802B true CN107759802B (en) | 2020-05-01 |
Family
ID=61270110
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711007346.4A Active CN107759802B (en) | 2017-10-25 | 2017-10-25 | Preparation method of high-molecular organic ligand, preparation method of high-molecular metal organic framework, ion separation membrane and preparation method of ion separation membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107759802B (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103846013A (en) * | 2012-12-05 | 2014-06-11 | 中国科学院大连化学物理研究所 | Porous material-polymer gas separation composite membrane |
| US10201803B2 (en) * | 2015-06-09 | 2019-02-12 | The Regents Of The University Of California | Polymer-metal organic framework materials and methods of using the same |
| CN106390765B (en) * | 2015-07-27 | 2019-04-05 | 北京工业大学 | A kind of doping covalent organic framework material prior-alcohol-permeacomposite composite membrane and preparation method |
| CN106588951B (en) * | 2017-01-23 | 2019-01-01 | 辽宁大学 | A kind of porous metal-organic framework compound and its preparation method and application based on zinc |
-
2017
- 2017-10-25 CN CN201711007346.4A patent/CN107759802B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107759802A (en) | 2018-03-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shan et al. | Influences of deprotonation and modulation on nucleation and growth of UiO-66: Intergrowth and Orientation | |
| CN102617646B (en) | Preparation method of nanoscale metal organic framework materials | |
| CN109763333B (en) | Method for preparing metal organic framework through modified carrier | |
| US10300478B2 (en) | Bipolar ion exchange sheet and manufacturing method therefor | |
| KR101845108B1 (en) | Quaternised polybenzimidazole | |
| JP2020518964A (en) | Battery separator membrane and battery using the same | |
| TW200815518A (en) | Polymeric electrolyte material, polymeric electrolyte article thereof and method for manufacturing the same, membrane electrode complex and solid polymeric fuel cell | |
| WO2009031676A1 (en) | Microphase separated structure film and process for producing the microphase separated structure film | |
| CN106866497B (en) | A kind of norborneol vinyl compound and its preparation method and application | |
| JP4137583B2 (en) | Use of sulfonic, phosphonic and phosphoric acids as dopants for polyaniline and conductive polyaniline based composites | |
| JP6767034B2 (en) | Composite nanofibers and electrolyte membranes containing the nanofibers | |
| KR20150064457A (en) | Separation membrane, and water treatment device using said separation membrane | |
| Zhang et al. | Efficiently boosting moisture retention capacity of porous superprotonic conducting MOF-802 at ambient humidity via forming a hydrogel composite strategy | |
| Sun et al. | Continuous covalent organic frameworks membranes: from preparation strategies to applications | |
| CN107722289B (en) | Organic ligand for MOF (metal organic framework), preparation method of organic ligand, separation membrane containing organic ligand MOF and preparation method of separation membrane | |
| CN114456339B (en) | Covalent organic framework film with high ionic group content, preparation method and application thereof | |
| Yang et al. | Hydrogen-bonded organic framework membrane with efficient proton conduction | |
| KR20120060645A (en) | Polyarylene ether copolymer having cation-exchange group, process of manufacturing the same, and use thereof | |
| CN107759802B (en) | Preparation method of high-molecular organic ligand, preparation method of high-molecular metal organic framework, ion separation membrane and preparation method of ion separation membrane | |
| JP2015122308A (en) | High polymer electrolyte, film electrode assembly and solid polymer-type fuel cell | |
| WO2018038049A1 (en) | Surface-modified nanofibers, electrolyte membrane, method for producing electrolyte membrane, membrane electrode assembly and solid polymer fuel cell | |
| TW201031676A (en) | Polymeric laminates, processes for producing the same, and use thereof | |
| EP3222349A1 (en) | Bipolar ion exchange sheet and manufacturing method therefor | |
| Sun et al. | ‘Proton escalator’PEI and phosphotungstic acid containing nanofiber membrane with remarkable proton conductivity | |
| Zeng et al. | Anionic MOFs Embedded in Anion-Exchange Membranes for the Separation of Lithium/Magnesium Cations |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |