CN107722289B - Organic ligand for MOF (metal organic framework), preparation method of organic ligand, separation membrane containing organic ligand MOF and preparation method of separation membrane - Google Patents
Organic ligand for MOF (metal organic framework), preparation method of organic ligand, separation membrane containing organic ligand MOF and preparation method of separation membrane Download PDFInfo
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Abstract
The invention provides an organic ligand for MOF, which has a structure shown in a formula (I), wherein x is 7-10, and n is 20-30. The invention provides an organic ligand MOF, wherein a coordination metal in the organic ligand MOF is iron. The invention also provides a separation membrane containing organic ligand MOF, which comprises a base membrane and the organic ligand MOF compounded on the surface of the base membrane. According to the invention, the specific chemical structure of the organic ligand is selected from the regulation and control of the MOF pore size, the specific coordination metal is combined, the influence of the MOF growth environment and the matrix structure is combined, the selective separation of ions is researched, the MOF framework size is accurately regulated and controlled, and the selective separation of ions is realized based on the pore size sieving effect, so that the selective adsorption separation in a multi-valence ion solution system is better realized.
Description
Technical Field
The invention relates to the technical field of metal-organic framework compound nano materials, and relates to an organic ligand and a preparation method thereof, an organic ligand MOF, a separation membrane and a preparation method thereof, in particular to an organic ligand for MOF and a preparation method thereof, an organic ligand MOF, a separation membrane containing the organic ligand MOF and a preparation method thereof.
Background
Metal-Organic Frameworks (MOFs), generally referred to as Metal-Organic Frameworks (MOFs), are crystalline materials having a periodic infinite network structure formed by a self-assembly process of Metal ions or Metal clusters and Organic ligands, which have Organic-inorganic hybrid characteristics, ordering and controllability of a crystal structure, microporosity, special optical, electrical and magnetic properties, and industrial potential applications, and thus become one of the hot research fields of current novel functional materials.
MOF materials have the characteristics of porosity and large specific surface area, which are important properties for catalysis, gas adsorption and separation, and thus one of the main purposes of continuously changing the metal centers and linker arms of MOFs materials in the existing research is to make the materials have larger specific surface area. The MOF material also has structural and functional diversity, the structural and functional diversity is caused by the variable metal center and the organic ligand, the selection of the metal center almost covers all metals including main group elements, transition elements, lanthanide series metals and the like, wherein Zn, Cu, Zr and the like are more applied. Different materials are caused by different valence states and coordination abilities of different metals, and the application range of the MOFs materials is greatly widened by the combination of different functional groups. Similarly, MOFs also have unsaturated metal sites to which unsaturated metal centers bind to meet coordination requirements due to the presence of small solvent molecules during the preparation process, which can be removed by heating or vacuum treatment to expose the unsaturated metal sites. The exposed unsaturated metal sites can achieve the effects of gas adsorption and separation, and can also be coordinated with substances with amino or carboxyl, so that the MOFs material can be used as an effective tool for separating drug carriers or peptide fragments. In addition, the MOFs material containing unsaturated metal sites can also be used as a catalyst for catalyzing the reaction to accelerate the reaction. The MOF material has the advantages of crystal framework openness, pore channel adjustability, ultrahigh specific surface area, framework composition diversity, composition designability, excellent surface post-modification property, post-functionalization and the like, so that the MOF material has a huge application prospect in various fields, particularly in the adsorption field.
However, the main focus of interest in adsorptive separation of MOF materials is on adsorptive separation of gas mixtures, while relatively little attention has been paid to liquid phase adsorption and separation. However, with the continuous development of MOF materials, especially with the reports of MOF materials with stable solution systems, the industry has also gradually focused on the adsorptive separation of solution systems. However, the application of the existing MOF material in ion separation is still only in the preliminary exploration stage, which not only has great difficulty in applicability, but also needs to be studied deeply for its own characteristics, such as size regulation, charge, stability of MOF framework, and controllability and cyclicity of MOF layer thickness.
Therefore, how to obtain a MOF material having an ion selective separation function and broaden the application of MOF in the field of ion selective separation has become one of the focuses of great concern to many prospective researchers in the industry.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an organic ligand for MOF and a preparation method thereof, an organic ligand MOF, a separation membrane containing the organic ligand MOF and a preparation method thereof.
The invention provides an organic ligand for MOF, which has a structure shown in a formula (I);
wherein x is 7-10, and n is 20-30.
The invention provides a preparation method of an organic ligand for MOF, which comprises the following steps:
1) mixing diester terephthalate, bromo-1-olefin, an acid-binding agent and a first solvent, and then carrying out condensation reaction to obtain a double-bond monomer;
2) under the action of a catalyst, carrying out polymerization reaction on the intermediate containing the double bonds obtained in the step in a second solvent to obtain a polymer containing a terephthalic acid diester structure;
3) and (3) carrying out hydrolysis reaction on the polymer containing the terephthalic acid diester structure obtained in the step and alkali in a third solvent, and then reacting with an acidic substance to obtain the organic ligand for the MOF.
Preferably, the phthalic acid diester comprises one or more of diethyl terephthalate, dipropyl terephthalate, and dibutyl terephthalate;
the bromo-1-olefin comprises one or more of 7-bromo-1-heptene, 8-bromo-1-octene, 9-bromo-1-nonene, and 10-bromo-1-decene;
the acid-binding agent comprises one or more of potassium carbonate, triethylamine, pyridine and diisopropylethylamine;
the first solvent comprises one or more of N, N-dimethylformamide, N-diethylformamide, N-dimethylacetamide, N-diethylacetamide and N-methylpyrrolidone;
the molar ratio of the terephthalic acid diester to the bromo-1-olefin is (3.0-3.4): (12.0-13.6);
the molar ratio of the terephthalic acid diester to the acid-binding agent is (0.1-0.5): 1;
the molar ratio of the first solvent to the terephthalic acid diester is (90-100): 1;
the temperature of the condensation reaction is 70-90 ℃; the condensation reaction time is 20-24 h.
Preferably, the catalyst comprises one or more of a first generation Grubbs catalyst, a second generation Grubbs catalyst and a third generation Grubbs catalyst;
the second solvent comprises one or more of dichloromethane, chloroform, dichloroethane and ethyl chloride;
the molar ratio of the double bond-containing monomer to the catalyst is (3.0-3.4): (0.03-0.034);
the molar ratio of the second solvent to the double-bond-containing monomer is (300-350): 1;
the temperature of the polymerization reaction is 30-50 ℃; the polymerization reaction time is 6-8 h.
Preferably, the base comprises one or more of potassium hydroxide, sodium hydroxide, ammonium hydroxide and triethylamine;
the acidic substance comprises hydrochloric acid and/or sulfuric acid;
the third solvent comprises one or more of N, N-dimethylformamide, N-diethylformamide, dimethyl sulfoxide, N-dimethylacetamide and N, N-diethylacetamide;
the molar ratio of the base to the polymer containing a terephthalic acid diester structure is (1.0-2.0): 1;
the pH value of the solution is 1-2 when the solution reacts with an acidic substance;
the molar ratio of the third solvent to the polymer containing a terephthalic acid diester structure is (450-500): 1;
the temperature of the hydrolysis reaction is 80-100 ℃; the hydrolysis reaction time is 10-12 h.
The invention provides an organic ligand MOF, wherein a coordination metal in the organic ligand MOF is iron;
the organic ligand in the organic ligand MOF is the organic ligand described in the above technical scheme or the organic ligand prepared by the preparation method described in any one of the above technical schemes.
The invention provides a separation membrane containing organic ligand MOF, which comprises a base membrane and the organic ligand MOF compounded on the surface of the base membrane;
the organic ligand MOF is the organic ligand MOF in the technical scheme.
Preferably, the surface of the separation membrane is densely grown with organic ligand MOF;
the thickness of the separation membrane is 150-200 mu m;
the base film is made of one or more of brominated polyphenylene oxide, polybenzimidazole, polyethersulfone ketone and polyetheretherketone;
the basement membrane is a finger-shaped hole basement membrane or a spongy hole basement membrane;
the thickness of the base film is 90-150 mu m.
The invention provides a preparation method of a separation membrane containing organic ligand MOF, which comprises the following steps:
A) putting the base membrane into a mixed solution of an organic ligand, a mineralizer, a soluble ferric salt and an organic solvent, and reacting to obtain a separation membrane containing the organic ligand MOF;
the organic ligand is the organic ligand described in the technical scheme or the organic ligand prepared by the preparation method described in any one of the technical schemes.
Preferably, the mineralizer comprises one or more of formic acid, hydrochloric acid and benzoic acid;
the soluble ferric salt comprises one or more of ferric trichloride, ferric sulfate and ferric nitrate;
the organic solvent comprises one or more of N, N-diethylformamide, N-dimethylformamide, N-dimethylacetamide, N-diethylacetamide and N-methylpyrrolidone;
the mass ratio of the mineralizer to the organic ligand is (70-90): 1;
the molar ratio of the organic ligand to the soluble iron salt is (0.02-0.04): (0.02-0.04);
the mass ratio of the organic solvent to the organic ligand is (110-130): 1;
the reaction temperature is 110-130 ℃; the reaction time is 36-48 h.
The invention provides an organic ligand for MOF, which has a structure shown as a formula (I). The invention provides an organic ligand MOF, wherein a coordination metal in the organic ligand MOF is iron. The invention also provides a separation membrane containing organic ligand MOF, which comprises a base membrane and the organic ligand MOF compounded on the surface of the base membrane. Compared with the prior art, the invention only establishes selective separation based on the utilization of the pore size and framework chemical modification of the MOF aiming at the prior MOF applicability research, and has limitations. The invention creatively selects the chemical structure of a specific organic ligand from the regulation and control of the MOF pore size, combines specific coordination metal, and then combines the influences of the MOF growth environment and the matrix structure to study the selective separation of ions, accurately regulates and controls the MOF framework size, and realizes the selective separation of ions based on the pore size sieving effect, thereby better realizing the selective adsorption and separation in a multi-valence state ion solution system.
The separation membrane containing organic ligand MOF provided by the invention takes an organic porous polymer substrate as a supporting layer, and takes functional groups on the surface of a polymer and an additional macromolecular organic ligand to participate in the construction and growth of a MOF dense layer membrane. The design of the porous polymer layer reduces the transmission resistance of ions in the film, so that the adverse effects of surface resistance increase and ion flux reduction caused by the surface MOF dense layer can be counteracted, meanwhile, the existence of the porous structure of the polymer base and the surface functional groups is more favorable for the growth of the MOF structure, and the adhesive force of the MOF layer and the porous base film is improved. The invention creatively uses the high molecular organic ligand to replace the organic micromolecular ligand, can enhance the capacity of precisely regulating the MOF framework pore size structure, is beneficial to screening multivalent ions, promotes the transmission of monovalent ions, and improves the chemical stability of the MOF layer due to the introduction of the high molecular chain.
The experimental result shows that the MOF-based separation membrane containing the high-molecular organic ligand provided by the invention utilizes the aperture sieving effect of the MOF to separate the mono/divalent ions in a solution system, and Na is contained in the film+With Mg2+The separation rate was 19.12 and Na+Flux of 100.57 x 10-10mol/cm2/s。
Drawings
FIG. 1 is a schematic flow chart of a preparation process of an iron-based MOF containing a high molecular organic ligand provided by the invention;
FIG. 2 is a scanning electron microscope image of the surface of the iron-based MOF separation layer membrane containing the polymeric organic ligand prepared in example 1 of the present invention.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are included merely to further illustrate the features and advantages of the invention and are not intended to limit the invention to the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in their purity, and the present invention preferably employs a purity that is conventional in the field of analytical purification or MOF nanomaterials.
The invention provides an organic ligand for MOF, which is characterized in that the organic ligand has a structure shown in a formula (I);
wherein x is 7-10, and n is 20-30.
The meaning of the group in the structure shown in formula (I) is not particularly limited in the present invention, and the group known to those skilled in the art may be used to represent the conventional meaning, and those skilled in the art may select and adjust the meaning according to the actual application situation, the raw material situation and the product requirement,
in the structure represented by formula (I), x is preferably 7 to 10, more preferably 8 to 9, and specifically may be any one of 7, 8, 9, or 10. In the invention, n is preferably 20-30, more preferably 22-28, and more preferably 24-26.
The Organic ligand for MOF (metal Organic frameworks) provided by the invention is a high-molecular Organic ligand, each repeating unit of the Organic ligand contains a terephthalic acid structure, so that a coordination structure can be conveniently formed with metal ions in the subsequent MOF preparation, and meanwhile, a terminal double bond can be subjected to further reaction to improve the separation performance of the Organic ligand.
The invention provides a preparation method of an organic ligand for MOF, which comprises the following steps:
1) mixing diester terephthalate, bromo-1-olefin, an acid-binding agent and a first solvent, and then carrying out condensation reaction to obtain a double-bond monomer;
2) under the action of a catalyst, carrying out polymerization reaction on the intermediate containing the double bonds obtained in the step in a second solvent to obtain a polymer containing a terephthalic acid diester structure;
3) and (3) carrying out hydrolysis reaction on the polymer containing the terephthalic acid diester structure obtained in the step and alkali in a third solvent, and then reacting with an acidic substance to obtain the organic ligand for the MOF.
Firstly, mixing diester terephthalate, bromo-1-olefin, an acid-binding agent and a first solvent, and then carrying out condensation reaction to obtain a double-bond monomer.
The selection of the phthalic acid diester is not particularly limited by the present invention, and may be a conventional phthalic acid diester known to those skilled in the art, and those skilled in the art may select and adjust the diester according to the actual application, raw material conditions, and product requirements, and the present invention further improves the final product performance to facilitate the production application by ensuring the effect of selective separation, and the phthalic acid diester preferably includes one or more of diethyl terephthalate, dipropyl terephthalate, and dibutyl terephthalate, and more preferably diethyl terephthalate, dipropyl terephthalate, or dibutyl terephthalate.
The invention has no special restriction on the selection of the bromo-1-olefin, and the conventional bromo-1-olefin known by the technicians in the field can be used, and the technicians in the field can select and adjust the bromo-1-olefin according to the actual application condition, the raw material condition and the product requirement, in order to ensure the effect of selective separation, further improve the product performance of the final product, be beneficial to production and application, the bromo-1-olefin preferably comprises one or more of 7-bromo-1-heptene, 8-bromo-1-octene, 9-bromo-1-nonene, and 10-bromo-1-decene, more preferably 7-bromo-1-heptene, 8-bromo-1-octene, 9-bromo-1-nonene, or 10-bromo-1-decene.
The acid-binding agent is not particularly limited in selection, and can be selected and adjusted by a conventional acid-binding agent known by a person skilled in the art according to the actual application situation, the raw material situation and the product requirement.
The first solvent is not particularly limited and may be selected and adjusted by a person skilled in the art according to practical application, raw material conditions and product requirements, and preferably includes one or more of N, N-dimethylformamide, N-diethylformamide, N-dimethylacetamide, N-diethylacetamide and N-methylpyrrolidone, more preferably N, N-dimethylformamide, N-diethylformamide, N-dimethylacetamide, N-diethylacetamide or N-methylpyrrolidone, and still more preferably N, N-dimethylformamide.
The addition amount of the raw materials is not particularly limited, and can be selected and adjusted according to the actual production situation, the raw material situation and the product requirement by the skilled in the art, and in order to further improve the final product performance, perfect and optimize the reaction process, the molar ratio of the terephthalic acid diester to the bromo-1-olefin is (3.0-3.4): (12.0 to 13.6), more preferably (3.05 to 3.35): (12.0 to 13.6), more preferably (3.1 to 3.3): (12.0-13.6), or (3.0-3.4): (12.2-13.4), or (3.0-3.4): (12.5-13.1), or (3.0-3.4): (12.7 to 12.9), most preferably 3.2: 12.8. the preferable molar ratio of the terephthalic acid diester to the acid-binding agent is (0.1-0.5): 1, more preferably (0.15 to 0.45): 1, more preferably (0.2 to 0.4): 1, more preferably (0.25 to 0.35): 1. the molar ratio of the first solvent to the terephthalic acid diester is preferably (90-100): 1, more preferably (92-98): 1, more preferably (94-96): 1.
the parameters of the condensation reaction are not particularly limited, and the parameters of the conventional condensation reaction well known by the technical personnel in the field can be selected and adjusted by the technical personnel in the field according to the actual production situation, the raw material situation and the product requirement, the temperature of the condensation reaction is preferably 70-90 ℃, more preferably 72-88 ℃, and more preferably 75-85 ℃ in order to further improve the performance of the final product, perfect and optimize the reaction process. The time of the condensation reaction is preferably 20-24 hours, more preferably 20.5-23.5 hours, and more preferably 21-23 hours.
In order to further improve the reaction effect and complete and optimize the reaction process, the preparation process specifically comprises the following steps:
dissolving diester terephthalate, bromo-1-olefin and acid-binding agent in a first solvent, carrying out condensation reaction on the solution at a certain temperature for a period of time, filtering out the acid-binding agent, evaporating the liquid phase to obtain a double-bond-containing monomer,
the invention then carries out polymerization reaction on the intermediate containing double bonds obtained in the step in a second solvent under the action of a catalyst to obtain the polymer containing the terephthalic acid diester structure.
The catalyst is selected without any particular limitation, and may be selected and adjusted according to practical application conditions, raw material conditions and product requirements, and the catalyst is preferably selected from one or more of first-generation Grubbs catalysts, second-generation Grubbs catalysts and third-generation Grubbs catalysts, more preferably selected from first-generation Grubbs catalysts, second-generation Grubbs catalysts and third-generation Grubbs catalysts, and even more preferably selected from second-generation Grubbs catalysts and third-generation Grubbs catalysts.
The second solvent is not particularly limited and may be selected from conventional organic solvents known to those skilled in the art, and may be selected and adjusted by those skilled in the art according to practical application, raw material conditions and product requirements, and preferably includes one or more of dichloromethane, chloroform, dichloroethane and ethyl chloride, more preferably dichloromethane, chloroform, dichloroethane or ethyl chloride, and still more preferably dichloromethane.
The addition amount of the raw materials is not particularly limited, and can be selected and adjusted according to the actual production situation, the raw material situation and the product requirement by the skilled in the art, and in order to further improve the final product performance, perfect and optimize the reaction process, the molar ratio of the double bond-containing monomer to the catalyst is preferably (3.0-3.4): (0.03 to 0.034), more preferably (3.05 to 3.35): (0.03 to 0.034), more preferably (3.1 to 3.3): (0.03-0.034), or (3.0-3.4): (0.0305-0.0335), or (3.0-3.4): (0.031-0.033), most preferably 3.2: 0.032. the molar ratio of the second solvent to the double bond-containing monomer is preferably (300-350): 1, more preferably (310-340): 1, more preferably (320 to 330): 1.
the parameters of the polymerization reaction are not particularly limited, and the parameters of the conventional polymerization reaction well known to a person skilled in the art can be selected and adjusted by the person skilled in the art according to the actual production situation, the raw material situation and the product requirements, and in order to further improve the performance of the final product, perfect and optimize the reaction process, the temperature of the polymerization reaction is preferably 30-50 ℃, more preferably 32-48 ℃, and more preferably 35-45 ℃. The time of the polymerization reaction is preferably 6 to 8 hours, more preferably 6.3 to 7.8 hours, and more preferably 6.5 to 7.5 hours.
In order to further improve the reaction effect and complete and optimize the reaction process, the preparation process specifically comprises the following steps:
the invention dissolves the double bond monomer obtained in the above steps in a second solvent, uses a catalyst to carry out polymerization reaction at a certain temperature to obtain a polymer containing a terephthalic acid diester structure (a polymer chain containing the terephthalic acid diester structure), then precipitates the polymer in methanol, and dries the polymer.
Finally, the polymer containing the terephthalic acid diester structure obtained in the step is subjected to hydrolysis reaction with alkali in a third solvent, and then is subjected to reaction with an acidic substance, so as to obtain the organic ligand for the MOF.
The base used in the present invention is not particularly limited, and may be selected and adjusted by those skilled in the art according to the actual application, raw material conditions and product requirements, and may be any base conventionally used in hydrolysis reactions, and preferably includes one or more of potassium hydroxide, sodium hydroxide, ammonium hydroxide and triethylamine, more preferably potassium hydroxide, sodium hydroxide, ammonium hydroxide or triethylamine, and still more preferably potassium hydroxide.
The choice of the acidic substance in the present invention is not particularly limited, and the acidic substance can be selected from those conventionally used in hydrolysis reaction, which are well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to the actual application, raw material condition and product requirement.
The third solvent is not particularly limited, and may be selected and adjusted by a person skilled in the art according to practical application, raw material conditions and product requirements, and preferably includes one or more of N, N-dimethylformamide, N-diethylformamide, dimethylsulfoxide, N-dimethylacetamide and N, N-diethylacetamide, more preferably N, N-dimethylformamide, N-diethylformamide, dimethylsulfoxide, N-dimethylacetamide or N, N-diethylacetamide, and still more preferably dimethylsulfoxide.
The addition amount of the raw materials is not particularly limited, and can be selected and adjusted by the ordinary addition amount well known by the technicians in the field according to the actual production situation, raw material situation and product requirements, and in order to further improve the final product performance, perfect and optimize the reaction process, the molar ratio of the alkali to the polymer containing the terephthalic acid diester structure is preferably (1.0-2.0): 1, more preferably (1.2 to 1.8): 1, more preferably (1.4 to 1.6): 1. the molar ratio of the third solvent to the polymer containing a terephthalic acid diester structure is preferably (450 to 500): 1, more preferably (460 to 490): 1, more preferably (470-480): 1.
the parameters of the hydrolysis reaction are not particularly limited, and the parameters of the conventional hydrolysis reaction well known to a person skilled in the art can be selected and adjusted by the person skilled in the art according to the actual production situation, the raw material situation and the product requirements, and in order to further improve the performance of the final product, perfect and optimize the reaction process, the temperature of the hydrolysis reaction is preferably 80-100 ℃, more preferably 83-98 ℃, and more preferably 85-95 ℃. The time of the hydrolysis reaction is preferably 10-12 hours, more preferably 10.3-11.8 hours, and more preferably 10.5-11.5 hours.
The amount of the acidic substance added in the present invention is not particularly limited, and may be a conventional amount of acid added after hydrolysis reaction, which is well known to those skilled in the art, and may be selected and adjusted by those skilled in the art according to actual production conditions, raw material conditions, and product requirements, and the amount of the acidic substance added in the present invention, that is, the pH value during the reaction (and the pH value during the reaction of the acidic substance) is preferably 1 to 2, more preferably 1, 1.5, or 2.
The parameters of the reaction (reaction by adding an acidic substance) are not particularly limited in the present invention, and those skilled in the art can select and adjust the parameters according to actual production conditions, raw material conditions and product requirements.
In order to further improve the reaction effect and complete and optimize the reaction process, the preparation process specifically comprises the following steps:
the polymer obtained in the step and alkali are dissolved in a third solvent, hydrolysis reaction is carried out at a certain temperature until the solution is clear, the pH value of the solution is adjusted to be acidic, namely, a solid is generated, and the solid is repeatedly washed by methanol and acetone to obtain an organic ligand for MOF, namely, a high molecular material with a double-bond terephthalic acid structure.
Specifically, when the phthalic acid diester is diethyl terephthalate, the above reaction formulae for preparing the organic ligand for MOF of the present invention are shown in the following formulas (1) to (3):
according to the organic ligand for MOF and the preparation method thereof, the organic ligand with a specific chemical structure is selected, the main structure of the organic ligand, the length of the branched chain and the functional group are adopted, so that the high-molecular organic ligand is automatically synthesized, the pore diameter of the organic ligand can be flexibly regulated and controlled according to the application condition after the organic ligand is coordinated into the MOF structure, compared with the traditional MOF structure which takes an inorganic material as a base material, the MOF structure grows on the surface of the organic porous base, and a layer of compact MOF crystal film can be formed.
The invention provides an organic ligand MOF, wherein a coordination metal in the organic ligand MOF is iron;
the organic ligand in the organic ligand MOF is the organic ligand described in the above technical scheme or the organic ligand prepared by the preparation method described in any one of the above technical schemes.
The definition of the MOF, i.e., the metal-organic framework material, is not particularly limited by the present invention, and may be in the concept of conventional metal-organic framework materials or MOFs well known to those skilled in the art. The organic ligand in the MOF material is the organic ligand in the technical scheme or the organic ligand prepared by the preparation method in any one of the technical schemes, and the coordination metal is iron.
The selection range and the optimization principle of the materials or the structures in the organic ligand MOF are consistent with those of the organic ligand used for MOF and the preparation method thereof, and the details are not repeated herein.
The invention provides a separation membrane containing organic ligand MOF, which comprises a base membrane and the organic ligand MOF compounded on one side of the base membrane;
the organic ligand MOF is the organic ligand MOF in the technical scheme.
The selection range and the optimization principle of the material or the structure of the organic ligand MOF in the separation membrane are consistent with those of the organic ligand MOF, and the details are not repeated here.
The selection of the base membrane is not particularly limited, and the base membrane can be selected and adjusted by a person skilled in the art according to actual production conditions, raw material conditions and product requirements, and is preferably a finger-shaped pore base membrane or a spongy pore base membrane, and the material of the base membrane preferably comprises one or more of brominated polyphenylene oxide, polybenzimidazole, polyethersulfone ketone and polyetheretherketone, and more preferably is brominated polyphenylene oxide, polybenzimidazole, polyethersulfone ketone or polyetheretherketone. The parameters of the base film are not particularly limited, and the parameters of the conventional base film for the separation membrane well known to those skilled in the art can be selected and adjusted by those skilled in the art according to actual production conditions, raw material conditions and product requirements, and the thickness of the base film is preferably 90 to 150 μm, more preferably 100 to 140 μm, more preferably 110 to 130 μm, and more preferably 115 to 125 μm.
The definition of the composite is not particularly limited by the present invention, and may be defined by a conventional composite known to those skilled in the art, and those skilled in the art can select and adjust the definition according to actual production conditions, raw material conditions and product requirements, and the composite of the present invention is preferably one or more of growth, bonding, grafting, deposition, coating and semi-coating, more preferably growth, bonding or grafting, more preferably growth, and specifically may be dense growth, that is, the surface of the separation membrane is densely grown with organic ligand MOF.
The separation membrane containing the organic ligand MOF can be considered to have a multi-layer structure, and comprises a base membrane layer and an organic ligand MOF layer compounded on one side surface of the base membrane layer. The organic ligand MOF layer (MOF separation layer) of the present invention is preferably a dense MOF layer containing polymeric organic ligands.
The invention has no special limitation on the performance parameters of the separation membrane containing the organic ligand MOF, and a person skilled in the art can obtain specific performance parameters after preparing the separation membrane according to the product, the method or the subsequent method, but can select and adjust the performance parameters according to the actual application condition, the raw material condition and the product requirement.
The separation membrane of the MOF layer of the meaning polymer organic ligand provided by the invention fully utilizes the aperture sieving effect of the MOF layer to separate ions, and the organic ligands are linked through a polymer chain, so that the separation membrane further plays a role in regulating and controlling MOF pore passages, and provides a wide prospect for the application of the membrane in ion separation, especially in liquid-phase multi-valence ion selective separation.
The invention also provides a preparation method of the separation membrane containing organic ligand MOF, which comprises the following steps:
A) putting the base membrane into a mixed solution of an organic ligand, a mineralizer, a soluble ferric salt and an organic solvent, and reacting to obtain a separation membrane containing the organic ligand MOF;
the organic ligand is the organic ligand described in the technical scheme or the organic ligand prepared by the preparation method described in any one of the technical schemes.
The selection range and the optimization principle of the materials or the structures in the preparation method of the separation membrane are consistent with those of the separation membrane containing the organic ligand MOF, and the details are not repeated herein.
The selection of the base membrane is not particularly limited in the present invention, and may be a conventional base membrane for a separation membrane well known to those skilled in the art, which may be selected and adjusted according to actual production conditions, raw material conditions, and product requirements, and the base membrane is preferably a porous base membrane, more preferably a finger-shaped pore base membrane or a sponge-shaped pore base membrane; the material of the base film preferably comprises one or more of brominated polyphenylene oxide, polybenzimidazole, polyethersulfone ketone and polyetheretherketone, and more preferably comprises brominated polyphenylene oxide, polybenzimidazole, polyethersulfone ketone or polyetheretherketone.
The selection of the mineralizer is not particularly limited by the present invention, and may be a mineralizer for preparing MOF materials, which is well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to actual production conditions, raw material conditions and product requirements, and the mineralizer of the present invention preferably comprises one or more of formic acid, hydrochloric acid and benzoic acid, more preferably formic acid, hydrochloric acid or benzoic acid, and most preferably formic acid.
The selection of the soluble ferric salt is not particularly limited by the present invention, and can be selected and adjusted by those skilled in the art according to actual production conditions, raw material conditions and product requirements, and the soluble ferric salt preferably comprises one or more of ferric trichloride, ferric sulfate and ferric nitrate, more preferably ferric trichloride, ferric sulfate or ferric nitrate, and most preferably ferric trichloride.
The selection of the organic solvent is not particularly limited in the present invention, and may be an organic solvent for such a reaction well known to those skilled in the art, and those skilled in the art can select and adjust the organic solvent according to actual production conditions, raw material conditions, and product requirements, and the organic solvent of the present invention preferably includes one or more of N, N-diethylformamide, N-dimethylformamide, N-dimethylacetamide, N-diethylacetamide, and N-methylpyrrolidone, more preferably N, N-diethylformamide, N-dimethylformamide, N-dimethylacetamide, N-diethylacetamide, or N-methylpyrrolidone, and more preferably N, N-diethylformamide.
The addition amount of the mineralizer is not particularly limited in the invention, and the mineralizer for such reaction is added, which is well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to actual production conditions, raw material conditions and product requirements, and the mass ratio of the mineralizer to the organic ligand in the invention is preferably (70-90): 1, more preferably (73 to 88): 1, more preferably (75-85): 1.
the adding amount of the soluble iron salt is not particularly limited, and the adding amount of the soluble iron salt for the reaction, which is well known to those skilled in the art, can be selected and adjusted by those skilled in the art according to actual production conditions, raw material conditions and product requirements, and the molar ratio of the organic ligand to the soluble iron salt is preferably (0.02-0.04): (0.02-0.04), more preferably (0.024-0.036): (0.02-0.04), more preferably (0.028-0.032): (0.02-0.04), or (0.022-0.038): (0.02-0.04), or (0.024-0.036): (0.02-0.04), or (0.026-0.034): (0.02-0.04).
The adding amount of the organic solvent is not particularly limited, the adding amount of the organic solvent for the reaction known by the technicians in the field can be used, the technicians in the field can select and adjust the adding amount according to the actual production situation, the raw material situation and the product requirement, and the mass ratio of the organic solvent to the organic ligand is (110-130): 1, more preferably (113 to 127): 1, more preferably (115-125): 1.
the parameters of the reaction are not particularly limited, and the parameters of the reaction known to those skilled in the art can be selected and adjusted by those skilled in the art according to actual production conditions, raw material conditions and product requirements, and the temperature of the reaction is preferably 110-130 ℃, more preferably 117-127 ℃, and more preferably 115-125 ℃; the reaction time is preferably 36-48 h, more preferably 38-46 h, and more preferably 40-44 h. The reaction according to the invention is preferably a solvothermal reaction.
In order to further improve the reaction effect and complete and optimize the reaction process, the preparation process specifically comprises the following steps:
ultrasonically dissolving the obtained double-bond-containing terephthalic acid structure polymer, soluble ferric salt and mineralizer in a fourth solvent to obtain a mixed solution, putting the mixed solution into a reaction kettle, putting the porous base membrane into the reaction kettle, and carrying out solvothermal reaction at a certain temperature to obtain a separation membrane containing organic ligands MOF, namely an iron-based MOF separation membrane containing polymer organic ligands.
Specifically, when the phthalic acid diester is diethyl terephthalate, in the separation membrane containing the organic ligand iron-based MOF of the present invention, the reaction formula for preparing the organic ligand iron-based MOF is shown as the following formula:
the steps of the invention provide an organic ligand for MOF and a preparation method thereof, the organic ligand MOF, a separation membrane containing organic ligand MOF and a preparation method thereof. According to the invention, a specific chemical structure of an organic ligand is selected from the regulation and control of the MOF pore size, a specific coordination metal is combined, the influence of the MOF growth environment and the matrix structure is combined, the selective separation of ions is researched, the MOF framework size is accurately regulated and controlled, and the selective separation of ions is realized based on the pore size sieving effect, so that the selective adsorption and separation in a multi-valence ion solution system are better realized.
The MOF ion selective separation membrane based on the high molecular organic ligand creatively takes a high molecular chain to replace organic micromolecules as organic ligands to be introduced into an MOF framework structure, and the configuration of a framework is regulated, so that the purpose of pore size screening is achieved, and the MOF is introduced into an organic porous base surface layer through a self-growth method, so that the selectivity of the membrane can be improved, and the ion flux can be increased. The invention takes the self-growth of novel MOF materials on the surface of a porous organic polymer material as a leading factor, and obtains more efficient and stable MOF layer membrane materials for the anion separation process by accurately regulating and controlling the sizes of the pore passages of an MOF framework, thereby expanding the types of the MOF materials, providing theoretical and technical support for the MOF materials to realize the selective separation of ions in a solution system from the application level and further finish the efficient separation of anions with different valence states, and having important scientific significance and wide application prospect. The invention provides theoretical basis and practical basis for the precise construction of the MOF selective separation membrane and the application of the MOF selective separation membrane in the fields of seawater concentration salt making, mixed acid recovery and separation and the like and single/multivalent anion selective separation.
The experimental result shows that the MOF-based separation membrane containing the high-molecular organic ligand provided by the invention utilizes the aperture sieving effect of the MOF to separate the mono/divalent ions in a solution system, and Na is contained in the film+With Mg2+The separation rate was 19.12 and Na+Flux of 100.57 x 10-10mol/cm2/s。
In order to further illustrate the present invention, the following detailed description of an organic ligand and a preparation method thereof, an organic ligand MOF, a separation membrane and a preparation method thereof provided by the present invention are provided in conjunction with examples, but it should be understood that the examples are implemented on the premise of the technical scheme of the present invention, and detailed embodiments and specific procedures are given only for further illustrating the features and advantages of the present invention, not for limiting the claims of the present invention, and the scope of the present invention is not limited to the following examples.
Example 1
1.1 preparation of a polymeric organic ligand containing a terephthalic acid Structure
3.2mmol of diethyl terephthalate, 12.0mmol of 7-bromo-1-olefin and 16.0mmol of potassium carbonate were dissolved in 24ml of N, N-dimethylformamide, and the solution was reacted at 90 ℃ for 24 hours, followed by filtration of the potassium carbonate and evaporation of the N, N-dimethylformamide to give the monomer (1).
0.3mmol of the monomer (1) and 0.032mmol of the second-generation Grubbs catalyst were dissolved in 6ml of dichloromethane, the solution was reacted at 40 ℃ for 8 hours, precipitated in 30ml of methanol and the solid was dried to give the polymer (2).
Dissolving 0.3mmol of polymer (2) and 4.5mmol of potassium hydroxide in 10ml of dimethyl sulfoxide, reacting at 90 ℃ for 12h until the solution is clear, then dropwise adding 2MHCl until the pH value of the solution is 1, and repeatedly washing the generated solid by 30ml of methanol and 30ml of acetone to obtain polymer (3) of terephthalic acid containing double bonds, namely the organic ligand.
1.2 preparation of iron-based MOF separation layer film of high molecular organic ligand
And (3) ultrasonically dissolving 0.136mmol of polymer (3), 0.111mmol of ferric trichloride and 2ml of formic acid in 4ml of N, N-diethylformamide, placing the finger-shaped hole-shaped base membrane in the solution, and reacting at 130 ℃ for 48 hours to obtain the iron-based MOF separation membrane containing the high-molecular organic ligand.
Referring to fig. 1, fig. 1 is a schematic flow chart of a preparation process of the iron-based MOF containing the polymeric organic ligand provided by the present invention.
The iron-based MOF separation layer membrane containing the polymeric organic ligand prepared in example 1 of the present invention was characterized.
Referring to fig. 2, fig. 2 is a scanning electron microscope image of the surface of the iron-based MOF separation layer film containing the polymeric organic ligand prepared in example 1 of the present invention.
As can be seen from fig. 2, since the functional groups on the surface of the base film are used to link the iron ions and then coordinate to link the high molecular organic ligands, a dense MOF layer grows on the surface of the base film, and the crystal pattern of the MOF also shows the regular octahedral structure of the MOF. Therefore, a layer of dense MOF crystal film can grow on the surface of the organic porous base.
The performance of the iron-based MOF separation layer membrane containing the high molecular organic ligand prepared in the embodiment 1 of the invention is detected.
The iron-based MOF separation layer membrane of the macromolecular organic ligand prepared by the embodiment utilizes an electrodialysis device to separate single and multivalent cations, a separation system contains sodium ions and magnesium ions, and the separation experiment result shows that the flux of the sodium ions is 80.51 x 10-10mol/cm2Magnesium ion flux of 4.56 x 10/s-10mol/cm2And/s, the separation coefficient is 17.63, so that the membrane shows better separation performance of single-valence and multi-valence cations.
Example 2
2.1 preparation of a polymeric organic ligand containing a terephthalic acid Structure
3.2mmol of diethyl terephthalate, 12.8mmol of 8-bromo-1-olefin and 16.0mmol of potassium carbonate were dissolved in 24ml of N, N-dimethylformamide, and the solution was reacted at 80 ℃ for 26 hours, followed by filtration of the potassium carbonate and evaporation of the N, N-dimethylformamide to give the monomer (1).
0.3mmol of the monomer (1) and 0.034mmol of a one-generation Grubbs catalyst were dissolved in 6ml of dichloromethane, the solution was reacted at 35 ℃ for 7 hours, it was precipitated in 30ml of methanol, and the solid was dried to give the polymer (2).
0.3mmol of the polymer (2) and 4.5mmol of potassium hydroxide were dissolved in 10ml of dimethyl sulfoxide, reacted at 100 ℃ for 10 hours until the solution was clear, 2M HCl was added dropwise until the pH of the solution became 1, and the resulting solid was washed repeatedly with 30ml of methanol and 30ml of acetone to give a polymer (3) of terephthalic acid containing double bonds.
2.2 preparation of iron-based MOF separation layer membranes of polymeric organic ligands
And (3) ultrasonically dissolving 0.101mmol of polymer (3), 0.093mmol of ferric trichloride and 2ml of formic acid in 4ml of N, N-diethylformamide, placing the finger-shaped hole-shaped base membrane in the solution, and reacting at 120 ℃ for 48 hours to obtain the iron-based MOF separation membrane containing the high-molecular organic ligand.
The performance of the iron-based MOF separation layer membrane containing the high molecular organic ligand prepared in the embodiment 2 of the invention is detected.
The iron-based MOF separation layer membrane of the macromolecular organic ligand prepared by the embodiment utilizes an electrodialysis device to separate single and multivalent cations, a separation system contains sodium ions and magnesium ions, and the separation experiment result shows that the flux of the sodium ions is 80.61 x 10-10mol/cm2Magnesium ion flux of 4.51 x 10/s-10mol/cm2And the separation coefficient is 17.86 per second, so that the membrane shows better separation performance of single-valence and multi-valence cations.
Example 3
3.1 preparation of a polymeric organic ligand containing a terephthalic acid Structure
3.4mmol of dipropyl terephthalate, 13.0mmol of 9-bromo-1-olefin and 16.0mmol of potassium carbonate are dissolved in 24ml of N, N-dimethylformamide, the solution is reacted at 70 ℃ for 20 hours, and the potassium carbonate is filtered off, and the N, N-dimethylformamide is evaporated to obtain the monomer (1).
0.3mmol of the monomer (1) and 0.034mmol of the second-generation Grubbs catalyst were dissolved in 6ml of dichloromethane, the solution was reacted at 30 ℃ for 6 hours, it was precipitated in 30ml of methanol, and the solid was dried to give the polymer (2).
0.3mmol of the polymer (2) and 4.5mmol of potassium hydroxide were dissolved in 10ml of dimethyl sulfoxide, reacted at 80 ℃ for 11 hours until the solution was clear, 2M HCl was added dropwise until the pH of the solution became 1, and the resulting solid was washed repeatedly with 30ml of methanol and 30ml of acetone to give a polymer (3) of terephthalic acid containing double bonds.
3.2 preparation of iron-based MOF separation layer membranes of polymeric organic ligands
And (3) ultrasonically dissolving 0.145mmol of polymer (3), 0.074mmol of ferric trichloride and 2ml of formic acid in 4ml of N, N-diethylformamide, placing the finger-shaped hole-shaped base membrane in the solution, and reacting at 110 ℃ for 40 hours to obtain the iron-based MOF separation membrane containing the high-molecular organic ligand.
The performance of the iron-based MOF separation layer membrane containing the high molecular organic ligand prepared in the embodiment 3 of the invention is detected.
The iron-based MOF separation layer membrane of the macromolecular organic ligand prepared by the embodiment utilizes an electrodialysis device to separate single and multivalent cations, a separation system contains sodium ions and magnesium ions, and the separation experiment result shows that the flux of the sodium ions is 88.75 x 10-10mol/cm2Magnesium ion flux of 4.78 x 10/s-10mol/cm2And/s, the separation coefficient is 18.56, so that the membrane shows better separation performance of single-valence and multi-valence cations.
Example 4
4.1 preparation of polymeric organic ligands containing terephthalic acid Structure
3.2mmol of dipropyl terephthalate, 12.8mmol of 9-bromo-1-olefin and 16.0mmol of potassium carbonate are dissolved in 24ml of N, N-dimethylformamide, the solution is reacted at 90 ℃ for 24 hours, and the potassium carbonate is filtered off, and the N, N-dimethylformamide is evaporated to obtain the monomer (1).
0.3mmol of the monomer (1) and 0.032mmol of the second-generation Grubbs catalyst were dissolved in 6ml of dichloromethane, the solution was reacted at 45 ℃ for 8 hours, precipitated in 30ml of methanol and the solid was dried to give the polymer (2).
0.3mmol of the polymer (2) and 4.5mmol of potassium hydroxide were dissolved in 10ml of dimethyl sulfoxide, reacted at 90 ℃ for 10 hours until the solution was clear, 2MHCl was added dropwise until the pH of the solution became 1, and the resulting solid was washed repeatedly with 30ml of methanol and 30ml of acetone to give a polymer (3) of terephthalic acid containing double bonds.
4.2 preparation of iron-based MOF separation layer membranes of polymeric organic ligands
And (3) ultrasonically dissolving 0.109mmol of polymer (3), 0.111mmol of ferric trichloride and 2ml of formic acid in 4ml of N, N-diethylformamide, placing the finger-shaped hole-shaped basement membrane in the solution, and reacting at 130 ℃ for 48 hours to obtain the iron-based MOF separation membrane containing the high-molecular organic ligand.
The performance of the iron-based MOF separation layer membrane containing the high molecular organic ligand prepared in the embodiment 4 of the invention is detected.
The iron-based MOF separation layer membrane of the macromolecular organic ligand prepared by the embodiment utilizes an electrodialysis device to separate single and multivalent cations, a separation system contains sodium ions and magnesium ions, and the separation experiment result shows that the flux of the sodium ions is 90.68 x 10-10mol/cm2(s) flux of magnesium ions of 4.84 x 10-10mol/cm2And/s, the separation coefficient is 18.72, so that the membrane shows better separation performance of single-valence and multi-valence cations.
Example 5
5.1 preparation of a polymeric organic ligand containing a terephthalic acid Structure
3.3mmol of diethyl terephthalate, 12.6mmol of 7-bromo-1-olefin and 16.0mmol of potassium carbonate were dissolved in 24ml of N, N-dimethylformamide, and the solution was reacted at 80 ℃ for 22 hours, followed by filtration of the potassium carbonate and evaporation of the N, N-dimethylformamide to give the monomer (1).
0.3mmol of the monomer (1) and 0.03mmol of a Grubbs' catalyst were dissolved in 6ml of dichloromethane, the solution was reacted at 35 ℃ for 8 hours, it was precipitated in 30ml of methanol, and the solid was dried to give the polymer (2).
0.3mmol of the polymer (2) and 4.5mmol of potassium hydroxide were dissolved in 10ml of dimethyl sulfoxide, reacted at 80 ℃ for 12 hours until the solution was clear, 2MHCl was added dropwise until the pH of the solution became 1, and the resulting solid was washed repeatedly with 30ml of methanol and 30ml of acetone to give a polymer (3) of terephthalic acid containing double bonds.
5.2 preparation of iron-based MOF separation layer film of high molecular organic ligand
And ultrasonically dissolving 0.091mmol of polymer (3), 0.148mmol of ferric trichloride and 2ml of formic acid in 4ml of N, N-diethylformamide, placing the finger-shaped hole-shaped base membrane in the solution, and reacting at 115 ℃ for 36 hours to obtain the iron-based MOF separation membrane containing the macromolecular organic ligand.
The performance of the iron-based MOF separation layer membrane containing the high molecular organic ligand prepared in the embodiment 5 of the invention is detected.
Adopt this realityThe iron-based MOF separation layer membrane of the macromolecular organic ligand prepared in the example is used for separating single and multivalent cations by using an electrodialysis device, a separation system contains sodium ions and magnesium ions, and the separation experiment result shows that the flux of the sodium ions is 100.57 x 10-10mol/cm2(s) flux of magnesium ions of 5.26 x 10-10mol/cm2And/s, the separation coefficient is 19.12, so that the membrane shows better separation performance of single-valence and multi-valence cations.
Example 6
6.1 preparation of a polymeric organic ligand containing a terephthalic acid Structure
3.2mmol of diethyl terephthalate, 12.8mmol of 8-bromo-1-olefin and 16.0mmol of potassium carbonate were dissolved in 24ml of N, N-dimethylformamide, and the solution was reacted at 70 ℃ for 24 hours, followed by filtration of the potassium carbonate and evaporation of the N, N-dimethylformamide to give the monomer (1).
0.3mmol of the monomer (1) and 0.032mmol of the second-generation Grubbs catalyst were dissolved in 6ml of dichloromethane, the solution was reacted at 50 ℃ for 6 hours, precipitated in 30ml of methanol and the solid was dried to give the polymer (2).
0.3mmol of the polymer (2) and 4.5mmol of potassium hydroxide were dissolved in 10ml of dimethyl sulfoxide, reacted at 100 ℃ for 10 hours until the solution was clear, 2M HCl was added dropwise until the pH of the solution became 1, and the resulting solid was washed repeatedly with 30ml of methanol and 30ml of acetone to give a polymer (3) of terephthalic acid containing double bonds.
6.2 preparation of iron-based MOF separation layer membranes of polymeric organic ligands
And (3) ultrasonically dissolving 0.121mmol of polymer (3), 0.148mmol of ferric trichloride and 2ml of formic acid in 4ml of N, N-diethylformamide, placing the finger-shaped hole-shaped basement membrane in the solution, and reacting at 130 ℃ for 36 hours to obtain the iron-based MOF separation membrane containing the high-molecular organic ligand.
The performance of the iron-based MOF separation layer membrane containing the high molecular organic ligand prepared in the embodiment 6 of the invention is detected.
The iron-based MOF separation layer membrane of the macromolecular organic ligand prepared by the embodiment utilizes an electrodialysis device to separate single and multivalent cations, and a separation system contains sodium ions and magnesium ionsIon, the flux of sodium ion is 82.08 × 10 as the result of separation experiment-10mol/cm2(s) flux of magnesium ions of 4.53 x 10-10mol/cm2And/s, the separation coefficient is 18.12, so that the membrane shows better separation performance of single-valence and multi-valence cations.
While the present invention has been described in detail with respect to a method for making an organic ligand for MOF and a method for making the same, an organic ligand MOF, a separation membrane comprising an organic ligand MOF and a method for making the same, and the principles and embodiments of the present invention are described herein using specific examples, the above description of the examples is merely intended to facilitate the understanding of the methods and their core concepts, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any combination of the methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (9)
1. A method for preparing an organic ligand for a MOF, comprising the steps of:
1) mixing 2, 5-dihydroxy terephthalic acid diester, bromo-1-olefin, an acid-binding agent and a first solvent, and then carrying out condensation reaction to obtain a double-bond-containing monomer;
2) carrying out polymerization reaction on the double bond-containing monomer obtained in the step in a second solvent under the action of a catalyst to obtain a polymer containing a 2, 5-dihydroxy terephthalic acid diester structure;
3) and (3) carrying out hydrolysis reaction on the polymer containing the 2, 5-dihydroxy terephthalic acid diester structure obtained in the step and alkali in a third solvent, and then reacting with an acidic substance to obtain the organic ligand for the MOF.
2. The method of claim 1, wherein the 2, 5-dihydroxyterephthalic acid diester comprises one or more of diethyl 2, 5-dihydroxyterephthalate, dipropyl 2, 5-dihydroxyterephthalate, and dibutyl 2, 5-dihydroxyterephthalate;
the bromo-1-olefin comprises one or more of 7-bromo-1-heptene, 8-bromo-1-octene, 9-bromo-1-nonene, and 10-bromo-1-decene;
the acid-binding agent comprises one or more of potassium carbonate, triethylamine, pyridine and diisopropylethylamine;
the first solvent comprises one or more of N, N-dimethylformamide, N-diethylformamide, N-dimethylacetamide, N-diethylacetamide and N-methylpyrrolidone;
the molar ratio of the 2, 5-dihydroxy terephthalic acid diester to the bromo-1-olefin is (3.0-3.4): (12.0-13.6);
the molar ratio of the 2, 5-dihydroxy terephthalic acid diester to the acid-binding agent is (0.1-0.5): 1;
the molar ratio of the first solvent to the 2, 5-dihydroxy terephthalic acid diester is (90-100): 1;
the temperature of the condensation reaction is 70-90 ℃; the condensation reaction time is 20-24 h.
3. The production method according to claim 1, wherein the catalyst includes one or more of a primary Grubbs catalyst, a secondary Grubbs catalyst, and a tertiary Grubbs catalyst;
the second solvent comprises one or more of dichloromethane, chloroform, dichloroethane and ethyl chloride;
the molar ratio of the double bond-containing monomer to the catalyst is (3.0-3.4): (0.03-0.034);
the molar ratio of the second solvent to the double-bond-containing monomer is (300-350): 1;
the temperature of the polymerization reaction is 30-50 ℃; the polymerization reaction time is 6-8 h.
4. The method of claim 1, wherein the base comprises one or more of potassium hydroxide, sodium hydroxide, ammonium hydroxide, and triethylamine;
the acidic substance comprises hydrochloric acid and/or sulfuric acid;
the third solvent comprises one or more of N, N-dimethylformamide, N-diethylformamide, dimethyl sulfoxide, N-dimethylacetamide and N, N-diethylacetamide;
the molar ratio of the base to the polymer containing a 2, 5-dihydroxyterephthalic acid diester structure is (1.0-2.0): 1;
the pH value of the solution is 1-2 when the solution reacts with an acidic substance;
the molar ratio of the third solvent to the polymer containing a 2, 5-dihydroxyterephthalic acid diester structure is (450-500): 1;
the temperature of the hydrolysis reaction is 80-100 ℃; the hydrolysis reaction time is 10-12 h.
5. An organic ligand MOF, wherein the coordination metal in the organic ligand MOF is iron;
the organic ligand in the organic ligand MOF is prepared by the preparation method of any one of claims 1-4.
6. A separation membrane containing organic ligand MOF is characterized by comprising a base membrane and the organic ligand MOF compounded on one side of the base membrane;
the organic ligand MOF is the organic ligand MOF of claim 5.
7. The separation membrane of claim 6, wherein the surface of the separation membrane is densely grown with organic ligands MOF;
the thickness of the separation membrane is 150-200 mu m;
the base film is made of one or more of brominated polyphenylene oxide, polybenzimidazole, polyethersulfone ketone and polyetheretherketone;
the basement membrane is a finger-shaped hole basement membrane or a spongy hole basement membrane;
the thickness of the base film is 90-150 mu m.
8. A preparation method of a separation membrane containing organic ligand MOF is characterized by comprising the following steps:
A) putting the base membrane into a mixed solution of an organic ligand, a mineralizer, a soluble ferric salt and an organic solvent, and reacting to obtain a separation membrane containing the organic ligand MOF;
the organic ligand is prepared by the preparation method of any one of claims 1 to 4.
9. The method of claim 8, wherein the mineralizer comprises one or more of formic acid, hydrochloric acid, and benzoic acid;
the soluble ferric salt comprises one or more of ferric trichloride, ferric sulfate and ferric nitrate;
the organic solvent comprises one or more of N, N-diethylformamide, N-dimethylformamide, N-dimethylacetamide, N-diethylacetamide and N-methylpyrrolidone;
the mass ratio of the mineralizer to the organic ligand is (70-90): 1;
the molar ratio of the organic ligand to the soluble iron salt is (0.02-0.04): (0.02-0.04);
the mass ratio of the organic solvent to the organic ligand is (110-130): 1;
the reaction temperature is 110-130 ℃; the reaction time is 36-48 h.
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