CN116376046A - Method for preparing metal-organic polymer based on cage-shaped supermolecular monomer - Google Patents
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- 239000000178 monomer Substances 0.000 title claims abstract description 75
- 229920000620 organic polymer Polymers 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000003446 ligand Substances 0.000 claims abstract description 40
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000000524 functional group Chemical group 0.000 claims abstract description 9
- PADPILQDYPIHQQ-UHFFFAOYSA-L zinc;diperchlorate;hexahydrate Chemical compound O.O.O.O.O.O.[Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O PADPILQDYPIHQQ-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 28
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- -1 vinylbenzyl methoxy Chemical group 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000004090 dissolution Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 6
- QHQSCKLPDVSEBJ-UHFFFAOYSA-N 1,3,5-tri(4-aminophenyl)benzene Chemical compound C1=CC(N)=CC=C1C1=CC(C=2C=CC(N)=CC=2)=CC(C=2C=CC(N)=CC=2)=C1 QHQSCKLPDVSEBJ-UHFFFAOYSA-N 0.000 claims description 5
- WHSQATVVMVBGNS-UHFFFAOYSA-N 4-[4,6-bis(4-aminophenyl)-1,3,5-triazin-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C1=NC(C=2C=CC(N)=CC=2)=NC(C=2C=CC(N)=CC=2)=N1 WHSQATVVMVBGNS-UHFFFAOYSA-N 0.000 claims description 4
- 125000003172 aldehyde group Chemical group 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002861 polymer material Substances 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 4
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- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
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Abstract
The invention discloses a method for preparing a metal-organic polymer based on cage-shaped supermolecular monomers, which relates to the technical field of metal-organic polymer materials, and designs and constructs different organic building units with polymerizable functional groups to obtain six different corresponding ligands L 1‑6 Then coordinates with zinc perchlorate hexahydrate to form cage supermolecular monomer MOC-WYU-1-6, and carries out free radical copolymerization with butyl methacrylate to obtain a series of metal-organic polymers. According to the method for preparing the metal-organic polymer based on the cage-shaped supermolecular monomer, a proper functional group is selected on the supermolecular structure to form a strong covalent bond with a high molecular chain, so that the supermolecular monomer is uniformly dispersed in a polymer material, can be more tightly combined on a polymer matrix, fully plays the function of a cage-shaped cavity, further improves the function of a composite material, and further provides application of picric acid adsorption of the metal-organic polymer.
Description
Technical Field
The invention relates to the technical field of metal-organic polymer materials, in particular to a method for preparing a metal-organic polymer based on cage-shaped supermolecular monomers.
Background
The coordination space of the cage-shaped supermolecule is good choice for removing pollutants such as anions, aromatic compounds and the like, but the method is expanded into practical industrial application, and the processability and stability of the material are also considered. The ligand skeleton is modified with reactive functional groups to change the surface function of cage supermolecule, and the cage supermolecule is connected to a high molecular network, so that the structure and physical and chemical properties of the metal-organic polymer can be effectively regulated.
Compared with the traditional polymer material, the cage cavity of the cage-shaped supermolecule can be used as a special space, so that the obtained new material not only contains gaps among polymer networks, but also contains nano cavities inherent to the cage-shaped structure. Therefore, after the two are combined, the cage-shaped supermolecule introduces the self nano cavity into the polymer matrix to construct the intelligent material with double porosity, so that the application prospect is wider.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a method for preparing a metal-organic polymer based on cage-shaped supermolecular monomers, which aims to solve the problems in the prior art.
In order to achieve the above purpose, the present invention provides the following technical solutions: a method for preparing a metal-organic polymer based on cage-like supermolecular monomers, comprising the steps of:
s1, weighing 0.60mmo L of compound containing three amino functional groups and 2.00mmo L of compound containing vinylbenzyl methoxy and aldehyde groups, dissolving in 20.0mL of ethanol solution, reacting for 24 hours at room temperature to generate a large amount of precipitate, and suction filtering and drying to obtain ligand L 1-6 ；
S2, dissolving 0.05mmo l of ligand in 5mL of chloroform to obtain yellow clear solution, slowly dripping 0.5mL of acetonitrile solvent in which 0.06mmo l of zinc perchlorate hexahydrate is dissolved, slowly turning the clear solution into turbidity, precipitating solid, stirring at room temperature for 1 hour, and performing suction filtration and drying to obtain cage-shaped supermolecular monomer MOC-WYU-1-6;
s3, weighing 0.40g of butyl methacrylate BMA and 4.00mg of azodiisobutyronitrile AI BN into a round bottom flask with 20mL, adding an N, N-dimethylformamide solvent dissolved with 0.06g of cage-shaped supermolecular monomer, introducing nitrogen for protection after ultrasonic dissolution, and heating to 70 ℃ for reaction for 12 hours to obtain the metal-organic polymer.
Further optimizing the technical scheme, in the step S1, the compound containing three amino functional groups is one of 1,3, 5-tri (4-aminophenyl) benzene or 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine.
Further optimizing the technical scheme, in the step S1, the compound containing vinylbenzyl methoxy and aldehyde group is one of 4- (4-vinylbenzyl methoxy) quinoline-2-formaldehyde, 3- (4-vinylbenzyl methoxy) pyridine-2-formaldehyde or 5- (4-vinylbenzyl methoxy) pyridine-2-formaldehyde.
Further optimizing the technical scheme, in the step S2, the cage-shaped supermolecular monomers MOC-WYU-1-6 are based on the ligand L 1-6 And (5) carrying out corresponding identification:
based on ligand L 1 The prepared complex is cage-shaped supermolecular monomer MOC-WYU-1;
based on ligand L 2 The prepared complex is cage-shaped supermolecular monomer MOC-WYU-2;
based on ligand L 3 The prepared complex is cage-shaped supermolecular monomer MOC-WYU-3;
based on ligand L 4 The prepared complex is cage-shaped supermolecular monomer MOC-WYU-4;
based on ligand L 5 The prepared complex is cage-shaped supermolecular monomer MOC-WYU-5;
based on ligand L 6 The prepared complex is cage-shaped supermolecular monomer MOC-WYU-6.
Further optimizing the technical scheme, in the step S1, the ligand L is obtained by suction filtration and drying 1-6 Ethanol is adopted for ligand L 1-6 Washing three times.
Further optimizing the technical scheme, in the step S2, the cage-shaped supermolecular monomer MOC-WYU-1-6 is obtained after suction filtration and drying, and the complex cage-shaped supermolecular monomer MOC-WYU-1-6 is washed three times by chloroform.
Further optimizing the technical scheme, and obtaining the ligand L 1-6 And the complex MOC-WYU-1-6 to obtain the yield of the ligand and the complex.
Further optimizing the technical scheme, the metal-organic polymer is prepared into materials with various forms according to requirements, and the materials comprise, but are not limited to, polymer powder, thin coating and block modules.
Compared with the prior art, the invention provides a method for preparing a metal-organic polymer based on cage-shaped supermolecular monomers, which has the following beneficial effects:
according to the method for preparing the metal-organic polymer based on the cage-shaped supermolecular monomer, a proper functional group is selected on the supermolecular structure to form a strong covalent bond with a high molecular chain, so that the supermolecular monomer can be uniformly dispersed in a polymer material, can be more tightly combined on a polymer matrix, the function of a cage-shaped cavity is fully exerted, and the function of the composite material is further improved.
Drawings
FIG. 1 is a schematic flow chart of a cage-like supermolecular monomer MOC-WYU-1 in a method for preparing a metal-organic polymer based on a cage-like supermolecular monomer according to the present invention;
FIG. 2 is a schematic flow chart of a cage-like supermolecular monomer MOC-WYU-2 in a method for preparing a metal-organic polymer based on a cage-like supermolecular monomer according to the present invention;
FIG. 3 is a schematic flow chart of a cage-like supermolecular monomer MOC-WYU-3 in a method for preparing a metal-organic polymer based on a cage-like supermolecular monomer according to the present invention;
FIG. 4 is a schematic flow chart of a cage-like supermolecular monomer MOC-WYU-4 in a method for preparing a metal-organic polymer based on a cage-like supermolecular monomer according to the present invention;
FIG. 5 is a schematic flow chart of a cage-like supermolecular monomer MOC-WYU-5 in a method for preparing a metal-organic polymer based on a cage-like supermolecular monomer according to the present invention;
FIG. 6 is a schematic flow chart of a cage-like supermolecular monomer MOC-WYU-6 in a method for preparing a metal-organic polymer based on a cage-like supermolecular monomer according to the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
As shown in fig. 1, a method for preparing a metal-organic polymer based on cage-like supermolecular monomers specifically comprises the following steps:
in the first step, 0.21g of 1,3, 5-tris (4-aminophenyl) benzene and 0.58g of 4- (4-vinylbenzyl methoxy) quinoline-2-carbaldehyde are weighed and dissolved in 20.0mL of ethanol solution, reacted for 24 hours at room temperature to produce a large amount of precipitate, and the precipitate is suction filtered and dried to obtain ligand L 1 。
In the second step, 0.05mmol of the ligand was dissolved in 5mL of chloroform to obtain a yellow clear solution, 0.5mL of acetonitrile solvent in which 22.34mg of zinc perchlorate hexahydrate was dissolved was slowly dropped, the clear solution was slowly cloudy, and a solid was precipitated. Stirring for 1 hour at room temperature, and filtering and drying to obtain the cage-shaped supermolecular monomer MOC-WYU-1.
Thirdly, weighing 0.40g of butyl methacrylate BMA and 4.00mg of azodiisobutyronitrile AI BN into a round bottom flask with 20mL, adding N, N-dimethylformamide solvent dissolved with 0.06g of cage-shaped supermolecular monomer, introducing nitrogen for protection after ultrasonic dissolution, and heating to 70 ℃ for reaction for 12 hours.
Example 2
As shown in fig. 2, a method for preparing a metal-organic polymer based on cage-like supermolecular monomers specifically comprises the following steps:
in the first step, 0.21g of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine and 0.58g of 4- (4-vinylbenzyl methoxy) quinoline-2-carbaldehyde are weighed and dissolved in 20.0mL of ethanol solution, reacted for 24 hours at room temperature to generate a large amount of precipitate, and the precipitate is filtered and dried to obtain ligand L 2 。
In the second step, 0.05mmol of the ligand was dissolved in 5mL of chloroform to obtain a yellow clear solution, 0.5mL of acetonitrile solvent in which 22.34mg of zinc perchlorate hexahydrate was dissolved was slowly dropped, the clear solution was slowly cloudy, and a solid was precipitated. Stirring for 1 hour at room temperature, and filtering and drying to obtain the cage-shaped supermolecular monomer MOC-WYU-2.
Thirdly, weighing 0.40g of butyl methacrylate BMA and 4.00mg of azodiisobutyronitrile AI BN into a round bottom flask with 20mL, adding N, N-dimethylformamide solvent dissolved with 0.06g of cage-shaped supermolecular monomer, introducing nitrogen for protection after ultrasonic dissolution, and heating to 70 ℃ for reaction for 12 hours.
Example 3
As shown in fig. 3, a method for preparing a metal-organic polymer based on cage-like supermolecular monomers specifically comprises the following steps:
in the first step, 0.21g of 1,3, 5-tris (4-aminophenyl) benzene and 0.48g of 3- (4-vinylbenzyl methoxy) pyridine-2-carbaldehyde are weighed and dissolved in 20.0mL of ethanol solution, reacted for 24 hours at room temperature to produce a large amount of precipitate, and the precipitate is suction filtered and dried to obtain ligand L 3 。
In the second step, 0.05mmol of the ligand was dissolved in 5mL of chloroform to obtain a yellow clear solution, 0.5mL of acetonitrile solvent in which 22.34mg of zinc perchlorate hexahydrate was dissolved was slowly dropped, the clear solution was slowly cloudy, and a solid was precipitated. Stirring for 1 hour at room temperature, and filtering and drying to obtain the cage-shaped supermolecular monomer MOC-WYU-3.
Thirdly, weighing 0.40g of butyl methacrylate BMA and 4.00mg of azodiisobutyronitrile AI BN into a round bottom flask with 20mL, adding N, N-dimethylformamide solvent dissolved with 0.06g of cage-shaped supermolecular monomer, introducing nitrogen for protection after ultrasonic dissolution, and heating to 70 ℃ for reaction for 12 hours.
Example 4
As shown in fig. 4, a method for preparing a metal-organic polymer based on cage-like supermolecular monomers specifically comprises the following steps:
in a first step, 0.21g of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine and 0.48g of 3- (4-vinylbenzyloxy) -pyridine-2-carbaldehyde are weighed out and dissolved in 20.0mL of ethanol solution,reacting at room temperature for 24 hours to generate a large amount of precipitate, and filtering and drying to obtain ligand L 4 。
In the second step, 0.05mmol of the ligand was dissolved in 5mL of chloroform to obtain a yellow clear solution, 0.5mL of acetonitrile solvent in which 22.34mg of zinc perchlorate hexahydrate was dissolved was slowly dropped, the clear solution was slowly cloudy, and a solid was precipitated. Stirring for 1 hour at room temperature, and filtering and drying to obtain the cage-shaped supermolecular monomer MOC-WYU-4.
Thirdly, weighing 0.40g of butyl methacrylate BMA and 4.00mg of azodiisobutyronitrile AI BN into a round bottom flask with 20mL, adding N, N-dimethylformamide solvent dissolved with 0.06g of cage-shaped supermolecular monomer, introducing nitrogen for protection after ultrasonic dissolution, and heating to 70 ℃ for reaction for 12 hours.
Example 5
As shown in fig. 5, a method for preparing a metal-organic polymer based on cage-like supermolecular monomers specifically comprises the following steps:
in the first step, 0.21g of 1,3, 5-tris (4-aminophenyl) benzene and 0.48g of 5- (4-vinylbenzyl methoxy) pyridine-2-carbaldehyde are weighed and dissolved in 20.0mL of ethanol solution, reacted for 24 hours at room temperature to produce a large amount of precipitate, and the precipitate is suction filtered and dried to obtain ligand L 5 。
In the second step, 0.05mmol of the ligand was dissolved in 5mL of chloroform to obtain a yellow clear solution, 0.5mL of acetonitrile solvent in which 22.34mg of zinc perchlorate hexahydrate was dissolved was slowly dropped, the clear solution was slowly cloudy, and a solid was precipitated. Stirring for 1 hour at room temperature, and filtering and drying to obtain the cage-shaped supermolecular monomer MOC-WYU-5.
Thirdly, weighing 0.40g of butyl methacrylate BMA and 4.00mg of azodiisobutyronitrile AI BN into a round bottom flask with 20mL, adding N, N-dimethylformamide solvent dissolved with 0.06g of cage-shaped supermolecular monomer, introducing nitrogen for protection after ultrasonic dissolution, and heating to 70 ℃ for reaction for 12 hours.
Example 6
As shown in fig. 6, a method for preparing a metal-organic polymer based on cage-like supermolecular monomers specifically comprises the following steps:
in the first step, 0.21g of 2,4, 6-tris (4-aminophenyl) was weighed1,3, 5-triazine and 0.48g of 5- (4-vinylbenzyl methoxy) pyridine-2-formaldehyde are dissolved in 20.0mL of ethanol solution, reacted for 24 hours at room temperature to generate a large amount of precipitate, and the precipitate is filtered and dried to obtain ligand L 6 。
In the second step, 0.05mmol of the ligand was dissolved in 5mL of chloroform to obtain a yellow clear solution, 0.5mL of acetonitrile solvent in which 22.34mg of zinc perchlorate hexahydrate was dissolved was slowly dropped, the clear solution was slowly cloudy, and a solid was precipitated. Stirring for 1 hour at room temperature, and filtering and drying to obtain the cage-shaped supermolecular monomer MOC-WYU-6.
Thirdly, weighing 0.40g of butyl methacrylate BMA and 4.00mg of azodiisobutyronitrile AI BN into a round bottom flask with 20mL, adding N, N-dimethylformamide solvent dissolved with 0.06g of cage-shaped supermolecular monomer, introducing nitrogen for protection after ultrasonic dissolution, and heating to 70 ℃ for reaction for 12 hours.
Regarding the application of the adsorption properties of the product to picric acid:
the specific test method comprises the following steps: 0.3mg of the metal-organic polymer was weighed into a 10mL glass bottle, 5mL of an aqueous solution of picric acid (0.10 mmo/L) was added, and the mixture was continuously oscillated for 48 hours at a place not irradiated with light, and the absorbance of picric acid in the solution was measured at 356nm by ultraviolet absorption photometry, whereby the absorption amount of picric acid by the metal-organic polymer was calculated.
The product performance test structures of examples 1-6 are shown in the following table:
the metal-organic polymer constructed by cage supermolecular monomer MOC-WYU-5 has strong adsorption (adsorption amount is 118.92 mg.g) -1 ) The adsorption mechanism is mainly ion exchange of supermolecule and picric acid and pi-pi interaction between cage cavity and aromatic compound, and can maintain excellent adsorption capacity and stability in water solution containing different inorganic salts in wide pH value range. The performance of the metal-organic polymer is improved and optimized to meet the requirements of different application scenes, and the metal-organic polymer has good research value and practicalityTrampling significance.
The beneficial effects of the invention are as follows:
the method for preparing the metal-organic polymer based on the cage-shaped supermolecular monomer selects proper functional groups on the supermolecular structure to form strong covalent bonds with high molecular chains, is favorable for the supermolecular monomer to be uniformly dispersed in a polymer material, can be more tightly combined on a polymer matrix, fully plays the function of a cage-shaped cavity, further improves the function of a composite material, simultaneously provides the application of picric acid adsorption of the metal-organic polymer, can keep better adsorption quantity and stability in aqueous solutions containing different inorganic salts in a wider pH value range, and improves and optimizes the performance of the metal-organic polymer so as to meet the requirements of different application scenes, and has good research value and practical significance.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A method for preparing a metal-organic polymer based on cage-like supermolecular monomers, characterized by comprising the steps of:
s1, weighing 0.60mmol of compound containing three amino functional groups and 2.00mmol of compound containing vinylbenzyl methoxy and aldehyde groups, dissolving in 20.0mL of ethanol solution, reacting for 24 hours at room temperature to generate a large amount of precipitate, and suction filtering and drying to obtain ligand L 1-6 ；
S2, dissolving 0.05mmol of ligand in 5mL of chloroform to obtain yellow clear solution, slowly dropwise adding 0.5mL of acetonitrile solvent in which 0.06mmol of zinc perchlorate hexahydrate is dissolved, slowly turning the clear solution into turbidity, separating out solid, stirring for 1 hour at room temperature, and performing suction filtration and drying to obtain cage-shaped supermolecular monomer MOC-WYU-1-6;
s3, weighing 0.40g of butyl methacrylate BMA and 4.00mg of azodiisobutyronitrile AIBN into a round bottom flask with 20mL, adding an N, N-dimethylformamide solvent dissolved with 0.06g of cage-shaped supermolecular monomer, introducing nitrogen for protection after ultrasonic dissolution, and heating to 70 ℃ for reaction for 12 hours to obtain the metal-organic polymer.
2. The method for preparing a metal-organic polymer based on cage-like supermolecular monomers according to claim 1, wherein in the step S1, the compound having three amino functional groups is one of 1,3, 5-tris (4-aminophenyl) benzene or 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine.
3. The method for preparing a metal-organic polymer based on cage-like supermolecular monomers according to claim 1, wherein in the step S1, the vinylbenzyl methoxy-and aldehyde-group-containing compound is one of 4- (4-vinylbenzyl methoxy) quinoline-2-carbaldehyde, 3- (4-vinylbenzyl methoxy) pyridine-2-carbaldehyde or 5- (4-vinylbenzyl methoxy) pyridine-2-carbaldehyde.
4. The method for preparing a metal-organic polymer based on cage-like supermolecular monomers according to claim 1, wherein in the step S2, cage-like supermolecular monomers MOC-WYU-1 to 6 are based on ligand L 1-6 And (5) carrying out corresponding identification:
based on ligand L 1 The prepared complex is cage-shaped supermolecular monomer MOC-WYU-1;
based on ligand L 2 The prepared complex is cage-shaped supermolecular monomer MOC-WYU-2;
based on ligand L 3 The prepared complex is cage-shaped supermolecular monomer MOC-WYU-3;
based on ligand L 4 The prepared complex is cage-shaped supermolecular monomer MOC-WYU-4;
based on ligand L 5 The prepared complex is cage-shaped supermolecular monomer MOC-WYU-5;
based on ligand L 6 The prepared complex is cage-shaped supermolecular monomer MOC-WYU-6.
5. The method for preparing metal-organic polymer based on cage-like supermolecular monomers according to claim 1, wherein in step S1, the ligand L is obtained by suction filtration and drying 1-6 Ethanol is adopted for ligand L 1-6 Washing three times.
6. The method for preparing metal-organic polymer based on cage-like supermolecular monomer according to claim 1, wherein in step S2, cage-like supermolecular monomer MOC-WYU-1-6 is obtained after suction filtration and drying, and complex cage-like supermolecular monomer MOC-WYU-1-6 is washed three times with chloroform.
7. The method for preparing a metal-organic polymer based on cage-like supermolecular monomers as claimed in claim 1, wherein the ligand L obtained 1-6 And the complex MOC-WYU-1-6 to obtain the yield of the ligand and the complex.
8. A method of preparing metal-organic polymers based on cage supermolecular monomers according to claim 1, wherein the metal-organic polymers are prepared as desired into various forms of materials including but not limited to polymer powder, thin coating, block modules.
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