CN112250587A - Tetraphenylbenzene-based heterogeneous covalent organic framework material and preparation method thereof - Google Patents
Tetraphenylbenzene-based heterogeneous covalent organic framework material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an isomeric covalent organic framework material based on tetraphenylbenzene and a preparation method thereof, wherein the isomeric covalent organic framework material based on tetraphenylbenzene is represented by a formula (III);
the isomeric covalent organic framework materials p-TPB-COF-H and p-TPB-COF-M based on tetraphenylbenzene can be successfully constructed by the same monomer 1, 4-di (4-formylphenyl) -2, 5-di (4-aminophenyl) benzene through regulation and control of a solvent, and provide a new idea for designing and synthesizing isomeric COFs12Selective adsorption and water vapor adsorption.
Description
Technical Field
The invention belongs to the field of high-molecular organic porous materials, and particularly relates to a tetraphenylbenzene-based heterogeneous covalent organic framework material p-TPB-COF-H, p-TPB-COF-M and a preparation method thereof.
Background
Isomerism is a phenomenon of great interest in the chemical field, meaning that substances have the same molecular formula but different structures and properties. This phenomenon is common in the fields of drug molecules, porous organic molecular cages, inorganic nanoclusters, and metal organic framework Materials (MOFs), and the properties of these isomers are often very different. The formation of isomers is related to many factors, and taking a metal organic framework material as an example, the types of organic ligands, the difference of synthetic solvents, the change of metal ions and the difference of synthetic modes can cause the appearance of isomers, but many of the isomers reported at present appear in a mixed state, and how to directionally synthesize an isomer with a specific structure is still a difficult problem.
Covalent Organic Frameworks (COFs) are a new class of crystalline organic porous materials, and due to inherent porosity and regular ordered pore channel structures, the materials have potential application values in the aspects of photocatalysis, gas storage and separation, organic pollutant adsorption and separation, drug sustained release and the like, and are widely researched and paid attention to in academia in recent years. However, the isomerization phenomenon is extremely rare in the field of COFs, and the phenomenon is probably closely related to the preparation of the conventional COFs by using two or three monomers to carry out copolycondensation under the condition of a specific solvent. Specific solvent systems may limit the selectivity of COFs in forming ordered structures, so even though two copolycondensation monomers may form isomeric framework structures, only one topological framework material is often obtained under the restriction of solvent conditions. Recently reported series A2B2Bifunctional monomers have low solvent dependence and good reproducibility in the construction of COFs, and these factors may be beneficial in the construction of isomeric COFs. And so far there is no use of isomeric A2B2The monomer constructs the relevant report of isomeric COFs material.
Disclosure of Invention
The object of the present invention is to overcome the disadvantages of the prior art and to provide a monomer 1, 4-bis (4-formylphenyl) -2, 5-bis (4-aminophenyl) benzene for the synthesis of tetraphenylbenzene-based isomeric covalent organic framework materials.
The second object of the present invention is to provide a process for producing 1, 4-bis (4-formylphenyl) -2, 5-bis (4-aminophenyl) benzene.
It is a third object of the present invention to provide a tetraphenylbenzene-based heterogeneous covalent organic framework material.
The fourth purpose of the invention is to provide a preparation method of the tetraphenylbenzene-based heterogeneous covalent organic framework material.
It is a fifth object of the present invention to provide another tetraphenylbenzene-based isomeric covalent organic framework material.
It is a sixth object of the present invention to provide a method for preparing another tetraphenylbenzene-based isomeric covalent organic framework material.
The technical scheme of the invention is summarized as follows:
1, 4-di (4-formylphenyl) -2, 5-di (4-aminophenyl) benzene, the structure of which is shown in formula (II), and the abbreviation is: p-TPB:
a process for the preparation of 1, 4-bis (4-formylphenyl) -2, 5-bis (4-aminophenyl) benzene comprising the steps of:
1) 1, 4-dibromo-2, 5-diiodobenzene and 4-formylphenylboronic acid are subjected to suzuki coupled reaction catalyzed by a palladium catalyst in a mixed solvent to obtain 1, 4-dibromo-2, 5- (4-formylphenyl) benzene (I);
2) 1, 4-dibromo-2, 5- (4-formylphenyl) benzene (I) and 4-aminobenzeneboronic acid pinacol ester are subjected to Suzuki coupled reaction catalyzed by a palladium catalyst to obtain 1, 4-bis (4-formylphenyl) -2, 5-bis (4-aminophenyl) benzene (II), which is called p-TPB for short; the reaction formula is as follows:
the mixed solvent is preferably toluene and ethanol in a volume ratio of 3: 1.
The palladium catalyst is palladium tetratriphenylphosphine or palladium bistriphenylphosphine dichloride.
An isomeric covalent organic framework material based on tetraphenylbenzene is shown in a formula (III) and is abbreviated as p-TPB-COF-H;
a preparation method of tetraphenylbenzene-based heterogeneous covalent organic framework material comprises the following steps: dissolving p-TPB in tetrahydrofuran, adding an acetic acid aqueous solution as a catalyst, uniformly mixing, and reacting under a reflux condition to obtain an isomeric covalent organic framework material based on tetraphenylbenzene, wherein the isomeric covalent organic framework material is shown as a formula (III) and is referred to as p-TPB-COF-H for short;
the reaction formula is as follows:
another tetraphenylbenzene-based isomeric covalent organic framework material is represented by the formula (IV), abbreviated as p-TPB-COF-M:
another method for preparing the tetraphenylbenzene-based heterogeneous covalent organic framework material comprises the following steps: 23.5 mg: dispersing p-TPB into n-butanol at a ratio of 1mL to obtain a dispersion, adding an acetic acid aqueous solution as a catalyst, uniformly mixing, and reacting under a reflux condition to obtain an isomeric covalent organic framework material based on tetraphenylbenzene, wherein the isomeric covalent organic framework material is shown as (IV) and is referred to as p-TPB-COF-M for short;
the reaction formula is as follows:
the invention has the advantages that:
the tetraphenylbenzene-based heterogeneous covalent organic framework materials p-TPB-COF-H and p-TPB-COF-M can be successfully constructed by the same monomer 1, 4-di (4-formylphenyl) -2, 5-di (4-aminophenyl) benzene through regulation and control of a solvent, a new thought is provided for design and synthesis of heterogeneous COFs, and in addition, the invention also provides the tetraphenylbenzene-based heterogeneous covalent organic framework materials p-TPB-COF-H and p-TPB-COF-MMethod for preparing frame material for vitamin B12Selective adsorption and water vapor adsorption.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of compound II.
FIG. 2a is the X-ray powder diffraction pattern of Polymer III and FIG. 2b is the X-ray powder diffraction pattern of Polymer IV.
FIG. 3a is solid nuclear magnetism of Polymer III13C spectrum, FIG. 3b solid nuclear magnetism of Polymer IV13And C, spectrum.
FIG. 4 is an infrared spectrum of compound II, and polymers III and IV.
FIG. 5 shows Polymer III vs. vitamin B12Adsorption of (3).
FIG. 6 shows the adsorption of water vapor by polymer IV.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
A process for the preparation of 1, 4-bis (4-formylphenyl) -2, 5-bis (4-aminophenyl) benzene comprising the steps of:
1) weighing 4.0g (8.2mmol) of 1, 4-dibromo-2, 5-diiodobenzene, 3.1g (20.6mmol) of 4-formylphenylboronic acid, 0.4g (0.32mmol) of tetrakistriphenylphosphine palladium as a catalyst and 4.0g (29.5mmol) of potassium carbonate in a 500mL two-neck flask, putting a magneton, adding 160mL of a degassed toluene and ethanol (volume ratio of 3:1) mixed solvent and 1mL of water, freezing and degassing for three times, carrying out oil bath reaction at 95 ℃ under the protection of argon for 36h, cooling to room temperature, carrying out vacuum concentration on the reaction liquid, then extracting with dichloromethane, drying an organic phase with anhydrous magnesium sulfate, carrying out spin drying, and carrying out column chromatography to obtain white solid powder 1, 4-dibromo-2, 5- (4-formylphenyl) benzene I (2.5g, the yield is 69%); (Suzuki coupling reaction catalyzed by palladium catalyst is carried out in the presence of alkali and water under the protection of inert gas)
2) Weighing 1.2g (2.7mmol) of 1, 4-dibromo-2, 5- (4-formylphenyl) benzene I, 1.6g (8.2mmol) of 4-aminobenzeneboronic acid pinacol ester, 0.15g (0.125mmol) of tetratriphenylphosphine palladium catalyst and 3.0g (26mmol) of potassium carbonate in a 100mL two-neck bottle, adding 45mL of degassed dioxane and 9mL of water, freezing and degassing for three times, heating to 100 ℃ and reacting for 36 h; after cooling to room temperature, the reaction mixture was poured into a large amount of water, extracted with dichloromethane, the organic phase was dried over anhydrous magnesium sulfate, then concentrated in vacuo, and finally recrystallized with dichloromethane and petroleum ether to give 1, 4-bis (4-formylphenyl) -2, 5-bis (4-aminophenyl) benzene II as a pale yellow solid powder, p-TPB (1.0g, yield 79%), whose nuclear magnetic hydrogen spectrum is shown in FIG. 1.
The reaction formula is as follows:
the palladium catalyst is bis-triphenylphosphine palladium dichloride, and other steps are the same as those in the embodiment, so that p-TPB can be prepared.
Example 2
A preparation method of tetraphenylbenzene-based heterogeneous covalent organic framework material comprises the following steps:
adding 23.5mg (0.05mmol) of p-TPB into a 10mL pressure resistant tube, then adding 1mL tetrahydrofuran, performing ultrasonic treatment for 5min to fully dissolve solid powder in a solvent, adding 0.1mL6M acetic acid aqueous solution, performing ultrasonic treatment for 2min, then performing freeze degassing for three times, putting the system into an oil bath for reflux reaction for 72H after the system is recovered to room temperature, filtering and collecting precipitates after the reaction is finished, and fully washing the precipitates with dichloromethane and tetrahydrofuran organic solvents to obtain the faint yellow isomeric covalent organic framework material III based on tetraphenylbenzene with excellent crystallinity and porosity, namely p-TPB-COF-H for short.
The structure is a double-hole structure (the double-hole structure refers to a structure with a hexagonal hole structure and a triangular hole structure)
FIG. 2a is an X-ray powder diffraction pattern of Polymer III; FIG. 3a is solid nuclear magnetism of Polymer III13C, spectrum; the infrared spectrum is shown in FIG. 4.
The reaction formula is as follows:
example 3
A preparation method of tetraphenylbenzene-based heterogeneous covalent organic framework material comprises the following steps:
adding 23.5mg (0.05mmol) of p-TPB into a 10mL pressure resistant pipe, then adding 1mL of n-butyl alcohol, performing ultrasonic treatment for 5min to fully disperse solid powder in a solvent, adding 0.1mL of 6M acetic acid aqueous solution, performing ultrasonic treatment for 2min, then performing freeze degassing for three times, putting the system into an oil bath for reflux reaction for 72h after the system is recovered to room temperature, filtering and collecting precipitates after the reaction is finished, and fully washing the precipitates with dichloromethane and tetrahydrofuran organic solvent to obtain an isomeric covalent organic framework material IV based on tetraphenylbenzene with excellent crystallinity and porosity, namely p-TPB-COF-M.
The structure is a single-hole structure (the single-hole structure refers to a structure with a diamond-shaped pore canal in the structure)
FIG. 2b is an X-ray powder diffraction pattern of Polymer IV; FIG. 3b is solid nuclear magnetism of Polymer IV13C, spectrum; the infrared spectrum is shown in FIG. 4.
The reaction formula is as follows:
the chemical compositions of two tetraphenylbenzene-based isomeric covalent organic framework materials p-TPB-COF-H and p-TPB-COF-M are not obviously different, but the crystallinity is obviously different, and the materials have X-ray powder diffraction patterns and solid nuclear magnetism13The C spectrum and the infrared spectrum are shown in figures 2,3 and 4.
Fig. 2,3 and 4 prove that the polymers III and VI have porous and regular ordered pore structures, and thus the two polymers have potential application values in the aspects of photocatalysis, gas storage and separation, adsorption and separation of organic pollutants, drug sustained release and the like.
The polymers III and IV have porous and regular ordered pore channel structures, but the sizes of the pore channels are obviously different, so that the polymers III and IV can be applied to different aspects.
The polymer III can adsorb vitaminElement B12(FIG. 5), Polymer IV showed good performance in water vapor adsorption (FIG. 6).
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other modifications, simplifications or simple modifications without departing from the design principle and construction strategy of the present invention are included in the protection scope of the present invention.
Claims (8)
1, 4-bis (4-formylphenyl) -2, 5-bis (4-aminophenyl) benzene, the structure of which is shown in formula (II), and is abbreviated as follows: p-TPB:
2. a process for the preparation of 1, 4-bis (4-formylphenyl) -2, 5-bis (4-aminophenyl) benzene according to claim 1, characterized by comprising the steps of:
1) 1, 4-dibromo-2, 5-diiodobenzene and 4-formylphenylboronic acid are subjected to suzuki coupled reaction catalyzed by a palladium catalyst in a mixed solvent to obtain 1, 4-dibromo-2, 5- (4-formylphenyl) benzene (I);
2) 1, 4-dibromo-2, 5- (4-formylphenyl) benzene (I) and 4-aminobenzeneboronic acid pinacol ester are subjected to Suzuki coupled reaction catalyzed by a palladium catalyst to obtain 1, 4-bis (4-formylphenyl) -2, 5-bis (4-aminophenyl) benzene (II), which is called p-TPB for short; the reaction formula is as follows:
3. the method as set forth in claim 2, wherein the mixed solvent is toluene and ethanol in a volume ratio of 3: 1.
4. The process as set forth in claim 2 characterized in that the palladium catalyst is tetrakistriphenylphosphine palladium or bistriphenylphosphine palladium dichloride.
5. A tetraphenylbenzene-based heterogeneous covalent organic framework material is characterized by being represented by a formula (III), and is referred to as p-TPB-COF-H for short;
6. a process for the preparation of a tetraphenylbenzene-based isomeric covalent organic framework material according to claim 4, characterized in that it comprises the following steps: dissolving p-TPB in tetrahydrofuran, adding an acetic acid aqueous solution as a catalyst, uniformly mixing, and reacting under a reflux condition to obtain an isomeric covalent organic framework material based on tetraphenylbenzene, wherein the isomeric covalent organic framework material is shown as a formula (III) and is referred to as p-TPB-COF-H for short;
the reaction formula is as follows:
7. a tetraphenylbenzene-based heterogeneous covalent organic framework material is characterized by being represented by a formula (IV) and abbreviated as p-TPB-COF-M:
8. the method of claim 7 for preparing a tetraphenylbenzene-based isomeric covalent organic framework material, characterized by the steps of: 23.5 mg: dispersing p-TPB into n-butanol at a ratio of 1mL to obtain a dispersion, adding an acetic acid aqueous solution as a catalyst, uniformly mixing, and reacting under a reflux condition to obtain an isomeric covalent organic framework material based on tetraphenylbenzene, wherein the isomeric covalent organic framework material is shown as (IV) and is referred to as p-TPB-COF-M for short;
the reaction formula is as follows:
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| CN114324695A (en) * | 2021-12-27 | 2022-04-12 | 山东英盛生物技术有限公司 | Method and kit for analyzing vitamin K1 and application of kit |
| CN114773550A (en) * | 2022-04-25 | 2022-07-22 | 四川大学 | Covalent organic framework material with hardness and softness as well as preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277217A (en) * | 2013-07-11 | 2015-01-14 | 中国科学院大连化学物理研究所 | Imine bond-connected polymer material and preparation method thereof |
| EP2832767A1 (en) * | 2013-07-31 | 2015-02-04 | Fundación Imdea Nanociencia | Method for the Synthesis of Covalent Organic Frameworks |
| CN110003026A (en) * | 2019-04-04 | 2019-07-12 | 天津大学 | A kind of covalent organic frame material Py-COF and preparation method |
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| CN104277217A (en) * | 2013-07-11 | 2015-01-14 | 中国科学院大连化学物理研究所 | Imine bond-connected polymer material and preparation method thereof |
| EP2832767A1 (en) * | 2013-07-31 | 2015-02-04 | Fundación Imdea Nanociencia | Method for the Synthesis of Covalent Organic Frameworks |
| CN110003026A (en) * | 2019-04-04 | 2019-07-12 | 天津大学 | A kind of covalent organic frame material Py-COF and preparation method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114324695A (en) * | 2021-12-27 | 2022-04-12 | 山东英盛生物技术有限公司 | Method and kit for analyzing vitamin K1 and application of kit |
| CN114773550A (en) * | 2022-04-25 | 2022-07-22 | 四川大学 | Covalent organic framework material with hardness and softness as well as preparation method and application thereof |
| CN114773550B (en) * | 2022-04-25 | 2023-04-07 | 四川大学 | Covalent organic framework material with hardness and softness as well as preparation method and application thereof |
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