阅读说明：本技术 一种基于三蝶烯的氨基衍生物的三维共价有机框架材料及其制备方法 (Three-dimensional covalent organic framework material based on triptycene amino derivative and preparation method thereof ) 是由 方千荣 李辉 陈冯钱 于 2020-12-09 设计创作，主要内容包括：本发明公开了一种基于三蝶烯的氨基衍生物的三维共价有机框架材料及其制备方法,属于新型共价有机骨架材料的合成与制备领域,该三维共价有机框架材料由2,3,6,7,14,15-六(4-甲酰基苯基)三蝶烯和2,3,6,7,14,15-六(2′,6′-二异丙基-4′-氨基)三蝶烯为构筑单元通过希夫碱反应缩合形成的有机框架结构。本发明首次基于三蝶烯合成了立体六连接的2,3,6,7,14,15-六(2′,6′-二异丙基-4′-氨基)三蝶烯,该材料具有高的结晶度,永久的孔隙度和良好的热稳定性,且由于三蝶烯基团的引入,本发明得到的共价有机框架具有良好的H_2吸附能力和不错的CO_2,CH_4吸附能力。(The invention discloses a three-dimensional covalent organic framework material based on an amino derivative of triptycene and a preparation method thereof, belonging to the field of synthesis and preparation of novel covalent organic framework materials, wherein the three-dimensional covalent organic framework material is an organic framework structure formed by condensing 2,3,6,7,14, 15-hexa (4-formylphenyl) triptycene and 2,3,6,7,14, 15-hexa (2 ', 6 ' -diisopropyl-4 ' -amino) triptycene serving as construction units through Schiff base reaction. The invention synthesizes the stereoscopically hexa-linked 2,3,6,7,14, 15-hexa (2 ', 6 ' -diisopropyl-4 ' -amino) triptycene for the first time based on triptycene, the material has high crystallinity, permanent porosity and good thermal stability, and due to the introduction of triptycene groups, the obtained covalent organic framework has good H 2 AdsorptionCapacity and good CO 2 ,CH 4 Adsorption capacity.)

1. A three-dimensional covalent organic framework material based on an amino derivative of triptycene is characterized in that the material is an organic framework structure formed by condensing 2,3,6,7,14, 15-hexa (4-formylphenyl) triptycene and 2,3,6,7,14, 15-hexa (2 ', 6 ' -diisopropyl-4 ' -amino) triptycene through Schiff base reaction as building units, and the structural formula is as follows:

。

2. the three-dimensional covalent organic framework material based on amino derivatives of triptycene of claim 1, characterized in that said 2,3,6,7,14, 15-hexa (2 ', 6 ' -diisopropyl-4 ' -amino) triptycene (hdiapt) has the chemical formula:

。

3. the three-dimensional covalent organic framework material based on an amino derivative of triptycene of claim 1, characterized by the following specific steps:

grinding two stereo six-node construction units, namely 2,3,6,7,14, 15-hexa (4-formylphenyl) triptycene and 2,3,6,7,14, 15-hexa (2 ', 6 ' -diisopropyl-4 ' -amino) triptycene on a mortar uniformly, adding the mixture into a glass tube, adding an organic solvent, adding a catalyst, namely an acetic acid aqueous solution, putting the glass tube into liquid nitrogen for freezing, vacuumizing, flame sealing the tube, and finally putting the tube into an oven for heating to obtain the three-dimensional covalent organic framework material (JUC-569) based on the triptycene amino derivative.

4. The method of claim 3, wherein the two stereo six-node building units 2,3,6,7,14, 15-hexa (4-formylphenyl) triptycene and 2,3,6,7,14, 15-hexa (2 ', 6 ' -diisopropyl-4 ' -amino) triptycene are present in a molar ratio of 1: 0.8-1.

5. The method for preparing the novel triptycene-based amino derivative three-dimensional covalent organic framework material as claimed in claim 3, wherein the organic solvent is a mixed solvent of 1-butanol and o-dichlorobenzene, and the mixing volume ratio is 1: 0.2-0.25.

6. The method for preparing the novel triptycene-based amino derivative three-dimensional covalent organic framework material of claim 3, wherein the concentration of the aqueous acetic acid solution is 6-9M.

7. The method for preparing novel triptycene-based amino derivative three-dimensional covalent organic framework material as claimed in claim 3, wherein the heating temperature is 120-140 ℃ and the reaction time is 3-7 days.

8. The method for preparing the novel triptycene-based amino derivative three-dimensional covalent organic framework material of claim 3, wherein the 2,3,6,7,14, 15-hexa (2 ', 6 ' -diisopropyl-4 ' -amino) triptycene is prepared by the following method:

reacting 2,3,6,7,14, 15-hexabromotriptycene, (N- (diphenylmethylene) -2, 6-diisopropyl-4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) aniline), tetrakis (triphenylphosphine) palladium and cesium carbonate in anhydrous tetrahydrofuran and water at 75-80 ℃, separating to remove a water phase after the reaction is finished, adding ethyl acetate to promote the product to be separated out, performing suction filtration, washing with ethyl acetate, and drying to obtain a first-step product; dissolving the product of the first step in tetrahydrofuran solution, adding hydrochloric acid, and hydrolyzing at 70-75 ℃ to obtain 2,3,6,7,14, 15-hexa (2 ', 6 ' -diisopropyl-4 ' -amino) triptycene.

9. The method for preparing the novel triptycene-based amino derivative three-dimensional covalent organic framework material as claimed in claim 8, wherein the molar ratio of 2,3,6,7,14, 15-hexabromotriptycene, (N- (diphenylmethylene) -2, 6-diisopropyl-4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) aniline), tetrakis (triphenylphosphine) palladium and cesium carbonate is 1:10-12:0.1-0.3: 12-14; the volume ratio of the tetrahydrofuran to the water is 2.5: 1; stirring for 72h at 80 ℃; the hydrochloric acid solution is 4 moL/L; stirring at 70 deg.C for 24 h.

10. The method for preparing the novel triptycene-based amino derivative three-dimensional covalent organic framework material of claim 9, wherein the 2,3,6,7,14, 15-hexabromotriptycene is prepared from triptycene through bromination, coupling with Suzuki and hydrolysis reaction;

the method comprises the following specific steps: dissolving triptycene and iron powder in dichloroethane, and slowly adding liquid bromine to reflux at 80 ℃; and (3) cooling to room temperature after the reaction is finished, removing residual liquid bromine, then removing the solvent by spin drying, washing and drying to obtain the 2,3,6,7,14, 15-hexabromotriptycene shown as (I):

the purification is to extract, wash and purify the mixture after reaction by using dichloromethane as a developing agent column;

wherein the molar ratio of the triptycene to the iron powder to the liquid bromine is 1:0.35-0.4:6-7, preferably 1:0.37: 6.5; the volume of the dichloroethane is 60 mL; refluxing was carried out at 85 ℃ for 6 h.

Technical Field

The invention belongs to the field of synthesis and preparation of novel covalent organic framework materials, and particularly relates to a method for synthesizing a novel covalent organic framework material with an acs topological structure based on two hexabromotriptycene derivatives.

Background

Since the first example of Covalent Organic Frameworks (COFs) prepared by Yaghi project composition work in 2005, the material, as a novel crystalline Organic porous polymer material, has attracted wide interest in different fields, including gas adsorption and separation, catalysis, photoelectron and other fields, due to the characteristics of regular channel structure, high porosity, high stability, structure designability and the like. Most of the research is currently focused on two-dimensional COFs with AA stacking patterns. Three-dimensional COFs are considered ideal platforms for many applications due to their interconnected channels and superior surface area. However, to date, only a few topologies have been available for 3D COFs, such as ctn, bor, dia, and pts, and almost all topologies are based on four-connection building blocks, the structures of which are extremely limited, severely restricting the development of three-dimensional COF materials.

Disclosure of Invention

In order to overcome the defects in the prior art and enrich the types of COFs, the invention provides a brand-new synthetic method of amino derivatives based on hexabromotriptycene, and a novel covalent organic framework material is obtained by utilizing the method, and the covalent organic framework material has high crystallinity, permanent porosity and good thermal stability, and has good H due to the introduction of triptycene groups₂Adsorption capacity and good CO₂,CH₄Adsorption capacity.

The invention is realized by the following technical scheme:

a three-dimensional covalent organic framework material based on an amino derivative of triptycene is an organic framework structure formed by condensation of 2,3,6,7,14, 15-hexa (4-formylphenyl) triptycene and 2,3,6,7,14, 15-hexa (2 ', 6 ' -diisopropyl-4 ' -amino) triptycene serving as building units through Schiff base reaction, and the structural formula is as follows:

further, the chemical structural formula of the 2,3,6,7,14, 15-hexa (2 ', 6 ' -diisopropyl-4 ' -amino) triptycene (HDIATP) is shown as follows:

a preparation method of a three-dimensional covalent organic framework material based on an amino derivative of triptycene comprises the following specific steps:

grinding two stereo six-node construction units, namely 2,3,6,7,14, 15-hexa (4-formylphenyl) triptycene and 2,3,6,7,14, 15-hexa (2 ', 6 ' -diisopropyl-4 ' -amino) triptycene on a mortar uniformly, adding the mixture into a glass tube, adding an organic solvent, adding a catalyst, namely an acetic acid aqueous solution, putting the glass tube into liquid nitrogen for freezing, vacuumizing, flame sealing the tube, and finally putting the tube into an oven for heating to obtain the three-dimensional covalent organic framework material (JUC-569) based on the triptycene amino derivative.

Further, the molar ratio of the two stereo six-node construction units 2,3,6,7,14, 15-hexa (4-formylphenyl) triptycene to 2,3,6,7,14, 15-hexa (2 ', 6 ' -diisopropyl-4 ' -amino) triptycene is 1: 0.8-1; the optimum molar ratio is 1: 1.

Further, the organic solvent is a mixed solvent of 1-butanol and o-dichlorobenzene, and the mixing volume ratio is 1: 0.2-0.25; the optimal ratio is 1: 0.25.

Further, the concentration of the acetic acid aqueous solution is 3-9M; the optimum concentration is 9M.

Further, the heating temperature is 120-140 ℃, and the reaction time is 3-7 days; the optimum reaction temperature and time were 120 ℃ and 5 days.

Further, the 2,3,6,7,14, 15-hexa (2 ', 6 ' -diisopropyl-4 ' -amino) triptycene is prepared by the following method:

reacting 2,3,6,7,14, 15-hexabromotriptycene, (N- (diphenylmethylene) -2, 6-diisopropyl-4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) aniline), tetrakis (triphenylphosphine) palladium and cesium carbonate in anhydrous tetrahydrofuran and water at 75-80 ℃, separating to remove a water phase after the reaction is finished, adding ethyl acetate to promote the product to be separated out, performing suction filtration, washing with ethyl acetate, and drying to obtain a first-step product; dissolving the product of the first step in tetrahydrofuran solution, adding hydrochloric acid, and hydrolyzing at 70-75 ℃ to obtain 2,3,6,7,14, 15-hexa (2 ', 6 ' -diisopropyl-4 ' -amino) triptycene.

Further, the molar ratio of the 2,3,6,7,14, 15-hexabromotriptycene, (N- (diphenylmethylene) -2, 6-diisopropyl-4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) aniline), tetrakis (triphenylphosphine) palladium and cesium carbonate is 1:10-12:0.1-0.3:12-14, preferably 1:11:0.18: 13.

Further, the volume ratio of the tetrahydrofuran to the water is 2.5: 1; stirring at 80 deg.C for 72 h.

Further, the hydrochloric acid solution is 4 moL/L; stirring at 70 deg.C for 24 h.

Further, the 2,3,6,7,14, 15-hexabromotriptycene is prepared by carrying out bromination on triptycene, coupling with Suzuki and carrying out hydrolysis reaction;

the method comprises the following specific steps: dissolving triptycene and iron powder in dichloroethane, and slowly adding liquid bromine to reflux at 80 ℃; and (3) cooling to room temperature after the reaction is finished, removing residual liquid bromine, then removing the solvent by spin drying, washing and drying to obtain the 2,3,6,7,14, 15-hexabromotriptycene shown as (I):

the purification is to extract, wash and dry the mixture after reaction by using dichloromethane as a developing agent column for separation and purification.

Further, the mole ratio of the triptycene to the iron powder to the liquid bromine is 1:0.35-0.4:6-7, preferably 1:0.37: 6.5.

Further, the volume of the dichloroethane is 60 mL; refluxing was carried out at 85 ℃ for 6 h.

Compared with the prior art, the invention has the following advantages:

(1) the invention synthesizes the stereo hexa-connected 2,3,6,7,14, 15-hexa (2 ', 6 ' -diisopropyl-4 ' -amino) triptycene based on triptycene for the first time;

(2) the three-dimensional covalent organic framework material with the acs topological structure, which is constructed by two three-dimensional six-connection units, is synthesized for the first time.

Drawings

FIG. 1 is a powder X-ray diffraction pattern of JUC-569 synthesized by the present invention;

FIG. 2 is a Fourier infrared spectrum of JUC-569 synthesized by the present invention and raw material monomers;

FIG. 3 is a thermogravimetric analysis of JUC-569 synthesized in accordance with the present invention;

FIG. 4 shows N of JUC-569 synthesized by the present invention₂Adsorption and pore size mapping;

FIG. 5 shows the synthesis of JUC-569H₂Drawing;

FIG. 6 shows the synthesized JUC-569 CO₂Drawing;

FIG. 7 shows the synthesized CH JUC-569 of the present invention₂And (5) absorbing the attached drawings.

Detailed Description

The present invention will be described in detail with reference to the drawings and the detailed description, and the embodiments described herein are only for the purpose of illustrating and explaining the present invention, but are not to be construed as limiting the present invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.

Example 1

A novel three-dimensional covalent organic framework material based on an amino derivative of triptycene is an organic framework structure formed by condensing 2,3,6,7,14, 15-hexa (4-formylphenyl) triptycene and 2,3,6,7,14, 15-hexa (2 ', 6 ' -diisopropyl-4 ' -amino) triptycene through Schiff base reaction as building units, and the structural formula is as follows:

further, the chemical structural formula of the 2,3,6,7,14, 15-hexa (2 ', 6 ' -diisopropyl-4 ' -amino) triptycene (HDIATP) is shown as follows:

a preparation method of a three-dimensional covalent organic framework material based on an amino derivative of triptycene comprises the following specific steps:

(1) synthesis of 2,3,6,7,14, 15-hexabromotriptycene:

triptycene (1.00g) and iron powder (80mg) were dissolved in 60mL 1, 2-dichloroethane. After which 1.32mL of liquid bromine was slowly added to the flask. The mixture was then refluxed for 6 hours. After cooling the reaction to 25 ℃, the solvent and excess bromine were removed under reduced pressure. The residue was taken up in CHCl₂For developing the column layer separation of the solvent, CHCl is used₃Recrystallization and pure product as colorless, needle-like crystals with a yield of 79%.

(2) Synthesis of 2,3,6,7,14, 15-hexa (2 ', 6 ' -diisopropyl-4 ' -amino) triptycene (II):

2,3,6,7,14, 15-hexabromotriptycene (500mg), (N- (diphenylmethylene) -2, 6-diisopropyl-4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) aniline) (3.50g), tetrakis (triphenylphosphine) palladium (1.60g), cesium carbonate (2.90g) were reacted in 33.6mL of anhydrous tetrahydrofuran and 14.4mL of water at 75 deg.C, under N₂And reacting for 72h under protection. After the reaction is finished, separating liquid and removing a water phase, adding ethyl acetate to promote the product to be separated out, carrying out suction filtration, washing with ethyl acetate, and drying to obtain a first-step product; 900mg of the product of the first step are dissolved in 300mL of tetrahydrofuran and 40mL of 4M hydrochloric acid are slowly added and stirred at 75 ℃ for 24h to give 2,3,6,7,14, 15-hexa (2 ', 6 ' -diisopropyl-4 ' -amino) triptycene in 72% yield.

(3) Synthesis of three-dimensional covalent organic framework materials based on amino derivatives of triptycene:

2,3,6,7,14, 15-hexa (4-formylphenyl) triptycene (HFTP, 22.0mg) and 2,3,6,7,14, 15-hexa (2 ', 6 ' -diisopropyl-4 ' -amino) triptycene (HDIATP, 32.3mg) were ground uniformly in a mortar and added to a glass tube, then 0.8mL of 1, 2-o-dichlorobenzene, 0.2mL of 1-butanol, 0.1mL of acetic acid (9mol/L) were slowly added, the glass tube was frozen in liquid nitrogen, and the glass tube was blocked under a methane/oxygen flame with vacuum. And finally, putting the mixture into a 120 ℃ oven for heating for 3 days, after the reaction is finished, opening a glass tube by using a glass cutter, washing the product by using tetrahydrofuran and acetone for three times respectively, and then filtering. The solid product was dried in a vacuum oven at 65 ℃ for 3 hours to give the desired product in 86% yield as pale yellow. The reaction formula is shown as the following formula.

Example 2

A preparation method of a three-dimensional covalent organic framework material based on an amino derivative of triptycene comprises the following specific steps:

(1) synthesis of 2,3,6,7,14, 15-hexabromotriptycene:

triptycene (1.00g) and iron powder (80mg) were dissolved in 60mL 1, 2-dichloroethane. After which 1.32mL of liquid bromine was slowly added to the flask. The mixture was then refluxed for 6 hours. After cooling the reaction to 25 ℃, the solvent and excess bromine were removed under reduced pressure. The residue was taken up in CHCl₂For developing the column layer separation of the solvent, CHCl is used₃Recrystallization and pure product as colorless, needle-like crystals in 77% yield.

(2) Synthesis of 2,3,6,7,14, 15-hexa (2 ', 6 ' -diisopropyl-4 ' -amino) triptycene (II):

2,3,6,7,14, 15-hexabromotriptycene (500mg), (N- (diphenylmethylene) -2, 6-diisopropyl-4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) aniline) (3.50g), tetrakis (triphenylphosphine) palladium (1.60g), cesium carbonate (2.90g) were reacted in 33.6mL of anhydrous tetrahydrofuran and 14.4mL of water at 75 deg.C, under N₂And reacting for 72h under protection. After the reaction is finished, separating liquid and removing a water phase, adding ethyl acetate to promote the product to be separated out, carrying out suction filtration, washing with ethyl acetate, and drying to obtain a first-step product; 900mg of the product of the first step are dissolved in 300mL of tetrahydrofuran and 40mL of 4M hydrochloric acid are slowly added and stirred at 80 ℃ for 24h to give 2,3,6,7,14, 15-hexa (2 ', 6 ' -diisopropyl-4 ' -amino) triptycene in 71% yield.

(3) Synthesis of three-dimensional covalent organic framework materials based on amino derivatives of triptycene:

2,3,6,7,14, 15-hexa (4-formylphenyl) triptycene (HFTP, 22.0mg) and 2,3,6,7,14, 15-hexa (2 ', 6 ' -diisopropyl-4 ' -amino) triptycene (HDIATP, 32.3mg) were ground uniformly in a mortar and added to a glass tube, then 0.7mL of 1, 2-o-dichlorobenzene, 0.3mL of 1-butanol, 0.1mL of acetic acid (6mol/L) were slowly added, the glass tube was frozen in liquid nitrogen, and the glass tube was blocked under a methane/oxygen flame with vacuum. Finally, the mixture is put into a 120 ℃ oven to be heated for 5 days, after the reaction is finished, a glass cutting knife is used for opening a glass tube, the product is washed by tetrahydrofuran and acetone for three times respectively, and then the filtration treatment is carried out. The solid product was dried in a vacuum oven at 65 ℃ for 3 hours to give the desired product in 78% yield as pale yellow. The reaction formula is shown as the following formula.

As shown in fig. 1, by comparing the powder X-ray diffraction pattern simulated by the Material Studio software with the powder X-ray diffraction pattern of the JUC-569 synthesized by the present invention, it can be determined that the three-dimensional covalent organic framework Material of the set target is successfully synthesized by the method of the present invention;

as shown in FIG. 2, two monomers (HFPTP and HDIAATP) were compared with the inventive compoundsFourier infrared spectrum of the formed JUC-569 by HFPTP at 3403cm^-1Of (2) is-NH₂Absorption peak and HDIATP at 1699cm^-1Disappearance of the-CHO absorption Peak of (1), while the JUC-569 value was found at 1625cm^-1The formation of imine bonds is evidenced by the appearance of an infrared absorption peak of (a) ═ N.

As shown in FIG. 3, the slight weight loss of the JUC-569 before 400 ℃ is caused by the volatilization of solvent base and a small amount of moisture, and the material does not start to have obvious weight loss until about 400 ℃, which shows that the JUC-569 can resist the high temperature of 400 ℃.

N of JUC-569 as shown in FIG. 4₂The adsorption proves that the specific surface area of JUC-569 reaches 1104m² g^-1The pore diameter is micropore which is mainly distributed about 1.8 nm.

As shown in FIG. 5, JUC-569 has a good H₂The adsorption capacity can reach up to 167cm under the condition of 77K and 1bar³/g。

As shown in FIG. 6, JUC-569 can adsorb CO at maximum under the conditions of 273K and 1bar₂ 48cm³Per g, maximum CO adsorption at 298K, 1bar₂ 31cm³/。

As shown in FIG. 7, JUC-569 can adsorb CH at maximum under the conditions of 273K and 1bar₄ 19cm³The highest CH can be adsorbed at 298K under 1bar₄ 11cm³/。

The preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.