CN114736343B - Preparation method of mild covalent organic framework material - Google Patents
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract 4
- -1 cetyl quaternary ammonium salt Chemical class 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- PNGBYKXZVCIZRN-UHFFFAOYSA-M sodium;hexadecane-1-sulfonate Chemical group [Na+].CCCCCCCCCCCCCCCCS([O-])(=O)=O PNGBYKXZVCIZRN-UHFFFAOYSA-M 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- MHXLAKJJNRIVDR-UHFFFAOYSA-N 2,4,6-trihydroxybenzene-1,3,5-tricarboxylic acid Chemical compound OC1=C(C(=C(C(=C1C(=O)O)O)C(=O)O)O)C(=O)O MHXLAKJJNRIVDR-UHFFFAOYSA-N 0.000 claims 3
- HYCOYJYBHKAKGQ-UHFFFAOYSA-N ethylmesitylene Natural products CCC1=C(C)C=C(C)C=C1C HYCOYJYBHKAKGQ-UHFFFAOYSA-N 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000003795 desorption Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000001308 synthesis method Methods 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000001144 powder X-ray diffraction data Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000003141 primary amines Chemical group 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000003408 phase transfer catalysis Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method of a mild covalent organic framework material, which takes a common organic compound as a raw material, takes water and an organic solvent as solvents, and synthesizes the covalent organic framework material with controllable morphology under the catalysis of a phase transfer catalyst (containing surfactants) at normal temperature and normal pressure. The method can prepare the covalent organic framework with controllable morphology by simple stirring in an open system, is simple to operate, is environment-friendly and is suitable for industrial mass production. The covalent organic framework prepared by the method has excellent crystallinity and high specific surface area, and has controllable morphology, so that the covalent organic framework has wide application prospects in the fields of gas adsorption and separation, photo (electro) catalysis and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of high polymer organic porous materials, relates to a method for preparing a covalent organic framework by utilizing phase transfer catalysis (including but not limited to surfactant), and particularly relates to a mild and efficient preparation method of the covalent organic framework.
Background
Covalent organic frameworks (Covalent organic frameworks, COFs) are organic polymers synthesized using topological design, in which the organic units can be covalently integrated into highly ordered topologies. The COFs have the characteristics of good crystallinity, high specific surface area, excellent stability, permanent porosity, low density and the like, and have wide application prospects in the fields of gas trapping, separation, sensing, catalysis, semiconductors and the like.
In the last decade, most of COFs synthesis was performed under severe solvothermal conditions, and the reaction process also requires an oxygen-free or inert gas atmosphere, high temperature and pressure, long-term reaction, etc. For industrial mass production, such reaction conditions certainly increase the risk in the production process, mass production is difficult and the synthesis cost is extremely high. Of course, some new synthetic methods have been developed, such as: ion thermal method, microwave heating method, mechanical synthesis method, photo-induced synthesis method, acoustic-induced synthesis method, electrochemical synthesis method, etc. Although the synthetic methods are somewhat simplified compared with solvothermal methods, the synthetic methods still have the technical problems of non-adjustable morphology, complex reaction device, complex operation, large energy consumption, incapability of mass preparation and the like.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for preparing a covalent organic framework by using a phase transfer method, which can solve the technical problems that the morphology of the covalent organic framework in the prior art is difficult to regulate, the energy consumption in the preparation process is high, the preparation process is dangerous and mass preparation cannot be carried out.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the invention discloses a preparation method of a mild covalent organic framework material, which comprises the steps of dissolving one organic compound in one solvent to serve as a continuous phase, dissolving the other organic compound in the other solvent to serve as a disperse phase, using a surfactant as a phase transfer catalyst, adding the disperse phase and the catalyst into the continuous phase, fully stirring to form emulsion, carrying out polymerization reaction, and then washing and drying a product to obtain the covalent organic framework.
Preferably, when an aldehyde compound is used as the organic compound for preparing the continuous phase, an amine compound is used as the organic compound for preparing the disperse phase; or when the amine compound is adopted as the organic compound for preparing the continuous phase, the aldehyde compound is adopted as the organic compound for preparing the disperse phase; the polycondensation reaction is rapidly carried out in the emulsion state when two phases are contacted, so that the uniform morphology is maintained;
wherein, when the aldehyde compound is an organic compound containing at least two aldehyde groups, the amine compound is an organic compound containing at least three primary amine groups; alternatively, when the aldehyde compound is an organic compound having at least three aldehyde groups, the amine compound is an organic compound having at least two primary amine groups.
Further preferably, the molar ratio of amine compound to aldehyde compound is 1:1 to 2.
Further preferably, the feed ratio of aldehyde compound or amine compound to solvent in the continuous phase is 0.01mmol: (1-3.5) mL;
in the disperse phase, the feeding ratio of aldehyde compounds or amine compounds to the solvent is 0.01mmol: (15-45) mL.
Further preferably, the ratio of the surfactant to the continuous phase solvent is (0.2 to 2) mg:1mL; in the formed emulsion system, the volume ratio of the disperse phase solvent to the continuous phase solvent is 3.5: (10-45).
Further preferably, the surfactant is a cationic surfactant having a side chain alkyl group or an anionic surfactant having a side chain alkyl group.
Still more preferably, a cationic surfactant having a side chain alkyl group such as cetyl quaternary ammonium salt and the like, and an anionic surfactant having a side chain alkyl group such as sodium cetyl sulfonate and the like.
Preferably, the solvent is water, dichloromethane, ethyl acetate, dioxane, mesitylene, n-butanol or o-dichlorobenzene.
Preferably, the polymerization temperature is 18-60 ℃, the reaction time is 1-24 h, and the stirring speed is 300-800 rpm.
Preferably, the disperse phase is added at a rate of 0.001-0.1 mL/s for regulating and controlling the covalent organic frameworks to have high specific surface area and uniform morphology.
Preferably, the washing is performed at least three times by using a good solvent of the surfactant, and then at least three times by using a good solvent of the organic compound;
the drying conditions are as follows: the temperature is 60-100 ℃ and the time is 12-24 h.
Covalent organic framework materials prepared by the synthetic methods of the present invention include, but are not limited to, imines, ketene amines, hydrazones, azines, olefins, or polyimides.
Compared with the prior art, the invention has the following beneficial effects:
the invention synthesizes the covalent organic framework with high specific area, high crystallinity and controllable morphology by using the surfactant with the catalytic function as the phase transfer catalyst. The invention selects the surfactant as the phase transfer catalyst to play a role in catalysis and emulsification, improves the specific surface area and crystallinity of the material, and can regulate and control the morphology, and the reaction can be carried out at room temperature, thus being a new synthesis method with multiple purposes. In addition, compared with a solvothermal synthesis method, a microwave synthesis method, an ion thermal synthesis method and the like, the method has the advantages of energy conservation, environmental protection, simplicity in operation, low cost, high yield and the like, and compared with a covalent organic framework material obtained by a mechanical synthesis method, the method has higher specific surface area. The method can also realize mass production and has industrial production potential.
Drawings
FIG. 1 is a PXRD picture of a covalent organic framework prepared in example 1 of the present invention;
FIG. 2 is a graph showing the adsorption and desorption of nitrogen from a covalent organic framework prepared in example 1 of the present invention;
FIG. 3 is an SEM image of a covalent organic framework prepared according to example 1 of the present invention; wherein (a) is an SEM photograph taken at 200nm scale and (b) is an SEM photograph taken at 500nm scale
FIG. 4 is a PXRD picture of a covalent organic framework prepared in example 2 of the present invention;
FIG. 5 is a graph showing the adsorption and desorption of nitrogen from a covalent organic framework prepared in example 2 of the present invention;
FIG. 6 is an SEM image of a covalent organic framework prepared according to example 2 of the present invention; wherein (a) is an SEM photograph taken at 200nm scale and (b) is an SEM photograph taken at 500nm scale
FIG. 7 is a PXRD picture of a covalent organic framework prepared in example 3 of the present invention;
FIG. 8 is a graph showing the adsorption and desorption of nitrogen from a covalent organic framework prepared in example 3 of the present invention;
FIG. 9 is an SEM image of a covalent organic framework prepared according to example 3 of the present invention; wherein, (a) is a photograph taken on a 1 μm scale; (b) photographs taken at a 1 μm scale;
FIG. 10 is a PXRD picture of a covalent organic framework prepared in example 4 of the present invention;
FIG. 11 is a graph showing the adsorption and desorption of nitrogen from a covalent organic framework prepared in example 4 of the present invention;
FIG. 12 is an SEM photograph of a covalent organic framework prepared according to example 4 of the present invention; wherein, (a) is an SEM photograph taken at a 2 μm scale and (b) is an SEM photograph taken at a 1 μm scale;
fig. 13 is a schematic view of the catalytic principle of the present invention.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which 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 present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present invention and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the invention described herein may be implemented in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the attached drawing figures:
referring to fig. 13, the preparation method of the covalent organic framework of the present invention adopts a solvent to dissolve one organic compound 1 as a continuous phase, another solvent to dissolve another organic compound 2 as a dispersed phase, a surfactant as a phase transfer catalyst, adding the dispersed phase and the catalyst into the continuous phase, fully stirring to form an emulsion for polymerization reaction, and then washing and drying the product to obtain the covalent organic framework.
Example 1
A method of preparing a covalent organic framework material comprising the steps of:
step 1: sodium hexadecyl sulfonate (15 mg) was dissolved in water (15 mL), and p-phenylenediamine (24 mg,0.225 mmol) was then added thereto and stirred for 10 minutes to prepare a mixed solution;
step 2: 2,4, 6-Triformylparaben (31.5 mg,0.15 mmol) was dissolved in methylene chloride (3.5 mL), which was added dropwise (v=0.005 mL/s) to the mixed solution prepared in step 1, and stirred at room temperature for 12 hours (r=500). After the reaction is finished, filtering, sequentially extracting with methanol and tetrahydrofuran respectively for 12h, and drying in a vacuum drying oven at 80 ℃ for 12h to obtain the enonamine covalent organic framework material TpPa of red powdery solid, wherein the yield is as follows: 89%.
The PXRD pattern of the covalent organic framework material TpPa of the product obtained in example 1 is shown in fig. 1, and it can be found from fig. 1 that TpPa forms a highly crystalline two-dimensional covalent organic framework, and that the diffraction peaks of TpPa correspond to the (100), (200), (210) and (001) crystal planes at positions with 2 theta values of 4.6,8.1, 12.6 and 27.1, respectively.
The specific surface area calculated from the nitrogen adsorption and desorption curve of the covalent organic framework material TpPa shown in fig. 2 is: 803.1m 2 /g
As is evident from FIG. 3, tpPa with spherical morphology is synthesized by the method.
Example 2
A method of preparing a covalent organic framework material comprising the steps of:
step 1: sodium hexadecyl sulfonate (15 mg) was dissolved in water (15 mL), and p-phenylenediamine (24 mg,0.225 mmol) was then added thereto and stirred for 10 minutes to prepare a mixed solution;
step 2: 2,4, 6-Triformylparaben (31.5 mg,0.15 mmol) was dissolved in ethyl acetate (3.5 mL), and was added dropwise (v=0.005 mL/s) to the mixed solution prepared in step 1, followed by stirring at room temperature for 12 hours (r=500). After the reaction is finished, filtering, sequentially extracting with methanol and tetrahydrofuran respectively for 12h, and drying in a vacuum drying oven at 80 ℃ for 12h to obtain the enonamine covalent organic framework material TpPa of red powdery solid, wherein the yield is as follows: 85%.
The PXRD pattern of the covalent organic framework material TpPa of the product obtained in example 2 is shown in fig. 4, and it can be found from fig. 4 that TpPa forms a highly crystalline two-dimensional covalent organic framework, and that the diffraction peaks of TpPa correspond to the (100), (200), (210) and (001) crystal planes at positions having 2 theta values of 4.7,8.2, 12.6 and 26.9, respectively.
Fig. 5 is a nitrogen adsorption and desorption curve of the covalent organic framework material TpPa prepared in example 2, and the calculated specific surface area is: 987.6m 2 /g。
Fig. 6 shows that TpPa of the fiber morphology is synthesized by the method.
Example 3
A method of preparing a covalent organic framework material comprising the steps of:
step 1: sodium hexadecyl sulfonate (15 mg) was dissolved in water (15 mL), and p-phenylenediamine (24 mg,0.225 mmol) was then added thereto and stirred for 10 minutes to prepare a mixed solution;
step 2: 2,4, 6-Triformylparaben (31.5 mg,0.15 mmol) was dissolved in mesitylene (3.5 mL), and was added dropwise (v=0.005 mL/s) to the mixed solution prepared in step 1, followed by stirring at room temperature for 12 hours (r=500). After the reaction is finished, filtering, sequentially extracting with methanol and tetrahydrofuran respectively for 12h, and drying in a vacuum drying oven at 80 ℃ for 12h to obtain the enonamine covalent organic framework material Tp-Pa of red powdery solid, wherein the yield is as follows: 91%.
The PXRD pattern of the covalent organic framework material TpPa of the product obtained in example 3 is shown in fig. 7, and it can be found from fig. 7 that TpPa forms a highly crystalline two-dimensional covalent organic framework, and that the diffraction peaks of TpPa are at positions with 2 theta values of 4.7,8.1, 12.6 and 27.1, corresponding to the (100), (200), (210) and (001) crystal planes, respectively.
Fig. 8 is a nitrogen adsorption and desorption curve of the covalent organic framework material TpPa prepared in example 3, and the calculated specific surface area is: 998.7m 2 /g。
FIG. 9 shows that TpPa of the cluster morphology is synthesized by the method.
Example 4
A method of preparing a covalent organic framework material comprising the steps of:
step 1: sodium hexadecyl sulfonate (15 mg) was dissolved in water (15 mL), and p-phenylenediamine (24 mg,0.225 mmol) was added thereto and stirred for 10 minutes to prepare a mixed solution;
step 2: 2,4, 6-Triformylparaben (31.5 mg,0.15 mmol) was dissolved in n-butanol (3.5 mL), and was added dropwise (v=0.005 mL/s) to the mixed solution prepared in step 1, followed by stirring at room temperature for 12 hours (r=500). After the reaction is finished, filtering, sequentially extracting with methanol and tetrahydrofuran respectively for 12h, and drying in a vacuum drying oven at 80 ℃ for 12h to obtain the enonamine covalent organic framework material Tp-Pa of red powdery solid, wherein the yield is as follows: 82%.
It can be seen from fig. 10 that TpPa forms a highly crystalline two-dimensional covalent organic framework, and that the diffraction peaks of TpPa correspond to the (100), (200), (210) and (001) crystal planes at positions having 2θ values 4.7,8.1, 12.5, 26.5, respectively.
Fig. 11 is a nitrogen adsorption and desorption curve of the covalent organic framework material TpPa prepared in example 4, and the calculated specific surface area is: 424.4m 2 /g。
FIG. 12 shows that TpPa with clustered morphology is synthesized by the method.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (6)
1. A method of preparing a mild covalent organic framework material comprising:
dissolving p-phenylenediamine with water to serve as a continuous phase, dissolving 2,4, 6-tricarboxyl phloroglucinol serving as a disperse phase with an organic solvent, using a surfactant as a phase transfer catalyst, adding the disperse phase and the catalyst into the continuous phase, fully stirring to form emulsion, performing polymerization reaction, and washing and drying a product to obtain a covalent organic framework; wherein:
the organic solvent is selected from one of dichloromethane, ethyl acetate, mesitylene and n-butanol;
the polycondensation reaction is rapidly carried out in the emulsion state when two phases are contacted, so that the uniform morphology is maintained;
the molar ratio of p-phenylenediamine to 2,4, 6-tricarboxyl phloroglucinol is 1: 1-2;
the polymerization reaction temperature is 18-60 ℃, the reaction time is 1-24 hours, and the stirring speed is 300-800 rpm;
the surfactant is sodium cetyl sulfonate or cetyl quaternary ammonium salt.
2. The method of preparing a mild covalent organic framework material according to claim 1, wherein a feeding ratio of p-phenylenediamine to water in the continuous phase is 0.225 mmol:15 mL;
the feed ratio of 2,4, 6-tricarboxyl phloroglucinol to organic solvent in the dispersed phase was 0.15 mmol:3.5mL.
3. The method of preparing a mild covalent organic framework material according to claim 1, wherein a ratio of surfactant to continuous phase solvent is 15 mg:15 mL; in the formed emulsion system, the volume ratio of the disperse phase solvent to the continuous phase solvent is 3.5:15.
4. the method of claim 1, wherein the dispersed phase is added at a rate of 0.001-0.1 mL/s.
5. The method of claim 1, wherein the washing is performed at least three times with a good solvent for the surfactant and then at least three times with a good solvent for the organic compound.
6. The method of preparing a mild covalent organic framework material according to claim 1, wherein said drying conditions are: the temperature is 60-100 ℃ and the time is 12-24 hours.
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| WO2022061666A1 (en) * | 2020-09-24 | 2022-03-31 | 浙江大学 | Method for preparing hollow covalent organic framework material |
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