CN109575308A - A kind of fluorine-containing covalent organic frame compound of two dimension without catalysis high efficiency preparation method - Google Patents
A kind of fluorine-containing covalent organic frame compound of two dimension without catalysis high efficiency preparation method Download PDFInfo
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 37
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000011737 fluorine Substances 0.000 title claims abstract description 35
- 150000001875 compounds Chemical class 0.000 title claims abstract description 29
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012043 crude product Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 239000000047 product Substances 0.000 claims abstract description 12
- 238000007872 degassing Methods 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000007789 sealing Methods 0.000 claims abstract description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 28
- 239000001569 carbon dioxide Substances 0.000 claims description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- SDXUIOOHCIQXRP-UHFFFAOYSA-N 1,2,4,5-tetrafluorobenzene Chemical compound FC1=CC(F)=C(F)C=C1F SDXUIOOHCIQXRP-UHFFFAOYSA-N 0.000 claims description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 9
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 9
- 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 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- -1 schiff bases amine aldehyde Chemical class 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 4
- 229940100630 metacresol Drugs 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000002262 Schiff base Substances 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 6
- 238000002604 ultrasonography Methods 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 239000011521 glass Substances 0.000 description 20
- 238000010992 reflux Methods 0.000 description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000000944 Soxhlet extraction Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000013310 covalent-organic framework Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- MCNQUWLLXZZZAC-UHFFFAOYSA-N 4-cyano-1-(2,4-dichlorophenyl)-5-(4-methoxyphenyl)-n-piperidin-1-ylpyrazole-3-carboxamide Chemical compound C1=CC(OC)=CC=C1C1=C(C#N)C(C(=O)NN2CCCCC2)=NN1C1=CC=C(Cl)C=C1Cl MCNQUWLLXZZZAC-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
Classifications
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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
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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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)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of fluorine-containing covalent organic frame compounds of two dimension without catalysis high efficiency preparation method, in organic solvent by monomer material dispersion, vacuumizes-degassing process, sealing ultrasound by liquid nitrogen frozen-, temperature control reacts to obtain crude product.Filtration of crude product is washed, then is dried up to the fluorine-containing covalent organic frame compound.The present processes are not necessarily to catalyst, and product of good performance can be obtained in five minutes in reaction, have high-specific surface area and regular meso-hole structure, and contain a large amount of fluorine atoms, store in gas absorption, ionic adsorption etc. has potential application prospect.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of fluorine-containing covalent organic frame (COFs) of two dimension
Compound without catalysis high efficiency preparation method.
Background technique
Covalent organic frame (COFs) is former molecular emerging by the one kind being covalently keyed by lightweights such as C, H, O, N, B
Organic porous material, the Omar.Yaghi group by University of California Berkeley in 2005 report for the first time (A.P.Cote,
Science.310(2005)1166–1170.).For example stability of material is good, density is low for COFs performance outstanding, large specific surface area,
Cellular structure is abundant, designability is strong, building monomer multiplicity etc. make its gas storage, absorption, catalysis, photoelectricity, energy stores,
Biology carries the various aspects such as medicine and has a wide range of applications.
Currently, preparing the most common method of covalent organic frame is solvent-thermal method, and using acetic acid as catalyst, the reaction time
3-10 days, wherein (Chen Long two dimension covalently manage by the synthesis of organic framework and performance study Beijing [D] for Beijing Institute of Technology
Work university, 2015.) and Central South University (D.-G.Wang, N.Li, Y.Hu, S.Wan, M. Song, G.Yu, Y.Jin, W.Wei,
K.Han,G.-C.Kuang,et al.,ACS Applied Materials& Interfaces 2018,DOI 10.1021/
Acsami.8b14213) synthesis of the fluorine-containing covalent organic frame containing triazine ring is studied, the synthetic method of proposition
It is both needed to acetic acid catalysis, is reacted three days.It can be seen that the existing reaction time is long, catalyst is needed, and it is good to be difficult to synthetic crystallization
Product.
Summary of the invention
Goal of the invention: for some defects present in existing research, the object of the present invention is to provide a kind of two dimension is fluorine-containing
Covalent organic frame compound without catalysis high efficiency preparation method, with the quickly good, specific surface without catalyst method preparation crystallinity
Greatly, the high covalent organic frame of stability.
Technical solution: in order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention are as follows:
A kind of fluorine-containing covalent organic frame compound of two dimension without catalysis high efficiency preparation method, with 2,3,5,6- tetrafluoros to benzene
Dicarbaldehyde and containing there are three the compound of 4- aminophenyl be construction unit, it is no catalysis efficiently carry out schiff bases amine aldehyde condensation reaction system
Standby organic frame compound covalent out；Reaction equation is as follows:
In formula, R is nitrogen, phenyl, triazine ring.
The compound of 4- aminophenyl, the monomer structure containing there are three is as follows:
The described fluorine-containing covalent organic frame compound of two dimension without catalysis high efficiency preparation method, include the following steps:
1) molar ratio for the 2,3,5,6- tetrafluorobenzene of 1:0.1~3, (4- the aminophenyl)-R of 2,4,6- tri- and is had
Solvent A is added in resistance to thermal reactor, chilled-to vacuumize-degassing process, ultrasonic disperse after sealing, and reaction is slightly produced
Object；
2) by filtration of crude product, washed with anhydrous organic solvent B, in solvent B flow back 1~for 24 hours；
3) product drying after flowing back will be washed to get the fluorine-containing covalent organic frame compound of two dimension is arrived.
The organic solvent A is ethyl alcohol, DMF, dioxane, mesitylene, n-butanol, DMSO, metacresol, o-dichlorohenzene
One or more of mixture.
The organic solvent B is ethyl alcohol, DMF, dioxane, mesitylene, n-butanol, DMSO, metacresol, o-dichlorohenzene
One or more of mixture.
In step 1), reaction temperature is 90~180 DEG C, and the reaction time is 1 minute to 24 hours.
The drying means be it is following any one: be put into baking oven, 60 DEG C~200 DEG C dry 0.1~24 hour；Or, putting
In supercritical carbon dioxide separating still, it is passed through the carbon dioxide of above-critical state, washing is 0.1~24 hour dry.
The supercritical carbon dioxide treatment, temperature are 30~80 DEG C, and pressure is 6~50MPa, and carbon dioxide flow is
0.1~100L/h, reaction kettle caliber are 1cm~10cm.
The application uses the monomer containing multiple fluorine atoms, and it is close to reduce aldehyde radical electron cloud by the biggish fluorine atom of electronegativity
Degree, so that the electrophilicity of aldehyde radical enhances, greatly improves the reactivity of aldehyde radical monomer, and enhance product crystallinity.
The application not only simplifies preparation process without using catalyst, and for the industrial applicability of covalent organic frame material, provide can
Energy property, and dramatically speeded up reaction rate.The introducing of fluorine element is also beneficial to further apply, fluorine-containing COFs battery with
And water pollutant and gas absorption, especially in the absorption containing fluoride pollution have great application potential.
Present application addresses need catalyst and reaction time longer difficult point, reaction process simpler in current research
Single, the reaction time foreshortened to five minutes from three days, and reaction speed is made to increase more than 800 times.The present processes can be covalently to have
The synthesis of machine frame frame structure provides reference, is conducive to synthesize a variety of covalent organic frameworks containing fluorine atom, is that it is wide
General application provides possibility.
The utility model has the advantages that compared with prior art, the present invention has the advantage that
1) monomer used in this application is 2,3,5,6- tetrafluorobenzene and 2, and 4,6- tri- (4- aminophenyl)-R contain
Four fluorine atoms can greatly enhance the reactivity of aldehyde compound, accelerate reaction rate, improve the crystallinity of reaction product
Energy.
2) the application simplifies reaction step using no catalyst method, and greatly accelerates reaction speed.
3) the fluorine-containing covalent organic frame yield that the application obtains is high, and has excellent crystallinity and big specific surface
Product, duct are abundant, and aperture is uniform, and can be used as active site containing a large amount of fluorine atoms, be conducive to adsorb needles of various sizes compared with
Big dyestuff contaminant and fluorine-containing organic pollutant.
Detailed description of the invention
Fig. 1 is the X-ray powder diffraction figure of the fluorine-containing covalent organic frame prepared；
Fig. 2 is the fluorine-containing covalent organic frame for preparing isothermal nitrogen adsorption desorption curve and pore size distribution curve figure at 77K；
Fig. 3 is the stereoscan photograph figure of the fluorine-containing covalent organic frame prepared；
Fig. 4 is the energy dispersion X-ray analysis result figure of the fluorine-containing covalent organic frame prepared；
Fig. 5 is the fourier infrared spectrogram of the fluorine-containing covalent organic frame prepared；
Fig. 6 is the thermal gravimetric analysis curve figure of the fluorine-containing covalent organic frame prepared.
Specific embodiment
The application is described in detail below with reference to embodiment.
Embodiment 1
A kind of fluorine-containing covalent organic frame compound of two dimension without catalysis high efficiency preparation method, include the following steps:
1) the 2,3,5,6- tetrafluorobenzene (82.4mg) and (the 4- phenalgin of 2,4,6- tri- that molar ratio is 1:1.5 are weighed
Base) for -1,3,5-triazines (94.4mg) in 2mL heat-resistant glass tube, addition 1mL dioxane/mesitylene (v/v=1:1) is molten
Agent；
2) liquid nitrogen frozen glass tube is evacuated to 0mbar and continues three minutes, degassing, in triplicate, seals vacuum glass
Pipe；By glass tube ultrasound 20 minutes, it is put into 120 DEG C of baking ovens and reacts 5 minutes, obtain crude product；
3) crude product is taken out and is filtered, washed, drained with tetrahydrofuran solution, wrap up investment Soxhlet extraction with clean filter paper
In device, 100 DEG C of tetrahydrofuran solution reflux washing 12h；
4) product after reflux washing is taken out, transfers the separating still into supercritical carbon dioxide abstraction instrument in moisture state
In, caliber 10cm, 35 DEG C of temperature, pressure 10MPa, flow velocity about 20L/h.Carbon dioxide reflux 2h.Obtain powder type yellow
Solid, quality 62.89mg, yield 38.7%.Isothermal nitrogen adsorption desorption curve is such as under X-ray powder diffraction figure such as Figure 1A, 77K
Fig. 2A, obtaining specific surface area according to BET theoretical calculation is 722m2/ g, pore-size distribution such as Fig. 2 C.
Embodiment 2
A kind of fluorine-containing covalent organic frame compound of two dimension without catalysis high efficiency preparation method, include the following steps:
1) the 2,3,5,6- tetrafluorobenzene (82.4mg) and (the 4- phenalgin of 2,4,6- tri- that molar ratio is 1:1.5 are weighed
Base) for -1,3,5-triazines (94.4mg) in 2mL heat-resistant glass tube, addition 1mL dioxane/mesitylene (v/v=1:1) is molten
Agent；
2) liquid nitrogen frozen glass tube is evacuated to 0mbar and continues three minutes, degassing, in triplicate, seals vacuum glass
Pipe.By glass tube ultrasound 20 minutes, it is put into 120 DEG C of baking ovens and reacts 24 hours, obtain crude product；
3) crude product is taken out and is filtered, washed, drained with tetrahydrofuran solution, wrap up investment Soxhlet extraction with clean filter paper
In device, 100 DEG C of tetrahydrofuran solution reflux washing 12h；
4) product after reflux washing is taken out, transfers the separating still into supercritical carbon dioxide abstraction instrument in moisture state
In, caliber 10cm, 35 DEG C of temperature, pressure 10MPa, flow velocity about 20L/h.Carbon dioxide reflux 2h.It obtains powdered orange red
Color solid, quality 153.0mg, yield 94.2%.
The X-ray diffractogram of fluorine-containing covalent organic frame manufactured in the present embodiment is as shown in Figure 1B, and one is presented at 2.85 °
There is weaker peak crystallization at a very strong X-ray diffraction peak at 4.92 °, 5.73 °, 7.60 ° and 25.90 °.Test result and simulation
Calculated result is completely the same.
Nitrogen adsorption desorption curve is as shown in Figure 2 C under 77K, obtains higher specific surface according to test data and BET theory
Product is 1927m2/g。
Pore-size distribution such as Fig. 2 D, aperture 2-3nm.
Stereoscan photograph is as shown in figure 3, be the sphere of surface imperfection, size about 300-400nm.
Energy dispersion X-ray analysis (EDX) such as Fig. 4, fluorinated volume 15%, with actual value 18.72% are carried out to FCOFs
It is close.
Infared spectrum is as shown in figure 5, there is apparent-C=N characteristic peak.
Thermogravimetric analysis as shown in fig. 6, decomposition temperature up to 481.2 DEG C, it was demonstrated that its good stability.
Embodiment 3
A kind of fluorine-containing covalent organic frame compound of two dimension without catalysis high efficiency preparation method, include the following steps:
1) the 2,3,5,6- tetrafluorobenzene (82.4mg) and (the 4- phenalgin of 2,4,6- tri- that molar ratio is 1:1.5 are weighed
Base)-benzene (93.6mg) is in 2mL heat-resistant glass tube, addition 1mL dioxane/mesitylene (v/v=1:1) solvent；
2) liquid nitrogen frozen glass tube is evacuated to 0mbar and continues three minutes, degassing, in triplicate, seals vacuum glass
Pipe.By glass tube ultrasound 20 minutes, it is put into 180 DEG C of baking ovens and reacts 1 minute, obtain crude product.
3) crude product is taken out and is filtered, washed, drained with tetrahydrofuran solution, wrap up investment Soxhlet extraction with clean filter paper
In device, 100 DEG C of tetrahydrofuran solution reflux washing 12h；
4) product after reflux washing is taken out, drying (being put into baking oven, 60 DEG C~200 DEG C dry 0.1~24 hour) is i.e.
Obtain orange red pulverulent solids 90.0mg.Yield 55.4%.
Embodiment 4
A kind of fluorine-containing covalent organic frame compound of two dimension without catalysis high efficiency preparation method, include the following steps:
1) the 2,3,5,6- tetrafluorobenzene (82.4mg) and (the 4- phenalgin of 2,4,6- tri- that molar ratio is 1:1.5 are weighed
Base)-benzene (93.6mg) is in 2mL heat-resistant glass tube, addition 1mL dioxane/mesitylene (v/v=1:1) solvent；
2) liquid nitrogen frozen glass tube is evacuated to 0mbar and continues three minutes, degassing, in triplicate, seals vacuum glass
Pipe.By glass tube ultrasound 20 minutes, it is put into 120 DEG C of baking ovens and reacts 24 hours, obtain crude product；
3) crude product is taken out and is filtered, washed, drained with tetrahydrofuran solution, wrap up investment Soxhlet extraction with clean filter paper
In device, 100 DEG C of tetrahydrofuran solution reflux washing 12h；
4) product after reflux washing is taken out, transfers the separating still into supercritical carbon dioxide abstraction instrument in moisture state
In, caliber 10cm, 35 DEG C of temperature, pressure 10MPa, flow velocity about 20L/h.Carbon dioxide reflux 2h.Obtain powdered brown
Solid, quality 99.3mg, yield 61.0%.
Embodiment 5
A kind of fluorine-containing covalent organic frame compound of two dimension without catalysis high efficiency preparation method, include the following steps:
1) the 2,3,5,6- tetrafluorobenzene (82.4mg) and (the 4- phenalgin of 2,4,6- tri- that molar ratio is 1:1.5 are weighed
Base)-benzene (93.6mg) is in 2mL heat-resistant glass tube, addition 1mL dioxane/mesitylene (v/v=1:1) solvent；
2) liquid nitrogen frozen glass tube is evacuated to 0mbar and continues three minutes, degassing, in triplicate, seals vacuum glass
Pipe.By glass tube ultrasound 20 minutes, it is put into 90 DEG C of baking ovens and reacts 3 days, obtain crude product；
3) crude product is taken out and is filtered, washed, drained with tetrahydrofuran solution, wrap up investment Soxhlet extraction with clean filter paper
In device, 100 DEG C of tetrahydrofuran solution reflux washing 12h；
4) product after reflux washing is taken out, drying (being put into baking oven, 60 DEG C~200 DEG C dry 0.1~24 hour) is i.e.
Obtain powdered brown solid, quality 94.4mg, yield 58.0%.
Claims (8)
1. a kind of fluorine-containing covalent organic frame compound of two dimension without catalysis high efficiency preparation method, which is characterized in that with 2,3,5,
6- tetrafluorobenzene and containing there are three the compound of 4- aminophenyl be construction unit, it is no catalysis efficiently carry out schiff bases amine aldehyde
Covalent organic frame compound is prepared in condensation reaction；Reaction equation is as follows:
In formula, R is nitrogen, phenyl, triazine ring.
2. the fluorine-containing covalent organic frame compound of two dimension according to claim 1 without catalysis high efficiency preparation method, it is special
Sign is that described containing there are three the compound of 4- aminophenyl, monomer structure is as follows:
3. the fluorine-containing covalent organic frame compound of two dimension according to claim 1 or 2 without catalysis high efficiency preparation method,
It is characterized in that, includes the following steps:
1) by molar ratio be 1: 0.1~3 2,3,5,6- tetrafluorobenzene, 2,4,6- tri- (4- aminophenyl)-R and organic molten
Agent A is added in resistance to thermal reactor, chilled-to vacuumize-degassing process, ultrasonic disperse after sealing, and reaction obtains crude product；
2) by filtration of crude product, washed with anhydrous organic solvent B, in organic solvent B flow back 1~for 24 hours；
3) product drying after flowing back will be washed to get the fluorine-containing covalent organic frame compound of two dimension is arrived.
4. the fluorine-containing covalent organic frame compound of two dimension according to claim 3 without catalysis high efficiency preparation method, it is special
Sign is that the organic solvent A is ethyl alcohol, DMF, dioxane, mesitylene, n-butanol, DMSO, metacresol, o-dichlorohenzene
One or more of mixture.
5. the fluorine-containing covalent organic frame compound of two dimension according to claim 3 without catalysis high efficiency preparation method, it is special
Sign is that the organic solvent B is ethyl alcohol, DMF, dioxane, mesitylene, n-butanol, DMSO, metacresol, o-dichlorohenzene
One or more of mixture.
6. the fluorine-containing covalent organic frame compound of two dimension according to claim 3 without catalysis high efficiency preparation method, it is special
Sign is, in step 1), reaction temperature is 90~180 DEG C, and the reaction time is 1 minute to 24 hours.
7. the fluorine-containing covalent organic frame compound of two dimension according to claim 3 without catalysis high efficiency preparation method, it is special
Sign is, in step 3), drying means be it is following any one: be put into baking oven, 60 DEG C~200 DEG C dry 0.1~24 hour；
Or, being put in supercritical carbon dioxide separating still, it is passed through the carbon dioxide of above-critical state, washing is 0.1~24 hour dry.
8. the fluorine-containing covalent organic frame compound of two dimension according to claim 7 without catalysis high efficiency preparation method, it is special
Sign is that the supercritical carbon dioxide treatment, temperature is 30~80 DEG C, and pressure is 6~50MPa, carbon dioxide flow 0.1
~100L/h, reaction kettle caliber are 1cm~10cm.
Priority Applications (1)
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