CN108219158A - Covalent organic framework material and preparation method thereof - Google Patents
Covalent organic framework material and preparation method thereof Download PDFInfo
- Publication number
- CN108219158A CN108219158A CN201810099731.4A CN201810099731A CN108219158A CN 108219158 A CN108219158 A CN 108219158A CN 201810099731 A CN201810099731 A CN 201810099731A CN 108219158 A CN108219158 A CN 108219158A
- Authority
- CN
- China
- Prior art keywords
- organic framework
- covalent organic
- framework material
- preparation
- ionic liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 58
- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002608 ionic liquid Substances 0.000 claims abstract description 24
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002262 Schiff base Substances 0.000 claims abstract description 7
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 28
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000178 monomer Substances 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 8
- 238000000034 method Methods 0.000 claims description 8
- -1 4,4'- biphenyl hypoboric acid Chemical compound 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- SKOWZLGOFVSKLB-UHFFFAOYSA-N hypodiboric acid Chemical compound OB(O)B(O)O SKOWZLGOFVSKLB-UHFFFAOYSA-N 0.000 claims description 3
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 3
- QMLILIIMKSKLES-UHFFFAOYSA-N triphenylene-2,3,6,7,10,11-hexol Chemical class C12=CC(O)=C(O)C=C2C2=CC(O)=C(O)C=C2C2=C1C=C(O)C(O)=C2 QMLILIIMKSKLES-UHFFFAOYSA-N 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000007513 acids Chemical class 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 5
- 230000035484 reaction time Effects 0.000 abstract description 5
- 230000004044 response Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000010189 synthetic method Methods 0.000 abstract description 3
- 230000008520 organization Effects 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 24
- 239000000843 powder Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 238000000227 grinding Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000002411 thermogravimetry Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000001144 powder X-ray diffraction data Methods 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 210000000988 bone and bone Anatomy 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000013474 COF-1 Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000371 solid-state nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010218 electron microscopic analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The invention discloses covalent organic framework materials and preparation method thereof, belong to covalent organic framework technical field of material, the present invention utilizes ion thermal response, the a variety of covalent organic framework materials of Fast back-projection algorithm under room temperature and open system, including Schiff bases covalent organic framework material and boric acid class covalent organic framework material, the also covalent organic framework material including 2 and 3 dimensional organization.This synthetic method have the reaction time is short, low energy consumption, non-volatility organic pollution, additive-free, simple operation and other advantages, while ionic liquid after being simply separated by filtration it is reusable at least three times.Have ionic liquid loaded in the covalent organic framework material that the present invention synthesizes, have potential application with detaching etc. in gas storage.
Description
Technical field
The invention belongs to covalent organic framework technical field of material, and in particular to covalent organic framework material and its system
Preparation Method.
Background technology
Covalent organic framework material (Covalent Organic Frameworks) be it is a kind of passed through by organic monomer it is covalent
What key connection was formed, there is the porous crystalline polymer of periodic network structure.Covalent organic framework material have duct rule,
The features such as density is low, crystallinity is higher, stability is preferable is stored with detaching, being catalyzed in gas, photoelectricity etc. has widely
Potential application.
Ionic liquid be it is a kind of in room temperature or it is near at room temperature (<100 DEG C) in liquid and the chemical combination that is composed entirely of ions
Object, have the characteristics that extremely low volatility, wide liquid journey, it is non-combustible and to it is many it is inorganic have special dissolubility with organic species, can
Replace green solvent of the volatility toxic organic solvents as reaction.Meanwhile the ionic liquid of support type is considered to have reduction
Cost increases service life and with better carbon dioxide selectivity absorption property.But up to the present, there are no use from
Sub- liquid is as solvent or the report of catalyst synthesis covalent organic framework material.
The method for preparing covalent organic framework material at present is mainly the hot method of high-temperature solvent, and this method is needed in higher temperature
It is carried out in closed system under (85-200 DEG C), energy consumption of reaction is high, and reaction condition is harsher, complicated for operation, reaction time length (3-7
My god), while have volatile organic matter (VOC) discharge.The hot method pole of high-temperature solvent is unfavorable for covalent organic framework material industrially
Mass production and extensive use.
Invention content
In order to overcome above-mentioned deficiency in the prior art, the present invention is using ion thermal response, in room temperature and open body
The lower a variety of covalent organic framework materials of Fast back-projection algorithm of system, it is covalently organic including Schiff bases covalent organic framework material and boric acid class
Framework material, also the covalent organic framework material including 2 and 3 dimensional organization.This synthetic method has that the reaction time is short, energy
Low, non-volatility organic pollution, additive-free, simple operation and other advantages are consumed, while ionic liquid is by simple filtering point
From it is rear it is reusable at least three times.
The present invention is achieved through the following technical solutions：
The preparation method of covalent organic framework material, is as follows：
Step (1)：Take the reaction monomers of Schiff bases or boric acid class covalent organic framework material according to molar ratio be 1:4~
4:1 is uniformly mixed；
Step (2)：Ionic liquid is added in the mixture of step (1), be uniformly mixed, wherein, ionic liquid is with mixing
The mass ratio for closing object is 1:1~100:1,3min-72h is reacted at normal temperatures and pressures；
Step (3)：It is washed, filtered with ethyl alcohol and acetone respectively after reaction, then vacuum drying obtains covalently organic
Framework material.
Further, the Schiff bases reaction monomers described in step (1) are four (4- aldehyde radicals phenyl) methane, four (4- amino
Phenyl) methane, 1,3,5- trifonnyl benzene, 2,4,6- trihydroxy benzenes -1,3,5- trioxins, p-phenylenediamine, benzidine or 4,4 " -
Terphenyl diamines.
Further, the boric acid class reaction monomers described in step (1) for Isosorbide-5-Nitrae-benzene hypoboric acid, 1,3,5- benzene, three boric acid, 4,
4'- biphenyl hypoboric acid, four (4- boric acid phenyl) methane, four (4- boric acid phenyl) silane, 1,2,4,5- phenetetrols or 2,3,6,7,
10,11- hexahydroxy triphenylenes.
Further, the ionic liquid described in step (2) for 1- butyl -3- methylimidazole bis-trifluoromethylsulfoandimide salt or
Room temperatures or the nearly ionic liquid at room temperature such as 1- butyl -3- methylimidazole dicyandiamide salt.
Compared with prior art, advantages of the present invention is as follows：
1) reaction carries out at room temperature, and low energy consumption；
2) reaction carries out under open system, easy to operate, safe；
3) reaction time is short, most can complete reaction in three minutes soon；
4) replace low boiling point organic solvent, non-volatility organic matter (VOC) and organic solvent discharging of waste liquid with ionic liquid,
It is environmental-friendly；
5) addition catalyst or other additives are not required to；
6) ionic liquid can be reached convenient recycling by filtering and be reused；
7) have in the covalent organic framework material of synthesis it is ionic liquid loaded, gas storage with detach etc. have it is potential
Using.
Description of the drawings
Fig. 1 is the X-ray diffractogram of covalent organic framework material prepared by the embodiment of the present invention 1；
Fig. 2 is the X-ray diffractogram of covalent organic framework material prepared by the embodiment of the present invention 2；
Fig. 3 is the X-ray diffractogram of covalent organic framework material prepared by the embodiment of the present invention 3；
Fig. 4 is the X-ray diffractogram of covalent organic framework material prepared by the embodiment of the present invention 4；
Fig. 5 is the scanning electron microscope spectrogram of covalent organic framework material prepared by the embodiment of the present invention 1；
Fig. 6 is the scanning electron microscope spectrogram of covalent organic framework material prepared by the embodiment of the present invention 4；
Fig. 7 is the thermogravimetric analysis spectrogram of covalent organic framework material prepared by the embodiment of the present invention 1；
Fig. 8 is the thermogravimetric analysis spectrogram of covalent organic framework material prepared by the embodiment of the present invention 2；
Fig. 9 is the thermogravimetric analysis spectrogram of covalent organic framework material prepared by the embodiment of the present invention 3；
Figure 10 is the thermogravimetric analysis spectrogram of covalent organic framework material prepared by the embodiment of the present invention 4；
Figure 11 is the infrared analysis spectrogram of covalent organic framework material prepared by the embodiment of the present invention 1；
Figure 12 is the infrared analysis spectrogram of covalent organic framework material prepared by the embodiment of the present invention 2；
Figure 13 is the infrared analysis spectrogram of covalent organic framework material prepared by the embodiment of the present invention 3；
Figure 14 is the infrared analysis spectrogram of covalent organic framework material prepared by the embodiment of the present invention 4；
Figure 15 is the solid core magnetic chart of covalent organic framework material prepared by the embodiment of the present invention 1；
Figure 16 is the powder of covalent organic framework material that the embodiment of the present invention 5 synthesizes in different cycle-index ionic liquids
Last XRD diffraction curves figure；
Figure 17 is the powder X-ray RD diffraction curves of the covalent organic framework material of differential responses time synthesis.
Specific embodiment
The following examples will be further described the present invention, but not thereby limiting the invention.
Experimental method described in following embodiments is conventional method unless otherwise specified；The reagent and material, such as
Without specified otherwise, commercially obtain.
The present invention is described further below in conjunction with the accompanying drawings.
1 1- butyl -3- methylimidazole bis-trifluoromethylsulfoandimides salt of embodiment prepares 3D-IL-COF-1 covalently organic bones
Frame material
Weigh (aldehyde radical phenyl) methane of 21.6mg tetra- and 10.8mg p-phenylenediamine, grinding is uniform, feed the mixture into 5mL from
In heart pipe, add in 100 μ L 1- butyl -3- methylimidazole bis-trifluoromethylsulfoandimide salt salt and be uniformly mixed, keep room temperature reaction
3min washs drying with ethyl alcohol and acetone after reaction, obtains buff powder.
Its product X RD and simulation powder XRD pattern spectrum are such as Fig. 1, it is seen that analogue spectrums and product spectrogram are identical.
2 1- butyl -3- methylimidazole bis-trifluoromethylsulfoandimides salt of embodiment prepares 2D-IL-COF-1 covalently organic bones
Frame material
2,4,6- trihydroxy benzenes -1,3 of 14.0mg, 5- trioxins and 10.8mg p-phenylenediamine are weighed, grinding is uniform, will be mixed
It closes object to add in 5mL centrifuge tubes, adds in 100 μ L1- butyl -3- methylimidazole bis-trifluoromethylsulfoandimide salt, be uniformly mixed, protect
Room temperature reaction 12h is held, drying is washed with acetone after reaction, obtains orange-yellow powder.
Its product X RD and simulation powder XRD pattern spectrum are such as Fig. 2, it is seen that analogue spectrums and product spectrogram are identical.
3 1- butyl -3- methylimidazole bis-trifluoromethylsulfoandimides salt of embodiment prepares 2D-IL-COF-2 covalently organic bones
Frame material
25.0mg Isosorbide-5-Nitraes-to 2,3,6,7,10,11- hexahydroxy triphenylene of benzene hypoboric acid and 16.0mg are weighed, grinding is equal
It is even, it feeds the mixture into 5mL centrifuge tubes, adds in 100 μ L 1- butyl -3- methylimidazole bis-trifluoromethylsulfoandimide salt, mixing
Uniformly, 60 DEG C of reaction 12h are kept, drying is washed with acetone after reaction, obtains grayish powder.
Its product X RD and simulation powder XRD pattern spectrum are such as Fig. 3, it is seen that analogue spectrums and product spectrogram are identical.
4 1- butyl -3- methylimidazole dicyandiamides salt of embodiment prepares 3D-IL-COF-1b covalent organic framework materials
Weigh (aldehyde radical phenyl) methane of 21.6mg tetra- and 10.8mg p-phenylenediamine, grinding is uniform, feed the mixture into 5mL from
In heart pipe, 100 μ L1- butyl -3- methylimidazole dicyandiamide salt are added in, are uniformly mixed, keep room temperature reaction 3min, reaction terminates
Drying is washed with ethyl alcohol and acetone afterwards, obtains buff powder.
Its product X RD and simulation powder XRD pattern spectrum are such as Fig. 4, it is seen that analogue spectrums and product spectrogram are identical.
Embodiment 1,4 products therefrom of embodiment are scanned electron-microscopic analysis, and the scanning of products therefrom scanning electron microscope is shone
Piece is respectively such as Fig. 5~Fig. 6, it is seen that synthesized product is the aggregation of bulk crystals.
Embodiment 1, embodiment 2, embodiment 3,4 products therefrom of embodiment carry out thermogravimetric analysis, and test condition is nitrogen gas
Atmosphere, flow velocity 30mL/min, 10 DEG C/min of heating rate, the thermogravimetric collection of illustrative plates of products therefrom is respectively such as Fig. 7~Figure 10.From the visible production of figure
At 320 DEG C and 520 DEG C or so there are two weightless peak, first weightless peak corresponds to caused by ionic liquid is detached from duct to be lost object
Weight, illustrates the presence of duct intermediate ion liquid, and second weightless peak corresponds to caving in for skeleton, illustrate that COF skeletons are stabilized to 520
℃。
Embodiment 1, embodiment 2, embodiment 3,4 products therefrom of embodiment carry out infrared analysis, using pellet technique,
The infared spectrum of products therefrom is respectively such as Figure 11~Figure 14.Exist from visible embodiment 1, embodiment 2,4 products therefrom of embodiment is schemed
1624cm-1Nearby there is stronger absorption, corresponding to the vibration of C=N, illustrate that condensation reaction has occurred in monomer.3 products therefrom of embodiment
In 1347,1332,1245,1026cm-1Nearby there is stronger absorption, corresponding to B-O, B-O, C-O, the vibration of C-B illustrates borate
Pentacyclic formation.Embodiment 1, embodiment 2,3 products therefrom of embodiment are in 1355cm-1And 1061cm-1Nearby there is absorption, point
It Dui Yingyu not SO in 1- butyl -3- methylimidazole bis-trifluoromethylsulfoandimide salt2Asymmetric stretching vibration and SNS asymmetric stretches
Vibration, illustrates that there are ionic liquid 1-butyl-3-methyl imidazolium bis-trifluoromethylsulfoandimide salt in resulting materials duct.Embodiment
4 products therefroms are in 2182cm-1Nearby there is absorption, corresponding to the absorption of C ≡ N in 1- butyl -3- methylimidazole dicyandiamide salt, explanation
There are ionic liquid 1-butyl-3-methyl imidazolium dicyandiamide salt in resulting materials duct.
1 products therefrom of embodiment carries out solid state nmr analysis, solid state nmr collection of illustrative plates such as Figure 15 of products therefrom.From figure
Products therefrom has peak near 158ppm, corresponding to the chemical shift of schiff bases, illustrates that condensation reaction has occurred in monomer.
The recycling of 5 ionic liquid of embodiment
Weigh (aldehyde radical phenyl) methane of 21.6mg tetra- and 10.8mg p-phenylenediamine, grinding is uniform, feed the mixture into 5mL from
In heart pipe, 100 μ L 1- butyl -3- methylimidazole bis-trifluoromethylsulfoandimide salt are added in, are uniformly mixed, keep room temperature reaction
Ionic liquid is recovered by filtration in 12h
Weigh (aldehyde radical phenyl) methane of 21.6mg tetra- and 10.8mg p-phenylenediamine, grinding is uniform, feed the mixture into 5mL from
In heart pipe, the ionic liquid of recycling is added in
In triplicate, solid washs drying with ethyl alcohol and acetone after reaction, obtains buff powder
The ionic liquid product obtained by the reaction of different recovered frequencies carries out the test of powder X-ray RD diffraction respectively, sees Figure 16.It should
As a result illustrate that ionic liquid can be used by simple filtration cycle and activity is not lost substantially.
The measure of 6 differential responses time of embodiment
Weigh (aldehyde radical phenyl) methane of 21.6mg tetra- and 10.8mg p-phenylenediamine, grinding is uniform, feed the mixture into 5mL from
In heart pipe, 100 μ L 1- butyl -3- methylimidazole bis-trifluoromethylsulfoandimide salt are added in, are uniformly mixed, keep room temperature reaction
30s-24h
Drying is washed with ethyl alcohol and acetone after reaction, obtains buff powder
The product that the differential responses time obtains carries out the test of powder X-ray RD diffraction respectively, sees Figure 17.The result illustrates this method
Reaction can be basically completed in 3 minutes.
To sum up, the present invention has been synthesized in a mild condition using ion process for thermosynthesizing including boric acid class and Schiff bases
Various new covalent organic framework material inside, this synthetic method is with the reaction time is short, low energy consumption, non-volatility is organic
Object pollution, additive-free, simple operation and other advantages, and ionic liquid can recycle.Such material thermal stability height (is more than
500 DEG C), to CO2There are preferable absorption property, CO2/CH4And CO2/N2Etc. in mixed gas to CO2Selective absorption performance is excellent
It is different, become potential CO2Selective absorption and a kind of material of separation.
Claims (5)
1. the preparation method of covalent organic framework material, which is characterized in that be as follows：
Step (1)：Take the reaction monomers of Schiff bases or boric acid class covalent organic framework material according to molar ratio be 1:4~4:1
It is uniformly mixed；
Step (2)：Ionic liquid is added in the mixture of step (1), be uniformly mixed, wherein, ionic liquid and mixture
Mass ratio be 1:1~100:1,3min-72h is reacted at normal temperatures and pressures；
Step (3)：It is washed, filtered with ethyl alcohol and acetone respectively after reaction, then vacuum drying obtains covalent organic framework
Material.
2. the preparation method of covalent organic framework material as described in claim 1, which is characterized in that the seat described in step (1)
Husband's bases reaction monomers be four (4- aldehyde radicals phenyl) methane, four (4- aminophenyls) methane, 1,3,5- trifonnyl benzene, 2,4,6-
Trihydroxy benzene -1,3,5- trioxins, p-phenylenediamine, benzidine or 4,4 "-terphenyl diamines.
3. the preparation method of covalent organic framework material as described in claim 1, which is characterized in that the boron described in step (1)
Acids reaction monomers be Isosorbide-5-Nitrae-benzene hypoboric acid, 1,3,5- benzene, three boric acid, 4,4'- biphenyl hypoboric acid, four (4- boric acid phenyl) methane,
Four (4- boric acid phenyl) silane, 1,2,4,5- phenetetrol or 2,3,6,7,10,11- hexahydroxy triphenylenes.
4. the preparation method of covalent organic framework material as described in claim 1, which is characterized in that described in step (2) from
Sub- liquid is 1- butyl -3- methylimidazole bis-trifluoromethylsulfoandimide salt or 1- butyl -3- methylimidazole dicyandiamide salt.
5. covalent organic framework material, which is characterized in that be prepared as the method described in any one of claim 1-4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810099731.4A CN108219158B (en) | 2018-02-01 | 2018-02-01 | Covalent organic framework material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810099731.4A CN108219158B (en) | 2018-02-01 | 2018-02-01 | Covalent organic framework material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108219158A true CN108219158A (en) | 2018-06-29 |
| CN108219158B CN108219158B (en) | 2020-10-13 |
Family
ID=62669997
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810099731.4A Expired - Fee Related CN108219158B (en) | 2018-02-01 | 2018-02-01 | Covalent organic framework material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108219158B (en) |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108855012A (en) * | 2018-07-19 | 2018-11-23 | 吉林大学 | A kind of polyarylether class covalent organic framework material and preparation method thereof |
| CN109320734A (en) * | 2018-10-29 | 2019-02-12 | 福州大学 | A kind of spherical shape covalent organic framework material and its preparation method and application |
| CN109456489A (en) * | 2018-09-30 | 2019-03-12 | 南京工业大学 | A kind of ordered porous poly ion liquid material, preparation method and applications |
| CN109749092A (en) * | 2019-02-21 | 2019-05-14 | 南京大学 | One kind being based on the construction method of schiff base reaction [4+3] type two dimension organic conjugate frame material |
| CN109894153A (en) * | 2019-03-01 | 2019-06-18 | 山西师范大学 | A kind of catalyst preparation and application of N-heterocyclic carbine covalent organic frame material supported palladium |
| CN109897190A (en) * | 2019-03-01 | 2019-06-18 | 山西师范大学 | A kind of covalent organic frame material and its synthetic method of N-heterocyclic carbine functionalization |
| CN109988079A (en) * | 2019-04-29 | 2019-07-09 | 山东师范大学 | A kind of three phase catalyst Pd@COF-QA and the preparation method and application thereof |
| CN110157008A (en) * | 2019-06-25 | 2019-08-23 | 哈尔滨理工大学 | A kind of diplopore covalent organic framework material of imines key connecting and its preparation and application |
| CN110229347A (en) * | 2019-06-25 | 2019-09-13 | 哈尔滨理工大学 | A kind of diplopore covalent organic framework material of metal-chelating and its preparation and application |
| CN110511357A (en) * | 2019-08-09 | 2019-11-29 | 山东省分析测试中心 | A kind of solid phase microextraction adsorbent and its preparation method and application of carbamate pesticide detection |
| CN111155143A (en) * | 2020-01-07 | 2020-05-15 | 中国科学院化学研究所 | Preparation method of two-dimensional layered metal organic framework nano material |
| CN111604039A (en) * | 2020-05-26 | 2020-09-01 | 首都师范大学 | Three-dimensional covalent organic framework material, open-tube capillary electrochromatography column and preparation method |
| CN111715278A (en) * | 2020-06-29 | 2020-09-29 | 西安科技大学 | Preparation method of Ni @ boron COFs catalyst for graphitizing carbon material |
| WO2020199463A1 (en) * | 2019-04-02 | 2020-10-08 | 深圳市华星光电技术有限公司 | Method for preparing pigment dispersion |
| CN111822055A (en) * | 2020-07-25 | 2020-10-27 | 合肥学院 | Preparation method and application of BiOBr/COF composite photocatalyst |
| CN111909389A (en) * | 2020-08-06 | 2020-11-10 | 山东师范大学 | Covalent organic framework material and preparation method and application thereof |
| CN112574370A (en) * | 2019-09-27 | 2021-03-30 | 台州学院 | Three-dimensional hydroxyl-containing covalent organic framework material and preparation method thereof |
| CN113024828A (en) * | 2021-03-09 | 2021-06-25 | 南开大学 | Method for preparing covalent organic framework material by utilizing high-pressure homogenization |
| CN113265033A (en) * | 2020-02-14 | 2021-08-17 | 台州学院 | Conjugated organic microporous polymer and preparation method thereof |
| CN113603912A (en) * | 2021-07-17 | 2021-11-05 | 河南师范大学 | Method for preparing high-crystallinity covalent organic framework film by using ionic liquid-water interface |
| CN114621433A (en) * | 2022-03-18 | 2022-06-14 | 浙江工业大学 | Ultrathin two-dimensional covalent organic framework nano enzyme-like catalytic material and preparation and application thereof |
| CN116478417A (en) * | 2023-04-20 | 2023-07-25 | 绍兴文理学院 | Chiral covalent organic framework material based on boric acid ester, chiral separation membrane, preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105440058A (en) * | 2015-11-04 | 2016-03-30 | 兰州大学 | Synthesis method for benzothiazole unit-based covalent organic framework material |
| US20160151762A1 (en) * | 2014-12-02 | 2016-06-02 | Numat Technologies, Inc. | Formation of high surface area metal-organic frameworks |
| CN105646901A (en) * | 2016-03-28 | 2016-06-08 | 吉林大学 | Green chemical preparation method for nano zeolitic imidazolate framework material |
| CN106554324A (en) * | 2016-10-28 | 2017-04-05 | 山东师范大学 | Metal-organic framework material and preparation method and application based on imidazoles salt form part |
| CN107459656A (en) * | 2016-06-02 | 2017-12-12 | 中国科学院大连化学物理研究所 | One kind ionization covalent organic frame material and preparation method thereof and catalytic applications |
-
2018
- 2018-02-01 CN CN201810099731.4A patent/CN108219158B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160151762A1 (en) * | 2014-12-02 | 2016-06-02 | Numat Technologies, Inc. | Formation of high surface area metal-organic frameworks |
| CN105440058A (en) * | 2015-11-04 | 2016-03-30 | 兰州大学 | Synthesis method for benzothiazole unit-based covalent organic framework material |
| CN105646901A (en) * | 2016-03-28 | 2016-06-08 | 吉林大学 | Green chemical preparation method for nano zeolitic imidazolate framework material |
| CN107459656A (en) * | 2016-06-02 | 2017-12-12 | 中国科学院大连化学物理研究所 | One kind ionization covalent organic frame material and preparation method thereof and catalytic applications |
| CN106554324A (en) * | 2016-10-28 | 2017-04-05 | 山东师范大学 | Metal-organic framework material and preparation method and application based on imidazoles salt form part |
Non-Patent Citations (2)
| Title |
|---|
| ADRIEN P. COTE ETAL: ""Porous, Crystalline, Covalent Organic Frameworks"", 《SCIENCE》 * |
| GUIQING LIN ETAL: ""A Pyrene-Based，Fluorescent Three-Dimensional Covalent Organic Framework"", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
Cited By (38)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108855012A (en) * | 2018-07-19 | 2018-11-23 | 吉林大学 | A kind of polyarylether class covalent organic framework material and preparation method thereof |
| CN109456489A (en) * | 2018-09-30 | 2019-03-12 | 南京工业大学 | A kind of ordered porous poly ion liquid material, preparation method and applications |
| CN109456489B (en) * | 2018-09-30 | 2021-12-03 | 南京工业大学 | Ordered porous polyion liquid material, preparation method and application thereof |
| CN109320734A (en) * | 2018-10-29 | 2019-02-12 | 福州大学 | A kind of spherical shape covalent organic framework material and its preparation method and application |
| CN109320734B (en) * | 2018-10-29 | 2021-04-27 | 福州大学 | Spherical covalent organic framework material and preparation method and application thereof |
| CN109749092A (en) * | 2019-02-21 | 2019-05-14 | 南京大学 | One kind being based on the construction method of schiff base reaction [4+3] type two dimension organic conjugate frame material |
| CN109749092B (en) * | 2019-02-21 | 2022-03-15 | 南京大学 | Construction method of [4+3] type two-dimensional organic conjugated framework material based on Schiff base reaction |
| CN109894153A (en) * | 2019-03-01 | 2019-06-18 | 山西师范大学 | A kind of catalyst preparation and application of N-heterocyclic carbine covalent organic frame material supported palladium |
| CN109897190A (en) * | 2019-03-01 | 2019-06-18 | 山西师范大学 | A kind of covalent organic frame material and its synthetic method of N-heterocyclic carbine functionalization |
| CN109897190B (en) * | 2019-03-01 | 2021-07-30 | 山西师范大学 | N-heterocyclic carbene functionalized covalent organic framework material and synthesis method thereof |
| CN109894153B (en) * | 2019-03-01 | 2021-07-16 | 山西师范大学 | Preparation and application of nitrogen heterocyclic carbene covalent organic framework material supported palladium catalyst |
| WO2020199463A1 (en) * | 2019-04-02 | 2020-10-08 | 深圳市华星光电技术有限公司 | Method for preparing pigment dispersion |
| CN109988079B (en) * | 2019-04-29 | 2022-05-17 | 山东师范大学 | Three-phase catalyst Pd @ COF-QA and preparation method and application thereof |
| CN109988079A (en) * | 2019-04-29 | 2019-07-09 | 山东师范大学 | A kind of three phase catalyst Pd@COF-QA and the preparation method and application thereof |
| CN110229347A (en) * | 2019-06-25 | 2019-09-13 | 哈尔滨理工大学 | A kind of diplopore covalent organic framework material of metal-chelating and its preparation and application |
| CN110157008A (en) * | 2019-06-25 | 2019-08-23 | 哈尔滨理工大学 | A kind of diplopore covalent organic framework material of imines key connecting and its preparation and application |
| CN110229347B (en) * | 2019-06-25 | 2021-10-01 | 哈尔滨理工大学 | Metal chelated double-hole covalent organic framework material and preparation and application thereof |
| CN110511357B (en) * | 2019-08-09 | 2022-03-15 | 山东省分析测试中心 | Solid-phase microextraction adsorbent for carbamate pesticide detection and preparation method and application thereof |
| CN110511357A (en) * | 2019-08-09 | 2019-11-29 | 山东省分析测试中心 | A kind of solid phase microextraction adsorbent and its preparation method and application of carbamate pesticide detection |
| CN112574370A (en) * | 2019-09-27 | 2021-03-30 | 台州学院 | Three-dimensional hydroxyl-containing covalent organic framework material and preparation method thereof |
| CN112574370B (en) * | 2019-09-27 | 2022-10-04 | 台州学院 | Three-dimensional hydroxyl-containing covalent organic framework material and preparation method thereof |
| CN111155143B (en) * | 2020-01-07 | 2021-06-01 | 中国科学院化学研究所 | Preparation method of two-dimensional layered metal organic framework nano material |
| CN111155143A (en) * | 2020-01-07 | 2020-05-15 | 中国科学院化学研究所 | Preparation method of two-dimensional layered metal organic framework nano material |
| CN113265033A (en) * | 2020-02-14 | 2021-08-17 | 台州学院 | Conjugated organic microporous polymer and preparation method thereof |
| CN113265033B (en) * | 2020-02-14 | 2022-06-10 | 台州学院 | Conjugated organic microporous polymer and preparation method thereof |
| CN111604039B (en) * | 2020-05-26 | 2023-05-23 | 首都师范大学 | Three-dimensional covalent organic framework material, open-tube capillary electrochromatography column and preparation method |
| CN111604039A (en) * | 2020-05-26 | 2020-09-01 | 首都师范大学 | Three-dimensional covalent organic framework material, open-tube capillary electrochromatography column and preparation method |
| CN111715278A (en) * | 2020-06-29 | 2020-09-29 | 西安科技大学 | Preparation method of Ni @ boron COFs catalyst for graphitizing carbon material |
| CN111822055A (en) * | 2020-07-25 | 2020-10-27 | 合肥学院 | Preparation method and application of BiOBr/COF composite photocatalyst |
| CN111909389B (en) * | 2020-08-06 | 2022-04-15 | 山东师范大学 | Covalent organic framework material and preparation method and application thereof |
| CN111909389A (en) * | 2020-08-06 | 2020-11-10 | 山东师范大学 | Covalent organic framework material and preparation method and application thereof |
| CN113024828B (en) * | 2021-03-09 | 2022-05-06 | 南开大学 | Method for preparing covalent organic framework material by utilizing high-pressure homogenization |
| CN113024828A (en) * | 2021-03-09 | 2021-06-25 | 南开大学 | Method for preparing covalent organic framework material by utilizing high-pressure homogenization |
| CN113603912A (en) * | 2021-07-17 | 2021-11-05 | 河南师范大学 | Method for preparing high-crystallinity covalent organic framework film by using ionic liquid-water interface |
| CN113603912B (en) * | 2021-07-17 | 2024-01-19 | 河南师范大学 | Method for preparing high-crystallinity covalent organic framework film by using ionic liquid-water interface |
| CN114621433A (en) * | 2022-03-18 | 2022-06-14 | 浙江工业大学 | Ultrathin two-dimensional covalent organic framework nano enzyme-like catalytic material and preparation and application thereof |
| CN114621433B (en) * | 2022-03-18 | 2023-12-05 | 浙江工业大学 | Ultrathin two-dimensional covalent organic framework nano enzyme-like catalytic material and preparation and application thereof |
| CN116478417A (en) * | 2023-04-20 | 2023-07-25 | 绍兴文理学院 | Chiral covalent organic framework material based on boric acid ester, chiral separation membrane, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108219158B (en) | 2020-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108219158A (en) | Covalent organic framework material and preparation method thereof | |
| Li et al. | Growth of high-quality covalent organic framework nanosheets at the interface of two miscible organic solvents | |
| Qiu et al. | Imidazolium‐Salt‐Functionalized Covalent Organic Frameworks for Highly Efficient Catalysis of CO2 Conversion | |
| Köppen et al. | Synthesis, Transformation, Catalysis, and Gas Sorption Investigations on the Bismuth Metal–Organic Framework CAU‐17 | |
| CN103316714B (en) | Catalyst for photo-catalytically decomposing water to produce hydrogen and preparation method of catalyst | |
| CN103044463B (en) | A kind of efficient method preparing zeolite imidazole metalloid organic frame ZIF-90 | |
| Sadeghzadeh | Ionic liquid immobilized onto fibrous nano-silica: A highly active and reusable catalyst for the synthesis of quinazoline-2, 4 (1 H, 3 H)-diones | |
| CN108822301B (en) | Method for preparing functional covalent organic framework material by monomer exchange | |
| CN109663512A (en) | The mixed substrate membrane containing nano-grade molecular sieve and preparation method and application of ionic liquid@hollow polyhedron filling | |
| CN103025650B (en) | From the phosphine oxide catalysis method as hydrogen manufacturing the silylanizing derivative of hydrogen carrier | |
| CN105399705B (en) | A kind of method that furfuryl alcohol is prepared using hydrogen transfer reaction | |
| Xu et al. | A silica-coated metal-organic framework/graphite-carbon nitride hybrid for improved fire safety of epoxy resins | |
| Sun et al. | Nitrogen-doped carbon supported ZnO as highly stable heterogeneous catalysts for transesterification synthesis of ethyl methyl carbonate | |
| Ye et al. | Simple carbonaceous-material-loaded mesoporous SiO2 composite catalyst for epoxide-CO2 cycloaddition reaction | |
| Bhanja et al. | Bifunctional crystalline microporous organic polymers: Efficient heterogeneous catalysts for the synthesis of 5-hydroxymethylfurfural | |
| Liu et al. | Core-shell catalyst with synergistic hydroxyl and nitrogen active sites for CO2 cycloaddition | |
| CN108864486A (en) | A kind of phosphorus nitrogen system nano-core-shell structure fire retardant and its preparation method and application | |
| Houshiar et al. | Polymer/ZIF‐67 composite as an effective and recyclable nanocatalyst for Biginelli reaction | |
| CN105778062A (en) | Polymer and preparing method thereof | |
| CN109622037A (en) | A kind of Pd@Co4(tpt)2(btb) composite material and preparation method and application | |
| CN108276574A (en) | A kind of cyclohexanediamine Quito hole covalent organic framework compound and preparation method thereof | |
| CN112851954B (en) | Covalent organic framework, composite material thereof, preparation method and application | |
| CN110628085B (en) | Mesoporous silicon resin flame retardant, preparation method and flame-retardant composite material thereof | |
| CN108160078A (en) | A kind of C-Co nanocomposites and its preparation method and application | |
| CN109762142B (en) | Conjugated polymer material for regulating and controlling carbon dioxide adsorption based on photothermal effect |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20201013 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |