CN106832268A - Hollow spheres covalent organic frame material, preparation method, purposes and its intermediate - Google Patents
Hollow spheres covalent organic frame material, preparation method, purposes and its intermediate Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims description 66
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 47
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 36
- 229910052740 iodine Inorganic materials 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 28
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000005859 coupling reaction Methods 0.000 claims description 11
- 238000003379 elimination reaction Methods 0.000 claims description 11
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 11
- 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 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 230000000269 nucleophilic effect Effects 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 150000002466 imines Chemical class 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 235000015110 jellies Nutrition 0.000 claims description 8
- 239000008274 jelly Substances 0.000 claims description 8
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical group [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Chemical group 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 125000005619 boric acid group Chemical group 0.000 claims 1
- 239000013474 COF-1 Substances 0.000 description 36
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 28
- 239000011630 iodine Substances 0.000 description 28
- 238000010521 absorption reaction Methods 0.000 description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 239000011148 porous material Substances 0.000 description 12
- 239000013310 covalent-organic framework Substances 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000011805 ball Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 238000000634 powder X-ray diffraction Methods 0.000 description 8
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 238000013178 mathematical model Methods 0.000 description 4
- 238000012805 post-processing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-OUBTZVSYSA-N Carbon-13 Chemical compound [13C] OKTJSMMVPCPJKN-OUBTZVSYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- -1 aldehyde radical Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 150000003141 primary amines Chemical group 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 description 1
- 239000000592 Artificial Cell Substances 0.000 description 1
- IERHLVCPSMICTF-XVFCMESISA-N CMP group Chemical group P(=O)(O)(O)OC[C@@H]1[C@H]([C@H]([C@@H](O1)N1C(=O)N=C(N)C=C1)O)O IERHLVCPSMICTF-XVFCMESISA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910019213 POCl3 Inorganic materials 0.000 description 1
- 208000009144 Pure autonomic failure Diseases 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical class C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013317 conjugated microporous polymer Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- JCWIWBWXCVGEAN-UHFFFAOYSA-L cyclopentyl(diphenyl)phosphane;dichloropalladium;iron Chemical compound [Fe].Cl[Pd]Cl.[CH]1[CH][CH][CH][C]1P(C=1C=CC=CC=1)C1=CC=CC=C1.[CH]1[CH][CH][CH][C]1P(C=1C=CC=CC=1)C1=CC=CC=C1 JCWIWBWXCVGEAN-UHFFFAOYSA-L 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 210000003643 myeloid progenitor cell Anatomy 0.000 description 1
- 239000011807 nanoball Substances 0.000 description 1
- 230000007903 penetration ability Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000013312 porous aromatic framework Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000000371 solid-state nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000010457 zeolite 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C223/00—Compounds containing amino and —CHO groups bound to the same carbon skeleton
- C07C223/06—Compounds containing amino and —CHO groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/202—Single element halogens
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of hollow spheres covalent organic frame material, preparation method, purposes and its intermediate.The invention provides a kind of hollow spheres covalent organic frame material, preparation method, purposes and its intermediate；The constitutional repeating unit of the hollow spheres covalent organic frame material is as shown in Formulas I or Formula II, the covalent organic frame material is hollow spheres structure, crystallinity is high, it is thermally-stabilised good, capture, inclusion or efficiency of storage to unwanted volatile matter is higher, and good cycle during for adsorbing, while, the material preparation method is simple, is adapted to industrialization.
Description
Technical field
The present invention relates to hollow spheres covalent organic frame material, preparation method, purposes and its intermediate.
Background technology
Porous material due to its gas absorption and separate, catalysis sensing etc. field extensive use (A.Stein, Z,
Wang, M.A.Fierke.Adv.Mater.2009,21,265), attract the extensive concern of numerous scientific research personnel.Porous-Organic
Material is formed by connecting by organic molecule by covalent bond, and consequence is seized of in the porous material.With zeolite molecular sieve
Compared Deng inorganic porous material, organic porous material has smaller density and bigger specific surface area, and molecular structure
Diversity and tailorability for the diversity of COFs material structures and function provide abundance guarantee.Generally,
The preparation method being polymerized by organic molecule monomer is typically only capable to obtain amorphous material, such as conjugation micropore COF (CMPs), many
The amorphous materials such as hole COF networks (PPNs), porous fragrant framework (PAFs).By comparison, have crystalline organic many
Porous materials have unrivaled advantage, can be by the control that changes construction unit to realize to frame structure atomic level precision
System, thus the accurate adjustment of device to hole size, pore structure and porous can be realized, obtain internal structure high-sequential Porous-Organic
Material.Covalent organic frame (COFs) material for successfully preparing recent years is a kind of new with predictable topological structure
Crystallinity organic porous material (P.A.Waller, F.Gandara, O.M.Yaghi.Acc.Chem.Res.2015,48,
3053).But compared with its homologue metal organic frame (MOFs), the topological structure of covalent organic frame is very limited, two
The property exploration for tieing up material C OFs materials is largely limited to the single of structure, therefore development has new topological structure
The synthesis strategy of COFs come increase its diversity simultaneously develop expand its application of function be this field a big difficult point, be also this
One of current main development direction of one research field.
Hollow ball structural material due to density is low, specific surface area big, good stability and with surface penetration ability
Feature, has important application (T.K.Mandal, M.S.Fleming, D.R in fields such as chemistry, biological and material science
Walt.Chem.Mater, 2000,12,3481), such as control release capsule, artificial cell, electricity component, filler, catalysis, separation
Material, coating etc..But, existing organic porous material is captured to unwanted volatile matter such as iodine etc., inclusion and storage are imitated
Rate is relatively low and cycle performance is poor during for adsorbing.
The content of the invention
The technical problems to be solved by the invention are, in order to overcome organic porous material in the prior art to be volatilized to harmful
Material such as iodine etc. is captured, inclusion or efficiency of storage is relatively low and technological deficiency of cycle performance difference during for adsorbing, and is provided
A kind of hollow spheres covalent organic frame material, preparation method, purposes and its intermediate.The covalent organic frame of the hollow spheres
As shown in Formulas I or Formula II, the covalent organic frame material is hollow spheres structure to the constitutional repeating unit of material, and crystallinity is high,
Thermally-stabilised good, the capture, inclusion or efficiency of storage to unwanted volatile matter are higher, and good cycle during for adsorbing, meanwhile,
The material preparation method is simple, is adapted to industrialization.
The invention provides a kind of hollow spheres covalent organic frame material, its constitutional repeating unit such as Formulas I or Formula II institute
Show：
In Formulas I,Represent the constitutional repeating unit shown in formula I for omitting；
In Formula II,Represent the constitutional repeating unit as shown in Formula II for omitting；
X, Y, Z, W, X ', Y ', Z ', W ', X ", Y ", Z " and W " be each independently C or N (such as X, Y, Z, W, X ', Y ',
Z ', W ', X ", Y ", Z " and W " is C)；And when X is N, R1Do not exist；When Y is N, R2Do not exist；When Z is N, R3Do not deposit
；When W is N, R4Do not exist；When X ' is N, R1' do not exist；When Y ' is N, R2' do not exist；When Z ' is N, R3' do not deposit
；When W ' is N, R4' do not exist；When X " is N, R1" do not exist；As Y " for N when, R2" do not exist；As Z " for N when, R3" do not deposit
；As W " for N when, R4" do not exist；
R1、R2、R3、R4、R1’、R2’、R3’、R4’、R1”、R2”、R3" and R4" be each independently-H ,-OH, SH, halogen,
C1-C6Alkyl, C1-C6Alkoxy or C1-C6Alkane sulfydryl (such as R1、R2、R3、R4、R1’、R2’、R3’、R4’、R1”、R2”、R3”
And R4" be-H).
The invention provides a kind of preparation method of the hollow spheres covalent organic frame material, comprise the following steps：
Under oxygen free condition, in solvent, in the presence of acid, by formula 2 or compound shown in formula 3, carry out nucleophilic with compound shown in formula 1 and add
Into-elimination reaction generation imines, you can the hollow spheres covalent organic frame material is obtained；
The substitution base is as defined above described.
The hollow spheres covalent organic frame material preparation method refers to this area aldehyde radical and primary amine groups occur nucleophilic
Condition and operation, following methods specifically preferred according to the invention and condition during addition-elimination reaction generation imines：
The acid preferably acetic acid, the further preferred acetic acid is present in the (acetic acid of such as 6mol/L in aqueous acetic acid
The aqueous solution).
The mixed solvent of the preferred mesitylene of solvent and dioxane, the mixing of the mesitylene and dioxane
The volumetric usage ratio preferably 1 of mesitylene and dioxane in solvent:10~10:1, such as 1:5~5:1, then such as 1:1.
The formula 2 or compound shown in formula 3, the used in molar ratio preferably 10 with compound shown in the formula 1:1~1:1,
Such as 5:1~2:1, then such as 3:1.
The sour volumetric usage ratio preferably 1 with the solvent:20~1:5, such as 1:12~1:8, then such as 1:10.
Preferably 60 DEG C -200 DEG C, such as 120 DEG C of the temperature of the nucleophilic addition-elimination reaction.
The time of the nucleophilic addition-elimination reaction is preferred 12-120 hours, such as 72 hours.
The preferred jelly of the operation of the oxygen free condition pumps oxygen (for example, jelly is taken out three times), is thawed under the conditions of argon gas.
The preparation method of the hollow spheres covalent organic frame material, after the reaction terminates, can also be comprising post processing；
It is preferred that described post processing includes：Dry, washing, immersion or re-dry etc..
The drying, washing, immersion or re-dry refer to this area routine operation, and vacuum specifically preferred according to the invention is done
It is dry.
The used solvent of the washing, immersion is preferably selected from the one kind in 1,4- dioxane, dichloromethane and acetone
Or it is various.
The preparation method of the hollow spheres covalent organic frame material, it is preferably further comprising the steps of：In solvent,
In the presence of palladium catalyst and alkali, by compound shown in formula 4 and compound carries out coupling reaction shown in formula 5, you can prepare
Compound shown in the formula 1；
Wherein, R is that borate or boric acid replace base (for example), the boron atom in R is connected with phenyl ring；RaAnd RbRespectively
From independently selected from I or Br.
The coupling reaction can refer to the conventional method and condition of such reaction of this area, specifically preferred according to the invention with lower section
Method and condition：
One or more in the preferred DMF of solvent, toluene, ethanol, water, dioxane and acetonitrile, such as DMF.
The preferred Pd of the palladium catalyst [P (Ph3)]4And/or Pd (OAc)2, such as Pd [P (Ph3)]4。
One or more in the preferred cesium carbonate of alkali, potassium carbonate, sodium carbonate and potassium orthophosphate, such as potassium orthophosphate.
The mole dosage ratio preferably 2.2 of compound shown in the formula 4 and compound shown in the formula 5:1~1.8:1, for example
1.98:1。
The mole dosage ratio preferably 25 of compound shown in the formula 4 and the palladium catalyst:1~20:1, such as 19.6:1.
Molal volume of the compound shown in the formula 4 in the solvent is than preferred, such as 0.137mol/L.
The mole dosage ratio preferably 1 of compound shown in the formula 4 and the alkali:1~2:1, such as 1.6:1.
Preferably 80 DEG C~120 DEG C, such as 100 DEG C of the temperature of the coupling reaction.
Present invention also offers a kind of preparation method of hollow spheres covalent organic frame material, comprise the following steps, nothing
Under the conditions of oxygen, in solvent, in the presence of acid, by formula 2 or compound shown in formula 3, carry out nucleophilic with compound shown in formula 1 and add
Into-elimination reaction generation imines, you can；
The substitution base is as defined above described.
The preparation method of the hollow spheres covalent organic frame material refers to this area aldehyde radical and primary amine groups occur parent
Condition and operation, following methods specifically preferred according to the invention and condition during core addition-elimination reaction generation imines：
The acid preferably acetic acid, the further preferred acetic acid is present in the (acetic acid of such as 6mol/L in aqueous acetic acid
The aqueous solution).
The mixed solvent of the preferred mesitylene of solvent and dioxane, the mixing of the mesitylene and dioxane
The volumetric usage ratio preferably 1 of mesitylene and dioxane in solvent:10~10:1, such as 1:5~5:1, then such as 1:1.
The formula 2 or compound shown in formula 3, the used in molar ratio preferably 10 with compound shown in the formula 1:1~1:1,
Such as 5:1~2:1, then such as 3:1.
The sour volumetric usage ratio preferably 1 with the solvent:20~1:5, such as 1:12~1:8, then such as 1:10.
Preferably 60 DEG C -200 DEG C, such as 120 DEG C of the temperature of the nucleophilic addition-elimination reaction.
The time of the nucleophilic addition-elimination reaction is preferred 12-120 hours, such as 72 hours.
The preferred jelly of the operation of the oxygen free condition pumps oxygen (for example, jelly is taken out three times), is thawed under the conditions of argon gas.
The preparation method of the hollow spheres covalent organic frame material, after the reaction terminates, can also be comprising post processing；
It is preferred that described post processing includes：Dry, washing, immersion or re-dry etc..
The drying, washing, immersion or re-dry refer to this area routine operation, and vacuum specifically preferred according to the invention is done
It is dry.
The used solvent of the washing, immersion is preferably selected from the one kind in 1,4- dioxane, dichloromethane and acetone
Or it is various.
The preparation method of the hollow spheres covalent organic frame material, it is preferably further comprising the steps of：In solvent,
In the presence of palladium catalyst and alkali, by compound shown in formula 4 and compound carries out coupling reaction shown in formula 5, you can prepare
Compound shown in the formula 1；
Wherein, R is that borate or boric acid replace base (for example), the boron atom in R is connected with phenyl ring；RaAnd RbRespectively
From independently selected from I or Br.
The coupling reaction can refer to the conventional method and condition of such reaction of this area, specifically preferred according to the invention with lower section
Method and condition：
One or more in the preferred DMF of solvent, toluene, ethanol, water, dioxane and acetonitrile, such as DMF.
The preferred Pd of the palladium catalyst [P (Ph3)]4And/or Pd (OAc)2, such as Pd [P (Ph3)]4。
One or more in the preferred cesium carbonate of alkali, potassium carbonate, sodium carbonate and potassium orthophosphate, such as potassium orthophosphate.
The mole dosage ratio preferably 2.2 of compound shown in the formula 4 and compound shown in the formula 5:1~1.8:1, for example
1.98:1。
The mole dosage ratio preferably 25 of compound shown in the formula 4 and the palladium catalyst:1~20:1, such as 19.6:1.
Molal volume of the compound shown in the formula 4 in the solvent is than preferred, such as 0.137mol/L.
The mole dosage ratio preferably 1 of compound shown in the formula 4 and the alkali:1~2:1, such as 1.6:1.
Preferably 80 DEG C~120 DEG C, such as 100 DEG C of the temperature of the coupling reaction.
Present invention also offers the hollow spheres covalent organic frame material that a kind of preparation method as described above is prepared.
It is harmful small in capture, inclusion and storage present invention also offers a kind of hollow spheres covalent organic frame material
Application in molecule, harmful preferred volatile materials of small molecule, further preferred iodine.
Present invention also offers compound shown in formula 1：
The present invention also additionally provides the preparation method of compound shown in formula 1, and it is comprised the steps of, and in solvent, is urged in palladium
In the presence of agent and alkali, by compound shown in formula 4 and compound carries out coupling reaction shown in formula 5, you can prepare described
Compound shown in formula 1；
Wherein, R is that borate or boric acid replace base (for example), the boron atom in R is connected with phenyl ring；
RaAnd RbIt is each independently selected from I or Br.
The coupling reaction can refer to the conventional method and condition of such reaction of this area, specifically preferred according to the invention with lower section
Method and condition：
One or more in the preferred DMF of solvent, toluene, ethanol, water, dioxane and acetonitrile, such as DMF.
The preferred Pd of the palladium catalyst [P (Ph3)]4And/or Pd (OAc)2, such as Pd [P (Ph3)]4。
One or more in the preferred cesium carbonate of alkali, potassium carbonate, sodium carbonate and potassium orthophosphate, such as potassium orthophosphate.
The mole dosage ratio preferably 2.2 of compound shown in the formula 4 and compound shown in the formula 5:1~1.8:1, for example
1.98:1。
The mole dosage ratio preferably 25 of compound shown in the formula 4 and the palladium catalyst:1~20:1, such as 19.6:1.
Molal volume of the compound in the solvent shown in the formula 4 is than preferred 0.09mol/L~0.15mol/L, example
Such as 0.137mol/L.
The mole dosage ratio preferably 1 of compound shown in the formula 4 and the alkali:1~2:1, such as 1.6:1.
Preferably 80 DEG C~120 DEG C, such as 100 DEG C of the temperature of the coupling reaction.
Present invention also offers a kind of covalent organic frame material answering in capture, inclusion or storage small molecule
With.
In the present invention, " 4,4 "-bis- (double (4- aldehyde radicals phenyl) amino)-[1', 1'：4', 1 "-biphenyl] 2', 5'- dicarbaldehydes "
Or BFATD refers both to the compound with the structure as shown in following formula 1：
Term " COFs " refers to covalent organic frame material of the invention；
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, can be combined, and obtain final product the present invention each preferably
Example.
Agents useful for same of the present invention and raw material are commercially available.
Positive effect of the invention is：
(1) COFs preparation methods of the invention are simple, realization easy to operate；
(2) COFs crystallinity of the invention is high, it is ensured that the orderly multi-stage artery structure in surface；
(3) COFs of the invention shows that the porous C OFs of preparation has good stability through thermogravimetic analysis (TGA)；
(4) COFs of the invention can form micro-/ nano hollow ball, can provide the memory space of harmful small molecule.
(5) Porous-Organic COFs of the invention unwanted volatile matter such as iodine etc. is captured, inclusion and efficiency of storage it is high
In all material of current report, therefore it is good sorbing material, can be used as storage/inclusion material, separation material, absorption
Agent, carrier material etc..
Brief description of the drawings
Accompanying drawing 1 is p-phenylenediamine of the present invention, compound shown in formula 1 and COF-1 infrared spectrograms；
Wherein a represents p-phenylenediamine；B represents compound shown in the Chinese style 1 of embodiment 1；C represents COF-1；Wherein
1619.8cm-1The C=N vibration peaks of appearance confirm the formation of imine linkage.
Accompanying drawing 2 is the solid state nmr spectrogram of carbon -13 of COF-1 in the embodiment of the present invention 1；Nuclear-magnetism peak card at wherein 155ppm
The real generation of imine linkage.
Accompanying drawing 3 is the thermogravimetric analysis spectrogram of COF-1 in the embodiment of the present invention 1；When sample is heated to 500 DEG C, also 91%
Weight retain, it was demonstrated that the COF-1 for being formed has heat endurance very high.
Accompanying drawing 4 is the X-ray powder diffraction spectrogram of COF-1 correlations in the embodiment of the present invention 1；A for actual measurement (on) and refine
(under) X-ray powder diffraction figure；B is the difference of X-ray powder diffraction figure after simulation and refine；C is AA Mathematical Model of heaped-up
The X-ray powder diffraction theoretical modeling collection of illustrative plates of COF-1；D is the X-ray powder diffraction theoretical modeling of AB Mathematical Model of heaped-up COF-1
Collection of illustrative plates.Gained diffraction maximum is compared with theoretical modeling figure, it was demonstrated that the COF-1 for being formed forms expected ordered dual-pore structure.
Accompanying drawing 5, accompanying drawing 6 are respectively the nitrogen adsorption-desorption curve figure and pore-size distribution of COF-1 in the embodiment of the present invention 1
Figure, further demonstrating the COF-1 formed in embodiment 1 has two kinds of different pore-size distributions.
Accompanying drawing 7 is the thermogravimetric analysis spectrogram after COF-1 absorption iodine in the embodiment of the present invention 1, it was demonstrated that after absorption in COF-1
Contain substantial amounts of elemental iodine.
Accompanying drawing 8, accompanying drawing 9, accompanying drawing 10 are for before COF-1 absorption iodine in the embodiment of the present invention 1, after absorption iodine and after desorption iodine
Transmission electron microscope picture, COF-1 is hollow spherical structure before illustrating absorption iodine, and the inside of hollow ball is accounted for by substantial amounts of iodine molecule after absorption iodine
According to being desorbed and formed again hollow spherical structure.
Accompanying drawing 11, accompanying drawing 12 are the EDX distribution diagram of element before COF-1 absorption iodine in the embodiment of the present invention 1 and after absorption iodine,
Tetra- kinds of elements of C, N, H, O are comprised only in COF-1 before illustrating absorption iodine.Also contain except above-mentioned element in COF-1 after absorption iodine
I.
Accompanying drawing 13 is EDX I mappings after COF-1 absorption iodine in the embodiment of the present invention 1, it was demonstrated that iodine is hollow
Being uniformly distributed in ball.
Accompanying drawing 14 is the dynamic experiment of COF-1 iodine adsorption processes in the embodiment of the present invention 1, it was demonstrated that I is quickly inhaled
Receive and adsorption efficiency high.
Accompanying drawing 15 is the hydrogen nuclear magnetic resonance spectrogram of compound shown in Chinese style of the present invention 1.
Accompanying drawing 16 is the carbon -13 nmr figure of compound shown in Chinese style of the present invention 1.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to described reality
Apply among a scope.The experimental technique of unreceipted actual conditions in the following example, conventionally and condition, or according to business
Product specification is selected.
Embodiment 1
The synthesis of covalent organic frame micro-/ nano hollow ball COF-1
4,4 are added in 10mL tube sealings "-bis- (double (4- aldehyde radicals phenyl) amino)-[1', 1'：4', 1 "-biphenyl] 2', 5'- bis-
Formaldehyde (BFATD) (30mg, 0.041mmol), p-phenylenediamine (13.3mg, 0.123mmol), mesitylene (0.5mL), dioxy six
Ring (0.5mL) and 6mol/L acetic acid (0.1mL).
Freeze in argon atmosphere after system is ultrasonic 3 minutes and take out three times, then thaw, be put into the reaction at 120 DEG C in baking oven,
It is observed that the solid for having yellow fluffy to fill is generated.After 3 days, tube sealing is taken out, be cooled to room temperature, extracted in vacuum drying chamber molten
Agent, remaining solid is immersed in 4 hours in dichloromethane, suction filtration, with substantial amounts of dichloromethane and acetone rinsing.Finally filter
To solid be dried overnight in 120 DEG C of vacuum drying ovens, obtain yellow product (31.4mg, 80.8%), i.e. COF-1.Element point
Analysis：Theoretical value, C66H44N8:C,83.52；H,4.67；N,11.81.Experiment value:C,80.00；H,4.78；N,10.99.
The analyze data of COF-1, is shown in accompanying drawing 1-7.
A represents p-phenylenediamine in accompanying drawing 1；B represents compound shown in the Chinese style 1 of embodiment 1；C represents COF-1；Wherein
1619.8cm-1The C=N vibration peaks of appearance confirm the formation of imine linkage.
Nuclear-magnetism peak in accompanying drawing 2 at 155ppm confirms the generation of imine linkage.
When sample is heated to 500 DEG C in accompanying drawing 3, also 91% weight retains, it was demonstrated that the COF-1 for being formed has very high
Heat endurance.
In accompanying drawing a for actual measurement (on) and refine (under) X-ray powder diffraction figure；B is X-ray powder after simulation and refine
The difference of last diffraction pattern；C is the X-ray powder diffraction theoretical modeling collection of illustrative plates of AA Mathematical Model of heaped-up COF-1；D is AB Mathematical Model of heaped-up
The X-ray powder diffraction theoretical modeling collection of illustrative plates of COF-1.Gained diffraction maximum compares with theoretical modeling figure, it was demonstrated that the COF- for being formed
1 forms expected ordered dual-pore structure.
Accompanying drawing 5, accompanying drawing 6 further demonstrate the COF-1 formed in embodiment 1 has two kinds of different pore-size distributions.
Accompanying drawing 7 to be demonstrated and contain substantial amounts of elemental iodine in COF-1 after adsorbing.
Embodiment 2
The synthesis of covalent organic frame micro-/ nano hollow ball COF-2
4,4 are added in 10mL tube sealings "-bis- (double (4- aldehyde radicals phenyl) amino)-[1', 1'：4', 1 "-biphenyl] 2', 5'- bis-
Formaldehyde (BFATD) (25mg, 0.034mmol), 4,4'- benzidines (18.8mg, 0.102mmol), mesitylene
(0.5mL), dioxane (0.5mL) and 6mol/L acetic acid (0.1mL).
Freeze in argon atmosphere after system is ultrasonic 3 minutes and take out three times, then thaw, be put into the reaction at 120 DEG C in baking oven,
It is observed that the solid for having yellow fluffy to fill is generated.After 3 days, tube sealing is taken out, be cooled to room temperature, extracted in vacuum drying chamber molten
Agent, remaining solid is immersed in 4 hours in dichloromethane, suction filtration, with substantial amounts of dichloromethane and acetone rinsing.Finally filter
To solid be dried overnight in 120 DEG C of vacuum drying ovens, obtain yellow product (34.3mg, 85.5%), i.e. COF-2.Element point
Analysis：Theoretical value, C84H56N8:C,85.69；H,4.79；N,9.52.Experiment value:C,80.74；H,4.86；N,8.73.
Embodiment 3
By taking unwanted volatile matter iodine as an example show gained covalently organic frame capture, inclusion and storage small molecule ability with should
With
The COF-1 of excessive elemental iodine and certain mass is separately added into two small beakers, two small beakers are put into
In slightly larger vial, sealed glass jars are put into baking oven and are warming up to 75 DEG C.Vial is taken out at regular intervals, is cooled to
Room temperature, weighs the change that COF-1 adsorbs percentage by weight after preceding and absorption.
Test shows that the adsorbent of present invention preparation is very good to the absorption property of iodine.Absorption percentage by weight can reach
481%, it was demonstrated that iodine being uniformly distributed in hollow ball.It is much higher than all porous materials of current report.
Embodiment 4
Sorption cycle performance test
Reaction method is basic such as embodiment 3, and adsorbed iodine is heated into removing under a high vacuum, then by desorption after be total to
Valency organic frame hollow ball continues on for iodine adsorption experiment, loop test to 5 times, often
Secondary iodine absorption percentage by weight is respectively calculated as follows.
| Number of times | 1 | 2 | 3 | 4 | 5 |
| Absorption weight (%) | 469 | 467 | 461 | 458 | 450 |
Test shows that adsorbent prepared by the present invention has good cycle performance.Adsorptivity after recycling at least 5 times
Can not be decreased obviously.
To COF-1 absorption iodine before and absorption iodine after pattern carry out TEM tests, as a result show, absorption before COF-1 be it is micro-/receive
The hollow spherical structure (accompanying drawing 8) of rice；The inner chamber of hollow ball is occupied (accompanying drawing 9) by iodine molecule after absorption；COF-1 is returned to after desorption
The hollow spherical structure of micro-/ nano (accompanying drawing 10) originally.
To COF-1 absorption iodine before (accompanying drawing 11) and absorption iodine after (accompanying drawing 12) carry out EDX element tests, as a result show, suction
Attached preceding COF-1 does not contain iodine molecule, contains substantial amounts of iodine molecule after absorption, and iodine molecule be uniformly distributed in it is (attached in micro-/ nano ball
Figure 13).
The preparation of compound shown in formula 1：
The preparation of compound shown in formula 6：Compound (6.0g, 18.5mmol) shown in formula 7 is added in the there-necked flask of 250mL,
DMF (23mL, 296mmol), is added dropwise over POCl3 (18.5mL, 198mmol) under condition of ice bath.Solution is in 100 DEG C of reactions
36 hours.After being cooled to room temperature, reaction solution is slowly poured into frozen water, is added 2N sodium hydroxide solutions and is neutralized to neutrality.Filtering,
Filter cake is washed with a large amount of water and ethanol, and dried product exhibited uses column chromatography (dichloromethane/n-hexane 3:1) yellow solid is obtained
(4.64g, 66%), i.e., compound shown in formula 6.1H NMR(400MHz,CDCl3):δ 9.91 (s, 2H), 7.79 (d, J=8.6Hz,
4H), 7.50 (d, J=8.7Hz, 2H), 7.18 (d, J=8.6Hz, 4H), 7.05 (d, J=8.7Hz, 2H).
The preparation of compound shown in formula 4：Compound (5.0g, 13.1mmol) shown in formula 6 is added in the there-necked flask of 250mL,
Connection pinacol borate (4.0g, 15.8mmol), potassium carbonate (3.9g, 39.7mmol), Pd (dppf)2Cl2(0.3g,
0.4mmol), dry dioxane (90mL), jelly is stirred 24 hours after taking out in 100 DEG C of argon atmospheres.After being cooled to room temperature,
Reaction solution is spin-dried for, then is extracted with ethyl acetate, and anhydrous magnesium sulfate is dried, and is spin-dried for solvent.The crude product for obtaining is used column chromatography
(petrol ether/ethyl acetate 10:1) faint yellow solid (5.4g, 96%), i.e., compound shown in formula 4 are obtained.1H NMR(400MHz,
CDCl3):δ 9.90 (s, 2H), 7.81 (d, J=8.4Hz, 2H), 7.78 (d, J=8.7Hz, 4H), 7.19 (d, J=8.6Hz,
4H), 7.15 (d, J=8.4Hz, 2H), 1.46-1.27 (m, 12H)13C NMR(125MHz,CDCl3):δ190.50,151.81,
148.18,136.56,131.59,131.30,125.55,123.27,84.01,24.88.MS(ESI):m/z 428.4[M+H
]+.HRMS(ESI):Calcd for C26H27BNO4[M+H]+:427.2064.Found:427.2064。
Compound shown in synthesis type 1：Compound (200mg, 0.69mmol), formula 4 shown in formula 5 are added in the there-necked flask of 25mL
Shown compound (586mg, 1.37mmol), potassium orthophosphate (182mg, 0.86mmol), Pd [P (Ph3)]4(81mg,
0.07mmol), DMF (10mL), jelly is stirred 24 hours in taking out rear 100 DEG C of argon atmospheres.After being cooled to room temperature, solution, water are spin-dried for
Wash, anhydrous magnesium sulfate is dried, and is spin-dried for solvent.The crude product for obtaining uses column chromatography (dichloromethane/ethyl acetate 50:1)
To orange solids (532mg, 53%).1H NMR(500MHz,DMSO-d6):δ10.11(s,2H),9.91(s,4H),8.02(s,
2H), 7.89 (d, J=8.6Hz, 8H), 7.62 (d, J=8.4Hz, 4H), 7.35 (d, J=8.4Hz, 4H), 7.29 (d, J=
8.6Hz,8H).13C NMR(125MHz,CDCl3):δ191.28,190.47,151.66,146.34,143.56,136.49,
133.43,131.94,131.64,131.48,130.49,126.27,123.52；
MS(MALDI-TOF):m/z 732.2.HRMS(MALDI-TOF):Calcd for C48H32N2O6:
732.2251.Found:732.2255。
Claims (10)
1. a kind of hollow spheres covalent organic frame material, it is characterised in that its constitutional repeating unit is as shown in Formulas I or Formula II：
In Formulas I,Represent the constitutional repeating unit shown in formula I for omitting；
In Formula II,Represent the constitutional repeating unit as shown in Formula II for omitting；
X, Y, Z, W, X ', Y ', Z ', W ', X ", Y ", Z " and W " be each independently C or N；Described X, Y, Z, W, X ', Y ', Z ', W ',
X ", Y ", Z " and W " is both preferably C；And when X is N, R1Do not exist；When Y is N, R2Do not exist；When Z is N, R3Do not exist；
When W is N, R4Do not exist；When X ' is N, R1' do not exist；When Y ' is N, R2' do not exist；When Z ' is N, R3' do not exist；
When W ' is N, R4' do not exist；When X " is N, R1" do not exist；As Y " for N when, R2" do not exist；As Z " for N when, R3" do not exist；
As W " for N when, R4" do not exist；
R1、R2、R3、R4、R1’、R2’、R3’、R4’、R1”、R2”、R3" and R4" it is each independently-H ,-OH, SH, halogen, C1-C6Alkane
Base, C1-C6Alkoxy or C1-C6Alkane sulfydryl, the R1、R2、R3、R4、R1’、R2’、R3’、R4’、R1”、R2”、R3" and R4"
Preferably-H.
2. a kind of preparation method of hollow spheres covalent organic frame material, it is characterised in that comprise the following steps：Oxygen free condition
Under, in solvent, in the presence of acid, by formula 2 or compound shown in formula 3, nucleophilic addition-elimination is carried out with compound shown in formula 1
Reaction generation imines, you can；
The substitution base definition is with described in claim 1.
3. the preparation method of hollow spheres covalent organic frame material as claimed in claim 2, it is characterised in that the acid is
Acetic acid, the acetic acid is preferably in aqueous acetic acid, and concentration of the further preferred acetic acid in aqueous acetic acid is 6mol/
L；
And/or, the solvent is the mixed solvent of mesitylene and dioxane, the mixing of the mesitylene and dioxane
The volumetric usage ratio preferably 1 of mesitylene and dioxane in solvent:10~10:1, further preferred 1:5~5:1, more preferably
1:1。
4. the preparation method of hollow spheres covalent organic frame material as claimed in claim 2, it is characterised in that the formula 2
Or compound shown in formula 3, it is 10 with the used in molar ratio of compound shown in the formula 1:1~1:1, preferably 5:1~2:1, it is more excellent
Select 3:1；
And/or, the sour volumetric usage ratio with the solvent is 1:20~1:5, preferably 1:12~1:8, further preferred 1:
10；
And/or, the nucleophilic addition-elimination reaction temperature is 60 DEG C -200 DEG C, preferably 120 DEG C；
And/or, the time of the nucleophilic addition-elimination reaction is 12-120 hours, preferably 72 hours；
And/or, the operation of the oxygen free condition pumps oxygen for jelly, is thawed under the conditions of argon gas；It is preferred that jelly is taken out three times.
5. the hollow spheres covalent organic frame material that a kind of preparation method as described in claim any one of 2-4 is prepared.
6. the preparation method of compound shown in a kind of formula 1, it is characterised in that comprise the following steps：In solvent, in palladium catalyst and
In the presence of alkali, by compound shown in formula 4 and compound carries out coupling reaction shown in formula 5, you can prepare shown in the formula 1
Compound；
Wherein, R is borate or boric acid substitution base, and the boron atom in R is connected with phenyl ring；The borate is preferred
RaAnd RbIt is each independently selected from I or Br.
7. the preparation method of compound shown in formula as claimed in claim 61, it is characterised in that the solvent is selected from DMF, first
One or more in benzene, ethanol, water, dioxane and acetonitrile；
And/or, the palladium catalyst is Pd [P (Ph3)]4And/or Pd (OAc)2；
And/or, the alkali is selected from one or more in cesium carbonate, potassium carbonate, sodium carbonate and potassium orthophosphate.
8. the preparation method of compound shown in formula 1 is planted as claimed in claim 6, it is characterised in that compound shown in the formula 4
It is 2.2 with the mole dosage ratio of compound shown in the formula 5:1~1.8:1, preferably 1.98:1；
The mole dosage ratio of compound and the palladium catalyst shown in the formula 4 is 25:1~20:1, preferably 19.6:1；
And/or, molal volume ratio of the compound shown in the formula 4 in the solvent is 0.09mol/L~0.15mol/L, excellent
Select 0.137mol/L；
And/or, the mole dosage ratio of compound and the alkali shown in the formula 4 is 1:1~2:1, preferably 1.6:1；
And/or, the temperature of the coupling reaction is 80 DEG C~120 DEG C, preferably 100 DEG C.
9. as any one of claim 1-5 hollow spheres covalent organic frame material is in capture, inclusion or stores
Application in evil volatile materials.
10. compound shown in formula 1：
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