CN109316978A - A kind of MOFs material and its preparation method and application - Google Patents
A kind of MOFs material and its preparation method and application Download PDFInfo
- Publication number
- CN109316978A CN109316978A CN201811246761.XA CN201811246761A CN109316978A CN 109316978 A CN109316978 A CN 109316978A CN 201811246761 A CN201811246761 A CN 201811246761A CN 109316978 A CN109316978 A CN 109316978A
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- Prior art keywords
- mof
- organic framework
- metal organic
- mofs material
- grafted
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 143
- 239000000463 material Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 69
- 229920002521 macromolecule Polymers 0.000 claims abstract description 33
- 239000012528 membrane Substances 0.000 claims description 32
- 239000002808 molecular sieve Substances 0.000 claims description 24
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 24
- -1 amino terphenyl dicarboxylic acids Chemical class 0.000 claims description 20
- 239000013110 organic ligand Substances 0.000 claims description 16
- 239000004642 Polyimide Substances 0.000 claims description 14
- 229920001721 polyimide Polymers 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 12
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 claims description 11
- 229910021645 metal ion Inorganic materials 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- CDOWNLMZVKJRSC-UHFFFAOYSA-N 2-hydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1 CDOWNLMZVKJRSC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
- 229920002492 poly(sulfone) Polymers 0.000 claims description 5
- 238000006068 polycondensation reaction Methods 0.000 claims description 5
- 229920006393 polyether sulfone Polymers 0.000 claims description 5
- 238000010526 radical polymerization reaction Methods 0.000 claims description 5
- 125000004070 6 membered heterocyclic group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical group NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 3
- QPBGNSFASPVGTP-UHFFFAOYSA-N 2-bromoterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(Br)=C1 QPBGNSFASPVGTP-UHFFFAOYSA-N 0.000 claims description 3
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 3
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 claims description 3
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 claims description 3
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- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 3
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- BVWCKYAYMBDPIP-UHFFFAOYSA-N NC=1C=C(C=C(C1)N)C=CC1=CC=CC=C1 Chemical compound NC=1C=C(C=C(C1)N)C=CC1=CC=CC=C1 BVWCKYAYMBDPIP-UHFFFAOYSA-N 0.000 claims description 3
- 229960000643 adenine Drugs 0.000 claims description 3
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- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 3
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- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 3
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- JWYUFVNJZUSCSM-UHFFFAOYSA-N 2-aminobenzimidazole Chemical compound C1=CC=C2NC(N)=NC2=C1 JWYUFVNJZUSCSM-UHFFFAOYSA-N 0.000 claims description 2
- OMEGITYKNVPYCS-UHFFFAOYSA-N 2-aminobenzene-1,3,5-tricarboxylic acid Chemical compound NC1=C(C(O)=O)C=C(C(O)=O)C=C1C(O)=O OMEGITYKNVPYCS-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 23
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
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- 230000015572 biosynthetic process Effects 0.000 description 4
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- 238000010998 test method Methods 0.000 description 4
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- 238000002604 ultrasonography Methods 0.000 description 4
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- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
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- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 2
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
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- 125000001246 bromo group Chemical group Br* 0.000 description 2
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- NFGHHSYAGGGNTC-UHFFFAOYSA-N 1-(azidomethyl)-2-phenylbenzene Chemical group [N-]=[N+]=NCC1=CC=CC=C1C1=CC=CC=C1 NFGHHSYAGGGNTC-UHFFFAOYSA-N 0.000 description 1
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- 150000003536 tetrazoles Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical class Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to Material Fields, more particularly to a kind of MOFs material and its preparation method and application.The present invention provides a kind of MOFs material, including metal organic framework substrate, and the metal organic framework substrate includes grafted moiety, and the grafted moiety passes through covalent bond grafted linear macromolecule.The mechanical stretching performance of MOFs material provided by the present invention has biggish promotion, under the premise of identical MOF load capacity, film containing grafting MOF contains the film of unmodified MOF to comparison, anti- plasticizing capacity is promoted obvious, and the film containing grafting MOF contains the film of unmodified MOF to comparison, the selectivity of gas is promoted obvious.
Description
Technical field
The present invention relates to Material Fields, more particularly to a kind of MOFs material and its preparation method and application.
Background technique
Ideal gas separation membrane material needs while meeting highly selective and high osmosis.However most macromolecules
Restriction of the performance of film by selectivity and permeability trade-off relationship, it is difficult to be broken through simultaneously in two performances.This is
Since macromolecule internal void unevenly causes it that can not carry out efficient size selection separation to various sizes of gas molecule.
In comparison, the inorganic material film of high-crystallinity usually has rigid, size uniformity cellular structure and consistent duct
Learn environment.Therefore the characteristic of size selection separation can be embodied effectively to show the separation property for far surmounting polymeric membrane
Energy.But since rigid powder material plasticity is poor, the cost of manufacture of inoranic membrane is generally high.Existing manufacture craft simultaneously
It is difficult to realize the production of large area zero defect membrane module.In order to combine the two respective strong points of class material, a side generally used
Case is that will there is the porous aggregate of good gas sieve performance to combine with the polymer matrix that can have process operation, is prepared into
To mixed substrate membrane containing nano-grade molecular sieve (Mixed Matrix Membranes, MMMs).In the selection of porous aggregate, metal organic frame
(Metal-Organic Frameworks, MOFs) compared to other porous aggregates, such as zeolite, carbon molecular sieve etc. has aobvious
The advantage of work.This is because MOFs is the tool being self-assembly of by organic ligand and metal ion or metal cluster by coordinate bond
There are the hybrid inorganic-organic materials of molecule inner pore.It has high porosity, bigger serface, duct rule, aperture is adjustable,
Topological structure diversity and the advantages that being easily introduced functional organic.In the past more than ten years, the mixed substrate membrane containing nano-grade molecular sieve based on MOFs
Research report it is not within minority, however only a small number of cases shows to meet expected separating property.Cause performance lower than reason
Think one of value be mainly due to dispersed phase (MOFs) and continuous phase (polymer matrix) interface compatibility it is poor cause it is non-
The generation of the problems such as increase, the hardening of interface macromolecule, the hole plug in hole of selectivity is to seriously affect the separation of film
Performance.Therefore MOFs how is improved by interface modification and polymer matrix interface fusion is one and urgently to be solved asks
Topic, undesirable interface compatibility will lead to phase interface and gas occur.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of MOFs material and its preparation sides
Method and purposes, for solving the problems of the prior art.
In order to achieve the above objects and other related objects, the present invention provides a kind of MOFs material, including metal organic framework
Substrate, the metal organic framework substrate includes grafted moiety, and the grafted moiety passes through covalent bond grafted linear macromolecule.
In some embodiments of the present invention, the partial size of the metal organic framework substrate particles is 10nm~10 μm.
In some embodiments of the present invention, the organic ligand in the metal organic framework substrate is matched including two or more
Position group, the coordinating group are selected from one of carboxylic acid, penta azacyclo or six-membered heterocycle or a variety of combinations.
In some embodiments of the present invention, the organic ligand in the metal organic framework substrate includes grafted moiety,
The grafted moiety is selected from one of amino, hydroxyl, nitrine, halogen, carbonyl, sulfydryl or carboxyl or a variety of combinations.
In some embodiments of the present invention, the organic ligand in the metal organic framework substrate is selected from amino to benzene two
Formic acid, 5- amino isophthalic acid, aminobphenyl dioctyl phthalate, amino terphenyl dicarboxylic acids, aminooimidazole, aminobenzimidazole,
3,5- diaminostilbene, 2,4- triazole, adenine, 3- amino -1,2,4- triazole, 5- aminotetrazole, the equal benzene front three of 2- amino
Acid, hydroxyterephthalic acid, 2- bromo terephthalic acid, bromomethylbiphenyl dioctyl phthalate, nitrine phthalic acid, azido-methyl biphenyl two
One of formic acid, nitrine biphenyl dicarboxylic acid or a variety of combinations.
In some embodiments of the present invention, the metal ion in the metal organic framework substrate be selected from Zr, Al, Cr,
The ion of one of Cu, Zn, Co, Ni, Ti, Fe, Mg, Hf or a variety of combinations in each valence state.
In some embodiments of the present invention, the grafted moiety in the metal organic framework substrate be selected from amino, hydroxyl,
One of nitrine, halogen, carbonyl, sulfydryl or carboxyl or a variety of combinations.
In some embodiments of the present invention, the duct of the metal organic framework substrate is 0.3nm~2nm.
In some embodiments of the present invention, the metal organic framework substrate is selected from UiO-66-NH2、UiO-67-NH2、
UiO-68-NH2、NH2-MIL-53(Al、Fe、Cr)、NH2-MIL-101(Cr)、NH2-MIL-101(Al)、NH2-MIL-101
(Fe)、NH2-MIL-68(In)、NH2-MIL-88(Al)、NH2-MIL-125、ZIF-7-NH2、ZIF-8-NH2、ZIF-9-NH2、
ZIF-11-NH2、UMCM-1-NH2、MOF-46、BiO-MOF-1、BiO-MOF-11、BiO-MOF-12、BiO-MOF-13、BiO-
MOF-14、Zn2(Atz)2、DMOF-1-NH2、NH2-CuBTC、MAF-66、CPF-13、ZnF(Am2TAZ)、CAU-1、IRMOF-3、
ZIF-96、UiO-66-(OH)2、MOF-74、UiO-66-Br、UiO-66-N3、UMCM-1-N3、UiO-67-N3、MIL-101-N3、
IRMOF-16-N3One of or a variety of combinations.
In some embodiments of the present invention, the linear polymeric and grafted moiety are poly- by polycondensation, free radical initiation
It closes, ring-opening polymerisation connection.
In some embodiments of the present invention, the linear polymeric is selected from polyimides, polyamide, polysulfones, polyether sulfone
One of or a variety of combinations.
In some embodiments of the present invention, molecular weight >=500Da of the linear polymeric.
In some embodiments of the present invention, metal organic framework substrate surface is modified with polymer brush.
Another aspect of the present invention provides the preparation method of the MOFs material, comprising:
Obtain the metal organic framework substrate including grafted moiety；
By at least part of grafted moiety grafted linear macromolecule.
Another aspect of the present invention provides the MOFs material in the purposes of Selective Separation field of material preparation.
Another aspect of the present invention provides a kind of mixed substrate membrane containing nano-grade molecular sieve, including the MOFs material.
Detailed description of the invention
Fig. 1, which is shown as surface grafting in the embodiment of the present invention, high molecular UiO-66-NH2Transmission electron microscope picture.
Fig. 2 is shown as extension test in the embodiment of the present invention, stress-strain diagram schematic diagram.
Fig. 3 is shown as the curve synoptic diagram that carbon dioxide permeability ability is converted with atmospheric pressure in the embodiment of the present invention.
Fig. 4 is shown as in the embodiment of the present invention 35 DEG C, and pure gas is tested under the conditions of 3.1bar, carbon dioxide permeability, with
Relation schematic diagram between carbon dioxide/nitrogen selective.
Fig. 5 is shown as in the embodiment of the present invention 35 DEG C, and pure gas is tested under the conditions of 3.1bar, carbon dioxide permeability, with
Relation schematic diagram between carbon dioxide/methane type selectivity.
Specific embodiment
Inventor passes through the combination of MOFs filler and polymer matrix, provides a kind of new MOFs material, described
MOFs material is gone forward side by side by the limitation that novel surface modification method breaks through the effect to enhancing interface compatibility in the prior art
One step reinforces interface compatibility, completes the present invention on this basis.
First aspect present invention provides a kind of MOFs material, including metal organic framework substrate, the metal organic framework
Substrate includes grafted moiety, and the grafted moiety is by covalent bond grafted linear macromolecule, so as in metal organic framework
Substrate surface forms polymer brush.
In MOFs material provided by the present invention, the metal organic framework substrate generally include one or more metals from
Sub and one or more organic ligands can be the crystalline substance with periodic network structure formed by metal ion and organic ligand
Porous body material can usually be prepared by way of self assembly by metal ion and organic ligand, can more specifically be led to
It crosses including but not limited to the methods of solvent heat, hydrothermal synthesis method, microwave synthesis, synthesis in solid state to prepare, metal obtained
Organic backbone substrate particles usually have good dispersion degree, can be with for example, sample is by scanning electron microscope or transmission electron microscope observing
It was found that monodisperse is kept between particle and particle, without obvious adhesion.The size of the metal organic framework substrate particles is usual
In 10nm between several microns, for example, the partial size of metal organic framework substrate particles can for 10~1000nm, 50~
300nm, 10~20nm, 20~40nm, 40~60nm, 60~100nm, 100~200nm, 200~400nm, 400~600nm,
600~800nm, 800~1000nm, 1 μm~5 μm or 1 μm~10 μm, for the particle size model of organic backbone substrate particles
The particle for being often referred in statistical significance > 50% is enclosed (to characterize based on SEM or TEM) in this section.The metal organic framework
The duct of substrate can for 0.3nm~2nm, 0.3nm~0.4nm, 0.4nm~0.6nm, 0.6nm~0.8nm, 0.8nm~1nm,
1nm~1.2nm, 1.2nm~1.4nm, 1.4nm~1.6nm, 1.6nm~1.8nm, 1.8nm~2nm (are used based on gas absorption instrument
N2, Ar or CO2Characterization).
In MOFs material provided by the present invention, the organic ligand in the metal organic framework substrate generally includes two
The above coordinating group (coordination site), the coordinating group are often referred to participate in the middle metal ion of metal organic framework substrate and have
The organo-functional group of coordination between machine ligand, for example, the coordinating group can be selected from including but not limited to carboxylic acid, five yuan of nitrogen
One of heterocycle or six-membered heterocycle etc. or a variety of combinations, the penta azacyclo can be selected from including but not limited to miaows
One of azoles, triazole, tetrazole etc. or a variety of combinations, the six-membered heterocycle can be selected from including but not limited to pyrroles
One of piperazine, pyrimidine, pyridine etc. or a variety of combinations.The organic ligand usually can also include grafted moiety (grafting position
Point), it can specifically include one or more grafted moieties, for example, the quantity of grafted moiety can be 1,2,3,4,5, it is described
Grafted moiety is often referred to the coordination between the metal ion being not involved in metal organic framework substrate and organic ligand and can be with
The organo-functional group that polymer brush is covalently attached, for example, the grafted moiety can be including but not limited to amino, hydroxyl, folded
One of nitrogen, halogen, carbonyl, sulfydryl or carboxyl etc. or a variety of combinations, the grafted moiety in metal organic framework substrate are logical
It often can be corresponding with the grafted moiety in organic ligand.In the embodiment of the invention, the organic ligand can be with
It is including but not limited to amino terephthalic acid (TPA), aminobphenyl dioctyl phthalate, amino terphenyl dicarboxylic acids, aminooimidazole, aminobenzene
And imidazoles, 3,5- diaminostilbene, 2,4- triazole, adenine, 3- amino -1,2,4- triazole, 5- aminotetrazole, 2- amino are equal
Benzenetricarboxylic acid, hydroxyterephthalic acid, 2- bromo terephthalic acid, nitrine phthalic acid, nitrine biphenyl dicarboxylic acid etc. are various to be applicable in
In one of organic ligand for preparing MOFs material or a variety of combinations.
In MOFs material provided by the present invention, the metal ion in the metal organic framework substrate can be transition gold
Belong to ion, the metal ion can also be the metal ion of each valence state corresponding to the metal.For example, the metal ion
Can be including but not limited to one of Zr, Al, Cr, Cu, Zn, Co, Ni, Ti, Fe, Mg, Hf etc. or a variety of combinations
The ion of each valence state.
In MOFs material provided by the present invention, the grafted moiety in metal organic framework substrate can usually match with organic
Grafted moiety in body is corresponding, the grafted moiety can be including but not limited to amino, hydroxyl, nitrine, halogen, carbonyl,
One of sulfydryl or carboxyl etc. or a variety of combinations.In the embodiment of the invention, the metal organic framework base
Material can be including but not limited to UiO-66-NH2It (include grafted moiety-NH2UiO-66 material, following material name ginseng
According to UiO-66-NH2)、UiO-67-NH2、UiO-68-NH2、NH2-MIL-53(Al、Fe、Cr)、NH2-MIL-101(Cr)、NH2-
MIL-101(Al)、NH2-MIL-101(Fe)、NH2-MIL-68(In)、NH2-MIL-88(Al)、NH2-MIL-125、ZIF-7-
NH2、ZIF-8-NH2、ZIF-9-NH2、ZIF-11-NH2、UMCM-1-NH2、MOF-46、BiO-MOF-1、BiO-MOF-11、BiO-
MOF-12、BiO-MOF-13、BiO-MOF-14、Zn2(Atz)2、DMOF-1-NH2、NH2-CuBTC、MAF-66、CPF-13、ZnF
(Am2TAZ)、CAU-1、IRMOF-3、ZIF-96、UiO-66-(OH)2、MOF-74、UiO-66-Br、UiO-66-N3、UMCM-1-
N3、UiO-67-N3、MIL-101-N3、IRMOF-16-N3Deng one of or a variety of combinations.
In MOFs material provided by the present invention, the linear polymeric usually can be corresponding with grafted moiety, linearly
Macromolecule usually may include the group for having reactivity with the grafted moiety in metal organic framework substrate, so as to logical
It crosses and chemically reacts linear polymeric with grafted moiety by being covalently keyed, the reaction, which can be, including but not limited to contracts
One of poly-, free radical polymerization, ring-opening polymerisation etc. or a variety of combinations, formation are modified with linear polymeric (material)
Metal organic framework substrate forms surface polymer brush.For example, relative to grafted moiety amino, linear polymeric usually can be with
Including but not limited to one of carboxylic acid, acid anhydrides, acyl halide group etc. or a variety of combinations；For another example relative to grafted moiety hydroxyl
Base, linear polymeric usually can include but is not limited to one of carboxylic acid, carboxylic acid halides, methoxy group etc. or a variety of combinations；Again
For example, linear polymeric usually can include but is not limited to end alkynyl radical etc. relative to grafted moiety azido group；For another example phase
For grafted moiety halogen, linear polymeric typically includes, but not limited to nucleophilic displacement of fluorine group etc., specifically can be including but not
It is limited to sulfydryl, hydroxyl, amino etc.；For another example relative to grafted moiety carbonyl, linear polymeric usually be can include but is not limited to
One of amino, alcoholic OH groups etc. or a variety of combinations；For another example linear polymeric is logical relative to grafted moiety sulfydryl
It often include alkene, halogen ion group etc.；Again for example relative to grafted moiety carboxyl, linear polymeric usually may include but unlimited
In one of amino, hydroxyl group etc. or a variety of combinations.Have included by linear polymeric as described above with grafted moiety
There is the group of reactivity usually can be at linear high molecular both ends, it can also be in side chain.For another example the linear polymeric
Can be including but not limited to polyimides (polyimides), polyamide (polyamides), polysulfones (polysulfone) with
And one of polyether sulfone (polyether sulfone) etc. or a variety of combinations.For another example the molecule of the linear polymeric
Usually >=500Da, >=600Da, >=800Da or >=1000Da is measured, mass spectrum hand usually can be used in the molecular weight of linear polymeric
Duan Jinhang characterization.For another example the degree of polymerization (number of repeat unit) of the linear polymeric quantity usually >=3, >=4, >=5, >=
>=8 or >=10 6,.For another example the molecular weight distributing index (PDI) of the linear polymeric usually > 1, >=2, >=3, >=4, >=
>=6, >=7, >=8, >=9 or >=10 5,.For another example the grafting density of the linear polymeric is usually in >=0.05/nm2、≥
0.08/nm2、≥0.1/nm2、≥0.2/nm2、≥0.3/nm2Or >=0.5/nm2。
In MOFs material provided by the present invention, the grafted moiety connects linear polymeric by covalent bond, so as to
To form linear polymeric material layer at least part of metal organic framework substrate surface, the linear polymeric material layer
Thickness can be 1nm~100nm, 1nm~5nm, 5nm~10nm, 10nm~20nm, 20nm~30nm, 30nm~40nm, 40nm
~60nm, 60nm~80nm or 80nm~100nm.
Second aspect of the present invention provides the preparation method of the MOFs material, comprising:
Obtain the metal organic framework substrate including grafted moiety；
By at least part of grafted moiety grafted linear macromolecule.
In the preparation method of MOFs material provided by the present invention, the high molecular method of grafted moiety grafted linear be can be
From MOF surface grafting (Grafting from).For example, the monomer of two or more polycondensations can directly be mixed with MOFs, pass through
It is covalently attached from the surface MOFs and grows polycondensation polymer brush, it is sub- that polycondensation macromolecule can be including but not limited to polyamide, polyamides
One of amine, polysulfones, polyether sulfone etc. or a variety of combinations.For another example free radical can be reacted on the amino on the surface MOFs
Cause group, and free radical polymerization macromolecule is grown by the site, it includes but is not limited to that 2- bromo is different that free radical, which causes group,
Butyryl bromide etc..Free radical polymerization reaction method includes but is not limited to atom transfer radical polymerization (ATRP), reversible addition fracture
One of chain tra nsfer (RAFT), nitroxide-mediated stable free-radical polymerization (NMP) etc. or a variety of combinations.The high polymer monomer packet of growth
Include but be not limited to one of phenylethylene, acrylic compounds, methacrylic etc. or multiple combinations.It is provided by the present invention
In the preparation method of MOFs material, the high molecular method of grafted moiety grafted linear is also possible to be grafted to the surface MOFs
(Grafting to).For example, linear polymeric can be reacted with the metal organic framework substrate for including grafted moiety.Example again
Such as, it is carried out under the conditions of reaction can be existing for the condensing agent, the condensing agent can be including but not limited to N, N'- dicyclohexyl
Carbodiimide (DCC), 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimine (EDC), tripyrrole alkane base phosphonium bromide hexafluoro phosphorus
One of hydrochlorate (PyBroP), hexafluorophosphoric acid benzotriazole -1- base-oxygroup tripyrrole alkyl phosphorus (PyBop) etc. are a variety of
Combination.For another example reaction carries out under the conditions of can be existing for the cyclization dehydrating agent, required dehydrating agent be can be including but not limited to
Trifluoromethanesulfonic acid, Loprazolam, p-methyl benzenesulfonic acid, ethane sulfonic acid, butane sulfonic acid, perfluorobutane, acetic anhydride, propionic andydride or
One of butyric anhydride etc. or multiple combinations.For another example reaction can carry out under alkaline condition, it can be by including but unlimited
Alkaline condition is provided in organic base, inorganic base etc., more specifically can be including but not limited to triethylamine, tripropyl amine (TPA), tri-n-butylamine, two
It is ring ethyl dimethylamine, 2,6- lutidines, 3,5- lutidines, picoline, 4-dimethylaminopyridine, diethylamine, anhydrous
One of potassium carbonate, Carbon Dioxide caesium etc. or a variety of combinations.For another example reaction can under conditions of gas shield into
Row, can be by including but is not limited to one of nitrogen, inert gas etc. or a variety of offer gas shield conditions.For another example
Reaction can carry out in the presence of a solvent, and the solvent is usually the good solvent of reaction raw materials, may include but unlimited
In dimethylformamide (DMF), dimethyl acetamide (DMAc), dimethyl sulfoxide (DMSO), diethyl acetamide (DEF), N-
One of methyl pyrrolidone (NMP), N- ethyl pyrrolidone (NEP) etc. or a variety of combinations.
Third aspect present invention provides the MOFs material in the purposes of Selective Separation field of material preparation, the selection
Property separation material can be including but not limited to selective absorption film etc., more specifically can be including but not limited to mixed-matrix
Film, fluid (for example, gas and/or liquid) seperation film etc..
Fourth aspect present invention provides a kind of mixed substrate membrane containing nano-grade molecular sieve, including MOFs material provided by first aspect present invention,
It further include matrix macromolecule.The MOFs material is usually uniformly distributed in matrix macromolecule, to form mixed substrate membrane containing nano-grade molecular sieve.Ability
Field technique personnel can select the MOFs material and matrix high score of suitable species and ratio according to the mixed substrate membrane containing nano-grade molecular sieve of required preparation
Son, for example, MOFs material and the high molecular weight ratio of matrix can be 1:99~2:1,1:99~1:90,1:90~1:80,1:
80~1:70,1:70~1:60,1:60~1:50,1:50~1:40,1:40~1:30,1:30~1:20,1:20~1:10,1:
10~1:5,1:5~1:3,1:3~1:2,1:2~1:1.5,1:1.5~1:1,1:1~1.5:1 or 1.5:1~2:1, then example
Such as, selected matrix macromolecule is usually corresponding with MOFs material, so as to so that MOFs material can be with Stable distritation in base
To form stable mixed substrate membrane containing nano-grade molecular sieve in matter macromolecule.
Fifth aspect present invention provides the preparation method of the mixed substrate membrane containing nano-grade molecular sieve, comprising:
The MOFs material and matrix macromolecule are mixed, mixed substrate membrane containing nano-grade molecular sieve is formed.It is formed by mixed substrate membrane containing nano-grade molecular sieve, institute
Stating MOFs material usually can be used as filler.
In the preparation method of mixed substrate membrane containing nano-grade molecular sieve provided by the present invention, mixing is formed by MOFs material and matrix macromolecule
The method of matrix membrane should be known to those skilled in the art.For example, MOFs material and matrix are high molecular mixed
Conjunction can carry out in the presence of a solvent, and the solvent usually can be fully dispersed by MOFs material and matrix macromolecule.
For another example after removing solvent, mixed substrate membrane containing nano-grade molecular sieve can be formed by the methods of blade coating, spin coating, spraying.
The present invention provides a kind of MOFs material, the high molecular MOF conduct containing surface modification prepared by the MOFs material
The mechanical stretching performance of the mixed substrate membrane containing nano-grade molecular sieve of filler has than the simple MOF of identical load amount as the mixed substrate membrane containing nano-grade molecular sieve of filler larger
Promotion, under the premise of identical MOF load capacity, contain grafting MOF film to comparison contain unmodified MOF film, anti-plasticizing
Performance boost is obvious, and the film containing grafting MOF contains the film of unmodified MOF to comparison, the selectivity of gas is promoted bright
It is aobvious.
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
It should be clear that in the following example not specifically dated process equipment or device be all made of conventional equipment in the art or
Device.
In addition, it should also be understood that, one or more method and step mentioned in the present invention does not repel before and after the combination step
It can also be inserted into other methods step there may also be other methods step or between these explicitly mentioned steps, unless separately
It is described；It should also be understood that the combination connection relationship between one or more equipment/device mentioned in the present invention is not repelled
The two equipment/devices specifically mentioned before and after the unit equipment/device there may also be other equipment/device or at these it
Between can also be inserted into other equipment/device, unless otherwise indicated.Moreover, unless otherwise indicated, the number of various method steps is only
Identify the convenient tool of various method steps, rather than for the arrangement order of limitation various method steps or limits the enforceable model of the present invention
It encloses, relativeness is altered or modified, and without material changes in technical content, when being also considered as, the present invention is enforceable
Scope.
Embodiment 1
The preparation of MOFs particle:
Metal salt solution and ligand solution are dissolved in DMF solution, obtain monodispersed MOFs by heating synthesis.
Metal salt is 13 parts of (parts by weight, similarly hereinafter) zirconium chlorides, and ligand selects 10 parts of 2- amino terephthalic acid (TPA)s, solvent DMF
It is 3032 parts, heating temperature is 120 DEG C, and the reaction time is 20 hours, obtains UiO-66-NH2Nano particle.
MOFs particle surface is connected to covalent connection linear polymeric, the preparation method is as follows:
Take above-mentioned 2 prepared part UiO-66-NH2Nano particle is distributed in 17 parts of DMF, adds 3 part 2,4,6-
Trimethyl -1,3- phenylenediamine (DAM), is completely dissolved with magnetic stirrer to DAM, and mixing speed is 800 revs/min,
3 part 4 is added under nitrogen protection, 4 '-biphenyl ether dianhydrides (ODPA) then add 17 parts of DMF, react under conditions of nitrogen protection
24 hours.After 24 hours, 1 part of triethylamine, 4 parts of acetic anhydrides are successively added, it is anti-to react completion cyclization in 1 hour by 10 parts of DMF
It answers.After reaction terminates, 11000 revs/min of reaction solution high speed centrifugation are centrifuged 10 minutes, sediment is surface grafting height
The UiO-66-NH of molecule2.There is high molecular UiO-66-NH as shown in Figure 1 for surface grafting2Transmission electron microscope picture, face on picture
The deeper part of color is MOF, and the shallower part of edge color is macromolecule layer.Distinct contrast Discrepancy Description, the method can be with
Successfully polymer brush is modified to the surface MOF, in Fig. 1, can be clearly seen that again the surface of MOF has one layer 5~10 to receive
The thick macromolecule of rice, MOF granular size is 150 rans.
The preparation of mixed substrate membrane containing nano-grade molecular sieve:
Polymer matrix be selected as with the consistent polyimides of the polymer brush of surface modification, solvent selection is dichloromethane
The mixed weight ratio of alkane, filler and polymer matrix is 1.0:19.0,1.0:10.1,1.0:4.9,1.0:2.7, corresponding to fill out
It is 5%, 9%, 17%, 27% that material, which accounts for the weight percent of mixed substrate membrane containing nano-grade molecular sieve,.Film-forming method selects the glass cylinder in diameter 5cm
Slowly volatilization forms a film in container.
Embodiment 2
Scheme 1:
Polyimides is made into the dichloromethane solution of 3wt%.The Polymer Solution prepared is taken to be added in glass container,
It is covered with aluminium-foil paper, so that solution is slowly volatilized under room temperature.After solvent volatilizees completely, film is placed in a vacuum drying oven 100
DEG C vacuum drying.
Scheme 2:
Take 5 parts of high molecular UiO-66-NH of surface grafting2(preparation of embodiment 1), 95 parts of polyimides macromolecules, 950 parts
Methylene chloride, it is uniform with ultrasonic mixing, the mixed solution prepared is added in glass container, is covered with aluminium-foil paper, under room temperature
Solution is set slowly to volatilize.After solvent volatilizees completely, film is placed into 100 DEG C of vacuum drying in a vacuum drying oven.
Scheme 3:
Take 9 parts of high molecular UiO-66-NH of surface grafting2(preparation of embodiment 1), 91 parts of polyimides macromolecules, 910 parts
Methylene chloride, it is uniform with ultrasonic mixing, the mixed solution prepared is added in glass container, is covered with aluminium-foil paper, under room temperature
Solution is set slowly to volatilize.After solvent volatilizees completely, film is placed into 100 DEG C of vacuum drying in a vacuum drying oven.
Scheme 4:
Take 17 parts of high molecular UiO-66-NH of surface grafting2(preparation of embodiment 1), 83 parts of polyimides macromolecules, 830
Part methylene chloride, it is uniform with ultrasonic mixing, the mixed solution prepared is added in glass container, is covered with aluminium-foil paper, room temperature
Under so that solution is slowly volatilized.After solvent volatilizees completely, film is placed into 100 DEG C of vacuum drying in a vacuum drying oven.
Scheme 5:
Take 27 parts of high molecular UiO-66-NH of surface grafting2(preparation of embodiment 1), 73 parts of polyimides macromolecules, 730
Part methylene chloride, it is uniform with ultrasonic mixing, the mixed solution prepared is added in glass container, is covered with aluminium-foil paper, room temperature
Under so that solution is slowly volatilized.After solvent volatilizees completely, film is placed into 100 DEG C of vacuum drying in a vacuum drying oven.
Scheme 6:
Take 5 parts of UiO-66-NH2(preparation of embodiment 1), 95 parts of polyimides macromolecules, 950 parts of methylene chloride, with ultrasound
It is uniformly mixed, the mixed solution prepared is added in glass container, is covered with aluminium-foil paper, so that solution is slowly volatilized under room temperature.
After solvent volatilizees completely, film is placed into 100 DEG C of vacuum drying in a vacuum drying oven.
Scheme 7:
Take 9 parts of UiO-66-NH2(preparation of embodiment 1), 91 parts of polyimides macromolecules, 910 parts of methylene chloride, with ultrasound
It is uniformly mixed, the mixed solution prepared is added in glass container, is covered with aluminium-foil paper, so that solution is slowly volatilized under room temperature.
After solvent volatilizees completely, film is placed into 100 DEG C of vacuum drying in a vacuum drying oven.
Scheme 8:
Take 9 parts of UiO-66-NH2(preparation of embodiment 1), 83 parts of polyimides macromolecules, 830 parts of methylene chloride, with ultrasound
It is uniformly mixed, the mixed solution prepared is added in glass container, is covered with aluminium-foil paper, so that solution is slowly volatilized under room temperature.
After solvent volatilizees completely, film is placed into 100 DEG C of vacuum drying in a vacuum drying oven.
Scheme 9:
Take 9 parts of UiO-66-NH2(preparation of embodiment 1), 27 parts of polyimides macromolecules, 730 parts of methylene chloride, with ultrasound
It is uniformly mixed, the mixed solution prepared is added in glass container, is covered with aluminium-foil paper, so that solution is slowly volatilized under room temperature.
After solvent volatilizees completely, film is placed into 100 DEG C of vacuum drying in a vacuum drying oven.
By carrying out extension test to scheme 1,2,6.The instrument that extension test uses is the survey of Instron5620 general-purpose mechanics
Instrument is measured, rate of extension is 2 mm/mins, and sample film thickness is 30 microns, and sample need to be cut to dumbbell shape, with
Product need to be tested at least 3 times (detailed test method: Chemistry of Materials, 2018,30 (5): 1484-1495.).Such as
Shown in Fig. 2, arrow pointed location is breaking point in figure, and corresponding abscissa is the maximum strain value that film can be born.Scheme 1 is
Pure macromolecule membrane sample, the strain value of breaking point are 70%；Scheme 2 is that the surface modification containing 5wt% has polymer brush
MOF mixed-matrix membrane sample, the strain value of breaking point are 67%；Scheme 6 is the mixed-matrix of the unmodified MOF containing 5wt%
Film, the strain value of breaking point are 15%.It can be found that although the load capacity of MOFs is all 5%, stretching of the scheme 2 in breaking point
Strain is 67%, this numerical value is closer to scheme 1, and the elongation strain of scheme 6 is 15%, is promoted to 447%.Compare this
Three samples, it can be found that surface modification has the mechanical ductility of film of the MOF of polymer brush as filler to compare identical load
The simple MOF of amount has biggish promotion as the mixed substrate membrane containing nano-grade molecular sieve of filler, illustrates the MOF mixed substrate membrane containing nano-grade molecular sieve comparison containing grafting not
The mixed substrate membrane containing nano-grade molecular sieve of the MOF of grafting, mechanical stretching performance have the improvement of highly significant.
By carrying out transformation carbon dioxide permeability test (detailed test method reference: Nature to scheme 1,5,9
materials,2016,15(8):845.).As shown in figure 3, the point that arrow indicates in figure is the point that film starts plasticizing, correspond to
Abscissa be plasticizing pressure.Scheme 1 is pure macromolecule membrane sample, and plasticizing pressure is 9bar；Scheme 5 is table containing 27wt%
Face has been grafted the mixed-matrix membrane sample of polymer brush, and plasticizing pressure is 17bar；Scheme 9 is the MOF unmodified containing 27wt%
Mixed-matrix membrane sample, plasticizing pressure is 11bar.It can be found that although the load capacity of MOFs is all 27%, the two of scheme 5
The plasticizing pressure of carbonoxide is 17 atmospheric pressure, and the plasticizing pressure of scheme 9 is 11 atmospheric pressure, and the plasticizing pressure of scheme 1 is 9
A atmospheric pressure, the promotion explanation of significant plasticizing pressure, be grafted on the surface MOF macromolecular chain can effective reinforcement filler with
The active force of polymer matrix, to effectively promote anti-plasticizing capacity.
By scheme 1-9, to separating property (CO2/N2) (test method is with reference to same with permeance property progress comprehensive assessment
On), 35 DEG C, pure gas is tested under the conditions of 3.1bar, the pass between carbon dioxide permeability, with carbon dioxide/nitrogen selective
System's figure is as shown in Figure 4.Scheme 2-5 hybrid films contain 5,9,17, the 27wt% MOFs for being grafted polymer brush respectively, correspond to
Carbon dioxide/nitrogen selective be 20,22,24,27 respectively；Scheme 6-9 hybrid films contain 5,9,17,27wt% not respectively
The MOFs of modification, corresponding carbon dioxide/nitrogen selective is 15,12,11,9 respectively.It can be clearly seen that from Fig. 4:
1) it increases and has been grafted high molecular sample load capacity, selectivity and permeance property can be made while rising, and for containing
Although the film of unmodified MOF, permeability increase, but the purer polymeric membrane decline of selectivity.2) for identical MOF load capacity
Sample (scheme 2 and scheme 6, scheme 3 and scheme 7, scheme 4 and scheme 8, scheme 5 and scheme 9), the MOF's containing grafting polymer
Mixed substrate membrane containing nano-grade molecular sieve shows better gas-selectively.
By scheme 1-4,6-8, to separating property (CO2/CH4) (test method is same with permeance property progress comprehensive assessment
On), 35 DEG C, pure gas is tested under the conditions of 3.1bar, carbon dioxide permeability, with the relational graph between carbon dioxide/methane type
As shown in Figure 5.Scheme 2-4 hybrid films contain 5,9, the 17wt% MOFs for being grafted polymer brush, corresponding titanium dioxide respectively
Carbon/methane selectively is 37,43,51 respectively；Scheme 6-8 hybrid films contain 5,9,17wt% unmodified MOFs respectively, right
Carbon dioxide/the methane selectively answered is 26,23,24 respectively.It can be clearly seen that from figure: 1) increasing and be grafted high score
The sample load capacity of son, can make selectivity and permeance property while rise, and the film for containing unmodified MOF, infiltration
Property although increase, but selectivity purer polymeric membrane decline.2) for the point of identical MOF load capacity (scheme 2 and scheme 6,
Scheme 3 and scheme 7, scheme 4 and scheme 8), the mixed substrate membrane containing nano-grade molecular sieve of the MOF containing grafting polymer shows better choice, sufficiently
Illustrate it is such by can effectively promote the interface compatibility of mixed substrate membrane containing nano-grade molecular sieve in the high molecular strategy of MOF surface grafting,
To effectively improve gas separating property.
In conclusion the present invention effectively overcomes various shortcoming in the prior art and has high industrial utilization value.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (10)
1. a kind of MOFs material, including metal organic framework substrate, the metal organic framework substrate includes grafted moiety, described
Grafted moiety passes through covalent bond grafted linear macromolecule.
2. MOFs material as described in claim 1, which is characterized in that the partial size of the metal organic framework substrate particles is
10nm~10 μm.
3. MOFs material as described in claim 1, which is characterized in that the organic ligand packet in the metal organic framework substrate
More than two coordinating groups are included, the coordinating group is selected from one of carboxylic acid, penta azacyclo or six-membered heterocycle or a variety of
Combination；
And/or the organic ligand in the metal organic framework substrate includes grafted moiety, the grafted moiety be selected from amino,
One of hydroxyl, nitrine, halogen, carbonyl, sulfydryl or carboxyl or a variety of combinations；
And/or the organic ligand in the metal organic framework substrate is selected from amino terephthalic acid (TPA), 5- amino isophthalic diformazan
Acid, aminobphenyl dioctyl phthalate, amino terphenyl dicarboxylic acids, aminooimidazole, aminobenzimidazole, 3,5- diaminostilbene, 2,4- tri-
Nitrogen azoles, adenine, 3- amino -1,2,4- triazole, 5- aminotetrazole, 2- amino trimesic acid, hydroxyterephthalic acid, 2-
Bromo terephthalic acid, bromomethylbiphenyl dioctyl phthalate, nitrine phthalic acid, azido-methyl biphenyl dicarboxylic acid, nitrine biphenyl dicarboxylic acid
One of or a variety of combinations；
And/or the metal ion in the metal organic framework substrate be selected from Zr, Al, Cr, Cu, Zn, Co, Ni, Ti, Fe, Mg,
The ion of one of Hf or a variety of combinations in each valence state；
And/or the grafted moiety in the metal organic framework substrate be selected from amino, hydroxyl, nitrine, halogen, carbonyl, sulfydryl or
One of carboxyl or a variety of combinations；
And/or the duct of the metal organic framework substrate is 0.3nm~2nm.
4. MOFs material as described in claim 1, which is characterized in that the metal organic framework substrate is selected from UiO-66-NH2、
UiO-67-NH2、UiO-68-NH2、NH2-MIL-53(Al、Fe、Cr)、NH2-MIL-101(Cr)、NH2-MIL-101(Al)、NH2-
MIL-101(Fe)、NH2-MIL-68(In)、NH2-MIL-88(Al)、NH2-MIL-125、ZIF-7-NH2、ZIF-8-NH2、ZIF-
9-NH2、ZIF-11-NH2、UMCM-1-NH2、MOF-46、BiO-MOF-1、BiO-MOF-11、BiO-MOF-12、BiO-MOF-13、
BiO-MOF-14、Zn2(Atz)2、DMOF-1-NH2、NH2-CuBTC、MAF-66、CPF-13、ZnF(Am2TAZ)、CAU-1、
IRMOF-3、ZIF-96、UiO-66-(OH)2、MOF-74、UiO-66-Br、UiO-66-N3、UMCM-1-N3、UiO-67-N3、
MIL-101-N3、IRMOF-16-N3One of or a variety of combinations.
5. MOFs material as described in claim 1, which is characterized in that the linear polymeric and grafted moiety by polycondensation,
Free radical polymerization, ring-opening polymerisation connection.
6. MOFs material as described in claim 1, which is characterized in that the linear polymeric be selected from polyimides, polyamide,
One of polysulfones, polyether sulfone or a variety of combinations；
And/or molecular weight >=500Da of the linear polymeric.
7. MOFs material as described in claim 1, which is characterized in that metal organic framework substrate surface is modified with macromolecule
Brush.
8. the preparation method of the MOFs material as described in claim 1~7 any claim, comprising:
Obtain the metal organic framework substrate including grafted moiety；
By at least part of grafted moiety grafted linear macromolecule.
9. MOFs material as described in claim 1~7 any claim is in the purposes of Selective Separation field of material preparation.
10. a kind of mixed substrate membrane containing nano-grade molecular sieve, including the MOFs material as described in claim 1~7 any claim.
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