CN116622074A - Modified MOFs and preparation method and application thereof - Google Patents
Modified MOFs and preparation method and application thereof Download PDFInfo
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- CN116622074A CN116622074A CN202310912900.2A CN202310912900A CN116622074A CN 116622074 A CN116622074 A CN 116622074A CN 202310912900 A CN202310912900 A CN 202310912900A CN 116622074 A CN116622074 A CN 116622074A
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- grafting reaction
- aqueous polyurethane
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000004814 polyurethane Substances 0.000 claims abstract description 40
- 229920002635 polyurethane Polymers 0.000 claims abstract description 40
- 238000001179 sorption measurement Methods 0.000 claims abstract description 18
- 125000003277 amino group Chemical group 0.000 claims abstract description 16
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 65
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- 239000004970 Chain extender Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- 239000000839 emulsion Substances 0.000 abstract description 10
- 125000005442 diisocyanate group Chemical group 0.000 description 18
- 238000001035 drying Methods 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 239000004721 Polyphenylene oxide Substances 0.000 description 9
- 229920000570 polyether Polymers 0.000 description 9
- 229920005862 polyol Polymers 0.000 description 9
- 150000003077 polyols Chemical class 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 150000001412 amines Chemical group 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 3
- KCWDJXPPZHMEIK-UHFFFAOYSA-N isocyanic acid;toluene Chemical class N=C=O.N=C=O.CC1=CC=CC=C1 KCWDJXPPZHMEIK-UHFFFAOYSA-N 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- CFQLQLSIZOWFNV-UHFFFAOYSA-M sodium;2-[bis(2-hydroxyethyl)amino]ethanesulfonate Chemical compound [Na+].OCCN(CCO)CCS([O-])(=O)=O CFQLQLSIZOWFNV-UHFFFAOYSA-M 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000009194 climbing Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 125000003916 ethylene diamine group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- UZMKOEWHQQPOBJ-UHFFFAOYSA-M sodium;2,3-dihydroxypropane-1-sulfonate Chemical compound [Na+].OCC(O)CS([O-])(=O)=O UZMKOEWHQQPOBJ-UHFFFAOYSA-M 0.000 description 2
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 206010024769 Local reaction Diseases 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
- B01D2253/204—Metal organic frameworks (MOF's)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
Abstract
The invention belongs to the technical field of MOFs materials, and particularly relates to a modified MOFs and a preparation method and application thereof. The invention provides a modified MOFs, which comprises MOFs and waterborne polyurethane grafted with the MOFs through an amide bond; the MOFs are MOFs containing amino groups. According to the invention, MOFs and aqueous polyurethane are grafted to enable the modified MOFs to be in emulsion form and easy to form a film, so that the modified MOFs can be applied to the catalysis field or the adsorption field in a film form, the MOFs can be ensured to fully exert the performance, and the application range of the MOFs is expanded.
Description
Technical Field
The invention belongs to the technical field of MOFs materials, and particularly relates to a modified MOFs and a preparation method and application thereof.
Background
The metal organic framework material (Metal Organic Frameworks, MOFs) is a crystalline porous framework material formed by metal ions or metal clusters and organic ligands through coordination bonds. MOFs have a designable structure, an adjustable aperture and a highly modified functional group, are unique inorganic-organic hybrid porous materials, and have wide application prospects in the fields of catalysis, sensing, adsorption and the like.
However, MOFs are generally in powder form, are easy to agglomerate when applied to the field of catalysis or adsorption, cannot fully exert functions, and limit application range.
Disclosure of Invention
In view of the above, the invention provides a modified MOFs, a preparation method and application thereof, and the modified MOFs provided by the invention are emulsion-shaped and easy to form a film, and overcome the defect of easy agglomeration when being applied to the field of catalysis or adsorption, and expand the application range of the modified MOFs.
In order to solve the technical problems, the invention provides a modified MOFs, which comprises MOFs and waterborne polyurethane grafted with the MOFs through an amide bond; the MOFs are MOFs containing amino groups.
Preferably, the mass percentage of isocyanate groups in the aqueous polyurethane is 14-22%;
the molar ratio of the waterborne polyurethane to the MOFs is 22-28:1.
Preferably, the modified MOFs further comprise hydrophilic groups grafted with the aqueous polyurethane.
Preferably, the hydrophilic group includes a sulfonic acid group or a carboxyl group.
The invention also provides a preparation method of the modified MOFs, which comprises the following steps:
and mixing the aqueous polyurethane and MOFs containing amino groups to perform a first grafting reaction to obtain the modified MOFs.
Preferably, the amino group-containing MOFs include UiO-66-NH 2 。
Preferably, the temperature of the first grafting reaction is 60-70 ℃, and the time of the first grafting reaction is 0.8-1.2 h.
Preferably, the first grafting reaction is preceded by: the MOFs containing amino groups were dispersed in acetone to obtain an acetone dispersion of MOFs.
Preferably, the first grafting reaction is preceded by: and mixing the aqueous polyurethane with a hydrophilic chain extender, and performing a second grafting reaction to obtain the aqueous polyurethane grafted with hydrophilic groups.
The invention also provides application of the modified MOFs in the field of catalysis or adsorption, wherein the modified MOFs are prepared by the technical scheme or the preparation method.
The invention provides a modified MOFs, which comprises MOFs and waterborne polyurethane grafted with the MOFs through an amide bond; the MOFs are MOFs containing amino groups. According to the invention, MOFs and aqueous polyurethane are grafted to enable the modified MOFs to be in emulsion form and easy to form a film, so that the modified MOFs can be applied to the catalysis field or the adsorption field in a film form, the MOFs can be ensured to fully exert the performance, and the application range of the MOFs is expanded.
Detailed Description
The invention provides a modified MOFs, which comprises MOFs and waterborne polyurethane grafted with the MOFs through an amide bond; the MOFs are MOFs containing amino groups. In the present invention, the amino group-containing MOFs preferably include UiO-66-NH 2 . In the invention, the mass percentage of isocyanate groups in the aqueous polyurethane is preferably 14-22%, more preferably 15-20%. In the invention, the molar ratio of the aqueous polyurethane to the MOFs is preferably 22-28:1, more preferably 23-25:1.
In the present invention, the modified MOFs preferably further include hydrophilic groups grafted to the aqueous polyurethane; the hydrophilic group preferably includes a sulfonic acid group or a carboxyl group, more preferably a sulfonic acid group. According to the invention, hydrophilic groups are introduced into the modified MOFs to enhance the intramolecular library force (intermolecular acting force) and hydrogen bonding action of the modified MOFs, so that the microphase separation degree between the soft segment and the hard segment is improved, and the crystallinity, the crystallization speed and the initial adhesion strength of the modified MOFs are further improved.
The invention also provides a preparation method of the modified MOFs, which comprises the following steps:
and mixing the aqueous polyurethane and MOFs containing amino groups to perform a first grafting reaction to obtain the modified MOFs.
In the present invention, the amino group-containing MOFs preferably include UiO-66-NH 2 . In the present invention, the UiO-66-NH 2 The preparation method of (2) preferably comprises the following steps:
dissolving a zirconium source and 2-amino terephthalic acid in an organic solvent, and carrying out hydrothermal reaction to obtain the UiO-66-NH 2 。
In the present invention, the zirconium source is preferably zirconium chloride; the organic solvent is preferably N, N-dimethylformamide. In the invention, the mass ratio of the zirconium source to the 2-amino terephthalic acid is preferably 350-400:296, more preferably 381.5:296. In the invention, the mass ratio of the zirconium source to the organic solvent is preferably 350-400 mg:189mL, more preferably 381.5mg:189mL.
The invention has no special requirement on the dissolution, so long as the dissolution is complete.
In the invention, the temperature of the hydrothermal reaction is preferably 110-130 ℃, more preferably 115-120 ℃; the time of the hydrothermal reaction is preferably 22-26 hours, more preferably 23-24 hours.
In the present invention, the hydrothermal reaction preferably further comprises:
filtering the hydrothermal reaction system to obtain a solid;
washing and drying the solid in sequence to obtain the UiO-66-NH 2 。
The invention has no special requirement on the filtration, and can be realized by adopting a conventional mode in the field.
In the present invention, the washing solvent is preferably chloroform; the number of times of washing is preferably 3.
In the present invention, the drying is preferably vacuum drying, and the temperature of the vacuum drying is preferably 55 to 65 ℃, more preferably 60 ℃. The time of the vacuum drying is not particularly limited as long as the moisture on the solid surface can be removed.
In the present invention, the preparation method of the aqueous polyurethane preferably comprises the steps of:
and mixing polyether polyol, diisocyanate and an organic metal catalyst for polymerization reaction to obtain the aqueous polyurethane.
According to the invention, the polyether polyol is preferably dried before mixing, wherein the drying is preferably vacuum drying, and the temperature of the vacuum drying is preferably 100-110 ℃, more preferably 105-108 ℃; the time of vacuum drying is preferably 1 to 1.5 hours, more preferably 1.2 to 1.4 hours.
In the present invention, the polyether polyol is preferably one or a mixture of several of polyethylene glycol, polypropylene glycol and polytetrahydrofuran glycol, more preferably polyethylene glycol or polypropylene glycol. In the present invention, the polyether polyol preferably has a number average molecular weight of 900 to 1100, more preferably 1000. In the present invention, the diisocyanate is preferably one or a mixture of several of isophorone diisocyanate, hydrogenated phenyl methane diisocyanate, hexamethylene diisocyanate and 1, 5-pentanediisocyanate, more preferably isophorone diisocyanate or hydrogenated phenyl methane diisocyanate. In the present invention, the organometallic catalyst is preferably one or a mixture of several of an organic silver catalyst, an organic bismuth catalyst and an organic zinc catalyst, more preferably an organic silver catalyst.
In the invention, the mass ratio of the polyether polyol to the diisocyanate is preferably 14-18:7-11, more preferably 15-17:8-10. In the invention, the mass ratio of the polyether polyol to the organometallic catalyst is preferably 14-18:0.01-0.03, more preferably 15-17:0.015-0.02.
The polyether polyol is preferably dried prior to mixing; the drying is preferably vacuum drying; the temperature of the vacuum drying is preferably 100-110 ℃, more preferably 105-108 ℃; the time of vacuum drying is preferably 1 to 2 hours, more preferably 1.3 to 1.5 hours. The invention has no special requirement on the mixing, so long as the mixing can be uniform. In the invention, the organometallic catalyst is preferably added when the polymerization reaction is carried out for 2-2.5 hours.
In the invention, the temperature of the polymerization reaction is preferably 80-90 ℃, more preferably 85-88 ℃; the polymerization reaction time is preferably 2 to 3.5 hours, more preferably 2.5 to 3 hours. The invention preferably judges the polymerization end point according to the reaction degree of the diisocyanate in the system, and preferably detects the residual amount of the diisocyanate in the system by using a di-n-butylamine method, and terminates the polymerization when the reaction degree of the diisocyanate in the reaction system reaches 65-70%.
In the present invention, the polymerization reaction is preferably carried out under a protective atmosphere, which is preferably nitrogen or argon, more preferably nitrogen. In the invention, the polymerization reaction is preferably accompanied by stirring. The invention has no special requirement on the stirring rotation speed.
In the present invention, when the modified MOFs have hydrophilic groups grafted thereto, the first grafting reaction preferably further includes, before: and mixing the aqueous polyurethane with a hydrophilic chain extender, and performing a second grafting reaction to obtain the aqueous polyurethane grafted with hydrophilic groups. In the present invention, the hydrophilic chain extender is preferably a sulfonate chain extender or a carboxylate chain extender, more preferably a sulfonate chain extender. In the present invention, the sulfonate chain extender is preferably one or a mixture of several of sodium 2- [ (2-aminoethyl) amino ] ethanesulfonate, sodium N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonate and sodium 1, 2-dihydroxy-3-propanesulfonate, more preferably sodium N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonate or sodium 1, 2-dihydroxy-3-propanesulfonate. In the invention, the mass ratio of the polyether polyol to the hydrophilic chain extender is preferably 14-18:10-15, more preferably 15-18:13.
The invention has no special requirement on the mixing, so long as the mixing can be uniform. In the invention, the temperature of the second grafting reaction is preferably 60-70 ℃, more preferably 63-68 ℃; the time of the second grafting reaction is preferably 1.5 to 3.5 hours, more preferably 2 to 3 hours. The end point of the second grafting reaction is preferably judged according to the reaction degree of the diisocyanate in the system, and the second grafting reaction is terminated when the reaction degree of the diisocyanate in the system is 75-80%.
In the present invention, acetone is preferably added to the reaction system when the viscosity of the reaction system increases (a pole climbing phenomenon occurs) during the second grafting reaction. The amount of acetone added in the invention is not particularly limited as long as the phenomenon of climbing the rod of the reaction system is avoided.
In the present invention, it is preferable to disperse MOFs containing amino groups in acetone before the first grafting reaction to obtain an acetone dispersion of MOFs. In the present invention, the dispersion is preferably performed under ultrasonic conditions; the power of the ultrasonic wave is preferably 2000-4000W, more preferably 3000-3500W; the time of the ultrasonic treatment is preferably 55-65 min, more preferably 60-62 min. According to the invention, MOFs are dispersed in acetone and then mixed with the aqueous polyurethane, so that the phenomena of local reaction and flocculation in the first grafting reaction process can be avoided.
The invention has no special requirement on the mixing of the aqueous polyurethane and the MOFs containing amino, and the aqueous polyurethane and the MOFs containing amino can be uniformly mixed. In the invention, the temperature of the first grafting reaction is preferably 60-70 ℃, more preferably 63-68 ℃; the time of the first grafting reaction is preferably 0.8 to 1.2 hours, more preferably 1 hour. The end point of the first grafting reaction is preferably judged by detecting the reaction degree of the diisocyanate in the reaction system, and the first grafting reaction is terminated when the reaction degree of the diisocyanate in the reaction system is 85-90%.
In the present invention, uiO-66-NH 2 For the MOFs containing amino groups, the equation of the first grafting reaction is shown in formula 1:
formula 1.
In the present invention, the first grafting reaction preferably further comprises: mixing the first grafting reaction system with water for emulsification, and then mixing the first grafting reaction system with an aqueous solution of an amine chain extender to obtain the modified MOFs. In the present invention, the water is preferably deionized water. In the invention, the volume ratio of the first grafting reaction system to water is preferably 1-2:1, more preferably 1.5-1.8:1. In the invention, the mixing of the first grafting reaction system and water is preferably performed under stirring, and the stirring speed is preferably 1400-160 r/min, more preferably 1500r/min. In the invention, the rotation speed of the emulsification is preferably 900-1100 r/min, more preferably 1000r/min; the time for emulsification is preferably 0.8 to 1.2 hours, more preferably 1 hour.
In the present invention, the amine chain extender is preferably one or a mixture of several of ethylenediamine, hydroxyethyl ethylenediamine and isophorone diamine, more preferably ethylenediamine or hydroxyethyl ethylenediamine. In the invention, the mass ratio of the polyether polyol to the amine chain extender is preferably 14-18:0.1-0.3, more preferably 15-18:0.1-0.2. In the present invention, the mass concentration of the aqueous solution of the amine chain extender is preferably 25 to 35%, more preferably 30%. The polyurethane chain extender can increase the hard segment content of polyurethane molecules, increase the strength (modulus), and improve the performances of heat resistance (thermal strength), medium resistance and the like under the action of the amine chain extender. In the present invention, the amine-based chain extender preferably has a functionality of 2, and is used for chain extension of oligomers, allowing molecular chain growth to form linear macromolecules.
In the invention, the mixing of the emulsified aqueous solution and the aqueous solution of the amine chain extender is preferably carried out under the condition of stirring, and the rotating speed of stirring is preferably 600-800 r/min, more preferably 650-700 r/min; the stirring time is preferably 0.4 to 0.6 hours, more preferably 0.5 hours.
The modified MOFs provided by the invention are in an emulsion state and are easy to form a film. The mode of film formation using the modified MOFs preferably includes cast film formation. In the present invention, the casting film is preferably performed on a polytetrafluoroethylene plate. After the film formation, the obtained film is preferably dried. In the present invention, the drying preferably includes sequentially performing room temperature airing and drying; the drying time at room temperature is preferably 20-35 ℃, more preferably 25-30 ℃. In the present invention, the drying preferably includes sequentially performing low-temperature drying and high-temperature drying; the temperature of the low-temperature drying is preferably 45-55 ℃, more preferably 50 ℃; the low-temperature drying time is preferably 4.5-5.5 hours, more preferably 5 hours; the temperature of the high-temperature drying is preferably 75-85 ℃, more preferably 80 ℃; the high-temperature drying time is preferably 7.5-8.5 h, more preferably 8h.
In the present invention, the thickness of the film material obtained by film formation of the modified MOFs is preferably 0.1 to 0.14mm, more preferably 0.12mm.
The invention also provides application of the modified MOFs in the field of catalysis or adsorption, wherein the modified MOFs are prepared by the technical scheme or the preparation method. The modified MOFs is preferably applied to the field of catalysis or adsorption after being formed into the film, so that the aggregation of MOFs is avoided, and the catalysis or adsorption performance is improved.
The technical solutions provided by the present invention are described in detail below in conjunction with examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1: zrCl is added to 4 (381.5 mg) and 2-aminoterephthalic acid (296 mg) were dissolved in (ultrasonic treatment for 30 min) N, N-dimethylformamide (189 mL), to obtain a mixed solution; transferring the mixed solution into a 5000mL polytetrafluoroethylene-lined stainless steel reaction kettle, performing hydrothermal reaction at 120 ℃ for 24 hours, cooling to room temperature after the reaction is finished, filtering, washing the solid obtained by filtering with chloroform for 3 times, and vacuum drying at 60 ℃ to obtain UIO-66-NH 2 ；
10g of UiO-66-NH 2 Ultrasonic treatment in 100g acetone at 3000W for 60min to obtain UiO-66-NH 2 A dispersion;
15g of polypropylene glycol is dried for 1.5 hours at 110 ℃ under vacuum, then is mixed with 8g of isophorone diisocyanate, and 0.015g of organic silver catalyst is added into the system when polymerization reaction (with stirring) is carried out for 2.0 hours at 85 ℃; measuring the residual diisocyanate amount in the system by using a di-n-butylamine method, and stopping the polymerization reaction when the diisocyanate reaction degree in the system is 65%, so as to obtain waterborne polyurethane; mixing aqueous polyurethane and 13g of sodium N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonate, performing a second grafting reaction at 70 ℃ for 2.5 hours, and stopping the second grafting reaction when the diisocyanate reaction degree in the system is 78% (13 g of acetone is added to reduce the viscosity when the viscosity is increased) to obtain aqueous polyurethane grafted with sulfonic acid groups;
the waterborne polyurethane grafted with sulfonic groups and UiO-66-NH 2 The dispersion is mixed at 70 ℃ for a first grafting reaction for 1.0h, when the reaction degree of diisocyanate in the reaction system is 85%, the first grafting reaction is stopped, the system after the first grafting reaction is added into 44g of deionized water under the stirring condition of 1500r/min, the mixture is emulsified for 1h under the condition of 1000r/min and then mixed with deionized water solution (containing 0.2g of hydroxyethyl ethylenediamine chain extender) with the mass concentration of 30 percent, and the mixture is dispersed for 0.5h under the condition of 700r/min, thus obtaining modified UiO-66-NH 2 An emulsion;
UiO-66-NH 2 The emulsion is cast on a polytetrafluoroethylene plate to form a film, dried at room temperature, dried at 50 ℃ for 5 hours, dried at 80 ℃ for 8 hours to obtain the modified UiO-66-NH with the thickness of 0.12mm 2 A film material.
Modified UiO-66-NH 2 Diluting the emulsion to 0.1wt%, performing ultrasonic treatment on the emulsion by using an ultrasonic instrument under the power condition of 3000W for 0.5-h, and performing dynamic light scattering measurement by using a Markov nanometer laser particle size meter within the range of 0.4-10000 nm to obtain the particle size of 350nm.
For the obtained modified UiO-66-NH 2 Testing carbon dioxide adsorption performance of the membrane material: CO is carried out on the adhesive film by adopting a microphone instrument company 3Flex gas adsorption instrument 2 Adsorption isotherm test at 273K on CO 2 The adsorption capacity of (C) was 8.7cm 3 /g。
And (3) testing physical properties of the film material by using a universal testing machine, and measuring the tensile strength of the film to 16.9MPa and the elongation at break to 721%.
Example 2: preparation of UiO-66-NH according to example 1 2 A dispersion;
18g of polypropylene glycol is dried for 1.0h under vacuum at 100 ℃ and then mixed with 10g of hydrogenated phenyl methane diisocyanate, and 0.01g of organic silver catalyst is added into the system when polymerization reaction (with stirring) is carried out for 2.0h at 90 ℃; measuring the residual diisocyanate by using a di-n-butylamine method, and stopping the polymerization reaction when the reaction degree of the diisocyanate in the system reaches 70%, so as to obtain waterborne polyurethane; mixing aqueous polyurethane and 13g of 1, 2-dihydroxy-3-propane sodium sulfonate, performing a second grafting reaction at 70 ℃ for 3.5 hours, and stopping the second grafting reaction when the reaction degree of diisocyanate in a reaction system is 78% (17 g of acetone is added to reduce the viscosity when the viscosity is increased) to obtain aqueous polyurethane grafted with sulfonic acid groups;
the waterborne polyurethane grafted with sulfonic groups and UiO-66-NH 2 The dispersion is mixed at 70 ℃ for a first grafting reaction for 1.0h, the first grafting reaction is stopped when the reaction degree of diisocyanate in the reaction system is 90%, the system after the first grafting reaction is added into 31g of deionized water under the stirring condition of 1500r/min, and after the emulsification for 1h under the condition of the rotating speed of 1000r/min, the mixture is mixed with deionized water solution (containing 0.2g of ethylenediamine chain extender) of ethylenediamine chain extender with the mass concentration of 30% (dispersed for 0.5h under the condition of the rotating speed of 700 r/min) to obtain modified UiO-66-NH 2 An emulsion;
UiO-66-NH 2 The emulsion is cast on a polytetrafluoroethylene plate to form a film, dried at room temperature, dried at 50 ℃ for 5 hours, dried at 80 ℃ for 8 hours to obtain the modified UiO-66-NH with the thickness of 0.12mm 2 A film material.
Modified UiO-66-NH 2 Diluting the emulsion to 0.1wt%, performing ultrasonic treatment for 0.5h under 3000W power by using an ultrasonic instrument, and performing dynamic light scattering measurement within the range of 0.4-10000 nm by using a Markov nanometer laser particle size meter to obtain the particle size of 920nm.
For the obtained modified UiO-66-NH 2 Testing carbon dioxide adsorption performance of the membrane material: CO is carried out on the adhesive film by adopting a microphone instrument company 3Flex gas adsorption instrument 2 Adsorption isotherm test at 273K on CO 2 The adsorption capacity of (C) was 8.9cm 3 /g。
And (3) testing physical properties of the film material by using a universal testing machine, and measuring the tensile strength of the film to 17.8MPa and the elongation at break to 632%.
Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the present embodiments without departing from the spirit and scope of the invention.
Claims (10)
1. A modified MOFs characterized by comprising MOFs and an aqueous polyurethane grafted to the MOFs by amide linkages; the MOFs are MOFs containing amino groups.
2. The modified MOFs of claim 1, wherein the mass percentage of isocyanate groups in the aqueous polyurethane is 14-22%;
the molar ratio of the waterborne polyurethane to the MOFs is 22-28:1.
3. The modified MOFs of claim 1, further comprising hydrophilic groups grafted to the aqueous polyurethane.
4. The modified MOFs of claim 3, wherein the hydrophilic group comprises a sulfonic acid group or a carboxyl group.
5. The method for preparing the modified MOFs of any one of claims 1 to 4, comprising the following steps:
and mixing the aqueous polyurethane and MOFs containing amino groups to perform a first grafting reaction to obtain the modified MOFs.
6. The method according to claim 5, wherein the amino group-containing MOFs comprise UiO-66-NH 2 。
7. The method according to claim 5, wherein the temperature of the first grafting reaction is 60-70 ℃, and the time of the first grafting reaction is 0.8-1.2 hours.
8. The method according to claim 5, wherein the first grafting reaction is preceded by: the MOFs containing amino groups were dispersed in acetone to obtain an acetone dispersion of MOFs.
9. The method according to claim 5, wherein the first grafting reaction is preceded by: and mixing the aqueous polyurethane with a hydrophilic chain extender, and performing a second grafting reaction to obtain the aqueous polyurethane grafted with hydrophilic groups.
10. Use of modified MOFs according to any one of claims 1 to 4 or prepared by a preparation method according to any one of claims 5 to 9 in the field of catalysis or adsorption.
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