CN117645768B - Block copolymer coated metal-organic framework material and preparation method thereof - Google Patents
Block copolymer coated metal-organic framework material and preparation method thereof Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 70
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002105 nanoparticle Substances 0.000 claims abstract description 63
- 239000002114 nanocomposite Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 43
- 239000002904 solvent Substances 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
- 229920001577 copolymer Polymers 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 17
- 239000003999 initiator Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000012046 mixed solvent Substances 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 12
- 238000012546 transfer Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 239000012986 chain transfer agent Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 230000000977 initiatory effect Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 239000012988 Dithioester Substances 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 125000005022 dithioester group Chemical group 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229920000469 amphiphilic block copolymer Polymers 0.000 claims description 2
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 1
- 239000011258 core-shell material Substances 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 5
- 238000005253 cladding Methods 0.000 abstract 1
- 230000005540 biological transmission Effects 0.000 description 15
- 239000002131 composite material Substances 0.000 description 13
- 238000001000 micrograph Methods 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000004005 microsphere Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- CDOWNLMZVKJRSC-UHFFFAOYSA-N 2-hydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1 CDOWNLMZVKJRSC-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- 229920005593 poly(benzyl methacrylate) Polymers 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 229910007926 ZrCl Inorganic materials 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- 238000013467 fragmentation Methods 0.000 description 3
- 238000006062 fragmentation reaction Methods 0.000 description 3
- -1 hydroxyl terephthalic acid Chemical compound 0.000 description 3
- 239000012924 metal-organic framework composite Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 2
- 229920000359 diblock copolymer Polymers 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- YLZSIUVOIFJGQZ-UHFFFAOYSA-N bis[4-(dimethylamino)phenyl]methanol Chemical compound C1=CC(N(C)C)=CC=C1C(O)C1=CC=C(N(C)C)C=C1 YLZSIUVOIFJGQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention relates to the technical field of nanocomposite materials, in particular to a block copolymer coated metal-organic framework material and a preparation method thereof. The specific technical scheme is as follows: a block copolymer cladding metal-organic framework material is a core-shell structure with metal-organic framework nano particles as cores and block copolymers as shells. Solves the difficult problem of MOFs nano particle surface modification.
Description
Technical Field
The invention relates to the technical field of nanocomposite materials, in particular to a block copolymer coated metal-organic framework material and a preparation method thereof.
Background
Metal-organic frameworks (MOFs) are a class of porous crystalline materials composed of metal ions (metal clusters) and organic linkers that are secondary building blocks. MOFs have a wide application prospect in a plurality of fields due to the abundant pore structure, large specific surface area and structural diversity and adjustability. MOFs, however, have their own drawbacks that are not negligible, such as poor thermal stability, chemical stability, dispersibility, and single surface chemistry, which greatly limit their development into more fields.
Modifying the surface energy of nanoparticles with polymers alters the surface chemistry and interactions with adjacent media of the nanoparticles and imparts new properties to the nanoparticles. The dispersibility, chemical stability, self-assembly behavior, etc. of the nanoparticles can be changed by adjusting the composition and structure of the polymer. The modification is also true for MOFs nano-particles, for example, the rigid MOFs nano-particles can have excellent application in aspects of biological imaging, gas membrane separation, catalysis and the like after being modified by soft polymers. In recent years, there have been endless working layers concerning modification of MOFs nanoparticles with polymer-modified nanoparticles. In most of these works, polymer modified MOFs nanoparticles are obtained by in situ reversible addition-fragmentation chain transfer polymerization or surface initiated atom transfer radical polymerization by adding monomers and initiators to a dispersion containing MOFs. There is no report on film-forming modification technology of MOFs surface using block copolymer nanoparticles.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a block copolymer coated metal-organic framework material and a preparation method thereof, and amphiphilic block copolymer nano particles with uniform particle size distribution and good colloid stability are obtained by a reversible addition-fragmentation chain transfer (RAFT) polymerization method. And then the segmented copolymer nano particles form a high molecular segmented copolymer film with uniform and controllable thickness and adjustable stable chain length on the surface of MOFs by a one-step method, and the film can uniformly coat the metal-organic framework nano particles, so that the segmented copolymer coated metal-organic framework nano composite material is formed.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
the invention discloses a block copolymer coated metal-organic framework material which is a core-shell structure taking metal-organic framework nano particles as cores and block copolymers as shells.
Preferably, the particle size of the metal-organic framework nano-particles is 100-600 nm, and the thickness of the block copolymer coated metal-organic framework nano-particles is 5-200 nm.
Correspondingly, a preparation method of the block copolymer coated metal-organic framework material is characterized in that metal-organic framework nano particles and the block copolymer are dispersed in a solvent and uniformly mixed, and the mixture is heated and stirred to form the block copolymer coated metal-organic framework nano composite material.
Preferably, the metal-organic framework nano-particles and the segmented copolymer are stirred and reacted in an oil bath at 60-90 ℃ for 12-24 hours, and the stirring speed is 100-500 rpm.
Preferably, the concentration of the metal-organic framework nanoparticles in the solvent is 0.5-2 g/L, and the concentration of the block copolymer is 5-50 g/L.
Preferably, the preparation process of the metal-organic framework nanoparticle is as follows: dissolving zirconium tetrachloride and 2-amino terephthalic acid/hydroxy terephthalic acid with a solvent, adding an acid solution, reacting, and centrifugally washing with different solvents after the reaction is finished to obtain the metal-organic framework nano-particles.
Preferably, the mass ratio of the zirconium tetrachloride to the 2-amino terephthalic acid/hydroxyl terephthalic acid is 0.5-1, and the feed liquid ratio of the zirconium tetrachloride to the solvent is 1-2:100, m/v; the feed liquid ratio of zirconium tetrachloride to acid solution is 1-2:10-20, m/v.
Preferably, the solvent is one or more of N, N-dimethylformamide or an alcohol solvent, and the acid solution is one or more of acetic acid or formic acid; the reaction temperature is 30-120 ℃ and the reaction time is 2-12 h.
Preferably, the preparation process of the block copolymer comprises the following steps: adding a polymerization monomer, a macromolecular chain transfer agent and an initiator into a mixed solvent, introducing inert gas to deoxidize, and polymerizing under the action of thermal initiation to form a block copolymer;
The polymerization monomer is methacrylate, the macromolecular chain transfer reagent is a single-end dithioester modified polymethacrylic acid macromolecular chain transfer reagent, and the initiator is azo initiator.
Preferably, the mass ratio of the polymerization monomer to the macromolecular chain transfer agent to the initiator is 600-6000:170-350:1-2, the mixed solvent is a mixture of ethanol and water, the mass volume ratio of the polymerization monomer to the mixed solvent is 3-5:20, nitrogen is introduced into an ice water bath to deoxidize for 10-20 min, and the mixture is placed into an oil bath at 50-70 ℃ to react for 12-36 h.
The invention has the following beneficial effects:
1. The invention provides a simple method, wherein a layer of high molecular block copolymer film with controllable thickness and adjustable structure is loaded on the surface of MOFs nano-particles, so that a block copolymer film coated metal-organic framework composite material with a core-shell structure is obtained.
2. The invention prepares the polymer nano-microsphere with uniform and adjustable size distribution by a reversible addition-chain fracture transfer polymerization method, the surface of the nano-microsphere is electronegative and can generate electrostatic interaction with MOFs nano-particles with positive charges, so that the nano-microsphere can be adsorbed on the surfaces of the MOFs nano-particles and reassembled on the surfaces to form a layer of polymer film, and the segmented copolymer film@metal-organic framework composite material with a core-shell structure is obtained.
Drawings
FIG. 1 is a transmission electron micrograph of block copolymer nanoparticle poly (methacrylic acid) 111 -poly (benzyl methacrylate) 500(PMAA111-PBzMA500) prepared in example 1;
FIG. 2 is a transmission electron micrograph of block copolymer nanoparticle poly (methacrylic acid) 111 -poly (benzyl methacrylate) 1000(PMAA111-PBzMA1000) prepared in example 2;
FIG. 3 is a transmission electron micrograph (low magnification) of UiO-66-NH 2 prepared in example 3;
FIG. 4 is a transmission electron micrograph (low magnification) of UiO-66-OH prepared in example 4;
FIG. 5 is a transmission micrograph (high magnification) of UiO-66-NH 2@PMAA111-PBzMA500 prepared in example 5;
FIG. 6 is a transmission micrograph (high magnification) of UiO-66-NH 2@PMAA111-PBzMA1000 prepared in example 6;
FIG. 7 is a transmission micrograph (high magnification) of UiO-66-OH@PMAA 111-PBzMA500 prepared in example 7;
FIG. 8 is a transmission micrograph (high magnification) of UiO-66-OH@PMAA 111-PBzMA500 prepared in comparative example 1;
FIG. 9 is a transmission micrograph (high magnification) of UiO-66-OH/PMAA 111-PBzMA500 prepared in comparative example 2.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated.
1. The invention discloses a block copolymer coated metal-organic framework material which is a core-shell structure with metal-organic framework nano particles as cores and block copolymers as shells. The particle size of the metal-organic framework nano-particles is 100-600 nm, and the thickness of the block copolymer wrapping the surfaces of the metal-organic framework nano-particles is 5-200 nm. The block copolymer is nano-particle with the particle size of 20-200 nm. During mixing with the metal-organic framework nanoparticles, the surface thereof fuses to form a block copolymer film.
2. The invention also discloses a preparation method of the segmented copolymer coated metal-organic framework material, which synthesizes amphiphilic high molecular segmented copolymer nano particles by a reversible addition-fragmentation chain transfer (RAFT) polymerization method; synthesizing MOFs by using a solvothermal method; and finally, adding the high molecular block copolymer with opposite charges into ethanol dispersion liquid containing MOFs nano particles, heating and stirring for 12-24 h, and centrifuging to obtain the block copolymer coated metal-organic framework composite material.
Specific: dispersing the metal-organic frame nano particles and the segmented copolymer in an ethanol solvent, uniformly mixing, heating and stirring to form the segmented copolymer coated metal-organic frame nano composite material. Wherein, the metal-organic framework nano particles and the segmented copolymer are stirred and reacted for 12 to 24 hours in an oil bath at the temperature of between 60 and 90 ℃ with the stirring rotation speed of between 100 and 500rpm. Wherein the concentration of the metal-organic framework nano particles in the solvent is 0.5-2 g/L, and the concentration of the block copolymer is 5-50 g/L. The mass ratio of the block copolymer to MOFs nano particles to ethanol is 70-7:2:1-2.
Further, the metal-organic framework nanoparticle is prepared by a hot solvent method, and the preparation process is as follows: dissolving zirconium tetrachloride (ZrCl 4) and 2-amino terephthalic acid (NH 2 -BDC)/hydroxyl terephthalic acid (OH-BDC) with a solvent, adding an acid solution, reacting, and centrifugally washing with different solvents (such as ethanol or an alcohol-water mixed solvent) after the reaction is finished to obtain the metal-organic framework nano-particles UIO-66-NH 2/UIO-66-OH. The solvent is one or more of N, N-dimethylformamide or an alcohol solvent, and the acid solution is one or more of acetic acid or formic acid; the reaction temperature is 30-120 ℃ and the reaction time is 2-12 h. The metal-organic frameworks (UiO-66-NH 2, uiO-66-OH) nanoparticle are characterized by a transmission electron microscope, the particle size is 200-600 nm, and the chemical formulas are respectively Zr6O4(OH)4(BDC-NH2)6、Zr6O4(OH)4(BDC-OH)6.
Wherein the mass ratio of the zirconium tetrachloride to the 2-amino terephthalic acid/hydroxyl terephthalic acid is 0.5-1, and the feed liquid ratio of the zirconium tetrachloride to the solvent is 1-2:100, m/v; the feed liquid ratio of zirconium tetrachloride to acid solution is 1-2:10-20, m/v.
Further, the block copolymer is synthesized by a reversible addition-fragmentation chain transfer (RAFT) -mediated polymerization-induced self-assembly (PISA) method, and the preparation process is as follows: adding a polymerization monomer, a macromolecular chain transfer agent and an initiator into a mixed solvent, introducing inert gas to deoxidize, and polymerizing under the action of thermal initiation to form a block copolymer; the polymerization monomer is methacrylate, the macromolecular chain transfer reagent is a single-end dithioester modified polymethacrylic acid macromolecular chain transfer reagent, the initiator is azo initiator, and the initiator is at least one azo initiator such as azodicarbonyl valeric acid, azodiisobutyronitrile, azodicyanovaleric acid, azodiisobutyronitrile and the like. The thermal initiation is to add a polymerization monomer, a macromolecular chain transfer reagent and an initiator into a mixed solvent.
Further, the mass ratio of the polymerization monomer to the macromolecular chain transfer agent to the initiator is 600-6000:170-350:1-2, the mixed solvent is a mixture of ethanol and water (the mass ratio of the ethanol to the water is 2:1), the mass volume ratio of the polymerization monomer to the mixed solvent is 3-5:20, nitrogen is introduced into an ice water bath to deoxidize for 10-20 min, and the mixture is placed into an oil bath at 50-70 ℃ to react for 12-36 h.
The invention is further illustrated below in conjunction with specific examples.
Example 1
The preparation process of the block copolymer nano-particles comprises the following steps:
196mg of poly (methacrylic acid) 111 macromolecular chain transfer agent (PMAA 111 -CTA), 1.76g of benzyl methacrylate (BzMA), 1.12mg of 4,4' -azobis (4-cyanovaleric acid) were added to a round bottom flask (mass ratio of ethanol to water is 2:1) filled with a mixed solvent of 7.8g of ethanol and water, deoxygenated by introducing nitrogen gas for 20min in an ice water bath, and then reacted for 24h in an oil bath at 70 ℃ to obtain diblock copolymer nanoparticle poly (methacrylic acid) 111 -poly (benzyl methacrylate) 500, i.e. M 111-B500 microspheres (FIG. 1 is a transmission microscopy picture of M 111-B500).
Example 2
The preparation process of the block copolymer nano-particles comprises the following steps:
98mg of poly (methacrylic acid) 111 macromolecular chain transfer agent (PMAA 111 -CTA), 1.76g of benzyl methacrylate (BzMA), 0.56mg of 4,4' -azobis (4-cyanovaleric acid) were added to a round bottom flask (mass ratio of ethanol to water is 2:1) filled with a mixed solvent of 7.4g of ethanol and water, deoxygenated in an ice-water bath by introducing nitrogen for 20min, and reacted in an oil bath at 70 ℃ for 24h to obtain diblock copolymer nanoparticle poly (methacrylic acid) 111 -poly (benzyl methacrylate) 1000, i.e., M 111-B1000 microspheres (FIG. 2 is a transmission microscope picture of M 111-B1000).
Example 3
The preparation process of the metal-organic framework nanoparticle comprises the following steps:
1.02g of ZrCl 4,0.29g NH2 -BDC (2-amino terephthalic acid) is dissolved in 100mL of DMF (N, N-dimethylformamide) solvent, then 12mL of glacial acetic acid is added after the dissolution, the mixture is allowed to stand at 120 ℃ for reaction for 3 hours, and the mixture is centrifuged to obtain metal organic framework (UiO-66-NH 2) particles, and a transmission electron microscope image of the metal organic framework (UiO-66-NH 2) nano particles is shown as a figure 3. Notably, the size of the UiO-66-NH 2 nanoparticles can be varied by adjusting the amount of glacial acetic acid added and the reaction time.
Example 4
The preparation process of the metal-organic framework nanoparticle comprises the following steps:
0.051g of ZrCl 4 and 0.0729g of OH-BDC (hydroxy terephthalic acid) are dissolved in 50mL of DMF (N, N-dimethylformamide) solvent, 6mL of glacial acetic acid is added after the dissolution, the mixture is allowed to stand still at 120 ℃ for reaction for 3 hours, and the mixture is centrifuged to obtain metal organic framework (UiO-66-OH) nano particles, and a transmission electron microscope image of the metal organic framework (UiO-66-OH) nano particles is shown as a figure 4. Notably, the size of the UiO-66-OH nanoparticles can be varied by adjusting the amount of glacial acetic acid added and the reaction time.
Example 5
The preparation process of the composite material with the segmented copolymer coated with the metal-organic framework comprises the following steps:
6.875mg of UiO-66-NH 2 is taken and dispersed into 5g of ethanol, 350mg of M 111-B500 nano particles are added into the ethanol, and the mixture is uniformly mixed and stirred in an oil bath at 70 ℃ for reaction for 12 hours, thus obtaining the composite material with the UiO-66-NH 2/M111-B500 segmented copolymer film coating the metal-organic framework. Fig. 5 is a transmission electron microscope picture of the composite material. The thickness of the film formed from the block copolymer was measured to be 20.+ -. 2nm.
Example 6
The preparation process of the composite material with the segmented copolymer coated with the metal-organic framework comprises the following steps:
6.875mg of UiO-66-NH 2 is dispersed in 5g of ethanol, 500mg of M 111-B500 nano particles are added to the mixture, the mixture is uniformly mixed and stirred in an oil bath at 70 ℃ for reaction for 12 hours, and a composite material with a metal organic framework coated by a UiO-66-NH 2/M111-B1000 segmented copolymer film is obtained, and a transmission electron microscope picture of the composite material is shown in FIG. 6. The thickness of the film formed from the block copolymer was measured to be 31.+ -. 4nm.
Example 7
The preparation process of the composite material with the segmented copolymer coated with the metal-organic framework comprises the following steps:
6.875mg of UiO-66-OH is dispersed into 5g of ethanol, 500mg of M 111-B500 nano particles are added into the ethanol, the mixture is uniformly mixed and stirred in an oil bath at 70 ℃ for reaction for 12 hours, and a composite material with a metal organic framework coated by a UiO-66-OH/M 111-B500 segmented copolymer film is obtained, and a transmission electron microscope picture of the composite material is shown in FIG. 7. The thickness of the film formed from the block copolymer was measured to be 20.+ -.5 nm.
Comparative example 1
The difference from example 5 is that: by changing the solvent ethanol for the reaction of the high molecular block copolymer and MOFs nano-particles to water, and by using a transmission electron microscope image as shown in FIG. 8, it can be seen from FIG. 8 that a composite material of UiO-66-NH 2/M111-B500 block copolymer coated with a metal-organic framework can not be obtained under the condition.
Comparative example 2
The only difference from example 5 is that: the temperature of the reaction of the high molecular block copolymer and MOFs nano-particles is changed to 70 ℃ to 25 ℃ at room temperature, and the transmission electron microscope picture of the result is shown in figure 9, so that the composite material of the UiO-66-NH 2/M111-B500 block copolymer coated with the metal-organic framework can not be obtained under the condition.
Performance test: the block copolymer coated metal-organic framework composite material has good alkali resistance, and specific performance test results are shown in the following table 1, and the results show that the alkali resistance of MOFs can be greatly improved by the composite material prepared by the invention.
Table 1 results of alkali resistance test of composite materials
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (6)
1. A preparation method of a block copolymer coated metal-organic framework material is characterized by comprising the following steps of: dispersing the metal-organic frame nano particles and the segmented copolymer in a solvent I, uniformly mixing, and stirring in an oil bath at 70 ℃ for reaction for 12-24 hours to form a segmented copolymer coated metal-organic frame nano composite material; the solvent I is ethanol; the concentration of the metal-organic framework nano particles in the solvent I is 0.5-2 g/L, and the mass ratio of the block copolymer to the solvent I is 7:100 or 1:10;
The preparation process of the metal-organic framework nanoparticle comprises the following steps: dissolving zirconium tetrachloride and 2-amino terephthalic acid with a solvent II, adding an acid solution to react I, and centrifugally washing with a solvent III after the reaction I is finished to obtain metal-organic framework nano particles;
The preparation process of the block copolymer comprises the following steps: adding a polymerization monomer, a macromolecular chain transfer agent and an initiator into a mixed solvent, introducing inert gas to deoxidize, and polymerizing under the action of thermal initiation by a RAFT polymerization method to form amphiphilic block copolymer nano particles; the macromolecular chain transfer reagent is a single-end dithioester modified polymethacrylic acid macromolecular chain transfer reagent; the polymerized monomer is benzyl methacrylate.
2. The method of manufacturing according to claim 1, characterized in that: the stirring rotation speed is 100-500 rpm.
3. The method of manufacturing according to claim 1, characterized in that: the mass ratio of the zirconium tetrachloride to the 2-amino terephthalic acid is 1.02:0.29, the feed liquid ratio of zirconium tetrachloride to the solvent II is (1-2) g, 100mL, m/v; the feed liquid ratio of zirconium tetrachloride to acid solution is (1-2) g (10-20) mL, m/v.
4. The method of manufacturing according to claim 1, characterized in that: the solvent II is one or more of N, N-dimethylformamide or an alcohol solvent, and the acid solution is one or more of acetic acid or formic acid; the temperature of the reaction I is 30-120 ℃ and the time is 2-12 h; the solvent III is ethanol or an ethanol-water mixed solvent.
5. The method of manufacturing according to claim 1, characterized in that: the initiator is azo initiator.
6. The method of manufacturing according to claim 5, wherein: the mass ratio of the polymerization monomer to the macromolecular chain transfer agent to the initiator is 600-6000:170-350:1-2, the mixed solvent is a mixture of ethanol and water, the mass volume ratio of the polymerization monomer to the mixed solvent is (3-5) g/20 mL, nitrogen is introduced into an ice water bath to deoxidize for 10-20 min, and the mixture is placed into an oil bath at 50-70 ℃ to react for 12-36 h.
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| CN104174388A (en) * | 2014-08-08 | 2014-12-03 | 复旦大学 | Metal organic frame composite material and preparation method thereof |
| CN115141408A (en) * | 2022-05-23 | 2022-10-04 | 佛山市三水佛水供水有限公司 | Molecular imprinting fluorescence sensor based on amphiphilic block copolymer-metal organic framework and preparation method and application thereof |
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| CN104001426A (en) * | 2014-05-29 | 2014-08-27 | 北京工业大学 | Preparation method of high dispersion metal-organic framework (MOF)/organic hybrid priority alcohol through composite membrane |
| CN104174388A (en) * | 2014-08-08 | 2014-12-03 | 复旦大学 | Metal organic frame composite material and preparation method thereof |
| CN115141408A (en) * | 2022-05-23 | 2022-10-04 | 佛山市三水佛水供水有限公司 | Molecular imprinting fluorescence sensor based on amphiphilic block copolymer-metal organic framework and preparation method and application thereof |
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