CN117645768A - 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
- Publication number
- CN117645768A CN117645768A CN202311768984.3A CN202311768984A CN117645768A CN 117645768 A CN117645768 A CN 117645768A CN 202311768984 A CN202311768984 A CN 202311768984A CN 117645768 A CN117645768 A CN 117645768A
- Authority
- CN
- China
- Prior art keywords
- organic framework
- metal
- block copolymer
- solvent
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 74
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002105 nanoparticle Substances 0.000 claims abstract description 66
- 239000011258 core-shell material Substances 0.000 claims abstract description 6
- 239000002114 nanocomposite Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 239000002904 solvent Substances 0.000 claims description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 17
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 16
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 14
- 239000012046 mixed solvent Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 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 9
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000002245 particle Substances 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
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 239000005457 ice water Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- -1 hydroxyl terephthalic acid Chemical compound 0.000 claims description 4
- 230000000977 initiatory effect Effects 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
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 4
- 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 16
- 239000002131 composite material Substances 0.000 description 11
- 229960000583 acetic acid Drugs 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000012924 metal-organic framework composite Substances 0.000 description 5
- 239000004005 microsphere Substances 0.000 description 5
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 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
- 230000002441 reversible effect Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 238000013467 fragmentation Methods 0.000 description 3
- 238000006062 fragmentation reaction Methods 0.000 description 3
- 238000001000 micrograph Methods 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
- 238000003917 TEM image Methods 0.000 description 2
- 229920000359 diblock copolymer Polymers 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004090 dissolution Methods 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
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- 229920000469 amphiphilic block copolymer Polymers 0.000 description 1
- 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
- 230000009881 electrostatic interaction Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 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
- 229920006254 polymer film Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 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
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
Landscapes
- 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 block copolymer nanoparticle poly (methacrylic acid) prepared in example 1 111 Poly (benzyl methacrylate) 500 (PMAA 111 -PBzMA 500 ) Transmission electron microscope photographs of (2);
FIG. 2 is a block copolymer nanoparticle poly (methacrylic acid) prepared in example 2 111 Poly (benzyl methacrylate) 1000 (PMAA 111- PBzMA 1000 ) Transmission electron microscope photographs of (2);
FIG. 3 is a diagram of UiO-66-NH obtained in example 3 2 Transmission electron micrographs (low magnification) of (a);
FIG. 4 is a transmission electron micrograph (low magnification) of UiO-66-OH prepared in example 4;
FIG. 5 is a diagram of UiO-66-NH obtained in example 5 2 @PMAA 111 -PBzMA 500 Transmission photomicrographs (high magnification);
FIG. 6 is a diagram of UiO-66-NH obtained in example 6 2 @PMAA 111 -PBzMA 1000 Transmission photomicrographs (high magnification);
FIG. 7 is a diagram of UiO-66-OH@PMAA prepared in example 7 111 -PBzMA 500 Transmission photomicrographs (high magnification);
FIG. 8 is a diagram of UiO-66-OH@PMAA prepared in comparative example 1 111 -PBzMA 500 Transmission photomicrographs (high magnification);
FIG. 9 is a diagram of UiO-66-OH/PMAA prepared in comparative example 2 111 -PBzMA 500 Transmission photomicrographs (high magnification).
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: zirconium tetrachloride (ZrCl) 4 ) And 2-amino terephthalic acid (NH) 2 Dissolving BDC/hydroxyl terephthalic acid (OH-BDC) with solvent, adding acid solution, reacting, and centrifugally washing with different solvents (such as ethanol or ethanol-water mixed solvent) to obtain metal-organic framework nanoparticle 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 framework (UiO-66-NH) 2 The UiO-66-OH) nano particles are characterized by a transmission electron microscope, the particle diameter is 200-600 nm, and the chemical formulas are Zr respectively 6 O 4 (OH) 4 (BDC-NH 2 ) 6 、Zr 6 O 4 (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) was charged into a round bottom flask containing 7.8g of a mixed solvent of ethanol and water (mass ratio of ethanol to water: 2:1), deoxygenated by introducing nitrogen gas into an ice water bath for 20min, and then reacted in an oil bath at 70℃for 24h to obtain diblock copolymer nanoparticle poly (methacrylic acid) 111 Poly (benzyl methacrylate) 500 I.e. M 111 -B 500 Microsphere (M in FIG. 1) 111 -B 500 Transmission microscope picture of (c).
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) was charged into a round bottom flask containing 7.4g of a mixed solvent of ethanol and water (mass ratio of ethanol to water: 2:1), deoxygenated by introducing nitrogen gas into an ice water bath for 20min, and reacted in an oil bath at 70℃for 24h to obtain a diblock copolymer nanoparticle poly (methacrylic acid) 111 Poly (benzyl methacrylate) 1000 I.e. M 111 -B 1000 Microsphere (M in FIG. 2) 111 -B 1000 Transmission microscope picture of (c).
Example 3
The preparation process of the metal-organic framework nanoparticle comprises the following steps:
1.02g ZrCl 4 ，0.29g NH 2 BDC (2-amino terephthalic acid) is dissolved in 100mL DMF (N, N-dimethylformamide) solvent, then 12mL glacial acetic acid is added after the dissolution, the mixture is kept stand at 120 ℃ for reaction for 3h, and the mixture is centrifuged to obtain a metal organic framework (UiO-66-NH) 2 ) Particles, the metal-organic frameworks (UiO-66-NH) 2 ) The transmission electron microscope image of the nanoparticle is shown in fig. 3. Notably, by adjusting the amount of glacial acetic acid added and the reaction time, the UiO-66-NH can be varied 2 Size of the nanoparticle.
Example 4
The preparation process of the metal-organic framework nanoparticle comprises the following steps:
0.051g ZrCl 4 0.0729g of OH-BDC (hydroxy terephthalic acid) is 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 microscopy image of the metal organic framework (UiO-66-OH) nano particles is shown as 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 was taken 2 Dispersing into 5g ethanol, and adding 350mg M 111 -B 500 The nano particles are evenly mixed and stirred in an oil bath at 70 ℃ for reaction for 12 hours to obtain UiO-66-NH 2 /M 111 -B 500 The block copolymer film coats the composite of metal-organic frameworks. 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 was taken 2 Dispersing into 5g ethanol, and adding 500mg M 111 -B 500 The nano particles are evenly mixed and stirred in an oil bath at 70 ℃ for reaction for 12 hours to obtain UiO-66-NH 2 /M 111 -B 1000 The block copolymer film coats the composite material of the metal organic framework, and fig. 6 is a transmission electron microscope picture of the composite material. 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:
dispersing 6.875mg of UiO-66-OH in 5g of ethanol, and adding 500mg of M thereto 111 -B 500 The nano particles are evenly mixed and stirred in an oil bath at 70 ℃ for reaction for 12 hours to obtain the UiO-66-OH/M 111 -B 500 The block copolymer film coats the composite material of the metal organic framework, and fig. 7 is a transmission electron microscope image of the composite material. 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 of the reaction of the polymer block copolymer and MOFs nano-particles into water, the transmission electron microscope image is shown in FIG. 8, and it can be seen from FIG. 8 that UiO-66-NH can not be obtained under the condition 2 /M 111 -B 500 The block copolymer coats the metal-organic framework composite.
Comparative example 2
The only difference from example 5 is that: the transmission electron microscope picture of the result obtained by changing the reaction temperature of the high molecular block copolymer and MOFs nano-particles to 70 ℃ to 25 ℃ at room temperature is shown in figure 9, under the condition that UiO-66-NH can not be obtained 2 /M 111 -B 500 The block copolymer coats the metal-organic framework composite.
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 (10)
1. A block copolymer coated metal-organic framework material characterized by: the material is a core-shell structure with metal-organic framework nano particles as cores and block copolymers as shells.
2. A block copolymer coated metal-organic framework material according to claim 1, characterized in that: 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.
3. A method for preparing the block copolymer coated metal-organic framework material of claim 1 or 2, characterized in that: dispersing the metal-organic frame nano particles and the segmented copolymer in a solvent, uniformly mixing, heating and stirring to form the segmented copolymer coated metal-organic frame nano composite material.
4. A method of preparation according to claim 3, characterized in that: the metal-organic framework nano particles and the segmented copolymer are stirred and reacted in an oil bath at 60-90 ℃ for 12-24 h, and the stirring speed is 100-500 rpm.
5. A method of preparation according to claim 3, characterized in that: 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.
6. A method of preparation according to claim 3, characterized in that: the preparation process of the metal-organic framework nanoparticle comprises the following steps: 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.
7. The method of manufacturing according to claim 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.
8. The method of manufacturing according to claim 6, wherein: 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.
9. The method of manufacturing according to claim 6, wherein: 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.
10. The method of manufacturing according to claim 9, 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 3-5:20, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311768984.3A CN117645768B (en) | 2023-12-21 | Block copolymer coated metal-organic framework material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311768984.3A CN117645768B (en) | 2023-12-21 | Block copolymer coated metal-organic framework material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117645768A true CN117645768A (en) | 2024-03-05 |
| CN117645768B CN117645768B (en) | 2024-05-31 |
Family
ID=
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20190290762A1 (en) * | 2016-06-13 | 2019-09-26 | Nitin Chopra | Nano-architectured colloidosomes for controlled and triggered release |
| 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 |
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20190290762A1 (en) * | 2016-06-13 | 2019-09-26 | Nitin Chopra | Nano-architectured colloidosomes for controlled and triggered release |
| 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ramli et al. | Core–shell polymers: a review | |
| CN106928465B (en) | PH response type metal organic framework nanocrystal and preparation method and application thereof | |
| Jonsson et al. | Suspension polymerization of thermally expandable core/shell particles | |
| CN103554325B (en) | A kind of preparation method of functional hollow polymer microballoon | |
| JP2614707B2 (en) | Method for producing emulsion polymer having hollow structure | |
| CN102659990B (en) | Method for preparing stable-dispersibility pigment/polymer core-shell structure composite granules by using by polymer-wrapped pigment particles | |
| Zou et al. | Synthetic strategies for raspberry-like polymer composite particles | |
| US7741378B2 (en) | Porous monodispersed particles and method for production thereof, and use thereof | |
| Fallahi-Samberan et al. | Investigating Janus morphology development of poly (acrylic acid)/poly (2‑(dimethylamino) ethyl methacrylate) composite particles: An experimental study and mathematical modeling of DOX release | |
| Abdollahi et al. | Morphology evolution of functionalized styrene and methyl methacrylate copolymer latex nanoparticles by one-step emulsifier-free emulsion polymerization | |
| CN104194003A (en) | Method for preparing black monodisperse polymer microspheres | |
| TW201317281A (en) | Method of manufacturing core-shell structure submicrospheres | |
| Bai et al. | Synthesis of core–shell microspheres with active hydroxyl groups by two‐stage precipitation polymerization | |
| WO2010139732A1 (en) | Fluorinated core-shell-polymers and process for preparing same | |
| CN108084348B (en) | Preparation method of strawberry type complex colloidal particle cluster emulsion for super-hydrophobic nano coating | |
| CN117645768B (en) | Block copolymer coated metal-organic framework material and preparation method thereof | |
| JP4192245B2 (en) | Process for producing irregular polymer particles | |
| CN117645768A (en) | Block copolymer coated metal-organic framework material and preparation method thereof | |
| CN109126649B (en) | Method for preparing microcapsule by using block copolymer as microcapsule wall material | |
| CN115677898A (en) | Monodisperse hollow polystyrene-divinylbenzene composite microsphere, preparation method thereof and application thereof in enzyme-linked immunosorbent assay | |
| CN111151224A (en) | Metal organic framework with polymer grafted on surface and preparation method thereof | |
| Xia et al. | Preparation of silver-poly (acrylamide-co-methacrylic acid) composite microspheres with patterned surface structures | |
| JP2002542318A (en) | Method for producing monodisperse polymer particles | |
| CN112851869B (en) | Method for preparing morphology-adjustable polyion liquid-based anisotropic composite particles based on seed polymerization method | |
| CN106807255A (en) | Three-dimensional structure TiO2Stannic oxide/graphene nano composite in-situ polymerization doped polyimide film and its preparation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |