CN117258562A - Plasma modified metal-organic framework/polyimide mixed matrix membrane and preparation method and application thereof - Google Patents
Plasma modified metal-organic framework/polyimide mixed matrix membrane and preparation method and application thereof Download PDFInfo
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 156
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 130
- 239000004642 Polyimide Substances 0.000 title claims abstract description 107
- 239000004941 mixed matrix membrane Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 225
- 239000002086 nanomaterial Substances 0.000 claims abstract description 127
- 239000011159 matrix material Substances 0.000 claims abstract description 86
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims abstract description 76
- 238000005266 casting Methods 0.000 claims abstract description 42
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000007787 solid Substances 0.000 claims abstract description 37
- 238000001291 vacuum drying Methods 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 21
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 238000000227 grinding Methods 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- 150000004985 diamines Chemical class 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 239000011701 zinc Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 187
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical group CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 57
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 57
- 239000011521 glass Substances 0.000 claims description 36
- 239000007789 gas Substances 0.000 claims description 33
- 238000006555 catalytic reaction Methods 0.000 claims description 22
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 claims description 20
- HHLMWQDRYZAENA-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 HHLMWQDRYZAENA-UHFFFAOYSA-N 0.000 claims description 20
- 150000008064 anhydrides Chemical class 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 19
- 238000004140 cleaning Methods 0.000 claims description 18
- 230000018044 dehydration Effects 0.000 claims description 18
- 238000006297 dehydration reaction Methods 0.000 claims description 18
- 229920005575 poly(amic acid) Polymers 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- -1 fluorenyl dianhydride Chemical compound 0.000 claims description 5
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 4
- FVFYRXJKYAVFSB-UHFFFAOYSA-N 2,3,5,6-tetrafluorobenzene-1,4-diamine Chemical compound NC1=C(F)C(F)=C(N)C(F)=C1F FVFYRXJKYAVFSB-UHFFFAOYSA-N 0.000 claims description 4
- WCZNKVPCIFMXEQ-UHFFFAOYSA-N 2,3,5,6-tetramethylbenzene-1,4-diamine Chemical compound CC1=C(C)C(N)=C(C)C(C)=C1N WCZNKVPCIFMXEQ-UHFFFAOYSA-N 0.000 claims description 4
- ZVDSMYGTJDFNHN-UHFFFAOYSA-N 2,4,6-trimethylbenzene-1,3-diamine Chemical compound CC1=CC(C)=C(N)C(C)=C1N ZVDSMYGTJDFNHN-UHFFFAOYSA-N 0.000 claims description 4
- PAPDRIKTCIYHFI-UHFFFAOYSA-N 4-[3,5-bis(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC(OC=2C=CC(N)=CC=2)=CC(OC=2C=CC(N)=CC=2)=C1 PAPDRIKTCIYHFI-UHFFFAOYSA-N 0.000 claims description 4
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 claims description 4
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 claims description 4
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 claims description 4
- 229930185605 Bisphenol Natural products 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000012024 dehydrating agents Substances 0.000 claims description 3
- 238000009832 plasma treatment Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 8
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 3
- 239000011147 inorganic material Substances 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000011368 organic material Substances 0.000 abstract description 3
- 238000005371 permeation separation Methods 0.000 abstract description 3
- 238000000935 solvent evaporation Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 32
- 230000002194 synthesizing effect Effects 0.000 description 17
- 230000009471 action Effects 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000003949 imides Chemical group 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01D53/22—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 diffusion
- B01D53/228—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 diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention belongs to the field of gas separation, and discloses a plasma modified metal-organic framework/polyimide mixed matrix membrane, and a preparation method and application thereof. The preparation method of the invention is that pyrazine and zinc fluosilicate are respectively dissolved in methanol to form solutions; adding a methanol solution of pyrazine into a methanol solution of zinc fluosilicate; and centrifugally collecting solids after the reaction, vacuum drying and grinding to obtain the metal-organic framework nano material, and carrying out plasma modification treatment on the metal-organic framework nano material. The polyimide film substrate is obtained by reacting dianhydride and diamine serving as monomer raw materials, the plasma modified metal-organic framework nano material is added into polyimide solution to obtain casting solution, and a solvent evaporation method is adopted to prepare the mixed substrate film. The mixed matrix film prepared by the method improves the interfacial compatibility between organic and inorganic materials; the crystallinity of the polymer is reduced, and the permeation separation performance of the gas is effectively enhanced.
Description
Technical Field
The invention relates to the field of gas separation, in particular to a plasma modified metal-organic framework/polyimide mixed matrix membrane, and a preparation method and application thereof.
Background
In the field of gas membrane separation, the polymer film is the most main separation layer material for industrial application, and has the advantages of easily available raw materials and easy large-scale processing. Conventional polymer materials include polyimides, polysulfones, polyethersulfones, polyacrylonitriles, polyvinylidene fluorides, aromatic polyamides, and the like. However, it is difficult to obtain high permeation rate and selectivity at the same time for the conventional polymer materials due to the trade-off effect. The mixed matrix membrane material is considered as an effective method for solving the problem, has the advantages of easy processing, low cost, high mechanical property and thermal stability and the like, and is a gas separation membrane material with wide application prospect.
Inorganic nano materials are mixed into an organic phase to construct a mixed matrix membrane so as to adjust the porous structure and the permeation selectivity of the membrane, and the method has practical significance. The mixed matrix membrane combines the advantages of inorganic nano materials and organic continuous phase matrixes, and can effectively improve the permeation rate of the mixed matrix membrane while keeping the gas selectivity. However, the preparation of the mixed matrix membrane often faces the problem of interfacial compatibility between organic and inorganic materials, which results in easy agglomeration of the doped nanomaterial, reduces the overall separation performance of the mixed matrix membrane, and limits the application of the mixed matrix membrane.
Disclosure of Invention
Aiming at the problems of insufficient organic-inorganic interface compatibility, easy agglomeration of nano materials and the like caused in the process of preparing the mixed matrix film by the metal-organic framework nano materials, the invention provides a plasma modified metal-organic framework/polyimide mixed matrix film, and a preparation method and application thereof.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a preparation method of a plasma modified metal-organic framework/polyimide mixed matrix membrane comprises the following steps:
respectively dissolving pyrazine and zinc fluosilicate in methanol to form a solution, and adding the methanol solution of pyrazine into the methanol solution of zinc fluosilicate;
centrifuging the reacted solution, cleaning the collected solid with methanol for many times, vacuum drying and grinding to obtain a metal organic framework nano material;
placing the metal organic framework nano material in a preset air source, setting the plasma frequency to be 13.56MHz, gradually increasing the voltage, and obtaining the plasma modified metal organic framework nano material after the treatment of the preset time;
preparing a polyamic acid solution by taking dianhydride and diamine as monomer raw materials, and obtaining a polyimide film substrate through catalysis and dehydration;
preparing polyimide solution by using polyimide film matrix, adding the plasma modified metal organic framework nano material into the polyimide solution to obtain casting solution, pouring the casting solution on a glass plate, drying and cooling to room temperature to obtain the plasma modified metal organic framework/polyimide mixed matrix film.
The preset air source is Ar/O 2 Or Ar/NH 3 ·H 2 O。
The preset time of the plasma treatment is 3-12 min.
The dianhydride is any one of pyromellitic dianhydride, 4'- (hexafluoro-isopropenyl) diphthalic anhydride, 4' -biphenyl ether dianhydride, bisphenol dianhydride, biphenyl tetracarboxylic dianhydride, 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 3', 4' -benzophenone tetracarboxylic dianhydride and fluorenyl dianhydride.
The diamine is any one of 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane/2, 2-bis (4-aminophenyl) hexafluoropropane, 4-diaminodiphenylmethane, 4-diaminodiphenyl ether, 1, 4-bis (4-aminophenoxy) benzene, 2,3,5, 6-tetramethyl-1, 4-phenylenediamine, 1,3, 5-tris (4-aminophenoxy) benzene, 2,3,5, 6-tetrafluoro-1, 4-phenylenediamine and 2,4, 6-trimethyl-1, 3-phenylenediamine.
The polyimide solution had a solids content of 11wt%.
The doping content of the plasma modified metal organic framework nano material in the film casting solution is 0-20%.
The dehydrating agent adopted in the preparation of the polyimide film matrix is acetic anhydride, and the catalyst adopted in the catalysis is triethylamine.
The mixed matrix film prepared by the preparation method of the plasma modified metal-organic framework/polyimide mixed matrix film forms hydrogen bonds or cross links between the plasma modified metal-organic framework nano material and polyimide.
The prepared plasma modified metal-organic framework/polyimide mixed matrix membrane is applied to gas separation.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a plasma modified metal-organic framework/polyimide mixed matrix membrane, and a preparation method and application thereof. The plasma modified metal-organic framework nano material is added into the polyimide matrix to be doped to form hydrogen bonds or cross links, so that the problem of agglomeration in the process of doping the nano material is solved; on the other hand, the problem that the permeation rate and the selectivity of the organic polymer material are difficult to be improved simultaneously in the gas separation process is solved. The prepared plasma modified metal-organic framework/polyimide mixed matrix membrane is added with the plasma modified metal-organic framework nano material, so that the interface compatibility between organic and inorganic materials is improved, the crystallinity of the polymer is reduced, and the gas separation performance is effectively enhanced.
Drawings
For a clearer description of the technical solutions of the embodiments of the present invention, the following briefly describes the drawings that are required to be used in the embodiments:
FIG. 1 is a FTIR spectrum of a nanomaterial made in comparative example 2, a plasma modified nanomaterial made in example 10 and example 13 of the present invention;
FIG. 2 is a FTIR spectrum of a polyimide film produced in comparative example 1, a mixed matrix film produced in comparative example 2, example 10 and example 13;
FIG. 3 is a TGA graph of the plasma modified nanomaterial made in comparative example 2, example 10, and example 13 of the present invention;
FIG. 4 is a TGA graph of the polyimide films prepared in comparative example 1, the mixed matrix films prepared in comparative example 2, example 10 and example 13 of the present invention;
FIG. 5 shows XRD patterns of the polyimide films produced in comparative example 1, and the mixed matrix films produced in comparative example 2, example 10 and example 13 according to the present invention;
FIGS. 6 (a 1), (a 2), (a 3) and (a 4) are SEM images of the surfaces of films produced in comparative examples 1,2, 10 and 13, respectively, according to the present invention; (b1) (b 2), (b 3) and (b 4) are SEM images of cross-sections of films produced in comparative examples 1,2, 10 and 13 of the present invention, respectively.
Detailed Description
The invention will be further illustrated with reference to examples.
The invention provides a preparation method of a plasma modified metal-organic framework/polyimide mixed matrix film, which specifically comprises the following steps:
preparing a metal organic framework nano material: pyrazine and zinc fluorosilicate (ZnSiF) 6 ) Respectively dissolving in methanol to form uniform solutions; under the combined action of ultrasonic wave and ice bath, the methanol solution of pyrazine is added into ZnSiF drop by drop 6 Synthesizing nano material in methanol solution; centrifuging the reacted solution, cleaning the collected solid with methanol for multiple times, vacuum drying and grinding to obtain the metal organic framework nano material.
Preparing a plasma modified metal-organic framework nano material: placing the metal organic framework nano material in a circular chamber, introducing a preset air source to replace air in the original chamber, setting the frequency of plasma to 13.56MHz, gradually increasing the voltage, and treating for a certain time to obtain the plasma modified metal organic framework nano material.
Synthesis of polyimide film matrix: the dianhydride and diamine are used as monomer raw materials to prepare a polyamic acid solution, and the polyimide film substrate is synthesized through catalysis and dehydration.
Preparing a mixed matrix film: preparing polyimide solution by using polyimide film matrix, adding the plasma modified metal-organic framework nano material into the polyimide solution, ultrasonically stirring to obtain casting solution, preparing a mixed matrix film by adopting a solvent evaporation method, pouring the casting solution on a glass plate, placing the glass plate in a vacuum drying oven, drying for 24 hours, and naturally cooling to room temperature to obtain the plasma modified metal-organic framework/polyimide mixed matrix film.
Further, the dianhydride used for preparing polyimide is any one of pyromellitic dianhydride, 4'- (hexafluoroisopropenyl) diphthalic anhydride, 4' -biphenyl ether dianhydride, bisphenol dianhydride, biphenyl tetracarboxylic dianhydride, 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 3', 4' -benzophenone tetracarboxylic dianhydride and fluorenyl dianhydride.
Further, the diamine used for preparing polyimide is any one of 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane/2, 2-bis (4-aminophenyl) hexafluoropropane, 4-diaminodiphenylmethane, 4-diaminodiphenyl ether, 1, 4-bis (4-aminophenoxy) benzene, 2,3,5, 6-tetramethyl-1, 4-phenylenediamine, 1,3, 5-tris (4-aminophenoxy) benzene, 2,3,5, 6-tetrafluoro-1, 4-phenylenediamine and 2,4, 6-trimethyl-1, 3-phenylenediamine.
Further, the dehydrating agent adopted in the preparation of the polyimide film matrix is acetic anhydride, and the catalyst adopted in the catalysis is triethylamine.
Further, the plasma modified gas source comprises Ar/O 2 Or Ar/NH 3 ·H 2 O。
Further, the treatment time of the plasma is 3-12 min.
Further, the solid content of the polyimide solution is 11wt%, and the doping content of the plasma modified metal-organic framework nano material in the casting film solution is 0-20%.
Example 1
(1) 0.3g of pyrazine and 0.38g of ZnSiF were added 6 Respectively dissolving in 6ml of methanol to form uniform solutions; under the combined action of ultrasonic wave and ice bath, the methanol solution of pyrazine is added into ZnSiF drop by drop 6 Synthesizing nano material in methanol solution; centrifuging the reacted solution, cleaning the collected solid with methanol for multiple times, vacuum drying, and grinding to obtain the metal organic framework nano material.
(2) Placing the metal organic framework nano material in a circular chamber, and introducing an air source Ar/O 2 And (3) replacing the gas in the original chamber, setting the frequency of plasma to 13.56MHz, gradually increasing the voltage, and treating for 3min to obtain the plasma modified metal-organic framework nano material.
(3) 4,4' - (hexafluoroisopropenyl) diphthalic anhydride and 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane/2, 2-bis (4-aminophenyl) hexafluoropropane are used as monomer raw materials to prepare a polyamic acid solution, and triethylamine is used for catalysis and acetic anhydride is used for dehydration to synthesize the polyimide film matrix.
(4) Preparing polyimide solution with polyimide film matrix, wherein the solid content of the polyimide solution is 11wt%, adding 5% of plasma modified metal-organic framework nano material into the polyimide solution, and stirring by ultrasonic to obtain film casting solution; pouring the casting solution on a glass plate, placing the glass plate in a vacuum drying oven, drying for 24 hours, and naturally cooling to room temperature to obtain the plasma modified metal-organic framework/polyimide mixed matrix film.
Example 2
(1) 0.3g of pyrazine and 0.38g of ZnSiF were added 6 Respectively dissolving in 6ml of methanol to form uniform solutions; under the combined action of ultrasonic wave and ice bath, the methanol solution of pyrazine is added into ZnSiF drop by drop 6 Synthesizing nano material in methanol solution; centrifuging the reacted solution, cleaning the collected solid with methanol for multiple times, vacuum drying, and grinding to obtain the metal organic framework nano material.
(2) Metal organic boneThe nanometer material is placed in a round chamber, and air source Ar/O is introduced 2 And (3) replacing the gas in the original chamber, setting the frequency of plasma to 13.56MHz, gradually increasing the voltage, and treating for 6min to obtain the plasma modified metal-organic framework nano material.
(3) 4,4' - (hexafluoroisopropenyl) diphthalic anhydride and 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane/2, 2-bis (4-aminophenyl) hexafluoropropane are used as monomer raw materials to prepare a polyamic acid solution, and triethylamine is used for catalysis and acetic anhydride is used for dehydration to synthesize the polyimide film matrix.
(4) Preparing polyimide solution with polyimide film matrix, wherein the solid content of the polyimide solution is 11wt%, adding 5% of plasma modified metal-organic framework nano material into the polyimide solution, and stirring by ultrasonic to obtain film casting solution; pouring the casting solution on a glass plate, placing the glass plate in a vacuum drying oven, drying for 24 hours, and naturally cooling to room temperature to obtain the plasma modified metal-organic framework/polyimide mixed matrix film.
Example 3
(1) 0.3g of pyrazine and 0.38g of ZnSiF were added 6 Respectively dissolving in 6ml of methanol to form uniform solutions; under the combined action of ultrasonic wave and ice bath, the methanol solution of pyrazine is added into ZnSiF drop by drop 6 Synthesizing nano material in methanol solution; centrifuging the reacted solution, cleaning the collected solid with methanol for multiple times, vacuum drying, and grinding to obtain the metal organic framework nano material.
(2) Placing the metal organic framework nano material in a circular chamber, and introducing an air source Ar/O 2 And (3) replacing the gas in the original chamber, setting the frequency of plasma to 13.56MHz, gradually increasing the voltage, and treating for 9min to obtain the plasma modified metal-organic framework nano material.
(3) 4,4' - (hexafluoroisopropenyl) diphthalic anhydride and 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane/2, 2-bis (4-aminophenyl) hexafluoropropane are used as monomer raw materials to prepare a polyamic acid solution, and triethylamine is used for catalysis and acetic anhydride is used for dehydration to synthesize the polyimide film matrix.
(4) Preparing polyimide solution with polyimide film matrix, wherein the solid content of the polyimide solution is 11wt%, adding 5% of plasma modified metal-organic framework nano material into the polyimide solution, and stirring by ultrasonic to obtain film casting solution; pouring the casting solution on a glass plate, placing the glass plate in a vacuum drying oven, drying for 24 hours, and naturally cooling to room temperature to obtain the plasma modified metal-organic framework/polyimide mixed matrix film.
Example 4
(1) 0.3g of pyrazine and 0.38g of ZnSiF were added 6 Respectively dissolving in 6ml of methanol to form uniform solutions; under the combined action of ultrasonic wave and ice bath, the methanol solution of pyrazine is added into ZnSiF drop by drop 6 Synthesizing nano material in methanol solution; centrifuging the reacted solution, cleaning the collected solid with methanol for multiple times, vacuum drying, and grinding to obtain the metal organic framework nano material.
(2) Placing the metal organic framework nano material in a circular chamber, and introducing an air source Ar/O 2 And (3) replacing the gas in the original chamber, setting the frequency of plasma to 13.56MHz, gradually increasing the voltage, and treating for 12min to obtain the plasma modified metal-organic framework nano material.
(3) 4,4' - (hexafluoroisopropenyl) diphthalic anhydride and 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane/2, 2-bis (4-aminophenyl) hexafluoropropane are used as monomer raw materials to prepare a polyamic acid solution, and triethylamine is used for catalysis and acetic anhydride is used for dehydration to synthesize the polyimide film matrix.
(4) Preparing polyimide solution with polyimide film matrix, wherein the solid content of the polyimide solution is 11wt%, adding 5% of plasma modified metal-organic framework nano material into the polyimide solution, and stirring by ultrasonic to obtain film casting solution; pouring the casting solution on a glass plate, placing the glass plate in a vacuum drying oven, drying for 24 hours, and naturally cooling to room temperature to obtain the plasma modified metal-organic framework/polyimide mixed matrix film.
Example 5
(1) 0.3g of pyrazine and 0.38g of ZnSiF were added 6 Respectively dissolving in 6ml of methanol to form uniform solutions; under the combined action of ultrasonic wave and ice bath, the methanol solution of pyrazine is dropped dropwiseAdded to ZnSiF 6 Synthesizing nano material in methanol solution; centrifuging the reacted solution, cleaning the collected solid with methanol for multiple times, vacuum drying, and grinding to obtain the metal organic framework nano material.
(2) Placing the metal organic framework nano material in a circular chamber, and introducing an air source Ar/NH 3 ·H 2 O replaces gas in the original cavity, the frequency of plasma is set to 13.56MHz, the voltage is gradually increased, and the plasma is processed for 3min, so that the plasma modified metal-organic framework nano material is obtained.
(3) 4,4' - (hexafluoroisopropenyl) diphthalic anhydride and 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane/2, 2-bis (4-aminophenyl) hexafluoropropane are used as monomer raw materials to prepare a polyamic acid solution, and triethylamine is used for catalysis and acetic anhydride is used for dehydration to synthesize the polyimide film matrix.
(4) Preparing polyimide solution with polyimide film matrix, wherein the solid content of the polyimide solution is 11wt%, adding 5% of plasma modified metal-organic framework nano material into the polyimide solution, and stirring by ultrasonic to obtain film casting solution; pouring the casting solution on a glass plate, placing the glass plate in a vacuum drying oven, drying for 24 hours, and naturally cooling to room temperature to obtain the plasma modified metal-organic framework/polyimide mixed matrix film.
Example 6
(1) 0.3g of pyrazine and 0.38g of ZnSiF were added 6 Respectively dissolving in 6ml of methanol to form uniform solutions; under the combined action of ultrasonic wave and ice bath, the methanol solution of pyrazine is added into ZnSiF drop by drop 6 Synthesizing nano material in methanol solution; centrifuging the reacted solution, cleaning the collected solid with methanol for multiple times, vacuum drying, and grinding to obtain the metal organic framework nano material.
(2) Placing the metal organic framework nano material in a circular chamber, and introducing an air source Ar/NH 3 ·H 2 O replaces gas in the original cavity, the frequency of plasma is set to 13.56MHz, the voltage is gradually increased, and the plasma is processed for 6min, so that the plasma modified metal-organic framework nano material is obtained.
(3) 4,4' - (hexafluoroisopropenyl) diphthalic anhydride and 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane/2, 2-bis (4-aminophenyl) hexafluoropropane are used as monomer raw materials to prepare a polyamic acid solution, and triethylamine is used for catalysis and acetic anhydride is used for dehydration to synthesize the polyimide film matrix.
(4) Preparing polyimide solution with polyimide film matrix, wherein the solid content of the polyimide solution is 11wt%, adding 5% of plasma modified metal-organic framework nano material into the polyimide solution, and stirring by ultrasonic to obtain film casting solution; pouring the casting solution on a glass plate, placing the glass plate in a vacuum drying oven, drying for 24 hours, and naturally cooling to room temperature to obtain the plasma modified metal-organic framework/polyimide mixed matrix film.
Example 7
(1) 0.3g of pyrazine and 0.38g of ZnSiF were added 6 Respectively dissolving in 6ml of methanol to form uniform solutions; under the combined action of ultrasonic wave and ice bath, the methanol solution of pyrazine is added into ZnSiF drop by drop 6 Synthesizing nano material in methanol solution; centrifuging the reacted solution, cleaning the collected solid with methanol for multiple times, vacuum drying, and grinding to obtain the metal organic framework nano material.
(2) Placing the metal organic framework nano material in a circular chamber, and introducing an air source Ar/NH 3 ·H 2 O replaces gas in the original cavity, the frequency of plasma is set to 13.56MHz, the voltage is gradually increased, and the plasma is processed for 9min, so that the plasma modified metal-organic framework nano material is obtained.
(3) 4,4' - (hexafluoroisopropenyl) diphthalic anhydride and 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane/2, 2-bis (4-aminophenyl) hexafluoropropane are used as monomer raw materials to prepare a polyamic acid solution, and triethylamine is used for catalysis and acetic anhydride is used for dehydration to synthesize the polyimide film matrix.
(4) Preparing polyimide solution with polyimide film matrix, wherein the solid content of the polyimide solution is 11wt%, adding 5% of plasma modified metal-organic framework nano material into the polyimide solution, and stirring by ultrasonic to obtain film casting solution; pouring the casting solution on a glass plate, placing the glass plate in a vacuum drying oven, drying for 24 hours, and naturally cooling to room temperature to obtain the plasma modified metal-organic framework/polyimide mixed matrix film.
Example 8
(1) 0.3g of pyrazine and 0.38g of ZnSiF were added 6 Respectively dissolving in 6ml of methanol to form uniform solutions; under the combined action of ultrasonic wave and ice bath, the methanol solution of pyrazine is added into ZnSiF drop by drop 6 Synthesizing nano material in methanol solution; centrifuging the reacted solution, cleaning the collected solid with methanol for multiple times, vacuum drying, and grinding to obtain the metal organic framework nano material.
(2) Placing the metal organic framework nano material in a circular chamber, and introducing an air source Ar/NH 3 ·H 2 O replaces gas in the original cavity, the frequency of plasma is set to 13.56MHz, the voltage is gradually increased, and the plasma is processed for 12min, so that the plasma modified metal-organic framework nano material is obtained.
(3) 4,4' - (hexafluoroisopropenyl) diphthalic anhydride and 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane/2, 2-bis (4-aminophenyl) hexafluoropropane are used as monomer raw materials to prepare a polyamic acid solution, and triethylamine is used for catalysis and acetic anhydride is used for dehydration to synthesize the polyimide film matrix.
(4) Preparing polyimide solution with polyimide film matrix, wherein the solid content of the polyimide solution is 11wt%, adding 5% of plasma modified metal-organic framework nano material into the polyimide solution, and stirring by ultrasonic to obtain film casting solution; pouring the casting solution on a glass plate, placing the glass plate in a vacuum drying oven, drying for 24 hours, and naturally cooling to room temperature to obtain the plasma modified metal-organic framework/polyimide mixed matrix film.
Example 9
(1) 0.3g of pyrazine and 0.38g of ZnSiF were added 6 Respectively dissolving in 6ml of methanol to form uniform solutions; under the combined action of ultrasonic wave and ice bath, the methanol solution of pyrazine is added into ZnSiF drop by drop 6 Synthesizing nano material in methanol solution; centrifuging the reacted solution, cleaning the collected solid with methanol for multiple times, vacuum drying, and grinding to obtain the metal organic framework nano material.
(2) Placing the metal-organic framework nano-materialIn the round chamber, air source Ar/O is introduced 2 And (3) replacing the gas in the original chamber, setting the frequency of plasma to 13.56MHz, gradually increasing the voltage, and treating for 9min to obtain the plasma modified metal-organic framework nano material.
(3) 4,4' - (hexafluoroisopropenyl) diphthalic anhydride and 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane/2, 2-bis (4-aminophenyl) hexafluoropropane are used as monomer raw materials to prepare a polyamic acid solution, and triethylamine is used for catalysis and acetic anhydride is used for dehydration to synthesize the polyimide film matrix.
(4) Preparing polyimide solution with polyimide film matrix, wherein the solid content of the polyimide solution is 11wt%, adding 10% of plasma modified metal-organic framework nano material into the polyimide solution, and stirring ultrasonically to obtain film casting solution; pouring the casting solution on a glass plate, placing the glass plate in a vacuum drying oven, drying for 24 hours, and naturally cooling to room temperature to obtain the plasma modified metal-organic framework/polyimide mixed matrix film.
Example 10
(1) 0.3g of pyrazine and 0.38g of ZnSiF were added 6 Respectively dissolving in 6ml of methanol to form uniform solutions; under the combined action of ultrasonic wave and ice bath, the methanol solution of pyrazine is added into ZnSiF drop by drop 6 Synthesizing nano material in methanol solution; centrifuging the reacted solution, cleaning the collected solid with methanol for multiple times, vacuum drying, and grinding to obtain the metal organic framework nano material.
(2) Placing the metal organic framework nano material in a circular chamber, and introducing an air source Ar/O 2 And (3) replacing the gas in the original chamber, setting the frequency of plasma to 13.56MHz, gradually increasing the voltage, and treating for 9min to obtain the plasma modified metal-organic framework nano material.
(3) 4,4' - (hexafluoroisopropenyl) diphthalic anhydride and 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane/2, 2-bis (4-aminophenyl) hexafluoropropane are used as monomer raw materials to prepare a polyamic acid solution, and triethylamine is used for catalysis and acetic anhydride is used for dehydration to synthesize the polyimide film matrix.
(4) Preparing polyimide solution with polyimide film matrix, wherein the solid content of the polyimide solution is 11wt%, adding 15% of plasma modified metal-organic framework nano material into the polyimide solution, and stirring by ultrasonic to obtain film casting solution; pouring the casting solution on a glass plate, placing the glass plate in a vacuum drying oven, drying for 24 hours, and naturally cooling to room temperature to obtain the plasma modified metal-organic framework/polyimide mixed matrix film.
Example 11
(1) 0.3g of pyrazine and 0.38g of ZnSiF were added 6 Respectively dissolving in 6ml of methanol to form uniform solutions; under the combined action of ultrasonic wave and ice bath, the methanol solution of pyrazine is added into ZnSiF drop by drop 6 Synthesizing nano material in methanol solution; centrifuging the reacted solution, cleaning the collected solid with methanol for multiple times, vacuum drying, and grinding to obtain the metal organic framework nano material.
(2) Placing the metal organic framework nano material in a circular chamber, and introducing an air source Ar/O 2 And (3) replacing the gas in the original chamber, setting the frequency of plasma to 13.56MHz, gradually increasing the voltage, and treating for 9min to obtain the plasma modified metal-organic framework nano material.
(3) 4,4' - (hexafluoroisopropenyl) diphthalic anhydride and 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane/2, 2-bis (4-aminophenyl) hexafluoropropane are used as monomer raw materials to prepare a polyamic acid solution, and triethylamine is used for catalysis and acetic anhydride is used for dehydration to synthesize the polyimide film matrix.
(4) Preparing polyimide solution with polyimide film matrix, wherein the solid content of the polyimide solution is 11wt%, adding 20% of plasma modified metal-organic framework nano material into the polyimide solution, and stirring by ultrasonic to obtain film casting solution; pouring the casting solution on a glass plate, placing the glass plate in a vacuum drying oven, drying for 24 hours, and naturally cooling to room temperature to obtain the plasma modified metal-organic framework/polyimide mixed matrix film.
Example 12
(1) 0.3g of pyrazine and 0.38g of ZnSiF were added 6 Respectively dissolving in 6ml of methanol to form uniform solutions; under the combined action of ultrasonic wave and ice bath, the methanol solution of pyrazine is added into ZnSi drop by dropF 6 Synthesizing nano material in methanol solution; centrifuging the reacted solution, cleaning the collected solid with methanol for multiple times, vacuum drying, and grinding to obtain the metal organic framework nano material.
(2) Placing the metal organic framework nano material in a circular chamber, and introducing an air source Ar/NH 3 ·H 2 O replaces gas in the original cavity, the frequency of plasma is set to 13.56MHz, the voltage is gradually increased, and the plasma is processed for 9min, so that the plasma modified metal-organic framework nano material is obtained.
(3) 4,4' - (hexafluoroisopropenyl) diphthalic anhydride and 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane/2, 2-bis (4-aminophenyl) hexafluoropropane are used as monomer raw materials to prepare a polyamic acid solution, and triethylamine is used for catalysis and acetic anhydride is used for dehydration to synthesize the polyimide film matrix.
(4) Preparing polyimide solution with polyimide film matrix, wherein the solid content of the polyimide solution is 11wt%, adding 10% of plasma modified metal-organic framework nano material into the polyimide solution, and stirring ultrasonically to obtain film casting solution; pouring the casting solution on a glass plate, placing the glass plate in a vacuum drying oven, drying for 24 hours, and naturally cooling to room temperature to obtain the plasma modified metal-organic framework/polyimide mixed matrix film.
Example 13
(1) 0.3g of pyrazine and 0.38g of ZnSiF were added 6 Respectively dissolving in 6ml of methanol to form uniform solutions; under the combined action of ultrasonic wave and ice bath, the methanol solution of pyrazine is added into ZnSiF drop by drop 6 Synthesizing nano material in methanol solution; centrifuging the reacted solution, cleaning the collected solid with methanol for multiple times, vacuum drying, and grinding to obtain the metal organic framework nano material.
(2) Placing the metal organic framework nano material in a circular chamber, and introducing an air source Ar/NH 3 ·H 2 O replaces gas in the original cavity, the frequency of plasma is set to 13.56MHz, the voltage is gradually increased, and the plasma is processed for 9min, so that the plasma modified metal-organic framework nano material is obtained.
(3) 4,4' - (hexafluoroisopropenyl) diphthalic anhydride and 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane/2, 2-bis (4-aminophenyl) hexafluoropropane are used as monomer raw materials to prepare a polyamic acid solution, and triethylamine is used for catalysis and acetic anhydride is used for dehydration to synthesize the polyimide film matrix.
(4) Preparing polyimide solution with polyimide film matrix, wherein the solid content of the polyimide solution is 11wt%, adding 15% of plasma modified metal-organic framework nano material into the polyimide solution, and stirring by ultrasonic to obtain film casting solution; pouring the casting solution on a glass plate, placing the glass plate in a vacuum drying oven, drying for 24 hours, and naturally cooling to room temperature to obtain the plasma modified metal-organic framework/polyimide mixed matrix film.
Example 14
(1) 0.3g of pyrazine and 0.38g of ZnSiF were added 6 Respectively dissolving in 6ml of methanol to form uniform solutions; under the combined action of ultrasonic wave and ice bath, the methanol solution of pyrazine is added into ZnSiF drop by drop 6 Synthesizing nano material in methanol solution; centrifuging the reacted solution, cleaning the collected solid with methanol for multiple times, vacuum drying, and grinding to obtain the metal organic framework nano material.
(2) Placing the metal organic framework nano material in a circular chamber, and introducing an air source Ar/NH 3 ·H 2 O replaces gas in the original cavity, the frequency of plasma is set to 13.56MHz, the voltage is gradually increased, and the plasma is processed for 9min, so that the plasma modified metal-organic framework nano material is obtained.
(3) 4,4' - (hexafluoroisopropenyl) diphthalic anhydride and 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane/2, 2-bis (4-aminophenyl) hexafluoropropane are used as monomer raw materials to prepare a polyamic acid solution, and triethylamine is used for catalysis and acetic anhydride is used for dehydration to synthesize the polyimide film matrix.
(4) Preparing polyimide solution with polyimide film matrix, wherein the solid content of the polyimide solution is 11wt%, adding 20% of plasma modified metal-organic framework nano material into the polyimide solution, and stirring by ultrasonic to obtain film casting solution; pouring the casting solution on a glass plate, placing the glass plate in a vacuum drying oven, drying for 24 hours, and naturally cooling to room temperature to obtain the plasma modified metal-organic framework/polyimide mixed matrix film.
The dianhydride used for producing polyimide in examples 1 to 14 may be any of pyromellitic dianhydride, 4 '-biphenyl ether dianhydride, bisphenol dianhydride, biphenyl tetracarboxylic dianhydride, 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 3',4 '-benzophenone tetracarboxylic dianhydride and fluorenyl dianhydride, and has the same effect as 4,4' - (hexafluoroisopropenyl) diphthalic anhydride.
The diamine used for preparing polyimide in examples 1 to 14 may also be any of 4, 4-diaminodiphenylmethane, 4-diaminodiphenyl ether, 1, 4-bis (4-aminophenoxy) benzene, 2,3,5, 6-tetramethyl-1, 4-phenylenediamine, 1,3, 5-tris (4-aminophenoxy) benzene, 2,3,5, 6-tetrafluoro-1, 4-phenylenediamine and 2,4, 6-trimethyl-1, 3-phenylenediamine, with the same effect as 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane/2, 2-bis (4-aminophenyl) hexafluoropropane.
Comparative example 1
(1) Preparing a polyamide acid solution by taking 4,4' - (hexafluoroisopropenyl) isophthalic anhydride and 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane/2, 2-bis (4-aminophenyl) hexafluoropropane as monomer raw materials, and synthesizing a polyimide film substrate by dehydrating acetic anhydride under the catalysis of triethylamine;
(2) And (3) dissolving the polyimide matrix to obtain a casting solution, pouring the casting solution on a glass plate, placing the glass plate in a vacuum drying oven, drying for 24 hours, and naturally cooling to room temperature to obtain the polyimide film.
Comparative example 2
(1) 0.3g of pyrazine and 0.38g of ZnSiF were added 6 Respectively dissolving in 6ml of methanol to form uniform solutions; under the combined action of ultrasonic wave and ice bath, the methanol solution of pyrazine is added into ZnSiF drop by drop 6 Synthesizing nano material in methanol solution; centrifuging the reacted solution, cleaning the collected solid with methanol for multiple times, vacuum drying, and grinding to obtain the metal organic framework nano material.
(2) 4,4' - (hexafluoroisopropenyl) diphthalic anhydride and 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane/2, 2-bis (4-aminophenyl) hexafluoropropane are used as monomer raw materials to prepare a polyamic acid solution, and triethylamine is used for catalysis and acetic anhydride is used for dehydration to synthesize the polyimide film matrix.
(3) Adding 15% of unmodified metal-organic framework nano materials into polyimide solution, wherein the solid content of the polyimide solution is 11wt%, and carrying out ultrasonic stirring to obtain a casting solution; pouring the casting solution on a glass plate, placing the glass plate in a vacuum drying oven, drying for 24 hours, and naturally cooling to room temperature to obtain the metal-organic framework/polyimide mixed matrix film.
The separation performance of the prepared membrane is tested by adopting a penetration test evaluation device, and the test structure is as follows:
FIG. 1 is a FTIR spectrum of the plasma modified nanomaterial made in comparative example 2, example 10, and example 13 of the present invention. As is clear from the graph, the absorption peak is 3200 to 3400cm -1 The band at this point is the stretching vibration of-OH, 1630cm -1 And 1335cm -1 The band at this point is the vibration of the triazine ring. Compared with the nanomaterial prepared in comparative example 2, the plasma modified nanomaterial prepared in example 10 is between 3200 and 3500cm -1 And 1335cm -1 The absorption band at the location broadens, indicating more stretching vibration of-OH. The plasma modified nanomaterial prepared in example 13 was at 3320cm -1 Characteristic absorption peaks appear here due to the formation of amino groups at the surface of the nanomaterial.
FIG. 2 is a FTIR spectrum of a polyimide film produced in comparative example 1, a mixed matrix film produced in comparative example 2, example 10 and example 13 according to the present invention. As can be seen from the graph, the absorption peak was 1780cm -1 The characteristic band at the position is an asymmetric vibration of c=o (amide I band), 1720cm -1 The absorption of (a) is C=O symmetrical vibration (amide II band), 1500cm -1 The local absorption band is the framework stretching vibration of the aromatic ring. 1369cm -1 The peak at this point is the C-N stretching vibration (amide III band) in the imide ring, 718cm -1 The peak at the position is the imide ring flexural vibration (amide IV band). The addition of the nanomaterial interacts with the polymer matrix as compared to the polyimide film prepared in comparative example 1. Plasma is carried outThe modified metal organic framework nano material is added into polyimide matrix to form hydrogen bond or cross-linking after doping. For example, the infrared absorption peak is 3200-3400 cm -1 Absorption peaks at the locations are enhanced while at the same time 1100cm -1 The absorption peak at this point shifts to low wavenumbers, indicating that hydrogen bonds are formed between the nanomaterial and the polymer, and that the interaction of the hydrogen bonds will increase the affinity between the nanomaterial and the polymer, thereby achieving better interfacial compatibility.
FIG. 3 is a TGA graph of the plasma modified nanomaterial made in comparative example 2, example 10, and example 13 of the present invention. From the graph, the characteristic decomposition temperatures (90% by weight) of several nanomaterials were 162 ℃, 157 ℃ and 154 ℃, respectively. Due to CO 2 The trapped separation temperature is typically less than 100 ℃, so these nanomaterials can meet the temperature requirements of gas separation.
FIG. 4 is a TGA graph of the polyimide films produced in comparative example 1, the mixed matrix films produced in comparative example 2, example 10 and example 13 of the present invention. As can be seen from the figure, compared with example 1, the membrane material added with the nanomaterial can still meet the requirement of gas separation on temperature.
FIG. 5 shows XRD patterns of the polyimide films produced in comparative example 1, and the mixed matrix films produced in comparative example 2, example 10 and example 13 according to the present invention. As can be seen from the graph, the film materials prepared by the invention all show amorphous diffraction peaks. The polyimide film prepared in comparative example 1 had only one diffraction peak at 2 theta to 16 deg., and the average chain spacing wasThe mixed matrix films prepared in comparative example 2, example 10 and example 13 have reduced diffraction peak intensities of the polymers after the addition of the nanomaterial, as compared to comparative example 1. The nano material is added to effectively break the accumulation of the polymer chain segments, so that the crystallinity is reduced, and the permeation of gas is facilitated. In addition, compared with a mixed matrix film added with different gas source plasma modified nano materials, ar/NH is added 3 ·H 2 O gas source plasma modified metal-organic framework nano materialThe mixed matrix membrane obtains the best permeation separation performance, and then Ar/O is added 2 The air source plasma modified metal organic framework nano material and the mixed matrix film added with the unmodified nano material. This shows that the addition of the plasma modified metal organic framework nanomaterial to the polyimide matrix can effectively enhance the gas permeation separation performance.
FIGS. 6 (a 1), (a 2), (a 3) and (a 4) are SEM images of the surfaces of films produced in comparative examples 1,2, 10 and 13, respectively, according to the present invention; (b1) (b 2), (b 3) and (b 4) are SEM images of cross-sections of films produced in comparative examples 1,2, 10 and 13 of the present invention, respectively. From the figure, the film produced exhibited a smooth, dense, defect-free morphology. In addition, it can be seen that three kinds of nanoparticles of comparative example 2, example 10 and example 13 were added with Ar/NH 3 ·H 2 The mixed matrix film prepared by the O gas source plasma modified metal-organic framework nano material has the best dispersion performance. This shows that the prepared ion modified metal organic framework nano material enhances the compatibility of organic and inorganic interfaces and can be effectively dispersed in a polymer matrix.
The plasma modified metal-organic framework/polyimide mixed matrix membrane prepared by the invention is applied to gas separation.
As shown in Table 1, the films prepared in examples 1 to 14, comparative example 1 and comparative example 2 according to the present invention were subjected to CO 2 /N 2 And CO 2 /CH 4 As can be seen from the table, ar/NH was added 3 ·H 2 The mixed matrix film prepared by the O gas source plasma modified metal-organic framework nano material has good CO 2 Permeability and selectivity, especially under the experimental conditions of example 13, the performance of the prepared plasma modified metal organic framework nanomaterial-doped polyimide mixed matrix film was optimal.
Table 1 membrane pairs CO prepared in examples 1 to 14, comparative example 1 and comparative example 2 2 /N 2 And CO 2 /CH 4 Permeation rate and selectivity test for separation
Units: 1 barrer=10 -10 cm 3 (STP)·cm/(cm 2 ·s·cmHg)
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the above embodiments, one skilled in the art may make modifications and equivalents to the specific embodiments of the present invention, and any modifications and equivalents not departing from the spirit and scope of the present invention are within the scope of the claims of the present invention.
Claims (10)
1. The preparation method of the plasma modified metal-organic framework/polyimide mixed matrix film is characterized by comprising the following steps of:
respectively dissolving pyrazine and zinc fluosilicate in methanol to form solutions; adding a methanol solution of pyrazine into a methanol solution of zinc fluosilicate;
centrifuging the reacted solution, cleaning the collected solid with methanol for many times, vacuum drying and grinding to obtain a metal organic framework nano material;
placing the metal organic framework nano material in a preset air source, setting the plasma frequency to be 13.56MHz, gradually increasing the voltage, and obtaining the plasma modified metal organic framework nano material after the treatment of the preset time;
preparing a polyamic acid solution by taking dianhydride and diamine as monomer raw materials, and obtaining a polyimide film substrate through catalysis and dehydration;
preparing polyimide solution by using polyimide film matrix, adding the plasma modified metal organic framework nano material into the polyimide solution to obtain casting solution, pouring the casting solution on a glass plate, drying and cooling to room temperature to obtain the plasma modified metal organic framework/polyimide mixed matrix film.
2. The method for preparing a plasma modified metal-organic framework/polyimide mixed matrix film according to claim 1, wherein the preset gas source is Ar/O 2 Or Ar/NH 3 ·H 2 O。
3. The method for preparing a plasma modified metal-organic framework/polyimide mixed matrix film according to claim 1, wherein the preset time for the plasma treatment is 3 to 12 minutes.
4. The method for preparing a plasma modified metal-organic framework/polyimide mixed matrix film according to claim 1, wherein the dianhydride is any one of pyromellitic dianhydride, 4'- (hexafluoroisopropenyl) diphthalic anhydride, 4' -biphenyl ether dianhydride, bisphenol dianhydride, biphenyl tetracarboxylic dianhydride, 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 3', 4' -benzophenone tetracarboxylic dianhydride and fluorenyl dianhydride.
5. The method for producing a plasma-modified metal-organic framework/polyimide mixed matrix film according to claim 1, wherein the diamine is any one of 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane/2, 2-bis (4-aminophenyl) hexafluoropropane, 4-diaminodiphenylmethane, 4-diaminodiphenyl ether, 1, 4-bis (4-aminophenoxy) benzene, 2,3,5, 6-tetramethyl-1, 4-phenylenediamine, 1,3, 5-tris (4-aminophenoxy) benzene, 2,3,5, 6-tetrafluoro-1, 4-phenylenediamine, and 2,4, 6-trimethyl-1, 3-phenylenediamine.
6. The method for preparing a plasma modified metal-organic framework/polyimide mixed matrix film according to claim 1, wherein the polyimide solution has a solid content of 11wt%.
7. The preparation method of the plasma modified metal-organic framework/polyimide mixed matrix membrane according to claim 1, wherein the doping content of the plasma modified metal-organic framework nano material in the casting solution is 0-20%.
8. The method for preparing the plasma modified metal-organic framework/polyimide mixed matrix membrane according to claim 1, wherein a dehydrating agent adopted in the preparation of the polyimide membrane matrix is acetic anhydride, and a catalyst adopted in the catalysis is triethylamine.
9. The mixed matrix membrane prepared by the method for preparing a plasma modified metal-organic framework/polyimide mixed matrix membrane according to any one of claims 1 to 8, wherein hydrogen bonds or crosslinks are formed between the plasma modified metal-organic framework nanomaterial and polyimide.
10. The use of a plasma modified metal organic framework/polyimide mixed matrix membrane according to claim 9 in gas separation.
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