CN113307999A - Preparation method of amino polyaryletherketone/graphene oxide composite material - Google Patents
Preparation method of amino polyaryletherketone/graphene oxide composite material Download PDFInfo
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- CN113307999A CN113307999A CN202110581647.8A CN202110581647A CN113307999A CN 113307999 A CN113307999 A CN 113307999A CN 202110581647 A CN202110581647 A CN 202110581647A CN 113307999 A CN113307999 A CN 113307999A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 49
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 37
- 229920006260 polyaryletherketone Polymers 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002131 composite material Substances 0.000 title claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 28
- 239000012528 membrane Substances 0.000 claims abstract description 25
- 239000011159 matrix material Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 64
- 239000000243 solution Substances 0.000 claims description 61
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 44
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 42
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 40
- 239000012153 distilled water Substances 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 33
- 229920000642 polymer Polymers 0.000 claims description 33
- 238000001914 filtration Methods 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 21
- 239000000706 filtrate Substances 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 21
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 20
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 20
- 239000003814 drug Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 claims description 14
- 238000005360 mashing Methods 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims description 14
- 229930185605 Bisphenol Natural products 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- BWQOPMJTQPWHOZ-UHFFFAOYSA-N (2,3-difluorophenyl)-phenylmethanone Chemical compound FC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1F BWQOPMJTQPWHOZ-UHFFFAOYSA-N 0.000 claims description 9
- 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 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 7
- 239000012954 diazonium Substances 0.000 claims description 7
- 150000001989 diazonium salts Chemical class 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 235000010288 sodium nitrite Nutrition 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- 239000008367 deionised water Substances 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 230000035699 permeability Effects 0.000 abstract description 7
- 230000032683 aging Effects 0.000 abstract 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 22
- 239000007789 gas Substances 0.000 description 15
- 239000002253 acid Substances 0.000 description 6
- -1 amino bisphenol Chemical compound 0.000 description 5
- 239000005357 flat glass Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000011085 pressure filtration Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000722949 Apocynum Species 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
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- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- 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
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- 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
- B01D71/021—Carbon
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- 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
- B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
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- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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Abstract
The invention discloses a preparation method of an amino polyaryletherketone/graphene oxide composite material, and relates to a mixed matrix gas separation membrane material and a preparation method thereof. The mass percentage of the two-dimensional layered material graphene oxide in the mixed matrix gas separation membrane material is 1-5%. The two are mixed to regulate the gas permeability and selectivity cooperatively, so that the novel mixed matrix gas separation membrane containing the amino polyaryletherketone/graphene oxide composite material has better gas permeability and separation performance, good thermal stability and physical aging resistance, and wide application prospect.
Description
Technical Field
The invention belongs to the field of high-molecular chemical gas separation membranes, and particularly relates to a mixed matrix gas separation membrane material and a preparation method thereof.
Background
CO2As a greenhouse gas, is the main product of fossil combustion. The greenhouse effect caused by the large amount of greenhouse gases is the biggest challenge for people from the beginning of this century. With the development of new fossil fuel power plants, the growth of energy-intensive industries, further increases in carbon dioxide emissions appear to be unavoidable. Therefore, Carbon Capture and Sequestration (CCS) is an important component of many national and global emission reduction programs. Compared with the traditional gas separation process, the membrane separation process has the advantages of simple operation, small occupied area, low cost, strong processability and the like, and becomes an ideal method for separating carbon dioxide. The permeability and selectivity of a gas separation membrane are important indicators for evaluating the overall performance thereof. However, there is a trade-off between gas permeability and selectivity, i.e. as the permeability increases, the selectivity decreases, which is called the Robertsonian ceiling by researchers. Therefore, the preparation of a gas separation membrane having both high permeability and high selectivity is a constantly sought goal of researchers. The hybrid matrix membrane can combine the advantages of polymer matrix and filler, which is an economically effective means of breaking the upper limit of apocynum, in the last two decades when mixed in CO2The use in separations has led to extensive research. Glassy aromatic polymers having a rigid benzene ring in the main chain are often used as separation membrane materials because of their high selectivity, mechanical properties, chemical resistance, and continuous operation at high temperatures. The polyaryletherketone polymer has good thermal stability and strong mechanical strength, so that the functionalized polyaryletherketone has been widely noticed as a membrane material. In contrast, the experiment selects the polyaryletherketone membrane material with higher selectivity, and introduces amino (-NH)2) To improve the separation performance of the polymer membrane. However, the aromatic polymer film has low permeability and thus is not effective in practical production. Graphene oxide is a derivative of graphene, and is also a new material which is hot nowadays. The graphene oxide is at the edge of the graphene sheet layerThe novel functional material obtained by introducing a large number of oxygen-containing functional groups into the edge and the interior mainly contains carboxyl groups on the edge of the graphene oxide, and the interior of the sheet layer mainly contains functional groups such as hydroxyl groups, epoxy groups and the like. On one hand, the introduction of the oxygen-containing functional group increases the interlayer spacing of graphene, so that the interlayer spacing is increased from 0.34 nm to about 1 nm; on the other hand, the introduction of the oxygen-containing functional groups enables the graphene oxide to have good dispersion performance in a polar solution. In recent years, studies on graphene oxide in the field of gas separation have been successively reported. Therefore, the experiment prepares an amino polyaryletherketone/graphene oxide composite material, and a novel mixed matrix gas separation membrane with graphene oxide as a filler and amino polyaryletherketone as a membrane matrix is prepared, so that the selectivity of a pure polymer membrane is further increased.
Disclosure of Invention
The invention provides a novel mixed matrix gas separation membrane containing an amino polyaryletherketone/graphene oxide composite material and a preparation method thereof. A preparation method of an amino polyaryletherketone/graphene oxide composite material comprises the following specific steps:
the method comprises the following steps: adopting diazo salt reaction, reducing and ammoniating reaction to prepare bisphenol monomer (4- (2, 5-diphenol) aniline) containing amino;
step two: adding the self-made amino-containing bisphenol monomer (4- (2, 5-diphenol) aniline) and difluorobenzophenone prepared in the step one into a reaction vessel for polymerization reaction by a direct polycondensation method to obtain amino polyaryletherketone (Am-PAEK);
step three: dissolving the amino polyaryletherketone polymer obtained in the step two to obtain a polymer solution;
step four: adding a certain amount of Graphene Oxide (GO) into chloroform, stirring for 12 hours, and then carrying out ultrasonic treatment at a low temperature of 35 ℃ for 72 hours to obtain a uniform graphene oxide dispersion liquid;
step five: and (3) uniformly mixing and stirring the graphene oxide dispersion liquid obtained in the fourth step and the polymer solution obtained in the third step, paving the mixture into a film after ultrasonic treatment, and soaking the paved film into methanol to finally obtain the novel mixed matrix gas separation film.
Preferably, in the above technical solution, the preparation method of the amino group-containing bisphenol monomer (4- (2, 5-diphenol) aniline) in step one is as follows: 13.84g of p-nitroaniline was added to a 500ml beaker, and 30ml of distilled water and then 30ml of absolute ethanol were added dropwise while stirring. 34ml of concentrated hydrochloric acid are added dropwise (half an hour over). 7.6g of sodium nitrite was dissolved in 50ml of distilled water, and the solution of nitrosic acid was added dropwise to the above p-nitroaniline solution (1 hour was completed). 8.64g of p-benzoquinone and 25.46g of sodium bicarbonate are weighed, the p-benzoquinone and the sodium bicarbonate are added into 100ml of water, the diazonium salt solution is dropwise added into the mixed solution of the p-benzoquinone and the sodium bicarbonate (after 1 hour), and the reaction is carried out for 4 hours after the dropwise addition. And after the reaction is finished, filtering the mixed solution under reduced pressure, and washing the mixed solution for 4-6 times by using distilled water until the filtrate is light yellow or colorless. Drying at 60 ℃. Adding the dried medicine into a three-mouth bottle connected with a condenser tube and stirring, adding a proper amount of zinc powder, heating in a water bath to 90 ℃, starting to dropwise add hydrochloric acid (dropwise adding is completed in half an hour), reacting for 4 hours, filtering while hot, standing and cooling the filtrate, separating out solids, filtering under reduced pressure, and drying at 60 ℃. Adding the dried medicine into a three-neck flask connected with a stirring and condensing tube, adding appropriate amount of distilled water, refluxing at 90 deg.C for 2 hr, filtering under reduced pressure, standing the filtrate, cooling to obtain pink needle-like solid, pressure filtering, and drying at 60 deg.C for use. The reaction equation is shown in the attached figure 1 of the specification.
Preferably, in the above technical solution, the preparation method of the amino polyaryletherketone (Am-PAEK) in step two is as follows: self-made amino-containing bisphenol monomer and difluorobenzophenone are mixed according to a molar ratio of 1: 1, putting materials into a three-mouth bottle connected with a stirrer, a water-carrying device, a condenser tube and a gas-guide tube, taking N-methyl pyrrolidone as a solvent, potassium carbonate as a salt forming agent, toluene as a water-carrying agent, refluxing at 130 ℃, beginning to drip the first drop of liquid in the condenser tube for timing, carrying water for 4 hours, evaporating toluene, raising the temperature of a system to 170 ℃, reacting for 30 hours, then cooling, discharging in cold water to obtain a strip polymer, mashing the obtained strip polymer by a mashing machine, boiling for 5-8 times by using distilled water, and then drying in a vacuum oven for 24 hours at 80 ℃ for later use. The reaction equation is shown in figure 2 in the attached figure of the specification.
Preferably, the solvent is one of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), or Dimethylsulfoxide (DMSO).
Preferably, the water-carrying agent is toluene.
Preferably, the mass ratio of the amino polyaryletherketone to the graphene oxide is 10: 1 to 5.
Drawings
FIG. 1 is a process for the preparation of an amino group-containing bisphenol monomer (4- (2, 5-biphenol) aniline);
FIG. 2A process for the preparation of amino polyaryletherketones (Am-PAEK).
Detailed description of the invention
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
13.84g of paranitroaniline is added into a 500ml beaker, 30ml of distilled water is dripped while stirring, and 30ml of absolute ethyl alcohol is dripped. 34ml of concentrated hydrochloric acid are added dropwise (half an hour over). 7.6g of sodium nitrite was dissolved in 50ml of distilled water, and the solution of nitrosic acid was added dropwise to the above p-nitroaniline solution (1 hour was completed). 8.64g of p-benzoquinone and 25.46g of sodium bicarbonate are weighed, the p-benzoquinone and the sodium bicarbonate are added into 100ml of water, the diazonium salt solution is dropwise added into the mixed solution of the p-benzoquinone and the sodium bicarbonate (after 1 hour), and the reaction is carried out for 4 hours after the dropwise addition. And after the reaction is finished, filtering the mixed solution under reduced pressure, and washing the mixed solution for 4-6 times by using distilled water until the filtrate is light yellow or colorless. Drying at 60 ℃. Adding the dried medicine into a three-mouth bottle connected with a condenser tube and stirring, adding a proper amount of zinc powder, heating in a water bath to 90 ℃, starting to dropwise add hydrochloric acid (dropwise adding is completed in half an hour), reacting for 4 hours, filtering while hot, standing and cooling the filtrate, separating out solids, filtering under reduced pressure, and drying at 60 ℃. Adding the dried medicine into a three-mouth bottle connected with a stirring and condensing tube, adding a proper amount of distilled water, refluxing for 2 hours at 90 ℃, filtering under reduced pressure when the medicine is hot, standing and cooling the filtrate to obtain a pink needle-shaped solid, and performing pressure filtration and drying at 60 ℃ for later use;
secondly, self-made amino bisphenol monomer and difluorobenzophenone are mixed according to a molar ratio of 1: 1, putting materials into a three-mouth bottle connected with a stirrer, a water-carrying device, a condenser tube and a gas-guide tube, taking N-methyl pyrrolidone as a solvent, potassium carbonate as a salt forming agent and toluene as a water-carrying agent, refluxing at 130 ℃, beginning timing when the first drop of liquid in the condenser tube is dripped, carrying water for 4 hours, evaporating the toluene, raising the temperature of a system to 170 ℃, reacting for 30 hours, then cooling, discharging in cold water to obtain a strip polymer, mashing the obtained strip polymer by a mashing machine, boiling for 5-8 times by using distilled water, and then drying in a vacuum oven for 24 hours at 80 ℃ for later use;
③ 0.01g of amino polyaryletherketone polymer is treated with 10ml of chloroform (CCl)3) Dissolving, and mechanically stirring the solution for 12 hours to obtain a uniformly mixed film forming solution;
fourthly, 0.001g of Graphene Oxide (GO) is added into 100ml of chloroform (CCl)3) Stirring for 12 hours, and then carrying out ultrasonic treatment for 72 hours at the low temperature of 35 ℃ to obtain a uniform graphene oxide dispersion liquid;
fifthly, mixing and stirring 5ml of the amino polyaryletherketone polymer solution obtained in the third step and 1ml of the graphene oxide dispersion solution obtained in the fourth step for 12 hours, carrying out ultrasonic treatment at the low temperature of 35 ℃ for 72 hours to obtain a uniform film forming solution, slowly pouring the film forming solution onto a smooth flat glass plate, slowly evaporating the solvent for 24 hours at room temperature, soaking the glass plate in methanol for demoulding after film forming, and drying. Thus obtaining the novel mixed matrix gas separation membrane with the mass fraction of the graphene oxide of 1%.
Example 2
13.84g of paranitroaniline is added into a 500ml beaker, 30ml of distilled water is dripped while stirring, and 30ml of absolute ethyl alcohol is dripped. 34ml of concentrated hydrochloric acid are added dropwise (half an hour over). 7.6g of sodium nitrite was dissolved in 50ml of distilled water, and the solution of nitrosic acid was added dropwise to the above p-nitroaniline solution (1 hour was completed). 8.64g of p-benzoquinone and 25.46g of sodium bicarbonate are weighed, the p-benzoquinone and the sodium bicarbonate are added into 100ml of water, the diazonium salt solution is dropwise added into the mixed solution of the p-benzoquinone and the sodium bicarbonate (after 1 hour), and the reaction is carried out for 4 hours after the dropwise addition. And after the reaction is finished, filtering the mixed solution under reduced pressure, and washing the mixed solution for 4-6 times by using distilled water until the filtrate is light yellow or colorless. Drying at 60 ℃. Adding the dried medicine into a three-mouth bottle connected with a condenser tube and stirring, adding a proper amount of zinc powder, heating in a water bath to 90 ℃, starting to dropwise add hydrochloric acid (dropwise adding is completed in half an hour), reacting for 4 hours, filtering while hot, standing and cooling the filtrate, separating out solids, filtering under reduced pressure, and drying at 60 ℃. Adding the dried medicine into a three-mouth bottle connected with a stirring and condensing tube, adding a proper amount of distilled water, refluxing for 2 hours at 90 ℃, filtering under reduced pressure when the medicine is hot, standing and cooling the filtrate to obtain a pink needle-shaped solid, and performing pressure filtration and drying at 60 ℃ for later use;
secondly, self-made amino bisphenol monomer and difluorobenzophenone are mixed according to a molar ratio of 1: 1, putting materials into a three-mouth bottle connected with a stirrer, a water-carrying device, a condenser tube and a gas-guide tube, taking N-methyl pyrrolidone as a solvent, potassium carbonate as a salt forming agent and toluene as a water-carrying agent, refluxing at 130 ℃, beginning timing when the first drop of liquid in the condenser tube is dripped, carrying water for 4 hours, evaporating the toluene, raising the temperature of a system to 170 ℃, reacting for 30 hours, then cooling, discharging in cold water to obtain a strip polymer, mashing the obtained strip polymer by a mashing machine, boiling for 5-8 times by using distilled water, and then drying in a vacuum oven for 24 hours at 80 ℃ for later use;
③ 0.01g of amino polyaryletherketone polymer is treated with 10ml of chloroform (CCl)3) Dissolving, and mechanically stirring the solution for 12 hours to obtain a uniformly mixed film forming solution;
fourthly, 0.002g of Graphene Oxide (GO) is added into 100ml of chloroform (CCl)3) Stirring for 12 hours, and then carrying out ultrasonic treatment for 72 hours at the low temperature of 35 ℃ to obtain a uniform graphene oxide dispersion liquid;
fifthly, mixing and stirring 5ml of the amino polyaryletherketone polymer solution obtained in the third step and 1ml of the graphene oxide dispersion solution obtained in the fourth step for 12 hours, carrying out ultrasonic treatment at the low temperature of 35 ℃ for 72 hours to obtain a uniform film forming solution, slowly pouring the film forming solution onto a smooth flat glass plate, slowly evaporating the solvent for 24 hours at room temperature, soaking the glass plate in methanol for demoulding after film forming, and drying. Thus obtaining the novel mixed matrix gas separation membrane with the graphene oxide mass fraction of 2%.
Example 3
13.84g of paranitroaniline is added into a 500ml beaker, 30ml of distilled water is dripped while stirring, and 30ml of absolute ethyl alcohol is dripped. 34ml of concentrated hydrochloric acid are added dropwise (half an hour over). 7.6g of sodium nitrite was dissolved in 50ml of distilled water, and the solution of nitrosic acid was added dropwise to the above p-nitroaniline solution (1 hour was completed). 8.64g of p-benzoquinone and 25.46g of sodium bicarbonate are weighed, the p-benzoquinone and the sodium bicarbonate are added into 100ml of water, the diazonium salt solution is dropwise added into the mixed solution of the p-benzoquinone and the sodium bicarbonate (after 1 hour), and the reaction is carried out for 4 hours after the dropwise addition. And after the reaction is finished, filtering the mixed solution under reduced pressure, and washing the mixed solution for 4-6 times by using distilled water until the filtrate is light yellow or colorless. Drying at 60 ℃. Adding the dried medicine into a three-mouth bottle connected with a condenser tube and stirring, adding a proper amount of zinc powder, heating in a water bath to 90 ℃, starting to dropwise add hydrochloric acid (dropwise adding is completed in half an hour), reacting for 4 hours, filtering while hot, standing and cooling the filtrate, separating out solids, filtering under reduced pressure, and drying at 60 ℃. Adding the dried medicine into a three-mouth bottle connected with a stirring and condensing tube, adding a proper amount of distilled water, refluxing for 2 hours at 90 ℃, filtering under reduced pressure when the medicine is hot, standing and cooling the filtrate to obtain a pink needle-shaped solid, and performing pressure filtration and drying at 60 ℃ for later use;
secondly, self-made amino bisphenol monomer and difluorobenzophenone are mixed according to a molar ratio of 1: 1, putting materials into a three-mouth bottle connected with a stirrer, a water-carrying device, a condenser tube and a gas-guide tube, taking N-methyl pyrrolidone as a solvent, potassium carbonate as a salt forming agent and toluene as a water-carrying agent, refluxing at 130 ℃, beginning timing when the first drop of liquid in the condenser tube is dripped, carrying water for 4 hours, evaporating the toluene, raising the temperature of a system to 170 ℃, reacting for 30 hours, then cooling, discharging in cold water to obtain a strip polymer, mashing the obtained strip polymer by a mashing machine, boiling for 5-8 times by using distilled water, and then drying in a vacuum oven for 24 hours at 80 ℃ for later use;
③ 0.01g of amino polyaryletherketone polymer is treated with 10ml of chloroform (CCl)3) Dissolving, and mechanically stirring the solution for 12 hours to obtain a uniformly mixed film forming solution;
fourthly, 0.003g of Graphene Oxide (GO) is added into 100ml of chloroform (CCl)3) Stirring for 12 hours, and then carrying out ultrasonic treatment for 72 hours at the low temperature of 35 ℃ to obtain a uniform graphene oxide dispersion liquid;
fifthly, mixing and stirring 5ml of the amino polyaryletherketone polymer solution obtained in the third step and 1ml of the graphene oxide dispersion solution obtained in the fourth step for 12 hours, carrying out ultrasonic treatment at the low temperature of 35 ℃ for 72 hours to obtain a uniform film forming solution, slowly pouring the film forming solution onto a smooth flat glass plate, slowly evaporating the solvent for 24 hours at room temperature, soaking the glass plate in methanol for demoulding after film forming, and drying. Thus obtaining the novel mixed matrix gas separation membrane with the graphene oxide mass fraction of 3%.
Example 4
13.84g of paranitroaniline is added into a 500ml beaker, 30ml of distilled water is dripped while stirring, and 30ml of absolute ethyl alcohol is dripped. 34ml of concentrated hydrochloric acid are added dropwise (half an hour over). 7.6g of sodium nitrite was dissolved in 50ml of distilled water, and the solution of nitrosic acid was added dropwise to the above p-nitroaniline solution (1 hour was completed). 8.64g of p-benzoquinone and 25.46g of sodium bicarbonate are weighed, the p-benzoquinone and the sodium bicarbonate are added into 100ml of water, the diazonium salt solution is dropwise added into the mixed solution of the p-benzoquinone and the sodium bicarbonate (after 1 hour), and the reaction is carried out for 4 hours after the dropwise addition. And after the reaction is finished, filtering the mixed solution under reduced pressure, and washing the mixed solution for 4-6 times by using distilled water until the filtrate is light yellow or colorless. Drying at 60 ℃. Adding the dried medicine into a three-mouth bottle connected with a condenser tube and stirring, adding a proper amount of zinc powder, heating in a water bath to 90 ℃, starting to dropwise add hydrochloric acid (dropwise adding is completed in half an hour), reacting for 4 hours, filtering while hot, standing and cooling the filtrate, separating out solids, filtering under reduced pressure, and drying at 60 ℃. Adding the dried medicine into a three-mouth bottle connected with a stirring and condensing tube, adding a proper amount of distilled water, refluxing for 2 hours at 90 ℃, filtering under reduced pressure when the medicine is hot, standing and cooling the filtrate to obtain a pink needle-shaped solid, and performing pressure filtration and drying at 60 ℃ for later use;
secondly, self-made amino bisphenol monomer and difluorobenzophenone are mixed according to a molar ratio of 1: 1, putting materials into a three-mouth bottle connected with a stirrer, a water-carrying device, a condenser tube and a gas-guide tube, taking N-methyl pyrrolidone as a solvent, potassium carbonate as a salt forming agent and toluene as a water-carrying agent, refluxing at 130 ℃, beginning timing when the first drop of liquid in the condenser tube is dripped, carrying water for 4 hours, evaporating the toluene, raising the temperature of a system to 170 ℃, reacting for 30 hours, then cooling, discharging in cold water to obtain a strip polymer, mashing the obtained strip polymer by a mashing machine, boiling for 5-8 times by using distilled water, and then drying in a vacuum oven for 24 hours at 80 ℃ for later use;
③ 0.01g of amino polyaryletherketone polymer is treated with 10ml of chloroform (CCl)3) Dissolving, and mechanically stirring the solution for 12 hours to obtain a uniformly mixed film forming solution;
fourthly, 0.004g of Graphene Oxide (GO) is added into 100ml of chloroform (CCl)3) Stirring for 12 hours, and then carrying out ultrasonic treatment for 72 hours at the low temperature of 35 ℃ to obtain a uniform graphene oxide dispersion liquid;
fifthly, mixing and stirring 5ml of the amino polyaryletherketone polymer solution obtained in the third step and 1ml of the graphene oxide dispersion solution obtained in the fourth step for 12 hours, carrying out ultrasonic treatment at the low temperature of 35 ℃ for 72 hours to obtain a uniform film forming solution, slowly pouring the film forming solution onto a smooth flat glass plate, slowly evaporating the solvent for 24 hours at room temperature, soaking the glass plate in methanol for demoulding after film forming, and drying. Thus obtaining the novel mixed matrix gas separation membrane with the graphene oxide mass fraction of 4%.
Example 5
13.84g of paranitroaniline is added into a 500ml beaker, 30ml of distilled water is dripped while stirring, and 30ml of absolute ethyl alcohol is dripped. 34ml of concentrated hydrochloric acid are added dropwise (half an hour over). 7.6g of sodium nitrite was dissolved in 50ml of distilled water, and the solution of nitrosic acid was added dropwise to the above p-nitroaniline solution (1 hour was completed). 8.64g of p-benzoquinone and 25.46g of sodium bicarbonate are weighed, the p-benzoquinone and the sodium bicarbonate are added into 100ml of water, the diazonium salt solution is dropwise added into the mixed solution of the p-benzoquinone and the sodium bicarbonate (after 1 hour), and the reaction is carried out for 4 hours after the dropwise addition. And after the reaction is finished, filtering the mixed solution under reduced pressure, and washing the mixed solution for 4-6 times by using distilled water until the filtrate is light yellow or colorless. Drying at 60 ℃. Adding the dried medicine into a three-mouth bottle connected with a condenser tube and stirring, adding a proper amount of zinc powder, heating in a water bath to 90 ℃, starting to dropwise add hydrochloric acid (dropwise adding is completed in half an hour), reacting for 4 hours, filtering while hot, standing and cooling the filtrate, separating out solids, filtering under reduced pressure, and drying at 60 ℃. Adding the dried medicine into a three-mouth bottle connected with a stirring and condensing tube, adding a proper amount of distilled water, refluxing for 2 hours at 90 ℃, filtering under reduced pressure when the medicine is hot, standing and cooling the filtrate to obtain a pink needle-shaped solid, and performing pressure filtration and drying at 60 ℃ for later use;
secondly, self-made amino bisphenol monomer and difluorobenzophenone are mixed according to a molar ratio of 1: 1, putting materials into a three-mouth bottle connected with a stirrer, a water-carrying device, a condenser tube and a gas-guide tube, taking N-methyl pyrrolidone as a solvent, potassium carbonate as a salt forming agent and toluene as a water-carrying agent, refluxing at 130 ℃, beginning timing when the first drop of liquid in the condenser tube is dripped, carrying water for 4 hours, evaporating the toluene, raising the temperature of a system to 170 ℃, reacting for 30 hours, then cooling, discharging in cold water to obtain a strip polymer, mashing the obtained strip polymer by a mashing machine, boiling for 5-8 times by using distilled water, and then drying in a vacuum oven for 24 hours at 80 ℃ for later use;
③ 0.01g of amino polyaryletherketone polymer is treated with 10ml of chloroform (CCl)3) Dissolving, and mechanically stirring the solution for 12 hours to obtain a uniformly mixed film forming solution;
fourthly, 0.005g of Graphene Oxide (GO) is added into 100ml of chloroform (CCl)3) Stirring for 12 hours, and then carrying out ultrasonic treatment for 72 hours at the low temperature of 35 ℃ to obtain a uniform graphene oxide dispersion liquid;
fifthly, mixing and stirring 5ml of the amino polyaryletherketone polymer solution obtained in the third step and 1ml of the graphene oxide dispersion solution obtained in the fourth step for 12 hours, carrying out ultrasonic treatment at the low temperature of 35 ℃ for 72 hours to obtain a uniform film forming solution, slowly pouring the film forming solution onto a smooth flat glass plate, slowly evaporating the solvent for 24 hours at room temperature, soaking the glass plate in methanol for demoulding after film forming, and drying. Thus obtaining the novel mixed matrix gas separation membrane with the mass fraction of the graphene oxide of 1%.
The above description of the embodiments is only for the purpose of assisting understanding of the method of the present invention and the core idea thereof, and it should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall into the protection scope of the claims of the present invention.
Claims (5)
1. A preparation method of a novel mixed matrix gas separation membrane containing an amino polyaryletherketone/graphene oxide composite material is characterized by specifically comprising the following steps:
the method comprises the following steps: adopting diazo salt reaction, reducing and ammoniating reaction to prepare bisphenol monomer (4- (2, 5-diphenol) aniline) containing amino;
step two: adding the self-made amino-containing bisphenol monomer (4- (2, 5-diphenol) aniline) and difluorobenzophenone prepared in the step one into a reaction vessel for polymerization reaction by a direct polycondensation method to obtain amino polyaryletherketone (Am-PAEK);
step three: dissolving the amino polyaryletherketone polymer obtained in the step two to obtain a polymer solution;
step four: adding a certain amount of Graphene Oxide (GO) into deionized water, stirring for 12 hours, and then carrying out ultrasonic treatment at a low temperature of 35 ℃ for 72 hours to obtain a uniform graphene oxide dispersion liquid;
step five: and (3) uniformly mixing and stirring the graphene oxide dispersion liquid obtained in the fourth step and the polymer solution obtained in the third step, paving the mixture into a film after ultrasonic treatment, and soaking the paved film into methanol to finally obtain the novel mixed matrix gas separation film.
2. The method for preparing a novel mixed matrix gas separation membrane comprising an amino polyaryletherketone/graphene oxide composite material according to claim 1, wherein the first step specifically comprises: adding 13.84g of p-nitroaniline into a 500ml beaker, dropwise adding 30ml of distilled water while stirring, and dropwise adding 30ml of absolute ethyl alcohol; then 34ml of concentrated hydrochloric acid is added dropwise (half an hour is finished); dissolving 7.6g of sodium nitrite in 50ml of distilled water, and dropwise adding the nitrous acid solution into the p-nitroaniline solution (after 1 hour); weighing 8.64g of p-benzoquinone and 25.46g of sodium bicarbonate, adding the p-benzoquinone and the sodium bicarbonate into 100ml of water, dropwise adding a diazonium salt solution into a mixed solution of the p-benzoquinone and the sodium bicarbonate (after the diazosalt solution is added for 1 hour), and reacting for 4 hours after the diazosalt solution is dropwise added; after the reaction is finished, filtering the mixed solution under reduced pressure, and then washing the mixed solution for 4-6 times by using distilled water until the filtrate is light yellow or colorless; drying at 60 ℃; adding the dried medicine into a three-mouth bottle connected with a condenser tube and stirring, adding a proper amount of zinc powder, heating to 90 ℃ in a water bath, starting to dropwise add hydrochloric acid (dropwise adding is completed half an hour), reacting for 4 hours, filtering while hot, standing and cooling the filtrate, separating out solids, filtering under reduced pressure, and drying the solids at 60 ℃; adding the dried medicine into a three-neck flask connected with a stirring and condensing tube, adding appropriate amount of distilled water, refluxing at 90 deg.C for 2 hr, filtering under reduced pressure, standing the filtrate, cooling to obtain pink needle-like solid, pressure filtering, and drying at 60 deg.C for use.
3. The method for preparing a novel mixed matrix gas separation membrane comprising an amino polyaryletherketone/graphene oxide composite material according to claim 1, wherein the second step is specifically: self-made amino-containing bisphenol monomer and difluorobenzophenone are mixed according to a molar ratio of 1: 1, putting materials into a three-mouth bottle connected with a stirrer, a water-carrying device, a condenser tube and a gas-guide tube, taking N-methyl pyrrolidone as a solvent, potassium carbonate as a salt forming agent, toluene as a water-carrying agent, refluxing at 130 ℃, beginning to drip the first drop of liquid in the condenser tube for timing, carrying water for 4 hours, evaporating toluene, raising the temperature of a system to 170 ℃, reacting for 30 hours, then cooling, discharging in cold water to obtain a strip polymer, mashing the obtained strip polymer by a mashing machine, boiling for 5-8 times by using distilled water, and then drying in a vacuum oven for 24 hours at 80 ℃ for later use.
4. The method for preparing a novel mixed matrix gas separation membrane comprising an aminopolyaryletherketone/graphene oxide composite material according to claim 1, wherein the solvent is preferably N, N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP) or dimethyl sulfoxide.
5. The method for preparing a novel mixed matrix gas separation membrane containing an amino polyaryletherketone/graphene oxide composite material according to claim 1, wherein the mass ratio of the amino polyaryletherketone to the graphene oxide is 10: 1 to 5.
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