CN115608171A - polyimide/MXene composite film for gas separation and preparation method thereof - Google Patents
polyimide/MXene composite film for gas separation and preparation method thereof Download PDFInfo
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- CN115608171A CN115608171A CN202211200969.4A CN202211200969A CN115608171A CN 115608171 A CN115608171 A CN 115608171A CN 202211200969 A CN202211200969 A CN 202211200969A CN 115608171 A CN115608171 A CN 115608171A
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- mxene
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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
- B01D71/56—Polyamides, e.g. polyester-amides
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- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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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
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Abstract
The embodiment of the invention provides a polyimide/MXene composite film for gas separation and a preparation method thereof, wherein the composite film takes polyimide as a matrix and MXene as a disperse phase; the MXene is a two-dimensional metal nitride material. The preparation method comprises the steps of ultrasonically dispersing MXene in an organic solvent, adding diamine and dianhydride, mechanically stirring for 6-12 hours at 0-30 ℃ to obtain a polyamic acid/MXene mixed solution, blade-coating the mixed solution on a glass plate to form a film, volatilizing the solvent and carrying out thermal imidization to obtain the polyimide/MXene composite film. The preparation method is simple, and the obtained composite film has the advantages of excellent mechanical property and dimensional stability, good thermal stability and chemical stability and the like.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a polyimide/MXene composite film for separating and purifying mixed gas and a preparation method thereof.
Background
The gas separation membrane technology is a novel and environment-friendly' green technology, and polyimide-based gas separation membranes are unique in a plurality of gas separation membrane materials and are expected to be widely applied in the field. Currently, the research on polyimide gas separation membranes mainly focuses on the research and development of novel polyimide separation membrane materials with enhanced high selectivity, high permeability, chemical stability, thermal stability and the like, mainly through chemical crosslinking, copolymerization, functional group introduction and other modes. MXene, a two-dimensional material, has ultrahigh volume specific capacity and abundant surface chemistry, is used as a dispersed phase, polyimide is used as a matrix phase, and the two phases are copolymerized to improve the gas passing coefficient, so that the method is a feasible gas separation membrane synthesis method.
Disclosure of Invention
The invention provides a preparation method of a polyimide/MXene composite film for solving the technical problem of separation and purification of mixed gas.
The embodiment of the invention provides a preparation method of a polyimide/MXene composite film for gas separation, which comprises the following steps:
s1, mixing MXene with an organic solvent, and carrying out ultrasonic treatment and stirring to obtain a suspension;
s2, adding diamine into the suspension, adding dianhydride after the diamine is dissolved, and carrying out mechanical stirring polymerization reaction at the temperature of 0-30 ℃ for 6-12 hours to obtain polyamic acid/MXene mixed solution;
s3, coating the polyamic acid/MXene mixed solution on a glass plate to form a film, and putting the film into a drying oven at 60-90 ℃ for curing and shaping for 30min;
and S4, taking down the cured and formed film on the glass plate, putting the film into a tube furnace for imidization, preserving heat for 10min at 260 ℃, and preserving heat for 10min at 360 ℃ to obtain the polyimide composite film.
In an alternative embodiment, the MXene has a single layer or multiple layers with dimensions of nanometer or micrometer scale.
In an alternative embodiment, the MXene mass is 0% -20% of the total mass of diamine and dianhydride.
In an alternative embodiment, the organic solvent is one or a mixture of several of N, N-Dimethylacetamide (DMAC), N-Dimethylformamide (DMF), dimethyldichlorous (DMSO), and N-methylpyrrolidone (NMP) in any ratio.
In an alternative embodiment, the diamine is one or more of 4,4' -diaminodiphenyl casein (4, 4' -ODA), 3,4' -diaminodiphenyl casein (3, 4' -ODA), p-phenylenediamine, m-phenylenediamine, 4' -diaminodiphenyl methane (4, 4' -MDA), 3' dimethyl-4, 4' -Diaminodiphenyl Methane (DMDA), 3', 5' -tetramethyl-4, 4' -diaminodiphenyl methane (TMDA), and any mixture ratio thereof.
In an alternative embodiment, the dianhydride is pyromellitic dianhydride (PMDA), 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride (BPADA), 3', one or more of 4,4' -biphenyl tetracid dianhydride (BPDA), 3', 4' -diphenyl tetracid dianhydride (ODPA) and 3,3', 4' -diphenyl ketone tetracid dianhydride (BTDA) in any proportion.
In an optional embodiment, in step S1, the ultrasonic treatment time is 5 to 30min, and the stirring time is 5 to 30min.
In an alternative embodiment, the molar ratio of diamine to dianhydride in step S2 is 1.
In an alternative embodiment, in step S2, the sum of the mass of diamine and dianhydride is 5-20% of the mass of organic solvent.
In an alternative embodiment, the protective gas used for imidization is one of nitrogen, argon and mixed gas.
In an alternative embodiment, the polyimide/MXene composite film for gas separation is prepared by the preparation method of the polyimide/MXene composite film for gas separation.
The invention has the beneficial effects that: the MXene is a two-dimensional material, the specific surface area of the MXene is large, the MXene surface contains a large number of functional groups, the MXene is added into polyimide to prepare the membrane, and the excellent surface-to-body ratio of the nano material can improve the separation effect of the traditional separation membrane on a complex system. By doping two-dimensional MXene nanosheets and using the two-dimensional MXene nanosheets as a filler of PI, MXene increases the free volume in a polymer grid, prolongs the path of gas molecules through a film and enables the film to show high barrier property, and on the other hand, MXene is oxidized in the imidization process to generate a large number of pores and TiO 2 The permeability efficiency of gas molecules can be effectively improved. Polyimide hybrid membranes exhibit unique heat resistance, air permeability coefficients, and air permeability selectivity. The preparation method disclosed by the invention is simple in preparation process, free of toxic solvent, green and environment-friendly, low in production cost and in line with the concept of green sustainable development.
Detailed Description
The invention will be further described with reference to the following description and specific embodiments:
reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in the present disclosure, it is understood that each intervening value, to the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in that stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
The specific embodiment is as follows:
example 1:
adding 0.45g of MXene into 8g of N, N-dimethylacetamide, performing ultrasonic dispersion for 30 minutes under stable mechanical stirring, adding 0.957g of 4,4 '-diaminodiphenylamine, adding 1.043g of pyromellitic dianhydride after the 4,4' -diaminodiphenylamine is completely dissolved, and performing mechanical stirring polymerization reaction for 12 hours at l5 ℃ to obtain mixed solution of polyamic acid (solid content is 4.5%)/MXene; standing and defoaming the mixed solution, pouring the mixed solution on a glass plate, blade-coating the mixed solution to form a film, drying the film in an oven at 60 ℃ for 30 minutes, transferring the dried film into a tubular furnace for thermal imidization, wherein the temperature rise program is as follows: maintaining at 260 deg.C for 10min and at 360 deg.C for 10min, and protecting with protector N 2 Then, the mixture was cooled to room temperature, and the film was peeled off from the glass plate to obtain a (4, 4' -ODA-PMDA) polyimide/MXene (4.5%) composite film as a composite film H 2 ，CH 4 And CO 2 Have a permeability of 4.71barrer, 0.02barrer and 1.43barrer, respectively 2 /CH 4 And H 2 /CO 2 The selectivities were 235.50 and 3.29.
Example 2:
adding 1.0g of MXene into 8g of N, N-dimethylacetamide, performing ultrasonic dispersion for 30 minutes under stable mechanical stirring, adding 0.957g of 4,4 '-diaminodiphenylamine, adding 1.043g of pyromellitic dianhydride after the 4,4' -diaminodiphenylamine is completely dissolved, and performing mechanical stirring polymerization reaction for 12 hours at l5 ℃ to obtain a polyamide acid/MXene mixed solution; standing the mixed solution for defoaming, pouring the mixed solution on a glass plate for blade coating to form a film, drying the film in an oven at 60 ℃ for 30 minutes, transferring the dried film into a tubular furnace for thermal imidization, wherein the temperature rise program comprises the following steps: maintaining at 260 deg.C for 10min and at 360 deg.C for 10min, and protecting with N 2 Cooling to room temperature, peeling the film from the glass plate to obtain (4, 4' -ODA-PMDA) polyimide/MXene (10%) composite film, composite film pair H 2 ，CH 4 And CO 2 Respectively 6.43barrer,0.03barrer and 2.21barrer, H 2 /CH 4 And H 2 /CO 2 The selectivities were 214.33 and 2.91.
Example 3:
adding 3.0g of MXene into 8g of N, N-dimethylacetamide, carrying out ultrasonic dispersion for 30 minutes under stable mechanical stirring, and adding 0.957g of 4,4 '-diaminodiphenylamine, adding 1.043g of pyromellitic dianhydride after the 4,4' -diaminodiphenylamine is completely dissolved, and carrying out mechanical stirring polymerization reaction at l5 ℃ for 12 hours to obtain polyamic acid (solid content is 4.5%)/MXene mixed solution; standing and defoaming the mixed solution, pouring the mixed solution on a glass plate, blade-coating the mixed solution to form a film, drying the film in an oven at 60 ℃ for 30 minutes, transferring the dried film into a tubular furnace for thermal imidization, wherein the temperature rise program is as follows: maintaining at 260 deg.C for 10min and at 360 deg.C for 10min, and protecting with protector N 2 Then, the mixture was cooled to room temperature, and the film was peeled off from the glass plate to obtain a (4, 4' -ODA-PMDA) polyimide/MXene (4.5%) composite film as a composite film H 2 ，CH 4 And CO 2 Respectively 18.64barrer, 0.21barrer and 8.43barrer 2 /CH 4 And H 2 /CO 2 The selectivities were 88.76 and 2.21.
Combining examples 1 and 2, it can be seen that the MXene doped polyimide film improves for small molecule gas flux, but the large molecule gas improvement is not significant. But the gas selectivity is obviously improved by doping MXene, so that the doping purpose is achieved, and the dimensional stability and the mechanical property of the film are relatively improved.
In the description herein, references to the description of the terms "one embodiment," "some embodiments," "some examples," "specific examples," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the above-described terms do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is a more detailed description of the invention in connection with specific embodiments thereof, and it is not intended that the invention be limited to the specific embodiments thereof. It will be apparent to those skilled in the art that a number of simple derivations or substitutions can be made without departing from the inventive concept.
Claims (9)
1. A preparation method of a polyimide/MXene composite film for gas separation is characterized by comprising the following steps:
s1, mixing MXene with an organic solvent, and carrying out ultrasonic treatment and stirring to obtain a suspension;
s2, adding diamine into the suspension, adding dianhydride after the diamine is dissolved, and carrying out mechanical stirring polymerization reaction at the temperature of 0-30 ℃ for 6-12 hours to obtain a polyamic acid/MXene mixed solution;
s3, coating the polyamic acid/MXene mixed solution on a glass plate to form a film, and putting the film into an oven at 60-90 ℃ for curing and shaping for 30min;
and S4, taking off the cured and formed film on the glass plate, putting the film into a tubular furnace for imidization, preserving the heat for 10min at 260 ℃, and preserving the heat for 10min at 360 ℃ to obtain the polyimide composite film.
2. The method for preparing the polyimide/MXene composite film for gas separation according to claim 1, wherein the MXene has a number of layers of monolayer or multilayer and a size of nano-scale or micro-scale.
3. The method for preparing a polyimide/MXene composite film for gas separation according to claim 1, wherein the MXene is contained by 0% to 20% by mass of the total mass of the diamine and the dianhydride.
4. The method according to claim 1, wherein the organic solvent is one or more selected from the group consisting of N, N-Dimethylacetamide (DMAC), N-Dimethylformamide (DMF), dimethyldichloromethylenes (DMSO)/N-methylpyrrolidinones (NMP).
5. The method for preparing the polyimide/MXene composite film for gas separation according to claim 1, wherein in S1, the ultrasonic treatment time is 5-30 min, and the stirring time is 5-30 min; in S2, the molar ratio of diamine to dianhydride is 1-1.02, and the mass sum of diamine and dianhydride is 5-20% of the mass of the organic solvent.
6. The method of claim 1, wherein the diamine is one or more selected from the group consisting of 4,4' -diaminodiphenyl-methane (4, 4' -ODA), 3,4' -diaminodiphenyl-methane (3, 4' -ODA), p-phenylenediamine, m-phenylenediamine, 4' -diaminodiphenylmethane (4, 4' -MDA), 3' -dimethyl-4, 4' -diaminodiphenylmethane (DMDA), and 3,3', 5' -tetramethyl-4, 4' -diaminodiphenylmethane (TMDA).
7. The method of preparing a polyimide/MXene composite film for gas separation according to claim 1, wherein the dianhydride is pyromellitic dianhydride (PMDA), 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride (BPADA), 3', one or more of 4,4' -biphenyl tetracarboxylic dianhydride (BPDA), 3', 4' -diphenyl tetracarboxylic dianhydride (ODPA) and 3,3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) in any proportion.
8. The method for preparing the polyimide/MXene composite film for gas separation according to claim 1, wherein the shielding gas used for imidization is one of nitrogen, argon and mixed gas.
9. A polyimide/MXene composite film for gas separation, wherein the polyimide/MXene composite film for gas separation is produced by the production method according to any one of claims 1 to 8.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211200969.4A CN115608171A (en) | 2022-09-29 | 2022-09-29 | polyimide/MXene composite film for gas separation and preparation method thereof |
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| CN202211200969.4A CN115608171A (en) | 2022-09-29 | 2022-09-29 | polyimide/MXene composite film for gas separation and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116026195A (en) * | 2023-03-02 | 2023-04-28 | 中国工程物理研究院激光聚变研究中心 | MXene composite film flying piece and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116026195A (en) * | 2023-03-02 | 2023-04-28 | 中国工程物理研究院激光聚变研究中心 | MXene composite film flying piece and preparation method thereof |
| CN116026195B (en) * | 2023-03-02 | 2023-11-21 | 中国工程物理研究院激光聚变研究中心 | MXene composite film flying piece and preparation method thereof |
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