CN113318614A - Preparation method and application of super cross-linked porous polymer mixed matrix membrane - Google Patents
Preparation method and application of super cross-linked porous polymer mixed matrix membrane Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
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- 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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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
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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
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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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Abstract
The invention relates to a preparation method of a super cross-linked porous polymer mixed matrix membrane and application thereof in gas separation. The method comprises the steps of firstly preparing the 2-phenylimidazole type super cross-linked porous polymer as an organic filler, physically blending the organic filler with a 6FDA/DAP polyimide matrix membrane to obtain a membrane material, and carrying out heat treatment to obtain the super cross-linked porous polymer mixed matrix membrane. The method can avoid stronger interface effect between the filler and the matrix membrane, greatly improves the gas permeation flux of the polyimide gas separation membrane, greatly improves the permeation flux of the prepared super cross-linked porous polymer mixed matrix membrane, and is suitable for CO2/N2、CO2/CH4、O2/N2And (5) gas separation.
Description
Technical Field
The invention belongs to the technical field of high polymer material preparation, and particularly relates to a preparation method of a super cross-linked porous polymer type mixed matrix membrane and application thereof in gas separation.
Background
Industrial production is often accompanied by a large number of gas separation processes. The mixed matrix membrane composed of the polymer matrix membrane and the filler is an effective gas separation membrane at present, and can efficiently solve the gas separation problem. Among these, the choice of filler is of critical importance. The proper filler can increase gas permeation flux, improve gas selectivity and separate different gases quickly, efficiently and with low energy consumption. At present, the fillers of the mixed matrix membrane are mainly inorganic materials. These inorganic fillers increase the polymer chain spacing, thereby allowing gas to permeate through the membrane more quickly, and thus increasing the permeation flux of the membrane. Modification of the inorganic filler can also enhance interaction with gas, thereby achieving dual enhancement of gas flux and gas separation selectivity. However, these inorganic fillers have a large interfacial effect with the organic polymer matrix film. The interface between these inorganic and organic materials often causes defects in the mixed matrix membrane, resulting in a decrease in separation efficiency.
In order to solve the problem, the super-crosslinked porous polymer is a porous material with an all-organic structure. According to the principle of similar compatibility, the compatibility between the organic polymer matrix film and the organic filler is better than the compatibility between the organic polymer matrix film and the inorganic filler. Therefore, there should be better compatibility between the hypercrosslinked porous polymer and the polymer matrix membrane. The super-crosslinked porous polymer also has the characteristics of high specific surface area, low density, low cost and simple synthesis, so that the super-crosslinked porous polymer can completely replace inorganic filler to enhance the gas permeation flux of the gas separation membrane. However, no mature method for preparing the super-crosslinked porous polymer mixed matrix membrane and improving the separation efficiency of the gas separation membrane exists at present.
Disclosure of Invention
Aiming at the defects of the prior art, the preparation method of the super-crosslinked porous polymer mixed matrix membrane which can greatly increase gas permeation and can rapidly separate gas is provided, and the super-crosslinked porous polymer mixed matrix membrane is applied to gas separation.
In order to achieve the purpose, the technical scheme of the preparation method of the super cross-linked porous polymer mixed matrix membrane is that a 2-phenylimidazole type super cross-linked porous polymer is synthesized and is dispersed in a mixed matrix membrane casting solution through ultrasound to prepare the super cross-linked porous polymer mixed matrix membrane, and the preparation method specifically comprises the following steps:
(1) dissolving 2-phenylimidazole and alpha, alpha' -dichloro-p-xylene in equal molar weight in 1, 2-dichloroethane, then adding an alkylating reagent, stirring and mixing uniformly, heating at 70-130 ℃ for 12-48h, and filtering and washing a mixed solution after the reaction is finished; treating the brown filter cake in a vacuum oven at 60-100 ℃ to obtain a 2-phenylimidazole type super cross-linked porous polymer;
in the step (1), the alkylating reagent refers to anhydrous FeCl3Or anhydrous AlCl3(ii) a The molar ratio of the alkylating reagent to the 2-phenylimidazole is 1-2;
(2) at-5-20 ℃ and N2Under an atmosphere, equimolar amounts of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 5(6) -amino-1- (4-aminophenyl) -1,3, 3-trimethylindane (DAPI) are dissolved with stirring in a strongly polar solution; then continuously stirring for 2-30h at the rotating speed of 50-600r/min to obtain a 6FDA/DAPI polyamic acid solution; adding acetic anhydride and triethylamine into 6FDA/DAPI polyamide acid solution, heating to 10-50 ℃, and continuously stirring at the rotating speed of 50-600r/min for 10-30h to obtain 6FDA/DAPI polyimide solution; pouring the obtained polyimide solution into anhydrous methanol solution, stirring for 12-36h for phase conversion, treating the obtained polyimide solid in a vacuum oven at 60-220 ℃ for 12-24h to obtain 6FDA/DAPI polyimideAn imine;
in the step (2), the strong polar solvent is one or a mixture of any more of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the molar ratio of acetic anhydride to triethylamine to 6FDA is 1-12: 3: 3;
(3) adding the 2-phenylimidazole type super cross-linked porous polymer into a strong polar solvent, and performing ultrasonic treatment for 0.5-6.0h to uniformly disperse the polymer; then adding 6FDA/DAPI polyimide to completely dissolve the polyimide to form a casting solution; uniformly distributing the casting solution in a container with a certain shape, and evaporating the polar solvent at 40-120 ℃ to obtain a membrane material; the obtained membrane material is subjected to heat treatment at 60-220 ℃ in a vacuum oven to obtain a 2-phenylimidazole type super cross-linked porous polymer mixed matrix membrane;
wherein the mass of the 6FDA/DAPI polyimide in the casting solution is 100-10000 times, preferably 500-5000 times that of the 2-phenylimidazole type super cross-linked porous polymer.
In the technical scheme, the heating in the step (1) is preferably carried out at 80-120 ℃ for 12-48 h.
The preferable reaction conditions in the step (2) are-5-20 ℃ and N2Under the atmosphere; triethylamine and acetic anhydride are added in the step (2), and the temperature is 25-35 ℃.
And (4) carrying out heat treatment on the membrane material obtained in the step (3) at 60-170 ℃ in a vacuum oven.
The invention also provides an application of the super cross-linked porous polymer mixed matrix membrane in gas separation of different gas systems.
The application of the super-crosslinked porous polymer mixed matrix membrane in the gas separation of different gas systems preferably comprises the following steps:
(1) cutting a 2-phenylimidazole type super cross-linked porous polymer mixed matrix membrane, placing the cut membrane in a membrane separation evaluation device, introducing a raw material gas, keeping the temperature of a membrane pool at 25-45 ℃, and keeping the pressure difference between two sides of the membrane at 0.2 Mpa;
(2) and after the gas is stably transmitted, testing the gas flow to obtain the permeation flux and the gas selection coefficient of the gas.
Wherein the raw material gas is CO2、CH4、N2、O2Any two or more of them.
The invention has the beneficial effects that: the preparation method adopts simple alkylation reaction to synthesize the porous filler super cross-linked porous polymer with an all-organic structure. The organic porous filler has good compatibility with a polymer matrix membrane, and can greatly improve gas permeation flux under the condition of slightly reducing selectivity, thereby breaking through the inherent 'trade-off effect' of the material and realizing high-efficiency separation of gas.
Drawings
FIG. 1 shows the molecular structure of a 2-phenylimidazole-type hypercrosslinked porous polymer in example 1 of the present invention.
FIG. 2 shows the molecular structure of 6FDA/DAPI polyimide in example 1 of the present invention.
FIG. 3 shows N of a 2-phenylimidazole-type hypercrosslinked porous polymer in example 1 of the present invention2Adsorption and desorption curve (BET).
FIG. 4 is a Scanning Electron Microscope (SEM) image of the mixed matrix membrane in example 1 of the present invention.
FIG. 5 is a Scanning Electron Microscope (SEM) image of a cross section of the mixed matrix membrane in example 1 of the present invention.
Detailed Description
To further illustrate the technical solution of the present invention, the following specific examples are given. It should be understood that the present invention has been shown and described only by way of illustration and description, and it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention or exceeding the scope of the claims.
CO used in the following examples of the invention2、CH4、N2、O2All are high purity gases.
Example 1
5mmol of 2-phenylimidazole and 5mmol of alpha, alpha' -dichloro-p-xylene are dissolved in 10mL of 1, 2-dichloroethane, after which 10mmol of AlCl are added3Heating at 80 deg.C after stirring and mixing uniformlyAnd 24h, filtering and washing the mixed solution after the reaction is finished. And treating the brown filter cake in a vacuum oven at 60 ℃ to obtain the 2-phenylimidazole type super cross-linked porous polymer (the molecular structure is shown in figure 1).
At-0 ℃ and N2Under an atmosphere, 10mmol of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 10mmol of 5(6) -amino-1- (4-aminophenyl) -1,3, 3-trimethylindane (DAPI) were dissolved in 50mL of N, N-dimethylformamide with stirring. Then, the mixture was stirred at a rotation speed of 300r/min for 24 hours to obtain a 6FDA/DAPI polyamic acid solution. Adding 30mmol of acetic anhydride and 10mmol of triethylamine, heating to 30 ℃, and continuously stirring at the rotating speed of 300r/min for 24 hours to obtain the polyimide solution. And pouring the obtained polyimide solution into an anhydrous methanol solution, stirring for 24h for phase conversion, and treating the obtained polyimide solid in a vacuum oven at 120 ℃ for 24h to obtain the 6FDA/DAPI polyimide (the molecular structure is shown in figure 2). 0.3mg of 2-phenylimidazole-type hypercrosslinked porous polymer was added to 4.8mL of N, N-dimethylacetamide and sonicated for 0.5h to disperse it uniformly. 0.5g of 6FDA/DAPI type polyimide was added thereto and completely dissolved to form a casting solution. And (3) uniformly distributing the casting solution in a container with a certain shape, and evaporating the polar solvent at 60 ℃ to obtain the membrane material. The obtained membrane material is treated for 4h at 60 ℃, 4h at 120 ℃, 4h at 180 ℃ and 12h at 220 ℃ in a vacuum oven to obtain the 2-phenylimidazole type super cross-linked porous polymer mixed matrix membrane.
The mixed matrix film was cut into a square of 2cm × 2cm and attached to an aluminum foil 7cm in diameter. A round hole with the diameter of 1cm is arranged in the middle of the aluminum foil. And then, attaching filter paper to the other side of the membrane, then integrally placing the membrane into a membrane pool, controlling the temperature to be 35 ℃, and sealing the membrane pool. Then, the upper side and the lower side of the membrane pool are vacuumized, so that the pressure at the lower side of the membrane pool reaches-0.1 MPa. Then N is introduced2Or CO2The gas pressure on the upper side reaches 0.1MPa, and the transmembrane pressure difference reaches 0.2MPa, so that the gas gradually permeates from the upper side to the lower side of the membrane. Gas permeation flux was calculated after gas permeation equilibrium.
Comparative example 1, the procedure was the same as in example 1 except that no 2-phenylimidazole-type hypercrosslinked porous polymer was added and the resulting product was designated as 6FDA/DAPI polyimide membrane.
The results show CO for 6FDA/DAPI polyimide membranes2And N2Respectively, at a permeate flux of 62.4barrer and 4.2barrer, CO2/N2The selectivity was 14.8. And 2-phenylimidazole type super cross-linked porous polymer mixed matrix membrane CO2And N2Respectively, at 86.2barrer and 6.4barrer, CO2/N2The selectivity was 13.4.
In the examples, N is derived from a 2-phenylimidazole-type hypercrosslinked porous polymer2As can be seen from the absorption and desorption curves (BET diagram shown in figure 3), the 2-phenylimidazole type super-crosslinked porous polymer has very large specific surface area reaching 721.37m2(ii) in terms of/g. It can also be uniformly dispersed in the matrix membrane (plan SEM image such as fig. 4, cross-sectional SEM image such as fig. 5) to form a mixed matrix membrane. The 2-phenylimidazole type super cross-linked porous polymer has better compatibility with a matrix membrane and is not easy to agglomerate.
Example 2
5mmol of 2-phenylimidazole and 5mmol of alpha, alpha' -dichloro-p-xylene were dissolved in 10mL of 1, 2-dichloroethane, after which 10mmol of FeCl were added3After stirring and mixing uniformly, heating at 80 ℃ for 24h, and filtering and washing the mixed solution after the reaction is finished. And treating the brown filter cake in a vacuum oven at 60 ℃ to obtain the 2-phenylimidazole type super cross-linked porous polymer.
At-0 ℃ and N2Under an atmosphere, 15mmol of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 15mmol of 5(6) -amino-1- (4-aminophenyl) -1,3, 3-trimethylindan (DAPI) were dissolved in 46mL of N, N-dimethylacetamide with stirring. Then stirring is continued for 24h at the rotating speed of 300r/min, and 6FDA/DAPI polyamic acid solution is obtained. Adding 5mmol of acetic anhydride and 15mmol of triethylamine, heating to 30 ℃, and continuously stirring at the rotating speed of 300r/min for 24 hours to obtain the polyimide solution. And pouring the obtained polyimide solution into an anhydrous methanol solution, stirring for 24h for phase conversion, and treating the obtained polyimide solid in a vacuum oven at 120 ℃ for 24h to obtain the 6FDA/DAPI polyimide (the molecular structure is shown in figure 2). 0.2mg of a 2-phenylimidazole type hypercrosslinkingThe porous polymer was added to 4.8mL of N, N-dimethylacetamide and sonicated for 1.0h to disperse it uniformly. 0.5g of 6FDA/DAPI type polyimide was added thereto and completely dissolved to form a casting solution. And (3) uniformly distributing the casting solution in a container with a certain shape, and evaporating the polar solvent at 60 ℃ to obtain the membrane material. The obtained membrane material is treated for 4h at 60 ℃, 4h at 120 ℃, 4h at 180 ℃ and 12h at 220 ℃ in a vacuum oven to obtain the 2-phenylimidazole type super cross-linked porous polymer mixed matrix membrane.
The mixed matrix film was cut into a square of 2cm × 2cm and attached to an aluminum foil 7cm in diameter. A round hole with the diameter of 1cm is arranged in the middle of the aluminum foil. And then, attaching filter paper to the other side of the membrane, then integrally placing the membrane into a membrane pool, controlling the temperature to be 35 ℃, and sealing the membrane pool. Then, the upper side and the lower side of the membrane pool are vacuumized, so that the pressure at the lower side of the membrane pool reaches-0.1 MPa. Then CH is introduced4Or CO2The gas pressure on the upper side reaches 0.1MPa, and the transmembrane pressure difference reaches 0.2MPa, so that the gas gradually permeates from the upper side to the lower side of the membrane. Gas permeation flux was calculated after gas permeation equilibrium.
The results show CO for 6FDA/DAPI polyimide membranes2And CH4Respectively, at a permeate flux of 62.4barrer and 3.0barrer, CO2/CH4The selectivity was 20.8. And 2-phenylimidazole type super cross-linked porous polymer mixed matrix membrane CO2And CH4Respectively, at a permeate flux of 105.9barrer and 6.7barrer, CO2/CH4The selectivity was 15.7.
Example 3
10mmol of 2-phenylimidazole and 10mmol of alpha, alpha' -dichloro-p-xylene are dissolved in 20mL of 1, 2-dichloroethane, after which 20mmol of FeCl are added3After stirring and mixing uniformly, heating at 80 ℃ for 24h, and filtering and washing the mixed solution after the reaction is finished. And treating the brown filter cake in a vacuum oven at 60 ℃ to obtain the 2-phenylimidazole type super cross-linked porous polymer.
At-0 ℃ and N2Under an atmosphere, 15mmol of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 15mmol of 5(6) -amino-1- (4-aminophenyl) -1,3, 3-trimethylindane (DAPI) were dissolved in 46mL in N, N-dimethylformamide. Then stirring is continued for 24h at the rotating speed of 300r/min, and 6FDA/DAPI polyamic acid solution is obtained. Adding 5mmol of acetic anhydride and 15mmol of triethylamine, heating to 30 ℃, and continuously stirring at the rotating speed of 300r/min for 24 hours to obtain the polyimide solution. And pouring the obtained polyimide solution into an anhydrous methanol solution, stirring for 24h for phase conversion, and treating the obtained polyimide solid in a vacuum oven at 120 ℃ for 24h to obtain the 6FDA/DAPI polyimide (the molecular structure is shown in figure 2). 0.2mg of 2-phenylimidazole-type hypercrosslinked porous polymer was added to 4.8mL of N, N-dimethylformamide and subjected to ultrasonic treatment for 1.0 hour to disperse the polymer uniformly. 0.5g of 6FDA/DAPI type polyimide was added thereto and completely dissolved to form a casting solution. And (3) uniformly distributing the casting solution in a container with a certain shape, and evaporating the polar solvent at 60 ℃ to obtain the membrane material. The obtained membrane material is treated for 4h at 60 ℃, 4h at 120 ℃, 4h at 180 ℃ and 12h at 220 ℃ in a vacuum oven to obtain the 2-phenylimidazole type super cross-linked porous polymer mixed matrix membrane.
The mixed matrix film was cut into a square of 2cm × 2cm and attached to an aluminum foil 7cm in diameter. A round hole with the diameter of 1cm is arranged in the middle of the aluminum foil. And then, attaching filter paper to the other side of the membrane, then integrally placing the membrane into a membrane pool, controlling the temperature to be 35 ℃, and sealing the membrane pool. Then, the upper side and the lower side of the membrane pool are vacuumized, so that the pressure at the lower side of the membrane pool reaches-0.1 MPa. Then N is introduced2Or O2The gas pressure on the upper side reaches 0.1MPa, and the transmembrane pressure difference reaches 0.2MPa, so that the gas gradually permeates from the upper side to the lower side of the membrane. Gas permeation flux was calculated after gas permeation equilibrium.
The results show O of 6FDA/DAPI polyimide films2And N2Respectively, at a permeate flux of 13.8barrer and 4.2barrer, O2/N2The selectivity was 3.2. And 2-phenylimidazole type super cross-linked porous polymer mixed matrix membrane O2And N2Respectively, at a permeate flux of 24.0barrer and 8.0barrer, O2/N2The selectivity was 3.0.
Example 4
5mmol of 2-phenylimidazole and 5mmol of α, α' -dichloro-p-xylene were dissolved in 20mL1, 2-dichloroethane, followed by addition of 10mmol of FeCl3After stirring and mixing uniformly, heating at 80 ℃ for 24h, and filtering and washing the mixed solution after the reaction is finished. And treating the brown filter cake in a vacuum oven at 60 ℃ to obtain the 2-phenylimidazole type super cross-linked porous polymer.
At-0 ℃ and N2Under an atmosphere, 15mmol of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 15mmol of 5(6) -amino-1- (4-aminophenyl) -1,3, 3-trimethylindan (DAPI) were dissolved in 46mL of N, N-dimethylacetamide with stirring. Then stirring is continued for 24h at the rotating speed of 300r/min, and 6FDA/DAPI polyamic acid solution is obtained. Adding 5mmol of acetic anhydride and 15mmol of triethylamine, heating to 30 ℃, and continuously stirring at the rotating speed of 300r/min for 24 hours to obtain the polyimide solution. And pouring the obtained polyimide solution into an anhydrous methanol solution, stirring for 24h for phase conversion, and treating the obtained polyimide solid in a vacuum oven at 120 ℃ for 24h to obtain the 6FDA/DAPI polyimide (the molecular structure is shown in figure 2). 1.0mg of 2-phenylimidazole type hypercrosslinked porous polymer was added to 4.8mL of N-methylpyrrolidone, and the mixture was subjected to ultrasonic treatment for 0.5 hour to disperse the polymer uniformly. 0.5g of 6FDA/DAPI type polyimide was added to each of the solutions to dissolve the polyimide completely to form a casting solution. And (3) uniformly distributing the casting solution in a container with a certain shape, and evaporating the polar solvent at 60 ℃ to obtain the membrane material. The obtained membrane material is treated for 4h at 60 ℃, 4h at 120 ℃, 4h at 180 ℃ and 12h at 220 ℃ in a vacuum oven to obtain the 2-phenylimidazole type super cross-linked porous polymer mixed matrix membrane.
The mixed matrix film was cut into a square of 2cm × 2cm and attached to an aluminum foil 7cm in diameter. A round hole with the diameter of 1cm is arranged in the middle of the aluminum foil. And then, attaching filter paper to the other side of the membrane, then integrally placing the membrane into a membrane pool, controlling the temperature to be 35 ℃, and sealing the membrane pool. Then, the upper side and the lower side of the membrane pool are vacuumized, so that the pressure at the lower side of the membrane pool reaches-0.1 MPa. Then introducing CH in sequence4、N2、O2、CO2The gas pressure on the upper side reaches 0.1MPa, and the transmembrane pressure difference reaches 0.2MPa, so that the gas gradually permeates from the upper side to the lower side of the membrane. Gas permeation flux was calculated after gas permeation equilibrium.
The results show CO for 6FDA/DAPI polyimide membranes2、CH4、O2And N2The permeate flux of (a) was 62.4barrer, 3.0barrer, 13.8barrer and 4.2barrer, respectively. CO 22/CH4And O2/N2The selectivities were not 20.8 and 3.2, respectively. CO of 2-phenylimidazole type super-crosslinked porous polymer mixed matrix membrane2、CH4、O2And N2The permeate flux of (a) was 95.8barrer, 5.7barrer, 22.2barrer and 7.2barrer, respectively. CO 22/CH4And O2/N2The selectivities were not 16.8 and 3.1, respectively.
As can be seen from Table 1, the 2-phenylimidazole type hypercrosslinked porous polymer mixed matrix membrane can greatly improve the permeation flux on the premise of slightly reducing the selectivity compared with the 6FDA/DAPI membrane. Compared with other polyimide mixed matrix membranes (Wrya Mohammadi Aframehr, Banafsh Molki, Rouholah Bagheri, Pejman Heidaian, Seyhed Mahmmodreza Davodi. polyimide with organic oxide nanoparticles [ J ]. Chemical Engineering Research and Design,2020,153:789-805), the membrane has a greatly improved permeation flux.
TABLE 1 gas permeation flux and gas selectivity of different membranes
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose of the embodiments is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
The invention is not the best known technology.
Claims (7)
1. A preparation method of a super cross-linked porous polymer mixed matrix membrane is characterized by comprising the following steps:
(1) dissolving 2-phenylimidazole and alpha, alpha' -dichloro-p-xylene in equal molar weight in 1, 2-dichloroethane, then adding an alkylating reagent, heating at 70-130 ℃ for 12-48h, filtering and washing the mixed solution after reaction until the filtrate is colorless; treating the brown product in a vacuum oven at 60-100 ℃ to obtain a 2-phenylimidazole type super cross-linked porous polymer;
wherein the alkylating agent is anhydrous FeCl3Or anhydrous AlCl3The molar ratio of the alkylating reagent to the 2-phenylimidazole is 1-2;
(2) at-5-25 ℃ and N2Under the atmosphere, stirring and dissolving 6FDA and DAPI in equal molar quantity in a strong polar solution, and then continuously stirring for 2-30h at the rotating speed of 50-600r/min to obtain a 6FDA/DAPI polyamic acid solution; adding acetic anhydride and triethylamine into 6FDA/DAPI polyamide acid solution, heating to 10-50 ℃, and continuously stirring at the rotating speed of 50-600r/min for 10-30h to obtain 6FDA/DAPI polyimide solution; pouring the obtained polyimide solution into an anhydrous methanol solution, stirring for 12-36h for phase conversion, and treating the obtained polyimide solid in a vacuum oven at 60-220 ℃ for 12-24h to obtain 6FDA/DAPI polyimide;
wherein the strong polar solvent is one or a mixture of any more of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the molar ratio of acetic anhydride to triethylamine to 6FDA is 1-12: 3: 3;
(3) adding the 2-phenylimidazole type super cross-linked porous polymer into a strong polar solvent, and performing ultrasonic treatment for 0.5-6.0h to uniformly disperse the polymer; then adding 6FDA/DAPI polyimide, and completely dissolving to obtain a casting solution; uniformly distributing the membrane casting solution in a container with a certain shape, evaporating a polar solvent at 40-120 ℃ to obtain a membrane material, and performing heat treatment on the membrane material in a vacuum oven at 60-220 ℃ to obtain a 2-phenylimidazole type super-crosslinked porous polymer mixed matrix membrane;
wherein the mass of the 6FDA/DAPI polyimide in the casting solution is 100-10000 times of that of the 2-phenylimidazole type super cross-linked porous polymer.
2. The method for preparing a hypercrosslinked porous polymer mixed matrix membrane as claimed in claim 1, wherein the heating at 80-120 ℃ for 12-48 hours in the step (1).
3. The method for preparing a hypercrosslinked porous polymer mixed matrix membrane as claimed in claim 1, wherein the reaction conditions in the step (2) are-5 to 20 ℃ and N2And (4) in an atmosphere.
4. The method for preparing a hypercrosslinked porous polymer mixed matrix membrane as claimed in claim 1, wherein the temperature after adding triethylamine and acetic anhydride in the step (2) is 25 to 35 ℃.
5. The method for preparing a hypercrosslinked porous polymer mixed matrix membrane as claimed in claim 1, wherein the membrane material obtained in the step (3) is subjected to a heat treatment at 60 to 170 ℃ in a vacuum oven.
6. Use of the hypercrosslinked porous polymer mixed matrix membrane prepared by the method of claim 1 for gas separation.
7. Use according to claim 6, characterized in that it comprises the following steps:
(1) cutting the super cross-linked porous polymer mixed matrix membrane of claim 1, placing the cut membrane in a membrane separation evaluation device, introducing raw material gas, keeping the temperature of a membrane pool at 25-45 ℃, and keeping the pressure difference between two sides of the membrane at 0.2 Mpa;
wherein the raw material gas is CO2、CH4、N2、O2Any two or more of them;
(2) and after the gas is stably transmitted, testing the gas flow to obtain the permeation flux and the gas selection coefficient of the gas.
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