CN107551835B - Preparation method of high-flux graphene oxide/polyimide mixed matrix membrane material - Google Patents

Preparation method of high-flux graphene oxide/polyimide mixed matrix membrane material Download PDF

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CN107551835B
CN107551835B CN201710928825.3A CN201710928825A CN107551835B CN 107551835 B CN107551835 B CN 107551835B CN 201710928825 A CN201710928825 A CN 201710928825A CN 107551835 B CN107551835 B CN 107551835B
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graphene oxide
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CN107551835A (en
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鲁云华
肖国勇
李琳
王同华
胡知之
侯旻辰
郝继璨
陈琳
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Dalian University of Technology
University of Science and Technology Liaoning USTL
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Abstract

The invention relates to a preparation method of a high-flux graphene oxide/polyimide mixed matrix membrane material, wherein the high-flux graphene oxide/polyimide mixed matrix membrane material is obtained by introducing graphene oxide into a polyimide matrix capable of generating a thermally-induced rearrangement reaction through an in-situ method to prepare a composite membrane, and then treating the composite membrane at 250-600 ℃ for at least 0.1h in an inert atmosphere; the mixed matrix gas separation membrane material prepared by the invention has the characteristics of excellent permeation separation performance and stable chemical structure, and solves the problems of limited separation performance, poor plasticizing resistance, poor temperature resistance and the like of the existing polymer separation membrane material.

Description

Preparation method of high-flux graphene oxide/polyimide mixed matrix membrane material
Technical Field
The invention relates to the technical field of gas separation membrane materials, in particular to a preparation method of a high-flux graphene oxide/polyimide mixed matrix membrane material.
Background
Compared with the traditional separation technology, the gas membrane separation technology has the advantages of low energy consumption, no pollution, simple equipment and the like, and is widely applied in the fields of natural gas purification, hydrogen recovery, oxygen enrichment, nitrogen enrichment, organic vapor recovery and the like. Gas separation membrane materials that have been commercialized to date are mainly polymeric membrane materials. However, the separation membranes prepared from these polymer membrane materials have either high gas selectivity but low permeability, such as polysulfone, polyethersulfone, polyimide or polyetherimide membrane materials; or high gas permeability with low selectivity, such as silicone rubber-based membrane materials. In addition, the polymer film has the problems of no high temperature resistance, high pressure resistance, poor chemical stability, easy plasticization and the like. With the increasing market requirements for the performance of gas separation membranes, the defects of traditional polymer membrane materials need to be solved. How to improve the gas permeation, separation performance and other comprehensive performances of polymer membrane materials through structural design and modification has become a focus of attention and a main research direction in the technical field of membranes.
It is known that increasing the free volume between polymer molecular chains plays a key role in improving the gas permeability of polymer membrane materials. "self-microporous polymers" polymerized from rigid twisted monomers, as developed by Budd, McKeown and Thomas, exhibit very high gas permeability due to their high free volume, but low separation selectivity. Park et al utilize a thermal rearrangement reaction in an inert gas atmosphere to cause the aromatic polyimide containing-OH groups at the ortho-position of the imide ring to undergo irreversible chemical structure change at a temperature of 350-450 ℃ and to be converted into a new rigid structure polymer, and release a small molecule gas to generate a microporous structure, thereby effectively improving the free volume of the polymer and the gas permeation and separation selectivity. Moreover, the thermotropic rearrangement process and the separation performance can be regulated and controlled by designing the chemical structure, the composition, the film thickness, the heat treatment atmosphere, the process conditions and the like of the polyimide. Therefore, polyimide-based gas separation membrane materials that can be thermally rearranged have become a focus of research in this field.
In order to further improve the performance of the polymer membrane, the preparation of Mixed Matrix Membranes (MMMs) by introducing inorganic porous materials with high gas permeability into polymers is also one of effective means for improving the gas permeability and separation performance of the polymer membrane, and for example, the introduction of inorganic particles such as metal organic framework materials, molecular sieves, zeolites, activated carbon, carbon nanotubes, porous silica and the like improves the gas permeability of the membrane. Although the introduction of the inorganic porous material can effectively increase the gas permeability of the polymer membrane, the gas selectivity is reduced, and due to the compatibility problem between the organic phase and the inorganic phase, organic functional groups need to be introduced on the surface of the inorganic particles to avoid the formation of defects inside the material.
In recent years, graphene has attracted much attention as a two-dimensional layered nanocarbon material with its special properties, and a great deal of research has been conducted on graphene/polymer mixed matrix membrane materials. Compared with graphene, the Graphene Oxide (GO) has better compatibility with polymers due to the fact that the surface or the edge of the graphene oxide contains a plurality of active oxygen-containing functional groups, and can effectively improve the mechanical property, the thermal property, the electrical property and the like of a matrix. Research on the aspect of gas separation of GO/polyimide mixed matrix membranes shows that the addition of GO mainly improves the separation selectivity of polyimide membrane materials, has limited improvement on gas permeability, sometimes even obviously reduces the gas permeability, and blocks gas molecules such as O2、CO2The permeation of water vapor and the like is closely related to the addition amount, functionalization, surface properties and the like of GO, and particularly the interaction between GO and a polymer matrix plays a key role in the diffusion of gas in the membrane. At present, the research on the high-flux graphene oxide/polyimide mixed matrix membrane for gas separation is rarely reported. Therefore, how to utilize the structural characteristics of the graphene oxide, the separation selectivity of the graphene oxide is improved, and the separation membrane material has high gas permeation flux, so that the graphene oxide membrane material has important significance for industrial application of the membrane material.
The method for preparing the graphene oxide/polyimide mixed matrix membrane mainly comprises a blending method and an in-situ method. The blending method is simple and convenient to operate, but the dispersion effect is not as uniform as that of the in-situ method. The achievement of uniform dispersion of the inorganic nano-components in the polymer matrix is the key to maximizing their effect. In addition, increasing the compatibility between the organic phase and the inorganic phase can also reduce internal defects and improve the performance of the mixed matrix membrane material. Therefore, after the graphene oxide or the functionalized graphene oxide is subjected to ultrasonic dispersion treatment, stable chemical bonds are formed with monomers for combination, and then polymerization reaction is performed, so that the graphene oxide can be uniformly dispersed in a polymer matrix, and the compatibility between two phases is effectively improved.
At present, the method for improving the permeation and separation performance of a mixed matrix membrane by using polyimide capable of generating a thermal rearrangement reaction as a matrix and using graphene oxide to regulate and control the size and distribution of a matrix pore structure has not been reported. How to design and prepare a mixed matrix gas separation membrane material with stable chemical properties and excellent gas permeation and separation performance is a problem which needs to be solved urgently in the technical field.
Disclosure of Invention
The invention provides a preparation method of a high-flux graphene oxide/polyimide mixed matrix membrane material, the prepared mixed matrix gas separation membrane material has the characteristics of excellent permeation separation performance and stable chemical structure, and the problems of limited separation performance, poor plasticizing resistance, poor temperature resistance and the like of the existing polymer separation membrane material are solved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the high-flux graphene oxide/polyimide mixed matrix membrane material comprises the steps of introducing graphene oxide into a polyimide substrate capable of generating a thermally induced rearrangement reaction through an in-situ method to prepare a composite membrane, and treating the composite membrane at 250-600 ℃ for at least 0.1h in an inert atmosphere;
the polyimide is a polyimide polymer capable of generating a thermal rearrangement reaction, and the chemical structure of the polyimide polymer has the following characteristics:
Figure BDA0001428216600000031
in the formula:
Figure BDA0001428216600000032
wherein n represents the degree of polymerization.
The graphene oxide is graphene oxide or functionalized graphene oxide; the content of the graphene oxide in the composite material film is 0.01-10 wt%.
The high-flux graphene oxide/polyimide mixed matrix film material is obtained by treating the prepared composite material film at 250-600 ℃ for 0.1-72 h in an inert atmosphere, wherein the heating rate is 1-20 ℃/min.
The inert atmosphere is one or more of nitrogen and argon, and the flow rate of the inert gas is 10-300 ml/min.
The method comprises the steps of introducing graphene oxide into a polyimide matrix capable of generating a thermal rearrangement reaction through an in-situ method, specifically dispersing the graphene oxide in a polar solvent, performing ultrasonic dispersion treatment to obtain a graphene oxide/polar solution suspension solution, adding a diamine monomer containing hydroxyl, reacting at 40-100 ℃ for 4-24 hours, cooling to room temperature, adding an equimolar amount of dianhydride monomer, and performing solution polycondensation reaction to obtain a graphene oxide/polyamide acid solution.
The graphene oxide is introduced into a polyimide substrate capable of generating a thermal rearrangement reaction to prepare a graphene oxide/polyamide acid solution, then the coated graphene oxide/polyamide acid liquid film is subjected to far infrared heating treatment at room temperature to 250 ℃ to obtain a self-supporting film, and then heat treatment is carried out at 250 to 600 ℃ to obtain the high graphene oxide/polyimide mixed substrate film material.
In the synthesis of the polyimide polymer capable of generating the thermal rearrangement reaction, diamine monomer NH2-R-NH2Selected from: bis (3-hydroxy-4-aminophenyl) diphenylmethane, 9, 9-bis (3-amino-4-hydroxyphenyl) fluorene, 3, 3-bis (3-amino-4-hydroxyphenyl) -1(3H) -isobenzofuranone, 3,3,3',3' -tetramethyl-5, 5 '-diamino-6, 6' -dihydroxy-1, 1 '-spirobiindane, 3,3,3',3 '-tetramethyl-6, 6' -bis [ 3-hydroxy-4-aminophenoxy ] phenoxy]-1,1' -spirobiindane, bis [4- (3-hydroxy-4-aminophenoxy) phenyl]Diphenylmethane, 9, 9-bis [4- (3-hydroxy-4-aminophenoxy) phenyl]Fluorene, 3, 3-bis [4- (3-hydroxy-4-aminophenoxy) phenyl]Any one or more of phthalide; the dianhydride monomer is selected from: 4,4' - (hexafluoroisopropylidene) diphthalic anhydride, 9, 9-bis (4- (isobenzofuran-1, 3-dione) -5-oxyphenyl) -9H-fluorene, 3, 3-bis (4- (isobenzofuran-1, 3-dione) -5-oxyphenyl) isobenzofuran-1 (3H) -one, bis (4- (isobenzofuran-1, 3-dione) -5-oxyphenyl) diphenylmethane.
Compared with the prior art, the invention has the beneficial effects that:
1) uniformly introducing graphene oxide into a polyimide substrate by an in-situ method, combining a thermotropic rearrangement reaction with the design of a high free volume space and a rigid structure of polyimide, and modifying the substrate by utilizing a two-dimensional layered structure of the graphene oxide to prepare a mixed substrate membrane material with high flux and high selectivity;
2) the prepared membrane material has the performance advantages of high mechanical property, excellent gas permeation and separation performance, stable chemical structure, high use temperature and the like, and has wide application prospect in the field of gas separation.
Detailed Description
The preparation method of the high-throughput graphene oxide/polyimide mixed matrix membrane material comprises the steps of introducing graphene oxide into a polyimide matrix capable of generating a thermally-induced rearrangement reaction through an in-situ method to prepare a composite membrane, and treating the composite membrane at 250-600 ℃ for at least 0.1h in an inert atmosphere;
the polyimide is a polyimide polymer capable of generating a thermal rearrangement reaction, and the chemical structure of the polyimide polymer has the following characteristics:
Figure BDA0001428216600000041
in the formula:
Figure BDA0001428216600000042
wherein n represents the degree of polymerization.
The graphene oxide is graphene oxide or functionalized graphene oxide; the content of the graphene oxide in the composite material film is 0.01-10 wt%.
The high-flux graphene oxide/polyimide mixed matrix film material is obtained by treating the prepared composite material film at 250-600 ℃ for 0.1-72 h in an inert atmosphere, wherein the heating rate is 1-20 ℃/min.
The inert atmosphere is one or more of nitrogen and argon, and the flow rate of the inert gas is 10-300 ml/min.
The method comprises the steps of introducing graphene oxide into a polyimide matrix capable of generating a thermal rearrangement reaction through an in-situ method, specifically dispersing the graphene oxide in a polar solvent, performing ultrasonic dispersion treatment to obtain a graphene oxide/polar solution suspension solution, adding a diamine monomer containing hydroxyl, reacting at 40-100 ℃ for 4-24 hours, cooling to room temperature, adding an equimolar amount of dianhydride monomer, and performing solution polycondensation reaction to obtain a graphene oxide/polyamide acid solution.
The graphene oxide is introduced into a polyimide substrate capable of generating a thermal rearrangement reaction to prepare a graphene oxide/polyamide acid solution, then the coated graphene oxide/polyamide acid liquid film is subjected to far infrared heating treatment at room temperature to 250 ℃ to obtain a self-supporting film, and then heat treatment is carried out at 250 to 600 ℃ to obtain the high graphene oxide/polyimide mixed substrate film material.
In the synthesis of the polyimide polymer capable of generating the thermal rearrangement reaction, diamine monomer NH2-R-NH2Selected from: bis (3-hydroxy-4-aminophenyl) diphenylmethane, 9, 9-bis (3-amino-4-hydroxyphenyl) fluorene, 3, 3-bis (3-amino-4-hydroxyphenyl) -1(3H) -isobenzofuranone, 3,3,3',3' -tetramethyl-5, 5 '-diamino-6, 6' -dihydroxy-1, 1 '-spirobiindane, 3,3,3',3 '-tetramethyl-6, 6' -bis [ 3-hydroxy-4-aminophenoxy ] phenoxy]-1,1' -spirobiindane, bis [4- (3-hydroxy-4-aminophenoxy) phenyl]Diphenylmethane, 9, 9-bis [4- (3-hydroxy-4-aminophenoxy) phenyl]Fluorene, 3, 3-bis [4- (3-hydroxy-4-aminophenoxy) phenyl]Any one or more of phthalide; the dianhydride monomer is selected from: 4,4' - (hexafluoroisopropylidene) diphthalic anhydride, 9, 9-bis (4- (isobenzofuran-1, 3-dione) -5-oxyphenyl) -9H-fluorene, 3, 3-bis (4- (isobenzofuran-1, 3-dione) -5-oxyphenyl) isobenzofuran-1 (3H) -one, bis (4- (isobenzofuran-1, 3-dione) -5-oxyphenyl) diphenylmethane.
The following examples are carried out on the premise of the technical scheme of the invention, and detailed embodiments and specific operation processes are given, but the scope of the invention is not limited to the following examples. The methods used in the following examples are conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
[ example 1 ]
Firstly, preparing aminated graphene according to a conventional method. Adding a certain amount of aminated graphene and N, N-dimethylacetamide into a 250mL three-neck round-bottom flask, and shaking for 2 hours under the action of ultrasonic waves. Then, 0.01mol of bis (3-hydroxy-4-aminophenyl) diphenylmethane was added, and the reaction was carried out for 16 hours at 40 ℃ under mechanical stirring and under a nitrogen atmosphere. After cooling to room temperature, 0.01mol of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA) was added, and stirring was continued at room temperature for 18 hours to form a viscous aminated graphene/polyamic acid mixed solution having a solid content of 15 wt%. The solution is evenly coated on a clean glass plate and is respectively dried for 6 hours in a far infrared drying oven at 80 ℃ and 150 ℃ to obtain the composite material film. The content of the aminated graphene in the composite film was 0.1 wt%.
And (2) placing the composite material film containing 0.1 wt% of aminated graphene in a heating furnace, introducing nitrogen, heating the furnace temperature to 250 ℃ at the speed of 2 ℃/min, heating to 480 ℃ at the speed of 1 ℃/min, maintaining the temperature for 1 hour, and naturally cooling to obtain the graphene oxide/polyimide mixed matrix film material.
[ example 2 ]
Firstly, preparing aminated graphene according to a conventional method. Adding a certain amount of aminated graphene and N, N-dimethylacetamide into a 250mL three-neck round-bottom flask, and shaking for 2 hours under the action of ultrasonic waves. Then, 9, 9-bis (4-aminophenyl) fluorene and 0.01mol of 9, 9-bis (3-amino-4-hydroxyphenyl) fluorene were added thereto, and the mixture was reacted at 70 ℃ for 12 hours under mechanical stirring and nitrogen protection. After cooling to room temperature, 0.02mol of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA) was added, and stirring was continued at room temperature for 18 hours to form a viscous aminated graphene/polyamic acid mixed solution having a solid content of 15 wt%. The solution is evenly coated on a clean glass plate, is dried for 24 hours at 40 ℃, is subjected to demoulding, and is then respectively dried for 6 hours at 80 ℃ and 150 ℃ in a far infrared drying oven to obtain the composite material film. The content of the aminated graphene in the composite material is 0.5 wt%.
And (2) placing the composite material film containing 0.5 wt% of aminated graphene in a heating furnace, introducing nitrogen, heating the furnace temperature to 250 ℃ at the speed of 2 ℃/min, heating to 450 ℃ at the speed of 1 ℃/min, maintaining the temperature for 1 hour, and naturally cooling to obtain the graphene oxide/polyimide mixed matrix film material.
[ example 3 ]
The preparation method of the composite material film in the embodiment is the same as that in the embodiment 2, and is different from the embodiment 2 in that the composite material film containing 0.5 wt% of aminated graphene is placed in a heating furnace, nitrogen is introduced, the gas flow rate is 100ml/min, the furnace temperature is increased to 250 ℃ at 2 ℃/min, then the temperature is increased to 550 ℃ at 1 ℃/min, the temperature is maintained for 1 hour, and the graphene oxide/polyimide mixed matrix film material is obtained after natural temperature reduction.
[ example 4 ]
Firstly, preparing aminated graphene according to a conventional method. Adding a certain amount of aminated graphene and N, N-dimethylacetamide into a 250mL three-neck round-bottom flask, and shaking for 2 hours under the action of ultrasonic waves. Then, 3, 3-bis [4- (3-hydroxy-4-aminophenoxy) phenyl ] phthalide (0.01 mol) was added and reacted at 70 ℃ for 12 hours under mechanical stirring and nitrogen protection. After cooling to room temperature, 0.01mol of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA) was added, and stirring was continued at room temperature for 18 hours to form a viscous aminated graphene/polyamic acid mixed solution having a solid content of 15 wt%. The solution is evenly coated on a clean glass plate and is dried in a far infrared drying oven for 2 hours at 100 ℃ and 200 ℃ respectively to obtain the composite material film. The content of the aminated graphene in the composite material is 0.1 wt%.
And (2) placing the composite material film containing 1.0 wt% of aminated graphene in a heating furnace, introducing nitrogen, introducing the nitrogen at the gas flow rate of 100ml/min, raising the furnace temperature to 250 ℃ at the speed of 2 ℃/min, then raising the furnace temperature to 420 ℃ at the speed of 1 ℃/min, maintaining the temperature for 1.5 hours, and naturally cooling to obtain the graphene oxide/polyimide mixed matrix film material.
[ example 5 ]
Firstly, the carboxylated graphene is prepared according to a conventional method. Adding a certain amount of carboxylated graphene and N, N-dimethylacetamide into a 250mL three-neck round-bottom flask, and oscillating for 2 hours under the action of ultrasonic waves. Then, 9, 9-bis (4-aminophenyl) fluorene and 0.01mol of 9, 9-bis (3-amino-4-hydroxyphenyl) fluorene were added thereto, and the mixture was reacted at 60 ℃ for 12 hours under mechanical stirring and nitrogen protection. After cooling to room temperature, 0.02mol of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA) was added, and stirring was continued at room temperature for 18 hours to form a viscous carboxylated graphene/polyamic acid mixed solution having a solid content of 15 wt%. The content of the carboxylated graphene in the composite material is 0.5 wt%. The solution is evenly coated on a clean glass plate, is dried for 24 hours at 40 ℃, is subjected to demoulding, and is then respectively dried for 12 hours at 80 ℃ and 120 ℃ in a far infrared drying oven to obtain the composite material film.
And (2) placing the composite material film containing 0.5 wt% of carboxylated graphene in a heating furnace, introducing nitrogen, heating the furnace temperature to 250 ℃ at the speed of 2 ℃/min, then heating to 450 ℃ at the speed of 1 ℃/min, maintaining the temperature for 1 hour, and naturally cooling to obtain the graphene oxide/polyimide mixed matrix film material.
[ example 6 ]
The preparation method of the composite material film in the embodiment is the same as that in the embodiment 5, and is different from the embodiment 5 in that the composite material film containing 0.5 wt% of carboxylated graphene is placed in a heating furnace, nitrogen is introduced, the gas flow rate is 200ml/min, the furnace temperature is increased to 250 ℃ at 2 ℃/min, then is increased to 550 ℃ at 1 ℃/min, the temperature is maintained for 1 hour, and the graphene oxide/polyimide mixed matrix film material is obtained after natural temperature reduction.
[ example 7 ]
Firstly, graphene oxide is prepared according to a conventional method. Adding a certain amount of graphene oxide and N, N-dimethylacetamide into a 250mL three-neck round-bottom flask, and oscillating for 2 hours under the action of ultrasonic waves. Then, 0.01mol of 9, 9-bis (4-aminophenyl) fluorene and 0.01mol of 9, 9-bis (3-amino-4-hydroxyphenyl) fluorene were added, and the mixture was reacted at 60 ℃ for 6 hours under mechanical stirring and nitrogen protection. After cooling to room temperature, 0.02mol of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA) was added, and stirring was continued at room temperature for 18 hours to form a viscous aminated graphene/polyamic acid mixed solution having a solid content of 15 wt%. The content of graphene in the composite material is 0.5 wt%. The solution is evenly coated on a clean glass plate, is dried for 24 hours at 40 ℃, is subjected to demoulding, and is then respectively dried for 12 hours at 80 ℃ and 120 ℃ in a far infrared drying oven to obtain the composite material film.
And (2) placing the composite material film containing 0.5 wt% of graphene oxide in a heating furnace, introducing nitrogen, wherein the flow rate of the gas is 100ml/min, heating the furnace temperature to 250 ℃ at 2 ℃/min, then heating to 450 ℃ at 1 ℃/min, maintaining the temperature for 1 hour, and naturally cooling to obtain the graphene oxide/polyimide mixed matrix film material.
[ example 8 ]
The preparation method of the composite material film in the embodiment is the same as that in the embodiment 7, and is different from the embodiment 7 in that the composite material film containing 0.5 wt% of graphene oxide is placed in a heating furnace, nitrogen is introduced, the gas flow rate is 100ml/min, the furnace temperature is increased to 250 ℃ at 2 ℃/min, then the temperature is increased to 550 ℃ at 1 ℃/min, the temperature is maintained for 1 hour, and the graphene oxide/polyimide mixed matrix film material is obtained after natural temperature reduction.
The gas permeability of the graphene oxide/polyimide mixed matrix membrane materials prepared in examples 1 to 8 is shown in table 1.
TABLE 1 gas permeation separation Performance of Mixed matrix Membrane materials
Figure BDA0001428216600000081
1Barrer=10-10cm3(STP)cm/cm2s cmHg=3.35×10-16mol m/m2s Pa。
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (5)

1. The preparation method of the high-flux graphene oxide/polyimide mixed matrix membrane material is characterized in that graphene oxide is introduced into a polyimide matrix capable of generating a thermal rearrangement reaction through an in-situ method, specifically, the graphene oxide is dispersed in a polar solvent, a graphene oxide/polar solution suspension solution is obtained after ultrasonic dispersion treatment, a diamine monomer containing hydroxyl is added, the reaction is carried out for 4-24 hours at the temperature of 40-100 ℃, the temperature is reduced to room temperature, then an equimolar amount of dianhydride monomer is added for solution polycondensation reaction, and a graphene oxide/polyamide acid solution is prepared; then carrying out far infrared heating treatment on the coated graphene oxide/polyamide acid liquid film at room temperature to 250 ℃ to obtain a self-supporting film, and carrying out heat treatment at 250-600 ℃ to obtain a high-graphene oxide/polyimide mixed matrix film material; treating the prepared composite material film for at least 0.1h at 250-600 ℃ in an inert atmosphere to obtain a high-flux graphene oxide/polyimide mixed matrix film material;
the polyimide is a polyimide polymer capable of generating a thermal rearrangement reaction, and the chemical structure of the polyimide polymer has the following characteristics:
Figure FDA0002398189890000011
in the formula:
Figure FDA0002398189890000012
wherein n represents the degree of polymerization.
2. The method for preparing the high-throughput graphene oxide/polyimide mixed matrix membrane material according to claim 1, wherein the graphene oxide is graphene oxide or functionalized graphene oxide; the content of the graphene oxide in the composite material film is 0.01-10 wt%.
3. The preparation method of the high-throughput graphene oxide/polyimide mixed matrix film material according to claim 1, wherein the high-throughput graphene oxide/polyimide mixed matrix film material is obtained by treating the prepared composite material film at 250-600 ℃ for 0.1-72 h in an inert atmosphere, and the heating rate is 1-20 ℃/min.
4. The preparation method of the high-throughput graphene oxide/polyimide mixed matrix membrane material according to claim 1, wherein the inert atmosphere is one or more of nitrogen and argon, and the flow rate of the inert gas is 10-300 ml/min.
5. The method for preparing the high-throughput graphene oxide/polyimide mixed matrix membrane material according to claim 1, wherein in the synthesis of the polyimide polymer capable of undergoing the thermal rearrangement reaction, a diamine monomer NH is used2-R-NH2Selected from: bis (3-hydroxy-4-aminophenyl) diphenylmethane, 9, 9-bis (3-amino-4-hydroxyphenyl) fluorene, 3, 3-bis (3-amino-4-hydroxyphenyl) -1(3H) -isobenzofuranone, 3,3,3',3' -tetramethyl-5, 5 '-diamino-6, 6' -dihydroxy-1, 1 '-spirobiindane, 3,3,3',3 '-tetramethyl-6, 6' -bis [ 3-hydroxy-4-aminophenoxy ] phenoxy]-1,1' -spirobiindane, bis [4- (3-hydroxy-4-aminophenoxy) phenyl]Diphenylmethane, 9, 9-bis [4- (3-hydroxy-4-aminophenoxy) phenyl]Fluorene, 3, 3-bis [4- (3-hydroxy-4-aminophenoxy) phenyl]Any one or more of phthalide; the dianhydride monomer is selected from: 4,4' - (hexafluoroisopropylidene) diphthalic anhydride, 9, 9-bis (4- (isobenzofuran-1, 3-dione) -5-oxyphenyl) -9H-fluorene, 3, 3-bis (4- (isobenzofuran-1, 3-dione) -5-oxyphenyl) isobenzofuran-1 (3H) -one, bis (4- (isobenzofuran-1, 3-dione) -5-oxyphenyl) diphenylmethane.
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