CN115382408A - Chemical vapor amination modified porous polymer film and preparation method and application thereof - Google Patents
Chemical vapor amination modified porous polymer film and preparation method and application thereof Download PDFInfo
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- 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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Abstract
The invention belongs to the technical field of high molecular chemistry, and particularly relates to a chemical gas phase amination modified porous polymer membrane and a preparation method and application thereof. The invention adopts a chemical vapor amination method to carry out nucleophilic substitution reaction on amine molecules and epoxy groups and terminal halogen groups in PIM, so as to induce PIM grafting, ring opening, crosslinking and chain scission. CO of porous polymer membranes using only small amounts of amine vapor 2 The affinity and the transmission channel are adjusted according to expectation, so that the adsorption-diffusion process and the carbon capture performance are improved simultaneously, and the used amine solution can be recycled, so that the reaction process is milder, simpler, green, efficient and controllable.
Description
Technical Field
The invention belongs to the technical field of high molecular chemistry, and particularly relates to a chemical gas phase amination modified porous polymer film, and a preparation method and application thereof.
Background
Carbon capture technology has proven to have great potential in reducing carbon emissions and achieving carbon neutralization. Compared to conventional energy-intensive processes, for example CO adsorption by aqueous amine solutions and amine-containing adsorbents 2 Energy-saving membrane separation is a promising alternative technology. CO 2 2 The development of selective membranes is crucial for carbon capture.
Polymeric membranes are widely used semipermeable barriers, but their performance is limited by the trade-off between selectivity and permeability, and therefore designing a highly perm-selective membrane is crucial for gas separation. Intrinsically microporous Polymers (PIMs), such as PIM-1 and the like, have a rigid and ladder-like backbone. This property gives solid PIMs a large number of interconnected nanopores and a high free volume, giving excellent permeability and diffusivity to gas molecules. PIM also has good solubility in organic solvents, making it easy to process, easy to film, and applicable to carbon capture technology. Typically, PIM membranes have gas permeability 2 to 3 orders of magnitude higher than traditional polymer membranes, but with respect to CO 2 /N 2 The selectivity of (a) is only 10-15, and the requirement of carbon capture cannot be met, so that the improvement of the selectivity is the primary task of the PIM membrane.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for modifying a porous polymer membrane by chemical vapor amination, which is simple, convenient and controllable, can simultaneously adjust gas adsorption and diffusion in the porous polymer membrane so as to improve the carbon trapping performance and improve the interface compatibility and the separation performance of a mixed matrix membrane.
The purpose of the invention is realized by the following technical scheme:
a method for chemical vapor amination modification of a porous polymer membrane, comprising the steps of:
(1) Preparation of the porous Polymer: mixing the monomer A, the monomer B and carbonate, adding an organic solvent, heating for reaction, and obtaining a porous polymer after the reaction is finished;
(2) Preparation of porous polymer membranes: dissolving the porous polymer prepared in the step (1) in a solvent to obtain a porous polymer solution, and then completely volatilizing the solvent to form a film;
(3) Preparation of vapor-phase aminated membranes: fixing the porous polymer membrane prepared in the step (2) above a container filled with an amine solution with the smooth surface facing downwards, placing the container in a sealed environment, and gasifying the amine solution in a heat treatment mode to prepare a gas-phase aminated membrane;
the monomer A in the step (1) is at least one of 5,5', 6' -tetrahydroxy-3, 3 '-tetramethyl-1, 1' -helical bisindane, 2,3,6, 7-tetrahydroxy-9, 10-dimethyl-9, 10-acetyl anthracene;
the monomer B in the step (1) is at least one of tetrafluoroterephthalonitrile and 7,7', 8' -tetrachlorophenylmethyl-3, 3 '-tetramethyl-1, 1' -spirobiindane.
The organic solvent in the step (1) is at least one of N-methyl pyrrolidone, N-dimethylformamide, N-dimethylacetamide, N-diethylformamide and toluene;
the carbonate in the step (1) is preferably potassium carbonate and/or sodium carbonate;
the ratio of the carbonate to the organic solvent in the step (1) is 0.01-2 g/mL, preferably 0.1-1 g/mL;
the mass ratio of the monomer A to the monomer B in the step (1) is 1:0.6 to 5, preferably 1:0.6 to 2;
the mass volume ratio of the monomer A to the organic solvent in the step (1) is 1g:5 to 15mL.
The heating reaction in the step (1) is stirring for 10-60 min at 100-200 ℃. Preferably, the heating reaction is performed under a nitrogen atmosphere;
and (2) after the heating reaction in the step (1) is finished, a purification step is also included, specifically, the obtained product is added into methanol, then water and acetone are used for stirring and washing, and finally vacuum drying is carried out for 24-72 h at the temperature of 80-150 ℃.
The solvent in the step (2) is at least one of dichloromethane, trichloromethane, tetrahydrofuran and benzyl alcohol;
the concentration of the porous polymer solution in the step (2) is 0.5 to 10wt%, preferably 3 to 5wt%;
the cylindrical culture dish in the step (2) is a polytetrafluoroethylene culture dish with a cover so as to slow down the volatilization speed;
and (3) after the porous polymer in the step (2) is formed into a film, the film is soaked in methanol for 12-48 h, then the film is clamped between two glass plates to be flattened, and the film is dried in vacuum for 12-48 h at the temperature of 60-120 ℃.
Preferably, metal organic framework particles can be added in the step (2), and the metal organic framework particles are mixed with the porous polymer to prepare a film; the preparation method of the metal organic framework particles comprises the following steps: the metal salt, the organic ligand and the solvent are uniformly mixed, a hydrothermal synthesis method is used for heating reaction, and the metal organic framework particles can be obtained after the reaction is finished.
The mass ratio of the metal-organic framework particles to the porous polymer is 0.03-0.07 g, more preferably 0.03-0.02 g.
In the preparation method of the metal organic framework particles, the metal element in the metal salt is at least one of V, zn, ti, cr, cu, co, fe, ni, mg, cd, sr, zr, nb, mo, ba, mg, mn, al and Gd; the preferable metal element is at least one of Zn and Zr; the metal salt is at least one of nitrate, chlorate, sulfate and acetate of metal; the preferred metal salt is at least one of zinc nitrate and zirconium chloride.
In the preparation method of the metal organic framework particles, the organic ligand is at least one of trimesic acid, terephthalic acid, 2-methylimidazole and imidazole-2-formaldehyde;
in the preparation method of the metal organic framework particles, the solvent is at least one of methanol, ethanol, propanol, isopropanol, tert-butanol, ethylene glycol, glycerol, N-dimethylformamide, N-dimethylacetamide and N, N-diethylformamide;
in the preparation method of the metal-organic framework particles, the mass ratio of the metal salt to the organic ligand is 1:0.65 to 5, preferably 1:0.65 to 2.2;
in the preparation method of the metal organic framework particles, the mass ratio of the metal salt to the solvent is 1:50 to 700, preferably 1:133 to 685;
in the preparation method of the metal organic framework particles, the heating reaction is carried out for 12-24 h at 100-150 ℃.
In the preparation method of the metal organic framework particles, the heating reaction also comprises a purification step, and specifically, the obtained product is added into methanol, stirred and washed, and finally dried under vacuum at 60-100 ℃ for 12-48 h.
The amine solution in the step (3) is at least one of ethylenediamine, 1, 3-propanediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, ammonia water and p-phenylenediamine, and the concentration of the amine solution is 25-99%, preferably 80-99%;
the container in the step (3) is preferably a polytetrafluoroethylene crucible which can resist high temperature;
the heat treatment temperature in the step (3) is 25-130 ℃, and the reaction time is 0.5-12 h;
and (3) after the gas-phase amination membrane is successfully prepared, cooling to room temperature, washing with deionized water to remove residual amine molecules, flattening by using two glass plates, and drying in vacuum at 60-120 ℃ for 12-48 h.
A chemical vapor amination modified porous polymer membrane is prepared by the method.
The chemical gas phase amination modified porous polymer membrane is used for separating CO 2 /N 2 Application in gas.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) Compared with the traditional porous polymer membrane and the existing modification technology, the method adopts a chemical vapor amination method to carry out nucleophilic substitution reaction on amine molecules and epoxy groups and terminal halogen groups in the PIM so as to induce PIM grafting, ring opening, crosslinking and chain scission. Using only small amounts of amineCO of porous polymer film by steam 2 The affinity and the transmission channel are adjusted according to expectation, so that the adsorption-diffusion process and the carbon capture performance are improved simultaneously, and the used amine solution can be recycled, so that the reaction process is milder, simpler, green, efficient and controllable.
(2) The invention can be used for reducing non-selective interface defects in the mixed matrix membrane, and can improve the compatibility by bridging molecules in the mixed matrix membrane through post-synthesis modification so as to simultaneously improve the selectivity and the permeability.
(3) The gas phase aminated film prepared by the invention has excellent CO 2 And N 2 The gas separation performance can be used for realizing better carbon capture effect, and a new idea is provided for the preparation of the high-efficiency separation membrane.
(4) The method has wide universality, can adopt various amine solutions, is suitable for various porous polymer films, and has good application value and development prospect.
Drawings
FIG. 1 is an SEM photograph of a ZIF-8@ PIM-A membrane prepared in example 3 of the present invention and a ZIF-8@ PIM-1 membrane prepared in comparative example 2;
FIG. 2 is a GPC chart of a PIM-A membrane prepared in example 1 of the present invention and a PIM-1 membrane prepared in comparative example 1;
FIG. 3 is an O1sXPS plot of a PIM-A membrane prepared according to example 1 of the present invention versus a PIM-1 membrane prepared according to comparative example 1;
FIG. 4 is FTIR spectra of PIM-A membranes, ZIF-8@ PIM-A membranes prepared in examples 1,3 of the present invention versus PIM-1 membranes, ZIF-8@ -PIM-1 membranes prepared in comparative examples 1, 2;
fig. 5 is a graph showing gas separation performance of the PIM-a membrane prepared in example 1 of the present invention and the PIM-1 membrane prepared in comparative example 1.
FIG. 6 is a graph showing gas separation performance of the ZIF-8@ PIM-A membrane prepared in example 3 of the present invention and the ZIF-8@ PIM-1 membrane prepared in comparative example 2.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Example 1
The porous polymer is PIM-1, the monomer A is 5,5', 6' -tetrahydroxy-3, 3 '-tetramethyl-1, 1' -helical bis-indane, the monomer B is tetrafluoroterephthalonitrile, and the reagent used for amination is ethylenediamine.
The preparation method comprises the following steps:
(1) Preparation of the porous Polymer: 5,5', 6' -tetrahydroxy-3, 3 '-tetramethyl-1, 1' -spirobiindane (6.8 g), tetrafluoroterephthalonitrile (4.0 g) and potassium carbonate (8.3 g) were added to a nitrogen-filled three-necked flask, and after introducing nitrogen for 30min, the three-necked flask was transferred to an oil bath, and after adding N-methylpyrrolidone (40 mL) and toluene (20 mL), gradual temperature rise to 160 ℃ was started for 40min. After the reaction was complete, the yellow viscous liquid was poured into methanol to obtain a yellow solid product. Dissolving the obtained product in trichloromethane, centrifuging to remove potassium carbonate, separating out the product through methanol, washing and purifying the product with deionized water and acetone at 80 ℃ for multiple times, and finally drying at 100 ℃ for 48 hours to obtain the PIM-1.
(2) Preparation of porous polymer film: the prepared PIM-1 (0.26 g) was dissolved in chloroform (3.5 ml) to obtain a porous polymer solution (5% by weight), and after filtering impurities with a 0.45 μm filter head, the solution was poured into a cylindrical petri dish with a lid to slowly volatilize the solvent and form a film. And after film formation, soaking the film in methanol for 36h, clamping between two glass plates, flattening, and finally drying in vacuum at 100 ℃ for 12h to obtain the PIM-1 film.
(3) Preparing a gas-phase aminated membrane: the prepared PIM-1 film was placed with the smooth surface facing downward on a filter screen above a small crucible containing 5mL of an ethylenediamine solution (99%), the small crucible was placed in a reaction vessel to be completely sealed, and reacted at 60 ℃ for 1 hour. And after the reaction is finished, quickly taking out the reaction kettle, cooling the reaction kettle to room temperature, taking out the membrane, cooling the membrane, washing the membrane for multiple times by using deionized water to remove residual amine molecules, clamping the membrane between two glass plates, flattening the membrane, and finally drying the membrane in vacuum at 100 ℃ for 12 hours to obtain the gas-phase aminated membrane PIM-A.
As shown by GPC chart in FIG. 2, the PIM-A membrane has a smaller molecular weight than the pristine PIM-1 membrane and a broader molecular weight distribution, indicating intermolecular chain scission and a broader molecular weight distribution in the vapor phase amination processAnd (4) crosslinking. FIG. 3 is an XPS plot, and it can be seen that the intensity of the C-O-C peak decreases after the gas phase amination modification. FIG. 4 is an infrared spectrum chart showing that the peak intensity of C-O-C of the PIM-A membrane after vapor phase amination modification is lower, and C-N and N-H peaks appear, and FIGS. 3 and 4 prove that substitution reaction occurs between ethylenediamine and PIM-1. FIG. 5 is a graph showing the results of gas separation tests on PIM-1 and PIM-A membranes (separation performance test using a mixed gas permeation analyzer Labtracking Co.), indicating that the PIM-A membrane is sensitive to CO at a pressure of 0.1MPa 2 Has a permeability of 4327barrer 2 /N 2 The selectivity was 19.8, which was increased to 146% compared to PIM-1 before modification (comparative example 1).
Example 2
The porous polymer is PIM-1, the monomer A is 5,5', 6' -tetrahydroxy-3, 3 '-tetramethyl-1, 1' -helical bisindane, the monomer B is tetrafluoroterephthalonitrile, and the reagent used for amination is 1, 3-propanediamine.
The preparation method comprises the following steps:
(1) Preparation of the porous Polymer: 5,5', 6' -tetrahydroxy-3, 3 '-tetramethyl-1, 1' -spirobiindane (2.3 g), tetrafluoroterephthalonitrile (1.3 g) and potassium carbonate (2.8 g) were added to a nitrogen-filled three-necked flask, the three-necked flask was transferred to an oil bath after 30min of nitrogen introduction, and after N-methylpyrrolidone (13.3 mL) and toluene (6.7 mL) were added, gradual temperature rise to 140 ℃ was started for 60min. After the reaction was complete, the yellow viscous liquid was poured into methanol to obtain a yellow solid product. Dissolving the obtained product in trichloromethane, centrifuging to remove potassium carbonate, separating out the product through methanol, washing and purifying the product with deionized water and acetone at 80 ℃ for multiple times, and finally drying at 80 ℃ for 48 hours to obtain the PIM-1.
(2) Preparation of porous polymer membranes: the prepared PIM-1 (0.52 g) was dissolved in chloroform (3.5 ml) to obtain a porous polymer solution (10% by weight), and after filtering impurities with a 0.45 μm filter head, the solution was poured into a cylindrical petri dish with a lid to slowly volatilize the solvent and form a film. And after film formation, soaking the film in methanol for 12h, clamping between two glass plates, flattening, and finally drying in vacuum at 60 ℃ for 48h to obtain the PIM-1 film.
(3) Preparing a gas-phase aminated membrane: the prepared PIM-1 membrane was placed with the smooth surface facing downward on a filter screen above a small crucible containing 5mL1, 3-propanediamine solution (80%), the small crucible was placed in a reaction vessel to be completely sealed, and the reaction was carried out at 80 ℃ for 0.5h. And after the reaction is finished, quickly taking out the reaction kettle, cooling the reaction kettle to room temperature, taking out the film, cooling the film, washing the film for multiple times by using deionized water to remove residual amine molecules, clamping the film between two glass plates, flattening the film, and finally drying the film for 48 hours in vacuum at 120 ℃ to obtain the gas-phase aminated film.
Example 3
The porous polymer is PIM-1, the monomer A is 5,5', 6' -tetrahydroxy-3, 3 '-tetramethyl-1, 1' -spiral biindane, the monomer B is tetrafluoroterephthalonitrile, the metal organic framework particles are ZIF-8, the metal salt is zinc nitrate hexahydrate, the organic ligand is 2-methylimidazole, and the reagent used for amination is ethylenediamine.
The preparation method comprises the following steps:
(1) Preparation of the porous Polymer: 5,5', 6' -tetrahydroxy-3, 3 '-tetramethyl-1, 1' -spirobiindane (4.6 g), tetrafluoroterephthalonitrile (2.6 g) and potassium carbonate (2.7 g) were added to a nitrogen-filled three-necked flask, and after introducing nitrogen for 30min, the three-necked flask was transferred to an oil bath, and after adding N, N-dimethylacetamide (26.6 mL), the temperature was gradually raised to 200 ℃ for 30min. After the reaction was complete, the yellow viscous liquid was poured into methanol to obtain a yellow solid product. And dissolving the obtained product in trichloromethane, centrifuging to remove potassium carbonate, separating out the product through methanol, washing and purifying the product with deionized water and acetone at the temperature of 80 ℃ for multiple times, and finally drying at the temperature of 150 ℃ for 72 hours to obtain the PIM-1.
(2) Preparing metal organic framework particles: respectively dissolving zinc nitrate hexahydrate (5.4 g) and 2-methylimidazole (11.8 g) in methanol (250 mL), uniformly mixing, placing in a reaction kettle for heat treatment at 150 ℃ for 12h, centrifuging to obtain white powder, washing with methanol for multiple times, and finally performing vacuum drying at 80 ℃ for 48h to obtain the metal organic framework ZIF-8.
(3) Preparation of porous polymer membranes: prepared PIM-1 (0.26 g) and ZIF-8 (0.08 g) were dissolved in chloroform (1.75 ml), and impurities in the porous polymer solution were filtered through a 0.45 μm filter, mixed well, and the solution was poured into a cylindrical petri dish with a lid to allow the solvent to slowly evaporate and form a film. Soaking the membrane in methanol for 48h after film formation, clamping between two glass plates, flattening, and vacuum drying at 120 deg.C for 36h to obtain ZIF-8@ PIM-1 membrane.
(4) Preparing a gas-phase aminated membrane: the prepared ZIF-8@ PIM-1 film was placed on a filter screen above a small crucible containing 5mL of ethylenediamine solution (99%) with the smooth surface facing downward, the small crucible was placed in a reaction vessel to be completely sealed, and the reaction was carried out at 60 ℃ for 1 hour. And after the reaction is finished, quickly taking out the reaction kettle, cooling the reaction kettle to room temperature, taking out the film, cooling the film, washing the film for multiple times by using deionized water to remove residual amine molecules, clamping the film between two glass plates, flattening the film, and finally drying the film for 36 hours in vacuum at 120 ℃ to obtain the gas-phase aminated film.
As shown in the SEM image in figure 1, the polymer stripes of the ZIF-8@ PIM-A membrane are more compact than those of the ZIF-8@ PIM-1 membrane without amination, which indicates that amine molecules bridge a metal organic framework and a PIM molecular chain, so that the interface compatibility is improved. FIG. 4 is an infrared spectrum, which shows that the peak intensity of the C-O-C of the ZIF-8@ PIM-A membrane after vapor phase amination modification is lower, and an N-H peak appears, thus confirming the success of amination reaction. FIG. 6 is a view showing a result of a gas separation test using ZIF-8@ PIM-1 and ZIF-8@ PIM-A membranes, and the result shows that the ZIF-8@ PIM-A membrane is responsible for CO at a pressure of 0.1MPa 2 Has a permeability of 7106Barrer, which is increased to 164% compared with the PIM-A membrane (example 1); CO 2 2 /N 2 The selectivity was 17.6, which was increased to 147% compared to ZIF-8@ PIM-1 before modification (comparative example 2).
Example 4
The porous polymer is PIM-7, the monomer A is 5,5', 6' -tetrahydroxy-3, 3' -tetramethyl-1, 1' -helical bisindane, the monomer B is 7,7', 8' -tetrachlorophenylmethyl-3, 3',3' -tetramethyl-1, 1' -spirobiindane, the metal organic framework particle is ZIF-90, the metal salt is zinc nitrate tetrahydrate, the organic ligand is imidazole-2-formaldehyde, and the reagent used for amination is diethylenetriamine.
The preparation method comprises the following steps:
(1) Preparation of the porous Polymer: 5,5',6,6' -tetrahydroxy-3,3,3 ',3' -tetramethyl-1, 1' -spirobiindane (1.5 g), 7,7', 8' -tetrachlorophenylmethyl-3,3, 3' -tetramethyl-1, 1' -spirobiindane (2.7 g) and potassium carbonate (4 g) were charged into a three-necked flask filled with nitrogen gas, after nitrogen is introduced for 30min, the three-neck flask is transferred to an oil bath pot, N-dimethylformamide (20 mL) is added, the temperature is gradually increased to 170 ℃, and the reaction time is 10min. After the reaction was complete, the yellow viscous liquid was poured into methanol to obtain a yellow solid product. And dissolving the obtained product in trichloromethane, centrifuging to remove potassium carbonate, separating out the product through methanol, washing and purifying the product with deionized water and acetone at the temperature of 80 ℃ for multiple times, and finally drying at the temperature of 150 ℃ for 72 hours to obtain the PIM-7.
(2) Preparing metal organic framework particles: respectively dissolving 5.4g of zinc nitrate tetrahydrate and 2-methylimidazole 2.9g in N, N-dimethylformamide (150 mL), uniformly mixing, placing in a reaction kettle, carrying out heat treatment at 100 ℃ for 18h, centrifuging to obtain light yellow powder, washing with methanol for multiple times, and finally carrying out vacuum drying at 80 ℃ for 12h to obtain the metal organic framework ZIF-90.
(3) Preparation of porous polymer film: the prepared PIM-7 (0.07 g) and ZIF-90 (0.03 g) were dissolved in dichloromethane (5 ml) respectively, and after filtering impurities in the porous polymer solution with a 0.45 μm filter, they were mixed well, and after filtering impurities with a 0.45 μm filter, the solution was poured into a cylindrical petri dish with a lid to slowly evaporate the solvent and form a film. Soaking the membrane in methanol for 36h after film formation, clamping between two glass plates, flattening, and vacuum drying at 110 deg.C for 24h to obtain ZIF-90@ PIM-7 membrane.
(4) Preparing a gas-phase aminated membrane: the prepared ZIF-90@ PIM-7 film was placed on a filter screen above a small crucible containing 5mL of diethylenetriamine solution (90%), the small crucible was placed in a reaction vessel to be completely sealed, and the reaction was carried out at 110 ℃ for 12 hours. And after the reaction is finished, quickly taking out the reaction kettle, cooling the reaction kettle to room temperature, taking out the film, cooling the film, washing the film for multiple times by using deionized water to remove residual amine molecules, clamping the film between two glass plates, flattening the film, and finally drying the film for 24 hours in vacuum at 110 ℃ to obtain the gas-phase aminated film.
Example 5
The porous polymer is PIM-7, the monomer A is 5,5', 6' -tetrahydroxy-3, 3 '-tetramethyl-1, 1' -spiral bisindane, the monomer B is 7,7', 8' -tetrachlorophenylmethyl-3, 3 '-tetramethyl-1, 1' -spirobiindane, and the amination reagent is ammonia water.
The preparation method comprises the following steps:
(1) Preparation of the porous Polymer: 5,5',6,6' -tetrahydroxy-3,3,3 ',3' -tetramethyl-1, 1' -spirobiindane (3.0 g), 7,7', 8' -tetrachlorophenylmethyl-3,3, 3' -tetramethyl-1, 1' -spirobiindane (5.4 g) and potassium carbonate (0.4 g) were added to a nitrogen-filled three-necked flask, after nitrogen is introduced for 30min, the three-neck flask is transferred to an oil bath pot, N-diethylformamide (40 mL) is added, the temperature is gradually increased to 100 ℃, and the reaction time is 30min. After the reaction was complete, the yellow viscous liquid was poured into methanol to obtain a yellow solid product. And dissolving the obtained product in trichloromethane, centrifuging to remove potassium carbonate, separating out the product through methanol, washing and purifying the product with deionized water and acetone at the temperature of 80 ℃ for multiple times, and finally drying at the temperature of 100 ℃ for 48 hours to obtain the PIM-7.
(2) Preparation of porous polymer membranes: the prepared PIM-7 (0.18 g) was dissolved in tetrahydrofuran (2 ml) to obtain a porous polymer solution (10% by weight), and after filtering impurities with a 0.45 μm filter head, the solution was poured into a cylindrical petri dish with a lid to slowly volatilize the solvent and form a film. And after film formation, soaking the film in methanol for 20h, clamping between two glass plates, flattening, and finally drying in vacuum at 60 ℃ for 20h to obtain the PIM-7 film.
(3) Preparing a gas-phase aminated membrane: the prepared PIM-7 film was placed with the smooth surface facing downward on a filter screen above a small crucible containing 5mL of ammonia (25%), the small crucible was placed in a reaction vessel to be completely sealed, and reacted at 25 ℃ for 12 hours. And after the reaction is finished, quickly taking out the reaction kettle, cooling the reaction kettle to room temperature, taking out the film, cooling the film, washing the film for multiple times by using deionized water to remove residual amine molecules, clamping the film between two glass plates, flattening the film, and finally drying the film for 20 hours in vacuum at the temperature of 60 ℃ to obtain the gas-phase aminated film.
Example 6
The porous polymer is PIM-8, the monomer A is 2,3,6, 7-tetrahydroxy-9, 10-dimethyl-9, 10-acetyl anthracene, the monomer B is 7,7', 8' -tetrachlorophenylmethyl-3, 3 '-tetramethyl-1, 1' -spirobiindane, the metal organic framework particles are UiO-66, the metal salt is zirconium chloride, the organic ligand is terephthalic acid, and the reagent for amination is triethylene tetramine.
The preparation method comprises the following steps:
(1) Preparation of the porous Polymer: 2,3,6, 7-Tetrahydroxy-9, 10-dimethyl-9, 10-acetylanthracene (1.7 g), 7', 8' -tetrachlorophenylmethyl-3, 3 '-tetramethyl-1, 1' -spirobiindane (3.4 g) and potassium carbonate (30 g) were added to a three-necked flask filled with nitrogen, the three-necked flask was transferred to an oil bath 30min after introduction of nitrogen, and after addition of N, N-dimethylformamide (15 mL), gradual temperature rise to 150 ℃ was started for a reaction time of 50min. After the reaction was complete, the yellow viscous liquid was poured into methanol to obtain a yellow solid product. Dissolving the obtained product in chloroform, centrifuging to remove potassium carbonate, separating out the product through methanol, washing and purifying the product with deionized water and acetone at 80 ℃ for multiple times, and finally drying at 120 ℃ for 30 hours to obtain the PIM-8.
(2) Preparing metal organic framework particles: zirconium chloride (5.3 g) and terephthalic acid (3.4 g) are completely dissolved in N, N-dimethylformamide (315 mL), the mixture is placed in a reaction kettle for heat treatment at 120 ℃ for 24h, white powder is obtained by centrifugation and is washed by N, N-dimethylformamide and methanol for multiple times, and finally vacuum drying is carried out at 100 ℃ for 24h, so as to obtain the metal organic framework UiO-66.
(3) Preparation of porous polymer film: the prepared PIM-8 (0.19 g) and UiO-66 (0.06 g) were dissolved in benzyl alcohol (2.3 ml), and impurities in the porous polymer solution were filtered with a 0.45 μm filter tip and mixed well, and the solution was poured into a cylindrical petri dish with a lid to allow the solvent to slowly evaporate and form a membrane. Soaking the film in methanol for 30h after film formation, clamping between two glass plates, flattening, and vacuum drying at 80 deg.C for 30h to obtain UiO-66@ PIM-8 film.
(4) Preparing a gas-phase aminated membrane: the prepared UiO-66@ PIM-8 film was placed on a filter screen above a small crucible containing 5mL of triethylenetetramine solution (98%), the small crucible was placed in a reaction vessel to be completely sealed, and the reaction was carried out at 70 ℃ for 10 hours. And after the reaction is finished, quickly taking out the reaction kettle, cooling the reaction kettle to room temperature, taking out the film, cooling the film, washing the film for multiple times by using deionized water to remove residual amine molecules, clamping the film between two glass plates, flattening the film, and finally drying the film for 30 hours in vacuum at 70 ℃ to obtain the gas-phase aminated film.
COMPARATIVE EXAMPLE 1 (unmodified pristine PIM-1 Membrane)
The porous polymer is PIM-1, the monomer A is 5,5', 6' -tetrahydroxy-3, 3 '-tetramethyl-1, 1' -helical biindane, and the monomer B is tetrafluoroterephthalonitrile.
The preparation method comprises the following steps:
(1) Preparation of the porous Polymer: 5,5',6,6' -tetrahydroxy-3,3,3 ',3' -tetramethyl-1, 1' -spirobiindane (6.8 g), tetrafluoroterephthalonitrile (4.0 g) and potassium carbonate (8.3 g) were charged into a nitrogen-filled three-necked flask, and after 30min by nitrogen gas introduction, 40mL of N-methylpyrrolidone and 20mL of toluene were added and reacted at 160 ℃ for 40min. And after the reaction is finished, pouring the yellow viscous liquid into methanol, purifying and drying to obtain a yellow solid product PIM-1.
(2) Preparation of porous polymer membranes: the prepared PIM-1 (0.26 g) was dissolved in chloroform (3.5 ml) to obtain a porous polymer solution (5 wt%), the solution was poured onto a glass plate, the solvent was slowly volatilized and a film was formed, and finally dried under vacuum at 100 ℃ for 12 hours to obtain a PIM-1 film.
As can be seen from FIG. 5, in the gas separation test, the unmodified pristine PIM-1 membrane exhibited inferior gas separation performance, CO, compared to the gas phase amination-modified porous polymer membrane in example 1 2 /N 2 CO selectivity of 13.6 only, while vapor phase amination modified membranes 2 /N 2 The selectivity is 19.8, which is improved to 146 percent, and the superiority of the gas-phase amination modified porous polymer membrane is proved.
COMPARATIVE EXAMPLE 2 (unmodified pristine ZIF-8@ PIM-1 film)
The porous polymer is PIM-1, the monomer A is 5,5', 6' -tetrahydroxy-3, 3 '-tetramethyl-1, 1' -helical biindane, and the monomer B is tetrafluoroterephthalonitrile.
The preparation method comprises the following steps:
(1) Preparation of the porous Polymer: 5,5',6,6' -tetrahydroxy-3,3,3 ',3' -tetramethyl-1, 1' -spirobiindane (6.8 g), tetrafluoroterephthalonitrile (4.0 g) and potassium carbonate (8.3 g) were charged into a nitrogen-filled three-necked flask, and after 30min by nitrogen gas introduction, 40mL of N-methylpyrrolidone and 20mL of toluene were added and reacted at 160 ℃ for 40min. And after the reaction is finished, pouring the yellow viscous liquid into methanol, purifying and drying to obtain a yellow solid product PIM-1.
(2) Preparing a metal organic framework material: respectively dissolving zinc nitrate hexahydrate (4.29 g) and 2-methylimidazole (9.43 g) in methanol (200 mL), uniformly mixing, placing in a reaction kettle for heat treatment at 150 ℃ for 12h, centrifuging to obtain white powder, washing with methanol for multiple times, and finally performing vacuum drying at 80 ℃ for 48h to obtain the metal organic framework ZIF-8.
(3) Preparation of porous polymer membranes: respectively dissolving the prepared PIM-1 (0.26 g) and ZIF-8 (0.08 g) in chloroform (1.75 ml) and mixing uniformly to obtain a mixed solution, pouring the solution on a glass plate, slowly volatilizing the solvent to form a membrane, and finally drying in vacuum at 100 ℃ for 12h to obtain the ZIF-8@ PIM-1 membrane.
As can be seen from FIG. 6, in the gas separation test, the unmodified pristine ZIF-8@ PIM-1 membrane exhibited inferior gas separation performance, CO, compared to the gas phase amination modified mixed matrix membrane of example 3 2 /N 2 CO selectivity of only 12.0, while vapor phase amination modified membranes 2 /N 2 The selectivity is 17.6, which is improved to 147 percent, and the superiority of the gas-phase amination modified porous polymer membrane is proved.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for chemical vapor amination modification of a porous polymer membrane, characterized by comprising the steps of:
(1) Preparation of the porous Polymer: mixing the monomer A, the monomer B and carbonate, adding an organic solvent, heating for reaction, and obtaining a porous polymer after the reaction is finished;
(2) Preparation of porous polymer membranes: dissolving the porous polymer prepared in the step (1) in a solvent to obtain a porous polymer solution, and then completely volatilizing the solvent to form a film;
(3) Preparation of vapor-phase aminated membranes: fixing the porous polymer membrane prepared in the step (2) above a container filled with an amine solution with the smooth surface facing downwards, placing the container in a completely sealed environment, and gasifying the amine solution in a heat treatment mode to prepare a gas-phase aminated membrane;
the monomer A in the step (1) is at least one of 5,5', 6' -tetrahydroxy-3, 3 '-tetramethyl-1, 1' -helical bis-indane, 2,3,6, 7-tetrahydroxy-9, 10-dimethyl-9, 10-acetyl anthracene;
the monomer B in the step (1) is at least one of tetrafluoroterephthalonitrile and 7,7', 8' -tetrachlorophenylmethyl-3, 3 '-tetramethyl-1, 1' -spirobiindane.
2. The method of claim 1, wherein: the organic solvent in the step (1) is at least one of N-methyl pyrrolidone, N-dimethylformamide, N-dimethylacetamide, N-diethylformamide and toluene; the carbonate in the step (1) is potassium carbonate and/or sodium carbonate; the ratio of the carbonate to the organic solvent in the step (1) is 0.01-2 g/mL.
3. The method of claim 1, wherein: the mass ratio of the monomer A to the monomer B in the step (1) is 1:0.6 to 5; the mass volume ratio of the monomer A to the organic solvent in the step (1) is 1g:5 to 15mL.
4. The method of claim 1, wherein: the solvent in the step (2) is at least one of dichloromethane, trichloromethane, tetrahydrofuran and benzyl alcohol;
the concentration of the porous polymer solution in the step (2) is 0.5 to 10 weight percent.
5. The method of claim 1, wherein: the amine solution in the step (3) is at least one of ethylenediamine, 1, 3-propanediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, ammonia water and p-phenylenediamine, and the concentration of the amine solution is 25-99%.
6. The method of claim 1, wherein: the heating reaction in the step (1) is stirring for 10-60 min at 100-200 ℃; the heat treatment temperature in the step (3) is 25-130 ℃, and the reaction time is 0.5-12 h.
7. The method of claim 1, wherein: metal organic framework particles can be added in the step (2), and the metal organic framework particles and the porous polymer are mixed to prepare a film; the preparation method of the metal organic framework particles comprises the following steps: the metal salt, the organic ligand and the solvent are uniformly mixed, a hydrothermal synthesis method is used for heating reaction, and the metal organic framework particles can be obtained after the reaction is finished.
8. The method of claim 1, wherein: the mass ratio of the metal organic framework particles to the porous polymer is 0.03: 0.07-0.5 g;
in the preparation method of the metal organic framework particles, the metal element in the metal salt is at least one of V, zn, ti, cr, cu, co, fe, ni, mg, cd, sr, zr, nb, mo, ba, mg, mn, al and Gd;
in the preparation method of the metal organic framework particles, the organic ligand is at least one of trimesic acid, terephthalic acid, 2-methylimidazole and imidazole-2-formaldehyde;
in the preparation method of the metal organic framework particles, the solvent is at least one of methanol, ethanol, propanol, isopropanol, tert-butanol, ethylene glycol, glycerol, N-dimethylformamide, N-dimethylacetamide and N, N-diethylformamide;
in the preparation method of the metal organic framework particles, the mass ratio of the metal salt to the organic ligand is 1:0.65 to 5;
in the preparation method of the metal organic framework particles, the heating reaction is heat treatment for 12-24 h at 100-150 ℃.
9. A chemical vapor amination-modified porous polymer membrane prepared by the method of any one of claims 1 to 8.
10. The chemical vapor amination modified porous polymer membrane of claim 9 in separating CO 2 /N 2 Application in gas.
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