CN115382357A - Adapt to medium and high concentration CO 2 Membrane separation technology with high-efficiency capture - Google Patents
Adapt to medium and high concentration CO 2 Membrane separation technology with high-efficiency capture Download PDFInfo
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Abstract
The invention discloses a method for adapting to medium-high concentration CO 2 High-efficiency trapping membrane separation technology for designing PI (polyimide) thin film from the perspective of molecular structure, wherein the thin film is prepared from hexafluoro dianhydride and specially prepared N 1 - (1, 1Phenyl radical]-3-yl) -N 1 - (4-aminophenyl) benzene-1, 4-diamine. In the structure of-CF 3 The group improves the rigidity of chain segment through strong electron-withdrawing effect, the bulk benzene ring side group reduces the stacking density through increasing steric hindrance, and-CF is utilized 3 The synergistic effect of the group and the benzene ring side group increases the free volume of the PI film, improves the gas permeability of the film and realizes CO 2 High efficiency capture and membrane separation.
Description
Technical Field
The invention belongs to the field of polymer chemistry, and particularly relates to a method for adapting to medium-high concentration CO 2 High-efficiency trapping membrane separation technology. The microporous material can generate a microporous structure with high specific surface area due to the twisting and folding of a rigid molecular chain of the microporous material, and the like, the corresponding membrane material has excellent gas separation performance, and polyimide with micropores is obtained by introducing a rigid twisted structural unit into a polyimide main chain. In particular to a preparation method of polyamide acid monomer containing rigid twisted unit and the synthesis of high molecular polyimide for CO 2 A separation membrane with high-efficiency capture.
Background
Reports on rapid climate change emphasize the risks of ecosystems and the severe impact on human life. The constant accumulation of artificial greenhouse gases in the atmosphere is one of the main causes of rapid climate change. Artificial greenhouse gases mainly comprise CH 4 、NO X And CO 2 (the latter accounts for approximately 77% of the anthropogenic greenhouse gases). 1.88 hundred million tons of CO according to Keeling Curve 2 Emission of CO in the atmosphere 2 The content increased by 1ppm. IPPC reported prediction that by 2035, CO 2 The concentration will rise to 450ppm, and the global temperature may rise by 2 ℃. In 2018, month 10, a report issued by IPCC indicated that controlling global warming to 1.5 ℃ would be more beneficial to humans and natural ecosystem than global warming of 2 ℃. Further control of the temperature rise means that we are faced with greater challenges and more effective measures are required. China promises the world, and compared with 2005, 2030 units of total domestic production value CO 2 Reduction of emissions by 60% -65% CO 2 The emission reaches a peak value and strives for early implementation. CO 2 2 The main emitters of (A) are the energy sector, the steel and cement industry, which are currently present in these sectorsMitigation strategies have mainly focused on processes that improve energy efficiency, turn to low carbon, energy intensive, and Carbon Capture and Sequestration (CCS) technologies. To control global temperature rise, CO is implemented 2 The emission reduction, the vigorous development and utilization of the CCS technology become a certain trend.
CO 2 The capture technique refers to the separation of CO 2 Separate from flue gas discharged from power plants, iron and steel plants, coal chemical plants and the like, and avoid CO 2 A technique for direct discharge to the atmosphere. According to the principle of the reaction, CO 2 The trapping technology mainly comprises an adsorption method, an absorption method, a membrane method and a cryogenic separation method. According to CO 2 The partial pressure, the working conditions and the composition of the mixed gas can be selected according to different sources and different technologies for capturing CO 2 。
In CO 2 Among the trapping technologies, membrane separation is one of the most promising environmental protection methods. The membrane separation process is a pressure-driven process in which a pressure difference between both sides of the membrane is used as a driving force. Membrane separation for CO capture 2 The principle of (1) is to utilize the difference of diffusivity, solubility and adsorption capacity of different gases to convert CO 2 Separated from the mixed gas, thereby trapping CO by using a membrane separation method 2 No matter phase change occurs. The key to membrane separation is the choice of membrane material. According to the difference of the preparation materials of the membrane, the membrane can be divided into an organic membrane, an inorganic membrane and a blending membrane. A more studied organic material is polyimide (PI film). With conventional CO 2 Compared with the trapping technology, the membrane separation method has the advantages of high separation performance, low cost, environmental friendliness and the like, and is widely concerned by researchers at home and abroad. However, membrane separation is industrially limited by membrane area, service life, etc., so that the membrane separation technology is mainly used for treating medium and small amounts of CO 2 Trapping, for use in large scale processes, requires further improvements in the thermal, mechanical and chemical stability of the membrane. The membrane material is the key to the membrane separation process.
In order to increase the medium and high concentration of CO 2 The invention designs a PI film from the perspective of molecular structure, wherein the PI film is prepared from hexafluoro dianhydride and specially prepared N 1 - (1, 1]-3-yl) -N 1 - (4-amino)Phenyl) benzene-1, 4-diamine monomer, -CF in this structure 3 The group improves the rigidity of a chain segment through a strong electron-withdrawing effect, so that the stability of the material is improved, and the bulk phenyl side group reduces the stacking density through increasing the steric hindrance, -CF 3 The group and the benzene ring side group have synergistic effect, the free volume of the PI film is increased together, and the gas permeability, the thermal stability and the chemical stability of the film are improved, so that CO is realized 2 High-efficiency trapping membrane separation technology.
Disclosure of Invention
The situation of warming the climate is more severe, and CO is implemented 2 Emission reduction measures are not very slow. CCS technology is one of the most effective measures. At present, CO 2 The most studied trapping techniques include adsorption, absorption, and membrane separation. Compared with other trapping technologies, the membrane separation method has the advantages of high separation performance, low cost, small environmental pollution and the like, and has wide development prospect. The preparation material of the membrane is the key of the membrane separation method. The polymer membrane is widely researched for 23428due to low cost and simple preparation method, but the permeability and the selectivity of the polymer membrane are mutually restricted, so that the polymer membrane is difficult to simultaneously improve, and the industrial application of the polymer membrane is limited.
To increase CO 2 The invention provides a separation technology of a high-efficiency trapping membrane, which adopts the following technical scheme:
synthesis of S1, 3-bromo-N, N-bis (4-nitrophenyl) aniline (N-TmBr): taking a solution prepared by using 3-8g of 3-bromoaniline to be 30mmol, taking a solution prepared by using 9-11g of cesium fluoride to be 60mmol, adding the solution into a 500mL three-neck round-bottom flask, and heating to 50-120 ℃ for mixing and dissolving for about 1-2h. Then 5-12g of 1-fluoro-4-nitrobenzene with the concentration of 75mmol, 150-300mL of dimethyl sulfoxide and 120-220mL of ethyl acetate are prepared and added into a 500mL three-neck round bottom flask, and the mixture reacts for 24-48h under nitrogen at the temperature of 150-180 ℃. Then poured into 500-900mL of cold saturated brine and the yellow precipitate was collected and purified by silica gel chromatography using dichloromethane/hexane as eluent, the purified product was light yellow needle crystals.
S2, N-bis (4-nitrophenyl) - [1,1':4', 1' -triphenyl]-synthesis of 3-amine (N-TmBP): taking the product of the step S12-8g of N-TmBr, formulated to 10-15mmol and using 2-4g of 4-biphenylboronic acid, formulated to 11-16mmol, was added to a 500mL three-necked round bottom flask, heated to 40-50 ℃ and subjected to reflux condensation with a Soxhlet extractor. Then 0.2-0.5g of triphenylphosphine palladium is dissolved by 50-70mL of ethanol solution, and 35-45mL of K is added 2 CO 3 The aqueous solution is mixed with 200-500mL tetrahydrofuran, and finally refluxed for 20-72h under nitrogen. After removal of the aqueous layer, the yellow precipitate silica gel was collected by rotary evaporation and purified by dichloromethane chromatography/hexane as eluent. The purified product was light yellow needle crystals. The Soxhlet extractor used in the step is a quadruple valve type JC-SSTQ2.
S3、N 1 - (1, 1]-3-yl) -N 1 Synthesis of- (4-aminophenyl) benzene-1, 4-diamine (A-TmBP): taking 4-8g of the product obtained in step S2, preparing a solution of 10-15mmol of N-TmBP with ethyl acetate, and adding a spoon of 0.05-0.08g of 10% palladium/carbon catalyst and 100-400mL of absolute ethanol into a 500mL three-neck round-bottom flask, then, adding dropwise 3-5mL of hydrazine hydrate with a dropping funnel and refluxing under nitrogen for 24-48 hours. The ethanol was removed by rotary evaporation and the grey precipitate was collected and then chromatographed on silica gel with dichloromethane/hexane as eluent. The purified product was gray crystals.
S4, synthesis and preparation of a PI film (TmBPHF): a solution of A-TmBP in the S3 step (0.3-0.7g) was taken and dissolved in ethyl acetate to give a 1-3mmol solution, and 0.3-0.8g hexafluorodianhydride was taken and dissolved in ethanol to give a 1-3mmol solution, and 5.8-6.9mL dimethylformamide was added to a 50mL flask, and the mixture was stirred at room temperature under argon for about 4-7 hours to form a viscous 5- (2- (4- (1, 1', 4', 1' -triphenyl) -3-yl (4-aminophenyl) amino) phenyl) isoindol-5-yl) -1, 3-hexafluoropropan-2-yl) isoindol-1, 3-dione solution (TmHF). And then uniformly coating a clean and dry glass plate with a film thickness control, and then performing a hot imidization temperature program in a vacuum to be an oven with the temperature of 100-200 ℃ to produce the PI film. The TmBPHF film was removed from the glass substrate after cooling to room temperature.
In the invention, S2 adopts Suzuki coupling reaction, suzuki-Miyaura reaction (Suzuki-Miyaura reaction) zero-valent palladium complex as catalyst, and aryl or alkenyl boric acid or boric acid ester and chlorine, bromine, iodo-arene or olefin are subjected to cross coupling.
Preferably: the 3-bromoaniline selected in the invention is an organic reagent with the purity of more than 96%.
Preferably: the eluent of the gel chromatographic column is totally dichloromethane chromatographic purification/hexane as a mobile phase.
Drawings
FIG. 1 is a simplified structural formula of N-TmBr organic compound in example 1 of the present invention.
FIG. 2 is a NMR spectrum of N-TmBr organic compound in example 1 of the present invention.
FIG. 3 is a schematic structural formula of an N-TmBP organic compound in example 2 of the present invention.
FIG. 4 is a NMR spectrum of N-TmBP organic compound in example 2 of the present invention.
FIG. 5 is a simplified structural formula of an A-TmBP organic compound in example 3 of the present invention.
FIG. 6 shows the NMR spectrum of the A-TmBP organic compound in example 3 of the present invention.
FIG. 7 shows CO in example 1 and comparative examples 1 and 2 of the present invention 2 The selectivity percentage histogram.
FIG. 8 shows CO in example 2 of the present invention and in comparative examples 3 and 4 2 Percent selectivity histogram.
FIG. 9 shows CO in example 3, comparative example 5 and comparative example 6 of the present invention 2 The selectivity percentage histogram.
FIG. 10 is a simplified structural diagram of an organic compound of TmBPHF monomer (PI film monomer) in example 4 of the present invention.
FIG. 11 is a nuclear magnetic resonance hydrogen spectrum of an organic compound of TmBPHF monomer (PI thin film monomer) in example 4 of the present invention.
Detailed Description
The gas separation membrane is a green technology which realizes gas separation by utilizing different rates of different components in mixed gas to permeate the membrane under the driving of pressure difference. The membrane separation has the advantages of high separation efficiency, low energy consumption, simple operation and the like, shows unique advantages in competition with the traditional separation technology (adsorption, absorption, cryogenic separation and the like), plays an important role in purification and purification of gas, energy utilization and environmental management, and has a long-term development in the gas separation membrane technology in the 21 st century so as to replace the existing energy-consuming separation processes of absorption, extraction, rectification and the like. The core of the gas separation membrane lies in the development of a novel membrane material with high flux, high selectivity, thermal stability, chemical stability and the like which are more ideal.
Example 1
Synthesis of S1, 3-bromo-N, N-bis (4-nitrophenyl) aniline (N-TmBr): a solution prepared from 3g of 3-bromoaniline (30 mmol) and a solution prepared from 9g of cesium fluoride (60 mmol) were added to a 500mL three-necked round-bottomed flask and mixed and dissolved at 50 ℃ for about 1 hour. Then, 5g of 1-fluoro-4-nitrobenzene with the concentration of 75mmol, 150mL of dimethyl sulfoxide and 120mL of ethyl acetate are prepared and added into a 500mL three-neck round-bottom flask, and the mixture is reacted for 24 hours at 150 ℃ under nitrogen. Then poured into 500mL of cold saturated brine and the yellow precipitate was collected and purified by silica gel chromatography using dichloromethane/hexane as eluent, the purified product being pale yellow needle crystals.
S2, N-bis (4-nitrophenyl) - [1,1':4', 1' -triphenyl]-synthesis of 3-amine (N-TmBP): 2g of the product of the S1 step, formulated to 10mmol and 11mmol using a 2g 4-biphenylboronic acid concentration, were taken and added to a 500mL three-necked round bottom flask, heated to 40 ℃ and subjected to reflux condensation using a Soxhlet extractor. Then 0.2g of palladium triphenylphosphine in 50mL ethanol is taken and 35mL K is added 2 CO 3 The aqueous solution was taken up with 200mL of tetrahydrofuran and finally refluxed under nitrogen for 20h. After removal of the aqueous layer, the yellow precipitate silica gel was collected by rotary evaporation and purified by dichloromethane chromatography/hexane as eluent. The purified product was light yellow needle crystals.
S3、N 1 - (1, 1]-3-yl) -N 1 Synthesis of- (4-aminophenyl) benzene-1, 4-diamine (A-TmBP): taking 4g of the product obtained in step S2, preparing a 10mmol solution of N-TmBP in ethyl acetate, and charging a 500mL three-necked round-bottom flask with a spoonful of 0.05g of 10% palladium on carbon catalyst and 100mL of anhydrous ethanolAfter that, 3mL of hydrazine hydrate was added dropwise with a dropping funnel and refluxed under nitrogen for 24 hours. The ethanol was removed by rotary evaporation and the grey precipitate was collected and then chromatographed on silica gel with dichloromethane/hexane as eluent. The purified product was gray crystals.
S4, synthesis and preparation of a PI film (TmBPHF): 0.3g of the A-TmBP of the S3 step was taken and dissolved in ethyl acetate to give a 1mmol solution, 0.3g of hexafluorodianhydride was taken and dissolved in ethanol to give a 1mmol solution, and 5.8mL of dimethylformamide was added to a 50mL flask and the mixture was stirred at room temperature under argon for about 4 hours to give a viscous 5- (2- (4- (1, 1. The clean and dry glass plate was then coated uniformly with a controlled film thickness and then subjected to a hot imidization temperature program in a vacuum oven at 100 ℃ to produce a PI film. The TmBPHF film was removed from the glass substrate after cooling to room temperature.
Comparative example 1 the procedures were the same as in example 1 except that 3-bromoaniline in step S1 was changed to 4-bromoaniline.
Comparative example 2 Each procedure was the same as in example 1 except that 3-bromoaniline in step S1 was changed to 2-bromoaniline.
TABLE 1
| Detecting items | Comparative example 1 | Comparative example 2 | Example 1 |
| CO 2 Selectivity (%) | 60±0.03 | 50±0.2 | 70±0.02 |
FIG. 1 is a schematic structural formula of an N-TmBr organic compound in example 1 of the present invention, and FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the N-TmBr organic compound in example 1 of the present invention. FIG. 7 shows CO obtained in example 1 of the present invention and comparative examples 1 and 2 2 The selectivity percentage histogram. Table 1 shows inventive example 1 and comparative examples 1 and 2CO 2 Statistical table of percent mean. From FIG. 1 and Table 1, it can be seen that CO is contained in example 1 2 The percentage of selectivity is higher than that of comparative examples 1 and 2. The result shows that rigid biphenyl is modified on the meta position of a benzene ring, the distortion unit can reduce the trade-off relationship, 3-bromoaniline is meta-position arrangement of a nitrogen-containing aromatic heterocyclic polymer, has excellent permeability and selectivity, and is the best choice as a gas separation membrane material, wherein the polyimide has the best comprehensive performance and is used for increasing CO of the polyimide 2 High efficiency of trapping and separation.
Example 2
Synthesis of S1, 3-bromo-N, N-bis (4-nitrophenyl) aniline (N-TmBr): a solution prepared from 8g of 3-bromoaniline (30 mmol) and a solution prepared from 11g of cesium fluoride (60 mmol) were added to a 500mL three-necked round-bottomed flask and mixed and dissolved at 120 ℃ for about 2 hours. Then, 12g of 1-fluoro-4-nitrobenzene with a concentration of 75mmol, 300mL of dimethyl sulfoxide and 220mL of ethyl acetate were added to a 500mL three-necked round-bottom flask and reacted at 180 ℃ under nitrogen for 48 hours. After pouring into 900mL of cold saturated brine, the yellow precipitate is collected and purified by chromatography on silica gel using dichloromethane/hexane as eluent, the purified product being pale yellow needle-like crystals.
S2, N-bis (4-nitrophenyl) - [1,1':4', 1' -Triphenyl]-synthesis of 3-amine (N-TmBP): taking 8g of N-TmBr of the product obtained in the step S1, preparing the product into 15mmol, preparing the product into 16mmol by using 4g of 4-biphenyl boric acid, adding the mixture into a 500mL three-neck round bottom flask, heating the flask to 50 ℃, and performing condensation reflux by using a Soxhlet extractor. Then 0.5g of palladium triphenylphosphine in 70mL ethanol is taken and 45mL K is added 2 CO 3 The aqueous solution was taken up with 500mL of tetrahydrofuran and finally refluxed under nitrogen for 72h. After removal of the aqueous layer, the yellow precipitate silica gel was collected by rotary evaporation and purified by dichloromethane chromatography/hexane as eluent. The purified product was light yellow needle crystals.
S3、N 1 - (1, 1]-3-yl) -N 1 Synthesis of- (4-aminophenyl) benzene-1, 4-diamine (A-TmBP): a15 mmol solution of the product obtained in step S2, 8g of N-TmBP, was taken and a spoon of 0.08g of 10% palladium on carbon catalyst and 400mL of absolute ethanol was added to a 500mL three-necked round-bottom flask, then 5mL of hydrazine hydrate was added dropwise from a dropping funnel and refluxed under nitrogen for 48 hours. The ethanol was removed by rotary evaporation and the grey precipitate was collected and then chromatographed on silica gel with dichloromethane/hexane as eluent. The purified product was gray crystals.
S4, synthesis and preparation of a PI film (TmBPHF): a solution of 0.7g of the A-TmBP from the S3 step was taken and dissolved in ethyl acetate to give a 3mmol solution, 0.8g of hexafluorodianhydride was taken and dissolved in ethanol to give a 3mmol solution, and 6.9mL of dimethylformamide was added to a 50mL flask and the mixture was stirred at room temperature under argon for about 4-7 hours to give a viscous 5- (2- (4- (1, 1. The clean and dry glass plate was then coated uniformly with a controlled film thickness and then subjected to a hot imidization temperature program in a vacuum oven at 200 ℃ to produce a PI film. The TmBPHF film was removed from the glass substrate after cooling to room temperature.
Comparative example 3-CF was prepared without the addition of hexafluoro-modified dianhydride in step S4 3 Is changed to-CH 3 The remaining steps were the same as in example 2.
Comparative example 4-CF was prepared without the addition of hexafluoro-modified dianhydride in step S4 3 Is changed to-C 2 H 5 The remaining steps were the same as in example 2.
TABLE 2
| Detecting items | Comparative example 3 | Comparative example 4 | Example 2 |
| CO 2 Selectivity (%) | 20±0.06 | 40±0.02 | 80±0.01 |
FIG. 3 is a schematic structural formula of an N-TmBP organic compound in example 2 of the present invention, and FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of the N-TmBP organic compound in example 2 of the present invention. FIG. 8 shows CO obtained in example 2 of the present invention and comparative examples 3 and 4 2 The selectivity percentage histogram. Table 2 shows inventive example 2 and comparative examples 3 and 4CO 2 Statistical table of percent mean of selectivity. From FIG. 8 and Table 2, it can be seen that CO is present in example 2 2 The selectivity and the trapping and separating effect are stronger than those of comparative examples 3 and 4. The result shows that fluorine atoms with higher electronegativity and lower molar polarizability are introduced into the polyimide, so that the material has higher light transmittance, lower water absorption and dielectric constant. For a gas separation membrane, the introduction of fluorine-containing groups reduces the acting force among polyimide molecules, limits the tight packing of molecular chains, increases the free volume, improves the gas permeability, and simultaneously, the larger free volume enables solvent molecules to easily enter the interior of a polymer, thereby improving the solubility of polyimide, improving the processability and increasing the CO content of the polyimide 2 High efficiency of trapping and separation.
Example 3
Synthesis of S1, 3-bromo-N, N-bis (4-nitrophenyl) aniline (N-TmBr): a solution prepared from 4g of 3-bromoaniline (30 mmol) and a solution prepared from 10g of cesium fluoride (60 mmol) were added to a 500mL three-necked round-bottomed flask and mixed and dissolved at 70 ℃ for about 1.3 hours. Then 7g of 1-fluoro-4-nitrobenzene with the concentration of 75mmol, 170mL of dimethyl sulfoxide and 150mL of ethyl acetate are prepared and added into a 500mL three-neck round-bottom flask, and the mixture is reacted for 30 hours at 160 ℃ under nitrogen. Then poured into 700mL of cold saturated brine and the yellow precipitate was collected and purified by silica gel chromatography using dichloromethane/hexane as eluent, the purified product being pale yellow needle crystals.
S2, N-bis (4-nitrophenyl) - [1,1':4', 1' -triphenyl]-synthesis of 3-amine (N-TmBP): the product of step S1 was taken 3g of N-TmBr, formulated at 10-15mmol and 2.5g of 4-biphenylboronic acid at 12mmol was added to a 500mL three-necked round bottom flask and heated to 44 ℃ with a Soxhlet extractor for reflux condensation. Then 0.25g of palladium triphenylphosphine dissolved in 50-70mL of ethanol is taken and 40mL of K is added 2 CO 3 The aqueous solution was taken up with 300mL of tetrahydrofuran and finally refluxed under nitrogen for 48h. After removal of the aqueous layer, the yellow precipitate silica gel was collected by rotary evaporation and purified by dichloromethane chromatography/hexane as eluent. The purified product was light yellow needle crystals.
S3、N 1 - (1, 1]-3-yl) -N 1 Synthesis of- (4-aminophenyl) benzene-1, 4-diamine (A-TmBP): 5g of the product obtained in step S2 were taken and made up into a 12mmol solution with ethyl acetate and a spoon of 0.07g of a 10% palladium on carbon catalyst and 200mL of absolute ethanol was added to a 500mL three-necked round bottom flask, then 4mL of hydrazine hydrate was added dropwise with a dropping funnel and refluxed under nitrogen for 36 hours. The ethanol was removed by rotary evaporation and the grey precipitate was collected and then chromatographed on silica gel with dichloromethane/hexane as eluent. The purified product was gray crystals.
S4, synthesis and preparation of a PI film (TmBPHF): a solution of 0.5g of the A-TmBP of the S3 step dissolved in ethyl acetate to 2mmol, 0.4g of hexafluorodianhydride dissolved in ethanol to make a 2mmol solution, and purified 6mL of dimethylformamide was added to a 50mL flask and the mixture was stirred at room temperature under argon for about 5 hours to form a viscous 5- (2- (4- (1, 1. The clean and dry glass plate was then coated uniformly with a controlled film thickness and then subjected to a hot imidization temperature program in a vacuum oven at 150 ℃ to produce a PI film. The TmBPHF film was removed from the glass substrate after cooling to room temperature.
Comparative example 5 the steps were the same as in example 3 except that 4-biphenylboronic acid was not added in step S2.
Comparative example 6 the respective steps of changing 4-biphenylboronic acid to boronic acid were the same as in example 3 except that 4-biphenylboronic acid was not added in step S2.
TABLE 3
| Detecting items | Comparative example 5 | Comparative example 6 | Example 3 |
| CO 2 Selectivity (%) | 10±0.04 | 20±0.01 | 80±0.02 |
FIG. 5 shows a simplified structure of the A-TmBP organic compound in example 3 of the present invention, and FIG. 6 shows NMR of the A-TmBP organic compound in example 3 of the present inventionAnd (4) a hydrogen spectrum. FIG. 9 shows CO obtained in example 3 of the present invention and comparative examples 5 and 6 2 The selectivity percentage histogram. Table 3 shows inventive example 3 and comparative examples 5 and 6CO 2 Statistical table of percent mean of selectivity. From FIG. 8 and Table 2, it can be seen that CO is present in example 2 2 The selectivity and the trapping and separating effect are stronger than those of comparative examples 5 and 6. The result shows that terphenyl introduced by Suzuki coupling reaction can effectively rotate in a molecular space, effectively limits the tight packing of molecular chains, generates more free spaces around the molecular chains, and is more beneficial to gas molecules to pass through, thereby improving the gas permeability of the polyimide film material. The rigid chain forging and the flexible chain forging are combined by multi-component copolymerization, the rigid chain segment provides a main framework structure, the thermal stability of the gas separation material can be kept, and meanwhile, the flexible chain segment is convenient for gas molecules to penetrate through, so that the gas permeability is ensured.
Example 4
Synthesis of S1, 3-bromo-N, N-bis (4-nitrophenyl) aniline (N-TmBr): a solution prepared from 6g of 3-bromoaniline to 30mmol and a solution prepared from 10g of cesium fluoride to 60mmol were added to a 500mL three-necked round-bottomed flask and mixed and dissolved at 70 ℃ for about 1.4h. Then 7g of 1-fluoro-4-nitrobenzene with the concentration of 75mmol, 170mL of dimethyl sulfoxide and 180mL of ethyl acetate are prepared and added into a 500mL three-neck round-bottom flask, and reacted for 40 hours at 160 ℃ under nitrogen. After pouring into 800mL of cold saturated brine, the yellow precipitate is collected and purified by chromatography on silica gel using dichloromethane/hexane as eluent, the purified product being pale yellow needle-like crystals.
S2, N-bis (4-nitrophenyl) - [1,1':4', 1' -triphenyl]-synthesis of 3-amine (N-TmBP): the product from step S1, 6g of N-TmBr, formulated to 12mmol and formulated to 12mmol using 2-4g of 4-biphenylboronic acid in concentration, was taken and added to a 500mL three-necked round bottom flask, heated to 46 ℃ and subjected to reflux condensation using a Soxhlet extractor. Then 0.4g of palladium triphenylphosphine in 55mL of ethanol are taken and 37mL of K are added 2 CO 3 The aqueous solution was taken up in 250mL of tetrahydrofuran and finally refluxed under nitrogen for 70h. After removal of the aqueous layer, the yellow precipitate was collected by rotary evaporation and evaporationThe precipitate was silica gel and chromatographed with dichloromethane/hexane as eluent. The purified product was light yellow needle crystals.
S3、N 1 - (1, 1]-3-yl) -N 1 Synthesis of- (4-aminophenyl) benzene-1, 4-diamine (A-TmBP): 5g of the product obtained in step S2 was taken to prepare an 11mmol solution of N-TmBP in ethyl acetate, and a spoon of 0.07g of 10% palladium on carbon catalyst and 300mL of absolute ethanol was added to a 500mL three-necked round-bottom flask, and then 4.5mL of hydrazine hydrate was added dropwise from a dropping funnel and refluxed under nitrogen for 36 hours. The ethanol was removed by rotary evaporation and the grey precipitate was collected and then chromatographed on silica gel with dichloromethane/hexane as eluent. The purified product was gray crystals.
S4, synthesis and preparation of a PI film (TmBPHF): 0.4g of the A-TmBP from the S3 step was taken and dissolved in ethyl acetate to give a 1.2mmol solution, 0.5g of hexafluorodianhydride was taken and dissolved in ethanol to give a 1.5mmol solution, and 6mL of dimethylformamide was added to a 50mL flask and the mixture was stirred at room temperature under argon for about 5 hours to give a viscous 5- (2- (4- (1, 1. The clean and dry glass plate was then coated uniformly with a controlled film thickness and then subjected to an oven in vacuum with a thermal imidization temperature program of 170 ℃ to produce PI films. The TmBPHF film was removed from the glass substrate after cooling to room temperature.
Fig. 10 is a simplified structural formula of an organic compound of the TmBPHF monomer (PI thin film monomer) in example 4 of the present invention, and fig. 11 is a nuclear magnetic resonance hydrogen spectrum of the organic compound of the TmBPHF monomer (PI thin film monomer) in example 4 of the present invention. The trifluoromethyl group introduced into the polyimide with the large benzene ring side group is interpenetrated on a polymer main chain, so that the rigidity of the main chain is enhanced, and meanwhile, the existence of the trifluoromethyl group increases the volume of the side group and generates more free spaces, so that the gas permeability is improved on the premise of keeping high selectivity; in addition, the trifluoromethyl group can also improve the solubility of gas, the bulky benzene ring side group reduces the stacking density by increasing steric hindrance, and-CF is utilized 3 Of radicals and phenyl ring side groupsThe free volume of the PI film is increased by the synergistic effect, the gas permeability of the PI film is improved, and CO is realized 2 High efficiency capture and membrane separation.
Finally, it should be noted that: the above-mentioned embodiments are only used for illustrating the technical solution of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. Adapt to medium and high concentration CO 2 The membrane separation method with high-efficiency capture is characterized in that: the specific steps for preparing the PI film are as follows: synthesis of S1, 3-bromo-N, N-bis (4-nitrophenyl) aniline (N-TmBr): taking a solution prepared from 3-8g of 3-bromoaniline to be 30mmol, taking a solution prepared from 9-11g of cesium fluoride to be 60mmol, adding the solution into a 500mL three-neck round-bottom flask, heating to 50-120 ℃, mixing and dissolving for about 1-2h, then preparing 5-12g of 1-fluoro-4-nitrobenzene with the concentration of 75mmol, 150-300mL of dimethyl sulfoxide and 120-220mL of ethyl acetate, continuously adding the mixture into the 500mL three-neck round-bottom flask, reacting for 24-48h at 150-180 ℃ under nitrogen, then pouring the mixture into 500-900mL of cold saturated saline, collecting and purifying yellow precipitate by silica gel chromatography, using dichloromethane/hexane as eluent, and obtaining a purified product which is light yellow needle-shaped light yellow needle crystals; s2, N-bis (4-nitrophenyl) - [1,1':4', 1' -triphenyl]-synthesis of 3-amine (N-TmBP): taking 2-8g of N-TmBr prepared into 10-15mmol and prepared into 11-16mmol by using the concentration of 2-4g of 4-biphenylboronic acid of the S1 step, adding the mixture into a 500mL three-neck round-bottom flask, heating the flask to 40-50 ℃, performing condensation reflux by using a Soxhlet extractor, then taking 0.2-0.5g of triphenylphosphine palladium dissolved by using 50-70mL of ethanol solution, and adding 35-45mL of K 2 CO 3 Mixing the aqueous solution with 200-500mL tetrahydrofuran, refluxing under nitrogen for 20-72 hr, removing water layer, collecting yellow precipitate silica gel by rotary evaporation and evaporation, and purifying with dichloromethane chromatographyUsing hexane/ethyl acetate as eluent, and purifying the product to obtain light yellow needle crystals; s3, N 1 - (1, 1]-3-yl) -N 1 Synthesis of- (4-aminophenyl) benzene-1, 4-diamine (A-TmBP): taking 4-8g of the product obtained in step S2, preparing a solution of 10-15mmol of N-TmBP with ethyl acetate, and adding a spoon of 0.05-0.08g of 10% palladium/carbon catalyst and 100-400mL of absolute ethanol into a 500mL three-neck round-bottom flask, then, dropwise adding 3-5mL of hydrazine hydrate with a dropping funnel and refluxing under nitrogen for 24-48 hours. The ethanol was removed by rotary evaporation and the grey precipitate was collected and then chromatographed on silica gel with dichloromethane/hexane as eluent. The purified product was gray crystals; s4, synthesis and preparation of a PI film (TmBPHF): taking a solution of a-TmBP dissolved in ethyl acetate to 1-3mmol in 0.3-0.7g of S3 step, taking a solution of 0.3-0.8g of hexafluorodianhydride dissolved in ethanol to make 1-3mmol, and purifying 5.8-6.9mL of dimethylformamide was added to a 50mL flask, the mixture was stirred under argon at room temperature for about 4-7 hours to form a viscous 5- (2- (4- (1, 1', 4 "-1" -triphenyl) -3-yl (4-aminophenyl) amino) phenyl) isoindol-5-yl) -1, 3-hexafluoropropane-2-yl) isoindol-1, 3-dione solution (bphf), followed by uniformly coating a control film thickness on a clean and dried glass plate, followed by a thermal imidization temperature program in vacuum oven at 100-200 ℃ to produce a PI film, the TmBPHF film was cooled to room temperature and removed from the glass substrate to obtain a film having a high concentration of CO 2 A PI film with high-efficiency trapping function.
2. An adapted medium-high concentration of CO according to claim 1 2 The membrane separation method with high-efficiency capture is characterized in that: the 3-bromoaniline selected in the S1 is an organic reagent with the purity of 96%.
3. An adapted medium-high concentration of CO according to claim 1 or 2 2 The membrane separation method with high-efficiency capture is characterized in that: the mass of the 3-bromoaniline selected in the S1 is 3g.
4. An adapted medium to high concentration of CO according to claim 3 2 The membrane separation method with high-efficiency capture is characterized in that: the eluent of the gel chromatographic column is all dichloromethane chromatographic purification/hexane as a mobile phase.
5. An adapted medium to high concentration of CO according to claim 2 2 The membrane separation method with high-efficiency capture is characterized in that: the Soxhlet extractor used in S2 is a quadruple valve type JC-SSTQ2.
6. An adapted medium to high concentration of CO according to claim 5 2 The membrane separation method with high-efficiency capture is characterized in that: when the palladium/carbon catalyst is prepared in the step S3, a spoon of 0.05g of 10% palladium/carbon catalyst is selected.
7. An adapted medium-high concentration CO according to claim 6 2 The membrane separation method with high-efficiency capture is characterized in that: when thermal imidization is performed in the step S4, a thermal imidization temperature program in vacuum is an oven temperature of 150 ℃.
8. Use of a moderate to high concentration of CO according to any one of claims 1 to 7 2 A PI separation membrane prepared by a high-efficiency trapping membrane separation technology.
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| JPH09173801A (en) * | 1995-12-28 | 1997-07-08 | Tokyo Electric Power Co Inc:The | Gas separation membrane and manufacture thereof |
| CN104829853A (en) * | 2015-05-15 | 2015-08-12 | 中国科学院化学研究所 | Polyimide gas separation membrane as well as preparation method and applications thereof |
| CN111363148A (en) * | 2020-03-26 | 2020-07-03 | 天津理工大学 | Preparation method of binaphthyl network type polyimide resin and film and application of binaphthyl network type polyimide resin and film in gas separation |
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| JPH09173801A (en) * | 1995-12-28 | 1997-07-08 | Tokyo Electric Power Co Inc:The | Gas separation membrane and manufacture thereof |
| CN104829853A (en) * | 2015-05-15 | 2015-08-12 | 中国科学院化学研究所 | Polyimide gas separation membrane as well as preparation method and applications thereof |
| CN111363148A (en) * | 2020-03-26 | 2020-07-03 | 天津理工大学 | Preparation method of binaphthyl network type polyimide resin and film and application of binaphthyl network type polyimide resin and film in gas separation |
| CN112275147A (en) * | 2020-09-01 | 2021-01-29 | 中国科学院山西煤炭化学研究所 | Self-polymerization microporous polyimide gas separation membrane and preparation method and application thereof |
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